JP6882922B2 - Toner Binder Resin, Toner, Toner Binder Resin Manufacturing Method and Toner Manufacturing Method - Google Patents

Description

The present invention relates to a toner binder resin, a toner, a method for producing a toner binder resin, and a method for producing a toner.

Generally, an electrophotographic method in a PPC (Plan Paper Copy) copying machine or printer for transferring a toner image formed on a photoconductor to a recording paper is performed by the following procedure. First, an electrostatic latent image is formed on the photophotoreceptor. Then, the latent image is developed with toner, the toner image is transferred onto a sheet to be fixed such as paper, and then heat-fixed with a heat roll or a film. In this method, fixing is performed under heating in a state where the thermal roll or film and the toner on the sheet to be fixed are in direct contact with each other, so that the method is quick and the thermal efficiency is extremely good. Therefore, the fixing efficiency is very good.

A binder resin is used as the toner used in such an electrophotographic method. Examples of such toners are described in Patent Documents 1 to 3 below.

Patent Document 1 contains at least a carboxyl group-containing vinyl resin (C) and a glycidyl group-containing vinyl resin (E), and has a mass ratio (S / A) of a styrene-based monomer to an acrylic-based monomer. Toners containing a binder resin of 4.6 or more and less than 8.5 are described.

Patent Document 2 describes a glass obtained from a cross-linking agent (A) having an epoxy equivalent of 1000 to 30,000 and a styrene / acrylic resin satisfying a specific requirement, containing 0.1 to 50% by mass of a gel. Toners containing a binder resin for toner having a transition temperature of 45 to 75 ° C. are described.

Patent Document 3 describes a styrene resin having a weight average molecular weight of 10,000 to 300,000, and one or more blocks of ethylene hydrocarbons and / or conjugated diene hydrocarbons with respect to 100 parts by mass of the styrene resin, and styrene. 0.1 to 20 parts by mass of the block copolymer and / or its hydrocarbon is mixed and dissolved in a uniform state by selecting a solvent having excellent compatibility with both resins, and then the solvent is removed by heating at 150 to 250 ° C. Described is a toner composition for electrophotographic photography, which comprises the resin mixture obtained as a main component as a main component.

International Publication No. 2008/075463 International Publication No. 2004/015498 Japanese Patent No. 3061443

According to the studies by the present inventors, for example, a toner using a binder resin such as the styrene / acrylic copolymer resin described in Patent Documents 1 and 2 has a large dispersion diameter of wax in the toner and falls off. It became clear that it was easy, that is, it was easy to bleed out.
Here, as the printing speed increases, the amount of heat applied to the toner at the time of fixing decreases, so that more advanced fixing performance is required. Further, it is required to improve the transfer efficiency from the photoconductor to the paper during development and reduce the amount of waste toner. When the toner approaches a true sphere, the fixing performance improves, so there are cases where spheroidization processing is performed.
According to the study by the present inventors, when the toner is spheroidized, the wax is more easily bleeded out by the heat treatment for spheroidization, and as a result, the photoconductor contamination resistance is further deteriorated. It became clear that it may end up. The toner using the electrophotographic toner composition described in Patent Document 3 also did not have sufficient photoconductor contamination resistance.

The present invention has been made in view of the above circumstances, and provides a toner having excellent photoconductor contamination resistance.

The present inventors have diligently studied to achieve the above-mentioned problems. As a result, a toner in which wax is finely dispersed in a crosslinked styrene / (meth) acrylic copolymer resin having a styrene-based monomer and a (meth) acrylic-based monomer as constituent units in a specific size. We have found that a toner having excellent photoconductor contamination resistance can be obtained by using a binder resin for use, and have reached the present invention.

According to the present invention, the following toner binder resin, toner, toner binder resin manufacturing method, and toner manufacturing method are provided.

[1]
A binder resin for toner containing a crosslinked styrene / (meth) acrylic copolymer resin (A), a styrene / olefin block copolymer (B), and a wax (C).
The crosslinked styrene / (meth) acrylic copolymer resin (A) contains a carboxyl group-containing vinyl resin (D), a glycidyl group-containing vinyl resin (E), and a reaction product thereof.
The wax (C) is dispersed in the toner binder resin in an island shape, and the maximum diameter of the island-shaped wax (C) is 0.01 μm or more and 0.2 μm or less.
The content of the styrene / olefin block copolymer (B) in the toner binder resin is 0.1% by mass or more and 3.0% by mass when the total content of the toner binder resin is 100% by mass. or less,
The content of the styrene / olefin block copolymer (B) is 0.7% by mass or more with respect to 100% by mass of the carboxyl group-containing vinyl resin (D) in the binder resin for toner.
A toner binder resin in which the styrene ratio in the styrene / olefin block copolymer (B) in the toner binder resin is 65% by mass or more.
[2]
In the toner binder resin according to the above [1],
A toner binder resin in which the content of a tetrahydrofuran-insoluble component in the toner binder resin is 1% by mass or more and 30% by mass or less, assuming that the entire toner binder resin is 100% by mass.
[3]
In the toner binder resin described in [2] above,
A binder resin for toner in which the tetrahydrofuran-insoluble component is an insoluble component derived from the crosslinked styrene / (meth) acrylic copolymer resin (A).
[4]
A toner containing the binder resin for toner and the colorant according to any one of the above [1] to [3].
[5]
The toner according to the above [4], which is for electrophotographic.
[6]
The toner according to the above [4] or [5], which is spherical.
[7]
A production method for producing the binder resin for toner according to any one of the above [1] to [3].
Including the step of polymerizing the carboxyl group-containing vinyl resin (D) in the presence of the styrene / olefin block copolymer (B).
The carboxyl group-containing vinyl resin (D) is a high molecular weight with a peak at molecular weight 5.0 × 10 ⁴ or more 5.0 × 10 ⁵ or less in the region in the molecular weight distribution of tetrahydrofuran (THF) soluble matter as measured by GPC A method for producing a binder resin for toner, which is a vinyl resin (H).
[8]
A manufacturing method for manufacturing the toner according to any one of the above [4] to [6].
A step of melt-kneading the binder resin for toner and the colorant according to any one of the above [1] to [3] to obtain a mixture.
A method for producing a toner, which comprises a step of obtaining a particulate toner by pulverizing the obtained mixture.
[9]
In the method for producing toner according to the above [8],
A method for producing toner, further comprising a step of heat-treating the obtained particulate toner with hot air to make it spherical.
[10]
In the method for producing toner according to the above [9],
A method for producing toner in which the temperature at which the particulate toner is heat-treated with hot air is 200 ° C. or higher and 400 ° C. or lower.

According to the present invention, it is possible to provide a toner having excellent photoconductor contamination resistance.

Hereinafter, embodiments of the present invention will be described. Unless otherwise specified, "A to B" in the numerical range represent A or more and B or less. Further, in the present embodiment, the word "polymerization" may be used to mean a copolymer, and the word "polymer" may be used to mean a copolymer.

The binder resin for toner according to the present embodiment contains a crosslinked styrene / (meth) acrylic copolymer resin (A), a styrene / olefin block copolymer (B), and a wax (C). The crosslinked styrene / (meth) acrylic copolymer resin (A) contains a carboxyl group-containing vinyl resin (D), a glycidyl group-containing vinyl resin (E), and a reaction product thereof, and the wax (C) is a toner. It is dispersed in an island shape in the binder resin for use, and the maximum diameter of the island-shaped wax (C) is 0.01 μm or more and 1.0 μm or less.
In the toner binder resin according to the present embodiment, when the maximum diameter of the island-shaped wax (C) is within the above range, the photoconductor contamination resistance of the obtained toner can be improved. The maximum diameter of the wax (C) is preferably 0.01 μm or more and 0.5 μm or less, and more preferably 0.01 μm or more and 0.2 μm or less. Hereinafter, the maximum diameter of the wax (C) is also referred to as a dispersion diameter.

The dispersion diameter can be confirmed by observing with a transmission electron microscope (TEM) at a magnification of 10,000 to 60,000 times. Here, the observation area is about 25.5 μm × 16 μm at 10000 times, and about 4.6 μm × 2.9 μm at 60,000 times. After trimming surface exposure, and stained with RuO _4, to observe to prepare a super-thin slice.
By observing by the above method, the maximum diameter of the wax (C) can be confirmed.
Specifically, the length of the longest portion of the island-shaped wax (C) is measured, and the largest value in the observation field of view is defined as the "maximum diameter". At that time, when the maximum diameter is 0.1 μm or more, the observation is performed at a magnification of 10000 times and the field of view is about 25.5 μm × 16 μm, and when the maximum diameter is less than 0.1 μm, the field of view is 4.6 μm × 2.9 μm at 60,000 times. Observe.

