JP7566577B2 - Toner and manufacturing method thereof - Google Patents

Description

The present invention relates to a toner for developing electrostatic latent images formed by methods such as electrophotography, electrostatic recording, and toner jet recording, and a method for producing the toner.

In recent years, energy saving has been considered a major technical issue in electrostatic copying electrophotography used in copiers, printers, faxes, etc., and a significant reduction in the amount of heat required for image fixing devices is desired. Therefore, there is an increasing need for toners that can fix images with less energy, that is, with so-called "low temperature fixability."
Common methods for improving the low-temperature fixability of a toner include lowering the glass transition temperature (Tg) of the binder resin or reducing the molecular weight of the binder resin in order to soften the binder resin used. However, simply lowering the Tg of the binder resin or reducing the molecular weight of the binder resin can result in a decrease in the storage stability of the toner and the occurrence of offset to the fixing member due to insufficient releasability during fixing.
In order to increase the strength of the toner while maintaining the glass transition temperature (Tg), it is common to increase the molecular weight of the binder resin or to make the binder resin have a crosslinked structure. However, if the toner strength is increased beyond a certain level by this method alone, the low-temperature fixability is inevitably impaired.
For example, Japanese Patent Application Laid-Open No. 2003-233633 discloses a method of increasing toner strength by adding pearl necklace-like silica.

JP 2009-42386 A

According to Patent Document 1, the toner strength can be increased compared to that of general silica. However, when the toner has good low-temperature fixing property, the toner is easily cracked at the interface between the binder resin and the silica, and there is a problem of contamination of components due to cracks and chips of the toner over long-term use.
In view of these problems, the present invention provides a toner that is excellent in preventing cracking and chipping during long-term use without impairing low-temperature fixability.

The present invention relates to a toner containing toner particles, the toner particles containing a binder resin, a resin A, and silicon,
The resin A has a structure represented by the formula (1) described below (wherein L ¹ in the formula is a linking group which is a structure represented by the formula (17) or a structure represented by the formula (18) described below) ,
The toner is characterized in that the silicon-containing particles are at least one selected from the group consisting of silica and organosilicon polymers.
The present invention also provides a method for producing the toner having the above-mentioned configuration, comprising the steps of:
The present invention relates to a method for producing a toner, the method comprising the steps of dispersing the resin A, the silicon-containing particles, and a polymerizable monomer composition containing a polymerizable monomer in an aqueous medium, forming particles of the polymerizable monomer composition in the aqueous medium, and polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition.
Furthermore, the present invention provides a method for producing the toner having the above-mentioned configuration,
The present invention relates to a method for producing a toner, comprising the steps of melt-kneading a mixture containing a binder resin, the resin A, and the silicon-containing particles to obtain a melt-kneaded product, and pulverizing the melt-kneaded product to obtain a pulverized product.

As described above, the present invention can provide a toner that is excellent in preventing cracking and chipping over long-term use without compromising low-temperature fixability.

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

In the present invention, the expressions "xx or more and xx or less" or "xx to xx" that express a numerical range refer to a numerical range including the lower and upper limit endpoints, unless otherwise specified.

The toner of the present invention is a toner having toner particles containing a binder resin, resin A, and silicon-containing particles, wherein the resin A has a substituted or unsubstituted silyl group in the molecule, the substituent of the substituted silyl group being 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, and the silicon-containing particles being at least one selected from silica or an organosilicon polymer.

The inventors have discovered that by using a toner having the above-described configuration, the low-temperature fixability is not compromised and cracking and chipping during long-term use are effectively prevented.

The reason for this is speculated to be as follows:

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

On the other hand, the toner of the present invention has substituted or unsubstituted silyl groups in the molecules of resin A. This improves the dispersibility of silicon-containing particles such as silica within the toner particles. It is also believed that resin A increases the adhesion between the binder resin and the silicon-containing particles, thereby suppressing cracking and chipping at the interface between the silicon-containing particles and the binder resin. It is believed that this has a positive effect on suppressing cracking and chipping of the toner over long-term use without impairing low-temperature fixability.

The following describes the preferred configuration of the present invention.

First, we will explain the binder resin used in the present invention.

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

If it has a styrene-acrylic copolymer moiety, it may consist of only a styrene-acrylic copolymer, or it may be a block copolymer or graft copolymer of a styrene-acrylic copolymer with another polymer, or a mixture of these.

Examples of styrene monomers constituting the styrene unit include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and divinylbenzene. Although one type of styrene monomer can be used, two or more types selected from these can also be used in combination.

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

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

The acrylic monomers and methacrylic monomers can be used alone or in combination of two or more selected from them.

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.

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

As a resin containing a polyester moiety, a condensation polymerization of the following carboxylic acid components and alcohol components can be used. Examples of the carboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid. Examples of the alcohol components include bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.

The polyester may also be a polyester containing a urea group. It is preferable that the carboxyl groups at the terminals of the polyester are not capped.

The binder resin may contain a crosslinking agent.

As a 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; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, and 1,6-hexanediol diacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups.

These may be used alone or in a mixture of two or more. The amount of crosslinking agent added is preferably 0.001 parts by mass or more and 15,000 parts by mass or less per 100 parts by mass of the binder resin.

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

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 formula (1), ^P1 represents a polymer moiety, ^L1 represents a single bond or a divalent linking group, ^R1 to ^R3 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group or a hydroxyl group, m represents a positive integer, and when m is 2 or more, a plurality of L1 ^'s , a plurality of R1 ^'s , a plurality of R2 ^'s and a plurality of R3 ^'s may be the same or different.)

In the resin represented by formula (1), silicon atoms (Si) are present in the side chains or at the ends of the resin. This is believed to produce the effect of efficiently placing silicon-containing particles in the vicinity of resin A. Through this resin A, the adhesion between the binder resin and the silicon-containing particles is increased, suppressing cracking and chipping at the particle interface. As a result, it is believed that a good effect is achieved in suppressing cracking and chipping of the toner over long-term use.

It is preferable that the content of the resin A in the toner particles is 0.1% by mass or more and 10.0% by mass or less. This range ensures that low-temperature fixability is not impaired and that the toner shows a good effect in preventing cracking and chipping during long-term use.

The polymer moiety ^P1 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, a polyolefin moiety, etc. Among these, it is preferable that the structure of ^P1 contains a polyester moiety or a vinyl resin moiety, and it is more preferable that the structure of ^P1 contains a polyester moiety.

It is believed that the inclusion of a polyester moiety in the structure of ^P1 produces an effect of improving the dispersibility of silicon-containing particles in toner particles. The adhesion between the binder resin and the silicon-containing particles is increased via this resin A, and cracking and chipping at the particle interface is suppressed. As a result, it is believed that a good effect is exhibited in suppressing cracking and chipping of the toner over long-term use.

An example in which the structure of ^P1 contains a polyester moiety will be described.

The polyester moiety is a condensation product of a dialcohol and a dicarboxylic acid. Examples of the polyester moiety include a condensation product of a unit of the following formula (12) and a unit (multiple units can be selected) selected from the following formulas (13) to (15), or a condensation polymer represented by a unit of the following formula (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, or an arylene group.]

［式（１３）中、Ｒ¹⁰はアルキレン基、フェニレン基を表す。］

[In formula (13), R ¹⁰ represents an alkylene group or 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. x and y each represent 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 or an alkenylene group.]

