JP7844239B2 - toner - Google Patents

Description

This invention relates to toner used in electrophotography, electrostatic recording, magnetic recording, and the like.

In recent years, electrophotographic image forming devices such as laser beam printers (LBPs) and photocopiers have been increasingly required to achieve higher printing speeds and greater energy efficiency.
Therefore, the toner, which is a developer, also needs to be addressed in the same way as above. Specifically, the importance of low-temperature fixing performance, which allows for fixing with less heat, is increasing year by year.
To achieve this, the addition of plasticizers to the main binder of toner has been widely practiced. Specifically, plasticizers are crystalline molecules such as hydrocarbon waxes and crystalline resins such as crystalline polyesters. Crystalline polyesters, in particular, which have a higher molecular weight than low molecular weight plasticizers, are currently widely used because they cause fewer problems such as bleeding (Patent Document 1).
However, since the toner softens after the plasticizer melts and then plasticizes the binder resin, there is a limit to the toner's melting speed, and further improvements in low-temperature fixation are desired.
Therefore, methods using crystalline resins as the main binder are being considered. When considered as a binder resin, crystalline resins have the property that they hardly soften at temperatures below their melting point due to the regular arrangement of their molecular chains. Furthermore, above the melting point, the crystals melt rapidly, resulting in a rapid decrease in viscosity. For this reason, they are attracting attention as materials that exhibit excellent sharp melt properties and low-temperature fixability.
However, as the amount of crystalline resin components increased in pursuit of even better low-temperature fixing performance, the deterioration of hot offset due to the low elasticity of the crystalline resin during melting, and the non-uniformity of gloss on rough paper with greater irregularities, became challenges.
To address these challenges, there is a conventional method of adding and increasing the amount of polymerizable crosslinking agents to increase the amount of gel components that exhibit high elasticity (Patent Document 2).

Patent No. 4192717 Japanese Patent Publication No. 2018-151619

However, as described in Patent Document 2 above, increasing the degree of crosslinking of the gel leads to a problem of decreased compatibility with other binder components. As a result, it tends to separate other low-viscosity components, limiting the effectiveness of improving hot offset and gloss non-uniformity, and also hindering low-temperature fixation.
The objective of the present invention is to solve the above problems and provide a toner that exhibits better low-temperature fixing performance than conventional toners, while also having excellent resistance to hot offset printing and gloss uniformity on rough paper.

The present invention relates to a toner having toner particles containing resin A as a binder resin,
The aforementioned resin A has a structure represented by the following formula (5) :

In formula (5) above, n represents an integer between 1 and 10,
In formula (5) above, X independently represents a hydrogen atom, a hydroxyl group, an alkoxyl group, or an alkyl group.
In formula (5) above, A contains 30% by mass or more of unit (a) represented by the following formula (1) ,

In formula (1) above, R1 _represents a hydrogen atom or a methyl group.
In formula (1) above, L1 _represents a single bond, an ester bond, or an amide bond.
In formula (1) above, m represents an integer between 15 and 30,
The content of resin A in the toner, based on the mass of the toner, is 20.0% by mass or more and 100.0% by mass or less.
In the viscoelasticity measurement of the toner, when the temperature at which the storage modulus G' of the toner is 1.0 × 10⁷ ^Pa is defined as T1 [°C], the ratio of the loss modulus G'' of the toner at temperature T1 [°C] to the storage modulus G' (tanδ) is defined as tanδ(T1), and the ratio of the loss modulus G'' of the toner at temperature T1-10 [°C] to the storage modulus G' (tanδ) is defined as tanδ(T1-10), the toner satisfies the following equations (2) to (4):
50.0 ≤ T1 ≤ 70.0 (2)
0.30≦tanδ(T1)≦1.00 (3)
1.00≦tanδ(T1)/tanδ(T1-10)≦1.90 (4)
The toner contains THF-insoluble components,
The THF-insoluble portion includes the structure represented by formula (5) of the resin A,
Using a PerkinElmer TGA7 thermal analyzer, the THF-insoluble matter was heated from 50°C to 900°C at a heating rate of 25°C/min, and the reduced mass of silicon was taken as the mass of silicon derived from the siloxane structure in the structure represented by formula (5). In this case, the mass of silicon derived from the siloxane structure was 0.005% or more and 0.150% or less of the THF-insoluble matter.
This toner has the following characteristics.

According to the present invention, it is possible to provide a toner that exhibits superior low-temperature fixing performance compared to conventional toners, while also providing excellent resistance to hot offset printing and gloss uniformity on rough paper.

This is a schematic diagram of a measurement sample and jig for measuring viscoelasticity.

In this disclosure, unless otherwise specified, the expressions "XX or greater and YY or less" or "XX to YY" refer to a numerical range that includes the lower and upper limits.

(Meth)acrylic acid ester refers to acrylic acid esters and/or methacrylic acid esters.

When numerical ranges are listed in steps, the upper and lower limits of each range can be combined in any way.

A "monomer unit" refers to the reacted form of monomer substances within a polymer. For example, one carbon-carbon bond in the main chain formed by the polymerization of polymerizable monomers in a polymer is considered one unit. A polymerizable monomer can be represented by the following formula (7).

[In formula (7), _RA represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and _RB represents any substituent.]

Crystalline resins are resins that exhibit a clear endothermic peak in differential scanning calorimeter (DSC) measurements.

[Features of the present invention]
The present invention relates to a toner having toner particles containing resin A as a binder resin,
The aforementioned resin A is
(i) Contains 30% by mass or more of the unit (a) shown in the following formula (1):

[In formula (1), R ₁ represents a hydrogen atom or a methyl group, L ₁ represents a single bond, an ester bond, or an amide bond, and m represents an integer between 15 and 30.]
(ii) The content, based on the mass of the toner, is 20.0% by mass or more and 100.0% by mass or less.
In the viscoelasticity measurement of the toner, when the temperature at which the storage modulus G' is 1.0 × ^10⁷ Pa is defined as T1 [°C], and the ratio of the loss modulus G'' at temperature T1 [°C] to the storage modulus G' (tanδ) is defined as tanδ(T1), and the tanδ at temperature T1-10 [°C] is defined as tanδ(T1-10), the following equations (2) to (4) are satisfied.
50.0 ≤ T1 ≤ 70.0 (2)
0.30≦tanδ(T1)≦1.00 (3)
1.00≦tanδ(T1)/tanδ(T1-10)≦1.90 (4)
The toner contains THF-insoluble components, and the THF-insoluble components have a structure represented by the following formula (5):

In formula (5), A independently represents resin A, n is an integer between 1 and 10, and X independently represents a hydrogen atom, a hydroxyl group, an alkoxyl group, or an alkyl group, and the mass of silicon derived from the siloxane structural site, as measured by the method described below, is 0.005% or more and 0.150% or less of the THF insoluble content.
[Using a PerkinElmer TGA7 thermal analyzer, the THF-insoluble components are heated from 50°C to 900°C at a heating rate of 25°C/min, and the reduced amount of Si is considered to be the Si mass derived from the siloxane structure.]

The toner is characterized in that the resin A has a structure represented by formula (5).

