JP7014378B2 - Toner manufacturing method - Google Patents

Description

The present invention relates to a method for producing a toner 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 corresponding to high image quality and high speed is required. Polyester resin, whose composition is easy to adjust, is widely used as a binder resin for toner in order to improve high image quality and high speed, especially to improve thermal characteristics. Further, a plurality of resin components are compounded. Attempts have been made to use the resin or to mix and use a plurality of resins. Attempts have also been made to appropriately select the wax contained in the toner.

In Patent Document 1, a binder resin composition for toner containing an amorphous polyester (A) and a crystalline polyester (C), wherein the amorphous polyester (A) is a hydrocarbon wax having a hydroxyl group. In the presence, it is obtained by polycondensing a raw material monomer containing an alcohol component (A-al) and a carboxylic acid component (A-ac), and the alcohol component (A-al) contains an aliphatic diol and is an alcohol. A binder resin for toner, wherein the content of the hydrocarbon wax having a hydroxyl group with respect to the total amount of 100 parts by mass of the component (A-al) and the carboxylic acid component (A-ac) is 0.5 parts by mass or more and 10 parts by mass or less. The composition is described. It is described that this makes it possible to obtain an electrophotographic toner having excellent low temperature fixability, storage stability, image density of printed matter, and dot reproducibility of printed matter.
In Patent Document 2, a binder resin composition for toner containing an amorphous composite resin having a polyester resin portion and a vinyl-based resin portion and crystalline polyester, wherein the composite resin has a melting point of 60 to 110. For toners, the crystalline polyester is obtained by using a raw material monomer containing an aliphatic diol having 6 to 12 carbon atoms and containing 0.5 to 10% by mass of a structural portion derived from a hydrocarbon wax having a hydroxyl group at ° C. Bundling resin compositions are described. It is described that the toner obtained by this can achieve both low temperature fixability and storage stability.
In Patent Document 3, it is a toner for static charge image development containing a binder resin, a colorant and a mold release agent, wherein the binder resin is polyester and the mold release agent is ester wax and petroleum wax. A toner for developing a static charge image is described. It is stated that the toner obtained thereby is excellent in fixability and durability.

Japanese Unexamined Patent Publication No. 2016-90854 Japanese Unexamined Patent Publication No. 2015-7765 Japanese Unexamined Patent Publication No. 2005-141189

However, with the toners described in Patent Documents 1 to 3, it is difficult to say that a toner that sufficiently balances two contradictory characteristics of excellent image density and offset resistance of printed matter can be obtained.

The present invention relates to a method for producing a toner that exhibits excellent image density and hot offset resistance of printed matter.

The present inventors focused on the constituent components of the toner and conducted a study. As a result, the combined use of a resin having a specific structure and two or more types of wax having a specific melting point has both excellent image density of printed matter and excellent hot offset resistance. Found to be effective in doing so.

That is, the present invention relates to the following toner manufacturing method.
Step 1: A step of melt-kneading a mixture containing a constituent component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxy group, an amorphous resin A having a polyester resin segment, a wax D1, a wax D2, and a colorant.
Step 2: A step of crushing and classifying the melt-kneaded product obtained in the above step 1 to obtain toner particles, and a step of obtaining toner particles.
It is a manufacturing method of toner including
The melting point Tm1 of the wax D1 is lower than the melting point Tm2 of the wax D2, and the temperature T at which the mixture is melt-kneaded in step 1 is a temperature exceeding the melting point Tm1 of the wax D1 and 5 from the melting point Tm2 of the wax D2. A method for manufacturing a toner, which has a temperature equal to or lower than a high temperature.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for producing a toner which exhibits excellent image density and hot offset resistance of printed matter.

[Toner manufacturing method]
The method for producing the toner of the present invention is
Step 1: A step of melt-kneading a mixture containing a constituent component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxy group, an amorphous resin A having a polyester resin segment, a wax D1, a wax D2, and a colorant.
Step 2: A step of crushing and classifying the melt-kneaded product obtained in the above step 1 to obtain toner particles, and a step of obtaining toner particles.
including.
In the method for producing the toner, the melting point Tm1 of the wax D1 is lower than the melting point Tm2 of the wax D2, and the temperature T at which the mixture is melt-kneaded in step 1 is a temperature exceeding the melting point Tm1 of the wax D1. Moreover, the temperature is 5 ° C. higher than the melting point Tm2 of the wax D2 and is lower than the temperature.
By this manufacturing method, a toner exhibiting excellent image density and hot offset resistance of printed matter can be obtained. The reason is not clear, but it can be considered as follows.

The toner obtained by the production method of the present invention contains an amorphous resin A having a constituent component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxy group and a polyester resin segment, and at least two kinds of waxes D1 and D2. However, the melting point Tm1 of the wax D1 is lower than the melting point Tm2 of the wax D2.
In the production method of the present invention, an amorphous resin A having a constituent component derived from the hydrocarbon wax W1 having a hydroxyl group or a carboxy group and a polyester resin segment is used. The temperature of the mixture containing the amorphous resin A, at least two kinds of waxes D1 and D2, and the colorant is higher than the melting point Tm1 of the wax D1 and 5 ° C. higher than the melting point Tm2 of the wax D2. By melt-kneading with, the wax D1 having a low melting point and easily melting acts with the colorant, and further interacts with the constituent components derived from the hydrocarbon wax W1 in the resin to finely disperse the colorant in the mixture. .. On the other hand, the wax D2, which has a high melting point and is difficult to melt, forms a domain of an appropriate size without being excessively finely dispersed in the mixture. Therefore, it is considered that the obtained toner not only has excellent image density of printed matter, but also has excellent hot offset resistance because wax can effectively act during development.

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 peak temperature (° C.)) in the measurement method described in Examples described later. The crystalline resin has a crystallinity index of 0.6 or more and 1.4 or less. Amorphous resins have a crystallinity index of less than 0.6 or more than 1.4. 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.
In the specification, the carboxylic acid component of polyester includes not only the 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 and 3 or less carbon atoms). included.
In the specification, the "binding resin" is a general term for resin components contained in a toner containing an amorphous resin A and a crystalline resin B.
Hereinafter, each step and the like of the manufacturing method of the present invention will be described.

[Step 1]
Step 1 is an amorphous resin A, a wax D1, a wax D2, and a coloring having a constituent component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxy group (hereinafter, also simply referred to as “hydrocarbon wax W1”) and a polyester resin segment. This is a step of melt-kneading the mixture containing the agent.
The melt-kneading is preferably performed in the presence of the crystalline resin B.
Hereinafter, each component used in step 1 will be described.