In the present embodiment, for example, the maximum diameter of the wax (C) is kept within the above range by appropriately selecting the type and blending amount of each resin component contained in the binder resin, the method for preparing the binder resin, and the like. It is possible to control. Among these, for example, the type and content of the styrene / olefin block copolymer (B), the crosslinked styrene / (meth) acrylic copolymer resin (A) and the styrene / olefin block copolymer (B). The mixing condition with and the like can be mentioned as an element for setting the maximum diameter of the wax (C) in a desired numerical range.
For example, by increasing the content of the styrene / olefin block copolymer (B) in the binder resin for toner according to the present embodiment, the maximum diameter of the wax (C) can be reduced.
Further, by increasing the content of the wax (C) according to the present embodiment, the maximum diameter of the wax (C) can be increased.
Further, the maximum diameter of the wax (C) can be reduced by polymerizing the carboxyl group-containing vinyl resin (D) in the presence of the styrene / olefin block copolymer (B).
The styrene / olefin block copolymer (B) may be present in the crosslinked styrene / (meth) acrylic copolymer resin (A) in an island shape, whereas the wax (C) is an island-shaped styrene / olefin. It is preferably contained in the system block copolymer (B). With this structure, it is possible to more easily disperse the wax (C) having a very small diameter of 0.01 μm or more and 1.0 μm or less. However, the styrene / olefin block copolymer (B) is not limited to the form existing in the crosslinked styrene / (meth) acrylic copolymer resin (A) in an island shape, and is mixed. It may be in a state. Further, the island-shaped styrene / olefin block copolymer (B) does not have to contain the wax (C), and the wax (C) is not contained in the styrene / olefin block copolymer (B). It may be present in the crosslinked styrene / (meth) acrylic copolymer resin (A).

[Binder resin]
Hereinafter, the binder resin for toner according to this embodiment will be described in detail.

<Cross-linked styrene / (meth) acrylic copolymer resin (A)>
The crosslinked styrene / (meth) acrylic copolymer resin (A) is a resin containing a styrene-based monomer and a (meth) acrylic-based monomer as constituent monomers, and at least one styrene-based single amount. It is obtained by using a known polymerization method using a body and at least one (meth) acrylic monomer.

Here, examples of the styrene-based monomer used in the present embodiment include styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-methoxystyrene, p-phenylstyrene, and p-chloro. Styrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, Examples thereof include pn-nonyl styrene, pn-decyl styrene and pn-dodecyl styrene. Of these, styrene is preferable.

Examples of the (meth) acrylic monomer used in the present embodiment include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, cyclohexyl acrylate, stearyl acrylate, and acrylic acid. Acrylic acid esters such as benzyl, furfuryl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, dimethylaminomethyl acrylate, dimethylaminoethyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, Methacrylic acid esters such as octyl methacrylate, cyclohexyl methacrylate, stearyl methacrylate, benzyl methacrylate, flufuryl methacrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate; acrylamide, Amids such as methacrylic amide, N-substituted acrylamide and N-substituted methacrylic amide; examples thereof include acrylonitrile and methacrylic nitrile. Of these, acrylate esters, methacrylic acid esters, acrylonitrile, and methacrylic nitrile are preferable, and butyl acrylate, methyl methacrylate, butyl methacrylate, and hydroxyethyl acrylate are more preferable.

In the present embodiment, in addition to the above-mentioned monomers, unsaturated dibasic acid diesters such as dimethyl fumarate, dibutyl fumarate, dioctyl fumarate, dimethyl maleate, dibutyl maleate, and dioctyl maleate are also used as monomers. Can be used.

The content of the crosslinked styrene / (meth) acrylic copolymer resin (A) in the toner binder resin according to the present embodiment is based on 100% by mass of the entire toner binder resin according to the present embodiment. It is preferably 70% by mass or more and 98% by mass or less, more preferably 75% by mass or more and 98% by mass or less, and further preferably 80% by mass or more and 97% by mass or less. As a result, a toner having a better balance of fixability, offset resistance, and storage stability can be obtained.

The crosslinked styrene / (meth) acrylic copolymer resin (A) according to the present embodiment has a viewpoint of improving the fixability, offset resistance, photoconductor contamination resistance, and storage stability required for the toner in a well-balanced manner. Contains a carboxyl group-containing vinyl resin (D), a glycidyl group-containing vinyl resin (E), and a reaction product thereof.
As a method for reacting the carboxyl group-containing vinyl resin (D) with the glycidyl group-containing vinyl resin (E), at least one carboxyl group-containing vinyl resin (D) and at least one glycidyl group-containing vinyl resin (E) are used. A method of reacting by mixing with and in a molten state is preferable. As such a method, a conventionally known method can be used.
Further, the carboxyl group-containing vinyl resin (D) and the glycidyl group-containing vinyl resin (E) may be reacted in the presence of the fatty acid metal salt (M) represented by the following general formula (1).

〔上記一般式（１）において、ｎは１１から２２の整数であり、ｍは２であり、ＭはＺｎおよびＣａから選択される金属原子である〕
脂肪酸金属塩（Ｍ）が、カルボキシル基含有ビニル樹脂（Ｄ）とグリシジル基含有ビニル樹脂（Ｅ）との反応において触媒として機能することにより、バインダー樹脂を適切な粘度に調整することができる。

[In the above general formula (1), n is an integer from 11 to 22, m is 2, and M is a metal atom selected from Zn and Ca]
The fatty acid metal salt (M) functions as a catalyst in the reaction between the carboxyl group-containing vinyl resin (D) and the glycidyl group-containing vinyl resin (E), so that the binder resin can be adjusted to an appropriate viscosity.

In the crosslinked styrene / (meth) acrylic copolymer resin (A) according to the present embodiment, the ratio (D / E) of the carboxyl group-containing vinyl resin (D) to the glycidyl group-containing vinyl resin (E) is the mass. The ratio is preferably 85/15 to 99/1, more preferably 87/13 to 97/3. As a result, a toner having excellent offset resistance can be obtained.
By setting the ratio of the glycidyl group-containing vinyl resin (E) to the above upper limit value or less, a toner having more excellent offset resistance can be obtained. Further, by setting the ratio of the glycidyl group-containing vinyl resin (E) to the above lower limit value or more, an appropriate amount of cross-linking component is generated by the reaction between the carboxyl group-containing vinyl resin (D) and the glycidyl group-containing vinyl resin (E). , The toner can be made excellent in offset resistance.
The crosslinked styrene / (meth) acrylic copolymer resin (A) according to the present embodiment contains a carboxyl group-containing vinyl resin (D) and a glycidyl group-containing vinyl resin (E), and further contains carboxyl. It contains a cross-linking component generated by the reaction of a carboxyl group derived from the group-containing vinyl resin (D) and a glycidyl group derived from the glycidyl group-containing vinyl resin (E).

(Carboxyl group-containing vinyl resin (D))
The carboxyl group-containing vinyl resin (D) according to the present embodiment includes at least one styrene-based monomer, at least one (meth) acrylic monomer, and at least one carboxyl group-containing monomer. It is obtained by using a known polymerization method using and.
The styrene-based monomer and (meth) acrylic-based monomer used in the carboxyl group-containing vinyl resin (D) have been exemplified in the description of the crosslinked styrene / (meth) acrylic copolymer resin (A). A monomer can be used.

Examples of the carboxyl group-containing monomer used in the carboxyl group-containing vinyl resin (D) include acrylic acid, methacrylic acid, maleic anhydride, maleic acid, fumaric acid, silicic acid, methyl fumaric acid, and ethyl fumaric acid. Examples thereof include monoesters of unsaturated dibasic acids such as propyl fumarate, butyl fumarate, octyl fumarate, methyl maleate, ethyl maleate, propyl maleate, butyl maleate, and octyl maleate. Among these, acrylic acid, methacrylic acid, fumaric acid, methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate, and octyl fumarate are preferable, and acrylic acid and methacrylic acid are particularly preferable.

As the carboxyl group-containing vinyl resin (D) in the present embodiment, a crosslinkable monomer having two or more double bonds may be used as the monomer, if necessary. Examples of the crosslinkable monomer include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, and 1,5-pentanediol di. Acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) ) Diacrylate compounds such as propanediacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propandiacrylate and their methacrylate compounds; pentaerythritol triacrylate, trimethylolethane triacrylate, tri. Examples thereof include polyfunctional crosslinkable monomers such as methylolpropane triacrylate and tetramethylolmethane tetraacrylate, and methacrylate compounds thereof.

When these polyfunctional crosslinkable monomers are used, it is preferably 0.5 parts by mass or less with respect to 100 parts by mass of other monomers of the carboxyl group-containing vinyl resin (D). By setting the value to the upper limit or less, the crosslinked product formed by the reaction of the carboxyl group and the glycidyl group described later is less likely to be cut during the toner production.

The acid value of the carboxyl group-containing vinyl resin (D) according to the present embodiment is preferably 0.5 to 30 mgKOH / g, more preferably 1 to 30 mgKOH / g.
When the acid value of the carboxyl group-containing vinyl resin (D) is at least the above lower limit value, the reaction with the glycidyl group-containing vinyl resin (E) proceeds satisfactorily, and a toner having more excellent offset resistance can be obtained.
On the other hand, when the acid value of the carboxyl group-containing vinyl resin (D) is not more than the above upper limit value, an excessive cross-linking reaction with the glycidyl group-containing vinyl resin (E) is suppressed, and as a result, the carboxyl group-containing vinyl resin (D) is suppressed. ) And the crosslinked component obtained by the reaction of the glycidyl group-containing vinyl resin (E) can suppress a decrease in offset resistance, which is considered to be caused by excessive phase separation from the non-crosslinked component.
In this embodiment, the acid value is the number of mg of potassium hydroxide required to neutralize 1 g of the resin.

