JP7392307B2 - Toner for electrostatic image development, electrostatic image developer, toner cartridge, process cartridge, printed matter manufacturing device, and printed matter manufacturing method - Google Patents

Description

The present disclosure relates to a toner for developing electrostatic images, an electrostatic image developer, a toner cartridge, a process cartridge, an apparatus for producing printed matter, and a method for producing printed matter.

Patent Document 1 states that Equation 1 "20°C≦T(1MPa)-T(10MPa) (T(1MPa) represents the temperature when the viscosity becomes 10 ⁴ Pa·s at an applied pressure of 1MPa, and T(10MPa) represents the temperature at which the viscosity becomes 10 ⁴ Pa·s at an applied pressure of 10 MPa.)” is described.

Patent Document 2 discloses an adhesion part for adhering powder that becomes sticky when pressure is applied to a surface to be adhered, and a recording medium to which the powder is attached to which pressure is applied to form an adhesive layer on the recording medium. A fixing part that fixes to the medium and an adhesive layer apply pressure to the recording medium formed on the surface to be adhered, and a folding part that folds the recording medium formed on the surface to be adhered so that the surfaces to be adhered face each other. A pressure-bonded printed matter production apparatus is described, which includes an application section that applies adhesive layers and adheres adhesive layers to each other.

Patent Document 3 includes a styrene resin and a (meth)acrylic acid ester resin whose glass transition temperature is 30°C or more lower than that of the styrene resin, and in a sea area containing the styrene resin and an island area containing the (meth)acrylic acid ester resin. A pressure fixing toner having a sea-island structure and having a core portion in which the major axis of the island portion is from 200 nm to 500 nm, and a shell layer covering the core portion and containing a resin having a glass transition temperature of 50° C. or more. Are listed.

Japanese Patent Application Publication No. 2018-002889 Japanese Patent Application Publication No. 2018-004966 Japanese Patent Application Publication No. 2018-163198

The present disclosure provides an electrostatic image development method that includes two or more types of binder resins, has at least two glass transition points, and has a difference between the lowest glass transition temperature and the highest glass transition temperature of 30° C. or more. To provide a toner for developing an electrostatic image, which is a toner for developing an electrostatic image that can suppress internal stains in a machine, compared to a toner for developing an electrostatic image that contains a yellow pigment and has a yellow pigment content of less than 5 ppm or more than 100 ppm. The task is to