<Amorphous resin A>
The amorphous resin A has a constituent component derived from the hydrocarbon wax W1 having a hydroxyl group or a carboxy group and a polyester resin segment from the viewpoint of obtaining a toner exhibiting excellent image density and hot offset resistance of printed matter. The amorphous resin A is a resin obtained by polycondensing an alcohol component and a carboxylic acid component in the presence of, for example, a hydrocarbon wax W1 having a hydroxyl group or a carboxy group.
The amorphous resin A has a constituent component derived from the hydrocarbon wax W1 having a hydroxyl group or a carboxy group, and a polyester resin segment, preferably further, from the viewpoint of further improving the image density and hot offset resistance of the printed matter of the toner. It has an addition polymerization resin segment.

(Constituents derived from hydrocarbon wax W1)
The constituent component derived from the hydrocarbon wax W1 is, for example, the hydrocarbon wax W1 covalently bonded to the polyester resin segment by reacting with a hydroxyl group or a carboxy group.
The hydrocarbon wax W1 has a hydroxyl group or a carboxy group. The hydrocarbon wax W1 may have one or both of a hydroxyl group and a carboxy group, but is preferably a hydroxyl group from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance. And has a carboxy group.
The hydrocarbon wax W1 is obtained, for example, by modifying an unmodified hydrocarbon wax by a known method. Examples of the raw material of the hydrocarbon wax W1 include paraffin wax, Fishertroph wax, microcrystalline wax, polyethylene wax, and polypropylene wax. Among these, paraffin wax and Fischer-Tropsch wax are preferable.
Examples of commercially available products of paraffin wax and Fischer-Tropsch wax, which are raw materials for hydrocarbon wax W1, include "HNP-11", "HNP-9", "HNP-10", "FT-0070", and "HNP-51". , "FNP-0090" (all manufactured by Nippon Seiro Co., Ltd.).

The hydrocarbon wax having a hydroxyl group is obtained by modifying a hydrocarbon wax such as paraffin wax or Fischer-Tropsch wax by an oxidation treatment. Examples of the oxidation treatment method include the methods described in JP-A-62-79267 and JP-A-2010-197979. Specifically, there is a method of liquid-phase oxidation of a hydrocarbon wax with a gas containing oxygen in the presence of boric acid.
Examples of commercially available products of hydrocarbon wax having a hydroxyl group include "Unilin 700", "Unilin 425", and "Unilin 550" (all manufactured by Baker Petrolite).

Examples of the hydrocarbon wax having a carboxy group include acid-modified hydrocarbon wax.
The acid-modified hydrocarbon wax can be obtained by introducing a carboxy group into a hydrocarbon wax such as paraffin wax or Fishertroph wax by acid modification. Examples of the acid denaturation method include the methods described in JP-A-2006-328388 and JP-A-2007-84787. Specifically, it is carboxy by adding an organic peroxide such as dicumyl peroxide as a reaction initiator to a melt of a hydrocarbon wax as a raw material and a carboxylic acid compound having an unsaturated bond. The group can be introduced.
Examples of commercially available products of hydrocarbon wax having a carboxy group include maleic anhydride-modified ethylene-propylene copolymer "High Wax 1105A" (manufactured by Mitsui Chemicals, Inc.).

The hydrocarbon wax having a hydroxyl group and a carboxy group can be obtained, for example, by the same method as the oxidation treatment of the hydrocarbon wax having a hydroxyl group.
Examples of commercially available products of hydrocarbon wax having a hydroxyl group and a carboxy group include "Paracol 6420", "Paracol 6470", and "Paracol 6490" (all manufactured by Nippon Seiro Co., Ltd.).

The hydroxyl value of the hydrocarbon wax W1 is preferably 35 mgKOH / g or more, more preferably 40 mgKOH / g or more, still more preferably 50 mgKOH / g, from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance. The above is more preferably 70 mgKOH / g or more, further preferably 90 mgKOH / g or more, and preferably 180 mgKOH / g or less, more preferably 150 mgKOH / g or less, still more preferably 120 mgKOH / g or less, still more preferably 100 mgKOH / g. It is less than or equal to g.

The acid value of the hydrocarbon wax W1 is preferably 1 mgKOH / g or more, more preferably 3 mgKOH / g or more, still more preferably 5 mgKOH / g, from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance. The above is more preferably 10 mgKOH / g or more, further preferably 15 mgKOH / g or more, and preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, still more preferably 20 mgKOH / g or less.

The total hydroxyl value and acid value of the hydrocarbon wax W1 is preferably 40 mgKOH / g or more, more preferably 60 mgKOH / g or more, and further, from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance. It is preferably 80 mgKOH / g or more, more preferably 90 mgKOH / g or more, and preferably 210 mgKOH / g or less, more preferably 175 mgKOH / g or less, still more preferably 140 mgKOH / g or less, still more preferably 120 mgKOH / g or less. be.

The number average molecular weight of the hydrocarbon wax W1 is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, and preferably 2000 or less, more preferably 1700, from the viewpoint of improving the image density of the printed matter. Below, it is more preferably 1500 or less.
The method for measuring the hydroxyl value, acid value, and number average molecular weight of the hydrocarbon wax W1 is as described in Examples.

(Polyester resin segment)
The polyester resin segment is, for example, a segment made of a polyester resin which is a polycondensate of an alcohol component and a carboxylic acid component.

（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、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含有量は、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８０モル％以上、更に好ましくは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。 Hereinafter, each component of the polyester resin segment of the amorphous resin A will be described.
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, 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 value of the sum of y is 1 or more, preferably 1.5 or more, 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. It is preferable to use one or more of these.
The content of the alkylene oxide adduct of bisphenol A is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and more preferably 95 mol% or more in the alcohol component. , 100 mol% or less, more preferably 100 mol%.

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 are 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.

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. Among these, at least one selected from aromatic dicarboxylic acids and linear or branched aliphatic dicarboxylic acids is 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 the aromatic dicarboxylic acid is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 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 80 mol% or less.