According to the inventors' research, the above-mentioned toner provides a toner that exhibits superior low-temperature fixing performance compared to conventional toners, while also offering excellent resistance to hot offset printing and uniform gloss on rough paper.

The details are explained below.

In order to achieve low-temperature fixation while suppressing drawbacks such as poor storage properties, it is necessary that the storage modulus is high up to the temperature required for heat-resistant storage, and then rapidly decreases at temperatures above that, i.e., exhibits sharp melt properties.

Furthermore, generally, the ratio of the loss modulus G'' to the storage modulus G' (tanδ) represents the ease of deformation of a polymer material, indicating whether it exhibits strong elastic or viscous properties. A smaller tanδ results in less deformation, making it more "rubber-like," while a larger tanδ results in greater deformation, making it more "gum-like." Therefore, by appropriately controlling the change in tanδ in the sharp-melting temperature range, the ease of toner deformation during low-temperature fixing can be controlled, thereby ensuring the gloss uniformity of the toner.

However, the above configuration was insufficient when seeking lower-temperature fixing performance than conventional methods. Furthermore, as the toner becomes more prone to melting with the pursuit of lower-temperature fixing, countermeasures against hot offset were essential. Therefore, the inventors discovered that the above problems could be solved by introducing a siloxane bonding site into the THF-insoluble component (gel component), which is the highly elastic part of the toner resin.

Conventionally, to improve the high-temperature elasticity of toner, the addition of crosslinking agent monomers was common. This increases the gel content, which consists of highly crosslinked areas, thereby improving the high-temperature elasticity of the toner.

However, when the gel component is highly crosslinked, it tends to separate from other resin components, and even with large amounts of addition, its effect tends to saturate. The presence of separated, low-elasticity components ultimately causes hot offset and gloss non-uniformity. Furthermore, this method had many drawbacks, such as inhibited low-temperature fixation.

Therefore, the inventors attempted to solve the above problem by introducing siloxane bonding sites into the gel resin in order to impart high elasticity and suppress the separation of the gel component from other resin components. This creates a large-scale gel structure in which gel domains are loosely bonded by generating affinity between siloxane bonding sites with different polarities relative to the carbon-based structure of the surrounding resin. This is expected to impart high elasticity to the toner without hindering low-temperature fixation, thereby improving hot offset and gloss uniformity.

The mechanism is thought to be due to the weak interaction between siloxane bond sites, which allows other resin components to be incorporated within a large gel structure. This makes it possible to impart high elasticity, similar to that achieved by increasing the crosslinking density using conventional techniques, without promoting separation of the gel from other resin components.

[Configuration of the toner of the present invention]
The present invention will be described in detail below.

The toner of the present invention contains resin A, and from the viewpoint of low-temperature fixation, it is necessary that resin A contains 30% by mass or more of unit (a) shown in the following formula (1). If it is less than 30% by mass, the low-temperature fixation will be insufficient.

[In formula (1), R ₁ represents a hydrogen atom or a methyl group, L ₁ represents a single bond, an ester bond, or an amide bond, and m represents an integer between 15 and 30.]

Furthermore, from the viewpoint of low-temperature fixation, the content of resin A, based on the mass of the toner, must be 20.0% by mass or more. If it is less than 20.0% by mass, low-temperature fixation will be insufficient. Preferably, the content of resin A is between 25.0% by mass and 85.0% by mass.

In the viscoelasticity measurement of toner, the present invention satisfies the following equation (2) when T1 [°C] is the temperature at which the storage modulus G' is 1.0 × ^10⁷ Pa, tanδ(T1) is the ratio (tanδ) of the loss modulus G'' at temperature T1 [°C] to the storage modulus G', and tanδ(T1-10) is the ratio at temperature T1-10 [°C].
50.0 ≤ T1 ≤ 70.0 (2)

Satisfying equation (2) results in good low-temperature fixing performance of the toner. While a T1 temperature below 50.0°C is advantageous for low-temperature fixing, it can lead to drawbacks such as reduced heat resistance during storage. Conversely, a T1 temperature above 70.0°C reduces low-temperature fixing performance.

T1 can be controlled by the length of the long-chain alkyl group and the proportion of the long-chain alkyl group in the binder resin when the crystalline resin in the toner is a vinyl resin with long-chain alkyl groups. When the crystalline resin is a polyester resin, T1 can be controlled by the number of carbon atoms in the diol and dicarboxylic acid components used.

Furthermore, the present invention satisfies the following formulas (3) and (4).
0.30≦tanδ(T1)≦1.00 (3)
1.00≦tanδ(T1)/tanδ(T1-10)≦1.90 (4)

Since T1 is the temperature during sharp melting, the fact that tanδ(T1) is within the range of equation (3) above ensures that the toner's deformability during low-temperature fixing is appropriately maintained. Combined with the gel component containing siloxane bonds described later, it is possible to enhance gloss on rough paper.

Furthermore, when tanδ(T1)/tanδ(T1-10) is within the range of formula (4) above, together with the gel component containing siloxane bonds described later, the ease of deformation in the convex and concave areas of the rough paper remains within a certain range, improving gloss uniformity.

If tanδ(T1) is less than 0.30, the elastic properties become too large during low-temperature fixing, resulting in a decrease in gloss on rough paper. Conversely, if it is greater than 1.00, the viscous properties become too large during low-temperature fixing, causing the toner to penetrate the paper more easily, thus worsening gloss uniformity.

tanδ(T1) can be controlled by the amount of crystalline resin added to the toner. In particular, when the crystalline resin is a vinyl resin with long-chain alkyl groups, it can be controlled by the length of the long-chain alkyl groups and the proportion of long-chain alkyl groups in the binder resin. It can also be controlled by the type and amount of crosslinking agent added during toner manufacturing.

Furthermore, if tanδ(T1)/tanδ(T1-10) is less than 1.00, deformation becomes less likely even with sharp melting, reducing the abrasion resistance of the fixed image. If tanδ(T1)/tanδ(T1-10) is greater than 1.90, the toner rapidly changes from elastic to viscous properties near the melting start temperature, making convex areas more prone to deformation and concave areas more resistant to deformation during low-temperature fixing. As a result, gloss uniformity deteriorates.

The tanδ(T1)/tanδ(T1-10) ratio can be controlled by the type and amount of amorphous resin used in the toner.

The toner of the present invention contains THF-insoluble components, and these THF-insoluble components have a structure represented by the following formula (5):

In formula (5), A independently represents resin A, n is an integer between 1 and 10, and X independently represents a hydrogen atom, a hydroxyl group, an alkoxyl group, or an alkyl group. Furthermore, the mass of silicon derived from the siloxane structural moiety, as measured by the method described below, is between 0.005% by mass and 0.150% by mass of the THF-insoluble content.

The method for measuring the silicon mass involves using a PerkinElmer TGA7 thermal analyzer to heat the THF-insoluble portion from 50°C to 900°C at a heating rate of 25°C/min. The amount of Si that decreases is considered to be the Si mass derived from the siloxane structure.