Specific means for solving the above problems include the following aspects: <1> A method comprising two or more binder resins and a yellow pigment,
The content of the yellow pigment is 5 ppm or more and 100 ppm or less, and
A toner for developing electrostatic images, which has at least two glass transition points, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30° C. or more.
<2> The toner for developing an electrostatic image according to <1>, wherein the yellow pigment is a pigment selected from the group consisting of a monoazo pigment, a disazo pigment, and a benzimidazolone disazo pigment.
<3> The yellow pigment is C.I. I. Pigment Yellow 74, C. I. Pigment Yellow 93 and C.I. I. The toner for developing an electrostatic image according to <1> or <2>, which is a pigment selected from the group consisting of Pigment Yellow 180.
<4> The binder resin contains a styrene resin containing styrene and other vinyl monomers as polymerization components, and at least two types of (meth)acrylic acid esters as polymerization components, and (meth)acrylic acid accounts for the entire polymerization component. The toner for developing an electrostatic image according to any one of <1> to <3>, comprising a (meth)acrylic acid ester resin in which the mass proportion of the acid ester is 90% by mass or more.
<5> The toner for developing an electrostatic image according to <4>, wherein the mass ratio of styrene to the entire polymerization component of the styrenic resin is 60% by mass or more and 95% by mass or less.
<6> Among the at least two types of (meth)acrylic esters contained as polymerization components in the (meth)acrylic ester-based resin, the mass ratio of the two types with the highest mass ratio is 80:20 to 20:80. The toner for developing an electrostatic image according to <4> or <5>.
<7> Of the at least two types of (meth)acrylic esters contained as polymerization components in the (meth)acrylic ester-based resin, the two types with the highest mass ratio are (meth)acrylic acid alkyl esters, and the The toner for developing an electrostatic image according to any one of <4> to <6>, wherein the difference in the number of carbon atoms in the alkyl groups of the two types of (meth)acrylic acid alkyl esters is 1 or more and 4 or less.
<8> The toner for developing an electrostatic image according to any one of <4> to <7>, wherein the other vinyl monomer contained as a polymerization component in the styrene resin contains a (meth)acrylic acid ester.
<9> The other vinyl monomer contained as a polymerization component in the styrenic resin includes at least one of n-butyl acrylate and 2-ethylhexyl acrylate, according to any one of <4> to <8>. Toner for developing electrostatic images.
<10> The electrostatic image according to any one of <4> to <9>, wherein the styrene resin and the (meth)acrylic acid ester resin contain the same type of (meth)acrylic acid ester as a polymerization component. Toner for development.
<11> The toner for developing an electrostatic image according to any one of <4> to <10>, wherein the (meth)acrylic acid ester resin contains 2-ethylhexyl acrylate and n-butyl acrylate as polymerization components. .
<12> The toner for developing an electrostatic image according to any one of <4> to <11>, wherein the content of the styrene resin is greater than the content of the (meth)acrylate resin.
<13> The method according to any one of <4> to <12>, comprising a sea phase containing the styrene resin and an island phase containing the (meth)acrylate resin dispersed in the sea phase. Toner for developing electrostatic images.
<14> The toner for developing an electrostatic image according to <13>, wherein the average diameter of the island phase is 200 nm or more and 500 nm or less.
<15> The method according to any one of <4> to <14>, comprising a core portion containing the styrene resin and the (meth)acrylic acid ester resin, and a shell layer covering the core portion. Toner for developing electrostatic images.
<16> The toner for developing an electrostatic image of a printed matter according to <15>, wherein the shell layer contains the styrene resin.
<17> The toner for developing an electrostatic image according to any one of <1> to <16>, which exhibits a viscosity of 10,000 Pa·s at a temperature of 90° C. or lower under a pressure of 4 MPa.
<18> An electrostatic image developer comprising the electrostatic image developing toner according to any one of <1> to <17>.
<19> A toner cartridge that accommodates the toner for developing an electrostatic image according to any one of <1> to <17> and is detachable from a printed matter manufacturing apparatus.
<20> A developing device containing the electrostatic image developer according to <18> and developing an electrostatic image formed on the surface of the photoreceptor as a toner image by the electrostatic image developer,
A process cartridge that can be attached to and removed from printed matter manufacturing equipment.
<21>
An arrangement in which an electrostatic image developer containing the electrostatic image developing toner according to any one of <1> to <17> is contained, and the electrostatic image developing toner is placed on a recording medium by an electrophotographic method. means and
crimping means for folding and crimping the recording medium or stacking and crimping the recording medium and another recording medium;
Printed matter manufacturing equipment, including:
<22> The apparatus for producing printed matter according to <21>, further comprising a colored image forming means for forming a colored image on a recording medium by an electrophotographic method using a colored electrostatic image developer.
<23> Using an electrostatic image developer containing the electrostatic image developing toner according to any one of <1> to <17>, the electrostatic image developing toner is electrophotographically transferred onto a recording medium. a placement process for placing;
a crimping step of folding and crimping the recording medium or stacking and crimping the recording medium and another recording medium;
A method of producing printed matter, including:
<24> The method for producing a printed matter according to <23>, further comprising a colored image forming step of forming a colored image on a recording medium by electrophotography using a colored electrostatic image developer.

According to the invention according to <1>, it is possible to provide a toner for developing an electrostatic image that contains a yellow pigment and can suppress in-machine staining compared to when the content of the yellow pigment is less than 5 ppm or more than 100 ppm. can.
According to the invention according to <2>, a toner for developing an electrostatic image that can suppress in-machine staining is provided, compared to when it contains a yellow pigment other than the group consisting of a monoazo pigment, a disazo pigment, and a benzimidazolone-based disazo pigment. can be provided.
According to the invention according to <3>, C. I. Pigment Yellow 74, C. I. Pigment Yellow 93 and C.I. I. It is possible to provide an electrostatic image developing toner that can suppress in-machine staining compared to the case where a yellow pigment other than the group consisting of Pigment Yellow 180 is included.
According to the invention according to <4>, the binder resin includes a styrene resin and a (meth)acrylic acid ester resin, and the (meth)acrylic acid ester resin is a homopolymer of (meth)acrylic acid ester. It is possible to provide a toner for developing electrostatic images that is more likely to undergo phase transition under pressure and has excellent adhesive properties than in the case of the present invention.
According to the invention according to <5>, there is provided a toner for developing an electrostatic image that undergoes a phase transition more easily due to pressure than when the mass proportion of styrene in the entire polymerization component of the styrenic resin is more than 95 mass%. be able to.
According to the invention according to <6>, the mass ratio of the two species having the highest mass ratio among at least two types of (meth)acrylic esters contained as polymerization components in the (meth)acrylic ester resin is 80:20. It is possible to provide an electrostatic image developing toner that is more likely to undergo phase transition under pressure and has excellent adhesive properties than when the ratio is outside the range of 20:80.
According to the invention according to <7>, compared to the case where the difference in the number of carbon atoms in the alkyl groups of the two types of (meth)acrylic acid alkyl esters is 5 or more, the phase transition is more likely to occur under pressure and the adhesiveness is improved. An excellent toner for developing electrostatic images can be provided.
According to the invention according to <8>, <9>, or <10>, it is possible to provide a toner for developing an electrostatic image that undergoes a phase transition more easily due to pressure than a toner containing polystyrene instead of a styrene resin. can.
According to the invention according to <11>, there is provided a toner for developing an electrostatic image containing a styrene resin and a (meth)acrylic acid ester resin, wherein the (meth)acrylic acid ester resin is a homopolymer of 2-ethylhexyl acrylate. It is possible to provide an electrostatic image developing toner that has superior adhesiveness compared to a polymer.
According to the invention according to <12>, an electrostatic image developing toner is provided in which adhesiveness is maintained compared to when the content of the styrene resin is less than the content of the (meth)acrylic acid ester resin. can do.
According to the invention according to <13>, it is possible to provide an electrostatic image developing toner that is more likely to undergo phase transition under pressure and has excellent adhesive properties than a toner that does not have the sea-island structure.
According to the invention according to <14>, it is possible to provide an electrostatic image developing toner that is more likely to undergo phase transition under pressure than when the average diameter of the island phase is more than 500 nm.
According to the invention according to <15>, the electrostatic charge image is more likely to undergo phase transition due to pressure than in the case where the core part has a core-shell structure containing only styrene resin or only (meth)acrylic acid ester resin. A developing toner can be provided.
According to the invention according to <16>, it is possible to provide a toner for developing an electrostatic image that undergoes a phase transition more easily under pressure than when the shell layer does not contain a styrene resin but contains other resins. .
According to the invention according to <17>, it is possible to provide an electrostatic image developing toner that exhibits a viscosity of 10,000 Pa·s under a pressure of 4 MPa and is more likely to undergo a phase transition under pressure than when the temperature exceeds 90°C. can.