The linear or branched aliphatic dicarboxylic acid has preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 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, sebacic acid, dodecanedic acid, and azelaic acid. , Succinic acid substituted with an alkyl group having 1 or more and 20 or less carbon atoms or an alkenyl group having 2 or more and 20 or less 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. Among these, fumaric acid, succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms is preferable, and fumaric acid is more preferable.
The amount of the linear or branched aliphatic dicarboxylic acid is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 3 mol% or more, and preferably 30 mol% or more in the carboxylic acid component. Below, it is more preferably 20 mol% or less, still more preferably 10 mol% or less.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, and examples thereof include trimellitic acid.
When a trivalent or higher polyvalent carboxylic acid is contained, the amount of the trivalent or higher polyvalent carboxylic acid is preferably 3 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 25 mol% or less, still more preferably 20 mol% or less.
These carboxylic acid components can be used alone or in combination of two or more.

The equivalent 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. It is preferably 1.2 or less.

(Addition polymerization resin segment)
The addition polymerization-based resin segment is preferably an addition polymerization of a raw material monomer containing a styrene-based compound from the viewpoint of improving the image density of the printed matter.

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 styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid or salts thereof. Of these, styrene is preferable.
The content of the styrene-based compound in the raw material monomer of the addition polymerization-based resin segment is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more from the viewpoint of improving the image density of the printed matter. It is more preferably 70% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 87% by mass or less, still more preferably 85% by mass or less.

Examples of the raw material monomers other than the styrene compound include (meth) acrylic acid esters such as alkyl (meth) acrylate, benzyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate; ethylene, propylene, and butadiene. Olefins; Halovinyls such as vinyl chloride; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as vinyl methyl ether; Vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone. Be done. Among these, (meth) acrylic acid ester is preferable, and (meth) acrylic acid alkyl is more preferable, from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance.
The carbon number of the alkyl group in the alkyl (meth) acrylate is preferably 1 or more, more preferably 6 or more, still more preferably 6 or more, from the viewpoint of further improving the image density of the printed matter and further improving the hot offset resistance. It is 10 or more, and preferably 24 or less, more preferably 22 or less, still more preferably 20 or less.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, (meth) propyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, and (meth). ) Acrylic acid (iso) amyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid (iso) octyl, (meth) acrylic acid (iso) decyl, (meth) acrylic acid ( Examples thereof include iso) dodecyl, (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, and (meth) acrylic acid (iso) behenyl. Among these, 2-ethylhexyl acrylate and stearyl methacrylate are preferable, and stearyl methacrylate is more preferable.
In addition, "(iso or tertiary)" means normal, iso or tertiary, and "(iso)" means normal or iso.
"(Meta) acrylic acid" means at least one selected from acrylic acid and methacrylic acid.

From the viewpoint of improving the image density of the printed matter, the raw material monomer of the addition polymerization resin segment is preferably made of styrene or contains styrene and (meth) acrylic acid ester, and more preferably styrene and (meth) acrylic acid. It contains an ester, more preferably styrene and an alkyl (meth) acrylate having an alkyl group having 6 or more and 20 or less carbon atoms.

The content of the (meth) acrylic acid ester in the raw material monomer of the addition polymerization resin segment is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15 from the viewpoint of improving the image density of the printed matter. It is by mass or more, more preferably 17% 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.
The total content of the styrene compound and the (meth) acrylic acid ester in the raw material monomer of the addition polymerization resin segment is preferably 80% by mass or more, more preferably 90% by mass, from the viewpoint of further improving the image density of the printed matter. The above is more preferably 95% by mass or more, 100% by mass or less, and further preferably 100% by mass.

When the amorphous resin A has an addition polymerization resin segment, the amorphous resin A is preferably a structural unit derived from a bireactive monomer bonded to the polyester resin segment and the addition polymerization resin segment via a covalent bond. Has.
The “structural unit derived from a bireactive monomer” means a unit in which the functional group and the unsaturated bond site of the bireactive monomer have reacted.
Examples of the bireactive monomer include an addition-polymerizable monomer 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, an addition-polymerizable monomer having a hydroxyl group or a carboxy group is preferable, and an addition-polymerizable monomer having a carboxy group is more preferable from the viewpoint of reactivity.
Examples of the bireactive monomer include acrylic acid, methacrylic acid, fumaric acid, maleic acid and the like. Among these, acrylic acid and methacrylic acid are 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 amorphous resin A. It is more than a molar portion, and 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 constituent component derived from the hydrocarbon wax W1 in the amorphous resin A is preferably 1% by mass or more, more preferably from the viewpoint of further improving the image density of the printed matter and further improving the hot offset resistance. Is 2% by mass or more, more preferably 3% by mass or more, and preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less.

The amount of the polyester resin segment in the amorphous resin A is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of further improving the image density of the printed matter and further improving the hot offset resistance. More preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 99% by mass or less, more preferably 98% by mass or more. And when it has the addition polymerization resin segment described later, it is preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less.

The amount of the addition polymerization resin segment in the amorphous resin A is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, from the viewpoint of further improving the image density of the printed matter. It is more preferably 25% by mass or more, further preferably 35% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less.

In the amorphous resin A, the amount of the structural unit derived from the bireactive monomer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more. Then, it is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.

The total amount of the constituents derived from the hydrocarbon wax W1, the polyester resin segment, the addition polymerization resin segment, and the constituent units derived from the bireactive monomer is preferably 80% by mass or more in the amorphous resin A. It is preferably 90% by mass or more, more preferably 93% by mass or more, further preferably 95% by mass or more, and 100% by mass or less, preferably 99% by mass or less.

In the amorphous resin A, the amounts of the constituent components derived from the hydrocarbon wax W1, the polyester resin segment, the addition polymerization resin segment, and the constituent units derived from the bireactive monomer are the polyester resin segment, the addition polymerization resin segment, and the like. It is expressed as a ratio to the total of the constituent units derived from both reactive monomers.
The above amount is calculated based on the ratio of the amounts of the raw material monomer of the polyester resin segment, the raw material monomer of the addition polymerization resin segment, the bireactive monomer, and the radical polymerization initiator, and the amount of dehydration due to polycondensation in the polyester resin segment or the like. Excludes. When a radical polymerization initiator is used, the mass of the radical polymerization initiator is included in the addition polymerization resin segment for calculation.

