JP2022069025A - Toner and method for producing the same - Google Patents

Abstract

To provide a toner that has resists cracking during long-term use without sacrificing low temperature fixability.SOLUTION: A toner contains a toner particle, where the toner particle comprises a binder resin, a resin A and a silicon-containing particle, the resin A has a substituted or unsubstituted silyl group in a molecule, and a substituent of the substituted silyl group is at least one selected from the group consisting of an alkyl group having one or more carbon atoms, an alkoxy group having one or more carbon atoms, a hydroxy group, a halogen atom, and an aryl group having 6 or more carbon atoms. The silicon-containing particle is at least one selected from silica or organic silicon polymers.SELECTED DRAWING: None

Description

The present invention relates to a toner for developing an electrostatic latent image formed by a method such as an electrophotographic method, an electrostatic recording method, or a toner jet recording method, and a method for producing the same.

In recent years, energy saving has been considered as a major technical issue in dry electrostatic copying electrographs used in copiers, printers, fax machines, etc., and a significant reduction in the amount of heat required for image fixing devices is desired. There is. Therefore, in toner, there is an increasing need for so-called "low temperature fixing property", which enables image fixing with less energy.
As a general method for improving the low temperature fixability of the toner, a method of lowering the glass transition temperature (Tg) of the binder resin or a method of reducing the molecular weight of the binder resin for the purpose of softening the binder resin used is used. There is a way to do it. However, simply lowering the Tg of the binder resin or reducing the molecular weight causes a decrease in the storage stability of the toner and an offset to the fixing member due to insufficient releasability at the time of fixing.
In order to increase the toner strength while maintaining the glass transition temperature (Tg), it is common practice to increase the molecular weight of the binder resin or to give the binder resin a crosslinked structure. However, if the toner strength is increased above a certain level by this method alone, the low temperature fixability is inevitably impaired.
For example, Patent Document 1 discloses a method of increasing the toner strength by adding silica in the form of a pearl necklace.

Japanese Unexamined Patent Publication No. 2009-42386

According to Patent Document 1, the toner strength can be increased as compared with general silica. However, when a toner having good low-temperature fixability is used, it is easily cracked at the interface between the binder resin and silica, and there is a problem in that the toner is contaminated due to cracking and chipping in long-term use.
In view of these problems, the present invention provides a toner that is excellent in suppressing cracking and chipping during long-term use without impairing low-temperature fixability.

The present invention is a toner containing toner particles, wherein the toner particles contain particles containing a binder resin, resin A, and silicon.
The resin A has a substituted or unsubstituted silyl group in the molecule, and the substituent of the substituted silyl group is an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, a hydroxy group, and the like. At least one selected from a halogen atom and an aryl group having 6 or more carbon atoms.
The silicon-containing particles relate to at least one selected from silica or organosilicon polymers.
Further, the present invention is a method for manufacturing a toner having the above configuration.
The resin A, the particles containing the silicon, and the polymerizable monomer composition containing the polymerizable monomer are dispersed in an aqueous medium, and the particles of the polymerizable monomer composition are dispersed in the aqueous medium. The present invention relates to a method for producing a toner, which comprises a step of forming the polymerizable monomer and a step of polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition.
Further, the present invention is a method for manufacturing a toner having the above-mentioned constitution.
The present invention relates to a method for producing a toner, which comprises a step of melt-kneading a mixture containing a binder resin, the resin A, and particles containing silicon to obtain a melt-kneaded product, and a step of crushing the melt-kneaded product to obtain a pulverized product. ..

As described above, according to the present invention, it is possible to provide a toner excellent in suppressing cracking and chipping in long-term use without impairing the low temperature fixability.

The toner of the present invention will be specifically described below, but the present invention is not limited thereto.

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.

The toner of the present invention is a toner having toner particles containing particles containing a binder resin, resin A, and silicon, and the resin A has a substituted or unsubstituted silyl group in the molecule. The substituent of the substituted silyl group is at least one selected from an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, a hydroxy group, a halogen atom, or an aryl group having 6 or more carbon atoms. The silicon-containing particles are characterized by being at least one selected from silica or an organic silicon polymer.

The present inventors have found that by adopting a toner having the above-mentioned structure, it is excellent in suppressing cracking and chipping in long-term use without impairing low-temperature fixability.

The reason for this is inferred as follows.

When a toner having good low-temperature fixability is rubbed by a roller or a developing blade during image formation, the toner particles are soft and easily crushed. Therefore, it is necessary to increase the strength of the toner in order to withstand the rubbing. It is generally known that the toner particles are hardened by adding silicon-containing particles such as silica (filler effect). On the other hand, silicon-containing particles such as silica have poor dispersibility in toner particles and need to be added in a large amount. Even if a large amount of silicon-containing particles are added to increase the strength of the toner, the interface between the silicon-containing particles and the binder resin is fragile and brittle, so that there is a problem of cracking and chipping in long-term use. Further, when a large amount of silicon-containing particles are added, there is a problem that the low-temperature fixability is impaired.

On the other hand, the toner of the present invention has a substituted or unsubstituted silyl group in the molecule of the resin A. This improves the dispersibility of silicon-containing particles such as silica in the toner particles. Further, it is presumed that the adhesion between the binding resin and the silicon-containing particles is improved through this resin A, and the effect of suppressing cracking and chipping at the interface between the silicon-containing particles and the binding resin is exhibited. ing. It is believed that this has a good effect on suppressing cracking and chipping of the toner in long-term use without impairing the low-temperature fixability.

Hereinafter, preferable constituent requirements of the present invention will be described.

First, the binder resin used in the present invention will be described.

The binder resin used for the toner of the present invention is not particularly limited, and conventionally known ones can be used. From the viewpoint of toner development characteristics and durability, the binder resin contains at least one unit (hereinafter referred to as a styrene acrylic copolymer moiety) selected from the group consisting of a styrene unit, an acrylic unit, and a methacrylic unit. It is preferable that the resin is a resin containing a polyester moiety or a resin containing a polyester moiety.

As long as it has a styrene-acrylic copolymer moiety, it may consist of only a styrene-acrylic copolymer, or a block copolymer or graft copolymer of a styrene-acrylic copolymer and another polymer. It may be a coalescence or a mixture thereof.

Examples of the styrene-based monomer constituting the styrene unit include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, divinylbenzene and the like. Can be mentioned. The styrene-based monomer can be used alone, but it can also be used in combination of two or more selected from these.

Examples of the acrylic monomer constituting the acrylic unit include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, and n. -Acrylic acid alkyl esters such as hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate; diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1, Acrylic acid diesters such as 6-hexanediol diacrylate; Acrylic acid and the like can be mentioned.

Examples of the methacrylic monomer constituting the methacrylic unit include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, and n. -Methacrylic acid alkyl esters such as hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate; methacrylic acid and the like.

The acrylic monomer and the methacrylic monomer can be used alone, but two or more selected from these can be used in combination.

The resin having the styrene-acrylic copolymer moiety preferably contains a styrene-acrylic acid alkyl ester copolymer or a styrene-methacrylic acid alkyl ester copolymer.

The proportion of the styrene-based monomer among the monomers forming the styrene-acrylic copolymer is preferably 45% by mass or more and 80% by mass or less. The ratio of the acrylic monomer (preferably acrylic acid alkyl ester and methacrylic acid alkyl ester) is preferably 20% by mass or more and 50% by mass or less.

As the resin containing the polyester moiety, a resin obtained by polycondensing the carboxylic acid component and the alcohol component listed below can be used. Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid. Examples of the alcohol component include bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.

Further, the polyester may be a polyester containing a urea group. As polyester, it is preferable not to cap the carboxyl group such as the end.

The binder resin may contain a cross-linking agent.

As the cross-linking agent, a compound having two or more polymerizable double bonds is mainly used.

For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, and 1,6-hexanediol diacrylate. Examples thereof include a carboxylic acid ester having two; a divinyl compound such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and a compound having three or more vinyl groups;

These may be used alone or as a mixture of two or more. The amount of the cross-linking agent added is preferably 0.001 part by mass or more and 15,000 parts by mass or less with respect to 100 parts by mass of the binder resin.

The resin A of the present invention will be described in detail below.

The resin A of the present invention is preferably a resin having a structure represented by the following formula (1).

（式（１）中、Ｐ¹は高分子部位を表し、Ｌ¹は単結合または二価の連結基を表し、Ｒ¹～Ｒ³はそれぞれ独立して水素原子、ハロゲン原子、アルキル基、アルコキシ基、アリール基またはヒドロキシ基を表し、ｍは正の整数を表し、ｍが２以上である場合の、複数のＬ¹、複数のＲ¹、複数のＲ²および複数のＲ³は、それぞれ同一であっても、異なっていてもよい。）

(In the formula (1), P ¹ represents a polymer moiety, L ¹ represents a single bond or a divalent linking group, and R ¹ to R ³ independently represent a hydrogen atom, a halogen atom, an alkyl group, and an alkoxy. A group, an aryl group or a hydroxy group, m represents a positive integer, and when m is 2 or more, a plurality of L ¹ , a plurality of R ¹ , a plurality of R ² and a plurality of R ³ are the same, respectively. However, they may be different.)

In the resin represented by the formula (1), a silicon atom (Si) is present in the side chain or the end of the resin. It is believed that this produces the effect of efficiently allowing the silicon-containing particles to exist in the vicinity of the resin A. Through this resin A, the adhesion between the binder resin and the particles containing silicon is improved, and cracking and chipping at the particle interface is suppressed. As a result, it is considered that a good effect is exhibited in suppressing cracking and chipping of toner in long-term use.