According to the invention according to <18>, in-machine staining is suppressed compared to an electrostatic image developer containing a toner for developing an electrostatic image that contains a yellow pigment and has a yellow pigment content of less than 5 ppm or more than 100 ppm. A liquid electrostatic image developer can be provided.

According to the invention according to <19>, a toner for developing an electrostatic image that can suppress in-machine staining compared to a toner for developing an electrostatic image that contains a yellow pigment and has a yellow pigment content of less than 5 ppm or more than 100 ppm. A toner cartridge containing the following can be provided.

According to the invention according to <20>, in-machine staining is suppressed compared to an electrostatic image developer containing a toner for developing an electrostatic image that contains a yellow pigment and has a yellow pigment content of less than 5 ppm or more than 100 ppm. A process cartridge containing a liquid electrostatic image developer can be provided.

According to the invention according to <21> or <22>, the electrostatic charge that can suppress in-machine staining is better than a toner for developing an electrostatic image that contains a yellow pigment and has a yellow pigment content of less than 5 ppm or more than 100 ppm. It is possible to provide a printed matter manufacturing apparatus to which an image developing toner is applied.

According to the invention according to <23> or <24>, the electrostatic charge that can suppress in-machine staining is better than a toner for developing an electrostatic image that contains a yellow pigment and has a yellow pigment content of less than 5 ppm or more than 100 ppm. It is possible to provide a method for producing a printed matter to which an image developing toner is applied.

FIG. 1 is a schematic diagram showing an example of a printed matter manufacturing apparatus according to the present embodiment. FIG. 2 is a schematic diagram showing another example of the printed matter manufacturing apparatus according to the present embodiment. FIG. 1 is a schematic diagram showing an example of a process cartridge according to the present embodiment.

Embodiments of the present invention will be described below. These descriptions and examples are illustrative of the embodiments and do not limit the scope of the embodiments.

In the present disclosure, a numerical range indicated using "~" indicates a range that includes the numerical values written before and after "~" as the minimum and maximum values, respectively.

In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step. good. Furthermore, in the numerical ranges described in this disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.

In the present disclosure, the term "step" is included not only in an independent step but also in the case where the intended purpose of the step is achieved even if the step cannot be clearly distinguished from other steps.

In this disclosure, when embodiments are described with reference to drawings, the configuration of the embodiments is not limited to the configuration shown in the drawings. Furthermore, the sizes of the members in each figure are conceptual, and the relative size relationships between the members are not limited thereto.

In the present disclosure, each component may contain multiple types of corresponding substances. When referring to the amount of each component in the composition in this disclosure, if there are multiple types of substances corresponding to each component in the composition, unless otherwise specified, the amount of each component in the composition is means the total amount of substance.

In the present disclosure, each component may include a plurality of types of particles. When a plurality of types of particles corresponding to each component are present in the composition, the particle diameter of each component means a value for a mixture of the plurality of types of particles present in the composition, unless otherwise specified.

In the present disclosure, the expression "(meth)acrylic" means either "acrylic" or "methacrylic".

In the present disclosure, "toner for developing an electrostatic image" is also simply referred to as "toner", and "electrostatic image developer" is also simply referred to as "developer".

In the present disclosure, a printed matter formed by folding a recording medium and bonding their opposing surfaces to each other, or a printed matter formed by stacking two or more recording media and bonding their opposing surfaces to each other is referred to as a "press-bonded printed matter."
In the present disclosure, "adhesiveness" refers to the adhesiveness between opposing surfaces of the recording medium described above.