Examples of the alkylene group for ^R9 in the formula (12) include the following: a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a hexamethylene group, a neopentylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, 1,3-cyclopentylene, 1,3-cyclohexylene, and 1,4-cyclohexylene group.

The alkenylene group for R ⁹ in the above formula (12) includes a vinylene group, a propenylene group, and a 2-butenylene group.

Examples of the arylene group for 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, a 2,7-naphthylene group, and a 4,4′-biphenylene group.

^R 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 combinations thereof.

Examples of the alkylene group for ^R in formula (13) include the following: a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a hexamethylene group, a neopentylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, 1,3-cyclopentylene, 1,3-cyclohexylene, and 1,4-cyclohexylene group.

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

^R in the formula (13) may be substituted with a substituent. In this case, the substituent that may be substituted includes a methyl group, an alkoxy group, a hydroxyl group, a halogen atom, and combinations thereof.

Examples of the alkylene group for R ¹¹ in the formula (16) include the following: a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a hexamethylene group, a neopentylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, and a 1,4-cyclohexylene group.

The alkenylene group in R ¹¹ in the formula (16) includes 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, triacontenylene group. These alkenylene groups may be linear, branched, or cyclic. The position of the double bond may be any position, as long as it has at least one double bond.

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

When the structure of ^P1 contains a vinyl resin moiety, it is preferable that the structure of P1 contains a styrene-acrylic copolymer moiety.

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

［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。］

[ ^R5 in formula (17) represents an alkylene group, an arylene group, or an alkylene group containing an -NH- group. (*) represents the bonding site to ^P1 in formula (1), and (**) represents the bonding site to the silicon atom in 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。］

[ ^R6 in formula (18) represents an alkylene group or an arylene group. (*) represents a bonding site to ^P1 in formula (1), and (**) represents a bonding site to the silicon atom in 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。］

[ ^R7 and ^R8 in formulas (19) and (20) each independently represent an alkylene group, an arylene group, or an oxyalkylene group. (*) represents the bonding site to ^P1 in formula (1), and (**) represents the bonding site to the silicon atom in formula (1)]

Among these, it was confirmed that when the structure of ^L1 has a structure containing an amide bond represented by the above formula (17), it produces an excellent effect in suppressing cracking and chipping during long-term use without impairing low-temperature fixing properties, and also improves tape peeling properties after toner fixing. This is presumably because the amide bond has a high affinity with the hydroxyl group of the cellulose that constitutes the paper fiber, which is the fixing medium.

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

The aminosilane compound is not particularly limited, but examples thereof include 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, and 3-aminopropylsilicon.

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 the reaction of a hydroxy group in a resin with an isocyanate silane compound.

The isocyanate silane compound is not particularly limited, but examples thereof include 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl methyl dimethoxy silane, 3-isocyanate propyl dimethyl methoxy silane, 3-isocyanate propyl triethoxy silane, 3-isocyanate propyl methyl diethoxy silane, and 3-isocyanate propyl dimethyl ethoxy silane.

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 may not necessarily be 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 an epoxysilane compound is as follows. It involves a process of inserting the epoxy group of an epoxysilane compound into the ester bond contained in the main chain of a resin.

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

This reaction mechanism can be expressed by a simple model formula as follows:

（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 represent the constituent parts of the resin, and F represents the constituent part of the epoxy compound.)

In the above model formula, the ring opening of the epoxy group can be either α-cleavage or β-cleavage, resulting in two types of compounds. In either case, the epoxy group is inserted into the ester bond in the resin; in other words, the components of the epoxy compound other than the epoxy moiety are grafted to the resin.

Epoxy silane compounds are not particularly limited, but examples include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, etc.

In addition, at least one of R ¹ to R ³ in the formula (1) is preferably an alkoxy group or a hydroxy group. Furthermore, it is more preferable that R ¹ to R ³ in the formula (1) are each independently an alkoxy group or a hydroxy group.

These alkoxy or hydroxy groups contain many Si-O- bonds, which is thought to enhance the adhesion between resin A and the silicon-containing particles. Resin A enhances the adhesion between the binder resin and the silicon-containing particles, suppressing cracking and chipping at the particle interface. As a result, it shows a good effect in suppressing cracking and chipping of the toner over long-term use.

In order to convert one or more of R ¹ to R ³ in the formula (1) into a hydroxyl group, a resin in which one or more of R ¹ to R ³ are alkoxy groups may be hydrolyzed to convert the alkoxy groups into hydroxy groups. Any method for hydrolysis may be used, but examples of the method include the following.

The resin in which one or more of R ¹ to R ³ in the formula (1) are alkoxy groups is dissolved or suspended in a suitable solvent (which may be a polymerizable monomer), and the pH is adjusted to acidic using an acid or alkali, and the mixture is mixed and hydrolyzed. Alternatively, hydrolysis may be caused during the production of toner particles.

Next, we will explain the suitable weight average molecular weight (Mw) of resin A represented by formula (1).

The weight average molecular weight (Mw) of the resin A represented by the formula (1) is preferably from 3,000 to 100,000, and more preferably from 5,000 to 30,000. When it is in this range, the affinity between the polymer moiety (L ¹ ) in the formula (1) and the binder resin is sufficient, and a good effect is shown in suppressing cracking and chipping during long-term use.

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

Next, we will explain the silicon-containing particles of the present invention.

The silicon-containing particles of the present invention are characterized by being at least one selected from the group consisting of silica and organosilicon polymers.

The silicon-containing particles are preferably present in an amount of 0.040% by mass or more and 0.800% by mass or less relative to the toner particles. This range ensures that low-temperature fixability is not compromised and that cracking and chipping are effectively prevented during 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 to 4 carbon atoms.)

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

The organosilicon polymer having the structure of formula (3) is preferably a condensation polymer of an 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 formula (4), R ²¹ represents a hydrocarbon group having 1 to 4 carbon atoms, and R ²² , R ²³ and R ²⁴ each independently represent a halogen atom, a hydroxyl group, an acetoxy group, or an alkoxy group.)

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

R ²² , R ²³ and R ²⁴ are each independently a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group (hereinafter also referred to as a reactive group). These reactive groups undergo hydrolysis, addition polymerization and condensation polymerization to form a crosslinked structure, and a toner having excellent resistance to member contamination and development durability can be obtained. From the viewpoint of mild hydrolysis at room temperature and deposition and coating properties on the surface of toner particles, an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable. In addition, 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.

The organosilicon polymer used in this invention can be obtained by using one or a combination of two or more organosilicon compounds having three reactive groups (R ²² , R ²³ and R ²⁴ ) in one molecule excluding R ²¹ in the formula (4) shown above (hereinafter referred to as trifunctional silanes).

Examples of the above formula (4) include the following:

Trifunctional methylsilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane, etc.

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

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

Methods for producing silica particles include the combustion method, in which a silane compound is burned (i.e., the method for producing fumed silica), the deflagration method, in which metal silicon powder is explosively burned, the wet method, in which silica is obtained by the neutralization reaction of sodium silicate with mineral acid (of these, the synthesis under alkaline conditions is called the precipitation method, and the synthesis under acidic conditions is called the gel method), and the sol-gel method, in which silica is obtained by hydrolysis of alkoxysilanes such as hydrocarbyloxysilanes (the so-called Stoeber method).

The number-average particle size of the silicon-containing particles in the present invention is preferably 5 nm or more and 200 nm or less. By being in this range, low-temperature fixability is not impaired and good cracking and chipping prevention effects are observed during long-term use.

Next, we will explain colorants.