The carboxyl group-containing vinyl resin (D) has a molecular weight of 5.0 × in the molecular weight distribution of tetrahydrofuran (THF) soluble content measured by GPC from the viewpoint of the overall balance of toner fixability, offset resistance, durability, etc. 10 ⁴ 5.0 × 10 ⁵ high molecular weight vinyl resin having a peak in a region (H), the molecular weight 1.0 × 10 ³ or more 5.0 × in the molecular weight distribution of THF-soluble matter as measured by GPC it is preferred to include a 10 ⁴ less than the area of the low molecular weight vinyl resin (L) having a peak. The peak here refers to the main peak (the peak with the highest intensity among the peaks).

When the carboxyl group-containing vinyl resin (D) is composed of a high molecular weight vinyl resin (H) and a low molecular weight vinyl resin (L), the ratio (H / L) is the fixing property, offset resistance, and durability of the toner. From the viewpoint of overall balance such as, it is preferably 10/90 to 90/10, preferably 10/90 to 65/35, and more preferably 10/90 to 50/50.
By setting the ratio of the high molecular weight vinyl resin (H) to the above lower limit value or more, it is possible to obtain a toner having excellent durability and offset resistance. Further, by setting the ratio of the high molecular weight vinyl resin (H) to the above upper limit value or less, a toner having better fixability and productivity can be obtained.

(High molecular weight vinyl resin (H))
High molecular weight vinyl resin in the present embodiment (H) may have a main peak in a molecular weight 5.0 × 10 ⁴ or more 5.0 × 10 ⁵ or less in the region in the molecular weight distribution THF-soluble content is measured by GPC preferably, more preferably has a peak at 1.0 × 10 ⁵ or more 3.5 × 10 ⁵ or less, excellent fixing properties, offset resistance, preferable for realizing a balance of durability.
By setting the molecular weight of the main peak of the high molecular weight vinyl resin (H) (hereinafter referred to as peak molecular weight) to the above lower limit value or more, the strength of the resin is improved and a toner having more durability can be obtained. Further, in the formation of a crosslinked body by the reaction with the glycidyl group described later, the crosslink formation proceeds satisfactorily, so that a toner having excellent offset resistance can be obtained. Further, by setting the peak molecular weight to the above upper limit value or less, even if the high molecular weight vinyl resin remains in an unreacted state, the viscosity of the toner at the time of fixing is less likely to increase, and a toner having better fixability can be obtained. In addition, the strength of the resin becomes appropriate, and the toner can be made more productive.

The high molecular weight vinyl resin (H) preferably has an acid value (AVH) of 3 to 35 mgKOH / g, more preferably 5 to 27 mgKOH / g, in terms of toner fixability and offset resistance. When the acid value is at least the above lower limit value, it easily reacts with the glycidyl group-containing vinyl resin (E), and a toner having more excellent offset resistance can be obtained. When the acid value is not more than the above upper limit value, an excessive cross-linking reaction with the glycidyl group-containing vinyl resin (E) is suppressed, and as a result, the loss elastic modulus in the fixing temperature range of the toner becomes appropriate, and the fixability It can be an excellent toner.

The high molecular weight vinyl resin (H) does not necessarily have to be a single polymer, and two or more kinds of high molecular weight vinyl resins may be used. In that case, it is preferable that the high molecular weight vinyl resin (H) as a whole satisfies the above characteristics. Further, when producing a single polymer, it is also possible to add the carboxyl group-containing monomer during the polymerization, or to add the carboxyl group-containing monomer separately in the early stage and the late stage of the polymerization.

(Low molecular weight vinyl resin (L))
Low molecular weight vinyl resin (L) in the present embodiment preferably has a main peak in a molecular weight 1.0 × 10 ³ or more 5.0 × 10 below ⁴ in the molecular weight distribution THF-soluble content is measured by GPC, fixability, from the viewpoint of productivity of the durability and toner, and more preferably has a main peak in a molecular weight 2.0 × 10 ³ or more 3.0 × 10 ⁴ or less. By setting the peak molecular weight to the above lower limit value or more, a toner having better durability can be obtained. By setting the peak molecular weight to the upper limit or less, it is possible to obtain a toner having more excellent fixability and productivity.

The low molecular weight vinyl resin (L) preferably has an acid value (AVL) of 1 to 20 mgKOH / g, and more preferably 2 to 18 mgKOH / g in order to exhibit excellent fixing performance and offset resistance. .. By setting the acid value (AVL) to the above lower limit value or more, the compatibility with the high molecular weight vinyl resin (H) becomes good, and the toner becomes excellent in durability and offset resistance. By setting the value to the above upper limit or less, the reaction inhibition between the glycidyl group-containing vinyl resin (E) and the high molecular weight vinyl resin (H) by the low molecular weight vinyl resin (L) can be suppressed, and the low molecular weight vinyl resin (L) can be suppressed. Since it is possible to suppress the increase in the molecular weight of itself, it is possible to obtain a toner having a better balance between offset resistance and fixability.

The low molecular weight vinyl resin (L) does not necessarily have to be a single polymer, and two or more kinds of low molecular weight vinyl resins may be used. At that time, it is preferable that the low molecular weight vinyl resin (L) as a whole satisfies the above-mentioned characteristics. Further, when producing a single polymer, it is also possible to add the carboxyl group-containing monomer during the polymerization, or to add the carboxyl group-containing monomer separately in the early stage and the late stage of the polymerization.

In the present embodiment, as a method for producing the carboxyl group-containing vinyl resin (D), known polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization, and combinations thereof can be adopted. Solution polymerization is preferably adopted because of the adjustment of the molecular weight distribution, the mixture of the high molecular weight vinyl resin (H) and the low molecular weight vinyl resin (L), and the ease of adjusting the distribution of the carboxyl group and the glycidyl group.

The carboxyl group-containing vinyl resin (D) according to the present embodiment is obtained by polymerizing a high molecular weight vinyl resin (H) and a low molecular weight vinyl resin (L) independently in advance and mixing them in a molten state or a solution state. Obtainable. It is also possible to obtain by polymerizing one of the high molecular weight vinyl resin (H) and the low molecular weight vinyl resin (L) alone and then polymerizing the other vinyl resin in the presence of the vinyl resin.
Further, it is preferable to polymerize the carboxyl group-containing vinyl resin (D) in the presence of the styrene / olefin block copolymer (B), and high molecular weight vinyl in the presence of the styrene / olefin block copolymer (B). It is more preferable to polymerize the resin (H).
As a result, the styrene-olefin block copolymer (B) can be present in the resin in a sufficiently dispersed state, and the wax (C) added thereafter can be highly dispersed.

Examples of the solvent used for solution polymerization include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, and cumene, and these alone or a mixture thereof are used, and xylene is preferable.

The polymerization may be carried out using a polymerization initiator, or so-called thermal polymerization may be carried out without using a polymerization initiator. As the polymerization initiator, one that can be used as a radical polymerization initiator can be usually used. For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1' -Azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4- Azo-based initiators such as methoxyvaleronitrile and 2,2'-azobis (2-methyl-propane); ketone peroxides such as methyl ethyl ketone peroxide, acetylacetone peroxide and cyclohexanone peroxide; 1,1-bis (t-). Peroxyketals such as butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane; t-butylhydro Hydroperoxides such as peroxides, cumene hydroperoxides, 1,1,3,3-tetramethylbutylhydroperoxides; di-t-butyl peroxides, t-butylcumyl peroxides, di-cumyl peroxides, Dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxyisopropyl) benzene; isobutyryl peroxide, octanoylper Diacyl peroxides such as oxide, decanoyyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-toluyl peroxide; di-isopropylperoxydicarbonate, di- 2-Ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-methoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) per Peroxydicarbonates such as oxydicarbonates; sulfonyl peroxides such as acetylcyclohexylsulfonyl peroxides; t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, kumi Luperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaure Examples thereof include peroxyesters such as g, t-butylperoxybenzoate, t-butylperoxyisobropyrcarbonate, and di-t-butyldiperoxyisophthalate. These initiators may be used alone or in combination of two or more.

The type and amount of the polymerization initiator can be appropriately selected and used depending on the reaction temperature, monomer concentration, etc., and is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the monomer used.

(Glysidyl group-containing vinyl resin (E))
The glycidyl group-containing vinyl resin (E) according to the present embodiment includes at least one styrene-based monomer, at least one (meth) acrylic monomer, and at least one glycidyl group-containing monomer. It is obtained by using a known polymerization method using and.

The styrene-based monomer and (meth) acrylic-based monomer used in the glycidyl group-containing vinyl resin (E) have been exemplified in the description of the crosslinked styrene / (meth) acrylic copolymer resin (A). Monomers can be used.

Examples of the glycidyl group-containing monomer used in the glycidyl group-containing vinyl resin (E) include glycidyl acrylate, -β-methylglycidyl acrylate, glycidyl methacrylic acid, and -β-methylglycidyl methacrylic acid. .. Among these, glycidyl methacrylic acid and -β-methylglycidyl methacrylic acid are preferable.