The content of the resin A in the toner particles is preferably 0.1% by mass or more and 10.0% by mass or less. Within the above range, the low temperature fixability is not impaired, and a good effect is exhibited in suppressing cracking and chipping in long-term use.

The polymer moiety P ¹ in the formula (1) is not particularly limited, and examples thereof include a polyester moiety, a vinyl resin moiety, a polyurethane moiety, a polycarbonate moiety, a phenol resin moiety, and a polyolefin moiety. Among these, it is preferable that the structure of P ¹ contains a polyester moiety and a vinyl resin moiety, and it is more preferable that the structure of P ¹ contains a polyester moiety.

It is considered that when the structure of P ¹ contains a polyester moiety, the effect of improving the dispersibility of the silicon-containing particles in the toner particles is produced. Through this resin A, the adhesion between the binder resin and the particles containing silicon is improved, and cracking and chipping at the particle interface is suppressed. As a result, it is considered that a good effect is exhibited in suppressing cracking and chipping of the toner in long-term use.

An example in which the structure of P ¹ contains a polyester moiety will be described.

The polyester moiety is a condensate of a dialcohol and a dicarboxylic acid. The polyester moiety is, for example, a condensate of a unit of the following formula (12) and a unit (multiple selections are possible) selected from any of the following formulas (13) to (15), or the following formula ( Examples thereof include a condensed polymer represented by the unit of 16).

［式（１２）中、Ｒ⁹はアルキレン基、アルケニレン基、アリーレン基を表す。］

[In formula (12), R ⁹ represents an alkylene group, an alkenylene group, and an arylene group. ]

［式（１３）中、Ｒ¹⁰はアルキレン基、フェニレン基を表す。］

[In the formula (13), R ¹⁰ represents an alkylene group and a phenylene group. ]

［式（１４）中、Ｒ¹⁸はエチレン基又はプロピレン基を表す。ｘ、ｙはそれぞれ０以上の整数値であり、且つｘ＋ｙの平均値は２以上１０以下である。］

[In formula (14), R ¹⁸ represents an ethylene group or a propylene group. Each of x and y is an integer value of 0 or more, and the average value of x + y is 2 or more and 10 or less. ]

［式（１６）中、Ｒ¹¹はアルキレン基、アルケニレン基を表す。］

[In formula (16), R ¹¹ represents an alkylene group and an alkenylene group. ]

Examples of the alkylene group in R ⁹ in the formula (12) include the following. Methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, neopentylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, 1,3- Cyclopentylene, 1,3-cyclohexylene, 1,4-cyclohexylene group.

Examples of the alkenylene group in R ⁹ in the formula (12) include a vinylene group, a propenylene group, and a 2-butenylene group.

Examples of the arylene group in R ⁹ in the formula (12) include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 2,6-naphthylene group and a 2,7-naphthylene group. Examples include 4,4'-biphenylene groups.

R ⁹ in the formula (12) may be substituted with a substituent. In this case, examples of the substituent that may be substituted include a methyl group, a halogen atom, a carboxyl group, a trifluoromethyl group, and a combination thereof.

Examples of the alkylene group in R ¹⁰ in the formula (13) include the following. Methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, neopentylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, 1,3- Cyclopentylene, 1,3-cyclohexylene, 1,4-cyclohexylene group.

Examples of the phenylene group in R ¹⁰ in the formula (13) include a 1,4-phenylene group, a 1,3-phenylene group and a 1,2-phenylene group.

R ¹⁰ in the above formula (13) may be substituted with a substituent. In this case, examples of the substituent that may be substituted include a methyl group, an alkoxy group, a hydroxyl group, a halogen atom and a combination thereof.

Examples of the alkylene group in R ¹¹ in the formula (16) include the following. Methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, neopentylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, 1,4- Cyclohexylene group.

Examples of the alkenylene group in R ¹¹ in the formula (16) include the following. Vinylene group, propenylene group, butenylene group, butadienylene group, pentenylene group, hexenylene group, hexadienylene group, heptenylene group, octanylene group, decenylene group, octadecenylene group, eicosenylene group, triacenylene group. These alkenylene groups may have any linear, branched, or cyclic structure. Further, the position of the double bond may be any place, and it is sufficient that it has at least one or more double bonds.

R ¹¹ in the formula (16) may be substituted with a substituent. In this case, examples of the substituent that may be substituted include an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom and a combination thereof.

When the structure of P ¹ contains a vinyl resin moiety, it is preferably a resin containing a styrene acrylic copolymer moiety.

L ¹ in the formula (1) is not particularly limited, but preferably has a partial structure as represented by the following formulas (17) to (20), for example.

［式（１７）中のＲ⁵は、アルキレン基、アリーレン基、または－ＮＨ－基を含有するアルキレン基を表す。（＊）は前記式（１）中のＰ¹への結合部位を表し、（＊＊）は前記式（１）中のケイ素原子への結合部位を表す。］

[R ⁵ in the formula (17) represents an alkylene group containing an alkylene group, an arylene group, or an —NH— group. (*) Represents the binding site to P ¹ in the formula (1), and (**) represents the binding site to the silicon atom in the formula (1). ]

［式（１８）中のＲ⁶は、アルキレン基、アリーレン基を表す。（＊）は前記式（１）中のＰ¹への結合部位を表し、（＊＊）は前記式（１）中のケイ素原子への結合部位を表す。］

[R ⁶ in the formula (18) represents an alkylene group and an arylene group. (*) Represents the binding site to P ¹ in the formula (1), and (**) represents the binding site to the silicon atom in the formula (1). ]

［式（１９）及び（２０）中のＲ⁷及びＲ⁸は、各々独立して、アルキレン基、アリーレン基、オキシアルキレン基を表す。（＊）は前記式（１）中のＰ¹への結合部位を表し、（＊＊）は前記式（１）中のケイ素原子への結合部位を表す。］

[R ⁷ and R ⁸ in the formulas (19) and (20) independently represent an alkylene group, an arylene group, and an oxyalkylene group, respectively. (*) Represents the binding site to P ¹ in the formula (1), and (**) represents the binding site to the silicon atom in the formula (1). ]

Among these, since the structure of L ¹ has a structure containing an amide bond represented by the above formula (17), it has an excellent effect of suppressing cracking and chipping in long-term use without impairing low-temperature fixability. In addition to producing, it was confirmed that the tape peeling characteristics after toner fixing were improved. It is presumed that this is because the amide bond has a high affinity with the hydroxyl group of the cellulose constituting the paper fiber which is the fixing medium.

The partial structure represented by the formula (17) is a divalent linking group containing an amide bond. The partial structure is formed, for example, by reacting a carboxy group in a resin with an aminosilane compound.

The aminosilane compound is not particularly limited, but for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β. (Aminoethyl) γ-aminopropylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N -6- (Aminohexyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethylsilane, 3-aminopropylsilicon and the like can be mentioned.

The partial structure represented by the formula (18) is a divalent linking group containing a urethane bond. The partial structure is formed, for example, by reacting a hydroxy group in a resin with an isocyanate silane compound.

The isocyanate silane compound is not particularly limited, but for example, 3-isocyanate propyltrimethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropyldimethylmethoxysilane, 3-isocyanatepropyltriethoxysilane, 3 -Isocyanatepropylmethyldiethoxysilane, 3-isocyanatepropyldimethylethoxysilane and the like can be mentioned.

The partial structure represented by the formula (19) or (20) is a divalent linking group containing a bond grafted to an ester bond in the resin.

The linking group is not limited to the case where it is formed by a reaction, but when it is reacted, it is formed, for example, by an insertion reaction of an epoxysilane compound.

The insertion reaction of the epoxysilane compound is the following reaction. It includes a step of inserting an epoxy group of an epoxysilane compound into an ester bond contained in a main chain in a resin.

The insertion reaction referred to here is, for example, a reaction described as "insertion reaction of an epoxy compound into an ester bond in a polymer chain" in Synthetic Organic Chemistry, Vol. 49, No. 3, p. 218, 1991. say.

This reaction mechanism is expressed by a simple model formula below.

（Ｄ及びＥは樹脂の構成部を示し、Ｆはエポキシ化合物の構成部を示す。）

(D and E indicate the constituent parts of the resin, and F indicates the constituent parts of the epoxy compound.)

In the above model formula, since there are α cleavage and β cleavage in the ring opening of the epoxy group, two kinds of compounds can be formed. In both cases, the epoxy group is inserted into the ester bond in the resin, in other words, the epoxy compound. The constituent parts excluding the epoxy part are grafted on the resin.

The epoxysilane compound is not particularly limited, and is, for example, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl. Examples thereof include methyldiethoxysilane.

Further, it is preferable that at least one of R ¹ to R ³ in the formula (1) is an alkoxy group or a hydroxy group. Further, it is more preferable that R ¹ to R ³ in the formula (1) are independently alkoxy groups or hydroxy groups, respectively.

It is considered that these alkoxy groups or hydroxy groups contain a large amount of Si—O— bonds, and the adhesion between the resin A and the silicon-containing particles is further enhanced. Through this resin A, the adhesion between the binder resin and the particles containing silicon is improved, and cracking and chipping at the particle interface is suppressed. As a result, it shows a good effect in suppressing cracking and chipping of toner in long-term use.

In order to use one or more of R ¹ to R ³ in the formula (1) as a hydroxyl group, a resin in which one or more of R ¹ to R ³ is an alkoxy group is hydrolyzed to obtain an alkoxy group. It may be converted to a hydroxy group. The method of hydrolysis may be any method, and for example, there are the following methods.

