JP2020148913A - Toner and toner manufacturing method - Google Patents

Abstract

To provide a toner which exhibits excellent low temperature fixability and transferability, and with which it is possible to suppress a density fluctuation for output the printing percentage of an image of which is high, and a manufacturing method for the toner.SOLUTION: Provided is a toner including a toner particle that contains silicone oil, wherein a vinyl polymer A exists in a region within 300 nm from the surface of the toner particle toward the center of it, the vinyl polymer A including a first monomer unit derived from a first polymerizable monomer and a second monomer unit derived from a second polymerizable monomer, the first polymerizable monomer being selected from (meth)acrylic ester including a C18-36 linear or branched alkyl group, the second polymerizable monomer including an ester group or a nitrile group, the content ratio of the first monomer unit in the vinyl polymer A being 5.0-60.0 mol%, the content ratio of the second monomer unit in the vinyl polymer A being 20.0-95.0 mol%, the SP value of the first monomer unit and the SP value of the second monomer unit satisfying a prescribed relationship, a formula A/B satisfying a prescribed relationship, where A represents the amount of Si at bond energy 102eV-103eV measured by the ESCA of the toner and B represents the amount of C at bond energy 285eV-288eV.SELECTED DRAWING: None

Description

The present invention relates to toners used in electrophotographic methods, electrostatic recording methods, electrostatic printing methods, and the like, and methods for producing the toners.

In recent years, with the widespread use of electrophotographic full-color copiers, not only higher speeds and higher image quality, but also the required performance has diversified as the user's usage environment changes. For example, in an office environment, there is a growing awareness of reducing running costs and an increase in the output of graphic documents in addition to text documents. Generally, most of the electric power consumed in a copying machine is consumed in the process of melting toner and fixing it on a paper medium. Further, if an image having a large print ratio such as a graphic document is output immediately after outputting an image having a small print ratio of an image such as a character document, the image density may gradually fluctuate. It is considered that such fluctuation is caused by the difference between the charge amount of the toner existing in the developing machine and the charge amount of the toner newly supplied into the developing machine.
Therefore, as a toner corresponding to energy saving, a toner that can be fixed at a lower temperature is required in order to reduce power consumption in the fixing process. Further, as a toner corresponding to image stability, a toner in which the charged amount of the replenished toner rises instantly is required.
Therefore, a toner using a crystalline resin has been proposed as a toner having excellent low-temperature fixability (Patent Document 1), and a toner using titanium oxide fine particles having low electrical resistance has been proposed as a toner having excellent rise in charging. (Patent Document 2).

Japanese Unexamined Patent Publication No. 2014-130243 Japanese Unexamined Patent Publication No. 2005-122151

Since the toner described in Patent Document 1 uses a crystalline acrylic resin having a sharp melt property in the side chain, excellent low temperature fixing is possible. In recent years, many toners containing a crystalline polyester resin have been proposed as a resin having a sharp melt property, but the crystalline polyester has a problem in terms of maintaining chargeability after being left in a high temperature and high humidity environment. It was a material. On the other hand, crystalline acrylic resin is a material that exhibits excellent maintainability of chargeability even after being left in a high temperature and high humidity environment. However, it has been found that toners using these crystalline acrylic resins as a binder resin have a slow rise in charging. Therefore, when outputting images having different printing ratios, the image density may fluctuate and the image stability may be impaired.
On the other hand, the toner described in Patent Document 2 exhibits excellent charge rising property because the surface of the toner particles is coated with titanium oxide fine particles having low electric resistance. However, since the surface of the toner particles is coated with a large amount of inorganic fine particles, fixation may be hindered and low-temperature fixability may be impaired.
From the above, in the crystalline acrylic resin, there is a trade-off relationship between low temperature fixability and image stability. Therefore, there is an urgent need to develop a toner that breaks away from this trade-off relationship, exhibits excellent low-temperature fixability, and exhibits excellent image stability even when outputting images having different printing ratios.
The present invention has been made in view of the above problems, and a toner that exhibits excellent low-temperature fixability and also exhibits excellent image stability even in the output of images having different printing ratios, and a method for producing the toner. The purpose is to provide.

According to one aspect of the present invention, the toner has toner particles containing silicone oil.
Vinyl polymer A is present in a region within 300 nm from the surface of the toner particles toward the center thereof.
The vinyl polymer A is derived from a first monomer unit derived from the first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer. Has two monomer units,
The first polymerizable monomer is a (meth) acrylic acid ester having a linear or branched alkyl group having 18 to 36 carbon atoms.
The second polymerizable monomer has an ester group or a nitrile group and has an ester group or a nitrile group.
When the SP value of the first monomer unit is SP ₁₁ and the SP value of the second monomer unit is SP ₂₁ , the SP ₁₁ and the SP ₂₁ are expressed by the following formulas (1) and (2). ) And meet
SP ₁₁ ≤ 18.40 (J / cm ³ ) ^0.5 ... (1)
21.00 (J / cm ³ ) ^0.5 ≤ SP ₂₁ ... (2)
The ratio of the first monomer unit in the vinyl polymer A is 5.0 to 60.0 mol% based on the total number of moles of all the monomer units in the vinyl polymer A.
The ratio of the second monomer unit in the vinyl polymer A is 20.0 to 95.0 mol% based on the total number of moles of all the monomer units in the vinyl polymer A.
When the amount of Si at the binding energies 102 ev to 103 ev measured by ESCA of the toner is A and the amount of C at the binding energies 285 ev to 288 ev is B, a toner satisfying the following formula (3) is provided.
1.0 ≤ A / B ≤ 3.0 ... (3)

Further, according to another aspect of the present invention, the toner has toner particles containing silicone oil.
Vinyl polymer A is present in a region within 300 nm from the surface of the toner particles toward the center thereof.
The vinyl polymer A is a polymer of a composition containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer.
The first polymerizable monomer is a (meth) acrylic acid ester having a linear or branched alkyl group having 18 to 36 carbon atoms.
The second polymerizable monomer has an ester group or a nitrile group and has an ester group or a nitrile group.
When the SP value of the first polymerizable monomer is SP ₁₂ and the SP value of the second polymerizable monomer is SP ₂₂ , the SP ₁₂ and the SP ₂₂ are represented by the following formula (4). ) And the following formula (5),
SP ₁₂ ≤ 17.72 (J / cm ³ ) ^0.5 ... (4)
18.30 (J / cm ³ ) ^0.5 ≤ SP ₂₂ ... (5)
The content ratio of the first polymerizable monomer in the composition is 5.0 mol% to 60.0 mol% based on the total number of moles of the total polymerizable monomers in the composition. ,
The content ratio of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of the total polymerizable monomer in the composition. ,
Let A be the peak area of the silicon atom whose binding energy peak position is 102 ev to 103 ev, and the carbon atom whose binding energy peak position is 285 ev to 288 ev, as measured by using the electron spectrochemical analysis method (ESCA) of the toner. When the peak area of is B, a toner in which A and B satisfy the following formula (3) is provided.
1.0 ≤ A / B ≤ 3.0 ... (3)

Furthermore, according to another aspect of the invention
A process of melt-kneading a toner composition containing silicone oil to obtain a melt-kneaded product,
A step of pulverizing and classifying the melt-kneaded product to obtain toner matrix particles, and
A step of heat-treating the toner mother particles and a method for producing the toner produced through the process are provided.

According to the present invention, it is possible to provide a toner that exhibits excellent low-temperature fixability and also exhibits excellent image stability even in the output of images having different printing ratios, and a method for producing the toner.

It is a figure of the thermosphere processing apparatus used in this invention.

In the present invention, the description of "○○ or more and XX or less" and "○○ to XX" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified.
In the present invention, the (meth) acrylic acid ester means an acrylic acid ester and / or a methacrylic acid ester.
In the present invention, the "monomer unit" refers to a reacted form of a monomer substance in a polymer.
Crystalline resin refers to a resin that exhibits a clear endothermic peak in differential scanning calorimetry (DSC) measurements.
In the present invention, the SP value is an abbreviation for a solubility parameter, and is a value that serves as an index of solubility. The calculation method will be described later.

The first toner of the present invention is a toner having toner particles containing silicone oil.
Vinyl polymer A is present in a region within 300 nm from the surface of the toner particles toward the center thereof.
The vinyl polymer A is derived from a first monomer unit derived from the first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer. Has two monomer units,
The first polymerizable monomer is a (meth) acrylic acid ester having a linear or branched alkyl group having 18 to 36 carbon atoms.
The second polymerizable monomer has an ester group or a nitrile group.

When the SP value of the first monomer unit is SP ₁₁ and the SP value of the second monomer unit is SP ₂₁ , the SP ₁₁ and the SP ₂₁ are expressed by the following formulas (1) and (2). ) And satisfy.
SP ₁₁ ≤ 18.40 (J / cm ³ ) ^0.5 ... (1)
21.00 (J / cm ³ ) ^0.5 ≤ SP ₂₁ ... (2)

The content ratio of the first monomer unit in the vinyl polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all the monomer units in the vinyl polymer A.
The content ratio of the second monomer unit in the vinyl polymer A is 20.0 mol% to 95.0 mol% based on the total number of moles of all the monomer units in the vinyl polymer A.

Let A be the peak area of the silicon atom whose binding energy peak position is 102 ev to 103 ev, and the carbon atom whose binding energy peak position is 285 ev to 288 ev, which is measured by using the electron spectrochemical analysis method (ESCA) of the toner. When the peak area of
The A and the B satisfy the following formula (3).
1.0 ≤ A / B ≤ 3.0 ... (3)

The present inventors have proceeded with the study of a toner that exhibits excellent low-temperature fixability and also exhibits excellent image stability even in the output of images having different printing ratios.
First, the present inventors examined means for improving the rising property of charging. In order to improve the rising property of the toner charge, it is considered important to instantly and uniformly transfer the charge generated on a part of the toner surface to the entire toner surface. The present inventors searched for a material that transfers charges over the entire surface of the toner, and found that silicone oil has a charge diverging effect. It is considered that this is due to the high molecular mobility of the liquid silicone oil.

However, when silicone oil was added to the toner using the crystalline acrylic resin described in the prior art document as the binder resin, excellent image stability could not be obtained in the output of images having different printing ratios. The present inventors investigated the cause, and a monomer unit derived from a (meth) acrylic acid ester having an alkyl group that expresses the crystallinity of a crystalline acrylic resin is randomly bonded to another monomer unit. I found that it was the cause. Specifically, the monomer unit derived from the (meth) acrylic acid ester having an alkyl group exhibits crystallinity by assembling the monomer units derived from the (meth) acrylic acid ester having an alkyl group. Usually, if other monomer units are incorporated, crystallization is likely to be inhibited. It is considered that this is because a monomer unit derived from a (meth) acrylic acid ester having an alkyl group and another monomer unit are randomly bonded in one molecule of the polymer. As a result, the silicone oil having a high affinity with the monomer unit derived from the (meth) acrylic acid ester having an alkyl group repels other monomer units having a low affinity adjacent to each other, and is domainized and formed on the toner surface. A thick silicone oil layer is formed. As a result, even if the other monomer unit has a polar group or the like, the friction opportunity with the magnetic carrier is hindered, so that the rising property of charging is not improved and the image stability in the output of images having different printing ratios is improved. It is considered to be damaged. Furthermore, it was confirmed that the non-electrostatic adhesive force to the electrostatic latent image carrier and the intermediate transfer body increases with the liquid cross-linking, so that the transferability is also impaired.