Glycidyl group-containing vinyl resin (E), the molecular weight distribution THF-soluble content is measured by GPC, preferably a molecular weight 1.0 × 10 ⁴ or more 1.0 × 10 ⁵ or less, more preferably 2.0 × 10 ^It has a peak at ⁴ or more and 8.0 × 10 4 or less. The epoxy value is preferably 0.003 to 0.100 Eq / 100 g, more preferably 0.003 to 0.080 Eq / 100 g. When the peak molecular weight and epoxy value of the glycidyl group-containing vinyl resin (E) are equal to or higher than the above lower limit values, the durability when used as a toner becomes good, and image deterioration does not occur due to toner destruction in long-term continuous printing, so-called. Development maintenance characteristics are further improved. At the same time, the reaction between the carboxyl group-containing vinyl resin (D) and the glycidyl group-containing vinyl resin (E) further increases the molecular weight of the high molecular weight component and imparts appropriate elasticity to the binder resin. The performance will be better. By setting the peak molecular weight to the above lower limit value or more and the epoxy value to the above lower limit value or more, it is possible to impart appropriate elasticity to the binder resin and obtain a toner having more excellent offset resistance. Further, by setting the peak molecular weight to be equal to or less than the above upper limit value and the epoxy value to be equal to or less than the above upper limit value, excessive elasticity of the binder resin can be suppressed, and a toner having better fixability can be obtained.
In this embodiment, the epoxy value is the number of moles of epoxy groups present in 100 g of the resin, and the measurement can be performed according to JIS K-7236.

The glycidyl group-containing vinyl resin (E) does not necessarily have to be a single polymer, and two or more kinds of glycidyl group-containing vinyl resins may be used. In that case, it is preferable that the glycidyl group-containing vinyl resin (E) as a whole satisfies the above characteristics. Further, when producing a single polymer, it is also possible to add the glycidyl group-containing monomer during the polymerization, or to add the glycidyl group-containing monomer separately in the early stage and the late stage of the polymerization.

The binder resin for toner according to this embodiment preferably contains a tetrahydrofuran (THF) insoluble component.
The content of the THF insoluble component is preferably 1 mass when the total amount of the binder resin according to the present embodiment is 100% by mass from the viewpoint of a good balance between fixability, offset resistance, durability and toner productivity. % Or more and 30% by mass or less, more preferably 4% by mass or more and 35% by mass or less, and further preferably 5% by mass or more and 30% by mass or less.
By setting the THF insoluble component to the above lower limit value or more, a toner having more excellent offset resistance can be obtained, and further, when the wax (C) is kneaded, a sufficient kneading share is applied, and the wax (C) is kneaded. The dispersion of the wax is improved, and the stain resistance of the photoconductor can be improved. Further, when the toner member such as a charge adjusting agent, a colorant, or a magnetic material and the binder resin of the present embodiment are kneaded and pulverized to obtain a toner, a sufficient kneading share is applied, and the toner member is well dispersed. Photoreceptor contamination resistance can be improved. By setting the THF insoluble component to the above upper limit value or less, the toner becomes excellent in fixing performance, prevents poor dispersion of members due to excessively separated gel, and further improves photoconductor contamination resistance.
Here, the THF-insoluble component in the toner binder resin according to the present embodiment is preferably an insoluble component derived from the crosslinked styrene / (meth) acrylic copolymer resin (A), and the crosslinked styrene described above is preferable. -It is derived from a cross-linked component generated by the reaction of the carboxyl group derived from the carboxyl group-containing vinyl resin (D) in the (meth) acrylic copolymer resin (A) and the glycidyl group derived from the glycidyl group-containing vinyl resin (E). Is more preferable.

<Styrene-olefin block copolymer (B)>
The styrene / olefin block copolymer (B) according to the present embodiment is, for example, a block composed of a chain of structural units derived from an ethylene-based hydrocarbon and / or a conjugated diene-based hydrocarbon, and a block composed of a chain derived from styrene. Includes at least one selected from the block copolymers comprising: and the hydrogenated block copolymers which are these hydrogenating agents.

The content of the styrene-olefin block copolymer (B) in the toner binder resin according to the present embodiment is preferably 0.1% by mass when the total amount of the binder resin according to the present embodiment is 100% by mass. % Or more and 3% by mass or less, more preferably 0.15% by mass or more and 2% by mass or less. By setting the content of the styrene / olefin block copolymer (B) to the above lower limit value or more, the photoconductor contamination resistance of the obtained toner can be further improved. Further, by setting the content of the styrene / olefin block copolymer (B) to the above upper limit value or less, the storage stability of the obtained toner can be further improved.

In order to obtain the styrene / olefin block copolymer (B) according to the present embodiment, generally, ethylene, propylene, 1-butene, 2-butene, isopylene, 1-pentene, 2-pentene, 2-methyl-1 are obtained. Ethylene hydrocarbons such as -butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-hexene and 2,3-dimethyl-2-butene, and conjugated diene hydrocarbons such as butadiene and isoprene One or more selected from may be used. Using these, a reactive group of a block copolymer generated by known living anionic polymerization or living cationic polymerization is used, and styrene is further blocked by the reactive group, and the styrene / olefin block according to the present embodiment is used. The copolymer (B) is produced. When the block copolymer has an unsaturated double bond, the unsaturated double bond may be reacted with hydrogen by a known method and used as a hydrogenator. However, the production method is not limited, and those produced by other conventionally known production methods may be used.

As the styrene-olefin block copolymer (B) according to the present embodiment, commercially available products are Clayton (styrene-ethylene / butylene-styrene block copolymer (SEBS), styrene-butadiene-) manufactured by Clayton Polymers Co., Ltd. Styrene-based block copolymer, styrene-isoprene-styrene-based block copolymer, styrene-ethylene / propylene-styrene-based block copolymer, styrene-ethylene / propylene-based block copolymer), Septon manufactured by Kuraray Co., Ltd. (styrene) -Anhydrogen of ethylene / propylene-based block copolymer, styrene-isoprene-based block copolymer) and the like.
The styrene ratio in the styrene / olefin block copolymer (B) according to the present embodiment is preferably 10 to 80% by mass, more preferably 25 to 70% by mass. When the styrene ratio is at least the above lower limit value, the fluidity and storage stability of the toner are further improved. Further, when the styrene ratio is not more than the above upper limit value, the dispersibility of the wax becomes even better.

<Wax (C)>
The binder resin for toner according to this embodiment contains wax (C) in order to exhibit better fixing performance and offset resistance.
The type of wax (C) is not limited, but an aliphatic hydrocarbon wax such as polyethylene wax, polypropylene wax, paraffin wax, and Fishertropsh wax is preferable. In particular, one or more selected from polyethylene wax, polypropylene wax, paraffin wax and Fischer-Tropsch wax are preferable. The wax (C) may be used alone or in combination of two or more.
Examples of the wax (C) other than the above include oxides of aliphatic hydrocarbon waxes such as polyethylene oxide wax; plant waxes such as candelilla wax, carnauba wax, wood wax, rice wax and jojoba wax; Animal waxes such as beeswax, lanolin and whale wax; mineral waxes such as ozokelite, selecin and petrolatum; fatty acid ester-based waxes such as montanic acid ester and caster wax; deoxidized carnauba wax Wax deoxidized in part or all of the fatty acid ester; saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or even long-chain alkylcarboxylic acids with long-chain alkyl groups; brassic acid, eleostea Unsaturated fatty acids such as acids, parinaphosphoric acid; saturated alcohols such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnauvir alcohol, ceryl alcohol, melicyl alcohol, or even long-chain alkyl alcohols with long-chain alkyl groups. Polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid amide Saturated fatty acid bisamides such as: ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N'-diorail adipic acid amide, N, N'-unsaturated fatty acid amides such as sebasic acid amide; m Aromatic bisamides such as -xylene bisstearic acid amide, N, N'-distearyl isophthalic acid amide; aliphatic hydrocarbon wax containing styrene-based monomer, (meth) acrylic-based monomer, and carboxyl group. Wax grafted using vinyl-based monomer such as monomer and glycidyl group-containing monomer; partial esterification of aliphatic and polyhydric alcohols such as behenic acid monoglyceride; hydrogenation of vegetable fats and oils Methyl ester compound having a hydroxyl group obtained by the above; polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyheptene, polyoctene, ethylene-propylene copolymer, ethylene-butene copolymer, butene-propylene synthesized by a metallocene catalyst. Copolymers, long-chain alkylcarboxylic acids and polyvalent alcohol Examples thereof include an ester group-containing wax obtained by condensing a mixture or reacting a halide of a long-chain alkylcarboxylic acid with a polyhydric alcohol. Further, a wax having a functional group such as a hydroxyl group, an ester group or a carboxyl group can be mentioned.

In the present embodiment, the content of the wax (C) is 1 with respect to 100 parts by mass of the crosslinked styrene / (meth) acrylic copolymer resin (A) from the viewpoint of the balance between offset resistance and storage stability. It is preferably 2 parts by mass or more and 10 parts by mass or less, and more preferably 2 parts by mass or more and 8 parts by mass or less. When the content of the wax (C) is at least the above lower limit value, the toner can be made to have more excellent offset resistance, and when it is at least the above upper limit value, deterioration of the storage stability of the toner can be suppressed.

[Manufacturing method of binder resin]
Next, an example of a method for producing a binder resin for toner according to the present embodiment will be described.
As an example of the method for producing the binder resin according to the present embodiment, the crosslinked styrene / (meth) acrylic copolymer resin (A), the styrene / olefin block copolymer (B) and the wax (C) are melted. There is a method of kneading.
As another example, the carboxyl group-containing vinyl resin (D) and the glycidyl group-containing vinyl resin (E) are melt-kneaded in the presence of the styrene / olefin block copolymer (B) and the wax (C). A production method including a step of cross-linking the carboxyl group-containing vinyl resin (D) and the glycidyl group-containing vinyl resin (E) to obtain a cross-linked styrene / (meth) acrylic copolymer resin (A) can be obtained. is there.
To make the maximum diameter of the wax (C) smaller, the latter method, namely, the carboxyl group-containing vinyl resin (D) and the glycidyl group in the presence of the styrene-olefin block copolymer (B) and the wax (C). A method including a step of cross-linking the contained vinyl resin (E) by melt-kneading is preferable.