<Toner for electrostatic image development>
The toner according to the present embodiment includes two or more types of binder resins and a yellow pigment, has a yellow pigment content of 5 ppm or more and 100 ppm or less, has at least two glass transition points, and has at least two glass transition points. The difference between the lowest glass transition temperature and the highest glass transition temperature is 30°C or more.

The toner according to the present embodiment "contains two or more types of binder resin" and "has at least two glass transition temperatures, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30°C or more. It exhibits the thermal properties of "existence" and undergoes a phase transition under pressure.
In the present disclosure, a toner that undergoes a phase transition due to pressure means a toner that satisfies the following formula 1.

Formula 1...10℃≦T1-T2
In Equation 1, T1 is a temperature at which the viscosity is 10,000 Pa·s under a pressure of 1 MPa, and T2 is a temperature at which the viscosity is 10,000 Pa·s at a pressure of 10 MPa. How to obtain the temperature T1 and the temperature T2 will be described later.

When the toner according to the present embodiment undergoes a phase transition under pressure as described above, it exhibits the function of adhering the opposing surfaces of the recording medium to each other in the production of the pressure-bonded printed matter described above.

Toners that undergo phase transition due to pressure have been known, but their charge distribution tends to be wide due to the specific selection of binder resins. When a toner with a wide charge distribution is used, the toner with a smaller charge amount cannot be transferred or developed and floats, thereby contaminating the inside of the image forming apparatus (so-called internal contamination).

The toner according to the present embodiment "contains two or more types of binder resin" and "has at least two glass transition temperatures, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30°C or more. In addition, it contains a yellow pigment, and the content of the yellow pigment is 5 ppm or more and 100 ppm or less.
In this manner, the present inventors have discovered that by adding a small amount of yellow pigment, it is possible to suppress the above-mentioned internal staining caused by toner that undergoes a phase transition due to pressure. The reason why the dirt inside the aircraft can be suppressed is not clear, but we speculate as follows.

It is thought that the yellow pigment added in a trace amount functions as a charge control agent in the toner. In particular, yellow pigments contain nitrogen atoms, which can suppress excessive negative charging of the toner and form locally low electrical resistance regions, resulting in narrowing the charging distribution. It is presumed that it can be done.
Therefore, it is thought that the staining inside the machine caused by the toner having a wide charge distribution as described above is suppressed.

The toner according to the present embodiment includes at least toner particles, and optionally includes an external additive.
That is, the toner particles contained in the toner according to the present embodiment include two or more types of binder resin and a yellow pigment, and the content of the yellow pigment is 5 ppm or more and 100 ppm or less, and at least two types of glass It has a transition point, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30° C. or more.

[Toner particles]
The toner particles include two or more types of binder resins and a yellow pigment.
The toner particles may contain a colorant other than the yellow pigment, a release agent, and other additives, if necessary.

[Two or more types of binder resin]
The toner particles contain two or more types of binder resins, have at least two glass transition points, and have thermal properties such that the difference between the lowest glass transition temperature and the highest glass transition temperature is 30° C. or more. have

The two or more binder resins used in the toner particles are not particularly limited as long as they exhibit the above thermal properties, but addition polymerization resins such as vinyl resins and acrylic resins are preferred; From the viewpoint of easy phase transition due to the styrene-based resin containing styrene and other vinyl monomers as polymerization components, and from the viewpoint of increasing the adhesion between the opposing surfaces of the recording medium in the production of the pressure-bonded printed matter described above, at least two It is preferable to include a (meth)acrylic ester-based resin that contains a seed (meth)acrylic ester as a polymerization component, and the mass proportion of the (meth)acrylic ester in the entire polymerization component is 90% by mass or more. .
Hereinafter, "styrenic resins containing styrene and other vinyl monomers as polymerization components" are also referred to as "specific styrenic resins", and "styrenic resins containing at least two types of (meth)acrylic acid esters as polymerization components and accounting for the entire polymerization component." A (meth)acrylic ester resin in which the mass proportion of (meth)acrylic ester is 90% by mass or more is also referred to as a "specific (meth)acrylic ester resin."

From the viewpoint of maintaining adhesion, the content of the specific styrene resin in the toner particles is preferably greater than the content of the specific (meth)acrylic acid ester resin. The content of the specific styrenic resin is preferably 55% by mass or more and 80% by mass or less, and 60% by mass or more and 75% by mass or less, based on the total content of the specific styrenic resin and the specific (meth)acrylate resin. is more preferable, and still more preferably 65% by mass or more and 70% by mass or less.

-Specified styrenic resin-
The toner particles constituting the toner according to this embodiment contain a specific styrenic resin containing styrene and other vinyl monomers as polymerization components.