A resin in which one or more of R ¹ to R ³ in the formula (1) is an alkoxy group is dissolved or suspended in an appropriate solvent (may be a polymerizable monomer), and the pH is adjusted using an acid or an alkali. To be acidic, mix and hydrolyze. Further, hydrolysis may occur during the production of toner particles.

Next, a suitable weight average molecular weight (Mw) of the resin A represented by the formula (1) will be described.

The weight average molecular weight (Mw) of the resin A represented by the formula (1) is preferably 3000 or more and 100,000 or less, and more preferably 5000 or more and 30,000 or less. Within the above range, the affinity between the polymer moiety (L ¹ ) in the formula (1) and the binder resin becomes sufficient, and a good effect is exhibited in suppressing cracking and chipping in long-term use.

The method for measuring the weight average molecular weight (Mw) of the resin A represented by the formula (1) will be described later.

Next, the silicon-containing particles in the present invention will be described.

The silicon-containing particles of the present invention are characterized in that they are at least one selected from the group consisting of silica or organosilicon polymers.

The silicon-containing particles are preferably 0.040% by mass or more and 0.800% by mass or less with respect to the toner particles. Within the above range, the low temperature fixability is not impaired, and a good effect is exhibited in suppressing cracking and chipping in long-term use.

The silicon-containing particles of the present invention are organosilicon polymers, and preferably have a structure represented by the following formula (3).
R-SiO _3/2 formula (3)
(In formula (3), R is an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms.)

When it is an organosilicon polymer and has the structure of the formula (3), the affinity with the resin A is high and the affinity with the binder resin is also high. As a result, the adhesion between the binder resin and the particles containing silicon is improved, and cracking and chipping at the particle interface is suppressed.

The organosilicon polymer having the structure of the formula (3) is preferably a polycondensation polymer of the organosilicon compound having the structure represented by the following formula (4).

（式（４）中、Ｒ²¹は、炭素数１以上４以下の炭化水素基を表し、Ｒ²²、Ｒ²³及びＲ²⁴は、それぞれ独立して、ハロゲン原子、ヒドロキシ基、アセトキシ基、又は、アルコキシ基を表す。）

(In the formula (4), R ²¹ represents a hydrocarbon group having 1 or more and 4 or less carbon atoms, and R ²² , R ²³ and R ²⁴ are independently halogen atoms, hydroxy groups, acetoxy groups, or Represents an alkoxy group.)

From the viewpoint of improving the affinity with the binder resin, R ²¹ is preferably a hydrocarbon group having 1 or more and 4 or less carbon atoms, and more preferably a methyl group.

R ²² , R ²³ and R ²⁴ are independently halogen atoms, hydroxy groups, acetoxy groups, or alkoxy groups (hereinafter, also referred to as reactive groups). These reactive groups are hydrolyzed, addition polymerized and polycondensed to form a crosslinked structure, and a toner having excellent stain resistance and development durability can be obtained. The hydrolyzability is mild at room temperature, and from the viewpoint of precipitation on the surface of the toner particles and coating property, an alkoxy group having 1 or more carbon atoms and 3 or less carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable. preferable. Further, the hydrolysis, addition polymerization and condensation polymerization of R ²² , R ²³ and R ²⁴ can be controlled by the reaction temperature, reaction time, reaction solvent and pH.

In order to obtain the organosilicon polymer used in the present invention, an organosilicon compound having three reactive groups (R ²² , R ²³ and R ²⁴ ) in one molecule other than R ²¹ in the above formula (4) is obtained. (Hereinafter, also referred to as trifunctional silane) may be used alone or in combination of two or more.

Examples of the above equation (4) include the following.

Methyltrimethoxysilane, Methyltriethoxysilane, Methyldiethoxymethoxysilane, Methylethoxydimethoxysilane, Methyltrichlorosilane, Methylmethoxydichlorosilane, Methylethoxydichlorosilane, Methyldimethoxychlorosilane, Methylmethoxyethoxychlorosilane, Methyldiethoxychlorosilane, Methyl Triacetoxysilane, Methyldiacetoxymethoxysilane, Methyldiacetoxyethoxysilane, Methylacetoxydimethoxysilane, Methylacetoxymethoxyethoxysilane, Methylacetoxydiethoxysilane, Methyltrihydroxysilane, Methylmethoxydihydroxysilane, Methylethoxydihydroxysilane, Methyldimethoxy Trifunctional methylsilanes such as hydroxysilanes, methylethoxymethoxyhydroxysilanes, and methyldiethoxyhydroxysilanes.

Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltri Trifunctional silanes such as methoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, and butyltrihydroxysilane.

In the present invention, silica particles can be used as the silicon-containing particles.

As a method for producing silica particles, a combustion method obtained by burning a silane compound (that is, a method for producing fumed silica), an explosive combustion method obtained by explosively burning metallic silicon powder, sodium silicate and mineral acid The wet method obtained by the neutralization reaction (of which the one synthesized under alkaline conditions is called the precipitation method and the one synthesized under acidic conditions is called the gel method), and the sol-gel method obtained by hydrolysis of alkoxysilanes such as hydrocarbyloxysilane (of these, the sol-gel method). The so-called Stoeber method) can be mentioned.

The average particle size of the number of silicon-containing particles in the present invention is preferably 5 nm or more and 200 nm or less. Within the above range, the low temperature fixability is not impaired, and a good effect is exhibited in suppressing cracking and chipping in long-term use.

Next, the colorant will be described.

The toner of the present invention can also use a colorant if necessary. The colorant is not particularly limited, and for example, known ones shown below can be used.

Examples of the yellow pigment include condensed azo compounds such as yellow iron oxide, nables yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartradin lake. Isoindolinone compounds, anthraquinone compounds, azometal complexes, methine compounds, and allylamide compounds are used. Specifically, the following can be mentioned.

C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180.

Examples of the orange pigment include the following.

Permanent Orange GTR, Pyrazolone Orange, Balkan Orange, Benzidine Orange G, Indanthrone Brilliant Orange RK, Indanthrone Brilliant Orange GK.

Condensations of red pigments such as Bengala, Permanent Red 4R, Resole Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Lake D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eoxin Lake, Rhodamin Lake B, Alizarin Lake, etc. Examples thereof include azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Specifically, the following can be mentioned.

C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221 and 254.

Examples of blue pigments include copper phthalocyanine compounds such as alkaline blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, and induslen blue BG and their derivatives, anthraquinone compounds, and basic dye lakes. Examples include compounds. Specifically, the following can be mentioned.

C. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

Examples of the purple pigment include Fast Violet B and Methyl Violet Lake.

Examples of the green pigment include Pigment Green B, Malachite Green Lake, and Final Yellow Green G. Examples of the white pigment include zinc oxide, titanium oxide, antimony white, and zinc sulfide.

Examples of the black pigment include carbon black, aniline black, non-magnetic ferrite, magnetite, the above-mentioned yellow colorant, red colorant and blue colorant to be toned to black. These colorants can be used alone or in admixture, and even in the form of a solid solution.

If necessary, the colorant may be surface-treated.

The content of the colorant is preferably 1.0 part by mass or more and 15.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

Next, wax will be described.

As the toner of the present invention, it is preferable to use wax as needed. Examples of the wax include the following. Fatty hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystallin wax, fishertropush wax, paraffin wax; oxides of fatty hydrocarbon waxes such as polyethylene oxide wax, or block copolymers thereof. Deoxidized fatty acid esters such as carnauba wax and montanic acid ester wax, which are mainly composed of fatty acid esters, and partially or wholly deoxidized fatty acid esters such as deoxidized carnauba wax; palmitic acid, stearic acid, montanic acid, etc. Saturated linear fatty acids; unsaturated fatty acids such as brushzic acid, eleostearic acid, parinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, ceryl alcohol, mericyl alcohol; sorbitol Polyhydric alcohols such as; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid amide, etc. Saturated fatty acid bisamides; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N'diorail adipic acid amide, N, N'diorail sevacinic acid amide; m-xylene bisstearate. Aromatic bisamides such as acid amide, N, N'distearyl isophthalic acid amide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally referred to as metal soap); Waxes grafted on aliphatic hydrocarbon wax using vinyl monomer such as styrene and acrylic acid; partial esterified product of fatty acid such as behenic acid monoglyceride and polyhydric alcohol; obtained by hydrogenation of vegetable fats and oils Examples thereof include methyl ester compounds having a hydroxyl group. The wax may be used alone or in combination of two or more.

Examples of aliphatic alcohols that form ester wax are 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, undecyl alcohol, lauryl alcohol, myristyl alcohol, 1-hexadecanol, stearyl. Examples include alcohols, arachidyl alcohols, behenyl alcohols and lignoceryl alcohols. Examples of aliphatic carboxylic acids include pentanoic acid, hexanoic acid, heptanic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid. Can be mentioned.

The wax content is preferably 0.5 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin or the polymerizable monomer.

Next, the charge control agent will be described.

The toner particles of the present invention may contain a charge control agent. As the charge control agent, known ones can be used. In particular, a charge control agent having a high charge speed and capable of stably maintaining a constant charge amount is preferable. Further, when the toner particles are produced by the direct polymerization method, a charge control agent having low polymerization inhibitory property and substantially no solubilized material in an aqueous medium is particularly preferable.

Examples of the charge control agent for controlling the toner particles in a load electric manner include the following.

Examples of the organic metal compound and chelate compound include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acid-based metal compounds. Others include aromatic oxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, anhydrides or esters, phenol derivatives such as bisphenols and the like. Further, urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthoic acid-based compounds, boron compounds, quaternary ammonium salts, calixarene and the like can be mentioned.

On the other hand, examples of the charge control agent for controlling the toner particles to be positively charged include the following.