The THF-insoluble components possess the structure of formula (5), which allows the aforementioned siloxane structural sites to exhibit affinity, forming a loose gel structure that includes non-gel components. This enables simultaneous achievement of low-temperature fixation, hot-off resistance, and gloss uniformity on rough paper.

If the siloxane structural portion is less than 0.005% by mass (calculated by silicon weight), the loose gel structure described above cannot be formed due to the insufficient amount of siloxane structural portion, making it difficult to achieve hot offset resistance and gloss uniformity. Conversely, if it is more than 0.150% by mass, the increased amount of siloxane structural portion leads to aggregation and domainization, making it difficult to form a loose gel structure.

In this invention, the resin A has a structure represented by formula (5). This suppresses the separation of the gel component from the other resin components, making it possible to achieve low-temperature fixation, hot offset resistance, and gloss uniformity simultaneously.

The proportion of unit (a) in resin A is preferably 50.0% by mass or more and 90.0% by mass or less, as this allows for low-temperature fixing while maintaining hot offset resistance and gloss uniformity.

In measuring the viscoelasticity of the toner of the present invention, when T2 [°C] is the temperature at which the storage modulus G' becomes 3.0 × ^10⁷ Pa, and T3 [°C] is the temperature at which the storage modulus G' becomes 3.0 × ^10⁶ Pa, it is preferable that the following equation (6) is satisfied.
|T3-T2|≦10.0 (6)

Satisfying equations (2) and (6) above is preferable because it allows for both low-temperature fixability and heat-resistant storage of the toner. |T3-T2| can be controlled by the proportion of crystalline resin in the toner, the proportion of crystalline parts in the crystalline resin, etc.

Furthermore, in formula (5), when n = 1, the dispersibility of the siloxane binding site in the toner binder is improved, resulting in good mixing of the loose gel structure and non-gel components. This is preferable because it allows for low-temperature fixation while maintaining hot offset resistance and gloss uniformity.

<Resin A>
The resin A used in this invention will be described in detail below.

Examples of resin A include crystalline vinyl resin, polyester resin, polyurethane resin, epoxy resin, etc., but crystalline vinyl resin is preferred.

Resin A has a monomer unit (a) represented by formula (1) above. Formula (1) indicates the presence of a long-chain alkyl group, which makes the resin more likely to exhibit crystallinity. Furthermore, the fact that n in formula (1) is between 15 and 30 makes it easier to control formula (2) within a specified range. Preferably, n is between 17 and 29.

One method for introducing monomer unit (a) is to polymerize (meth)acrylic acid esters, such as stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosa (meth)acrylate, myricyl (meth)acrylate, dodoriaconta (meth)acrylate, and 2-decyltetradecyl (meth)acrylate.

The unit in formula (2) may be used individually or in combination of two or more types.

If resin A is a crystalline vinyl resin, it is possible to have other monomer units in addition to the monomer unit (a). One method for introducing other monomer units is to polymerize the (meth)acrylic acid ester with other vinyl monomers.

Other vinyl monomers include the following:

(Meth)acrylic acid esters such as styrene, α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

Monomers containing a urea group: For example, monomers obtained by reacting an amine having 3 to 22 carbon atoms [primary amines (n-butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amines (di-normal ethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline, and cycloxylamine, etc.)] with an isocyanate having 2 to 30 carbon atoms and possessing an ethylenically unsaturated bond, using known methods.

Monomers containing a carboxyl group; for example, methacrylic acid, acrylic acid, and (meth)acrylate-2-carboxyethyl.

Monomers containing a hydroxyl group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.

Monomers having an amide group; for example, acrylamide, monomers obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms and an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) by known methods.

In particular, styrene, methyl (meth)acrylate, and t-butyl (meth)acrylate are preferred.

If resin A is a polyester resin, then any crystalline polyester resin obtained by the reaction of a divalent or higher polycarboxylic acid with a polyhydric alcohol can be used.

Examples of polycarboxylic acids include the following compounds: dibasic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, and dodecenylsuccinic acid, and their anhydrides or lower alkyl esters; and aliphatic unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid. Also included are 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and their anhydrides or lower alkyl esters. These may be used individually or in combination of two or more.

Examples of polyhydric alcohols include the following compounds: alkylene glycols (ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol); alkylene ether glycols (polyethylene glycol and polypropylene glycol); alicyclic diols (1,4-cyclohexanedimethanol); bisphenols (bisphenol A); and alkylene oxide (ethylene oxide and propylene oxide) adducts of alicyclic diols. The alkyl portions of alkylene glycols and alkylene ether glycols may be linear or branched. Furthermore, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol are also examples. These may be used individually or in combination of two or more.

Furthermore, monohydric acids such as acetic acid and benzoic acid, and monohydric alcohols such as cyclohexanol and benzyl alcohol may be used as needed to adjust the acid value and hydroxyl value.

The method for producing the polyester resin is not particularly limited, but for example, the transesterification method or the direct polycondensation method can be used alone or in combination.

The method for introducing the structure represented by formula (5) above into resin A is not particularly limited, but one method is to add a silane coupling agent having a vinyl polymerizable portion during the polymerization of the vinyl monomer, and then condense the silane coupling agent in a subsequent manufacturing process. Specific examples of polymerizable silane coupling agents having a vinyl polymerizable portion include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

Another method involves reacting the epoxy group of an epoxysilane compound with the carboxyl group of resin A to introduce a silanol structure, followed by condensation of a silane coupling agent in a subsequent manufacturing process. Specific examples of epoxysilane compounds include 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

Another method involves reacting the carboxyl group of resin A with the amino group of an aminosilane compound to introduce a silanol structure, followed by condensation with a silane coupling agent in a subsequent manufacturing process. Specific examples of aminosilane compounds include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane.

<Other binding resins and resin components>
In addition to the resin A mentioned above, the toner of the present invention may use known binder resins such as a polymer of (meth)acrylate lauryl and the vinyl monomer.

Furthermore, the toner of the present invention may contain resin components for various purposes other than the binder resin. Examples of usable resins include vinyl resins, polyesters, polyurethanes, epoxy resins, etc., which are not binder resins.

<Release agent>
The toner may contain a release agent. The release agent is at least one selected from the group consisting of hydrocarbon waxes and ester waxes. Using hydrocarbon waxes and/or ester waxes makes it easier to ensure effective release properties.

There are no particular limitations on hydrocarbon-based waxes, but examples include the following:

Aliphatic hydrocarbon waxes: Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymers, Fischer-Tropsch waxes, or waxes obtained by oxidation or acid addition of these materials.

Ester waxes only need to have at least one ester bond in each molecule; either natural or synthetic ester waxes may be used.

There are no particular limitations on ester waxes, but examples include the following:

Esters of monohydric alcohols and monocarboxylic acids, such as behenyl behenate, stearyl stearate, and palmityl palmitate;
Esters of divalent carboxylic acids and monoalcohols, such as dibehenyl sebacate;
Esters of dihydric alcohols such as ethylene glycol distearate and hexanediol dibehenate with monocarboxylic acids;
Esters of trihydric alcohols such as glycerol tribehenate and monocarboxylic acids;
Esters of tetrahydric alcohols such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate with monocarboxylic acids;
Esters of hexahydritol alcohols such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabéhenate with monocarboxylic acids;
Esters of polyfunctional alcohols such as polyglycerin behenates and monocarboxylic acids; natural ester waxes such as carnauba wax and rice wax;
Among these, esters of hexahydritols and monocarboxylic acids, such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabéhenate, are preferred.