The mass proportion of styrene in the entire polymerization component of the specific styrenic resin is preferably 60 mass% or more, more preferably 70 mass% or more, from the viewpoint of suppressing fluidization of the toner in an unpressurized state. More preferably, the content is 75% by mass or more.
The mass proportion of styrene in the entire polymerization component of the specific styrenic resin is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less, from the viewpoint of forming a toner that easily undergoes phase transition under pressure. preferable.
That is, the mass proportion of styrene in the total polymerization components of the specific styrenic resin is preferably 60% by mass or more and 95% by mass or less.

Examples of vinyl monomers other than styrene (hereinafter also referred to as other vinyl monomers) included in the polymerization component of the specific styrenic resin include styrene monomers, acrylic monomers, and the like.

Examples of other styrenic monomers include vinylnaphthalene; α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p- Alkyl substitution of n-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, etc. Styrene; Aryl-substituted styrene such as p-phenylstyrene; Alkoxy-substituted styrene such as p-methoxystyrene; Halogen-substituted styrene such as p-chlorostyrene, 3,4-dichlorostyrene, p-fluorostyrene, 2,5-difluorostyrene, etc. ; nitro-substituted styrenes such as m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; and the like.
These styrene monomers may be used alone or in combination of two or more.

As the acrylic monomer in the other vinyl monomers, at least one acrylic monomer selected from the group consisting of (meth)acrylic acid and (meth)acrylic ester is preferable. (Meth)acrylic acid esters include (meth)acrylic acid alkyl ester, (meth)acrylic acid carboxy-substituted alkyl ester, (meth)acrylic acid hydroxy-substituted alkyl ester, (meth)acrylic acid alkoxy-substituted alkyl ester, di(meth)acrylic acid alkoxy-substituted alkyl ester, ) acrylic esters, etc.
These acrylic monomers may be used alone or in combination of two or more.

Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate. Isobutyl methacrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclo (meth)acrylate Examples include pentanyl and isobornyl (meth)acrylate.
Examples of the carboxy-substituted alkyl (meth)acrylate include 2-carboxyethyl (meth)acrylate and the like.
The (meth)acrylic acid hydroxy-substituted alkyl esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxy (meth)acrylate. Examples include butyl, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
Examples of the alkoxy-substituted alkyl (meth)acrylate include 2-methoxyethyl (meth)acrylate.
Examples of di(meth)acrylic acid esters include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, pentanediol di(meth)acrylate, Examples include hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, and decanediol di(meth)acrylate.

Examples of the (meth)acrylic ester include 2-(diethylamino)ethyl (meth)acrylate, benzyl (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate.

In addition to styrene monomers and acrylic monomers, other vinyl monomers included in the polymerization components of specific styrene resins include (meth)acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl methyl ketone; Also included are vinyl ketones such as vinyl ethyl ketone and vinyl isopropenyl ketone; and olefins such as isoprene, butene and butadiene.

In the specific styrene resin, from the viewpoint of forming a toner that easily undergoes a phase transition under pressure, it is preferable that the other vinyl monomer contained as a polymerization component contains a (meth)acrylic acid ester, and a (meth)acrylic acid alkyl ester. It is more preferable to include a (meth)acrylic acid alkyl ester in which the alkyl group has 2 to 10 carbon atoms, and it is even more preferable to include a (meth)acrylic acid alkyl ester in which the alkyl group has 4 to 8 carbon atoms (meth). ) It is more preferable to include an acrylic acid alkyl ester.
In the specific styrene resin, from the viewpoint of forming a toner that easily undergoes a phase transition under pressure, it is particularly preferable that the other vinyl monomer contained as a polymerization component contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate. .
The specific styrene resin and the specific (meth)acrylic acid ester resin described below preferably contain the same type of (meth)acrylic acid ester as a polymerization component from the viewpoint of forming a toner that easily undergoes a phase transition under pressure.

The mass proportion of the (meth)acrylic acid ester in the total polymerization components of the specific styrene resin is preferably 40% by mass or less, and 30% by mass from the viewpoint of suppressing fluidization of the toner in an unpressurized state. The content is more preferably 25% by mass or less, still more preferably 25% by mass or less, and from the viewpoint of forming a toner that easily undergoes a phase transition under pressure, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. As the (meth)acrylic ester here, (meth)acrylic acid alkyl ester is preferable, and (meth)acrylic acid alkyl ester in which the number of carbon atoms in the alkyl group is 2 or more and 10 or less is more preferable. More preferred are (meth)acrylic acid alkyl esters having 4 or more and 8 or less carbon atoms.

It is particularly preferable that the specific styrenic resin contains at least one of n-butyl acrylate and 2-ethylhexyl acrylate as a polymerization component, and n-butyl acrylate and 2-ethylhexyl acrylate account for the entire polymerization component of the styrenic resin. The total amount is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less, from the viewpoint of suppressing fluidization of the toner in a non-pressurized state. From the viewpoint of forming a toner that is easy to apply, the amount is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more.