Niglosin modifications due to niglosin and fatty acid metal salts; guanidine compounds; imidazole compounds; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, and these. Onium salts such as phosphonium salts and their lake pigments which are similar to Lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); Metal salt of higher fatty acid; Resin-based charge control agent.

These charge control agents can be contained alone or in combination of two or more. The amount of these charge control agents added is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

Next, the external additive will be described.

The toner particles of the present invention may be used as toner as they are, but in order to improve fluidity, chargeability, cleaning property, etc., so-called external additives such as a fluidizing agent and a cleaning aid are added to the toner. May be.

Examples of the external additive include inorganic oxide fine particles composed of silica fine particles, alumina fine particles, titanium oxide fine particles, and inorganic stearic acid compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, or strontium titanate and titanium. Examples thereof include inorganic titanium acid compound fine particles such as zinc acid. These can be used alone or in combination of two or more.

It is preferable that these inorganic fine particles are surface-treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil, or the like in order to improve heat storage stability and environmental stability. The BET specific surface area of the external additive is preferably 10 m ² / g or more and 450 m ² / g or less.

The BET specific surface area can be determined by a low-temperature gas adsorption method based on a dynamic constant pressure method according to the BET method (preferably the BET multipoint method). For example, by using a specific surface area measuring device (trade name: Gemini 2375 Ver.5.0, manufactured by Shimadzu Corporation) to adsorb nitrogen gas on the sample surface and measuring using the BET multipoint method. The BET specific surface area (m ² / g) can be calculated.

The total amount of these various external additives added is preferably 0.05 parts by mass or more and 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the toner particles. It is as follows. Further, as the external additive, various agents may be used in combination.

Next, the developer will be described.

The toner of the present invention can be used as a magnetic or non-magnetic one-component developer, but may be mixed with a carrier and used as a two-component developer.

As the carrier, magnetic particles made of known materials such as metals such as iron, ferrite and magnetite, and alloys of these metals with metals such as aluminum and lead can be used. Among these, it is preferable to use ferrite particles. Further, as the carrier, a coat carrier in which the surface of the magnetic particles is coated with a coating agent such as a resin, a resin dispersion type carrier in which a magnetic fine powder is dispersed in a binder resin, or the like may be used.

The carrier preferably has a volume average particle size of 15 μm or more and 100 μm or less, and more preferably 25 μm or more and 80 μm or less.

Next, the toner particles and the method for manufacturing the toner will be described.

As a method for producing the toner particles, a known means can be used, and a kneading and pulverizing method or a wet production method can be used. Examples of the wet production method include a suspension polymerization method, a dissolution suspension method, an emulsion polymerization aggregation method, and an emulsion aggregation method. Above all, the suspension polymerization method and the kneading and pulverizing method are more preferable because the particles containing silicon in the toner particles can be efficiently present in the vicinity of the resin A.

Next, a case where toner particles are produced by the suspension polymerization method will be described.

(Preparation step of polymerizable monomer composition)
In the suspension polymerization method, first, a polymerizable monomer for producing a binder resin, a resin A represented by the above formula (1), particles containing silicon, and if necessary, a wax and a colorant. , Charge control agents, cross-linking agents, polymerization initiators, and other additives are uniformly dissolved or dispersed using a disperser such as a ball mill or an ultrasonic disperser to obtain a polymerizable monomer composition. .. Examples of the polymerizable monomer include those exemplified as the monomer forming the above-mentioned styrene-acrylic copolymer.

The silicon-containing particles and the colorant may be previously dispersed in a polymerizable monomer or an organic solvent with a medium stirring mill or the like and then mixed with other compositions, or all the compositions are mixed. It may be dispersed later.

Further, the silicon-containing particles may be added alone, or may be added by using the toner particles containing the silicon-containing particles in advance as a raw material.

(Dispersion step of polymerizable monomer composition (granulation step))
Next, the polymerizable monomer composition is put into a prepared aqueous medium, and a droplet made of the polymerizable monomer composition is desired by a stirrer or a disperser having a high shearing force. Formed to the size of the toner particles.

It is preferable that the aqueous medium in the granulation step contains a dispersion stabilizer in order to control the particle size of the toner particles, sharpen the particle size distribution, and suppress the coalescence of the toner particles in the manufacturing process. The dispersion stabilizer is generally classified into a polymer that develops a repulsive force due to steric hindrance and a poorly water-soluble inorganic compound that stabilizes the dispersion by an electrostatic repulsive force. Since the fine particles of the poorly water-soluble inorganic compound are dissolved by an acid or an alkali, they can be easily dissolved and easily removed by washing with an acid or an alkali after polymerization, and thus are preferably used. As the dispersion stabilizer of the poorly water-soluble inorganic compound, one containing any one of magnesium, calcium, barium, zinc, aluminum and phosphorus is preferably used. More preferably, it is desired that any one of magnesium, calcium, aluminum and phosphorus is contained. Specifically, the following can be mentioned.

Magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, hydroxyapatide. When the poorly water-soluble inorganic dispersant is used, it may be used as it is, but in order to obtain finer particles, the inorganic dispersant particles can be generated and used in an aqueous medium. For example, in the case of tricalcium phosphate, a water-insoluble calcium phosphate can be produced by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring, and more uniform and fine dispersion becomes possible.

Organic compounds such as polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, and starch may be used in combination with the dispersion stabilizer. It is preferable to use these dispersion stabilizers in an amount of 0.1 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

Further, in order to make these dispersion stabilizers finer, a surfactant of 0.1 part by mass or more and 10.0 parts by mass or less may be used in combination with 100 parts by mass of the polymerizable monomer. Specifically, commercially available nonionic, anionic, and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate are preferably used.

(Polymerization process)
After the granulation step or while performing the granulation step, the temperature is preferably set to 50 ° C. or higher and 90 ° C. or lower to polymerize the polymerizable monomer contained in the polymerizable monomer composition, and the toner is polymerized. Obtain a particle dispersion.

In the polymerization step, it is preferable to perform a stirring operation so that the temperature distribution in the container becomes uniform. When the polymerization initiator is added, it can be carried out at any timing and required time. Further, the temperature may be raised in the latter half of the polymerization reaction for the purpose of obtaining a desired molecular weight distribution, and further, in the latter half of the reaction or the end of the reaction in order to remove unreacted polymerizable monomers, by-products, etc. from the system. Later, the partially aqueous medium may be distilled off by a distillation operation. The distillation operation can be performed under normal pressure or reduced pressure.

The polymerization initiator used in the suspension polymerization method preferably has a half-life of 0.5 hours or more and 30 hours or less during the polymerization reaction. Further, when the polymerization reaction is carried out by using an addition amount of 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum molecular weight between 5,000 and 50,000 is obtained. be able to. As the polymerization initiator, an oil-soluble initiator is generally used. For example, the following can be mentioned.

2,2'-Azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4 -Azo compounds such as methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropyl peroxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, tert- Butylperoxy-2-ethylhexanoate, benzoyl peroxide, tert-butylperoxyisobutyrate, cyclohexanone peroxide, methylethylketone peroxide, dicumyl peroxide, tert-butylhydroperoxide, di-tert-butylper Peroxide-based initiators such as oxide, tert-butylperoxypivalate, and cumenehydroperoxide can be mentioned.

As the polymerization initiator, a water-soluble initiator may be used if necessary, and examples thereof include the following.

Ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) hydrochloride, 2,2'-azobis (2-aminodinopropane) hydrochloride, azobis (isobutylamidin) Hydrochloride, 2,2'-azobisisobutyronitrile sodium sulfonate, ferrous sulfate or hydrogen peroxide.

These polymerization initiators can be used alone or in combination of two or more, and a chain transfer agent, a polymerization inhibitor, or the like can be further added and used in order to control the degree of polymerization of the polymerizable monomer.

(Solid-liquid separation process, cleaning process and drying process)
The toner particle dispersion may be treated with an acid or an alkali for the purpose of removing the dispersion stabilizer adhering to the surface of the toner particles.

Solid-liquid separation for obtaining toner particles from the obtained toner particle dispersion can be performed by a general filtration method, and then reslurry or washing water is used to remove foreign substances that could not be completely removed from the surface of the toner particles. It is preferable to carry out further washing by washing with a toner. After sufficient washing, solid-liquid separation is performed again to obtain a toner cake. Then, it is dried by a known drying means, and if necessary, a group of particles having an unpredictable particle size is separated by classification to obtain toner particles.

Next, an example of manufacturing toner particles using the kneading and pulverizing method will be described.

In the kneading and pulverizing method, first, a binder resin, a resin A represented by the above formula (1), particles containing silicon, and if necessary, a wax, a colorant, a charge control agent, and other additions are added. The mixture containing the agent is sufficiently mixed with a mixer such as a Henchel mixer or a ball mill. After that, it is melt-kneaded using a heat kneader such as a heating roll, a kneader, and an extruder to disperse or melt various materials to obtain a melt-kneaded product, and a cooling solidification step, a crushing step, a classification step, and if necessary. Toner particles are obtained through a surface treatment step.

In the crushing step, a known crushing device such as a mechanical impact type or a jet type may be used. In addition, either of the order of the classification step and the surface treatment step may come first.

(External process)
If necessary, an external additive may be added to the obtained toner particles. The external addition step is performed by putting the external addition agent and the toner particles in a mixing device equipped with blades that rotate at high speed and mixing them sufficiently.

The particle size of the toner particles of the present invention is preferably 3.0 μm or more and 10.0 μm or less in terms of weight average particle size from the viewpoint of obtaining a high-definition and high-resolution image. The weight average particle size of the toner can be measured by the pore electric resistance method. For example, it can be measured using "Coulter Counter Multisizer 3" (manufactured by Beckman Coulter, Inc.).