The toner of the present invention may contain a colorant as necessary. There are no particular limitations on the colorant, and the following known colorants may be used.

Yellow pigments include condensed azo compounds such as yellow iron oxide, navel yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartrazine lake, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following:

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

Orange pigments include the following:

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

Red pigments include condensed azo compounds such as red iron oxide, permanent red 4R, lithol red, pyrazolone red, watching red calcium salt, lake red C, lake D, brilliant carmine 6B, brilliant carmine 3B, eoxin lake, rhodamine lake B, and alizarin lake, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following.

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, 254.

Blue pigments include alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, fast sky blue, copper phthalocyanine compounds such as indanthrene blue BG and their derivatives, anthraquinone compounds, basic dye lake compounds, etc. Specific examples include the following:

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

Purple pigments include Fast Violet B and Methyl Violet Lake.

Green pigments include Pigment Green B, Malachite Green Lake, and Final Yellow Green G. White pigments include zinc oxide, titanium oxide, antimony white, and zinc sulfide.

Black pigments include carbon black, aniline black, non-magnetic ferrite, magnetite, and pigments toned to black using the above yellow, red, and blue colorants. These colorants can be used alone or in mixtures, or 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 to 15.0 parts by weight per 100.0 parts by weight of the binder resin.

Next, I'll explain about wax.

The toner of the present invention preferably uses a wax as necessary. Examples of wax include the following: aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, Fischer-Tropsch wax, and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; waxes mainly composed of fatty acid esters such as carnauba wax and montanic acid ester wax, and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax; saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and parinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bismuth acid, methyl methacrylate ... Examples of such waxes include saturated fatty acid bisamides such as stearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and hexamethylene bisstearic acid amide; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'dioleyl adipic acid amide, and N,N'dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bisstearic acid amide and N,N'distearyl isophthalic acid amide; fatty metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats. The waxes mentioned above can be used alone or in combination of two or more.

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

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

Next, we will explain the charge control agent.

The toner particles of the present invention may contain a charge control agent. Any known charge control agent can be used. In particular, charge control agents that have a high charging speed and can stably maintain a constant charge amount are preferred. Furthermore, when the toner particles are produced by a direct polymerization method, charge control agents that have low polymerization inhibition properties and are substantially free of solubilized substances in aqueous media are particularly preferred.

Examples of charge control agents that control toner particles to be negatively charged include the following:

Organometallic compounds and chelating compounds include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acid-based metal compounds. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides or esters, and phenol derivatives such as bisphenol. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, and calixarenes.

On the other hand, examples of charge control agents that control the toner particles to be positively charged include the following:

Nigrosine and nigrosine modifications such as fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts that are analogues of these, and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (lake forming agents include phosphotungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; resin-based charge control agents.

These charge control agents can be used alone or in combination of two or more. The amount of these charge control agents added is preferably 0.01 parts by weight or more and 10 parts by weight or less per 100 parts by weight of the binder resin.

Next, we will explain about external additives.

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

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

These inorganic fine particles are preferably surface-treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil, etc., to improve heat resistance storage property and environmental stability. The BET specific surface area of the external additive is preferably 10 ^m2 /g or more and 450 ^m2 /g or less.

The BET specific surface area can be determined by a low-temperature gas adsorption method using a dynamic constant pressure method according to the BET method (preferably the BET multipoint method). For example, a specific surface area measuring device (product name: Gemini 2375 Ver. 5.0, manufactured by Shimadzu Corporation) is used to adsorb nitrogen gas onto the surface of a sample, and the BET multipoint method is used to measure the BET specific surface area ( ^m2 /g).

The total amount of these various external additives added is preferably 0.05 parts by weight or more and 10 parts by weight or less, more preferably 0.1 parts by weight or more and 5 parts by weight or less, per 100 parts by weight of the toner particles. Also, various external additives may be used in combination.

Next, we will explain about the developer.

The toner of the present invention can be used as a magnetic or non-magnetic one-component developer, but it may also 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. Of these, it is preferable to use ferrite particles. As the carrier, coated carriers in which the surfaces of magnetic particles are coated with a coating agent such as resin, and resin dispersion carriers in which magnetic fine powder is dispersed in a binder resin, etc. may also 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, we will explain the toner particles and the method for producing the toner.

The toner particles can be manufactured by known means, and a kneading and grinding method or a wet manufacturing method can be used. Examples of wet manufacturing methods include the suspension polymerization method, the dissolution suspension method, the emulsion polymerization aggregation method, and the emulsion aggregation method. Among these, the suspension polymerization method and the kneading and grinding method are more preferable because they can efficiently cause silicon-containing particles in the toner particles to be present in the vicinity of the resin A.

Next, we will explain how to produce toner particles using the suspension polymerization method.

(Preparation 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), silicon-containing particles, and, if necessary, a wax, a colorant, a charge control agent, a crosslinking agent, a polymerization initiator, and other additives are uniformly dissolved or dispersed using a dispersing machine such as a ball mill or an ultrasonic dispersing machine to obtain a polymerizable monomer composition. Examples of the polymerizable monomer include those exemplified as the monomers forming the above-mentioned styrene-acrylic copolymer.

The silicon-containing particles and colorant may be dispersed in advance in a polymerizable monomer or organic solvent using a medium stirring mill or the like and then mixed with the other compositions, or may be dispersed after all of the compositions have been mixed.

The silicon-containing particles may be added alone, or they may be added by reusing toner particles that already contain silicon-containing particles as a raw material.

(Dispersion step (granulation step) of polymerizable monomer composition)
Next, the polymerizable monomer composition is poured into a previously prepared aqueous medium, and droplets of the polymerizable monomer composition are formed into a desired toner particle size using a stirrer or disperser having high shear force.

It is preferable that the aqueous medium in the granulation process contains a dispersion stabilizer in order to control the particle size of the toner particles, to sharpen the particle size distribution, and to suppress the coalescence of toner particles during the manufacturing process. Dispersion stabilizers are generally broadly divided into polymers that exhibit repulsive forces due to steric hindrance and poorly water-soluble inorganic compounds that stabilize dispersion by electrostatic repulsive forces. Fine particles of poorly water-soluble inorganic compounds are preferably used because they dissolve in acids or alkalis and can be easily removed by washing with acids or alkalis after polymerization. As dispersion stabilizers for poorly water-soluble inorganic compounds, those containing magnesium, calcium, barium, zinc, aluminum, or phosphorus are preferably used. More preferably, it is desirable to contain magnesium, calcium, aluminum, or phosphorus. Specific examples include the following.

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 using such poorly water-soluble inorganic dispersants, they may be used as is, but in order to obtain finer particles, the inorganic dispersant particles can be generated in an aqueous medium and then used. For example, in the case of tricalcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution can be mixed under high speed stirring to generate water-insoluble calcium phosphate, which enables a more uniform and finer dispersion.

The dispersion stabilizer may be used in combination with an organic compound, such as polyvinyl alcohol, gelatin, methyl cellulose, methylhydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, or starch. It is preferable to use 0.1 to 20.0 parts by mass of these dispersion stabilizers per 100 parts by mass of the polymerizable monomer.

Furthermore, in order to make these dispersion stabilizers finer, a surfactant may be used in an amount of 0.1 parts by mass to 10.0 parts by mass to 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 the granulation step is being carried out, the temperature is preferably set to 50° C. or more and 90° C. or less to polymerize the polymerizable monomers contained in the polymerizable monomer composition, thereby obtaining a toner particle dispersion.