In such a method, for example, a styrene / olefin block copolymer (B), a wax (C), a carboxyl group-containing vinyl resin (D), and a glycidyl group-containing vinyl resin (E) are placed in a reaction vessel equipped with a stirrer. A method of charging, heating and reacting in a molten state can be adopted, and a method using a twin-screw kneader is particularly preferable.

In the presence of the styrene / olefin block copolymer (B) and the wax (C), the carboxyl group-containing vinyl resin (D) and the glycidyl group-containing vinyl resin (E) are melt-kneaded and subjected to a cross-linking reaction. The wax (C) can be further finely dispersed.
It is considered that the wax (C) is further finely dispersed due to an increase in the stirring share due to thickening during the cross-linking reaction between the carboxyl group-containing vinyl resin (D) and the glycidyl group-containing vinyl resin (E).

The temperature during melt-kneading is not particularly limited because it varies depending on the functional group amount and molecular weight of the carboxyl group-containing vinyl resin (D) and the glycidyl group-containing vinyl resin (E), but is preferably 140 ° C. or higher and 230 ° C. or lower, preferably 170 ° C. or higher. 220 ° C. or lower is more preferable. By setting the temperature at the time of melt-kneading to the above lower limit value or more, the crosslinked body formation becomes good, the share of kneading becomes appropriate, and the wax (C) can be further finely dispersed.
By setting the temperature during melt-kneading below the above upper limit, it is possible to prevent the cross-linking reaction from proceeding excessively, suppress the phase separation between the cross-linked component and the non-cross-linked component, and obtain a toner with even better offset resistance. Obtainable. In addition, depolymerization can be suppressed, and the concern that problems such as toner development maintenance characteristics and odor due to residual volatile matter in the binder resin can be reduced can be reduced.

In the method of melt-kneading using a twin-screw kneader, water and volatile components are removed by injecting water into the twin-screw kneader from an injection port and depressurizing from a pressure reducing port installed on the outlet side of the injection port. There is also. By this method, water is sufficiently mixed with the resin, and when the pressure is reduced, volatile components such as monomers and solvents remaining in the resin can be easily removed.

The resin thus obtained is cooled and pulverized to obtain a binder resin for toner. Any conventionally known method can be adopted as the cooling / crushing method. Further, as a cooling method, it is also possible to quench using a steel belt cooler or the like.

[toner]
Next, the toner according to this embodiment will be described.

The toner according to this embodiment contains a colorant as a toner member other than the binder resin for toner according to this embodiment. Further, one or more selected from a charge adjusting agent, a magnetic material, a resin other than the binder resin according to the present embodiment, a surface treatment agent, and the like may be further contained.
Hereinafter, toner members other than the toner binder resin will be described.

Conventionally known pigments and dyes can be used as the colorant.
Examples of pigments include Mineral Fast Yellow, Nable Yellow, Naftor Yellow S, Hansa Yellow G, Permanent Yellow NCG, Tartrazine Lake, Molybdenum Orange, Permanent Orange GTR, Pyrazolon Orange, Benzidine Orange G, Permanent Red 4R, Watching Red. Calcium salt, eosin lake, brilliant carmine 3B, manganese purple, fast violet B, methyl violet lake, cobalt blue, alkaline blue lake, Victoria blue lake, phthalocyanine blue, first sky blue, indanslen blue BC, chrome green, pigment green B, Malakite Green Lake, Final Yellow Green G, etc. can be mentioned. Examples of the magenta coloring pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209, 238, C.I. I. Pigment Violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35 and the like can be mentioned. Examples of the cyan pigment include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 16, 17, C.I. I. Acid Blue 6, C.I. I. Examples thereof include acid blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalocyanine groups are substituted in the phthalocyanine skeleton. Examples of the yellow coloring pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 83, 93, 97, 155, 180, 185, C.I. I. Bat Yellow 1, 3, 20 and the like can be mentioned. Examples of the black pigment include carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black. As the dye, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct green 6, C.I. I. Basic Green 4, C.I. I. Examples include Basic Green 6 and Solvent Yellow 162.
These colorants may be used alone or in combination of two or more.

The content of the colorant in the toner is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and further preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the binder resin. Is.

A magnetic material can also be used instead of the colorant. Examples of the magnetic material include metal oxides containing elements such as iron, cobalt, nickel, copper, magnesium, manganese, aluminum and silicon, and specific examples thereof include iron trioxide, iron sesquioxide, and zinc iron oxide. Ittium oxide, cadmium iron oxide, gadolinium oxide, copper oxide, lead iron oxide, nickel oxide, neodymium oxide, barium oxide, magnesium oxide, manganese oxide, lantern oxide, iron powder, cobalt powder, Examples include nickel powder. Two or more kinds of these magnetic materials may be used in combination as needed. Further, as the shape, it is preferable to use a spherical shape, an octahedron, or a hexahedron, and further, it is preferable to use a spherical shape in that the magnetic material is uniformly dispersed in the toner.

The content of the magnetic material is preferably 4 to 200 parts by mass, more preferably 10 to 170 parts by mass, and further preferably 20 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

Further, the toner according to the present embodiment may be, for example, polyvinyl chloride, polyvinyl acetate, polyester, polyvinyl butyral, polyurethane, polyamide, polystyrene, rosin, or polymerized rosin, as long as it does not impair the effects of the present embodiment. , Modified rosin, terpene resin, phenol resin, aromatic petroleum resin, vinyl chloride resin, styrene-butadiene resin, styrene- (meth) acrylic copolymer, chroman-inden resin, melamine resin, etc. You may.

Further, for the purpose of improving the dispersion of the colorant, a method may be performed in which the colorant is dispersed in a binder resin or a raw material resin thereof in advance to produce a so-called masterbatch, and the colorant is added to the toner. Specifically, 20 to 60% by mass of the colorant and 80 to 40% by mass of the resin component are mixed in a powder state, and the obtained mixture is a batch type such as a twin-screw kneader, an open roll kneader, or a pressurized kneader. You may knead it with a kneader or the like and crush it and use it at the time of toner production.

The toner according to this embodiment may contain a charge adjusting agent in order to maintain positive chargeability or negative chargeability. As the charge adjusting agent, conventionally known ones can be used.
Positive charge adjusting agents include, for example, modified products such as niglosin and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammoniumtetrafluoroborate. , And their analogs, onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and their lake pigments (as lake agents include phosphotungstate, phosphomolybdic acid, phosphotungenemolydic acid, Tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); Metal salts of higher fatty acids; Diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltinoxide; dibutyltinborate, dioctyltinborate , Diorganos tin borates such as dicyclohexyl tin borate; guanidine compounds; imidazole compounds; imidazolium salts; and also dialkylaminoalkyl (meth) acrylates, styrene-based monomers and optionally (meth) acrylic-based monomers. Examples thereof include a quaternary ammonium base-containing copolymer obtained by a method such as quaternization with a paratoluene sulfonic acid alkyl ester after polymerization.

As the negatively charged charge adjusting agent, for example, an organic metal complex and a chelate compound are effective, and a monoazo metal complex, an acetylacetone metal complex, an aromatic hydroxycarboxylic acid metal complex, an aromatic dicarboxylic acid metal complex, and an aromatic hydroxycarboxylic complex are effective. There are acids, aromatic monocarboxylic acids, aromatic polycarboxylic acids and their metal salts, anhydrides and esters, bisphenol derivatives such as bisphenol, and the coordination center metals are Sc, Ti, V, Cr, Co, An azo-based metal compound selected from Ni, Mn, and Fe and whose cation is selected from hydrogen ion, sodium ion, potassium ion, and ammonium ion, and the coordination center metal is Cr, Co, Ni, Mn, Fe, and Ti. , Zr, Zn, Si, B, Al, and aromatic hydroxycarboxylic acid derivatives and aromatic polycarboxylic acid derivatives whose cations are selected from hydrogen ion, sodium ion, potassium ion, ammonium ion, and aliphatic ammonium. (Aromatic hydroxycarboxylic acid derivatives and aromatic polycarboxylic acids are alkyl groups, aryl groups, cycloalkyl groups, alkenyl groups, alkoxy groups, aryloxy groups, hydroxyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups as substituents. , Acyl group, acyloxy group, carboxyl group, halogen, nitro group, cyano group, amide group, amino group, carbamoyl group), sulfonic acid group-containing acrylamide-based monomer and styrene-based monomer Examples thereof include a polymer having a sulfonic acid group-containing monomer as a constituent component, such as a copolymer of a (meth) acrylic monomer. These charge regulators may be used alone or in combination of two or more.

The content of the charge adjuster in the toner is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin, from the viewpoint of the balance between the charge amount and the fluidity of the toner. Parts, more preferably 0.2 to 3 parts by mass. Further, as the addition method, a method of adding to the inside of the toner, a method of externally adding the toner, or a combination thereof can be applied.