The weight average molecular weight of the specific styrene resin is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more, from the viewpoint of suppressing fluidization of the toner in a non-pressurized state. From the viewpoint of forming a toner that is easy to apply, it is preferably 60,000 or less, more preferably 55,000 or less, and even more preferably 50,000 or less.

In the present disclosure, the weight average molecular weight of the resin is measured by gel permeation chromatography (GPC). Molecular weight measurement by GPC is performed using Tosoh HLC-8120GPC as a GPC device, Tosoh TSKgel SuperHM-M (15 cm) as a column, and tetrahydrofuran as a solvent. The weight average molecular weight of the resin is calculated using a molecular weight calibration curve prepared from monodisperse polystyrene standard samples.

The glass transition temperature of the specific styrene resin is preferably 30° C. or higher, more preferably 40° C. or higher, and 50° C. from the viewpoint of suppressing fluidization of the toner in an unpressurized state. The temperature is more preferably at least 110°C, more preferably at most 100°C, and even more preferably at most 90°C, from the viewpoint of forming a toner that easily undergoes phase transition under pressure.

In the present disclosure, the glass transition temperature of the resin is determined from a differential scanning calorimetry curve (DSC curve) obtained by performing differential scanning calorimetry (DSC). More specifically, it is determined according to the "extrapolated glass transition start temperature" described in the method for determining the glass transition temperature of JIS K7121:1987 "Method for measuring transition temperature of plastics".

The glass transition temperature of the resin can be controlled by the type and polymerization ratio of polymerization components. The glass transition temperature decreases as the density of flexible units such as methylene, ethylene, and oxyethylene groups in the main chain increases, and the higher the density of rigid units such as aromatic rings and cyclohexane rings in the main chain. It tends to be higher. Moreover, the glass transition temperature tends to be lower as the density of aliphatic groups in the side chain is higher.

In this embodiment, the mass ratio of the specific styrene resin to the entire toner particles is preferably 55% by mass or more, and more preferably 60% by mass or more, from the viewpoint of suppressing fluidization of the toner in an unpressurized state. It is preferably 65% by mass or more, and more preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less, from the viewpoint of forming a toner that easily undergoes a phase transition under pressure.

-Specific (meth)acrylic acid ester resin-
The toner particles constituting the toner according to the present embodiment include at least two types of (meth)acrylic esters as polymerization components, and the mass ratio of the (meth)acrylic esters to the entire polymerization component is 90% by mass or more. Contains (meth)acrylic acid ester resin.

The mass ratio of the (meth)acrylic ester to the entire polymerization component of the (meth)acrylic ester resin is 90% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more, and 100% by mass or more. % is more preferable.

(Meth)acrylic acid esters include (meth)acrylic acid alkyl ester, (meth)acrylic acid carboxy-substituted alkyl ester, (meth)acrylic acid hydroxy-substituted alkyl ester, (meth)acrylic acid alkoxy-substituted alkyl ester, di(meth)acrylic acid alkoxy-substituted alkyl ester, ) acrylic esters, etc.

Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate. Isobutyl methacrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclo (meth)acrylate Examples include pentanyl and isobornyl (meth)acrylate.
Examples of the carboxy-substituted alkyl (meth)acrylate include 2-carboxyethyl (meth)acrylate and the like.
The (meth)acrylic acid hydroxy-substituted alkyl esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxy (meth)acrylate. Examples include butyl, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
Examples of the alkoxy-substituted alkyl (meth)acrylate include 2-methoxyethyl (meth)acrylate.
Examples of di(meth)acrylic acid esters include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, pentanediol di(meth)acrylate, Examples include hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, and decanediol di(meth)acrylate.

Examples of the (meth)acrylic ester include 2-(diethylamino)ethyl (meth)acrylate, benzyl (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate.

One type of (meth)acrylic acid ester may be used alone, or two or more types may be used in combination.

The (meth)acrylic acid ester is preferably a (meth)acrylic acid alkyl ester from the viewpoint of forming a toner that easily undergoes a phase transition under pressure and has excellent adhesive properties, and the alkyl group has 2 or more carbon atoms and 10 or less carbon atoms. Certain (meth)acrylic acid alkyl esters are more preferred, (meth)acrylic acid alkyl esters in which the alkyl group has 4 to 8 carbon atoms are even more preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred. preferable.
As mentioned above, the specific (meth)acrylic ester resin and the specific styrene resin contain the same type of (meth)acrylic ester as a polymerization component from the viewpoint of forming a toner that easily undergoes a phase transition under pressure. is preferred.

The mass proportion of the (meth)acrylic acid alkyl ester in the entire polymerization component of the specific (meth)acrylic acid ester resin is 90% by mass or more, from the viewpoint of forming a toner that easily undergoes a phase transition under pressure and has excellent adhesive properties. It is preferably 95% by mass or more, more preferably 98% by mass or more, even more preferably 100% by mass. Here, the (meth)acrylic acid alkyl ester is preferably a (meth)acrylic acid alkyl ester in which the number of carbon atoms in the alkyl group is 2 or more and 10 or less, and the number of carbon atoms in the alkyl group is 4 or more and 8 or less. Certain (meth)acrylic acid alkyl esters are more preferred.