In the polymerization step, it is preferable to carry out a stirring operation so that the temperature distribution in the vessel is uniform. When a polymerization initiator is added, it can be added at any timing and for any required time. In addition, the temperature may be raised in the latter half of the polymerization reaction in order to obtain the desired molecular weight distribution, and further, in order to remove unreacted polymerizable monomers, by-products, etc. from the system, a part of the aqueous medium may be distilled off by a distillation operation in the latter half of the reaction or after the reaction is completed. The distillation operation can be carried out under normal pressure or reduced pressure.

The polymerization initiator used in the suspension polymerization method is preferably one whose half-life during the polymerization reaction is 0.5 to 30 hours. Furthermore, when the polymerization reaction is carried out using an amount of 0.5 to 20 parts by mass added per 100 parts by mass of polymerizable monomer, a polymer having a maximum molecular weight between 5,000 and 50,000 can be obtained. Generally, an oil-soluble initiator is used as the polymerization initiator. Examples include the following.

Azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), and 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile; peroxide initiators such as acetylcyclohexylsulfonyl peroxide, diisopropyl peroxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, tert-butylperoxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, tert-butyl peroxypivalate, and cumene hydroperoxide.

If necessary, a water-soluble polymerization initiator may be used, such as the following:

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

These polymerization initiators can be used alone or in combination, and chain transfer agents, polymerization inhibitors, etc. can also be added to control the degree of polymerization of the polymerizable monomer.

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

Solid-liquid separation to obtain toner particles from the obtained toner particle dispersion can be performed by a general filtration method, and then, in order to remove foreign matter that has not been completely removed from the toner particle surface, it is preferable to perform further washing by reslurrying or washing with washing water. After sufficient washing, solid-liquid separation is performed again to obtain a toner cake. Thereafter, it is dried by a known drying means, and if necessary, particle groups having particle sizes other than the specified are separated by classification to obtain toner particles.

Next, we will explain an example of how toner particles are produced using the kneading and pulverizing method.

In the kneading and grinding method, first, a mixture containing a binder resin, resin A represented by the above formula (1), silicon-containing particles, and, if necessary, wax, a colorant, a charge control agent, and other additives is thoroughly mixed using a mixer such as a Henschel mixer or a ball mill. After that, the mixture is melt-kneaded using a thermal kneader such as a heated roll, kneader, or extruder to disperse or dissolve various materials to obtain a molten kneaded product, which is then passed through a cooling and solidifying process, a grinding process, a classification process, and, if necessary, a surface treatment process to obtain toner particles.

In the pulverization process, a known pulverization device such as a mechanical impact type or a jet type may be used. In addition, the order of the classification process and the surface treatment process does not matter.

(External Addition Process)
If necessary, an external additive may be added to the obtained toner particles. The external addition step is carried out by putting the external additive and the toner particles into a mixer equipped with a blade rotating at high speed and thoroughly mixing them.

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

The methods for measuring the various physical properties of the toner of the present invention are described below.

<Separation of toner and additives>
In the case of 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.

160 g of sucrose (Kishida Chemical) is added to 100 mL of ion-exchanged water and dissolved in a hot water bath to prepare a concentrated sucrose solution. 31 g of the concentrated sucrose solution and 6 mL of Contaminon N (a 10% aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a centrifuge tube (volume 50 mL) to prepare a dispersion. 1.0 g of toner is added to this dispersion, and the toner clumps are loosened with a spatula or the like.

The centrifuge tube is shaken in a shaker at 350 strokes per minute (spm) for 20 minutes. After shaking, the solution is transferred to a glass tube for a swing rotor (volume 50 mL) and separated in a centrifuge (H-9R, manufactured by Kokusan Co., Ltd.) at 3,500 rpm for 30 minutes. This operation separates the toner particles from the removed external additives. Visually check that the toner and aqueous solution are sufficiently separated, and collect the toner that has separated into the top layer with a spatula or the like. The collected toner is filtered with a vacuum filter and then dried in a dryer for at least 1 hour to obtain toner particles. This operation is carried out multiple times to obtain the required amount of toner particles.

<Extraction of Resin A represented by Formula (1) from Toner Particles>
The resin represented by formula (1) in the toner particles was extracted with tetrahydrofuran (THF) and separated by a solvent gradient elution method.

10.0 g of toner particles were weighed out, placed in a cylindrical filter paper (Toyo Roshi No. 86R) and placed in a Soxhlet extractor. Extraction was performed for 20 hours using 200 mL of THF as a solvent, and the solid obtained by removing the solvent from the extract is the THF-soluble fraction. The THF-soluble fraction contains a resin represented by formula (1). This was repeated multiple times to obtain the required amount of THF-soluble fraction.

For the solvent gradient elution method, gradient preparative HPLC (Shimadzu LC-20AP high pressure gradient preparative system, Waters SunFire preparative column 50 mm φ 250 mm) was used, and separation was performed at a flow rate of 50 ml/min. THF, chloroform, and toluene were appropriately selected as good solvents for the mobile phase, and acetonitrile, acetone, methanol, and n-hexane were appropriately selected as poor solvents. By repeating the solvent gradient elution as necessary, resin A represented by formula (1) was obtained.

<Method for measuring silicon concentration in resin A represented by formula (1)>
The content of silicon in resin A represented by formula (1) is measured using a wavelength dispersive X-ray fluorescence analyzer "Axios" (manufactured by PANalytical Co., Ltd.) and the accompanying dedicated software "SuperQ ver. 4.0F" (manufactured by PANalytical Co., Ltd.) for setting measurement conditions and analyzing measurement data. Note that 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.

The measurement sample is either resin A represented by formula (1) itself, or resin A extracted from toner particles using the extraction method described above.

Silica (SiO ₂ ) fine powder [product name: AEROSIL NAX50, specific surface area: 40±10, carbon content: 0.45-0.85%; manufactured by Nippon Aerosil Co., Ltd.] was added to 100.00 parts by mass of the measurement sample to make 0.50 parts by mass, and thoroughly mixed using a coffee mill. Similarly, silica fine powder was mixed with the measurement sample to make 5.00 parts by mass, 10.00 parts by mass, and 15.00 parts by mass, respectively, and these were used as samples for the calibration curve. The measurement pellets were prepared using a tablet molding compression machine "BRE-32" (manufactured by Maekawa Test Machinery Manufacturing Co., Ltd.). 4 g of the measurement sample was placed in a dedicated press aluminum ring, flattened, and pressed at 20 MPa for 60 seconds to obtain a measurement pellet molded to 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) of 109.08° when PET is used as the analyzing crystal is measured. In this case, the acceleration voltage and current value of the X-ray generator are 24 kV and 100 mA, respectively. A linear function calibration curve is obtained by plotting the obtained X-ray count rate on the vertical axis and the Si additive concentration in each calibration curve sample on the horizontal axis.

Next, similarly, measurement pellets are prepared for the measurement sample, and the count rate of the Si-Kα ray is measured. The silicon concentration (mass%) in the resin, expressed by formula (1), is then calculated from the obtained calibration curve.

<Identification of the Structure of Resin A Represented by Formula (1) (R ¹ to R ³ )>
The functional groups contained in resin A represented by formula (1) and the polymer moieties P ¹ , L ¹ , and R ¹ to R ³ in the structure represented by formula (1) are analyzed by ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR, and FT-IR. The measurement sample is resin A itself, or resin A extracted from toner particles by the above-mentioned extraction method.