In the toner according to the present embodiment, it is preferable to add a surface treatment agent to the surface of the toner so that the surface treatment agent is present between the toner and the carrier or between the toners. By adding the surface treatment agent, the powder fluidity, storage stability, charge stability, and environmental stability can be improved, and the life of the developer can also be improved.

As the surface treatment agent, conventionally known ones can be used. For example, silica fine powder, titanium oxide fine powder, and hydrophobic products thereof and the like can be mentioned. As the silica fine powder, wet silica, dry silica, a composite of dry silica and a metal oxide and the like can be used, and further, those obtained by hydrophobizing these with an organosilicon compound or the like can be used. Examples of the hydrophobization treatment include a method in which silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with a silane compound and then treated with an organosilicon compound. Examples of the silane compound used for the hydrophobization treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorsilane, methyltrichlorosilane, allyldimethylchlorsilane, allylphenyldichlorosilane, and benzyl. Dimethylchlorsilane, Brommethyldimethylchlorsilane, α-Chlorethyltrichlorosilane, β-Chlorethyltrichlorosilane, Chlormethyldimethylchlorsilane, Triorganosilyl mercaptan, trimethylsilyl mercaptan, Triorganosilyl acrylate, Vinyl dimethylacetoxysilane, Dimethyldi Examples thereof include ethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, and 1,3-diphenyltetramethyldisiloxane. Examples of the organosilicon compound used for the hydrophobization treatment include silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, chlorphenyl silicone oil, and fluorine-modified silicone oil. Further, an oil-treated titanium oxide fine powder, fine particles of vinyl resin having a size of 0.03 μm to 1 μm, or the like may be used.

Other surface treatment agents include lubricants such as ethylene polyfluoride, zinc stearate, vinylidene polyfluoride, cerium oxide, silicon carbide, strontium titanate, magnetic powder, abrasives such as alumina, carbon black, zinc oxide, and oxidation. Conductivity-imparting agents such as antimony and tin oxide may also be used. Further, as the shape of the surface treatment agent, various shapes such as small particle size particles having a particle size of 100 nm or less, large particle size particles having a particle size of 100 nm or more, octahedron shape, hexahedron shape, needle shape, fibrous shape, etc. May be used. The surface treatment agent may be used alone or in combination of two or more.

The amount of the surface treatment agent added is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the toner.

When the toner according to this embodiment is used as a two-component developer, a conventionally known carrier can be used. For example, particles having a number average particle size of 15 to 300 μm composed of metals such as surface-oxidized or unoxidized iron, cobalt, manganese, chromium, copper, zinc, nickel, magnesium, lithium, rare earth and alloys or oxides thereof. Can be used. As these carriers, those whose surface is coated with a styrene resin, an acrylic resin, a silicone resin, a polyester resin, a fluorine resin or the like may be used. Further, a magnetic carrier having a magnetic fine particle dispersion type core in which magnetic fine particles are dispersed in a resin and a coating layer containing a coating resin for coating the surface of the magnetic fine particle dispersion type core may be used.

The toner according to this embodiment can be used in various known development processes. For example, although not particularly limited, it is required by a cascade development method, a magnetic brush method, a powder cloud method, a touch-down development method, a so-called microtoning method using magnetic toner manufactured by a pulverization method as a carrier, and triboelectric charging between magnetic toners. Examples thereof include a so-called bipolar magnetic toner method for obtaining a high toner charge. Further, the toner according to this embodiment can also be used in various cleaning methods such as a conventionally known fur brush method and a blade method. In addition, the toner according to this embodiment can be used in various conventionally known fixing methods. Specifically, an oilless heat roll method, an oil coating heat roll method, a heat belt fixing method, a flush method, an oven method, a pressure fixing method and the like are exemplified. Further, it may be used for a fixing device adopting an electromagnetic induction heating method. Further, it may be used in an image forming method having an intermediate transfer step.

[Toner manufacturing method]
Next, a method for producing toner according to this embodiment will be described.
The method for producing a toner according to the present embodiment includes a step of mixing the binder resin for toner and the colorant according to the present embodiment. In the step of mixing the toner binder resin and the colorant, a toner member other than the toner binder resin may also be mixed.

The toner according to the present embodiment is produced by mixing the binder resin for toner and the colorant using the binder resin for toner according to the present embodiment. The mixing method may be a conventionally known method. For example, a binder resin, a colorant, and a toner member such as a charge adjuster, if necessary, are sufficiently mixed by a powder mixer such as a Henschel mixer, and then a kneader such as a twin-screw kneader or an open roll kneader. Is melt-kneaded using the above to thoroughly mix each component. After cooling this, pulverization and classification are performed to collect particles usually in the range of 4 to 15 μm, and a surface treatment agent is sprinkled by a powder mixing method to obtain toner.
Further, the toner may be spherically treated by a surface treatment device or the like. Examples of the surface treatment method include a method of inflowing into a high-temperature air jet to make the toner spherical, and a method of removing the corners of the toner by a mechanical impact. For the purpose of improving image quality and the like, these surface treatments may be performed to adjust the average circularity measured by a flow type particle image measuring device (for example, FIPA-3000 manufactured by Sysmex) to 0.960 or more.
Further, in the method of making the toner spherical by flowing into a high-temperature air jet, the particulate toner is heat-treated with hot air. The temperature at this time is preferably 200 ° C. or higher and 400 ° C. or lower.

The toner according to this embodiment can be suitably used as an electrophotographic toner for developing an electrostatic charge image in electrophotographic, electrostatic recording, electrostatic printing, and the like.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.
Hereinafter, examples of reference embodiments of the present invention will be added.
[1]
A binder resin for toner containing a crosslinked styrene / (meth) acrylic copolymer resin (A), a styrene / olefin block copolymer (B), and a wax (C).
The crosslinked styrene / (meth) acrylic copolymer resin (A) contains a carboxyl group-containing vinyl resin (D), a glycidyl group-containing vinyl resin (E), and a reaction product thereof.
A toner binder resin in which the wax (C) is dispersed in an island shape in the toner binder resin, and the maximum diameter of the island-shaped wax (C) is 0.01 μm or more and 1.0 μm or less.
[2]
In the toner binder resin according to the above [1],
The content of the styrene / olefin block copolymer (B) in the toner binder resin is 0.1% by mass or more and 3.0% by mass when the total content of the toner binder resin is 100% by mass. The following binder resin for toner.
[3]
In the toner binder resin according to the above [1] or [2],
A toner binder resin in which the content of a tetrahydrofuran-insoluble component in the toner binder resin is 1% by mass or more and 30% by mass or less when the total content of the toner binder resin is 100% by mass.
[4]
In the toner binder resin described in [3] above,
A binder resin for toner in which the tetrahydrofuran-insoluble component is an insoluble component derived from the crosslinked styrene / (meth) acrylic copolymer resin (A).
[5]
A toner containing the binder resin for toner and the colorant according to any one of the above [1] to [4].
[6]
The toner according to the above [5], which is for electrophotographic.
[7]
The toner according to the above [5] or [6], which is spherical.
[8]
A production method for producing the binder resin for toner according to any one of the above [1] to [4].
A method for producing a binder resin for toner, which comprises a step of polymerizing the carboxyl group-containing vinyl resin (D) in the presence of the styrene / olefin block copolymer (B).
[9]
In the method for producing a binder resin for toner according to the above [8],
By melt-kneading the carboxyl group-containing vinyl resin (D) and the glycidyl group-containing vinyl resin (E) in the presence of the styrene / olefin block copolymer (B) and the wax (C). A method for producing a binder resin for toner, which comprises a cross-linking step of reacting the carboxyl group of the carboxyl group-containing vinyl resin (D) with the glycidyl group of the glycidyl group-containing vinyl resin (E).
[10]
In the method for producing a binder resin for toner according to the above [9],
A method for producing a binder resin for toner, in which the temperature at which the carboxyl group-containing vinyl resin (D) and the glycidyl group-containing vinyl resin (E) are melt-kneaded is 140 ° C. or higher and 230 ° C. or lower.
[11]
A manufacturing method for manufacturing the toner according to any one of the above [5] to [7].
A step of melt-kneading the binder resin for toner and the colorant according to any one of the above [1] to [4] to obtain a mixture.
A method for producing a toner, which comprises a step of obtaining a particulate toner by pulverizing the obtained mixture.
[12]
In the method for producing toner according to the above [11],
A method for producing toner, further comprising a step of heat-treating the obtained particulate toner with hot air to make it spherical.
[13]
In the method for producing toner according to the above [12],
A method for producing toner in which the temperature at which the particulate toner is heat-treated with hot air is 200 ° C. or higher and 400 ° C. or lower.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. The data measurement method and determination method are as follows. Further, in the table, St represents styrene, Mac represents methacrylic acid, BA represents n-butyl acrylate, and GMA represents glycidyl methacrylate.