Hereinafter, a method for measuring each physical property of the toner of the present invention will be described.

<Separation of toner and external additive>
In a toner having an external additive on the surface of the toner particles, the toner particles and the external additive are separated by the following method to obtain toner particles.

Add 160 g of sucrose (manufactured by Kishida Chemical) to 100 mL of ion-exchanged water and dissolve in a water bath to prepare a sucrose concentrate. 31 g of the sucrose concentrate in a centrifuge tube (capacity 50 mL) and 10 of a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of Contaminone N (nonionic surfactant, anionic surfactant, and organic builder). Add 6 mL of mass% aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a dispersion. Add 1.0 g of toner to this dispersion and loosen the toner lumps with a spatula or the like.

Shake the centrifuge tube on a shaker for 350 spm (strokes per min) for 20 minutes. After shaking, the solution is replaced with a glass tube for a swing rotor (capacity: 50 mL), and the solution is separated by a centrifuge (H-9R, manufactured by Kokusan Co., Ltd.) at 3500 rpm for 30 minutes. By this operation, the toner particles and the detached external additive are separated. Visually confirm that the toner and the aqueous solution are sufficiently separated, and collect the separated toner in the uppermost layer with a spatula or the like. The collected toner is filtered with a vacuum filter and then dried with a dryer for 1 hour or more to obtain toner particles. This operation is performed a plurality of times to obtain the required amount of toner particles.

<Removal of resin A represented by the formula (1)) in the toner particles>
The resin represented by the formula (1) in the toner particles was taken out by separating the extract using tetrahydrofuran (THF) by the solvent gradient elution method. The preparation method is shown below.

10.0 g of toner particles are weighed, placed in a cylindrical filter paper (No. 86R manufactured by Toyo Filter Paper), and subjected to a Soxhlet extractor. The solid obtained by extracting with 200 mL of THF as a solvent for 20 hours and removing the solvent from the extract is a THF-soluble component. The THF-soluble component includes a resin represented by the formula (1). This was done multiple times to obtain the required amount of THF soluble.

For the solvent gradient elution method, separation was performed at a flow rate of 50 ml / min using a gradient preparative HPCL (LC-20AP high-pressure gradient preparative system manufactured by Shimadzu Corporation, SunFire preparative column 50 mm φ250 mm manufactured by Waters). For the mobile phase, THF, chloroform, and toluene were selected as good solvents in a timely manner, and acetonitrile, acetone, methanol, and n-hexane were selected as poor solvents in a timely manner. By repeating solvent gradient elution as needed, the resin A represented by the formula (1) was obtained.

<Measuring method of silicon concentration in resin A represented by the formula (1)>
The measurement of the silicon content in the resin A represented by the formula (1) is accompanied by a wavelength dispersive fluorescent X-ray analyzer "Axios" (manufactured by PANalytical), measurement condition setting, and measurement data analysis. Dedicated software "SuperQ ver. 4.0F" (manufactured by PANalytical) is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds.

As the measurement sample, the resin A itself represented by the formula (1) is used, or the resin A taken out from the toner particles by the above-mentioned taking-out method is used.

Silica (SiO ₂ ) fine powder with respect to 100.00 parts by mass of the measurement sample [trade name: AEROSIL NAX50, specific surface area: 40 ± 10, carbon content: 0.45 to 0.85%; Nippon Aerosil Co., Ltd. ) Is added so as to be 0.50 parts by mass, and the mixture is sufficiently mixed using a coffee mill. Similarly, the silica fine powder was mixed with the measurement sample so as to be 5.00 parts by mass, 10.00 parts by mass, and 15.00 parts by mass, and these were used as samples for the calibration curve. A tablet molding compressor "BRE-32" (manufactured by Maekawa Testing Machine Mfg. Co., Ltd.) is used to prepare pellets for measurement. 4 g of the measurement sample is placed in a dedicated aluminum ring for pressing, flattened, and pressed at 20 MPa for 60 seconds to obtain measurement pellets having a thickness of 2 mm and a diameter of 39 mm.

For each measurement pellet, the count rate (unit: cps) of Si—Kα rays observed at a diffraction angle (2θ) = 109.08 ° when PET is used for a spectroscopic crystal is measured. At this time, the acceleration voltage and current value of the X-ray generator are set to 24 kV and 100 mA, respectively. A calibration curve having a linear function is obtained with the count rate of the obtained X-rays on the vertical axis and the Si addition concentration in each calibration curve sample on the horizontal axis.

Next, for the measurement sample, measurement pellets are prepared in the same manner, and the count rate of Si—Kα rays is measured. Then, the silicon concentration (mass%) in the resin represented by the formula (1) is obtained from the obtained calibration curve.

<Structural confirmation of resin A represented by the formula (1) (R ¹ to R ³ )>
The functional groups contained in the resin A represented by the formula (1) and the polymer sites P ¹ , L ¹ and R ¹ to R ³ in the structure represented by the formula (1) are ¹ H-NMR analysis. , ¹³ C-NMR analysis, ²⁹ Si-NMR analysis and FT-IR analysis are used. As the measurement sample, the resin A itself is used, or the resin A taken out from the toner particles by the above-mentioned taking-out method is used.

When L ¹ contains an amide bond as represented by the above formula (17), it can be identified by ^{1 1} H-NMR analysis. Specifically, it can be identified by the chemical shift value of the proton of the NH site of the amide group, and the amide group can be quantified by calculating the integral value.

When R ¹ to R ³ in the structure represented by the formula (1) contain an alkoxy group or a hydroxy group, the method shown in “ ²⁹ Si-NMR (solid) measurement conditions” described later is used. It is possible to determine the valence of an alkoxy group or a hydroxy group for a silicon atom.

( ²⁹ Si-NMR (solid-state) measurement conditions)
Equipment: JEM-ECX500II manufactured by JEOL RESONANCE
Sample tube: 3.2 mmφ
Sample: Resin A represented by the formula (1) 150 mg
Measurement temperature: Room temperature Pulse mode: CP / MAS
Measured nuclear frequency: 97.38 MHz (29Si)
Reference substance: DSS (external standard: 1.534 ppm)
Sample rotation speed: 10 kHz
Contact time: 10ms
Delay time: 2s
Accumulation number: 8192 times

By the above measurement, the abundance ratio can be obtained by peak separation and integration of a plurality of silane components corresponding to the number of oxygen atoms bonded to silicon by curve fitting. In this way, the number of alkoxy groups or hydroxy groups of R ¹ to R ³ of the resin A represented by the formula (1) can be confirmed.

<Structural confirmation of resin A represented by the formula (1) (P ¹ and L ¹ )>
The structures of P ¹ , L ¹ and R ¹ to R ³ in the resin represented by the formula (1) can be confirmed by ¹³ C-NMR (solid-state) measurement. The measurement conditions are as follows.

( ¹³ C-NMR (solid) measurement conditions)
Equipment: JEM-ECX500II manufactured by JEOL RESONANCE
Sample tube: 3.2 mmφ
Sample amount: 150 mg
Measurement temperature: Room temperature Pulse mode: CP / MAS
Measured nuclear frequency: 123.25 MHz ( ¹³ C)
Reference substance: Adamantane (external standard: 29.5 ppm)
Sample rotation speed: 20 kHz
Contact time: 2ms
Delay time: 2s
Number of integrations: 1024 times

( ¹ Measurement conditions for 1 H-NMR analysis (solution))
Equipment: JEM-EX400 manufactured by JEOL RESONANCE
Sample tube: 3.2 mmφ
Sample amount: 10 mg
Solvent: CDCl ₃
Measurement temperature: Room temperature Measurement frequency: 400MHz
Pulse condition: 5.0 μs
Frequency range: 10500Hz
Number of integrations: 64 times Separate into various peaks according to the types of P ¹ , L ¹ and R ¹ to R ³ in equation (1), identify each and identify the types of P ¹ , L ¹ and R ¹ to R ³ . decide.

<Method for confirming an organosilicon polymer having the structure of the formula (3)>
To confirm the structure of the organosilicon polymer contained in the toner particles, the organosilicon polymer represented by the formula (3) itself is used, or the toner is subjected to the method described below. Organosilicon polymers taken from the particles can be used.

1 g of the toner particles collected by the method described above is placed in a vial, dissolved in 31 g of chloroform, and dispersed. For dispersion, an ultrasonic homogenizer is used for 30 minutes to prepare a dispersion.
Sonication device: Ultrasonic homogenizer VP-050 (manufactured by TIETECH Co., Ltd.)
Microchip: Step type microchip, tip diameter φ2 mm
Microchip tip position: central part of glass vial and height 5 mm from the bottom of the vial Ultrasonic conditions: Intensity 30%, 30 minutes. At this time, ultrasonic waves are applied while cooling the vial with ice water so that the temperature of the dispersion does not rise.

The dispersion is replaced with a glass tube for a swing rotor (50 mL), and a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.) is used to centrifuge under the conditions of 58.33S ^-1 for 30 minutes. Organosilicon polymer particles are separated in the glass tube after centrifugation. This is extracted, dispersed again in 10 g of chloroform for washing, and the organic silicon polymer particles are separated using a centrifuge. After the washing operation is performed again, chloroform is removed by vacuum drying (40 ° C./24 hours) of the extracted organosilicon polymer particles to prepare a sample.

By weighing the obtained sample, the content of the organosilicon polymer particles contained in the toner particles can be determined.

The presence or absence of the alkyl group represented by R in the formula (3) is confirmed by ¹³ C-NMR. The detailed structure of the formula (1) is confirmed by ¹ H-NMR, ¹³ C-NMR and ²⁹ Si-NMR. The equipment and measurement conditions used are shown below.