(Manufacturing of amorphous resin A)
The amorphous resin A is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component in the presence of a hydrocarbon wax W1 having a hydroxyl group or a carboxy group.
If necessary, add an esterification catalyst such as di (2-ethylhexanoic acid) tin (II), dibutyl tin oxide, and titanium diisopropyrate bistriethanol aminated to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. 0.01 part by mass or more and 5 parts by mass or less, 0 parts by mass of an esterification co-catalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) for a total amount of 100 parts by mass of alcohol component and carboxylic acid component. It may be polycondensed by using 001 parts by mass or more and 0.5 parts by mass or less.
When a monomer having an unsaturated bond such as fumaric acid is used for polycondensation, it is preferably 0.001 part by mass or more with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component, if necessary. A radical polymerization inhibitor of 0.5 parts by mass or less may be used. Examples of the radical polymerization inhibitor include 4-tert-butylcatechol and the like.
The temperature of the polycondensation reaction 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.

When the amorphous resin A has an addition polymerization resin segment, for example, in the step A of the polycondensation reaction with the alcohol component and the carboxylic acid component, and the addition polymerization reaction with the raw material monomer and the bireactive monomer of the addition polymerization resin segment. It may be manufactured by a method including step B.
The process B may be performed after the process A, the process A may be performed after the process B, or the process A and the process B may be performed at the same time.
In step A, a part of the carboxylic acid component is subjected to a polycondensation reaction, then step B is carried out, the reaction temperature is raised again, the rest of the polyvalent carboxylic acid component is added to the polymerization system, and the weight of step A is increased. A method of further advancing the condensation reaction and, if necessary, the reaction with the bireactive monomer is more preferable.

The conditions for the polycondensation reaction are as described above.
Examples of the radical polymerization initiator for the addition polymerization reaction include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile). Can be mentioned.
The amount of the radical polymerization initiator used is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the raw material monomer.
The temperature of the addition polymerization reaction is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, and preferably 220 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 180 ° C. or lower.

(Physical characteristics of amorphous resin A)
The softening point of the amorphous resin A is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C., from the viewpoint of further improving the image density of the printed matter and further improving the hot offset resistance. Above, it is more preferably 110 ° C. or higher, and preferably 140 ° C. or lower, more preferably 135 ° C. or lower, still more preferably 130 ° C. or lower.

The glass transition temperature of the amorphous resin A is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, still more preferably 40, from the viewpoint of further improving the image density of the printed matter and further improving the hot offset resistance. ° 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 of the amorphous resin A is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 16 mgKOH / g or more, and preferably 16 mgKOH / g or more, from the viewpoint of further improving the image density of the printed matter. It is 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, still more preferably 30 mgKOH / g or less.

The softening point, glass transition temperature, and acid value of the amorphous resin A can be appropriately adjusted depending on the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, reaction time, and cooling rate, and these The value is determined by the method described in the examples.
When two or more kinds of amorphous resin A are mixed and used, it is preferable that the softening point, the glass transition temperature and the acid value obtained as the mixture thereof are within the above-mentioned ranges.

<Crystalline resin B>
It is preferable to perform the step 1 in the presence of the crystalline resin B. Examples of the crystalline resin B include a crystalline polyester resin.
Crystalline polyester is a polycondensate of an alcohol component and a carboxylic acid component.

As the alcohol component, α, ω-aliphatic diol is preferable.
The number of carbon atoms of the α, ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less. be.
Examples of the α, ω-aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol Can be mentioned. Among these, 1,6-hexanediol, 1,10-decanediol, and 1,12-dodecanediol are preferable, and 1,10-decanediol is more preferable.

The amount of α, ω-aliphatic diol is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 in the alcohol component. It is less than or equal to mol%, more preferably 100 mol%.

The alcohol component may contain other alcohol components different from the α, ω-aliphatic diol. Examples of other alcohol components include aliphatic diols other than α and ω-aliphatic diols such as 1,2-propylene glycol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; glycerin and penta. Examples thereof include trihydric or higher alcohols such as erythritol and trimethylol propane. These alcohol components can be used alone or in combination of two or more.

As the carboxylic acid component, an aliphatic dicarboxylic acid is preferable.
The aliphatic dicarboxylic acid has preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less.
Examples of the aliphatic dicarboxylic acid include fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, sebacic acid and dodecanedioic acid are preferable, and sebacic acid is more preferable. These carboxylic acid components can be used alone or in combination of two or more.

The amount of the aliphatic dicarboxylic acid is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol in the carboxylic acid component. % Or less, more preferably 100 mol%.

The carboxylic acid component may contain another carboxylic acid component different from the aliphatic dicarboxylic acid. Examples of other carboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and polyvalent carboxylic acids having a valence of 3 or more. 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. Is 1.2 or less.

The crystalline resin B is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component.
The conditions of the polycondensation reaction are as shown in the above-mentioned method for producing the amorphous resin A.

(Physical characteristics of crystalline resin B)
The softening point of the crystalline resin B is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, and the image density and hot resistance of the printed matter from the viewpoint of improving the image density of the printed matter. From the viewpoint of improving the offset property, it is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 100 ° C. or lower.

The melting point of the crystalline resin B is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 65 ° C. or higher, and preferably 100 ° C. or lower, more preferably 100 ° C. or higher, from the viewpoint of improving the image density of the printed matter. Is 90 ° C. or lower, more preferably 80 ° C. or lower.

The acid value of the crystalline resin B is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and more preferably 15 mgKOH / g or more, from the viewpoint of improving the dispersion stability of the resin particles Y described later. It is preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, and further preferably 25 mgKOH / g or less.

The softening point, melting point, and acid value of the crystalline resin B can be appropriately adjusted depending on the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, reaction time, and cooling rate, and their values can be adjusted. , Obtained by the method described in the examples.
When two or more kinds of crystalline resin B are mixed and used, it is preferable that the values of the softening point, the melting point, and the acid value obtained as the mixture thereof are within the above ranges.

<Wax D1 and Wax D2>
In step 1, two types of wax, wax D1 and wax D2, are used. The melting point Tm1 of the wax D1 is lower than the melting point Tm2 of the wax D2.
Examples of the wax D1 and the wax D2 include hydrocarbon waxes, ester waxes, silicone waxes, and fatty acid amides.
Examples of the hydrocarbon wax include polypropylene wax, polyethylene wax, polypropylene-polyethylene copolymer wax, microcrystalline wax, paraffin wax, Fishertropch wax, and sazole wax.
Examples of the ester wax include carnauba wax, montan wax, deoxidizing waxes thereof, and fatty acid ester wax. These can be used alone or in combination of two or more.