When ^L1 contains an amide bond as represented by the formula (17), it can be identified by ^1H -NMR analysis. Specifically, it can be identified by the chemical shift value of the proton at the NH moiety of the amide group, and the amount of the amide group can be quantified by calculating the integral value.

Furthermore, when R ¹ to R ³ in the structure represented by formula (1) contain an alkoxy group or a hydroxy group, the valence of the alkoxy group or the hydroxy group relative to the silicon atom can be determined by the method shown in the "Measurement conditions for ²⁹ Si-NMR (solid)" described later.

( ^29Si -NMR (solid) measurement conditions)
Equipment: JEOL RESONANCE JNM-ECX500II
Sample tube: 3.2 mm diameter
Sample: Resin A represented by formula (1) 150 mg
Measurement temperature: room temperature Pulse mode: CP/MAS
Measurement nuclear frequency: 97.38MHz (29Si)
Reference substance: DSS (external standard: 1.534ppm)
Sample rotation speed: 10 kHz
Contact time: 10 ms
Delay time: 2s
Accumulation count: 8192

The abundance ratio of multiple silane components according to the number of oxygen atoms bonded to silicon can be determined by peak separation and integration using curve fitting. In this way, the number of alkoxy or hydroxy groups of R ¹ to R ³ of resin A represented by formula (1) can be confirmed.

<Confirmation of the Structure of Resin A Represented by Formula (1) ( ^P1 and ^L1 )>
The structures of P ¹ , L ¹ and R ¹ to R ³ in the resin represented by formula (1) can be confirmed by ¹³ C-NMR (solid) measurement. The measurement conditions are as follows.

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

(Measurement conditions for ¹ H-NMR analysis (solution))
Equipment: JEOL RESONANCE JNM-EX400
Sample tube: 3.2 mm diameter
Sample amount: 10 mg
Solvent: _CDCl3
Measurement temperature: room temperature Measurement frequency: 400MHz
Pulse condition: 5.0 μs
Frequency range: 10,500 Hz
Number of accumulations: 64 times. Various peaks are separated according to the types of P ¹ , L ¹ and R ¹ to R ³ in formula (1), and each is identified to determine the types of P ¹ , L ¹ and R ¹ to R ³ .

<Method for identifying organosilicon polymer having the structure of formula (3)>
To confirm the structure of the organosilicon polymer contained in the toner particles represented by formula (3), the organosilicon polymer represented by formula (3) itself can be used, or an organosilicon polymer extracted from the toner particles by the method described below can be used.

1 g of the toner particles collected by the method described above is placed in a vial, dissolved and dispersed in 31 g of chloroform, and treated for 30 minutes using an ultrasonic homogenizer to prepare a dispersion liquid.
Ultrasonic treatment device: Ultrasonic homogenizer VP-050 (manufactured by Taitec Co., Ltd.)
Microchip: Step type microchip, tip diameter φ2mm
Position of the tip of the microchip: at the center of the glass vial and at a height of 5 mm from the bottom of the vial. Ultrasonic conditions: intensity 30%, 30 minutes. During this time, ultrasonic waves are applied while cooling the vial with ice water so that the temperature of the dispersion liquid does not rise.

The dispersion is transferred to a glass tube (50 mL) for a swing rotor and centrifuged in a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.) at 58.33 S ^-1 for 30 minutes. After centrifugation, the organosilicon polymer particles are separated in the glass tube. These are extracted and dispersed again in 10 g of chloroform for washing, and the organosilicon polymer particles are separated using a centrifuge. After washing again, the extracted organosilicon polymer particles are vacuum dried (40°C/24 hours) to remove the chloroform, and a sample is prepared.

The weight of the obtained sample can be weighed to determine the content of organosilicon polymer particles in the toner particles.

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

(Measurement conditions)
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 (a tetrahydrofuran (THF)-insoluble portion of toner particles for NMR measurement) is placed in a sample tube having a diameter of 4 mm.

Using this method, the presence or absence of the alkyl group represented by R in formula (3) is confirmed. If a signal is confirmed, the structure of formula (3) is deemed to be "present."

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

(Method of measuring ^29Si -NMR (solid))
(Measurement conditions)
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 portion 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: 1.534ppm)
Observation width: 29.76kHz
Measurement method: DD/MAS, CP/MAS
²⁹ Si 90° Pulse width: 4.00 μs @ -1 dB
Contact time: 1.75ms to 10ms
Repeat time: 30s (DD/MASS), 10s (CP/MASS)
Number of times of integration: 2048 times LB value: 50 Hz

<Method for determining the number average particle size of silicon-containing particles>
The number average particle size of the silicon-containing particles is measured by scanning electron microscope (SEM) observation. The SEM observation method is as follows. Images taken with a Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation) are used. The image taking conditions for the S-4800 are as follows.

(1) Sample preparation A thin layer of conductive paste (TED PELLA, Inc., Product No. 16053, PELCO Colloidal Graphite, Isopropanol base) is applied to a sample stage (aluminum sample stage 15 mm x 6 mm), and the target sample is sprayed onto it. After removing excess sample from the sample stage with air blowing, platinum is evaporated at 15 mA for 15 seconds. The sample stage is set in the sample holder, and the sample stage height is adjusted to 30 mm using the sample height gauge.

(2) Setting the S-4800 observation conditions Inject liquid nitrogen into the anti-contamination trap attached to the S-4800 housing until it overflows, and leave it for 30 minutes. Start the S-4800's "PC-SEM" and perform flushing (cleaning the FE chip, which is the electron source). Click the accelerating voltage display area on the control panel on the screen, and press the [Flushing] button to open the flushing execution dialog. Check that the flushing intensity is 2, and execute it. Check that the emission current due to flushing is 20 to 40 μA. Insert the specimen holder into the specimen chamber of the S-4800 housing. Press [Origin] on the control panel to move the specimen 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], select the SE detector to [Down (L)], and switch to the mode for observing backscattered electron images. In the same [Basic] tab of the operation panel, set the probe current in the electron optical system condition block to [Normal], the focus mode to [UHR], and the WD to [8.0 mm]. Press the [ON] button on the acceleration voltage display on the control panel to apply the acceleration voltage.

(3) Focus adjustment Drag within the magnification display on the control panel to set the magnification to 5000 (5k). Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment once the image is in focus to a certain extent. Click [Align] on the control panel to display the alignment dialog and select [Beam]. Rotate the STIGMA/ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circle.

Next, select [Aperture] and turn the STIGMA/ALIGNMENT knobs (X, Y) one by one to stop the image movement or adjust it so that it moves as little as possible. Close the Aperture dialog and use autofocus to adjust the focus. Repeat this operation two more times to adjust the focus. With the midpoint of the maximum diameter of the observed particle aligned with the center of the measurement screen, drag within the magnification display section of the control panel to set the magnification to 10,000 (10k). Turn the focus knob [COARSE] on the operation panel to adjust the aperture alignment once the image is in focus to a certain extent. Click [Align] on the control panel to display the alignment dialog and select [Beam]. Turn the STIGMA/ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circle.

Next, select [Aperture] and turn the STIGMA/ALIGNMENT knobs (X, Y) one by one to stop the image movement or adjust it so that it moves as little as possible. Close the Aperture dialog and use autofocus to adjust the focus. After that, set the magnification to 100,000 (100k)x and adjust the focus using the focus knob and STIGMA/ALIGNMENT knob as above, then use autofocus to focus again. Repeat this operation to adjust the focus.