Among the at least two types of (meth)acrylic esters contained as polymerization components in the specific (meth)acrylic ester-based resin, the two types having the highest mass ratio easily undergo a phase transition under pressure and have excellent adhesive properties. From the viewpoint of toner formation, the ratio is preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and even more preferably 60:40 to 40:60.

Of the at least two types of (meth)acrylic esters contained as polymerization components in the specific (meth)acrylic ester-based resin, it is preferable that the two types having the highest mass proportions are alkyl (meth)acrylic esters. Here, the (meth)acrylic acid alkyl ester is preferably a (meth)acrylic acid alkyl ester in which the number of carbon atoms in the alkyl group is 2 or more and 10 or less, and the number of carbon atoms in the alkyl group is 4 or more and 8 or less. Certain (meth)acrylic acid alkyl esters are more preferred.

If two of the at least two types of (meth)acrylic esters that are included as polymerization components in the specific (meth)acrylic ester resin are alkyl (meth)acrylate esters, the two types are The difference in the number of carbon atoms in the alkyl groups of the (meth)acrylic acid alkyl ester is preferably 1 or more and 4 or less, and 2 or more and 4 or less, from the viewpoint of forming a toner that is easily transferred by pressure and has excellent adhesive properties. It is more preferable that the number is less than 1, and even more preferably 3 or 4.

The specific (meth)acrylic acid ester resin preferably contains n-butyl acrylate and 2-ethylhexyl acrylate as polymerization components, from the viewpoint of forming a toner that easily undergoes a phase transition under pressure and has excellent adhesive properties. In particular, it is preferable that the two types with the highest mass proportions among at least two types of (meth)acrylic esters contained as polymerization components in the meth)acrylic ester resin are n-butyl acrylate and 2-ethylhexyl acrylate. preferable. The total amount of n-butyl acrylate and 2-ethylhexyl acrylate in the total polymerization components of the (meth)acrylic acid ester resin is preferably 90% by mass or more, more preferably 95% by mass or more, and 98% by mass or more. More preferably, 100% by mass is even more preferred.

The specific (meth)acrylic ester resin may contain a vinyl monomer other than the (meth)acrylic ester as a polymerization component.
Examples of vinyl monomers other than (meth)acrylic acid esters include (meth)acrylic acid; styrene; styrenic monomers other than styrene; (meth)acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl methyl ketone; Vinyl ketones such as vinyl ethyl ketone and vinyl isopropenyl ketone; olefins such as isoprene, butene and butadiene; These vinyl monomers may be used alone or in combination of two or more.

When the specific (meth)acrylic ester resin contains a vinyl monomer other than the (meth)acrylic ester as a polymerization component, the vinyl monomer other than the (meth)acrylic ester is preferably at least one of acrylic acid and methacrylic acid. , acrylic acid is more preferred.

The weight average molecular weight of the specific (meth)acrylic acid ester resin is preferably 100,000 or more, more preferably 120,000 or more, and 150,000 or more, from the viewpoint of suppressing fluidization of the toner in an unpressurized state. is more preferable, and from the viewpoint of forming a toner that easily undergoes phase transition under pressure, it is preferably 250,000 or less, more preferably 220,000 or less, and even more preferably 200,000 or less.

The glass transition temperature of the specific (meth)acrylic acid ester resin is preferably 10°C or lower, more preferably 0°C or lower, and -10°C or lower, from the viewpoint of forming a toner that easily undergoes a phase transition under pressure. The temperature is more preferably -90°C or higher, more preferably -80°C or higher, and -70°C or higher, from the viewpoint of suppressing fluidization of the toner in an unpressurized state. It is more preferable that the temperature is at least ℃.

In the present embodiment, the mass ratio of the specific (meth)acrylic acid ester resin to the entire toner particles is preferably 20% by mass or more, more preferably 25% by mass or more, from the viewpoint of forming a toner that easily undergoes a phase transition under pressure. , more preferably 30% by mass or more, and from the viewpoint of suppressing fluidization of the toner in an unpressurized state, 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less. .

In the present embodiment, the total amount of the specific styrene resin and specific (meth)acrylate resin contained in the toner particles is preferably 70% by mass or more, more preferably 80% by mass or more, based on the entire toner particles. It is more preferably 90% by mass or more, even more preferably 95% by mass or more, and still more preferably 100% by mass.

The toner particles may contain, if necessary, for example, polystyrene; non-vinyl resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and modified rosins; and the like.
These resins may be used alone or in combination of two or more.