That is, it has been found that the following is important in order to show excellent low-temperature fixability and also to show excellent image stability even in the output of images having different printing ratios. That is, a thin silicone oil layer is formed on the toner surface, and while maintaining a good friction opportunity between the polar group and the magnetic carrier, the electric charge generated by the friction is transferred to the entire toner surface by the charge divergence effect of the silicone oil. We found that it is important to parry evenly.
The present inventors have further studied, and by using a crystalline acrylic resin having a specific structure, a thin silicone oil layer can be formed on the toner surface, and a desired toner can be obtained. I found it.

In particular,
A toner having toner particles containing silicone oil, wherein the vinyl polymer A is present in a region within 300 nm from the surface of the toner particles toward the center thereof.
The vinyl polymer A is derived from a first monomer unit derived from the first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer. Has two monomer units,
The first polymerizable monomer is a (meth) acrylic acid ester having a linear or branched alkyl group having 18 to 36 carbon atoms.
The second polymerizable monomer has an ester group or a nitrile group and has an ester group or a nitrile group.
The SP value of the first monomer unit and the SP value of the second monomer unit,
By controlling the ratio of the first monomer unit in the vinyl polymer A and the ratio of the second monomer unit in the vinyl polymer A, the first monomer unit and the second monomer unit can be formed. We have found that they can be combined to some extent continuously rather than randomly.

As a result, the silicone oil having a high affinity with the first monomer unit spreads, and a thin silicone oil layer is formed on the toner surface. As a result, the second monomer unit has a good friction opportunity with the magnetic carrier, and the electric charge generated by the friction is uniformly transferred to the entire toner surface by the charge divergence effect of the silicone oil. Then, it is considered that excellent image stability is obtained in the output of images having different printing ratios.

The toner of the present invention contains silicone oil. Since it contains silicone oil, the charge generated by friction is uniformly passed over the entire toner surface due to the charge divergence effect of the silicone oil, resulting in excellent image stability in the output of images with different print ratios. Is obtained.
On the other hand, when the silicone oil is not contained, the charge divergence effect of the silicone oil cannot be obtained, and the charge generated by friction is localized on the toner surface, so that the rising property of the charge is impaired and the printing ratio is different. Excellent image stability cannot be obtained in image output. Further, since the electric charge is localized on the toner surface, the electrostatic adhesion force to the electrostatic latent image carrier and the intermediate transfer member increases, so that excellent transferability cannot be obtained.

In the toner of the present invention, the vinyl polymer A is present in a region within 300 nm from the surface of the toner particles toward the center thereof.
Since the vinyl polymer A is present on the surface of the toner particles, the affinity with the silicone oil is enhanced, and a thin silicone oil layer is formed on the toner surface. Therefore, the electric charge generated by friction is uniformly passed over the entire surface of the toner due to the electric charge divergence effect of the silicone oil, so that excellent image stability can be obtained in the output of images having different printing ratios.

On the other hand, when the vinyl polymer A is not present in the region within 300 nm from the surface of the toner particles toward the center thereof, the affinity with the silicone oil becomes low, the silicone oil becomes a domain, and a thick film is formed on the toner surface. A silicone oil layer is formed. Therefore, the opportunity of friction with the magnetic carrier is hindered, the rising property of charging is not improved, and excellent image stability cannot be obtained in the output of images having different printing ratios. Further, since the non-electrostatic adhesive force to the electrostatic latent image carrier and the intermediate transfer body increases with the liquid cross-linking, excellent transferability cannot be obtained.

The vinyl polymer A of the toner of the present invention is a polymer of a composition containing a first polymerizable monomer and a second polymer monomer different from the first polymerizable monomer. Is. Further, the vinyl polymer A is derived from a first monomer unit derived from the first polymerizable monomer and a second monomer unit derived from a second polymer monomer different from the first polymerizable monomer. It has a monomer unit and.

The first polymerizable monomer is at least one selected from the group consisting of (meth) acrylic acid esters having linear or branched alkyl groups having 18 to 36 carbon atoms. Further, the first monomer unit is derived from the first polymerizable monomer. Since the first polymerizable monomer has an alkyl group having a long chain length, crystallinity can be imparted to the vinyl polymer A. Therefore, the toner exhibits sharp meltability, and excellent low-temperature fixability can be obtained.

Further, since the first polymerizable monomer has a high affinity with silicone oil, a thin silicone oil layer is formed on the toner surface. Therefore, the electric charge generated by friction is uniformly passed over the entire surface of the toner due to the electric charge divergence effect of the silicone oil, so that excellent image stability can be obtained in the output of images having different printing ratios.
On the other hand, when the first polymerizable monomer is a (meth) acrylic acid ester having an alkyl group having less than 18 carbon atoms, the chain length of the alkyl group is short, so that the affinity with silicone oil is low. The silicone oil is domainized and a thick silicone oil layer is formed on the surface of the toner. Therefore, the opportunity of friction with the magnetic carrier is hindered, the rising property of charging is not improved, and excellent image stability cannot be obtained in the output of images having different printing ratios. Further, since the non-electrostatic adhesive force to the electrostatic latent image carrier and the intermediate transfer body increases with the liquid cross-linking, excellent transferability cannot be obtained.
When the first polymerizable monomer is a (meth) acrylic acid ester having an alkyl group having more than 36 carbon atoms, the (meth) acrylic acid ester has an alkyl group having a long chain length and therefore has a melting point. However, excellent low-temperature fixability cannot be obtained.

Examples of the (meth) acrylic acid ester having a linear alkyl group having 18 to 36 carbon atoms include the following. Stearyl (meth) acrylate, Nonadecil (meth) acrylate, Eikosyl (meth) acrylate, Heneikosanyl (meth) acrylate, Behenyl (meth) acrylate, Lignoceryl (meth) acrylate, Ceryl (meth) acrylate, (meth) Octacosa acrylate, myricyl (meth) acrylate, dodria contour (meth) acrylate, etc.
Examples of the (meth) acrylic acid ester having a branched-chain alkyl group having 18 to 36 carbon atoms include 2-decyltetradecyl (meth) acrylic acid.

Of these, at least one selected from the group consisting of (meth) acrylic acid esters having a linear alkyl group having 18 to 36 carbon atoms is preferable from the viewpoint of obtaining excellent low-temperature fixability. At least one selected from the group consisting of (meth) acrylic acid esters having a linear alkyl group having 18 to 30 carbon atoms is more preferable, and linear stearyl (meth) acrylate or behenyl (meth) acrylate. Is even more preferable.
The first polymerizable monomer may be used alone or in combination of two or more.

The second polymerizable monomer of the toner of the present invention is a polymerizable monomer different from the first polymerizable monomer and has an ester group or a nitrile group. The second monomer unit is derived from the second polymerizable monomer. Since the second polymerizable monomer has an ester group or a nitrile group, an electric charge due to friction with a magnetic carrier is likely to be generated. Then, the electric charge generated by friction is uniformly passed over the entire surface of the toner due to the electric charge divergence effect of the silicone oil, so that excellent image stability can be obtained in the output of images having different printing ratios. On the other hand, when the second polymerizable monomer does not have an ester group or a nitrile group, it becomes difficult to generate an electric charge due to friction with a magnetic carrier. Therefore, the rising property of charging is not improved, and excellent image stability cannot be obtained in the output of images having different printing ratios.

Specifically, as the second polymerizable monomer, for example, the following polymerizable monomers can be used.
Monomer having a nitrile group; for example, acrylonitrile, methacrylonitrile, etc.
Monomer having an ester group; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, Vinyl esters such as vinyl octylate, acrylate esters such as acrylamide and methyl acrylate, and methacrylic acid esters such as methyl methacrylate.
Among them, the vinyl esters selected from the group consisting of the following formula (A) are non-conjugated monomers, and the reactivity with the first polymerizable monomer is easily maintained, and the crystals of the vinyl polymer A are crystallized. Since it is easy to improve the properties, it is easy to achieve both low temperature fixability and suppression of image stability.

（Ｒ^１は、炭素数１〜４のアルキル基を示し、Ｒ^２は、それぞれ独立して水素原子又はメチル基を示す。）

(R ¹ represents an alkyl group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom or a methyl group independently of each other.)

The second monomer unit is derived from the second polymerizable monomer. The second polymerizable monomer may be used alone or in combination of two or more.

For the vinyl polymer A of the first toner, the SP value of the first monomer unit is SP ₁₁ (J / m ³ ) ^0.5, and the SP value of the second monomer unit is SP ₂₁ (J / m ³ ). ^When it is set to ^0.5 , the SP ₁₁ and the SP ₂₁ satisfy the following formula (1) and the following formula (2).
SP ₁₁ ≤ 18.40 (J / cm ³ ) ^0.5 ... (1)
21.00 (J / cm ³ ) ^0.5 ≤ SP ₂₁ ... (2)

Further, in the vinyl polymer A of the second toner, the SP value of the first polymerizable monomer is SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP. When SP ₂₂ (J / cm ³ ) is ^0.5 , the SP ₁₂ and the SP ₂₂ satisfy the following equations (4) and (5).
SP ₁₂ ≤ 17.72 (J / cm ³ ) ^0.5 ... (4)
18.30 (J / cm ³ ) ^0.5 ≤ SP ₂₂ ... (5)

The unit of the SP value was (J / m ³ ) ^0.5 , but 1 (cal / cm ³ ) ^0.5 = 2.045 × 10 ³ (J / m ³ ) ^0.5 was used. (Cal / cm ³ ) It can be converted to a unit of ^0.5 .

When the above formulas (1) and (2) are satisfied, or when the above formulas (4) and (5) are satisfied, a polarity difference occurs between the first and second monomer units. Due to this polarity difference, the first monomer unit and the second monomer unit can be bonded continuously to some extent instead of being randomly bonded at the time of polymerization. As a result, the silicone oil having a high affinity with the first monomer unit derived from the (meth) acrylic acid ester having an alkyl group spreads, and a thin silicone oil layer is formed on the toner surface. As a result, the second monomer unit having an ester group or a nitrile group has a good friction opportunity with the magnetic carrier, and the charge generated by the friction is uniformly spread over the entire surface of the toner due to the charge divergence effect of the silicone oil. Parryed. As a result, excellent image stability can be obtained in the output of images having different printing ratios.

On the other hand, when the above formulas (1) and (2) are not satisfied or when the above formulas (4) and (5) are not satisfied, there is not much difference in polarity between the first and second monomer units. Therefore, the first monomer unit and the second monomer unit are randomly bonded. As a result, the silicone oil having a high affinity with the monomer unit derived from the (meth) acrylic acid ester having an alkyl group may repel the adjacent second monomer unit having an ester group or a nitrile group having a low affinity. Together, they are domained and a thick silicone oil layer is formed on the toner surface. As a result, the second monomer unit having an ester group or a nitrile group hinders the friction opportunity with the magnetic carrier, so that the rising property of charging is not improved, and the image stability is excellent in the output of images having different printing ratios. I can't get sex. Further, since the non-electrostatic adhesive force to the electrostatic latent image carrier and the intermediate transfer body increases with the liquid cross-linking, excellent transferability cannot be obtained.