As the wax D1, hydrocarbon wax and ester wax are preferable, hydrocarbon wax is more preferable, and paraffin wax is further preferable.
The melting point Tm1 of the wax D1 is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, still more preferably 70 ° C. or higher, and preferably 100 ° C. or lower, more preferably 100 ° C. or higher, from the viewpoint of further improving the image density of the printed matter. Is 90 ° C. or lower, more preferably 80 ° C. or lower.

As the wax D2, a hydrocarbon wax and an ester wax are preferable, a hydrocarbon wax and a carnauba wax are more preferable, a hydrocarbon wax is further preferable, and a Fisher Tropsch wax is further preferable.
The melting point Tm2 of the wax D2 is preferably 60 ° C. or higher, more preferably 75 ° C. or higher, still more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher, and preferably 100 ° C. or higher, from the viewpoint of further improving the hot offset resistance. Is 150 ° C. or lower, more preferably 130 ° C. or lower, still more preferably 110 ° C. or lower.
The difference between the melting point Tm1 of the wax D1 and the melting point Tm2 of the wax D2 | Tm1-Tm2 | is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and further, from the viewpoint of further improving the image density and hot offset resistance of the printed matter. It is preferably 15 ° C. or higher, more preferably 20 ° C. or higher, and preferably 70 ° C. or lower, more preferably 55 ° C. or lower, still more preferably 35 ° C. or lower.

<Colorant>
In step 1, a colorant is used.
As the colorant, all of the dyes and pigments 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 obtained by the method of the present invention may be either black toner or color toner.
The colorants can be used alone or in combination of two or more.

<Charge control agent>
In step 1, a charge control agent may be contained in the mixture. 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 a tertiary amine as a side chain, for example, a quaternary ammonium salt compound, 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.) and the like. Will be.

Examples of the negative charge control agent 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.); 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, "COMPY 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, negative charge control agents are preferable, and metal compounds of salicylic acid compounds are more preferable.
The charge control agent can be used alone or in combination of two or more.

The toner according to the present invention also contains additives such as magnetic powder, fluidity improver, conductivity adjusting agent, reinforcing filler such as fibrous substance, antioxidant, antiaging agent, and cleaning property improving agent. You may be.
The toner according to the present invention is preferably used as a dry toner.

The blending amount of the amorphous resin A is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and preferably 95% by mass or less in the binder resin. It is preferably 90% by mass or less, more preferably 85% by mass or less.
The blending amount of the crystalline resin B is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 50% by mass or more in the binder resin. Is 40% by mass or less, more preferably 30% by mass or less.
The total blending amount of the amorphous resin A and the crystalline resin B is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass in the binder resin. That is all, and it is 100% by mass or less.

The blending amount of the wax D1 is preferably 1 part by mass or more, more preferably 1.5 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance. By mass or more, more preferably 2 parts by mass or more, still more preferably 4 parts by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 7 parts by mass or less, still more preferably. It is 5 parts by mass or less.

The blending amount of the wax D2 is preferably 1 part by mass or more, more preferably 1.5 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance. By mass or more, more preferably 2 parts by mass or more, still more preferably 4 parts by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 7 parts by mass or less, still more preferably. It is 5 parts by mass or less.

The total blending amount of the wax D1 and the wax D2 is preferably 2 parts by mass or more, more preferably 2 parts by mass or more, based on 100 parts by mass of the binder resin from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance. Is 4 parts by mass or more, more preferably 6 parts by mass or more, further preferably 8 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less. ..

The mass ratio of wax D1 to wax D2 (wax D1 / wax D2) is preferably 0.1 or more, more preferably 0.3 or more, and further, from the viewpoint of further improving the image density of the printed matter and the hot offset resistance. It is preferably 0.5 or more, preferably 3.5 or less, more preferably 2 or less, still more preferably 1.5 or less.

The blending amount of the colorant is preferably 3 parts by mass or more, more preferably 5 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance. The above is more preferably 7 parts by mass or more, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less.

The blending amount of the charge control agent is preferably 0.01 part by mass or more, more preferably 0.08 part by mass or more, and further preferably 0.15 part by mass or more with respect to 100 parts by mass of the binder resin. And, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, still more preferably 1.5 parts by mass or less.

In step 1, an additive such as a charge control agent may be contained in the mixture containing the binder resin, the wax D1, the wax D2, and the 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 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. Among these, a twin-screw extruder capable of setting a wide kneading temperature is preferable.
A twin-screw extruder generally has a closed structure in which a barrel covers two screws. A twin-screw extruder can typically be equipped with a heater in any or all of the parts corresponding to the screw supply, compression, and metering, and the parts corresponding to the supply, compression, and weighing section. The barrel temperature (the temperature of the inner wall surface of the twin-screw extruder) can be adjusted by heating the barrel. The kneading temperature T can be adjusted by adjusting the barrel temperature.

In step 1, the kneading temperature T is a temperature exceeding the melting point Tm1 of the wax D1 and a temperature 5 ° C. higher than the melting point Tm2 of the wax D2 from the viewpoint of obtaining a toner showing the image density and hot offset resistance of the printed matter. From the viewpoint of further improving the image density of the printed matter, the temperature is preferably 1 ° C. higher than the melting point Tm1 of the wax D1, more preferably the temperature is 3 ° C. higher than the melting point Tm1 of the wax D1, and more preferably the melting point of the wax D1. The temperature is 5 ° C. higher than Tm1, more preferably 10 ° C. higher than the melting point Tm1 of the wax D1, and from the viewpoint of further improving the hot offset resistance, the melting point Tm2 or less of the wax D2 is more preferable. A temperature 2 ° C. lower than the melting point Tm2 of the wax D2, more preferably a temperature 4 ° C. lower than the melting point Tm2 of the wax D2, still more preferably a temperature 7 ° C. lower than the melting point Tm2 of the wax D2, still more preferably a melting point Tm2 of the wax D2. It is 10 ° C. lower than the temperature.
The kneading temperature T means, for example, in the case of a twin-screw extruder, the set temperature of the barrel (kneading extruder outer cylinder portion). In the case of an open roll type kneader, it means the temperature measured by a non-contact thermometer at the end of the kneaded material discharge side of the high rotation side roll.