The release agent may be a hydrocarbon wax or an ester wax alone, or a combination of hydrocarbon waxes and ester waxes, or a mixture of two or more types. It is particularly preferable to use a hydrocarbon wax alone or two or more types. It is even more preferable that the release agent is a hydrocarbon wax.

In toner, the release agent content in the toner particles is preferably 1.0% by mass or more and 30.0% by mass or less, more preferably 2.0% by mass or more and 25.0% by mass or less. Having the release agent content in the toner particles within this range makes it easier to ensure release properties during fixing.

The melting point of the release agent is preferably between 60°C and 120°C. A melting point within this range allows the release agent to melt during fixing and easily seep onto the toner particle surface, thus facilitating release properties. More preferably, the melting point is between 70°C and 100°C.

<Coloring agents>
The toner may contain a colorant. Examples of colorants include known organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, and magnetic particles. Other colorants conventionally used in toners may also be used.

Examples of yellow colorants include: condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, C.I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, and 180 are preferably used.

Examples of magenta colorants include: condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolon compounds, thioindigo compounds, and perylene compounds. Specifically, C.I. Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254 are preferably used.

Examples of cyanide colorants include: copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specifically, C.I. Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66 are preferably used.

The colorants are selected based on factors such as hue angle, saturation, brightness, lightfastness, OHP transparency, and dispersibility in toner.

The colorant content is preferably 1.0 part by mass or more and 20.0 parts by mass or less per 100.0 parts by mass of the binder resin. When magnetic particles are used as the colorant, their content is preferably 40.0 parts by mass or more and 150.0 parts by mass or less per 100.0 parts by mass of the binder resin.

<Charge Control Agent>
A charge control agent may be incorporated into the toner particles as needed. Alternatively, the charge control agent may be added externally to the toner particles. By incorporating a charge control agent, the charge characteristics can be stabilized, and the optimal amount of triboelectric charge can be controlled according to the developing system.

As the charge control agent, known agents can be used, and charge control agents that have a fast charging speed and can stably maintain a constant charge level are particularly preferred.

Examples of charge control agents that control the toner's load charge include the following: Organometallic compounds and chelate compounds are effective, including monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds.

Examples of substances that control the positive charge of toner include: nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorganosucroses, guanidine compounds, and imidazole compounds.

The charge control agent content is preferably 0.01 parts by mass to 20.0 parts by mass, and more preferably 0.5 parts by mass to 10.0 parts by mass, per 100.0 parts by mass of toner particles.

<External Additives>
The toner particles can be used as toner as is, or, if necessary, external additives can be mixed in and attached to the surface of the toner particles to create toner.

Examples of external additives include inorganic fine particles selected from the group consisting of silica fine particles, alumina fine particles, and titania fine particles, or composite oxides thereof. Examples of composite oxides include silica-aluminum fine particles and strontium titanate fine particles.

The content of the external additive is preferably 0.01 parts by mass or more and 8.0 parts by mass or less per 100 parts by mass of toner particles, and more preferably 0.1 parts by mass or more and 4.0 parts by mass or less.

<Toner manufacturing method>
The toner particles of the present invention may be manufactured by any of the conventionally known methods, such as suspension polymerization, emulsification and agglutination, dissolution and suspension, or pulverization, as long as they are within the scope of the present configuration, but it is preferable that they be manufactured by suspension polymerization.

The suspension polymerization method will be described in detail.

For example, a pre-synthesized resin A is added to a mixture of polymerizable monomers that produce an amorphous resin. If necessary, other materials such as colorants, release agents, and charge control agents are added, and the mixture is uniformly dissolved or dispersed to prepare a polymerizable monomer composition.

Subsequently, the polymerizable monomer composition is dispersed in an aqueous medium using a stirrer or the like to prepare suspended particles of the polymerizable monomer composition. Then, the polymerizable monomers contained in the particles are polymerized using an initiator or the like to obtain toner particles.

After polymerization is complete, the toner particles should be filtered, washed, and dried using known methods, and external additives should be added as needed to obtain the toner.

A known polymerization initiator can be used as the polymerization initiator.

Examples include azo or diazo polymerization initiators such as 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitride), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobisisobutyronitrile; and peroxide polymerization initiators such as benzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumenehydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide.

Furthermore, known chain transfer agents and polymerization inhibitors may be used.

The aqueous medium may contain inorganic or organic dispersion stabilizers. Known dispersion stabilizers can be used as the dispersion stabilizer.

Examples of inorganic dispersion stabilizers include phosphates such as hydroxyapatite, tricalcium phosphate, dicalcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; metal hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide; sulfates such as calcium sulfate and barium sulfate; calcium metasilicate; bentonite; silica; and alumina.

On the other hand, examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salts of carboxymethylcellulose, polyacrylic acid and its salts, and starch.

When using inorganic compounds as dispersion stabilizers, commercially available compounds may be used as is. However, to obtain finer particles, the inorganic compounds may be generated in an aqueous medium before use.

For example, in the case of calcium phosphate such as hydroxyapatite or tricalcium phosphate, it is best to mix the phosphate aqueous solution with the calcium salt aqueous solution under high agitation.

The aqueous medium may contain a surfactant. Known surfactants can be used as the surfactant. Examples include anionic surfactants such as sodium dodecylbenzene sulfate and sodium oleate; cationic surfactants; amphoteric surfactants; and nonionic surfactants.

[Method for measuring the physical properties of the toner of the present invention]
The following describes the calculation and measurement methods for various physical properties of toner and toner materials.

<Measurement Method for Storage Modulus G' and tanδ>
In this invention, the storage modulus G' and tanδ are measured using a viscoelasticity measuring device (rheometer) ARES (manufactured by Rheometrics Scientific). The general procedure for measurement is described in the ARES operation manuals 902-30004 (August 1997 edition) and 902-00153 (July 1993 edition) published by Rheometrics Scientific, and is as follows.
• Measurement jig: torsion rectangular
• Measurement sample: For the toner, a rectangular parallelepiped sample with a width of approximately 12 mm, a height of approximately 20 mm, and a thickness of approximately 2.5 mm is prepared using a pressure molding machine (maintaining 25 kN at room temperature for 30 minutes). The pressure molding machine used is the NPa Systems 100 kN press NT-100H.

After leaving the jig and sample at room temperature (23°C) for one hour, attach the sample to the jig. Fix it so that the measuring section is approximately 12 mm wide, 2.5 mm thick, and 10.0 mm high, as shown in Figure 1. After adjusting the temperature to 30°C over 10 minutes, perform the measurement with the settings described below.
・Measurement frequency: 6.28rad/s
- Setting the measurement strain: Set the initial value to 0.1% and perform the measurement in automatic measurement mode. - Sample elongation correction: Adjust in automatic measurement mode. - Measurement temperature: Increase the temperature from 30°C to 150°C at a rate of 2°C per minute. - Measurement interval: Measure viscoelastic data every 30 seconds, i.e., every 1°C.