Further, when the above formula (1) or (4) is not satisfied, the first monomer unit means that the chain length of the alkyl group is short, so that the affinity with the silicone oil becomes low, and the silicone oil has a domain. A thick silicone oil layer is formed on the surface of the toner. Therefore, the opportunity of friction with the magnetic carrier is hindered, the rising property of charging is not improved, and excellent image stability cannot be obtained in the output of images having different printing ratios. Further, since the non-electrostatic adhesive force to the electrostatic latent image carrier and the intermediate transfer body increases with the liquid cross-linking, excellent transferability cannot be obtained.

Further, when the above formula (2) or (5) is not satisfied, it means that the second monomer unit has a low polarity, so that it is difficult to generate an electric charge due to friction with the magnetic carrier. Therefore, the rising property of charging is not improved, and excellent image stability cannot be obtained in the output of images having different printing ratios.

In the present invention, when a plurality of types of monomer units satisfying the requirements of the first monomer unit are present in the vinyl polymer A, the value of SP ₁₁ in the formula (1) is a weighted average of the SP values of each monomer unit. The value is set to For example:
Monomer unit A having an SP value of SP ₁₁₁ contains A mol% based on the number of moles of the entire monomer unit satisfying the requirements of the first monomer unit.
The SP value (SP ₁₁ ) when the monomer unit B having an SP value of SP ₁₁₂ is contained in (100-A) mol% based on the number of moles of the entire monomer unit satisfying the requirements of the first monomer unit is calculated by the following formula. Is calculated using.
SP ₁₁ = (SP ₁₁₁ x A + SP ₁₁₂ x (100-A)) / 100
The same calculation is performed when three or more monomer units satisfying the requirements of the first monomer unit are included.
Similarly, SP _{12 is} also used as a weighted average value calculated using the molar ratio of each first polymerizable monomer.

On the other hand, when the second polymerizable monomer is two or more kinds of polymerizable monomers, SP ₂₁ represents the SP value of the monomer unit derived from each polymerizable monomer, and each SP ₂₁ represents the above. Equation (2) is satisfied. Similarly, SP ₂₂ represents the SP value of each polymerizable monomer, and each SP ₂₂ satisfies the above formula (5).

The content ratio of the first monomer unit in the vinyl polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all the monomer units in the vinyl polymer A.
The content ratio of the second monomer unit in the vinyl polymer A is 20.0 mol% to 95.0 mol% based on the total number of moles of all the monomer units in the vinyl polymer A.

The content ratio of the first polymerizable monomer in the composition constituting the vinyl polymer A is 5.0 mol% or more based on the total number of moles of the total polymerizable monomers in the composition. 60.0 mol%,
The content ratio of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of the total polymerizable monomer in the composition.

When the content ratio of the first monomer unit and the content ratio of the first polymerizable monomer are within the above ranges, crystallinity can be imparted to the vinyl polymer A. Therefore, the toner exhibits sharp meltability, and excellent low-temperature fixability can be obtained. Further, since the first polymerizable monomer has a high affinity with silicone oil, a thin silicone oil layer is formed on the toner surface. Therefore, the electric charge generated by friction is uniformly passed over the entire surface of the toner due to the electric charge divergence effect of the silicone oil, so that excellent image stability can be obtained in the output of images having different printing ratios.

Further, when the content ratio of the second monomer unit and the content ratio of the second polymerizable monomer are within the above ranges, electric charges due to friction with the magnetic carrier are likely to be generated. Then, the electric charge generated by friction is uniformly passed over the entire surface of the toner due to the electric charge divergence effect of the silicone oil, so that excellent image stability can be obtained in the output of images having different printing ratios.

On the other hand, when the content ratio of the first monomer unit is less than 5.0 mol% and when the content ratio of the first polymerizable monomer is less than 5.0 mol%, there are few crystalline parts. , Sharp melt property cannot be exhibited, and excellent low temperature fixability cannot be obtained.
Further, when the content ratio of the first monomer unit is more than 60.0 mol%, and when the content ratio of the first polymerizable monomer is more than 60.0 mol%, the second monomer unit is relatively relative. It means that the content ratio of and the content ratio of the second polymerizable monomer are small. Then, electric charges due to friction with the magnetic carrier are less likely to be generated. Therefore, the rising property of charging is not improved, and excellent image stability cannot be obtained in the output of images having different printing ratios.

Further, when the content ratio of the second monomer unit is less than 20.0 mol%, and when the content ratio of the second polymerizable monomer is less than 20.0 mol%, the electric charge due to friction with the magnetic carrier is charged. It is less likely to occur. Therefore, the rising property of charging is not improved, and excellent image stability cannot be obtained in the output of images having different printing ratios.
Further, when the content ratio of the second monomer unit is more than 95.0 mol% and when the content ratio of the second polymerizable monomer is more than 95.0 mol%, there are few crystalline parts. , Sharp melt property cannot be exhibited, and excellent low temperature fixability cannot be obtained.

The content ratio of the first monomer unit and the content ratio of the first polymerizable monomer are preferably 10.0 mol% to 60 from the viewpoint that excellent low temperature fixability and image stability can be obtained. It is 0.0 mol%, more preferably 20.0 mol% to 40.0 mol%.
The content ratio of the second monomer unit and the content ratio of the second polymerizable monomer are preferably 40.0 mol% to 95 from the viewpoint that excellent low temperature fixability and image stability can be obtained. It is 0.0 mol%, more preferably 40.0 mol% to 70.0 mol%.

When the vinyl polymer A has a monomer unit derived from (meth) acrylic acid ester having two or more kinds of alkyl groups having 18 to 36 carbon atoms, the content ratio of the first monomer unit is the total of them. Represents the molar ratio of.
Similarly, when the composition used for the vinyl polymer A contains two or more kinds of (meth) acrylic acid esters having an alkyl group having 18 to 36 carbon atoms, the content ratio of the first polymerizable monomer is the same. , Represents the total molar ratio of them.

When there are two or more types of monomer units derived from the second polymerizable monomer satisfying the formula (2) in the vinyl polymer A, the ratio of the second monomer unit is the total mole of them. Represents a ratio.
Similarly, when the composition used for the vinyl polymer A contains two or more kinds of second polymerizable monomers, the content ratio of the second polymerizable monomer is the total molar ratio thereof. Represent.

Let A be the peak area of a silicon atom whose binding energy peak position measured using the electron spectrochemical analysis method (ESCA) of the toner and toner particles of the present invention is 102 ev to 103 ev.
When the peak area of the carbon atom whose binding energy peak position is 285 ev to 288 ev is B, A / B satisfies the following formula (3).
1.0 ≤ A / B ≤ 3.0 ... (3)

This shows the ratio of the silicone oil present on the surface of the toner particles, and the surface portion coated with the silicone oil with respect to the surface portion derived from the surface of the toner particles (the surface portion not coated with the silicone oil). Shows the ratio of.
When A / B satisfies the above formula (3), it means that a thin silicone oil layer is formed on the toner surface. Therefore, the electric charge generated by friction is uniformly passed over the entire surface of the toner due to the electric charge divergence effect of the silicone oil, so that excellent image stability can be obtained in the output of images having different printing ratios.

On the other hand, when A / B is less than 1.0, the coverage of the silicone oil on the surface of the toner particles is low, so that the charge divergence effect of the silicone oil cannot be obtained, and the charge generated by friction is localized on the toner surface. Incorporate. Therefore, the rising property of charging is impaired, and excellent image stability cannot be obtained in the output of images having different printing ratios. Further, since the electric charge is localized on the toner surface, the electrostatic adhesion force to the electrostatic latent image carrier and the intermediate transfer member increases, so that excellent transferability cannot be obtained.

Further, when the A / B is more than 3.0, it means that a thick film of silicone oil is formed on the surface of the toner particles, the friction opportunity with the magnetic carrier is hindered, and the rising property of charging is improved. However, excellent image stability cannot be obtained in the output of images having different printing ratios. Further, since the non-electrostatic adhesive force to the electrostatic latent image carrier and the intermediate transfer body increases with the liquid cross-linking, excellent transferability cannot be obtained.

Even when measuring toner in which inorganic fine particles such as silica are externally attached to the toner particles, the surface portion covered with the inorganic fine particles is not measured, so the measured value of the toner and the measured value of the toner particles are different. , Basically the same value. Furthermore, since the resistance of inorganic fine particles such as silica is low, the charge divergence effect of the unmeasured portion is at a level that does not cause any problem. Therefore, if the A / B is in the above range, printing is performed regardless of the presence or absence of the inorganic fine particles. Excellent image stability can be obtained in the output of images having different ratios.

In the vinyl polymer A, the molar ratio of the first monomer unit derived from the first polymerizable monomer and the second monomer unit derived from the second polymerizable monomer described above is not impaired. , A monomer unit derived from a third polymerizable monomer may be contained.
As the third polymerizable monomer, among the monomers exemplified as the second polymerizable monomer, a monomer that does not satisfy the above formula (1) or the above formula (2) can be used. ..
In addition, the following monomers can also be used. For example, styrene and derivatives thereof such as styrene, o-methylstyrene, (meth) such as -n-butyl (meth) acrylate, -t-butyl (meth) acrylate, and -2-ethylhexyl (meth) acrylate. Acrylic acid esters. When the formula (1) or the formula (2) is satisfied, it can be used as the second polymerizable monomer.

The acid value of the vinyl polymer A is preferably 30.0 mgKOH / g or less, preferably 20.0 mgKOH / g or less, from the viewpoint that excellent image stability can be obtained in the output of images having different printing ratios. More preferably. When the acid value is in the above range, the affinity with the vinyl polymer A is enhanced, and a thin silicone oil layer is formed on the toner surface. Therefore, the electric charge generated by friction is uniformly passed over the entire surface of the toner due to the electric charge divergence effect of the silicone oil, so that excellent image stability can be obtained in the output of images having different printing ratios. The lower limit of the acid value is not particularly limited, but is preferably 0 mgKOH / g or more.

Further, the vinyl polymer A preferably has a weight average molecular weight (Mw) of a tetrahydrofuran (THF) soluble component measured by GPC of 10,000 or more and 200,000 or less, and is preferably 20,000 or more and 150,000 or less. More preferably:
When the GPC: gel permeation chromatography Mw is within the above range, the affinity with the vinyl polymer A is enhanced, and a thin silicone oil layer is formed on the toner surface. Therefore, the electric charge generated by friction is uniformly passed over the entire surface of the toner due to the electric charge divergence effect of the silicone oil, so that excellent image stability can be obtained in the output of images having different printing ratios.

The melting point of the vinyl polymer A is preferably 50 ° C. or higher and 80 ° C. or lower, and more preferably 53 ° C. or higher and 70 ° C. or lower. When the melting point of the vinyl polymer A is within the above range, better low temperature fixability can be obtained.
The melting point of the vinyl polymer A can be adjusted depending on the type and amount of the first polymerizable monomer used, the type and amount of the second polymerizable monomer, and the like.