<Acid value>
The acid value (AV) in this example was calculated as follows. The sample was precisely weighed in a mixed solvent with a xylene: n-butanol = 1: 1 mass ratio. Pre-standardized 0.1 mol / L potassium hydroxide alcohol (5 g of ion-exchanged water added to 7 g of special grade potassium hydroxide to make 1 L (liter) with primary ethyl alcohol, 0.1 mol / L hydrochloric acid and 1% phenolphthalein It was titrated with a rain solution with a titer of F), and calculated from the neutralized amount according to the following formula.
Acid value (mgKOH / g) = (0.1 mol / L KOH droplet quantification (ml) x F x 5.61) / (sample g x 0.01)

<Peak molecular weight>
The peak molecular weight in this example was determined by the GPC (gel permeation chromatography) method, and is a converted molecular weight obtained by preparing a calibration curve with monodisperse standard polystyrene. The measurement conditions are as follows.
GPC device: SHODEX (registered trademark) GPC-101 (manufactured by Showa Denko KK)
Detector: RI detector Column: SHODEX (registered trademark) One GPC KF-G, three GPC KF-807L, and one GPC KF-800D (manufactured by Showa Denko KK) in this order. It was used in connection with.
Solvent: tetrahydrofuran (THF)
Flow velocity: 1.2 ml / min Sample concentration: 0.002 g-resin / ml-THF
Injection volume: 100 μL
The sample solution was filtered immediately before the measurement to remove the components insoluble in THF.

<Melting point>
The melting point of the wax (C) was measured by Q1000 (manufactured by TA Instruments) according to the differential scanning calorimetry (DSC). About 10 mg of the sample was heated from −20 ° C. to 200 ° C. at 10 ° C./min, and the melting point was determined from the heat absorption peak of the obtained curve.

<Epoxy value>
The epoxy value was calculated by the following procedure. 0.2-5 g of the resin sample was precisely weighed and placed in a 200 ml Erlenmeyer flask. Then, 25 ml of dioxane was added and dissolved. 25 ml of a 1/5 specified hydrochloric acid solution (dioxane solvent) was added, and the mixture was tightly closed and thoroughly mixed. Then, it was allowed to stand for 30 minutes. Next, 50 ml of a toluene-ethanol mixed solution (1: 1 volume ratio) was added, and then titrated with a 1/10 specified sodium hydroxide aqueous solution using cresol red as an indicator. Based on the titration result, the epoxy value (Eq / 100 g) was calculated according to the following formula.
Epoxy value (Eq / 100g) = [(BS) x N x F] / (10 x W)
Here, W is the amount of sample collected (g), B is the amount of sodium hydroxide aqueous solution required for the blank test (ml), S is the amount of sodium hydroxide aqueous solution required for the sample test (ml), and N is water. The normality of the aqueous sodium oxide solution and F are the titers of the aqueous sodium hydroxide solution.

<THF insoluble content>
The THF insoluble content of the binder resin in this example was determined as follows.
0.4 g of resin and 39.5 g of THF were put into a 50 ml glass sample tube with a lid, and the sample tube was stirred under the conditions of a rotation speed of 50 rpm and 22 ° C. for 48 hours, and then allowed to stand at 22 ° C. for 48 hours. Then, the mass of 5 g of the supernatant liquid in the sample tube after being dried at 150 ° C. for 1 hour was measured, and the THF insoluble fraction (mass%) was calculated by the following formula with the mass as Xg.

<Measurement of maximum diameter of wax (C)>
Using a transmission electron microscope H-7000 (manufactured by Hitachi, Ltd.), the dispersed state of the wax (C) was confirmed at magnifications of 10000 times and 60,000 times. The observation area was 25.5 μm × 16 μm at 10000 times and 4.6 μm × 2.9 μm at 60,000 times.
From the obtained images, the lengths of the longest portions of the wax (C) were measured, and the largest value among them was taken as the maximum diameter.

<Evaluation of toner>
Next, the toner evaluation method performed in this example will be described below.
1. 1. Fixation evaluation An unfixed image was created with a copying machine that was a modification of a commercially available electrophotographic copying machine. Then, this unfixed image was fixed at a fixing speed of 190 mm / sec by using a hot roller fixing device obtained by modifying the fixing portion of a commercially available copying machine, and at temperatures of 130 ° C. and 150 ° C., respectively. The obtained fixed image was rubbed 6 times with a load of 1.0 kgf applied by a sand eraser (manufactured by Tombow Pencil Co., Ltd.), and the image density before and after this friction test was measured by a Macbeth type reflection densitometer. The rate of change was defined as the image density after rubbing ÷ the image density before rubbing × 100. The rate of change was measured in the same manner by changing the density of the image, and the value with the lowest rate of change was taken as the lowest rate of change at each temperature. The average value of the lowest rate of change at 130 ° C. and 150 ° C. was calculated as the fixing rate, and the determination was made according to the following evaluation criteria. The thermal roller fixing device used here did not have a silicone oil supply mechanism. The environmental conditions were normal temperature and pressure (temperature 22 ° C., relative humidity 55%).
(Evaluation criteria)
◯: 65% ≤ fixing rate Δ: 60% <fixing rate <65%
×: Retention rate ≤ 60%

2. Offset resistance The measurement was performed according to the above fixing evaluation measurement. That is, an unfixed image was created by the above-mentioned copying machine. After that, the fixing process was performed by the above-mentioned thermal roller fixing device, and it was observed whether or not toner stains were generated in the non-image portion. The set temperature of the heat roller of the heat roller fixing device was repeatedly raised from 100 ° C. to 5 ° C. in order from 250 ° C., and the range of the set temperature at which stains by toner did not occur was defined as the offset resistant temperature range. The atmosphere of the copying machine was a temperature of 22 ° C. and a relative humidity of 55%.
(Evaluation criteria)
◯: 100 ° C. ≤ offset resistant temperature range Δ: 80 ° C. ≤ offset resistant temperature range <100 ° C.
×: Offset resistant temperature range <80 ° C

3. 3. Preservability Under environmental conditions of a temperature of 50 ° C. and a relative humidity of 60%, 5 g of toner was left for 24 hours. This was placed on a 150 mesh sieve, and the scale of the control resistor of a powder tester (manufactured by Hosokawa Powder Engineering Laboratory Co., Ltd.) was set to 3, and vibration was applied for 1 minute. The mass remaining on the sieve of 150 mesh after vibration was measured, and the residual mass ratio was determined.
(Evaluation criteria)
◯: Residual mass ratio <25%
Δ: 25% ≤ residual mass ratio <30%
×: 30% ≤ residual mass ratio

4. Photoreceptor Contamination With a non-magnetic one-component development type laser beam printer, continuous printing was performed on A4 paper at a temperature of 22 ° C. and a relative humidity of 55% using a chart with a printing rate of 5%. A solid image was printed every 1000 sheets, and the presence or absence of white spots was visually confirmed, and the contaminating property of the photoconductor was indirectly evaluated.
(Evaluation criteria)
◎: No white spots occur even if the number of sheets exceeds 15,000 ○: White spots occur at 10001 to 15000 sheets △: White spots occur at 5001 to 10000 sheets ×: White spots occur at 5000 sheets or less

[Production example of glycidyl group-containing vinyl resin (E)]
(Manufacturing Example E-1)
50 parts by mass of xylene was placed in a flask substituted with nitrogen, the temperature was raised, and 0.5 part by mass of dit-butyl peroxide was previously mixed and dissolved in 100 parts by mass of the monomer shown in Table 1 under reflux of xylene. The mixture was continuously added over 5 hours, and reflux was continued for 1 hour. Then, the internal temperature was kept at 130 ° C., 0.5 part by mass of di-t-butyl peroxide was added, and the reaction was continued for 2 hours to obtain a polymerization solution. This was flushed into a container at 160 ° C. and 1.33 kPa to distill off the solvent and the like to obtain resin E-1. The physical property values are shown in Table 1.

(Manufacturing Examples E-2, E-3)
Resins E-2 and E-3 were obtained in the same manner as in Production Example E-1 with the compositions shown in Table 1. Table 1 shows their physical property values.

[Production example of low molecular weight vinyl resin (L)]
(Manufacturing Example L-1)
100 parts by mass of xylene was placed in a flask substituted with nitrogen, the temperature was raised, and 10 parts by mass of t-butylperoxy-2-ethylhexanoate was mixed and dissolved in 100 parts by mass of the monomer shown in Table 2 in advance under reflux of xylene. The prepared mixed solution is continuously added over 5 hours, and reflux is continued for another 1 hour. After that, the internal temperature was maintained at 98 ° C., 0.5 part by mass of t-butylperoxy-2-ethylhexanoate was added, and the reaction was continued for 1 hour, and then t-butylperoxy-2-ethylhexanoate 0. .5 parts by mass was added and the reaction was continued for 2 hours to obtain a polymer solution of L-1. The physical property values are shown in Table 2.

(Manufacturing Example L-2)
75 parts by mass of xylene was placed in a flask substituted with nitrogen, the temperature was raised, and 5 parts by mass of t-butylperoxy-2-ethylhexanoate was mixed and dissolved in 100 parts by mass of the monomer shown in Table 2 in advance under reflux of xylene. The prepared mixed solution is continuously added over 5 hours, and reflux is continued for another 1 hour. After that, the internal temperature was kept at 98 ° C., 0.3 part by mass of t-butylperoxy-2-ethylhexanoate was added, and the reaction was continued for 1 hour, and then t-butylperoxy-2-ethylhexanoate 0. .5 parts by mass was added and the reaction was continued for 2 hours to obtain a polymer solution of L-2. The physical property values are shown in Table 2.