The temperature T at which the mixture is melt-kneaded is preferably 80 ° C. or higher and 150 ° C. or lower.
Further, the temperature T at which the mixture is melt-kneaded is preferably 10 ° C. higher than the glass transition temperature of the amorphous resin A, more preferably 15 ° C. or higher, and further, from the viewpoint of improving the productivity of the toner. It is preferably 20 ° C. or higher, and is preferably 60 ° C. higher or lower, more preferably 50 ° C. higher or lower, and still more preferably 40 ° C. higher than the glass transition temperature of the amorphous resin A. ..
The melt-kneaded product obtained in step 1 is cooled to a extent that it can be pulverized, and then subjected to the subsequent step 2.

[Step 2]
Step 2 is a step of pulverizing and classifying the melt-kneaded product obtained in Step 1 to obtain toner particles.
The pulverization in step 2 may be performed in multiple stages. For example, the melt-kneaded product 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.

[toner]
Toner particles can be obtained by the above steps.
The toner particles can be used as they are as toner, but it is preferable to use toner particles that have been treated by adding a fluidizing agent or the like as an external agent to the surface of the toner particles as described later.

The toner contains a constituent component derived from the hydrocarbon wax W1 having a hydroxyl group or a carboxy group, an amorphous resin A having a polyester resin segment, a wax D1, a wax D2, and a colorant. The content of each component in the toner is the same as the preferable range of the blending amount of each component in the above-mentioned step 1.
The toner is, for example, a toner for developing an electrostatic charge image. The toner for developing an electrostatic charge image is used for developing a latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like.

The volume median particle size (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably, from the viewpoint of improving the productivity of the toner, the viewpoint of improving the image density of the printed matter, and the viewpoint of improving the hot offset resistance. Is 3 μm or more, more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, still more preferably 7 μm or less.
The CV value of the toner particles is preferably 12% or more, more preferably 14% or more, still more preferably 16% or more from the viewpoint of improving the productivity of the toner, and from the viewpoint of obtaining a high-quality image. It is preferably 40% or less, more preferably 30% or less.

Examples of the external additive include inorganic fine particles such as hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, and carbon black; and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Of these, hydrophobic silica is preferred.
The amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, and preferably 10 parts by mass or less with respect to 100 parts by mass of the toner particles. , More preferably 7 parts by mass or less, still more preferably 5 parts by mass or less.

The toner can be used as a one-component developer or mixed with a carrier as a two-component developer.

Each property value was measured by the following method. Various evaluations were made by the following methods.

[measurement]
[Acid value and hydroxyl value of resin and wax]
The acid value and hydroxyl value of the resin and wax were measured according to the neutralization titration method described in JIS K 0070: 1992. However, the measurement solvent was chloroform.

[Resin softening point, crystallinity index, melting point and 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 while a load of 1.96 MPa is applied by a plunger to give a diameter of 1.96 MPa. Extruded from a 1 mm, 1 mm long nozzle. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was used as the softening point.
(2) Crystallinity index Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.02 g of the sample into an aluminum pan and cool it to 0 ° C at a temperature lowering rate of 10 ° C / min. did. Then, the sample was allowed to stand still for 1 minute, and then the temperature was raised to 180 ° C. at a heating rate of 10 ° C./min to measure the calorific value. Of the observed endothermic peaks, the temperature of the peak with the largest endothermic area is defined as the maximum endothermic temperature (1), and is determined by (softening point (° C)) / (maximum endothermic temperature (1) (° C)). The crystallinity index was calculated.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample is weighed in an aluminum pan, heated to 200 ° C, and the temperature thereof. It was cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. Next, the temperature of the sample was raised at a heating rate of 10 ° C./min, and the amount of heat was measured. Among the observed endothermic peaks, the temperature of the peak having the largest peak area was defined as the maximum endothermic temperature (2). In the case of crystalline resin, the peak temperature was taken as the melting point.
Further, in the case of an amorphous resin, when a peak is observed, the temperature of the peak is observed, and when a step is observed without a peak, a tangent line indicating the maximum inclination of the curve of the step portion and the step. The temperature at the intersection with the extension of the baseline on the low temperature side of the glass transition temperature was defined as the glass transition temperature.

[Melting point of wax]
Using a 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. Was cooled to 0 ° C. Next, the sample was heated at a heating rate of 10 ° C./min, the amount of heat was measured, and the maximum peak temperature of endotherm was taken as the melting point.

[Wax number average molecular weight (Mn)]
The number average molecular weight (Mn) was measured by the gel permeation chromatography (GPC) method shown below.
(1) Preparation of sample solution The sample is dissolved in chloroform at 25 ° C. so that the concentration becomes 0.5 g / 100 mL, and then this solution is dissolved in a fluororesin filter "DISMIC, 25JP" (ADVANTEC) having a pore size of 0.2 μm. The insoluble component was removed by filtration using (manufactured by) to prepare a sample solution.
(2) Measurement Using the following measuring device and analytical column, chloroform was flowed as an eluent at a flow rate of 1 mL / min, the column was stabilized in a constant temperature bath at 40 ° C, and 100 μL of the sample solution was injected therein. The molecular weight was measured. The molecular weight (weight average molecular weight Mw, number average molecular weight Mn) of the sample is the type name (Mw) of several types of monodisperse polystyrene "TSKgel standard polystyrene": "A-500 (5.0 ^x 102)", "A-". 1000 (1.01 x 10 ³ ) "," A-2500 (2.63 x 10 ³ ) "," A-5000 (5.97 x 10 ³ ) "," F-1 (1.02 x 10 ⁴ ) " ) ”,“ F-2 (1.81 × 10 ⁴ ) ”,“ F-4 (3.97 × 10 ⁴ ) ”,“ F-10 (9.64 × 10 ⁴ ) ”,“ F-20 ( 1.90 × 10 ⁵ ) ”,“ F-40 (4.27 × 10 ⁵ ) ”,“ F-80 (7.06 × 10 ⁵ ) ”,“ F-128 (1.09 × 10 ⁶ ) ” (The above is manufactured by Tosoh Corporation) was used as a standard sample, and the calculation was performed based on a calibration line prepared in advance.
-Measuring device: "HLC-8220GPC" (manufactured by Tosoh Corporation)
-Analytical columns: "GMHXL" and "G3000HXL" (manufactured by Tosoh Corporation)