The silicone oil of the toner of the present invention is preferably dimethyl silicone oil from the viewpoint that excellent image stability can be obtained in the output of images having different printing ratios. When the silicone oil is dimethyl silicone, the affinity with the vinyl polymer A is enhanced, and a thin silicone oil layer is formed on the toner surface. Therefore, the electric charge generated by friction is uniformly passed over the entire surface of the toner due to the electric charge divergence effect of the silicone oil, so that excellent image stability can be obtained in the output of images having different printing ratios.

The silicone oil of the toner of the present invention has a weight average molecular weight (hereinafter, also referred to as Mw) measured by GPC of 1,000 or more and 25,000 or less, which is excellent in image stability in the output of images having different printing ratios. It is preferable from the viewpoint that By setting the weight average molecular weight of the silicone oil to 1,000 or more, it is easy to control the exudation of the silicone oil to the surface of the toner particles, and a thin silicone oil layer is formed on the toner surface. Therefore, the electric charge generated by friction is uniformly passed over the entire surface of the toner due to the electric charge divergence effect of the silicone oil, so that excellent image stability can be obtained in the output of images having different printing ratios.

Further, in the molecular weight distribution measured by GPC, the content of the component having a weight average molecular weight of 500 or less contained in the silicone oil is 0.05% by mass or less, which is an excellent image in the output of images having different printing ratios. It is preferable from the viewpoint that stability can be obtained. By setting the content of the component having a weight average molecular weight of 500 or less contained in the silicone oil to 0.05% by mass or less, it becomes easy to control the exudation of the silicone oil to the surface of the toner particles, and a thin film is formed on the toner surface. Silicone oil layer is formed. Therefore, the electric charge generated by friction is uniformly passed over the entire surface of the toner due to the electric charge divergence effect of the silicone oil, so that excellent image stability can be obtained in the output of images having different printing ratios.

I think the reason is as follows. Since low molecular weight silicone oil having a weight average molecular weight of 500 or less has high mobility in toner particles, it is specifically likely to precipitate on the surface of toner particles during storage. Further, it is considered that when the low molecular weight silicone oil is present in the toner particles in a certain amount or more, the silicone oil having a high molecular weight, which is the main component, also has high motility and is easily deposited on the surface.
The content of the component having a weight average molecular weight of 500 or less is preferably 0.03% by mass or less. The lower limit is not particularly limited, but is preferably 0.001% by mass or more.
The method for reducing the content of the component having a weight average molecular weight of 500 or less in the silicone oil to 0.05% by mass or less is not particularly limited, and a known method can be used. As an example, the heating and depressurizing method is shown below.

<Heating and depressurizing method>
The silicone oil is put into a container that can obtain high airtightness, and heated at a temperature or lower at which the high molecular weight component of the silicone oil used does not undergo a thermal oxidation reaction. As for the heating temperature, the higher the temperature at which the high molecular weight component does not undergo a thermal oxidation reaction, the faster the low molecular weight component can be reduced. Low molecular weight components can be removed more efficiently by reducing the pressure with a vacuum pump or the like while heating. The pressure when the pressure is reduced is preferably reduced to 10 torr or less, and the lower the pressure, the more preferable. When the content of the component having a weight average molecular weight of 500 or less becomes 0.05% by mass or less, heating and depressurization is terminated and the mixture is recovered.

The toner of the present invention
A process of melt-kneading a toner composition containing silicone oil to obtain a melt-kneaded product,
The process of crushing and classifying the melt-kneaded product to obtain toner matrix particles,
For example, from the viewpoint that the step of heat-treating the toner matrix particles with hot air using the surface treatment apparatus shown in FIG. 1 can obtain excellent image stability in the output of images having different printing ratios. preferable.

Since the toner particles are treated with hot air by receiving centrifugal force by the surface treatment apparatus shown in FIG. 1, excess silicone oil on the surface of the toner particles is removed, and a thin silicone oil layer is formed on the toner surface. .. Therefore, the electric charge generated by friction is uniformly passed over the entire surface of the toner due to the electric charge divergence effect of the silicone oil, so that excellent image stability can be obtained in the output of images having different printing ratios.

The toner of the present invention is a known toner production method such as a suspension polymerization method, a kneading pulverization method, an emulsification / aggregation method, and a dissolution / suspension method, in which the toner obtained during or after the production process is brought into contact with an organic solvent. It is preferable to have a step of causing. This is because excellent image stability can be obtained in the output of images having different printing ratios by having the step of bringing the toner into contact with the organic solvent. By having the step of bringing the toner into contact with the organic solvent, the low molecular weight silicone compound having a high affinity with the organic solvent is washed, and a thin film of the silicone compound having a sharp molecular weight distribution is formed on the surface of the toner particles. Therefore, the electric charge generated by friction is uniformly passed over the entire surface of the toner due to the electric charge divergence effect of the silicone oil, so that excellent image stability can be obtained in the output of images having different printing ratios.

<Resin other than vinyl polymer A>
If necessary, the binder resin may contain a resin other than the vinyl polymer A. Examples of the resin other than the vinyl polymer A used for the binder resin include the following resins.
Monopolymers of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and its substitutions; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene -Acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinylmethyl ether copolymer, styrene-vinyl ethyl ether Styrene-based copolymers such as copolymers, styrene-vinylmethylketone copolymers, styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenolic resin, natural resin-modified phenolic resin, natural resin-modified maleic acid resin, acrylic Examples thereof include resins, methacrylic resins, polyvinyl acetates, silicone resins, polyester resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpen resins, kumaron-indene resins, and petroleum resins.
Among these, styrene-based copolymers and polyester resins are preferable. Further, the resin other than the vinyl polymer A is preferably amorphous.

Further, when the content of the vinyl polymer A in the binder resin is 50.0% by mass or more, excellent low-temperature fixability can be obtained. It is more preferably 80.0% by mass to 100.0% by mass, and it is further preferable that the binder resin is the vinyl polymer A.

<Colorant>
The toner may contain a colorant, if necessary. Examples of the colorant include the following.
Examples of the black colorant include carbon black; a color toned black using a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, the pigment may be used alone, or the dye and the pigment may be used in combination. From the viewpoint that excellent image quality can be obtained in a full-color image, it is preferable to use a dye and a pigment in combination.

Examples of the magenta toner pigment include the following. C. 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: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment Violet 19; C.I. I. Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

Examples of the magenta toner dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. I. Dispar Thread 9; C.I. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1,2,9,12,13,14,15,17,18,22,23,24,27,29,32,34,35,36,37,38,39,40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of the cyan toner pigment include the following. C. I. Pigment Blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; C.I. I. Bat Blue 6; C.I. I. Acid blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalocyanine groups are substituted in the phthalocyanine skeleton.
Examples of dyes for cyan toner include C.I. I. Solvent blue 70 can be mentioned.

Examples of the pigment for yellow toner include the following. C. I. Pigment Yellow 1,2,3,4,5,6,7,10,11,12,13,14,15,16,17,23,62,65,73,74,83,93,94,95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; C.I. I. Bat Yellow 1, 3, 20.
Examples of the dye for yellow toner include C.I. I. Solvent Yellow 162 can be mentioned.

These colorants can be used alone or in admixture, and even in the form of a solid solution. The colorant is selected in terms of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner.
The content of the colorant is preferably 0.1 part by mass to 30.0 parts by mass with respect to the total amount of the resin components.

<Release agent>
The toner particles may contain wax as a release agent. Examples of such wax include the following.
Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystallin wax, paraffin wax, Fishertropch wax; oxides of hydrocarbon waxes such as polyethylene oxide wax or block copolymers thereof. Waxes whose main component is a fatty acid ester such as carnauba wax; deoxidized A part or all of a fatty acid ester such as carnauba wax is deoxidized. Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brushzic acid, eleostearic acid, and parinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, and ceryl alcohol. , Saturated alcohols such as melisyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol , Esters with alcohols such as ceryl alcohol, melisyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislaurin Saturated fatty acid bisamides such as acid amides and hexamethylene bisstearic acid amides; ethylene bisoleic acid amides, hexamethylene bisoleic acid amides, N, N'diorail adipate amides, N, N'diorail sebasic acid amides Unsaturated fatty acid amides such as; aromatic bisamides such as m-xylene bisstearate amide, N, N'distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate. Aliphatic metal salts (generally called metal soaps); waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; waxes such as behenic acid monoglyceride. Partial esterified product of fatty acid and polyhydric alcohol; methyl ester compound having a hydroxyl group obtained by hydrogenation of vegetable fats and oils.

Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, and fatty acid ester waxes such as carnauba wax are preferable from the viewpoint of improving low temperature fixability and fixing separability. Hydrocarbon waxes are more preferred in that they have better hot offset resistance.
The content of the wax is preferably 3 parts by mass to 8 parts by mass per 100 parts by mass of the binder resin.

Further, the peak temperature of the maximum endothermic peak of the wax in the endothermic curve at the time of temperature rise measured by the differential scanning calorimetry (DSC) device is preferably 45 ° C. to 140 ° C. When the peak temperature of the maximum endothermic peak of the wax is within the above range, both the storage stability of the toner and the hot offset resistance can be achieved at the same time.

<Charge control agent>
The toner particles may contain a charge control agent, if necessary. By blending a charge control agent, it is possible to stabilize the charge characteristics and control the optimum triboelectric charge amount according to the developing system.
As the charge control agent, known ones can be used, but in particular, a metal compound of an aromatic carboxylic acid, which is colorless, has a high charging speed of the toner, and can stably maintain a constant charge amount, is preferable.

Examples of the negative charge control agent include the following. Metallic salicylate compound, metal naphthoate compound, metal dicarboxylic acid compound. Polymer-type compounds having sulfonic acid or carboxylic acid in the side chain, polymer-type compounds having sulfonic acid or sulfonic acid esterified products in the side chain, polymer-type compounds having carboxylate or carboxylic acid esterified products in the side chain .. Boron compounds, urea compounds, silicon compounds, calixarene.
The charge control agent may be added internally or externally to the toner particles. The content of the charge control agent is preferably 0.2 parts by mass to 10.0 parts by mass, and more preferably 0.5 parts by mass to 10.0 parts by mass with respect to 100 parts by mass of the binder resin.

<Inorganic fine particles>
The toner may contain inorganic fine particles, if necessary.
The inorganic fine particles may be internally added to the toner particles, or may be mixed with the toner as an external additive. Examples of the inorganic fine particles include fine particles such as silica fine particles, titanium oxide fine particles, alumina fine particles, and their double oxide fine particles. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferable for improving fluidity and homogenizing charging.

The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.
From the viewpoint of improving the fluidity, the inorganic fine particles as an external additive preferably has a specific surface area of ^{50m 2} / ^g~400m 2 / g. Further, from the viewpoint of improving the running stability, inorganic fine particles as an external additive preferably has a specific surface area of ^{10m 2} / ^g~50m 2 / g. Inorganic fine particles having a specific surface area in the above range may be used in combination in order to achieve both improved fluidity and durability stability.
The content of the external additive is preferably 0.1 part by mass to 10.0 parts by mass with respect to 100 parts by mass of the toner particles. A known mixer such as a Henschel mixer can be used for mixing the toner particles and the external additive.