Data is transferred via an interface to RSI Orchestrator (control, data acquisition, and analysis software) (manufactured by Rheometrics Scientific), which runs on Microsoft Windows 2000.

Of the measured data, the temperature at which the storage modulus G' becomes 1.0 × ^10⁷ Pa is defined as T1 [°C], the temperature at which the storage modulus G' becomes 3.0 × ^10⁷ Pa is defined as T2 [°C], and the temperature at which the storage modulus G' becomes 3.0 × ^10⁶ Pa is defined as T3 [°C]. Furthermore, the ratio of the loss modulus G'' to the storage modulus G' at temperature T1 [°C] (tanδ) is defined as tanδ(T1), and the tanδ at temperature T1-10 [°C] is defined as tanδ(T1-10).

<Method for measuring the mass of silicon derived from the siloxane structural moiety of THF-insoluble components>
The mass of silicon derived from the siloxane moiety in the THF insoluble matter can be measured using a PerkinElmer TGA7 thermal analyzer.

The THF-insoluble portion is heated from 50°C to 900°C at a heating rate of 25°C/min, and the reduced silicon mass is considered to be the Si mass derived from the siloxane structure.

The silicon content in the THF-insoluble matter before and after the reduction is measured using X-ray fluorescence.

The measurement of X-ray fluorescence will conform to JIS K 0119-1969, specifically as follows: The measurement equipment used will be the wavelength-dispersive X-ray fluorescence analyzer "Axios" (manufactured by PANical), and the accompanying dedicated software "SuperQ ver. 5.0L" (manufactured by PANical) for setting measurement conditions and analyzing measurement data.

Furthermore, Rh will be used as the anode of the X-ray tube, the measurement atmosphere will be a vacuum, and the measurement diameter (collimator mask diameter) will be 27 mm. The measurement will be performed using the Omnian method to measure elements from F to U. Light elements will be detected using a proportional counter (PC), and heavy elements will be detected using a scintillation counter (SC).

Furthermore, the acceleration voltage and current values of the X-ray generator are set to an output of 2.4 kW (voltage 32 kV, current 125 mA). For the measurement sample, 4 g of THF-insoluble material is placed in a dedicated aluminum ring for pressing, leveled, and then compressed at 20 MPa for 60 seconds using a tablet molding compressor "BRE-32" (manufactured by Maekawa Testing Machinery Co., Ltd.) to form pellets with a thickness of 2 mm and a diameter of 39 mm.

The pellets formed under the above conditions are irradiated with X-rays, and the resulting characteristic X-rays (fluorescent X-rays) are spectrally analyzed using a spectrometer. Next, the intensity of the fluorescent X-rays spectrally separated at angles corresponding to the wavelengths specific to each element in the sample is analyzed using the FP method (fundamental parameter method). This allows us to obtain the content ratio of each element in the THF insoluble matter as the analysis result, and to determine the silicon atom content in the THF insoluble matter.

<Method for measuring THF-insoluble content in toner>
Weigh approximately 1.5 g of toner (W1 g) and place it in a pre-weighed cylindrical filter paper (for example, product name No. 86R (size 28 x 100 mm), manufactured by Advantec Toyo Co., Ltd.) and set it in a Soxhlet extractor. Extract using 200 ml of tetrahydrofuran (THF) as the solvent for 20 hours, performing the extraction at a reflux rate such that the solvent extraction cycle occurs approximately once every 5 minutes.

After extraction is complete, the cylindrical filter paper is removed and air-dried. Then, it is vacuum-dried at 40°C for 8 hours. The mass of the cylindrical filter paper containing the extraction residue is weighed, and the mass of the extraction residue (W2g) is calculated by subtracting the mass of the cylindrical filter paper.

Next, the content of components other than resin (W3g) is determined by the following procedure. Approximately 2g of toner is weighed (Wg) into a pre-weighed 30ml magnetic crucible. The crucible is placed in an electric furnace and heated at approximately 900°C for approximately 3 hours. After cooling in the electric furnace, it is allowed to cool at room temperature in a desiccator for at least 1 hour. The mass of the crucible containing the incineration residue ash is weighed, and the incineration residue ash (Wbg) is calculated by subtracting the mass of the crucible. Then, the mass of incineration residue ash in 1g of material W (W3g) is calculated using the following formula (A).
W3=W1×(Wb/Wa) (A)

In this case, the THF-insoluble portion can be calculated using the following formula (B).
THF insoluble content (mass%) = {(W2-W3)/(W1-W3)}×100 (B)

<Method for verifying the structure of formula (5) in resin A>
The structure of formula (5) contained in resin A is confirmed using a nuclear magnetic resonance spectrometer (NMR).

Samples for NMR measurement are prepared as follows:

Preparation of the measurement sample: Weigh 10.0 g of resin A, place it in cylindrical filter paper (Toyo Filter Paper Co., Ltd. No. 86R), and place it in a Soxhlet extractor. Extraction is carried out for 20 hours using 200 ml of tetrahydrofuran as the solvent. The filtered material in the cylindrical filter paper is then vacuum-dried at 40°C for several hours to obtain the sample for NMR measurement.

The X bonded to the silicon atom in the structure represented by equation (5) is confirmed by ^13C -NMR (solid-state) measurement. The measurement conditions are shown below.

"13. Measurement conditions for ^13C -NMR (solid)"
Equipment: JEOL RESONANCE JNM-ECX500II
Sample tube: 3.2 mm diameter
Sample: 150 mg of tetrahydrofuran-insoluble matter from toner particles for NMR measurement.
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: 2ms
Delay time: 2 seconds
Total number of times: 1024

Of the structure represented by formula (5), the siloxane bond portion was confirmed by ²⁹ Si-NMR (solid) measurement. The measurement conditions are shown below.

" ^29. Measurement conditions for Si-NMR (solid)"
Equipment: JEOL RESONANCE JNM-ECX500II
Sample tube: 3.2 mm diameter
Sample: 150 mg of tetrahydrofuran-insoluble matter from toner particles for NMR measurement.
Measurement temperature: Room temperature Pulse mode: CP/MAS
Measured nuclear frequency: 97.38MHz ( ^29Si )
Reference substance: DSS (external standard: 1.534ppm)
Sample rotation speed: 10 kHz
Contact time: 10 ms
Delay time: 2 seconds
Cumulative number of times: 2000 to 8000 times

<Method for measuring the molecular weight of toner>
The molecular weight (weight-average molecular weight Mw) of the THF-soluble component of the toner is measured by gel permeation chromatography (GPC) as follows.