[Production example of high molecular weight vinyl resin (H)]
(Manufacturing Example H-1)
100 parts by mass of the monomer shown in Table 3 was placed in a nitrogen-substituted flask, the internal temperature was raised to 120 ° C., and the temperature was maintained at the same temperature, and bulk polymerization was performed for 3 hours. Next, 30 parts by mass of xylene was added, 0.2 parts by mass of divinylbenzene was added, and then the temperature was raised to 130 ° C. 0.1 part by mass of di-t-butyl peroxide and 70 parts by mass of xylene, which had been mixed and dissolved in advance, were continuously added over 5.5 hours while maintaining the temperature at 130 ° C., and then the reaction was continued for 1 hour. Then, 0.1 part by mass of di-t-butyl peroxide was added, and the reaction was continued for 10 hours to complete the polymerization, and a polymerization solution of H-1 was obtained. The physical property values are shown in Table 3.

(Manufacturing Example H-2)
A polymer solution of H-2 was obtained in the same manner as in Production Example H-1 with the preparation composition shown in Table 3. The physical property values are shown in Table 3.

(Manufacturing Example H-3)
100 parts by mass of the monomer and styrene / olefin block copolymer (B) shown in Table 3 (styrene / olefin block copolymer (B-1) shown in Table 4) was charged into a nitrogen-substituted flask. After raising the temperature to 120 ° C., the temperature was maintained at the same temperature, and bulk polymerization was carried out for 3 hours. Next, 30 parts by mass of xylene was added, 0.2 parts by mass of divinylbenzene was added, and then the temperature was raised to 130 ° C. 0.1 part by mass of di-t-butyl peroxide and 70 parts by mass of xylene, which had been mixed and dissolved in advance, were continuously added over 5.5 hours while maintaining the temperature at 130 ° C., and then the reaction was continued for 1 hour. Then, 0.1 part by mass of di-t-butyl peroxide was added, and the reaction was continued for 10 hours to complete the polymerization, and a polymerization solution of H-3 was obtained. The physical characteristic values of the high molecular weight vinyl resin (H) are shown in Table 3.

(Manufacturing Example H-4)
A polymer solution of H-4 was obtained in the same manner as in Production Example H-3 with the preparation composition shown in Table 3. The physical characteristic values of the high molecular weight vinyl resin (H) are shown in Table 3.

[Production example of a mixture (F) of a carboxyl group-containing vinyl resin (D), a styrene / olefin block copolymer (B), and a wax (C)]
(Manufacturing Example F-1)
Table 6 shows the high molecular weight vinyl resin (H), the low molecular weight vinyl resin (L), the styrene / olefin block copolymer (B) shown in Table 4, and the wax (C) shown in Table 5 as solid contents. The mixture was mixed so as to have the shown preparation composition. Then, it was mixed under reflux of xylene for 30 minutes, and this was flushed into a vessel (container) at 190 ° C. and 1.33 kPa to distill off a solvent and the like to obtain a resin F-1.

(Production Examples F-2 to F-15)
Resins of F-2 to F-15 were obtained in the same manner as in Production Example F-1 with the preparation composition shown in Table 6.
Here, since F5 to F10 use H-3 or H-4 containing the styrene / olefin block copolymer (B), they are not shown in Table 6, but the styrene / olefin block co-weight. Contains coalescence (B).

[Production example of binder resin (G)]
(Production Examples G-1 to G-15)
Table 7 shows the mass ratio of the mixture (F) of the carboxyl group-containing vinyl resin (D), the styrene / olefin block copolymer (B), and the wax (C) to the glycidyl group-containing vinyl resin (E). Each resin was mixed so as to have a ratio. Then, a kneading reaction was carried out at 25 kg / hr and a motor rotation speed of 1400 rpm with a twin-screw kneader (KEXN S-40 type, manufactured by Kurimoto, Ltd.) whose temperature was set to the kneading temperature shown in Table 7. This kneaded product is rapidly cooled using a steel belt cooler (NR3-Hi double cooler, manufactured by Nippon Belting Co., Ltd.) under the conditions of cooling water temperature of 10 ° C., cooling water volume of 90 L / min, and belt speed of 6 m / min, and then crushed. , Binder resins G-1 to G-15 were obtained. Table 7 shows the maximum diameters of the THF insoluble matter and the wax (C).
In the transmission electron microscope observation of the measurement of the maximum diameter of the wax (C), the binder resins G-1 to G-11 and G-13 to G-15 were styrene-olefins in which the wax (C) was island-shaped. Those contained in the system block copolymer (B) were also observed.

[Manufacturing example of electrophotographic toner (T)]
(Manufacturing Examples T-1 to T-15)
Henschel the binder resin (G), carbon black (Regal 330R; manufactured by Cabot Corporation), and charge adjuster (T-77; manufactured by Hodogaya Chemical Co., Ltd.) shown in Table 7 so as to have the composition shown in Table 8. It was mixed with a mixer. Then, the mixture was kneaded with a twin-screw kneader (PCM-30 type, manufactured by Ikegai Machinery Co., Ltd.) at a resin temperature of the discharge part of the twin-screw kneader at 120 ° C. and a residence time of 30 seconds. Next, after cooling this melt-kneaded product, it was pulverized with a jet crusher (IDS-2UR type, manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to a volume medium diameter D50 of 7.6 μm. Subsequently, the pulverized product was cut into fine particles with a classifier (DSX-2 type, manufactured by Nippon Pneumatic Industries, Ltd.) to obtain toner particles having a medium volume diameter D50 of 7.9 μm. Next, 0.7 parts by mass of hydrophobic silica (R-812, manufactured by Nippon Aerodil Co., Ltd.) was added to 100 parts by mass of the toner particles and mixed with a Henschel mixer, and then a surface modifier (MR) was added. A -10 type, manufactured by Nippon Pneumatic Mfg. Co., Ltd.) was subjected to spheroidizing treatment at a toner feed amount of 2 kg / hr, a hot air volume of 800 L / min, and a hot air temperature of 300 ° C. Finally, 0.5 parts by mass of hydrophobic silica (R-812, manufactured by Nippon Aerodil Co., Ltd.) and 0.2 mass of hydrophobic titanium oxide (NKT-90, manufactured by Nippon Aerosil Co., Ltd.) with respect to 100 parts by mass of toner particles. Partially added to obtain toners T-1 to T-15 having an average circularity of 0.967 and a volume median diameter D50 of about 8.4 μm. The physical property values are shown in Table 8.

(Examples 5 to 10, Comparative Example 1 and Reference Examples 1 to 4 and 11 to 14 )
The storage stability and photoconductor contamination resistance were evaluated using the toners shown in Table 8. Further, 97% by mass of a carrier (F-150 manufactured by Powdertech Co., Ltd.) was mixed with 3% by mass of the toner shown in Table 8 to prepare a developer, and the fixability and offset resistance were evaluated.

As is clear from the results in Table 9, all the toners produced in this example were excellent in photocontamination resistance.

Claims (10)

A binder resin for toner containing a crosslinked styrene / (meth) acrylic copolymer resin (A), a styrene / olefin block copolymer (B), and a wax (C).
The crosslinked styrene / (meth) acrylic copolymer resin (A) contains a carboxyl group-containing vinyl resin (D), a glycidyl group-containing vinyl resin (E), and a reaction product thereof.
The wax (C) is dispersed in an island shape in the binder resin for toner, and the maximum diameter of the island-shaped wax (C) is 0.01 μm or more and 0.2 μm or less.
The content of the styrene-olefin block copolymer (B) in the toner binder resin is 0.1% by mass or more and 3.0% by mass when the total content of the toner binder resin is 100% by mass. or less,
The content of the styrene / olefin block copolymer (B) is 0.7% by mass or more with respect to 100% by mass of the carboxyl group-containing vinyl resin (D) in the binder resin for toner.
A toner binder resin in which the styrene ratio in the styrene / olefin block copolymer (B) in the toner binder resin is 65% by mass or more. In the toner binder resin according to claim 1,
A toner binder resin in which the content of a tetrahydrofuran-insoluble component in the toner binder resin is 1% by mass or more and 30% by mass or less, assuming that the entire toner binder resin is 100% by mass. In the toner binder resin according to claim 2.
A binder resin for toner in which the tetrahydrofuran-insoluble component is an insoluble component derived from the crosslinked styrene / (meth) acrylic copolymer resin (A). A toner containing the binder resin for toner and the colorant according to any one of claims 1 to 3. The toner according to claim 4, which is for electrophotographic. The toner according to claim 4 or 5, which is spherical. A production method for producing the binder resin for toner according to any one of claims 1 to 3.
Including the step of polymerizing the carboxyl group-containing vinyl resin (D) in the presence of the styrene / olefin block copolymer (B).
The carboxyl group-containing vinyl resin (D) is a high molecular weight with a peak at molecular weight 5.0 × 10 ⁴ or more 5.0 × 10 ⁵ or less in the region in the molecular weight distribution of tetrahydrofuran (THF) soluble matter as measured by GPC A method for producing a binder resin for toner, which is a vinyl resin (H). A manufacturing method for manufacturing the toner according to any one of claims 4 to 6.
A step of melt-kneading the binder resin for toner and a colorant according to any one of claims 1 to 3 to obtain a mixture.
A method for producing toner, which comprises a step of obtaining particulate toner by pulverizing the obtained mixture. In the method for producing a toner according to claim 8,
A method for producing a toner, further comprising a step of heat-treating the obtained particulate toner with hot air to make it spherical. In the method for producing toner according to claim 9,
A method for producing toner in which the temperature at which the particulate toner is heat-treated with hot air is 200 ° C. or higher and 400 ° C. or lower.