(Measurement condition)
Equipment: Bruker AVANCE III 500
Probe: 4mm MAS BB / 1H
Measurement temperature: Room temperature Sample rotation speed: 6 kHz
Sample: 150 mg of a measurement sample (tetrahydrofuran THF insoluble component of toner particles for NMR measurement) is placed in a sample tube having a diameter of 4 mm.

By this method, the presence or absence of an alkyl group represented by R in the formula (3) is confirmed. If the signal can be confirmed, the structure of equation (3) is assumed to be "yes".

( ¹³ C-NMR (solid) measurement conditions)
Equipment: JEM-ECX500II manufactured by JEOL RESONANCE
Measured nuclear frequency: 125.77 MHz
Reference substance: Glycine (external standard: 176.03 ppm)
Observation width: 37.88 kHz
Measurement method: CP / MAS
Contact time: 1.75ms
Repeat time: 4s
Number of integrations: 2048 times LB value: 50Hz

( ²⁹ Si-NMR (solid-state) measurement method)
(Measurement condition)
Equipment: Bruker AVANCE III 500
Probe: 4mm MAS BB / 1H
Measurement temperature: Room temperature Sample rotation speed: 6 kHz
Sample: 150 mg of a measurement sample (THF insoluble component of toner particles for NMR measurement) is placed in a sample tube having a diameter of 4 mm.
Measurement nuclear frequency: 99.36MHz
Reference substance: DSS (external standard: 1.534 ppm)
Observation width: 29.76 kHz
Measurement method: DD / MAS, CP / MAS
²⁹ Si 90 ° Pulse width: 4.00 μs @ -1 dB
Contact time: 1.75ms-10ms
Repeat time: 30s (DD / MASS), 10s (CP / MAS)
Number of integrations: 2048 times LB value: 50Hz

<Method of confirming the average particle size of the number of particles containing silicon>
The number average particle size of the silicon-containing particles is determined by observation with a scanning electron microscope (SEM). The method of SEM observation is as follows. This is performed using an image taken by a Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation). The image shooting conditions of S-4800 are as follows.

(1) Sample preparation A conductive paste (TED PELLA, Inc, Product No. 16053, PELCO Colloidal Graphite, Isopropanol base) is thinly applied to a sample table (aluminum sample table 15 mm × 6 mm), and the target sample is sprayed on it. Further air blow is performed to remove excess sample from the sample table, and then platinum is vapor-deposited at 15 mA for 15 seconds. Set the sample table on the sample holder and adjust the sample table height to 30 mm with the sample height gauge.

(2) Setting of observation conditions for S-4800 Inject liquid nitrogen into the anti-contamination trap attached to the housing of S-4800 until it overflows, and leave it for 30 minutes. Start the "PC-SEM" of S-4800 and perform flushing (cleaning of the FE chip which is an electron source). Click the acceleration voltage display part of the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Confirm that the flushing intensity is 2, and execute. Confirm that the emission current due to flushing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position.

Click the acceleration voltage display to open the HV setting dialog, and set the acceleration voltage to [2.0 kV] and the emission current to [10 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE] and select [Bottom (L)] for the SE detector to set the mode for observing the reflected electron image. Similarly, in the [Basic] tab of the operation panel, set the probe current of the electro-optical system condition block to [Normal], the focal mode to [UHR], and the WD to [8.0 mm]. Press the [ON] button on the acceleration voltage display of the control panel to apply the acceleration voltage.

(3) Focus adjustment Drag the inside of the magnification display section of the control panel to set the magnification to 5000 (5k) times. Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the focus is reached to some extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the control panel to move the displayed beam to the center of the concentric circles.

Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and focus with autofocus. Repeat this operation twice more to focus. With the midpoint of the maximum diameter of the observed particles aligned with the center of the measurement screen, drag the inside of the magnification display section of the control panel to set the magnification to 10000 (10k) times. Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the focus is reached to some extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the control panel to move the displayed beam to the center of the concentric circles.

Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and focus with autofocus. After that, the magnification is set to 100,000 (100k) times, the focus is adjusted using the focus knob and the STIGMA / ALIGNMENT knob in the same manner as above, and the focus is adjusted again by autofocus. Repeat this operation again to focus.

(4) Image saving Perform brightness adjustment in ABC mode, take a picture with a size of 640 x 480 pixels, and save it.

From the obtained SEM observation results, the number average particle size (D1) of silicon-containing particles having 500 particles is calculated by image processing software (Image J). The measurement method is as follows.
-Measurement of organosilicon polymer particles Select the maximum length of the selected shape from the measurement commands, and measure the particle size of the organosilicon polymer particles. By performing this operation a plurality of times and obtaining the average value at 500 points, the number average particle size of the silicon-containing particles is calculated.

<Measurement method of weight average molecular weight (Mw)>
The weight average molecular weight (Mw) of the resin A represented by the formula (1) is measured by gel permeation chromatography (GPC) as follows.

First, the sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Mysholidisc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is prepared so that the concentration of the component soluble in THF is 0.6% by mass or more and 1.0% by mass or less. This sample solution is used for measurement under the following conditions.
Equipment: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: 7 series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL

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

<Measurement method of acid value of resin>
The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of the resin is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure.

(1) Preparation of Reagents 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), and ion-exchanged water is added 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 touch carbon dioxide gas, leave it for 3 days, and then filter it to obtain a potassium hydroxide solution. The resulting 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 the hydroxylation required for neutralization. Obtained from the amount of potassium 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 the sample.

<Measuring method of weight average particle size (D4)>
The weight average particle diameter (D4) of the toner particles is measured as follows.

As the measuring device, a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter) equipped with a 100 μm aperture tube by the pore electric resistance method is used. For the setting of measurement conditions and the analysis of measurement data, the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) is used. The measurement is performed with 25,000 effective measurement channels.

As the electrolytic aqueous solution used for the measurement, one in which special grade sodium chloride is dissolved in ion-exchanged water so that the concentration becomes 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) 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). The value obtained by using (manufactured by) is set. By pressing the "threshold / noise level measurement 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, set the bin spacing to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range from 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Put 200 mL of the electrolytic aqueous solution in a 250 mL round bottom beaker made of glass exclusively for 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 30 mL of the electrolytic aqueous solution in a 100 mL flat-bottomed beaker made of glass. In this, as a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a pH 7 precision measuring instrument consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Is diluted 3 times by mass with ion-exchanged water, and 0.3 mL of the diluted solution is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with their phases shifted by 180 degrees, and an ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios) with an electrical output of 120 W is prepared. Put 3.3 L of ion-exchanged water in the water tank of the ultrasonic disperser, and add 2 mL of contaminationon N to this 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 solution in the beaker is maximized.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is 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. For ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, the electrolytic aqueous solution of (5) in which toner particles are dispersed is dropped onto the round bottom beaker of (1) installed in the sample stand, and the measured concentration is adjusted to 5%. .. 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 diameter (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).

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, all "parts" of each material in Examples and Comparative Examples are based on mass.

<Production example of polyester resin (a-1)>
The polyester resin (a-1) was synthesized by the following procedure.

The following materials were placed in an autoclave equipped with a depressurizing device, a water separating device, a nitrogen gas introducing device, a temperature measuring device, and a stirring device, and the reaction was carried out under a nitrogen atmosphere at normal pressure at 200 ° C. for 5 hours.
・ Bisphenol A-propylene oxide 2.1 mol Additive: 39.6 parts ・ Terephthalic acid: 8.0 parts ・ Isophthalic acid: 7.6 parts ・ Tetrabutoxytitanate: 0.1 parts Then, Trimellitic acid 0.01 A part and 0.12 part of tetrabutoxytitanate were added, and the reaction was carried out at 220 ° C. for 3 hours, and further reacted under a reduced pressure of 10 to 20 mmHg for 2 hours to obtain a polyester resin (a-1).

The acid value of the obtained polyester resin (a-1) was 6.1 and Mw = 10200.

<Production example of styrene acrylic resin (a-2)>
A styrene acrylic resin (a-2) was synthesized by the following procedure.

100.0 parts of propylene glycol monomethyl ether was heated while substituting with nitrogen, and the mixture was refluxed at a liquid temperature of 120 ° C. or higher. There, as a polymerizable monomer, 83.4 parts of styrene, 20.9 parts of butyl acrylate, 1.0 part of acrylic acid, and as a polymerization initiator, tert-butylperoxybenzoate [NOF CORPORATION]. Manufactured by, trade name: Perbutyl Z] 0.6 parts mixed was added dropwise over 3 hours. After completion of the dropping, the solution was stirred for 3 hours and then distilled under atmospheric pressure while raising the liquid temperature to 170 ° C. After the liquid temperature reached 170 ° C., the pressure was reduced to 1 hPa, and the mixture was distilled for 1 hour to remove the solvent to obtain a resin solid. The resin solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was filtered off to obtain a styrene acrylic resin (a-2).

The acid value of the obtained styrene acrylic resin (a-2) was 10.6 and Mw = 13000.

<Production example of resin A (A-1) represented by formula (1)>
Resin A (A-1) represented by the formula (1) was synthesized by the following procedure.

50.00 parts of the polyester resin (a-1) was dissolved in 2000.00 parts of N, N-dimethylacetamide, and 1.20 parts of 3-aminopropyltriethoxysilane, 1.70 parts of triethylamine, and condensation were used as the silane compound. 1.70 parts of DMT-MM (4- (4,4-dimethoxy-1,3,5-triazine-2-yl) -4-methylmorpholinium chloride) was added as an agent, and the mixture was stirred at room temperature for 5 hours. .. After completion of the reaction, this solution was added dropwise to methanol, reprecipitated and filtered to obtain resin A (A-1) represented by the formula (1). The weight average molecular weight Mw of the obtained resin A (A-1) represented by the formula (1) was 10400. Table 2 shows the physical characteristics of the obtained resin A (A-1) represented by the formula (1).