First, the toner is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is then filtered through a solvent-resistant membrane filter, "Myshoridisk" (manufactured by Tosoh Corporation), with a pore diameter of 0.2 μm, to obtain the sample solution. The sample solution is adjusted so that the concentration of THF-soluble components is 0.8% by mass. This sample solution is then used for measurement under the following conditions.
• Equipment: HLC8120 GPC (Detector: RI) (Manufactured by Tosoh Corporation)
• Columns: Shodex KF-801, 802, 803, 804, 805, 806, 807 (7-row) (manufactured by Showa Denko)
• Eluent: Tetrahydrofuran (THF)
・Flow rate: 1.0ml/min
Oven temperature: 40.0℃
Sample injection volume: 0.10 ml

To calculate the molecular weight of the sample, a molecular weight calibration curve created using standard polystyrene resin (for example, "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 separating resin A from toner>
The separation of resin A from toner can be done by known methods, and one example is shown below.

Gradient LC is used as a method for separating resin components from toner. This analysis allows for separation based on the polarity of the resin in the binder resin, regardless of molecular weight.

First, the toner was dissolved in chloroform. The sample was adjusted to a sample concentration of 0.1% by mass using chloroform, and the solution was filtered through a 0.45 μm PTFE filter before being used for measurement. The measurement conditions for gradient polymer LC are shown below.
Equipment: Ultimate 3000 (manufactured by Thermo Fisher Scientific)
Mobile phase: A. Chloroform (HPLC), B. Acetonitrile (HPLC)
Gradient: 2 min (A/B = 0/100) → 25 min (A/B = 100/0)
(Note that the gradient of the mobile phase change was made to be a straight line.)
Flow rate: 1.0mL/min Injection: 0.1% by mass x 20μL
Column: Tosoh TSKgel ODS (4.6 mmφ x 150 mm x 5 μm)
Column temperature: 40°C
Detector: Corona Charged Particle Detector (Corona-CAD) (manufactured by Thermo Fisher Scientific)

The time-intensity graph obtained from the measurement shows that the resin component can be separated into two peaks depending on its polarity. Then, by repeating the above measurement and separating the samples at the time of the trough between each peak, it is possible to separate the two types of resin. DSC measurement is performed on the separated resins, and the resin with a melting point peak is designated as resin A.

Furthermore, if the toner contains a release agent, it is necessary to separate the release agent from the toner. The release agent is separated using recycled HPLC, which separates components with a molecular weight of 2000 or less as the release agent. The measurement method is as follows. First, a chloroform solution of the toner is prepared using the method described above. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshoridisk" (manufactured by Tosoh Corporation) with a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in chloroform is 1.0% by mass. This sample solution is used for measurement under the following conditions.
・Device: LC-Sakura NEXT (manufactured by Nippon Analytical Industry Co., Ltd.)
• Columns: JAIGEL 2H, 4H (manufactured by Nippon Analytical Engineering Co., Ltd.)
• Eluent: Chloroform • Flow rate: 10.0 ml/min
Oven temperature: 40.0℃
Sample injection volume: 1.0 ml

To calculate the molecular weight of the sample, a molecular weight calibration curve created using standard polystyrene resin (for example, "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.

From the molecular weight curve obtained in this way, components with a molecular weight of 2000 or less are repeatedly isolated, and the release agent is removed from the toner.

<Method for measuring the content ratio of various monomer units in resin>
The content ratio of various monomer units in the resin is measured by ^1H -NMR under the following conditions.
Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400 MHz
Pulse condition: 5.0 μs
Frequency range: 10500Hz
Total number of measurements: 64 Measurement temperature: 30℃
Sample: 50 mg of the sample to be measured is placed in a sample tube with an inner diameter of 5 mm, deuterated chloroform ( _CDCl3 ) is added as a solvent, and the mixture is dissolved in a constant temperature bath at 40°C to prepare the sample. The resulting ^1H -NMR chart is analyzed to identify the structure of each monomer unit. Here, as an example, the measurement of the content ratio of monomer unit (a) in crystalline resin A is described. In the resulting ^1H -NMR chart, a peak independent of the peaks attributed to the components of monomer unit (a) is selected from among the peaks attributed to the components of other monomer units, and the integral value S1 of this peak is calculated. The integral values are calculated similarly for each of the other monomer units contained in resin A.

If the monomer units constituting resin A consist of monomer unit (a) and one other monomer unit, the content ratio of monomer unit (a) is determined as follows using the integral value S1 and the integral value S2 of the peak of the other monomer unit. Note that n1 and n2 are the number of hydrogen atoms in the constituent element to which the peak of interest belongs for each part.
Percentage of monomer unit (a) content (mol%) =
{(S1/n1)/((S1/n1)+(S2/n2))}×100

The content ratio of monomer unit (a) can be calculated similarly even if there are two or more other monomer units.

Furthermore, if polymerizable monomers that do not contain hydrogen atoms in components other than the vinyl group are used, the measurement nucleus is set to ^13C using ^13C NMR and measured in single-pulse mode, and the same calculation is performed using ^1H NMR. The proportion (mol%) of each monomer unit calculated by the above method is multiplied by the molecular weight of each monomer unit to convert the content of each monomer unit into mass %,.

The present invention will be described in detail below with reference to examples, but these examples are not intended to limit the invention in any way. In the following formulations, parts are measured by mass unless otherwise specified.

(Preparation of resin A1)
The following materials were added to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere.
• 100,000 parts of toluene • 100,000 parts of monomer composition (The monomer composition shall be a mixture of the following monomers in the proportions shown below)
• Behenyl acrylate (monomer (a)) 80,000 parts • Styrene 18,000 parts • Methacrylic acid 2,000 parts • 3-Methacryloxypropyltrimethoxysilane 2,036 parts • Polymerization initiator t-Butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV)
0.500 parts The reaction vessel was heated to 70°C while stirring at 200 rpm, and the polymerization reaction was carried out for 12 hours to obtain a solution in which the monomer composition polymer was dissolved in toluene. Subsequently, the solution was cooled to 25°C, and then added to 1000.0 parts methanol while stirring to precipitate the methanol-insoluble components. The obtained methanol-insoluble components were filtered off, washed with methanol, and then vacuum dried at 40°C for 24 hours to obtain resin A1.

(Preparation of resins A2 to A14)
Resins A2 to A14 were prepared in the same manner as in the preparation of resin A1, except that the amount of each component added to the monomer composition was changed to that shown in Table 1.

(Preparation of resin B1)
The following materials were added to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere.
• 100.0 parts toluene • 100.0 parts monomer composition (The monomer composition shall be a mixture of the following monomers in the proportions shown below)
- 25.0 parts of lauryl acrylate (monomer (b)) - 75.0 parts of styrene - 0.5 parts of polymerization initiator t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) The above reaction vessel was heated to 70°C while stirring at 200 rpm and the polymerization reaction was carried out for 12 hours to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Subsequently, the above solution was cooled to 25°C and then added to 1000.0 parts of methanol while stirring to precipitate the methanol-insoluble matter. The obtained methanol-insoluble matter was filtered off, and after further washing with methanol, it was vacuum dried at 40°C for 24 hours to obtain resin B1.

(Preparation of resins B2 to B7)
Resins B2 to B7 were prepared in the same manner as resin B1, except that the amounts of each component of the monomer composition were changed as shown in Table 2. For resins B4 and B7, a predetermined amount of crosslinking agent (HDDA; 1,6-hexanediol-diacrylate) was added.