[Volume medium particle size (D ₅₀ ) and CV value of toner particles]
(1) Measuring device: "Coulter Multisizer (registered trademark) III" (manufactured by Beckman Coulter Co., Ltd.)
(2) Analysis software: "Multisizer (registered trademark) III version 3.51" (manufactured by Beckman Coulter Co., Ltd.)
(3) Measurement conditions:
-Electrolytic solution: "Isoton (registered trademark) II" (manufactured by Beckman Coulter Co., Ltd.)
・ Aperture diameter: 50 μm
(4) Sample dispersion The polyoxyethylene lauryl ether "Emargen (registered trademark) 109P" (HLB (Hydrophile-Lipophile Balance) = 13.6) manufactured by Kao Corporation was dissolved in the electrolytic solution to a concentration of 5% by mass. A dispersion was obtained.
To 5 mL of the above dispersion, 10 mg of the measured sample of the dried toner particles is added and dispersed for 1 minute with an ultrasonic disperser, then 25 mL of the electrolytic solution is added and further dispersed with an ultrasonic disperser for 1 minute. To prepare a sample dispersion.
(5) Measurement method: 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. The volume median particle size (D ₅₀ ) and the volume average particle size were determined from the particle size distribution.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) x 100

[evaluation]
[Evaluation of toner hot offset resistance]
Using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Corporation) on high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the amount of toner adhered to the paper is 0.35 ± 0. A solid image of 0.01 mg / cm ² was output with a length of 50 mm without fixing, leaving a margin of 5 mm from the upper end of the A4 paper.
Next, the same printer in which the fuser was modified to have a variable temperature was prepared, the temperature of the fuser was set to 130 ° C., and the toner was fixed at a speed of 1.7 seconds per sheet in the A4 vertical direction to obtain a printed matter. It was visually confirmed that cold offset and hot offset did not occur when the temperature of the fuser was 130 ° C.
In the same manner, the temperature of the fuser was raised from 130 ° C. to 5 ° C. to fix the toner to obtain a printed matter, and the occurrence of hot offset was visually confirmed. This test was carried out up to the temperature at which hot offset occurs.
The cold offset refers to a phenomenon in which toner adheres to the fixing roller because the toner on the unfixed image is not sufficiently melted or the releasability is not good when the fixing temperature is low. On the other hand, hot offset means that when the fixing temperature is raised to a high temperature, the viscoelasticity of the toner on the unfixed image is lowered, or the releasability is not good under high temperature, so that the toner adheres to the fixing roller. Refers to a phenomenon. The occurrence of cold offset or hot offset can be judged by whether or not the toner adheres to the paper again when the fixing roller goes around. In this test, whether or not the toner adheres to the part 87 mm from the upper end of the solid image. I decided whether or not.
The hot offset generation temperature refers to the temperature at which the hot offset begins to occur. Here, the maximum temperature at which the temperature 5 ° C. lower than the hot offset generation temperature does not generate the hot offset is defined as the hot offset generation temperature. The higher the hot offset generation temperature, the better the hot offset resistance.
In the evaluation of the hot offset generation temperature, a difference in the evaluation temperature of 5 ° C. clearly shows a difference in the fixability of the toner.

[Image density of printed matter]
Using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Corporation) on high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the amount of toner adhered to the paper is 0.35 ± 0. A solid image of 0.01 mg / cm ² was output.
Next, the temperature of the fuser was set to 130 ° C., and the toner was fixed at a speed of 1.7 seconds per sheet in the A4 vertical direction to obtain a printed matter.
30 sheets of high-quality paper "Excellent White Paper A4 size" (manufactured by Oki Data Co., Ltd.) are laid under the printed matter, and the reflected image density of the solid image part of the output printed matter is measured by the colorimeter "SpectroEye" (manufactured by GretagMacbeth). Irradiation conditions; standard light source D50, observation field 2 °, density standard DINNB, absolute white standard) were used for measurement, and the measured values of any 10 points on the image were averaged to obtain the image density. The larger the value, the better the image density.

[Manufacturing of resin]
Production Example A1 (Production of amorphous resin A-1)
Nitrogen was substituted inside a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, and 3268 g of a propylene oxide (2.2) adduct of bisphenol A, 1085 g of terephthalic acid, and di. Add 30 g of tin (II) (2-ethylhexanoic acid), 3 g of 3,4,5-trihydroxybenzoic acid, and 394 g of hydrocarbon wax W1 "Paracol 6490" (manufactured by Nippon Seiwa Co., Ltd.) under a nitrogen atmosphere. The temperature was raised to 235 ° C. while stirring, and the temperature was maintained at 235 ° C. for 8 hours, then the pressure inside the flask was lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 155 ° C. and kept at 155 ° C., and a mixture of 2138 g of styrene, 534 g of stearyl methacrylate, 108 g of acrylic acid, and 321 g of dibutyl peroxide was added dropwise over 3 hours. Then, after holding at 155 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 190 ° C., 70 g of fumaric acid, 269 g of trimellitic acid anhydride, and 2.5 g of 4-tert-butylcatechol were added, and the temperature was raised to 210 ° C. at 10 ° C./hr. Then, the reaction was carried out at 8 kPa to a desired softening point to obtain an amorphous resin A-1. The physical characteristics are shown in Table 1.

Production Examples A2, A4 to A6 (Production of amorphous resins A-2, A-4 to A-6)
Amorphous resins A-2 and A-4 to A-6 were obtained in the same manner as in Production Example A1 except that the raw material composition was changed as shown in Table 1. The physical characteristics are shown in Table 1.

Production Example A3 (Production of amorphous resin A-3)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 4771 g of a propylene oxide (2.2) adduct of bisphenol A, 1923 g of terephthalic acid, and didi. Add 30 g of tin (II) (2-ethylhexanoic acid), 3 g of 3,4,5-trihydroxybenzoic acid, and 349 g of hydrocarbon wax W1 "Paracol 6490" (manufactured by Nippon Seiwa Co., Ltd.) under a nitrogen atmosphere. The temperature is raised to 230 ° C. with stirring, kept at 230 ° C. for 8 hours, cooled to 180 ° C., 73 g of dodecenyl succinic anhydride and 314 g of trimellitic acid anhydride are added, and the temperature rises to 220 ° C. at 10 ° C./hr. After warming, the pressure in the flask was lowered, and the reaction was carried out at 8 kPa to a desired softening point to obtain an amorphous resin A-3. The physical characteristics are shown in Table 1.