<Production example of resin A (A-2) represented by formula (1)>
In the synthesis of the resin A (A-1) represented by the formula (1), the same operation was performed except that the silane compound was changed as shown in Table 1, and the resin A (A-) represented by the formula (1) was operated in the same manner. 2) was obtained. The physical characteristics are shown in Table 2.

<Production example of resin A (A-3) represented by formula (1)>
A solution prepared by dissolving 10.0 parts of the resin A (A-1) represented by the formula (1) in 90.0 parts of toluene is mixed and stirred with 400.0 parts of pure water, and the pH is adjusted to 4 using dilute hydrochloric acid. After adjusting to 0.0 and stirring at room temperature for 10.8 hours, the stirring was stopped and the mixture was transferred to a liquid separation funnel to extract the oil phase. The oil phase was concentrated and reprecipitated with methanol to obtain the resin A (A-3) represented by the formula (1).

When the obtained resin A (A-3) represented by the formula (1) was analyzed by ²⁹ Si-NMR (solid state) measurement, all of R ¹ to R ³ in the formula (1) were hydroxy groups. rice field. The physical characteristics are shown in Table 2.

<Production example of resin A (A-4) represented by formula (1)>
Resin A (A-4) represented by the formula (1) was synthesized by the following procedure.

50.00 parts of polyester resin (a-1) is dissolved in 500.00 parts of chloroform, and 1.30 parts of 3-isocyanatepropyltriethoxysilane and 0.50 parts of titanium (IV) tetraisopropoxide are dissolved in a nitrogen atmosphere. Was added, and the mixture was stirred at room temperature for 5 hours. After completion of the reaction, this solution was added dropwise to methanol, reprecipitated and filtered to obtain resin A (A-4) represented by the formula (1). The physical characteristics are shown in Table 2.

<Production example of resin A (A-5) represented by formula (1)>
In the synthesis of the resin A (A-1) represented by the formula (1), the same operation is performed except that the polyester resin (a-1) is changed to the styrene acrylic resin (a-2), according to the formula (1). The represented resin A (A-5) was obtained. The physical characteristics are shown in Table 2.

<Production example of resin A (A-6) represented by the formula (1)>
In the formula (1), the linking group represented by the following formula (19) or the formula (20) is formed by the insertion reaction of the ester bond in the polyester resin (a-1) with the epoxy group in the epoxy silane. The represented resin A (A-6) was obtained.

50.0 parts of the polyester resin (A-2) is dissolved in 100.0 parts of anisole, and 2.90 parts of 5,6-epoxyhexyltrimethoxysilane and 10.00 parts of tetrabutylphosphonium bromide are added under a nitrogen atmosphere. It was added and stirred at 140 ° C. for 5 hours. After allowing to cool, the reaction mixture was dissolved in 200 ml of chloroform, added dropwise to methanol, reprecipitated and filtered to obtain resin A (A-6). The physical characteristics are shown in Table 2.

<Synthesis of resin for comparative example>
As a comparative example resin of the resin A, a polyester resin (a-1) was used as the resin A (A-7).

［式（１７）中の（＊）は式（１）中のＰ¹への結合部位を表し、（＊＊）は前記式（１）中のケイ素原子への結合部位を表す。］

[(*) In the formula (17) represents a binding site to P ¹ in the formula (1), and (**) represents a binding site to a silicon atom in the formula (1). ]

［式（１８）中の（＊）は式（１）中のＰ¹への結合部位を表し、（＊＊）は前記式（１）中のケイ素原子への結合部位を表す。］

[(*) In the formula (18) represents a binding site to P ¹ in the formula (1), and (**) represents a binding site to a silicon atom in the formula (1). ]

［式（１９）及び（２０）中の（＊）は前記式（１）中のＰ¹への結合部位を表し、（＊＊）は式（１）中のケイ素原子への結合部位を表す。］

[(*) In the formulas (19) and (20) represents a binding site to P ¹ in the formula (1), and (**) represents a binding site to a silicon atom in the formula (1). .. ]

The silicon concentration in Table 2 indicates the content (mass%) of silicon atoms in the resin A.

<Production example of organosilicon polymer particles 1 represented by the formula (3)>
The organosilicon polymer particles 1 represented by the formula (3) were synthesized by the following procedure.

A container equipped with a stirrer and a nitrogen tube was prepared in a water bath at 25 ° C., and 800 parts of a hydrochloric acid aqueous solution adjusted to pH 3.0 was prepared. 100 parts of methyltriethoxysilane was added thereto, and the mixture was stirred for 120 minutes to obtain a hydrolyzed solution of methyltriethoxysilane.

On the other hand, 1620 parts of water was placed in a container equipped with a stirrer and heated to 70 ° C. in a warm bath, and then a 1.0 mol / L sodium hydroxide solution was added to adjust the pH to 9.0. The above-mentioned hydrolysis solution was added thereto over 1 hour, and the mixture was kept at 70 ° C. for 1 hour to carry out polycondensation. Then, a 0.1 mol / L sodium hydroxide solution was gradually added to adjust the pH to 10.5, and then polycondensation was performed at 70 ° C. for another 3 hours to obtain a dispersion liquid of the organic silicon polymer particles 1.

The dispersion liquid of the obtained organosilicon polymer particles 1 was obtained by filtering, washing and drying after removing coarse particles by a centrifugation step to obtain organosilicon polymer particles 1.

The number average particle size of the organosilicon polymer particles 1 was 40 nm. Table 3 shows the organosilicon polymer particles 1.

<Production Examples of Organosilicon Polymer Particles 2 and 3 Represented by Formula (3)>
In the production example of the organosilicon polymer particles 1, the organosilicon polymer particles 2 and 3 were obtained in the same manner except that the changes were made as shown in Table 3 below.

表中の略称は以下のとおり。
ＭＴＥＳ：メチルトリエトキシシラン
ＰｒＴＭＳ：プロピルトリメトキシシラン

The abbreviations in the table are as follows.
MTES: Methyltriethoxysilane PrTMS: Propyltrimethoxysilane

As the silica particles, those in Table 4 below were used.

<Manufacturing of toner particles 1>
390.0 parts of ion-exchanged water and 14.0 parts of sodium phosphate (12-hydrate) [manufactured by Lhasa Industry Co., Ltd.] were put into a reaction vessel equipped with a stirrer, a thermometer, and a return pipe. The mixture was kept warm at 65 ° C. for 1.0 hour while purging with nitrogen. Next, T. K. A calcium chloride aqueous solution in which 9.2 parts of calcium chloride (dihydrate) is dissolved in 10.0 parts of ion-exchanged water while stirring at 12,000 rpm using a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.). To prepare an aqueous medium containing a dispersion stabilizer. Further, hydrochloric acid was added to the aqueous medium to adjust the pH to 6.0 to obtain an aqueous medium 1.

On the other hand, the following materials were put into an attritor (manufactured by Nippon Coke Industries, Ltd.), and zirconia particles having a diameter of 1.7 mm were further put into the mixture, dispersed at 220 rpm for 5.0 hours, and then the zirconia particles were removed to remove the colorant. A dispersion liquid 1 in which the above was dispersed was prepared.
-Styrene 60.0 parts-Colorant (CI Pigment Blue 15: 3) 6.5 parts Next, the following materials were added to the prepared dispersion liquid 1.
・ Styrene 15.0 parts ・ N-butyl acrylate 25.0 parts ・ Resin A (A-1) 4.0 parts ・ Organic silicon polymer particles 1 0.2 parts ・ Divinylbenzene 0.3 parts ・ Wax (Fisher) Tropsch wax, melting point: 78 ° C) 3.0 parts, wax (ethylene glycol distearate) 10.0 parts Keep this warm at 65 ° C, and T.I. K. The polymerizable monomer composition 1 was prepared by uniformly dissolving and dispersing at 500 rpm using a homomixer.

While maintaining the temperature of the aqueous medium 1 at 72 ° C. and the rotation speed of the stirring device at 12,000 rpm, the polymerizable monomer composition 1 was put into the aqueous medium 1 and t-butyl was used as a polymerization initiator. 9.0 parts of peroxypivalate was added. Granulation was carried out for 10 minutes while maintaining 12,000 rpm with the stirring device as it was.

The stirring device was changed to a stirrer equipped with a propeller stirring blade, and the mixture was kept at 72 ° C for 5.0 hours while stirring at 150 rpm, then heated to 85 ° C and kept heated for 2.0 hours. gone.

The return tube of the reaction vessel was replaced with a cooling tube, and the slurry was heated to 100 ° C. to carry out distillation for 6 hours to distill off the unreacted polymerizable monomer to obtain a toner particle dispersion liquid 1.

Hydrochloric acid was added to the obtained toner particle dispersion liquid 1, the pH was set to 1.4 or less, the dispersion stabilizer was dissolved, and filtration, washing, drying, and classification were performed to obtain toner particles 1.

<Manufacturing examples of toner particles 2 to 4 and 6 to 23>
In the production example of the toner particles 1, the toner particles 2 to 4, 6 to 23 are prepared in the same manner except that the resin A and the silicon compound-containing particles represented by the formula (1) are changed as shown in Table 5 below. Obtained.

Table 5 shows the physical properties of the obtained toner particles 2 to 4 and 6 to 23.