(4) Image storage Adjust the brightness in ABC mode, take a photo with a size of 640 x 480 pixels, and save it.

From the obtained SEM observation results, the number average particle size (D1) of 500 silicon-containing particles is calculated using 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. This operation is repeated several times to obtain the average value of 500 points, thereby calculating the number average particle size of the silicon-containing particles.

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

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

When calculating the molecular weight of the sample, a molecular weight calibration curve created using standard polystyrene resins (product names: "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

<Method for measuring the acid value of resin>
The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of a sample. The acid value of a resin is measured in accordance with JIS K 0070-1992, and specifically, is measured according to the following procedure.

(1) Preparation of Reagents 1.0 g of phenolphthalein was dissolved in 90 mL of ethyl alcohol (95% by volume), and ion-exchanged water was 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. Place in an alkali-resistant container to avoid contact with carbon dioxide, etc., and leave for 3 days. Filter to obtain potassium hydroxide solution. Store the resulting potassium hydroxide solution in an alkali-resistant container.

The factor of the potassium hydroxide solution is calculated by placing 25 mL of 0.1 mol/L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution, and then calculating the amount of potassium hydroxide solution required for neutralization. The 0.1 mol/L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

(2) Procedure (A) Main Test 2.0 g of the crushed sample is accurately weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene/ethanol (2:1) is added and dissolved over 5 hours. Then, several 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: A blank test is carried out in the same manner as above, except that no sample is used (i.e., only a mixed solution of toluene/ethanol (2:1) is used).

(3) The obtained result is substituted into the following formula to calculate the acid value.
A=[(CB)×f×5.61]/S
Here, A is the acid value (mg KOH/g), B is the amount of potassium hydroxide solution added for the blank test (ml), C is the amount of potassium hydroxide solution added for the main test (ml), f is the factor of the potassium hydroxide solution, and S is the mass of the sample (g).

<Method of measuring weight average particle diameter (D4)>
The weight average particle diameter (D4) of the toner particles is measured as follows.

The measuring device used is a precision particle size distribution measuring device using the pore electrical resistance method, the Coulter Counter Multisizer 3 (registered trademark, manufactured by Beckman Coulter, Inc.), equipped with a 100 μm aperture tube. The measurement conditions are set and the measurement data is analyzed using the accompanying dedicated software, Beckman Coulter Multisizer 3 Version 3.51 (manufactured by Beckman Coulter, Inc.). The measurement is performed using an effective measurement channel count of 25,000.

The aqueous electrolyte solution used for the measurements is one in which special grade sodium chloride is dissolved in ion-exchanged water to give a concentration of 1% by mass, for example "ISOTON II" (manufactured by Beckman Coulter).

Before performing measurements and analysis, configure the dedicated software as follows:

On the "Change Standard Measurement Method (SOM)" screen of the dedicated software, set the total count number in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman Coulter). Press the "Threshold/Noise Level Measurement Button" to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check "Flush aperture tube after measurement."

In the dedicated software's "Pulse to particle size conversion setting" screen, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Pour 200 mL of the electrolyte solution into a 250 mL round-bottom glass beaker made exclusively for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, remove dirt and air bubbles from inside the aperture tube using the "Aperture Tube Flush" function of the dedicated software.
(2) 30 mL of the aqueous electrolyte solution is placed in a 100 mL flat-bottom glass beaker, and 0.3 mL of a dilution of "Contaminon N" (a 10% aqueous solution of a neutral detergent for cleaning precision measuring instruments with a pH of 7, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted 3 times by mass with ion-exchanged water is added as a dispersant.
(3) Prepare an ultrasonic disperser "Ultrasonic Dispersion System Tetorara 150" (manufactured by Nikkaki Bios Co., Ltd.) that has two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees and an electrical output of 120 W. Place 3.3 L of ion-exchanged water in the water tank of the ultrasonic disperser, and add 2 mL of Contaminon N to this water tank.
(4) The beaker from (2) 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 surface of the electrolyte solution in the beaker is maximized.
(5) While the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, 10 mg of toner particles are added little by little to the electrolyte solution and dispersed. Then, ultrasonic dispersion treatment is continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10°C or higher and 40°C or lower.
(6) The electrolyte solution (5) in which the toner particles are dispersed is dropped into the round-bottom beaker (1) placed in the sample stand using a pipette to adjust the measurement concentration to 5%. Then, measurements are continued until the number of particles measured reaches 50,000.
(7) The measurement data is analyzed using dedicated software that comes with the device, and the weight-average particle diameter (D4) is calculated. Note that when the dedicated software is set to Graph/Volume%, the "Average diameter" on the "Analysis/Volume Statistics (Arithmetic Mean)" screen is the weight-average particle diameter (D4).

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Example 18 is a reference example. In the examples and comparative examples, the "parts" of each material are all based on mass unless otherwise specified.

<Production Example of Polyester Resin (a-1)>
Polyester resin (a-1) was synthesized according to the following procedure.

The following materials were charged into an autoclave equipped with a pressure reducing device, a water separating device, a nitrogen gas introducing device, a temperature measuring device, and a stirrer, and a reaction was carried out under a nitrogen atmosphere at normal pressure and 200° C. for 5 hours.
Bisphenol A-propylene oxide 2.1 mol adduct: 39.6 parts Terephthalic acid: 8.0 parts Isophthalic acid: 7.6 parts Tetrabutoxy titanate: 0.1 part Thereafter, 0.01 part of trimellitic acid and 0.12 part of tetrabutoxy titanate were added and reacted at 220° C. for 3 hours, and further reacted under a reduced pressure of 10 to 20 mmHg for 2 hours to obtain polyester resin (a-1).

The acid value of the resulting polyester resin (a-1) was 6.1 and Mw was 10,200.

<Production Example of Styrene Acrylic Resin (a-2)>
Styrene-acrylic resin (a-2) was synthesized according to the following procedure.

100.0 parts of propylene glycol monomethyl ether was heated while replacing with nitrogen, and refluxed at a liquid temperature of 120°C or higher. A mixture of 83.4 parts of styrene, 20.9 parts of butyl acrylate, 1.0 part of acrylic acid, and 0.6 parts of tert-butyl peroxybenzoate [manufactured by NOF Corp., product name: Perbutyl Z] as a polymerization initiator was added dropwise to the mixture over 3 hours. After the addition was completed, the solution was stirred for 3 hours, and then distilled at normal 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 solvent was removed by distillation for 1 hour to obtain a resin solid. The resin solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was filtered to obtain a styrene acrylic resin (a-2).

The acid value of the resulting styrene acrylic resin (a-2) was 10.6 and Mw was 13,000.

<Production Example of Resin A (A-1) Represented by Formula (1)>
Resin A (A-1) represented by formula (1) was synthesized according to the following procedure.

50.00 parts of polyester resin (a-1) was dissolved in 200.00 parts of N,N-dimethylacetamide, and 1.20 parts of 3-aminopropyltriethoxysilane and 1.70 parts of triethylamine as silane compounds and 1.70 parts of DMT-MM (4-(4,4-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride) as condensation agents were added, and the mixture was stirred at room temperature for 5 hours. After the reaction was completed, the solution was dropped into methanol, reprecipitated, and filtered to obtain resin A (A-1) represented by formula (1). The weight average molecular weight Mw of the resin A (A-1) represented by formula (1) obtained above was 10,400. The physical properties of the resin A (A-1) represented by formula (1) obtained above are shown in Table 2.