Production Example A7 (Production of amorphous resin A-7)
Nitrogen was substituted inside a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, and 3290 g of a propylene oxide (2.2) adduct of bisphenol A, 1092 g of terephthalic acid, and di. 30 g of (2-ethylhexanoic acid) tin (II) and 3 g of 3,4,5-trihydroxybenzoic acid were added, the temperature was raised to 235 ° C while stirring under a nitrogen atmosphere, and the temperature was maintained at 235 ° C for 8 hours. After that, the pressure in the flask was lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 155 ° C. and kept at 155 ° C., and a mixture of 2152 g of styrene, 538 g of stearyl methacrylate, 108 g of acrylic acid, and 323 g of dibutyl peroxide was added dropwise over 3 hours. Then, after holding at 155 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 190 ° C., 71 g of fumaric acid, 271 g of trimellitic acid anhydride, and 2.5 g of 4-tert-butylcatechol were added, and the temperature was raised to 210 ° C. at 10 ° C./hr. After that, the pressure in the flask was reduced, and the reaction was carried out at 4 kPa to a desired softening point to obtain an amorphous resin A-7. The physical characteristics are shown in Table 1.

Production Example B1 (Production of crystalline resin B-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3416 g of 1,10-decanediol and 4084 g of sebacic acid were added, and 135 was stirred. The temperature was raised to ° C., kept at 135 ° C. for 3 hours, and then raised from 135 ° C. to 200 ° C. over 10 hours. Then, 23 g of di (2-ethylhexanoic acid) tin (II) was added and held at 200 ° C. for 1 hour, then the pressure in the flask was lowered, and the mixture was held under a reduced pressure of 8 kPa for 1 hour to obtain a crystalline resin. B-1 was obtained. The physical characteristics are shown in Table 2.

[Manufacturing of toner]
Example 1
(Manufacturing of toner 1)
Amorphous resin A-1 80 parts by mass, crystalline resin B-1 20 parts by mass, negative charge control agent "Bontron E-81" (Orient Chemical Industries Co., Ltd.) in Henschel mixer (manufactured by Nippon Coke Industries Co., Ltd.) 0.2 parts by mass (manufactured by the company), 9 parts by mass of copper phthalocyanine pigment "ECB-301" (manufactured by Dainichi Seika Kogyo Co., Ltd.), paraffin wax "HNP-9" (manufactured by Nippon Seiwa Co., Ltd., melting point: 75 ° C) Add 4 parts by mass and 4 parts by mass of Fisher Tropsch wax "FT-115" (manufactured by Nippon Seiwa Co., Ltd., melting point: 105 ° C.), mix well, and then rotate in the same direction, twin-screw extruder "PCM-30". (Made by Ikekai Co., Ltd., shaft diameter 2.9 cm, shaft cross-sectional area 7.06 cm ² ) was melt-kneaded. The operating conditions are a barrel set temperature of 90 ° C., a shaft rotation speed of 200 r / min (peripheral speed of shaft rotation 0.30 m / sec), and a mixture supply speed of 10 kg / h (mixture supply amount per unit cross-sectional area of the shaft 1.42 kg). / H · cm ² ). The obtained melt-kneaded product is cooled, coarsely pulverized using Rotoplex (manufactured by Toa Kikai Kogyo Co., Ltd.), and then used with an IDS-2 type jet mill (collision plate type jet mill, manufactured by Nippon Pneumatic Mfg. Co., Ltd.). The pulverization pressure was adjusted so that the volume median particle diameter (D ₅₀ ) was 5.5 μm, and fine pulverization was performed. Using a DSX-2 type airflow classifier (manufactured by Nippon Pneumatic Industries, Ltd.), the obtained finely pulverized material has a volume median particle size (D ₅₀ ) of 6.0 μm and a CV value of 25%. The static pressure (internal pressure) was adjusted and classification was performed to obtain toner particles.
100 parts by mass of the toner particles, 2.5 parts by mass of hydrophobic silica "RY50" (manufactured by Nippon Aerosil Co., Ltd., number average particle size; 0.04 μm), and hydrophobic silica "Cabosil (registered trademark) TS720" (Cabot Japan) Manufactured by Co., Ltd., number average particle size; 0.012 μm) 1.0 part by mass was placed in a Henshell mixer and stirred, and passed through a 150 mesh sieve to obtain toner 1. Table 3 shows the evaluation results of the obtained toner.

Examples 2 to 17 and Comparative Examples 1 to 3
(Manufacturing of toners 2 to 17 and 51 to 53)
Except for changing the type of amorphous resin, the type of crystalline resin, the ratio of amorphous resin to crystalline resin, the type of wax, the amount of wax added, and the barrel set temperature of the operating conditions as shown in Table 3. A toner was obtained in the same manner as in Example 1. Table 3 shows the evaluation results of the obtained toner.

From the results in Table 3, it can be seen that the toners of Examples 1 to 17 are superior in image density of printed matter and excellent in hot offset resistance as compared with the toners of Comparative Examples 1 to 3.

Claims (6)

Step 1: A step of melt-kneading a mixture containing a constituent component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxy group, an amorphous resin A having a polyester resin segment, a wax D1, a wax D2, and a colorant.
Step 2: A step of crushing and classifying the melt-kneaded product obtained in the above step 1 to obtain toner particles, and a step of obtaining toner particles.
It is a manufacturing method of toner including
The melting point Tm1 of the wax D1 is lower than the melting point Tm2 of the wax D2, and the temperature T at which the mixture is melt-kneaded in step 1 is a temperature exceeding the melting point Tm1 of the wax D1 and 5 from the melting point Tm2 of the wax D2. The temperature is below the high temperature ,
The melting point Tm2 of the wax D2 is 60 ° C. or higher and 130 ° C. or lower.
The difference between the melting point Tm1 of the wax D1 and the melting point Tm2 of the wax D2 is 5 ° C. or higher and 35 ° C. or lower.
A method for producing a toner, wherein the blending amount of the wax D1 is 1.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin . The method for producing toner according to claim 1, wherein the difference between the melting point Tm1 of the wax D1 and the melting point Tm2 of the wax D2 is 20 ° C. or higher and 35 ° C. or lower . The method for producing a toner according to claim 1 or 2, wherein the step 1 is performed in the presence of the crystalline resin B. The method for producing a toner according to any one of claims 1 to 3, wherein the wax D1 is a hydrocarbon wax. The method for producing a toner according to any one of claims 1 to 4, wherein the wax D2 is a hydrocarbon wax. The crystalline resin B is a carboxylic acid containing 80 mol% or more of α and ω-aliphatic diol having 4 or more and 16 or less carbon atoms and 80 mol% or more of an aliphatic dicarboxylic acid having 8 or more and 16 or less carbon atoms. The method for producing a toner according to claim 3, which is a polycondensate product with a component.