<Example 1>
[Toner manufacturing by suspension polymerization method]
(Manufacturing of toner particles 1)
A mixture consisting of 15.0 parts of lauryl acrylate (monomer (b)), 45.0 parts of styrene, and 6.5 parts of a coloring agent (pigment blue 15:3) was prepared. The above mixture was placed in an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed at 200 rpm for 2 hours using 5 mm diameter zirconia beads to obtain a raw material dispersion.

Meanwhile, in a container equipped with a high-speed homomixer (Primix Corporation) and a thermometer, 735.0 parts of deionized water and 16.0 parts of trisodium phosphate (dodecahydrate) were added, and the mixture was heated to 60°C while stirring at 12,000 rpm. Then, a calcium chloride aqueous solution, prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of deionized water, was added, and the mixture was stirred at 12,000 rpm for 30 minutes while maintaining a temperature of 60°C. Finally, 10% hydrochloric acid was added to adjust the pH to 6.0, obtaining an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water.

Next, the above raw material dispersion was transferred to a container equipped with a stirring device and a thermometer, and heated to 60°C while stirring at 100 rpm.
• Resin A1: 40.0 parts • Resin B1: 60.0 parts • Release agent 1: 9.0 parts (Release agent 1: DP18 (Dipentaerythritol stearate wax, melting point 79°C, manufactured by Nippon Seiro Co., Ltd.)
After adding the mixture and stirring at 100 rpm for 30 minutes while maintaining a temperature of 60°C, 9.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) were added as a polymerization initiator and stirred for another minute. Subsequently, the mixture was added to an aqueous medium being stirred at 12,000 rpm using the high-speed stirring device described above. Stirring was continued at 12,000 rpm for 20 minutes while maintaining a temperature of 60°C using the high-speed stirring device described above to obtain a granulated liquid.

The granulated liquid was transferred to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube, and heated to 70°C under a nitrogen atmosphere while stirring at 150 rpm. The polymerization reaction was carried out at 150 rpm for 12 hours while maintaining the temperature at 70°C to obtain a toner particle dispersion.

The obtained toner particle dispersion was cooled to 45°C while stirring at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45°C. Afterward, while maintaining stirring, dilute hydrochloric acid was added until the pH reached 1.5, dissolving the dispersion stabilizer. The solid components were filtered off, thoroughly washed with deionized water, and then vacuum-dried at 30°C for 24 hours to obtain toner particles 1.

(Preparation of Toner 1)
To 1:98.0 parts of the above toner particles, 2.0 parts of silica fine particles (hydrophobized with hexamethyldisilazane, number-average particle size of primary particles: 10 nm, BET specific surface area: 170 ^m² /g) were added as an external additive and mixed using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) at 3000 rpm for 15 minutes to obtain toner 1. The physical properties of the obtained toner 1 are shown in Table 4.

<Examples 2-19>
In Example 1, toner particles 2 to 19 were obtained in the same manner as in Example 1, except that the types and amounts of resins A and B used were changed as shown in Table 3.

Furthermore, toners 2 to 19 were obtained by performing the same external additive procedure as in Example 1. The physical properties of the toners are shown in Table 4.

<Comparative Examples 1-11>
Comparative toner particles 1 to 11 were obtained in the same manner as in Example 1, except that the types and amounts of resins A and B used were changed as shown in Table 3.

Furthermore, comparative toners 1 to 11 were obtained by performing the same external additive procedure as in Example 1. The physical properties of the toners are shown in Table 4.

<Comparative Example 12>
In Example 1, comparative toner particles 12 were obtained in the same manner as in Example 1, except that 3-methacryloxypropyltrimethoxysilane was removed from resin A1 and added at the start of the polymerization reaction at 70°C during toner production.

Furthermore, a comparative toner 12 was obtained by performing the same external additive procedure as in Example 1. The physical properties of the toner are shown in Table 4.

<Comparative Example 13>
50.0 mol parts of bisphenol A ethylene oxide (2.2 mol adduct), 50.0 mol parts of bisphenol A propylene oxide (2.2 mol adduct), 90.0 mol parts of terephthalic acid, and 10.0 mol parts of trimellitic anhydride. 97 parts of the above monomers for forming the polyester moiety and 3 parts of silicone oil having hydroxyl groups at both ends (KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with 500 ppm of titanium tetrabutoxide in a 5-liter autoclave.

A reflux condenser, moisture separator, _N2 gas introduction tube, thermometer, and stirring device were attached to the autoclave, and a condensation polymerization reaction was carried out at 230°C while introducing _N2 gas into the autoclave. The reaction time was adjusted to achieve the desired softening point, and after the reaction was complete, the material was removed from the container, cooled, and pulverized to obtain the binder resin P1.
• Solvent: 100.0 parts toluene • 100.0 parts monomer composition (The monomer composition is a mixture of behenyl acrylate, methacrylonitrile, and styrene in the proportions shown below.)
(Behenyl acrylate (first monomer) 67.0 parts (28.9 mol%))
(Methacrylonitrile (second monomer) 22.0 parts (53.8 mol%))
(Styrene (third monomer) 11.0 parts (17.3 mol%))
- Polymerization initiator t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) 0.5 parts The above materials were added to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. The reaction vessel was heated to 70°C while stirring at 200 rpm and the polymerization reaction was carried out for 12 hours to obtain a solution in which the monomer composition polymer was dissolved in toluene. Subsequently, the above solution was cooled to 25°C and then added to 1000.0 parts methanol while stirring to precipitate the methanol-insoluble components. The obtained methanol-insoluble components were filtered off, washed with methanol, and then vacuum dried at 40°C for 24 hours to obtain polymer A1.

- Binding resin P1 100.0 parts - Polymer A1 5.0 parts - Fischer-Tropsch wax (peak temperature of maximum endothermic peak 90°C) 6.0 parts - C.I. Pigment Blue 15:3 9.0 parts The raw materials shown in the formulation were mixed using a Henschel mixer (FM75J model, manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) at a rotation speed of 20 ^s⁻¹ and a rotation time of 5 min. The mixed raw materials were then kneaded in a twin-screw kneader (PCM-30 model, manufactured by Ikegai Co., Ltd.) set to a temperature of 130°C and a barrel rotation speed of 200 rpm.

The resulting mixture was cooled and coarsely ground to a size of 1 mm or less using a hammer mill to obtain coarse material. This coarse material was then finely ground using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain comparative toner particles 13. The weight-average particle size (D4) of the obtained comparative toner particles 13 was 6.5 μm.

Comparative toner particles 13:100.0 parts were mixed with 2.0 parts of hydrophobic silica (BET: 200 ^m² /g) using a Henschel mixer (FM75J model, manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) at a rotation speed of 30 ^s⁻¹ and a rotation time of 5 min. The resulting mixture was passed through an ultrasonic vibrating sieve with a mesh size of 54 μm to obtain comparative toner 13.

The physical properties of the toner are shown in Table 4.