<Developer>
Toner can be used as a one-component developer, but it is mixed with a magnetic carrier and used as a two-component developer in order to further improve dot reproducibility and to supply a stable image for a long period of time. Is preferable.
Examples of the magnetic carrier include the following. Iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earths, their alloy particles, their oxide particles. Magnetic material such as ferrite; A magnetic material-dispersed resin carrier (so-called resin carrier) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state.
When the toner is mixed with a magnetic carrier and used as a two-component developer, the mixing ratio of the magnetic carriers at that time may be 2% by mass to 15% by mass as the toner concentration in the two-component developer. It is preferably, more preferably 4% by mass to 13% by mass or less.

<Toner manufacturing method>
The method for producing the toner particles is not particularly limited, but the pulverization method is preferable from the viewpoint of dispersing the silicone oil. The reason is that when toner particles are produced in an aqueous medium, silicone oil is deposited on the surface of the toner particles, so that a thick silicone oil layer is formed on the surface of the toner particles. As a result, the opportunity of friction with the magnetic carrier is hindered, so that the rising property of charging is not improved, and excellent image stability cannot be obtained in the output of images having different printing ratios.
Hereinafter, the toner manufacturing procedure by the pulverization method will be described.

<Mixing process>
In the raw material mixing step, other components such as a binder resin, a mold release agent, a colorant, a crystalline polyester, and a charge control agent, if necessary, are weighed and blended as materials constituting the toner particles. , Mix. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a mechano hybrid (manufactured by Nippon Coke Industries Co., Ltd.) and the like.

<Kneading process>
Next, the mixed materials are melt-kneaded to disperse wax and the like in the binder resin. In the melt-kneading process, a batch-type kneader such as a pressure kneader or a Bambary mixer or a continuous-type kneader can be used, and a single-screw or twin-screw extruder has become the mainstream because of the advantage of continuous production. ing. For example, KTK type twin-screw extruder (manufactured by Kobe Steel, Ltd.), TEM type twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Iron Works), twin-screw extruder (KTC).・ Ktk Inc.), Co-Kneader (Bus), Kneedex (Nippon Coke Industries Co., Ltd.), etc. Further, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.

<Crushing process>
The cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the crushing step, after coarse crushing with a crusher, it is further pulverized with a fine crusher.
Examples of the crusher include a crusher, a hammer mill, and a feather mill.
Examples of the pulverizer include a cryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nisshin Engineering Co., Ltd.), a turbo mill (manufactured by Turbo Industries, Ltd.), and an air jet method. The opportunity is mentioned.

<Classification process>
Classify using a classifier or a sieve as necessary.
Examples of the classifier and the sieving machine include the following. Inertial classification type elbow jet (manufactured by Nittetsu Mining Co., Ltd.), centrifugal force classification type turboplex (manufactured by Hosokawa Micron Co., Ltd.), TSP separator (manufactured by Hosokawa Micron Co., Ltd.), faculty (manufactured by Hosokawa Micron Co., Ltd.).

<Surface treatment process>
The surface treatment of the toner particles by heating is performed to increase the circularity of the toner. For example, the surface treatment apparatus shown in FIG. 1 can be used to perform surface treatment with hot air.
In the surface treatment apparatus shown in FIG. 1, the mixture quantitatively supplied by the raw material quantitative supply means 1 is supplied to the introduction pipe 3 installed on the vertical line of the raw material supply means by the compressed gas adjusted by the compressed gas adjusting means 2. Be guided. The mixture that has passed through the introduction pipe 3 is uniformly dispersed by the conical protrusion-shaped member 4 provided in the central portion of the raw material supply means, and is guided to the supply pipe 5 in eight directions that spread radially to perform heat treatment. Guided to 6.

At this time, the flow of the mixture supplied to the processing chamber 6 is regulated by the regulating means 9 for regulating the flow of the mixture provided in the processing chamber. Therefore, the mixture supplied to the treatment chamber is heat-treated while swirling in the treatment chamber, and then cooled.
The hot air for heat-treating the supplied mixture is supplied from the hot air supply means 7, distributed by the distribution member 12, and introduced by spirally swirling the hot air into the processing chamber by the swirling member 13 for swirling the hot air. Will be done. As its configuration, the swirling member 13 for swirling the hot air has a plurality of blades, and the swirling of the hot air can be controlled by the number and angles thereof. The temperature of the hot air supplied to the processing chamber at the hot air supply means outlet 11 is preferably 100 ° C. to 300 ° C. When the temperature at the hot air supply means outlet 11 is within the above range, it is possible to uniformly spheroidize the toner particles while suppressing the fusion and coalescence of the toner particles due to overheating of the mixture. ..

Further, the heat-treated heat-treated toner particles are cooled by the cold air supplied from the cold air supply means 8, and the temperature supplied from the cold air supply means 8 is preferably −20 ° C. to 30 ° C. When the temperature of the cold air is within the above range, the heat-treated toner particles can be efficiently cooled, and the fusion and coalescence of the heat-treated toner particles are suppressed without hindering the uniform spherical treatment of the mixture. be able to. The absolute water content of the cold air is preferably 0.5 g / m ³ or more and 15.0 g / m ³ or less.

Next, the cooled heat-treated toner particles are recovered by the recovery means 10 at the lower end of the processing chamber 6. A blower (not shown) is provided at the tip of the collecting means, and the suction is conveyed by the blower.
Further, the powder particle supply port 14 is provided so that the swirling direction of the supplied mixture and the swirling direction of the hot air are in the same direction, and the recovery means 10 of the surface treatment apparatus is a swirling powder particle. It is provided on the outer peripheral portion of the processing chamber 6 so as to maintain the turning direction. Further, the cold air supplied from the cold air supply means 8 is configured to be supplied horizontally and tangentially from the outer peripheral portion of the apparatus to the peripheral surface of the processing chamber. The swirling direction of the toner supplied from the powder particle supply port 14, the swirling direction of the cold air supplied from the cold air supply means 8, and the swirling direction of the hot air supplied from the hot air supply means 7 are all in the same direction. Therefore, turbulent flow does not occur in the processing chamber, the swirling flow in the device is strengthened, a strong centrifugal force is applied to the toner, and the dispersibility of the toner is further improved, so that the toner has a uniform shape with few coalesced particles. Can be obtained.
When the average circularity of the toner is 0.960 or more and 0.980 or less, the non-electrostatic adhesive force can be suppressed low, which is preferable from the viewpoint that excellent transferability can be obtained.

<Process of contact with organic solvent and separation process>
In the step of contacting with the organic solvent and the separation step, if necessary, the toner particles that have undergone the surface treatment step are brought into contact with the organic solvent and separated. By doing so, the low molecular weight silicone oil having a high affinity with the organic solvent can be washed, and a thin film of the silicone oil having a sharp molecular weight distribution can be formed on the toner surface. It is important that the organic solvent used has an affinity for silicone oil. If the affinity is too high, the silicone oil will be drawn too much from the toner particles, and the charge divergence effect will be impaired. Specific examples of the organic solvent include ethanol, methanol, propanol, isopropanol, ethyl acetate, methyl acetate, butyl acetate, and mixtures thereof.

The organic solvent may contain water, and the water content is preferably 0 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the organic solvent. By setting the water content of the organic solvent to 10 parts by mass or less with respect to 100 parts by mass of the organic solvent, the low molecular weight silicone compound existing near the surface of the toner particles can be removed.

The treatment time of the contact step between the toner particles and the organic solvent is preferably 1 minute or more and 60 minutes or less.
In the step of contacting the toner particles and the organic solvent, when the toner particles and the organic solvent are mixed to obtain an organic solvent dispersion of the toner particles, the stirring may be performed by stirring with a stirring blade or by a homogenizer or an ultrasonic disperser. good. However, from the viewpoint of uniformly treating the toner particles, it is preferable to perform the treatment under stirring with a homogenizer or an ultrasonic disperser.

The step of separating the toner particles and the organic solvent is a step of physically separating the organic solvent dispersion of the toner particles obtained in the contact step or the mixture of the toner wet cake and the organic solvent by filtration or the like. As long as the toner particles and the organic solvent can be separated, the method is not particularly limited, and examples thereof include a separation method by suction filtration, pressure filtration, or centrifugation.

In the contact step and the separation step of the toner particles and the organic solvent, the contact and separation steps may be repeated a plurality of times. In particular, when treating a mixture of the toner wet cake and the organic solvent, it is more preferable to treat the mixture multiple times because the removability of the silicone compound may be lowered due to the influence of water present in the toner wet cake.

<Drying process>
In the drying step, the toner particles obtained in the above step are dried.

<External process>
After that, as a method of externalizing, the following method can be mentioned. A mixer such as a double-con mixer, V-type mixer, drum-type mixer, super mixer, Henschel mixer, Nautamixer, Mechanohybrid (manufactured by Nippon Coke Industries Co., Ltd.), Nobilta (manufactured by Hosokawa Micron Co., Ltd.) is used as an external mixer. A method of stirring and mixing. At that time, if necessary, an external additive other than the silica fine particles A such as a fluidizing agent may be externally added.
A method for measuring various physical properties of toner particles and raw materials will be described below.

<A / B measurement method by ESCA>
The amount of Si derived from the silicone oil on the surface layer of the toner was determined by electron spectroscopic analysis (ESCA: Electron Spectroscopy for Chemical Analysis).
Equipment: Quantum2000 (manufactured by ULVAC-PHI Co., Ltd.)
Sample measurement range: Φ100 μm
Photoelectron uptake angle: 45 °
X-ray: Beam diameter 50 μm, 12.5 W, 15 kV
PassEnergy: 46.95eV
Step Size: 0.200eV
No of Sweeps: 1-20
Set measurement time: 30 min

As a measurement principle, photoelectrons are generated using an X-ray source, and energy based on the unique chemical bond of a substance is measured. As X-rays, monochromatic Al-Kα is used, and measurement is performed under the conditions of a beam diameter of 50 μm and Pass Energy 46.95 eV. Then, the ratio of the silicone oil present on the surface of the toner particles can be calculated from the following formula.
Percentage of silicone oil present on the surface of toner particles = (A / B)
A indicates the peak area of the silicon (Si) atom whose binding energy peak position is 102 ev to 103 ev.
B indicates the peak area of the carbon (C) atom whose binding energy peak position is between 285 ev and 288 ev.

Even when silica is externally added to the toner as inorganic fine particles, the peak area of silicon atoms derived from silicone oil and the peak area of silicon atoms derived from silica can be obtained, respectively. The peak position of the binding energy at 102 ev to 103 ev is derived from silicone oil. On the other hand, the peak position of the binding energy at 103 eV to 104 eV is derived from silica (SiO ₂ ).