<Production Example of Resin A (A-2) Represented by Formula (1)>
Resin A (A-2) represented by formula (1) was obtained in the same manner as in the synthesis of Resin A (A-1) represented by formula (1) above, except that the silane compound was changed as shown in Table 1. The physical properties are shown in Table 2.

<Production Example of Resin A (A-3) Represented by Formula (1)>
A solution of 10.0 parts of resin A (A-1) represented by the formula (1) in 90.0 parts of toluene was mixed with 400.0 parts of pure water and stirred, the pH was adjusted to 4.0 using dilute hydrochloric acid, and the mixture was stirred at room temperature for 10.8 hours. The stirring was then stopped and the mixture was transferred to a separatory funnel to extract the oil phase. The oil phase was concentrated and reprecipitated with methanol to obtain resin A (A-3) represented by the formula (1).

The resin A (A-3) represented by the formula (1) thus obtained was analyzed by ²⁹ Si-NMR (solid) measurement, which revealed that R ¹ to R ³ in the formula (1) were all hydroxy groups. The physical properties are shown in Table 2.

<Production Example of Resin A (A-4) Represented by Formula (1)>
Resin A (A-4) represented by formula (1) was synthesized according to the following procedure.

50.00 parts of polyester resin (a-1) was dissolved in 500.00 parts of chloroform, and 1.30 parts of 3-isocyanatepropyltriethoxysilane and 0.50 parts of titanium (IV) tetraisopropoxide were added under a nitrogen atmosphere, followed by stirring at room temperature for 5 hours. After the reaction was completed, the solution was dropped into methanol for reprecipitation and filtration to obtain resin A (A-4) represented by formula (1). The physical properties are shown in Table 2.

<Production Example of Resin A (A-5) Represented by Formula (1)>
Resin A (A-5) represented by formula (1) was obtained in the same manner as in the synthesis of Resin A (A-1) represented by formula (1) above, except that polyester resin (a-1) was replaced with styrene acrylic resin (a-2). Its physical properties are shown in Table 2.

<Production Example of Resin A (A-6) Represented by Formula (1)>
Resin A (A-6) represented by formula (1) was obtained in which a linking group represented by the following formula (19) or formula (20) was formed by an insertion reaction of an epoxy group in an epoxysilane with an ester bond in a polyester resin (a-1).

50.0 parts of the polyester resin (A-2) was dissolved in 100.0 parts of anisole, and 2.90 parts of 5,6-epoxyhexyltrimethoxysilane and 10.00 parts of tetrabutylphosphonium bromide were added under a nitrogen atmosphere, followed by stirring at 140°C for 5 hours. After cooling, the reaction mixture was dissolved in 200 ml of chloroform, dropped into methanol, reprecipitated, and filtered to obtain resin A (A-6). The physical properties are shown in Table 2.

<Synthesis of Comparative Resin>
As a comparative resin for resin A, polyester resin (a-1) was used as 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 formula (17), (*) represents a bonding site to ^P1 in formula (1), and (**) represents a bonding site to the silicon atom in 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 formula (18), (*) represents the bonding site to ^P1 in formula (1), and (**) represents the bonding site to the silicon atom in 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 formulas (19) and (20), (*) represents a bonding site to ^P1 in formula (1), and (**) represents a bonding site to the silicon atom in formula (1).]

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

<Preparation Example of Organosilicon Polymer Particle 1 Represented by Formula (3)>
Organosilicon polymer particles 1 represented by formula (3) were synthesized according to the following procedure.

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

Meanwhile, 1,620 parts of water was placed in a container equipped with a stirrer and heated to 70°C in a warm bath, after which 1.0 mol/L sodium hydroxide solution was added to adjust the pH to 9.0. The above hydrolysis solution was added over 1 hour, and the mixture was maintained at 70°C for 1 hour to carry out condensation polymerization. After that, 0.1 mol/L sodium hydroxide solution was gradually added to adjust the pH to 10.5, and condensation polymerization was carried out at 70°C for an additional 3 hours to obtain a dispersion of organosilicon polymer particles 1.

The resulting dispersion of organosilicon polymer particles 1 was centrifuged to remove coarse particles, and then filtered, washed, and dried to obtain organosilicon polymer particles 1.

The number average particle size of organosilicon polymer particles 1 was 40 nm. The results of organosilicon polymer particles 1 are shown in Table 3.

<Production Examples of Organosilicon Polymer Particles 2 and 3 Represented by Formula (3)>
Organosilicon polymer particles 2 and 3 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except for the changes 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

The silica particles used were those shown in Table 4 below.

<Production of Toner Particle 1>
In a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 390.0 parts of ion-exchanged water and 14.0 parts of sodium phosphate (12-hydrate) [manufactured by Rasa Kogyo Co., Ltd.] were charged, and the mixture was kept warm at 65°C for 1.0 hours while purging with nitrogen. Next, a calcium chloride aqueous solution in which 9.2 parts of calcium chloride (dihydrate) was dissolved in 10.0 parts of ion-exchanged water was charged all at once using a T.K. homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) while stirring at 12,000 rpm, to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, hydrochloric acid was charged into the aqueous medium, and the pH was adjusted to 6.0, to obtain aqueous medium 1.

On the other hand, the following materials were charged into an attritor (manufactured by Nippon Coke & Engineering Co., Ltd.), and then zirconia particles having a diameter of 1.7 mm were added and dispersed at 220 rpm for 5.0 hours. After that, the zirconia particles were removed, and dispersion liquid 1 in which a colorant was dispersed was prepared.
Styrene 60.0 parts Colorant (C.I. 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 Organosilicon polymer particles 1 0.2 parts Divinylbenzene 0.3 parts Wax (Fischer-Tropsch wax, melting point: 78°C) 3.0 parts Wax (ethylene glycol distearate) 10.0 parts This was kept at 65°C and uniformly dissolved and dispersed at 500 rpm using a T.K. homomixer to prepare polymerizable monomer composition 1.

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 added to the aqueous medium 1, and 9.0 parts of t-butyl peroxypivalate was added as a polymerization initiator. Granulation was continued for 10 minutes while maintaining the stirring device at 12,000 rpm.

The stirring device was replaced with a stirrer equipped with a propeller stirring blade, and polymerization was carried out for 5.0 hours while stirring at 150 rpm and maintaining the temperature at 72°C, and then the temperature was raised to 85°C and maintained at this temperature for 2.0 hours.

The reflux tube of the reaction vessel was replaced with a cooling tube, and the slurry was heated to 100°C. Distillation was carried out for 6 hours to remove the unreacted polymerizable monomer, and toner particle dispersion 1 was obtained.

Hydrochloric acid was added to the obtained toner particle dispersion liquid 1 to adjust the pH to 1.4 or less, and the dispersion stabilizer was dissolved. The mixture was then filtered, washed, dried, and classified to obtain toner particles 1.

<Production Examples of Toner Particles 2 to 4, and 6 to 23>
Toner particles 2 to 4 and 6 to 23 were obtained in the same manner as in the production example of toner particle 1, except that the resin A represented by formula (1) and the silicon compound-containing particles were changed as shown in Table 5 below.

The physical properties of the resulting toner particles 2 to 4 and 6 to 23 are shown in Table 5.