<Comparative Example 14>
• Styrene 72.1 mol, Butyl acrylate 19.5 mol, Silane coupling agent 0.1 mol (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBM503)
A monomer mixture consisting of the above composition was subjected to radical polymerization to produce high-molecular-weight and low-molecular-weight compounds with the following molecular weights.
High molecular weight Mw=9.0×10 ⁵ Mn=3.9×10 ⁵
Low molecular weight substance Mw=8.0×10 ³ Mn=2.7×10 ³
Next, the obtained high molecular weight and low molecular weight materials were mixed in a ratio of low molecular weight material:high molecular weight material = 70:30 to obtain styrene-butyl acrylate-silane copolymer resin A.

The raw materials, consisting of the following composition, were mixed in a super mixer, melt-kneaded, and then pulverized and classified to obtain negatively charged toner matrix particles (comparative toner particles 14) with a weight-average particle size (D4) of 11.0 μm.
Styrene-butyl acrylate-silane copolymer resin A: 100 parts Carbon black (MA-100, manufactured by Mitsubishi Chemical Industries, Ltd.): 6.5 parts Chromium-containing metal dye (S-34, manufactured by Orient Chemical Industries, Ltd.): 2.0 parts Polypropylene: 3.0 parts Then, using a Henschel mixer, hydrophobic silica (R-972, manufactured by Nippon Aerosil Co., Ltd.): 0.3 parts was attached to the surface of the obtained comparative toner particles 14:100 parts to obtain comparative toner 14.

The physical properties of the toner are shown in Table 4.

[Toner Evaluation Method]
The performance evaluations for toners 1 to 19 related to Examples 1 to 19 and comparative toners 1 to 14 related to Comparative Examples 1 to 14 were performed according to the following procedures.

<1> Low-temperature fixing performance A process cartridge filled with toner was left at 25°C and 40% RH humidity for 48 hours. Using an LBP-712Ci modified to operate even without the fuser, an unfixed image of an image pattern with 10mm x 10mm square images evenly arranged at 9 points across the entire transfer paper was printed. The amount of toner on the transfer paper was set to 0.80 mg/ ^cm² , and the fixing start temperature was evaluated. The transfer paper used was A4 paper equivalent to rough paper ("Proverbond paper": 105 g/ ^m² , manufactured by Fox River).

The fuser used was an external fuser, which was created by removing the fuser unit from the LBP-712Ci and operating it outside the laser beam printer. The external fuser was used to perform fixing at a process speed of 260 mm/sec, with the fixing temperature gradually increased in 5°C increments starting from 90°C.

The fixed image was visually inspected, and the lowest temperature at which no cold offset occurred was defined as the fixing start temperature. Low-temperature fixing performance was evaluated according to the following criteria. The evaluation results are shown in Table 5.

[Evaluation Criteria]
A: Fixing start temperature is 100°C or lower B: Fixing start temperature is 105°C or higher and 110°C or lower C: Fixing start temperature is 115°C or higher and less than 120°C D: Fixing start temperature is 125°C or higher

<2> Evaluation of Gloss and Gloss Unevenness The fixed image at the fixing start temperature used in the evaluation in <1> above was used. The gloss value was measured using a handy gloss meter PG-1 (manufactured by Nippon Denshoku Industries Co., Ltd.). The measurement conditions were set to a light projection angle and a light reception angle of 75°, and all 9-point arranged image patterns were measured and the average value was evaluated. The standard deviation of the measured values was used to evaluate gloss unevenness. The evaluation results are shown in Table 5.

[Gross Evaluation Criteria]
A: Gross average score is 25.0 or higher B: Gross average score is 20.0 or higher but less than 25.0 C: Gross average score is 15.0 or higher but less than 20.0 D: Gross average score is less than 15.0

[Gloss and unevenness evaluation criteria]
A: Gross standard deviation is 1.00 or less B: Gross standard deviation is greater than 1.00 and 2.00 or less C: Gross standard deviation is greater than 2.00 and 3.00 or less D: Gross standard deviation is greater than 3.00

<3> Evaluation of Hot Offset Under normal temperature and humidity conditions (25°C/50%RH), a solid image (toner coverage: 0.9 mg/ ^cm² ) was formed at a process speed of 260 mm/sec, with the fixing temperature changed in 10°C increments. Plain paper (Xerox 4200 paper, LETTER size, manufactured by Xerox, 75 g/ ^m² ) was used for the transfer paper. Hot offset resistance was evaluated visually. In this invention, a rating of C or higher was considered good. The evaluation results are shown in Table 5.

[Evaluation Criteria]
A: Offset occurs at temperatures above 160°C B: Offset occurs between 150°C and 160°C C: Offset occurs between 140°C and 150°C D: Offset occurs below 140°C

Claims (4)

A toner having toner particles containing resin A as a binder resin,
The aforementioned resin A has a structure represented by the following formula (5):
In formula (5) above, n represents an integer between 1 and 10,
In formula (5) above, X independently represents a hydrogen atom, a hydroxyl group, an alkoxyl group, or an alkyl group.
In formula (5) above, A contains 30% by mass or more of unit (a) represented by the following formula (1),
In formula (1) above , _R1 represents a hydrogen atom or a methyl group .
In formula (1) above , _L1 represents a single bond , an ester bond, or an amide bond .
In formula (1) above , m represents an integer between 15 and 30,
The content of resin A in the toner , based on the mass of the toner , is 20.0% by mass or more and 100.0% by mass or less.
In the viscoelasticity measurement of the toner, when the temperature at which the storage modulus G' of the toner is 1.0 × ^10⁷ Pa is defined as T1 [°C], the ratio of the loss modulus G'' of the toner at temperature T1 [°C] to the storage modulus G' (tanδ) is defined as tanδ(T1), and the ratio of the loss modulus G'' of the toner at temperature T1-10 [°C] to the storage modulus G' ( tanδ ) is defined as tanδ(T1-10), the toner satisfies the following equations (2) to (4):
50.0 ≤ T1 ≤ 70.0 (2)
0.30≦tanδ(T1)≦1.00 (3)
1.00≦tanδ(T1)/tanδ(T1-10)≦1.90 (4)
The toner contains THF - insoluble components ,
The THF-insoluble portion includes the structure represented by formula (5) of the resin A ,
Using a PerkinElmer TGA7 thermal analyzer, the THF-insoluble matter was heated from 50°C to 900°C at a heating rate of 25°C/min, and the reduced mass of silicon was taken as the mass of silicon derived from the siloxane structure in the structure represented by formula (5). In this case, the mass of silicon derived from the siloxane structure was 0.005% or more and 0.150% or less of the THF-insoluble matter .
A toner characterized by the following features . The toner according to claim 1, wherein A in formula (5) contains 50.0% by mass or more and 90.0% by mass or less of the unit (a). In the viscoelasticity measurement of the toner, when the temperature at which the storage modulus G' of the toner becomes 3.0 × ^10⁷ Pa is set to T2 [°C], and the temperature at which the storage modulus G' of the toner becomes 3.0 × ^10⁶ Pa is set to T3 [°C], the toner satisfies the following formula (6) , as described in claim 1 or 2.
|T3-T2|≦10.0 (6) The toner according to claim 1 , wherein n in formula (5) is 1 .