<Measurement method of weight average molecular weight and molecular weight distribution of silicone oil by GPC>
Toluene and silicone oil for high performance liquid chromatography are placed in a sample bottle and dissolved.
After confirming that the silicone oil has dissolved, it is filtered using a disposable disc filter (trade name: Myshori disc, opening 0.5 μm) manufactured by Tosoh Corporation, and the passed product is used as a GPC sample.
The sample solution is adjusted so that the concentration is about 1.0% by mass.

This sample solution is used for measurement under the following conditions.
Equipment: Prominence GPC system (manufactured by Shimadzu Corporation)
Detector: RID
Column: Toluene dedicated LF804 Double temperature: 45.0 ° C
Solvent: Toluene flow rate for high performance liquid chromatography: 1.0 mL / min
Injection volume: 0.05 mL

In calculating the molecular weight of silicone oil, a molecular weight calibration curve prepared using the following standard polystyrene resin is used.
-Standard polystyrene resin: Product name "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2 , F-1, A-5000, A-2500, A-1000, A-500 "manufactured by Toso Co., Ltd.

<Method for measuring the content ratio of monomer units derived from various polymerizable monomers in vinyl polymer A>
The content ratio of the monomer unit derived from various polymerizable monomers in the vinyl polymer A is measured by ¹ H-NMR under the following conditions.
Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0 μs
Frequency range: 10500Hz
Number of integrations: 64 times Measurement temperature: 30 ° C
Sample: 50 mg of a measurement sample (vinyl polymer A) is placed in a sample tube having an inner diameter of 5 mm, deuterated chloroform (CDCl ₃ ) is added as a solvent, and this is dissolved in a constant temperature bath at 40 ° C. to prepare.

From the obtained ¹ H-NMR chart, among the peaks assigned to the components of the monomer unit derived from the first polymerizable monomer, the components of the monomer unit derived from other polymerizable monomers Select a peak that is independent of the peak attributed to. Then, to calculate the integral values S ₁ for the peak.
Similarly, among the peaks attributed to the components of the monomer unit derived from the second polymerizable monomer, the peaks attributed to the components of the monomer unit derived from other polymerizable monomers are select separate peaks, an integrated value S ₂ is calculated for this peak.

Further, when the third polymerizable monomer is used, it is derived from another polymerizable monomer from the peak attributed to the component of the monomer unit derived from the third polymerizable monomer. Select peaks that are independent of the peaks that belong to the components of the monomer unit. Then, it calculates an integrated value S ₃ of the peak.
The content ratio of the monomer unit derived from the first polymerizable monomer is determined as follows using the above integrated values S ₁ , S ₂ and S ₃ . In addition, n ₁ , n _{2, and} n ₃ are the number of hydrogens in the component to which the peak focused on each site is assigned.
Content ratio (mol%) of monomer unit derived from the first polymerizable monomer =
{(S ₁ / n ₁ ) / ((S ₁ / n ₁ ) + (S ₂ / n ₂ ) + (S ₃ / n ₃ ))} x 100

Similarly, the content ratio of the monomer unit derived from the second polymerizable monomer and the third polymerizable monomer is determined as follows.
Content ratio (mol%) of monomer unit derived from the second polymerizable monomer =
{(S ₂ / n ₂ ) / ((S ₁ / n ₁ ) + (S ₂ / n ₂ ) + (S ₃ / n ₃ ))} × 100
Content ratio (mol%) of monomer unit derived from the third polymerizable monomer =
{(S ₃ / n ₃ ) / ((S ₁ / n ₁ ) + (S ₂ / n ₂ ) + (S ₃ / n ₃ ))} x 100
When a polymerizable monomer containing no hydrogen atom is used in the constituent elements other than the vinyl group in the vinyl polymer A, the measurement nucleus is set to ¹³ C by using ¹³ C-NMR, and a single pulse is used. The measurement is performed in the mode, and the calculation is performed in the same manner as in the case of ¹ H-NMR.
Further, when the toner is produced by the suspension polymerization method, the peaks of the release agent and other resins may overlap and independent peaks may not be observed. As a result, the content ratio of the monomer units derived from various polymerizable monomers in the vinyl polymer A may not be calculated. In that case, the vinyl polymer A'can be produced by performing the same suspension polymerization without using a release agent or other resin, and the vinyl polymer A'can be regarded as the vinyl polymer A and analyzed. it can.

<SP value calculation method>
The SP value of the polymerizable monomer and the SP value of the monomer unit derived from the polymerizable monomer are determined as follows according to the calculation method proposed by Fedors.
-SP value of polymerizable monomer For each polymerizable monomer or mold release agent, Δei and Δvi were obtained from the table described in the following documents for atoms or atomic groups in the molecular structure, and the following formula was obtained. The SP value is calculated from the above.
R. F. Fedors: “A Method for Estimating Both the Solubility Parameters and Molar Volumes of Liquids”, polym. Eng. Sci. , Vol. 14 (2), 147-154 (1974)
SP value (J / cm ³ ) ^0.5 = (4.184 × ΣΔei / ΣΔvi) ^0.5
Δei: Evaporation energy (cal / mol) of each atom or atomic group
Δvi: Molar volume of each atom or group of atoms (cm ³ / mol)

-SP value of the monomer unit derived from the polymerizable monomer Note that SP ₁₁ and SP ₂₁ are for atoms or atomic groups having a molecular structure in which the double bond of the polymerizable monomer is cleaved by polymerization. , Calculate by the same calculation method as above.
SP ₁₁ : SP value of the monomer unit derived from the first polymerizable monomer SP ₂₁ : SP value of the monomer unit derived from the second polymerizable monomer

SP ₃₁ (SP value of the monomer unit derived from the third polymerizable monomer) is determined as follows.
First, the evaporation energy (Δei) and molar volume (Δvi) of the monomer units derived from the polymerizable monomer constituting the vinyl polymer A are determined for each monomer unit, and the molar ratio of each monomer unit in the vinyl polymer A (2). The product with j) is calculated respectively. Then, the SP ₃₁ value is calculated by the following formula.
SP ₃₁ = {4.184 × (Σj × ΣΔei) / (Σj × ΣΔvi)} ^0.5

<Measurement of vinyl polymer A weight average molecular weight by GPC>
The molecular weight (Mw) of the THF-soluble component of the vinyl polymer A is measured by gel permeation chromatography (GPC) as follows.
First, the toner is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshori Disc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. This sample solution is used for measurement under the following conditions.

Equipment: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation)
Column: 7 stations of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: tetrahydrofuran (THF)
Flow velocity: 1.0 mL / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL

In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using the following standard polystyrene resin is used.
-Standard polystyrene resin: Product name "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2 , F-1, A-5000, A-2500, A-1000, A-500 "manufactured by Toso Co., Ltd.

<Measurement of melting point (Tp) of vinyl polymer A>
The melting point (Tp) is measured according to ASTM D3418-82 using a differential scanning calorimetry apparatus "Q2000" (manufactured by TA Instruments).
The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value.

Specifically, 3 mg of a sample is precisely weighed, placed in an aluminum pan, and measured under the following conditions using an empty aluminum pan as a reference.
Heating rate: 10 ° C / min
Measurement start temperature: 30 ° C
Measurement end temperature: 180 ° C

In the measurement, the temperature is first raised to 180 ° C. and held for 10 minutes, then lowered to 30 ° C. at a temperature lowering rate of 10 ° C./min, and then the temperature is raised again. In this second temperature raising process, the temperature at which the temperature-endothermic amount curve shows the maximum endothermic peak (melting peak) in the temperature range of 60 ° C. to 90 ° C. is defined as the melting point (Tp) of the vinyl polymer A.

<Method of measuring acid value of vinyl polymer A>
The acid value is the number of mg of potassium hydroxide required to neutralize acid components such as free fatty acids and resin acids contained in 1 g of a sample. The measuring method is as follows according to JIS-K0070-1992.

(1) Reagent Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume) and add ion-exchanged water to make 100 mL to obtain a phenolphthalein solution.
Dissolve 7 g of special grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide, leave it to stand for 3 days, and then filter it to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. As for the factor of the potassium hydroxide solution, take 25 mL of 0.1 mol / L hydrochloric acid in a triangular flask, add a few drops of the phenolphthalein solution, titrate with the potassium hydroxide solution, and neutralize the potassium hydroxide. Obtained from the amount of solution. As the 0.1 mol / L hydrochloric acid, those prepared according to JIS K 8001-1998 are used.

(2) Operation (A) Main test 2.0 g of the crushed sample is precisely weighed in a 200 mL Erlenmeyer flask, 100 mL of a mixed solution of toluene / ethanol (2: 1) is added, and the mixture is dissolved over 5 hours. Then, a few drops of the phenolphthalein solution are added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).

(3) Substitute the obtained result into the following formula to calculate the acid value.
A = [(CB) x f x 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (mL), C: addition amount of potassium hydroxide solution in this test (mL), f: potassium hydroxide Solution factor, S: mass (g) of sample.

<Measuring method of toner weight average particle size (D4)>
The weight average particle size (D4) of the toner is calculated as follows. As the measuring device, a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter Co., Ltd.) equipped with a 100 μm aperture tube by the pore electrical resistance method is used. The attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter Co., Ltd.) is used for setting the measurement conditions and analyzing the measurement data. The measurement is performed with 25,000 effective measurement channels.

As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.) can be used. ..
Before performing measurement and analysis, set the dedicated software as follows.

On the "Change standard measurement method (SOM)" screen of the dedicated software, set the total count number in the control mode to 50,000 particles, measure once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter (Beckman Coulter) The value obtained by using (manufactured by Co., Ltd.) is set. By pressing the "Measure threshold / noise level" button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check “Flash of aperture tube after measurement”.
On the "Pulse to particle size conversion setting" screen of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Put about 200 mL of the electrolytic aqueous solution in a 250 mL round bottom beaker made of glass dedicated to Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "flash of the aperture tube" function of the dedicated software.

(2) Put about 30 mL of the electrolytic aqueous solution in a 100 mL flat bottom beaker made of glass. Approximately 0.3 mL of a diluted solution prepared by diluting "Contaminone N" with ion-exchanged water 3 times by mass as a dispersant is added thereto.
-Contaminone N: A 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument with a pH of 7, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.

(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and an ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W is prepared. To do. 3.3 L of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 mL of the contaminanton N is added into the water tank.

(4) The beaker of (2) above is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) With the electrolytic aqueous solution in the beaker of (4) above being irradiated with ultrasonic waves, 10 mg of toner particles are added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. to 40 ° C.

(6) Using a pipette, the electrolytic aqueous solution of (5) above, in which toner particles are dispersed, is dropped onto the round-bottom beaker of (1) above installed in the sample stand, and the measured concentration is adjusted to about 5%. To do. Then, the measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) is calculated. The "average diameter" of the "analysis / volume statistical value (arithmetic mean)" screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

<Measuring method of average circularity of toner>
The average circularity of the toner is measured by the flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions at the time of calibration work.
The measurement principle of the flow-type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) is to image the flowing particles as a still image and perform image analysis. The sample added to the sample chamber is sent to the flat sheath flow cell by the sample suction syringe. The sample sent to the flat sheath flow cell is sandwiched between the sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Moreover, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, and the captured image is image-processed at an image processing resolution of 512 pixels × 512 pixels (0.37 μm × 0.37 μm per pixel), the contour of each particle image is extracted, and the particles are captured. The projected area S of the image, the peripheral length L, and the like are measured.