<Production Example of Toner Particle 5>
Preparation of binder resin: 1200 parts of bisphenol A-propylene oxide 2.2 mol adduct, 475 parts of bisphenol A-ethylene oxide 2.2 mol adduct, 250 parts of terephthalic acid, 190 parts of trimellitic anhydride, 290 parts of fumaric acid, and 0.1 parts of dibutyltin oxide were placed in a 4-liter 4-neck glass flask, and a thermometer, a stirring rod, a condenser, and a nitrogen inlet tube were attached, and the flask was placed in a mantle heater. The mixture was reacted at 220° C. for 5 hours under a nitrogen atmosphere to obtain a binder resin. Next,
The binder resin was 100.0 parts, colorant (C.I. Pigment Blue 15:3) was 6.5 parts, resin A (A-1) was 4.0 parts, organosilicon polymer particles 1 was 0.2 parts, wax (Fischer-Tropsch wax, melting point: 78°C) was 3.0 parts, wax (ethylene glycol distearate) was 10.0 parts, and the toner materials were thoroughly premixed using a Henschel mixer, melted and kneaded using a twin-screw extruder, cooled, and then coarsely pulverized to a particle size of about 1 to 2 mm using a hammer mill. The particles were then finely pulverized using an air jet type fine pulverizer. The finely pulverized material was further classified using a multi-division classifier to obtain toner particles 5.

[Examples 1 to 18 and Comparative Examples 1 to 5]
<Production of Toners 1 to 18 and Comparative Toners 19 to 23>
100.0 parts of each of the obtained toner particles 1 to 23 was mixed with 0.8 parts of silica fine particles (hydrophobized with hexamethyldisilazane, number average particle size of primary particles: 8 nm, BET specific surface area: 160 m ² /g) in a Henschel mixer (manufactured by Mitsui Miike Chemical Engineering Co., Ltd.).

After the above mixing process, the mixture was sieved through a 200 μm mesh to obtain toners 1 to 18 and comparative toners 19 to 23. The physical properties of the obtained toners are shown in Table 5.

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

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

An image forming device (LBP712Ci (Canon)) was prepared, the toner was removed from the cyan cartridge, and the toner to be evaluated was filled in its place. Evaluations were also performed by installing dummy cartridges.

The process speed was set to 240 mm/s in cyan monochrome mode. 500 copies of the letter "E" (image printing rate 1%) were printed out in intermittent printing mode (2-second pause after every two copies).

The cyan cartridge was removed, and the developing roller was removed. The newly prepared toner and developing roller were then removed from the cyan cartridge, and the developing roller that had been removed earlier was then attached.

Next, we modified the image forming device so that it could output images even if the toner was not loaded.

This creates a condition in which the toner coated on the developing roller is repeatedly rubbed by the developing blade.

After the toner on the developing member was rubbed with this cartridge for a number of prints equivalent to 150 sheets, the developing member was removed and air was 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/ ^m2 ).

The density of this tape was measured at five points, and the average value was used as an index of the degree of component contamination. Color measurements were performed using a "504 Spectrodensitometer" (manufactured by X-Rite Corporation) to measure image density, with the standard value of 0.00 being the value when the developing roller was not taped. The results are shown in Table 6.

(Evaluation Criteria)
A: The density difference from the standard is less than 0.050. B: The density difference from the standard is 0.050 or more and less than 0.100. C: The density difference from the standard is 0.100 or more and less than 0.200. D: The density difference from the standard is 0.200 or more.

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

An image forming apparatus (LBP712Ci (Canon)) was prepared, the toner was removed from the cyan cartridge, and the toner to be evaluated was filled in its place.

Next, an unfixed toner image (toner loading: 0.9 mg/cm ² ) measuring 2.0 cm length and 15.0 cm width was formed on an image receiving paper (HP Laser Jet 90, manufactured by HP, 90 g/m ² ) at a position 1.0 cm from the upper end in the paper feed direction.

Next, the removed fixing unit was modified to allow adjustment of the fixing temperature and process speed, and this was used to conduct a fixing test of an unfixed image.

First, in a normal temperature and humidity environment (23°C/relative humidity 60%), the process speed was set to 300 m/s, and the initial temperature was 120°C, with the set temperature being raised in increments of 2°C, while the unfixed image was fixed at each temperature.

The evaluation criteria for low temperature fixation are as follows:

The low-temperature fixing start point is the lowest temperature at which the low-temperature offset phenomenon (where part of the toner adheres to the fixing device) is not observed. The results are shown in Table 6.

(Evaluation Criteria)
A: The low-temperature side fixing start point is less than 140° C. B: The low-temperature side fixing start point is 140° C. or more and less than 150° C. C: The low-temperature side fixing start point is 150° C. or more and less than 160° C. D: The 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, the toner was removed from the cyan cartridge, and the toner to be evaluated was filled in place of the cyan cartridge.

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

The image to be evaluated is a line image. By increasing the amount of toner on the image by varying the development bias and setting a high image density, and by using thick paper with a large surface unevenness, the toner in the recesses of the paper and in the lower part of the toner layer is less likely to melt during the fixing process, allowing for a strict evaluation of peeling.

First, the image forming device was left overnight in a low-temperature, low-humidity environment (15°C, 10% RH). If the evaluation environment is low, the fixing unit will not warm up easily, resulting in a strict evaluation.

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

(Evaluation Criteria)
A: No defects B: Slight defects are visible, but not visible to the naked eye C: Slight defects are visible to the naked eye D: Defects are visible to the naked eye, and there are broken lines

Claims (8)

A toner containing toner particles, the toner particles containing a binder resin, a resin A, and silicon,
The resin A has a structure represented by the following formula (1) :
The toner is characterized in that the silicon-containing particles are at least one selected from the group consisting of silica and organosilicon polymers.

(In formula (1), P1 ^represents a polymer moiety, L1 ^represents a divalent linking group having a structure represented by formula (17) or a structure represented by formula (18), R1 ^to R3 ^each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group or a hydroxyl group, m represents a positive integer, and when m is 2 or more, a plurality of L1 ^'s , a plurality of R1 ^'s , a plurality of R2 ^'s and a plurality of R3 ^'s may be the same or different.)

[ ^R5 in formula (17) represents an alkylene group, an arylene group, or an alkylene group containing an -NH- group. (*) represents the bonding site to ^P1 in formula (1) , and (**) represents the bonding site to the silicon atom in formula (1)]

[ ^R6 in formula (18) represents an alkylene group or an arylene group. (*) represents a bonding site to ^P1 in formula (1) , and (**) represents a bonding site to the silicon atom in formula (1)] The toner according to claim 1 , wherein the content of the resin A in the toner particles is from 0.1% by mass to 10.0% by mass. 3. The toner according to claim 1, wherein P ¹ in the formula (1) is a polyester moiety. 4. The toner according to claim 1, wherein at least one of R ¹ to R ³ in the formula (1) is an alkoxy group or a hydroxy group. 5. The toner according to claim 1, wherein the silicon-containing particles are present in an amount of 0.040% by mass or more and 0.800% by mass or less based on the toner particles. 6. The toner according to claim 1, wherein the silicon-containing particles are an 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 to 4 carbon atoms.) A method for producing the toner according to any one of claims 1 to 6 ,
A toner manufacturing method comprising the steps of: dispersing the resin A, the silicon-containing particles, and a polymerizable monomer composition containing a polymerizable monomer in an aqueous medium; forming particles of the polymerizable monomer composition in the aqueous medium; and polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition. A method for producing the toner according to any one of claims 1 to 6 ,
A method for producing a toner, comprising the steps of melt-kneading a mixture containing a binder resin, the resin A, and the silicon-containing particles to obtain a melt-kneaded product, and pulverizing the melt-kneaded product to obtain a pulverized product.