<Manufacturing example of toner particles 5>
Preparation of binder resin ・ Bisphenol A ・ propylene oxide 2.2 mol adduct 1200 parts ・ Bisphenol A ・ ethylene oxide 2.2 mol adduct 475 parts ・ terephthalic acid 250 parts ・ anhydrous trimellitic acid 190 parts ・ fumaric acid 290 parts -0.1 part of dibutyltin oxide was placed in a 4-liter glass 4-necked flask, and a thermometer, a stirring rod, a condenser, and a nitrogen introduction tube were attached and placed in a mantle heater. The reaction was carried out at 220 ° C. for 5 hours in a nitrogen atmosphere to obtain a binder resin. next,
・ 100.0 parts of the above-mentioned binding resin ・ Colorant (CI Pigment Blue 15: 3) 6.5 parts ・ Resin A (A-1) 4.0 parts ・ Organic silicon polymer particles 1 0.2 parts・ Wax (Fishertropus wax, melting point: 78 ° C) 3.0 parts ・ Wax (ethylene glycol distearate) 10.0 parts After sufficient premixing of the above toner material with a Henchel mixer, use a twin-screw extruder. After melt-kneading and cooling, the mixture was coarsely pulverized to a particle size of about 1 to 2 mm using a hammer mill. Then, it was finely pulverized with a fine pulverizer by an air jet method. Further, the obtained finely pulverized material was classified by a multi-division classification device to obtain toner particles 5.

[Examples 1 to 18 and Comparative Examples 1 to 5]
<Manufacturing of toners 1 to 18 and toners 19 to 23 for comparison>
Silica fine particles (hydrophobication treatment with hexamethyldisilazane: average particle size of primary particles: 8 nm, BET specific surface area: 160 m ² / g) with respect to 100.0 parts of each of the obtained toner particles 1 to 23. 0.8 parts were mixed with Henchel Mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.).

After the mixing treatment, the mixture was sieved with a mesh having an opening of 200 μm to obtain toners 1 to 18 and toners 19 to 23 for comparison. Table 5 shows the physical characteristics of the obtained toner.

The performance of each of the obtained toners was evaluated according to the following method.

<Evaluation of contamination of developing materials>
After leaving 100 g of the toner in an environment of 23 ° C. / 50% relative humidity for 24 hours, an image was evaluated at a temperature of 23 ° C. and a relative humidity of 50% using LBP712Ci (manufactured by Canon) as an image forming apparatus.

An image forming apparatus (LBP712Ci (manufactured by Canon)) was prepared, toner was taken out from the cyan cartridge, and the toner to be evaluated was filled instead. In addition, the evaluation was carried out by installing a dummy cartridge.

The process speed was set to 240 mm / s in the cyan monochromatic mode. 500 sheets of "E" character (image printing rate 1%) were printed out in the intermittent printing (stopping for 2 seconds for every two sheets printed) mode.

The cyan cartridge was taken out, and the developing roller was taken out. The developing roller taken out earlier was attached to the cyan cartridge from which the newly prepared toner and the developing roller were taken out.

Next, the image forming apparatus was modified so that the image could be output even if the toner was not filled.

As a result, the toner coated on the developing roller is repeatedly rubbed by the developing blade.

With this cartridge, toner was rubbed on a developing member having a print count of 150 sheets, and then the developing member was taken out and air blown to remove the toner on the developing member. This developing roller was taped and attached to A4 color laser copier paper (manufactured by Canon, 80 g / m ² ).

The density of this tape was measured at 5 points, and the average value was used as an index of the degree of material contamination. The color measurement was evaluated using a "504 spectroscopic densitometer" (manufactured by X-Rite Co., Ltd.) for the image density, using the one without taping of the developing roller as a standard of 0.00. The results are shown in Table 6.

(Evaluation criteria)
A: Concentration difference from the standard is less than 0.050 B: Concentration difference from the standard is 0.050 or more and less than 0.100 C: Concentration difference from the standard is 0.100 or more and less than 0.200 D: Concentration from the standard Difference is 0.200 or more

<Low temperature fixability evaluation>
After leaving 100 g of the toner in an environment of 23 ° C. / 50% relative humidity for 24 hours, an image was evaluated at a temperature of 23 ° C. and a relative humidity of 50% using LBP712Ci (manufactured by Canon) as an image forming apparatus.

An image forming apparatus (LBP712Ci (manufactured by Canon)) was prepared, toner was taken out from the cyan cartridge, and the toner to be evaluated was filled instead.

Next, an unfixed toner image (toner loading amount: 0.9 mg / cm ² ) of 2.0 cm in length and 15.0 cm in width was placed on a receiving paper (HP Laser Jet90, manufactured by HP, 90 g / m ² ). It was formed at a portion 1.0 cm from the upper end in the paper passing direction.

Next, the removed fixing unit was modified so that the fixing temperature and process speed could be adjusted, and the fixing test of the unfixed image was performed using this.

First, in a normal temperature and humidity environment (23 ° C / 60% relative humidity), the process speed is set to 300 m / s, the initial temperature is 120 ° C, and the set temperature is gradually increased by 2 ° C, and the above undecided at each temperature. The ringtone image was fixed.

The evaluation criteria for low temperature fixability are as follows.

The low temperature side fixing start point is the lower limit temperature at which the low temperature offset phenomenon (a phenomenon in which a part of the toner adheres to the fuser) is not observed. The results are shown in Table 6.

(Evaluation criteria)
A: Low temperature side fixing start point is less than 140 ° C B: Low temperature side fixing start point is 140 ° C or more and less than 150 ° C C: Low temperature side fixing start point is 150 ° C or more and less than 160 ° C D: Low temperature side fixing start point is 160 ° C or more

<Evaluation of tape peelability>
An image forming apparatus (LBP712Ci (manufactured by Canon)) was prepared, toner was taken out from the cyan cartridge, and the toner to be evaluated was filled instead.

The image forming apparatus was modified so that the development bias could be adjusted, and FOX RIVER BOND paper (110 g / m ² ) having a relatively large surface unevenness and basis weight was used as the fixing medium.

The evaluation image is a line image. By shaking the development bias and setting the image density high, the amount of toner on the image is increased, and by using thick paper with large surface irregularities, the toner in the recesses of the paper and the toner in the lower layer of the toner layer are melted in the fixing process. Since it becomes difficult, it can be evaluated strictly against peeling.

First, the image forming apparatus was left overnight in a low temperature and low humidity environment (15 ° C., 10% RH). If the evaluation environment is low, the fuser will not warm up easily and the evaluation will be severe.

Then, using FOX RIVER BOND paper, a horizontal line image adjusted for development bias is printed so that the line width becomes 180 μm. Further, after leaving it for 1 hour in a low temperature and low humidity environment, a polypropylene tape (Klebeband 19 mm × 10 mm manufactured by tesa) was attached to the horizontal line image and slowly peeled off. The image after peeling was visually observed and observed under a microscope, and evaluated according to the following evaluation criteria. The results are shown in Table 6.

(Evaluation criteria)
A: No defect B: Slight defects are visible but not visible C: Slight defects that can be visually recognized D: There are visually recognizable defects and the line is interrupted

Claims (10)

A toner containing toner particles, wherein the toner particles contain particles containing a binder resin, resin A, and silicon.
The resin A has a substituted or unsubstituted silyl group in the molecule, and the substituent of the substituted silyl group is an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, a hydroxy group, and the like. At least one selected from a halogen atom or an aryl group having 6 or more carbon atoms.
The toner is characterized in that the silicon-containing particles are at least one selected from silica or an organosilicon polymer. The toner according to claim 1, wherein the resin A has a structure represented by the following formula (1).

(In the formula (1), P ¹ represents a polymer moiety, L ¹ represents a single bond or a divalent linking group, and R ¹ to R ³ independently represent a hydrogen atom, a halogen atom, an alkyl group, and an alkoxy. A group, an aryl group or a hydroxy group, m represents a positive integer, and when m is 2 or more, a plurality of L ¹ , a plurality of R ¹ , a plurality of R ² and a plurality of R ³ are the same, respectively. However, they may be different.) The toner according to claim 1 or 2, wherein the content of the resin A in the toner particles is 0.1% by mass or more and 10.0% by mass or less. The toner according to any one of claims 1 to 3, wherein P ¹ of the formula (1) is a polyester moiety. The toner according to any one of claims 1 to 4, wherein L ¹ of the formula (1) has a structure represented by the following formula (17).

[R ⁵ in the formula (17) represents an alkylene group containing an alkylene group, an arylene group, or an —NH— group. (*) Represents the binding site to P ¹ in the formula (1), and (**) represents the binding site to the silicon atom in the formula (1). ] The toner according to any one of claims 1 to 5, wherein at least one of R ¹ to R ³ of the formula (1) is an alkoxy group or a hydroxy group. The toner according to any one of claims 1 to 6, wherein the silicon-containing particles are 0.040% by mass or more and 0.800% by mass or less with respect to the toner particles. The toner according to any one of claims 1 to 7, wherein the silicon-containing particles are the organosilicon polymer and have a structure represented by the following formula (3).
R-SiO _3/2 formula (3)
(In formula (3), R is an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms.) The method for manufacturing a toner according to any one of claims 1 to 8.
The resin A, the particles containing the silicon, and the polymerizable monomer composition containing the polymerizable monomer are dispersed in an aqueous medium, and the particles of the polymerizable monomer composition are dispersed in the aqueous medium. A method for producing a toner, which comprises a step of forming the polymerizable monomer and a step of polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition. The method for manufacturing a toner according to any one of claims 1 to 8.
A method for producing a toner, which comprises a step of melt-kneading a mixture containing a binder resin, the resin A, and particles containing silicon to obtain a melt-kneaded product, and a step of crushing the melt-kneaded product to obtain a pulverized product.