Next, the equivalent circle diameter and circularity are obtained using the area S and the peripheral length L. The circle equivalent diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity C is the value obtained by dividing the circumference length of the circle obtained from the circle equivalent diameter by the circumference length of the particle projection image. It is defined as and calculated by the following formula.
Circularity C = 2 × (π × S) ^1/2 / L
When the particle image is circular, the circularity is 1.000, and the greater the degree of unevenness on the outer periphery of the particle image, the smaller the circularity. After calculating the circularity of each particle, the range of circularity of 0.200 or more and 1.000 or less is divided into 800, the arithmetic mean value of the obtained circularity is calculated, and the value is defined as the average circularity.

The specific measurement method is as follows.
First, about 20 mL of ion-exchanged water from which impure solids and the like have been removed in advance is placed in a glass container. About 0.2 mL of a diluted solution obtained by diluting the contaminantin N with ion-exchanged water about 3 times by mass as a dispersant is added thereto.

Further, about 0.02 g of the measurement sample is added, and the dispersion treatment is performed for 2 minutes using an ultrasonic disperser to prepare a dispersion liquid for measurement. At that time, the dispersion liquid is appropriately cooled so that the temperature becomes 10 ° C. to 40 ° C. As the ultrasonic disperser, a desktop ultrasonic cleaner disperser (“VS-150” (manufactured by Vervocrea Co., Ltd.)) having an oscillation frequency of 50 kHz and an electrical output of 150 W is used, and a predetermined amount is contained in the water tank. The ion-exchanged water of No. 1 is put in, and about 2 mL of the contaminone N is added into this water tank.

For the measurement, the flow type particle image analyzer equipped with a standard objective lens (10 times) is used, and a particle sheath "PSE-900A" (manufactured by Sysmex Corporation) is used as the sheath liquid. The dispersion prepared according to the procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the total count mode in the HPF measurement mode.
Then, the binarization threshold value at the time of particle analysis is set to 85%, the diameter of the analyzed particle is set to 1.98 μm to 39.96 μm, and the average circularity of the toner is obtained.

In the measurement, automatic focus adjustment is performed using standard latex particles before the start of measurement. After that, it is preferable to perform focus adjustment every 2 hours from the start of measurement.
Examples of standard latex particles include the following. "RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" manufactured by Duke Scientific, diluted with ion-exchanged water.

Hereinafter, the present invention will be specifically described with reference to Examples, but these are not intended to limit the present invention in any way. In the following formulations, parts are based on mass unless otherwise specified.

<Production example of vinyl polymer A1>
-Solvent: 100.0 parts of toluene-100.0 parts of monomer composition (The monomer composition shall be a mixture of behenyl acrylate, methacrylonitrile, and styrene in the following proportions).
Behenyl acrylate (first polymerizable monomer) 60.0 parts (26.2 mol%)
-Methacrylonitrile (second polymerizable monomer) 30.0 parts (57.9 mol%)
-Styrene (third polymerizable monomer) 10.0 parts (15.9 mol%)
-Polymerization initiator t-butyl peroxypivalate (manufactured by NOF CORPORATION: perbutyl PV) 0.5 part

The above materials were put into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen introduction tube under a nitrogen atmosphere. The inside of the reaction vessel was stirred at 200 rpm and heated to 70 ° C. for 12 hours to carry out a polymerization reaction to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Subsequently, after the temperature of the solution was lowered to 25 ° C., the solution was poured into 1000.0 parts of methanol with stirring to precipitate the insoluble methanol. The obtained methanol-insoluble matter was filtered off, washed with methanol, and dried under reduced pressure at 40 ° C. for 24 hours to obtain a vinyl polymer A1. The weight average molecular weight of the vinyl polymer A1 was 64,600, the melting point was 56 ° C., and the acid value was 0.0 mgKOH / g.
When the vinyl polymer A1 was analyzed by NMR, the monomer unit derived from behenyl acrylate was 26.2 mol%, the monomer unit derived from methacrylnitrile was 57.9 mol%, and the monomer unit derived from styrene was 15.9 mol%. % Was included. The SP values of the polymerizable monomer and the monomer unit derived from the polymerizable monomer were calculated by the above method. Tables 2 and 3 show the physical property values including the calculated SP value.

<Production example of vinyl polymers A2 to A13>
In the production example of the vinyl polymer A1, the reaction was carried out in the same manner except that the respective polymerizable monomers and the number of copies were changed as shown in Table 1, to obtain vinyl polymers A2 to A13. Tables 2 to 4 show the physical property values including the calculated SP values for the vinyl polymers A2 to A13.

The abbreviations in Tables 1 to 4 are as follows.
BEA: Behenyl acrylate (alkyl group carbon number: 22)
SA: Stearyl acrylate (alkyl group carbon number: 18)
MYA: Myricyl acrylate (alkyl group carbon number: 30)
HA: Hexadecyl acrylate (alkyl group carbon number: 16)
MN: Methacrylonitrile (CH ₂ = C (CH ₃ ) CN)
AA: Acrylamide (CH ₂ = CH (C = O) NH ₂ )
VA: Vinyl acetate (CH ₂ = CHO (C = O) CH ₃ )
MA: Methyl acrylate (CH ₂ = CH (C = O) OCH ₃ )
St: Styrene (C ₆ H ₅ CH = CH ₂ )
MM: Methyl methacrylate (CH ₂ = C (CH ₃ ) (C = O) OCH ₃ )

<Production example of low molecular weight reduced silicone oil 1>
100 parts of dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: KF96-500CS, kinematic viscosity at 25 ° C. 500 mm ² / S, Mw 20,000)
The above was placed in a 500 mL eggplant flask, and the low molecular weight component was reduced using a rotary evaporator R-100 (manufactured by BUCHI). The mixture was heated at 180 ° C. using an oil bath, depressurized to 10 torr while rotating at 100 rpm, and treated for 3 hours to obtain a low molecular weight reduced silicone oil 1. The weight average molecular weight was 20,000, and the component having a weight average molecular weight of 500 or less was 0.03% by mass of the low molecular weight reduced silicone oil 1.

<Production example of low molecular weight reduced silicone oil 2 to low molecular weight reduced silicone oil 6>
In the production example of the low molecular weight reduced silicone oil 1, the reaction was carried out in the same manner except that each silicone oil was changed as shown in Table 5, to obtain low molecular weight reduced silicone oil 2 to low molecular weight reduced silicone oil 6. Table 5 shows the physical properties of the low molecular weight reduced silicone oil 2 to the low molecular weight reduced silicone oil 6.

<Manufacturing example of toner 1>
・ Vinyl polymer A1 100 parts ・ Low molecular weight reduction silicone oil 14 parts ・ Carbon black 10 parts Rotation speed 1,500 rpm, rotation speed, using Henschel mixer (FM-75 type, manufactured by Mitsui Mine Co., Ltd.) After mixing for 5 minutes, the mixture was kneaded using a biaxial kneader (PCM-30 type, manufactured by Ikekai Co., Ltd.) set at a temperature of 130 ° C. The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely crushed product. The obtained pyroclastic material was finely pulverized using a mechanical crusher (T-250, manufactured by Turbo Industries, Ltd.). Further, using Faculti (F-300, manufactured by Hosokawa Micron Co., Ltd.), classification was performed to obtain toner particles 1. The operating conditions were a classification rotor rotation speed of 11,000 rpm and a distributed rotor rotation speed of 7,200 rpm.

Using the obtained toner particles 1, heat treatment was performed by the surface treatment apparatus shown in FIG. 1 to obtain toner particles 1 which had undergone the heat treatment step. The operating conditions are feed amount = 5 kg / hr, hot air temperature C = 160 ° C., hot air flow rate = 6 m ³ / min. , Cold air temperature E = -5 ° C, cold air flow rate = 4 m ³ / min. , Blower air volume = 20m ³ / min. , Injection air flow rate = 1 m ³ / min. And said.
1 100 parts of toner particles that have undergone the heat treatment process 400 parts of ethanol

Next, after mixing the above, the mixture was dispersed for 5 minutes using an ultrasonic cleaner to obtain an ethanol dispersion of the toner particles 1 that had undergone heat treatment. Subsequently, the ethanol dispersion of the heat-treated toner particles 1 was filtered and solid-liquid separated, and then dried using a vacuum dryer to obtain the toner particles 1 that had undergone the heat treatment step and the organic solvent contact step.
-Toner particles 1 100 parts that have undergone a heat treatment process and an organic solvent contact process-Silica fine particles A: Fumeed silica surface-treated with hexamethyldisilazane (median diameter (D50) based on the number is 120 nm) 8 parts

The above materials were mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Kakoki Co., Ltd.) at a rotation speed of 1,900 rpm and a rotation time of 10 min to obtain toner 1. The weight average particle size (D4) of the toner 1 was 6.1 μm, the average circularity was 0.975, and the A / B measured using ESCA was 1.5. Table 6 shows the physical properties of the toner 1.

<Manufacturing example of toner 2 to toner 20>
In the production example of the toner 1, the same operation was performed except that the vinyl polymer A, the low molecular weight reduced silicone oil, the heat treatment step, and the organic solvent contact step were changed as shown in Table 6, and the toner 2 to the toner 20 were obtained. Obtained. Table 6 shows the physical properties of the toners 2 to 20.

<Manufacturing example of magnetic carrier 1>
-Magnetite 1 with an average particle size of 0.30 μm and (magnetization strength of 65 Am ² / kg under a magnetic field of 1000 / 4π (kA / m))
-Magnetite ^{2 with a} number average particle size of 0.50 μm and (magnetization strength of 65 Am ² / kg under a magnetic field of 1000 / 4π (kA / m))

4.0 parts of a silane compound (3- (2-aminoethylaminopropyl) trimethoxysilane) was added to 100 parts of each of the above materials, and the mixture was mixed and stirred at 100 ° C. or higher in a container at high speed, and each fine particle was mixed. Was processed.
・ Phenol: 10% by mass
・ Formaldehyde solution: 6% by mass
(Formaldehyde 40% by mass, methanol 10% by mass, water 50% by mass)
-Magnetite treated with the above silane compound: 58% by mass
-Magnetite treated with the above silane compound: 26% by mass

100 parts of the above material, 5 parts of a 28 mass% aqueous ammonia solution, and 20 parts of water are placed in a flask, and the temperature is raised to 85 ° C. in 30 minutes while stirring and mixing, and the mixture is held for 3 hours to carry out a polymerization reaction. The phenolic resin was cured.
Then, the cured phenol resin was cooled to 30 ° C., water was further added, the supernatant was removed, the precipitate was washed with water, and then air-dried. Next, this was dried under reduced pressure (5 mmHg or less) at a temperature of 60 ° C. to obtain a magnetic material-dispersed spherical magnetic carrier 1. The volume-based 50% particle size (D50) was 34.21 μm.

<Production example of two-component developer 1>
92.0 parts of the magnetic carrier 1 and 8.0 parts of the toner 1 were mixed by a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain a two-component developer 1.

<Production example of two-component developer 2 to two-component developer 20>
In the production example of the two-component developer 1, the same operation was performed except for the changes as shown in Table 7, to obtain the two-component developer 2 to the two-component developer 20.

<Example 1>
Evaluation was performed using the above two-component developer 1.
As an image forming apparatus, a digital commercial printing printer imageRUNNER ADVANCE C5560 modified machine manufactured by Canon Inc. (hereinafter, also referred to as an "evaluation machine") was used, and the two-component developer 1 was put into the developer at the cyan position. The modification points of the device were changed so that the fixing temperature, process speed, DC voltage V _DC of the developer carrier, charging voltage V _D of the electrostatic latent image carrier, and laser power could be set freely. Image output evaluation outputs FFh image (solid image) of a desired image ratio, V _DC as the toner amount on the FFh image in paper is _desired, by adjusting the _V D and laser _power, The evaluation described later was performed.
FFh is a value obtained by displaying 256 gradations in hexadecimal, 00h is the first gradation of 256 gradations (white background portion), and FFh is the 256th gradation of 256 gradations (solid portion). ..
Evaluation is performed based on the following evaluation methods, and the results are shown in Table 8.

[Low temperature fixability]
Paper: GFC-081 (81.0 g / m ² ) (sold by Canon Marketing Japan Inc.)
Amount of toner on paper: 0.50 mg / cm ²
(Adjusted by the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power)
Evaluation image: An image of 2 cm x 5 cm is placed in the center of the above A4 paper Test environment: Low temperature and low humidity environment: Temperature 15 ° C / Relative humidity 10% (hereinafter "L / L")
Fixing temperature: 150 ° C
Process speed: 377 mm / sec

The above evaluation image was output and the low temperature fixability was evaluated. The value of the image density reduction rate was used as an evaluation index of low temperature fixability.
The image density reduction rate is determined by first measuring the image density at the center using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). Next, a load of 4.9 kPa (50 g / cm ² ) is applied to the portion where the image density is measured, and the fixed image is rubbed (5 reciprocations) with Sylbon paper, and the image density is measured again.
Then, the rate of decrease in image density before and after friction was calculated using the following formula. The rate of decrease in the obtained image density was evaluated according to the following evaluation criteria. If the evaluation was A to D, it was judged that the effect of the present invention was obtained.
Image density reduction rate = (image density before friction-image density after friction) / image density before friction x 100

(Evaluation criteria)
A: Image density reduction rate less than 3.0% B: Image density reduction rate 3.0% or more and less than 5.0% C: Image density reduction rate 5.0% or more and less than 7.0% D: Image density reduction rate of 7.0% or more, less than 9.0% E: Image density reduction rate of 9.0% or more

[Transferability]
Paper: CS-680 (68.0 g / m ² ) (sold by Canon Marketing Japan Inc.)
Amount of toner on paper: 0.35 mg / cm ²
(Adjusted by the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power)
Evaluation image: An image of 2 cm x 5 cm is placed in the center of the above A4 paper Test environment: High temperature and high humidity environment (temperature 30 ° C / relative humidity 80% (hereinafter "H / H"))

As a stabilization and durability evaluation of the evaluation machine, 10,000 sheets were output on A4 paper using a band chart with an image ratio of 0.1%. Then, the evaluation image was formed on the electrostatic latent image carrier, and the evaluation machine was stopped after being transferred to the intermediate transfer body and before being transferred to the recording paper. The intermediate transfer body of the stopped evaluation machine was taken out, a transparent adhesive tape was attached to the transferred image, toner was collected, and the adhesive tape was attached to a recording paper. The density of the image was measured with an optical densitometer, and the density of the portion where only the adhesive tape was attached to the recording paper was subtracted to obtain the transfer density A. Further, the electrostatic latent image carrier of the evaluation machine was taken out, and the transfer residual concentration B was determined for the transfer residual toner by the same method. A transparent and weakly adhesive Super Stick (manufactured by Lintec Corporation) was used as the adhesive tape, and an X-Rite color reflection densitometer (manufactured by X-Rite Co., Ltd.) was used as the optical densitometer. Then, the transfer efficiency was calculated using the following formula. The obtained transfer efficiency was evaluated according to the following evaluation criteria. If the evaluation was A to D, it was judged that the effect of the present invention was obtained.
Transfer efficiency = {Transfer concentration A / (Transfer concentration A + Residual transfer concentration B)} x 100

(Evaluation criteria)
A: Transfer efficiency 98.0% or more B: Transfer efficiency 95.0% or more, less than 98.0% C: Transfer efficiency 92.0% or more, less than 95.0% D: Transfer efficiency 87.0% or more, 92 Less than 0.0% E: Transfer efficiency less than 87.0%

[Image stability]
Paper: GFC-081 (81.0 g / m ² ) (Canon Marketing Japan Inc.)
Amount of toner on paper: 0.35 mg / cm ²
(Adjusted by the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power)
Evaluation image: An image of 2 cm x 5 cm is placed in the center of the above A4 paper. Fixing test environment: Room temperature and humidity environment: Temperature 23 ° C./Relative humidity 50% (hereinafter "N / N")
To stabilize the evaluation machine, output was performed on 100 sheets of A4 paper using a band chart with an image ratio of 1%. Then, the evaluation image was output, the density of the image was measured with an optical densitometer, and the image density A was determined.
Next, using a band chart with an image ratio of 80%, output was performed on 100 sheets of A4 paper. Then, the evaluation image was output, the density of the image was measured with an optical densitometer, and the image density B was obtained.
An X-Rite color reflection densitometer (manufactured by X-Rite) was used as the optical densitometer. Then, the difference in concentration fluctuation was calculated using the following formula. The obtained concentration fluctuation difference was evaluated according to the following evaluation criteria. If the evaluation was A to D, it was judged that the effect of the present invention was obtained.
Density fluctuation difference = | Image density A-Image density B |

(Evaluation criteria)
A: Concentration fluctuation difference less than 0.02 B: Concentration fluctuation difference 0.02% or more and less than 0.04 C: Concentration fluctuation difference 0.04% or more and less than 0.06% D: Concentration fluctuation difference 0.06% or more , Less than 0.10% E: Concentration fluctuation difference 0.10% or more

<Examples 2 to 15 and Comparative Examples 1 to 5>
Evaluation was carried out in the same manner as in Example 1 except that the two-component developer 2 to the two-component developer 20 were used. The evaluation results are shown in Table 8.

1. 1. Raw material quantitative supply means 2. Compressed gas flow rate adjusting means 3. Introduction pipe 4. Protruding member 5. Supply pipe 6. Processing room 7. Hot air supply means 8. Cold air supply means 9. Regulatory means 10. Recovery means 11. Hot air supply means outlet 12. Distributor 13. Swivel member 14. Powder particle supply port

Claims (9)

A toner having toner particles containing silicone oil.
Vinyl polymer A is present in a region within 300 nm from the surface of the toner particles toward the center thereof.
The vinyl polymer A is derived from a first monomer unit derived from the first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer. Has two monomer units,
The first polymerizable monomer is a (meth) acrylic acid ester having a linear or branched alkyl group having 18 to 36 carbon atoms.
The second polymerizable monomer has an ester group or a nitrile group and has an ester group or a nitrile group.
When the SP value of the first monomer unit is SP ₁₁ and the SP value of the second monomer unit is SP ₂₁ , the SP ₁₁ and the SP ₂₁ are expressed by the following formulas (1) and (2). ) And meet
SP ₁₁ ≤ 18.40 (J / cm ³ ) ^0.5 ... (1)
21.00 (J / cm ³ ) ^0.5 ≤ SP ₂₁ ... (2)
The content ratio of the first monomer unit in the vinyl polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all the monomer units in the vinyl polymer A.
The content ratio of the second monomer unit in the vinyl polymer A is 20.0 mol% to 95.0 mol% based on the total number of moles of all the monomer units in the vinyl polymer A.
Let A be the peak area of the silicon atom whose binding energy peak position is 102 ev to 103 ev, and the carbon atom whose binding energy peak position is 285 ev to 288 ev, which is measured by using the electron spectrochemical analysis method (ESCA) of the toner. A toner characterized in that A and B satisfy the following formula (3), where B is the peak area of.
1.0 ≤ A / B ≤ 3.0 ... (3) The content ratio of the second monomer unit in the vinyl polymer A is 40.0 mol% to 95.0 mol% based on the total number of moles of all the monomer units in the vinyl polymer A. Item 1. The toner according to Item 1. A toner having toner particles containing silicone oil.
Vinyl polymer A is present in a region within 300 nm from the surface of the toner particles toward the center thereof.
The vinyl polymer A is a polymer of a composition containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer.
The first polymerizable monomer is a (meth) acrylic acid ester having a linear or branched alkyl group having 18 to 36 carbon atoms.
The second polymerizable monomer has an ester group or a nitrile group and has an ester group or a nitrile group.
When the SP value of the first polymerizable monomer is SP ₁₂ and the SP value of the second polymerizable monomer is SP ₂₂ , the SP ₁₂ and the SP ₂₂ are represented by the following formula (4). ) And the following formula (5),
SP ₁₂ ≤ 17.72 (J / cm ³ ) ^0.5 ... (4)
18.30 (J / cm ³ ) ^0.5 ≤ SP ₂₂ ... (5)
The content ratio of the first polymerizable monomer in the composition is 5.0 mol% to 60.0 mol% based on the total number of moles of the total polymerizable monomers in the composition. ,
The content ratio of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of the total polymerizable monomer in the composition. ,
Let A be the peak area of the silicon atom whose binding energy peak position is 102 ev to 103 ev, and the carbon atom whose binding energy peak position is 285 ev to 288 ev, which is measured by using the electron spectrochemical analysis method (ESCA) of the toner. A toner characterized in that A and B satisfy the following formula (3), where B is the peak area of.
1.0 ≤ A / B ≤ 3.0 ... (3) The content ratio of the second polymerizable monomer in the composition is 40.0 mol% to 95.0 mol% based on the total number of moles of the total polymerizable monomer in the composition. The toner according to claim 3. A is the peak area of a silicon atom whose binding energy peak position measured using ESCA of the toner particles is 102 ev to 103 ev.
The toner according to any one of claims 1 to 4, wherein B is the peak area of a carbon atom whose binding energy peak position measured by using the ESCA of the toner particles is 285 ev to 288 ev. The toner according to any one of claims 1 to 5, wherein the silicone oil contains dimethyl silicone oil. The invention according to any one of claims 1 to 6, wherein the content of the component having a weight average molecular weight of 500 or less is 0.05% by mass or less of the silicone oil in the molecular weight distribution measured by GPC of the silicone oil. toner. The toner according to any one of claims 1 to 7, wherein the second polymerizable monomer is at least one selected from the group consisting of the polymerizable monomer represented by the following formula (A).

(R ¹ represents an alkyl group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom or a methyl group independently of each other.) A process of melt-kneading a toner composition containing silicone oil to obtain a melt-kneaded product,
A step of pulverizing and classifying the melt-kneaded product to obtain toner matrix particles, and
The method for producing a toner according to claim 1 or 3, wherein the toner matrix particles are heat-treated and then produced.

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