[Yellow pigment]
The toner particles contain a yellow pigment, and the content of the yellow pigment is 5 ppm or more and 100 ppm or less on a mass basis.
When the content of the yellow pigment is 5 ppm or more, the effect of suppressing the inside of the machine due to the yellow pigment is exerted. It is thought that when the content of the yellow pigment is 100 ppm or less, the average charge amount of the toner is not lowered too much, so that staining inside the machine is suppressed.
In addition, since the content of the yellow pigment is 100 ppm or less, there is also an effect that the visibility of the image in the pressure-bonded printed matter does not deteriorate.

Examples of the method for measuring the content of yellow pigment in the toner (toner particles) according to the present embodiment include the following method.
The content of yellow pigment was determined by GC-MS (gas chromatography mass spectrometry), TG-DTA (simultaneous thermal analysis-differential thermogravimetry), IPC-OES (inductively coupled plasma optical emission spectrometry), IPC-AES (plasma emission spectrometry), It can be quantified by combining analysis such as spectroscopic analysis), IPC-MS (inductively coupled plasma mass spectrometry), and atomic absorption.
Quinacridone pigments can be quantitatively determined, for example, by combining structural analysis by pyrolysis GC/MS with analysis by IPC-MS, atomic absorption, or the like.
In addition, C.I., which is a monoazo pigment, I. Regarding Pigment Yellow 74, the pigment content may be determined by, for example, quantifying pigment-derived atoms such as the amount of chlorine atoms in the pigment by analysis such as IPC (inductively coupled plasma analysis) or atomic absorption. According to these analyses, the relationship between the amount of pigment charged and the detected amount is as shown in the table below, and based on this table, the content of yellow pigment in the toner (toner particles) may be determined.

The content of the yellow pigment is preferably 5 ppm or more and 80 ppm or less, more preferably 10 ppm or more and 70 ppm or less, and even more preferably 15 ppm or more and 60 ppm or less, from the viewpoint of suppressing in-machine staining.
On the other hand, the content of the yellow pigment is preferably 10 ppm or more and 80 ppm or less, more preferably 15 ppm or more and 70 ppm or less, and even more preferably 20 ppm or more and 60 ppm or less.
Moreover, one type of yellow pigment may be used alone, or two or more types may be used in combination.

The yellow pigment is not particularly limited as long as it has an absorption peak wavelength of 530 nm or more and 620 nm or less, and can be appropriately selected from known yellow pigments.
As the yellow pigment, C.I. I. Pigment Yellow 74, C. I. Pigment Yellow 1, 2, 3, 5, 6, 49, 65, 73, 75, 97, 98, 111, 116, 130 and other monoazo pigments; C.I. I. Pigment Yellow 154, C. I. Pigment Yellow 120, 151, 175, 180, 181, 194 and other benzimidazolone pigments; C.I. I. Pigment Yellow 93, C. I. Pigment Yellow 94, 95, 128, 166, 12, 13, 14, 17, 55, 63, 81, 83, 87, 90, 106, 113, 114, 121, 124, 126, 127, 136, 152, 170, Disazo pigments such as 171, 172, 174, 176, and 188; C.I. I. Pigment Yellow 110, C. I. Isoindolinone pigments such as Pigment Yellow 109; C.I. pigments represented by the following formula (5); I. Pigment Yellow 147, C. I. Anthraquinone pigments such as Pigment Yellow 24, 108, 193, 199; C.I. I. Pigment Yellow 61, 62, 133, 168, 169 and other azo lake pigments; C.I. I. Isoindoline pigments such as Pigment Yellow 139; C.I. I. Examples include quinophthalone pigments such as Pigment Yellow 138.

Among these, the yellow pigment is preferably a pigment selected from the group consisting of monoazo pigments, disazo pigments, and benzimidazolone pigments, from the viewpoint of suppressing machine interior stains. Pigments selected from the group consisting of disazo pigments are more preferred.
More specifically, as a monoazo pigment, C.I. I. Pigment Yellow 74 is preferred, and as the disazo pigment, C.I. I. Pigment Yellow 93 is preferred, and as the benzimidazolone disazo pigment, C.I. I. Pigment Yellow 180 is preferred.
As the yellow pigment, C. I. Pigment Yellow 74, C. I. Pigment Yellow 93, and C.I. I. Particular preference is given to pigments selected from Pigment Yellow 180.

-Dispersion of yellow pigment-
In the toner particles, the yellow pigment is preferably dispersed in the binder resin. In particular, it is preferable that it is dispersed in the binder resin in the shell layer of the core-shell structure particles described below.
When toner particles are manufactured by a kneading and pulverizing method, the yellow pigment may be used as it is, or it may be dispersed in a binder resin in advance at a high concentration and then mixed with the binder resin during kneading, in a so-called masterbatch. Alternatively, flushing may be used, in which the yellow pigment is dispersed in the binder resin in the form of a wet cake before drying after synthesis.
If the toner particles are manufactured by suspension polymerization, the yellow pigment may be used as is. In the suspension polymerization method, the yellow pigment dispersed in the binder resin is dissolved or dispersed in the polymerizable monomer, thereby dispersing the yellow pigment in the granulated particles.
When the toner manufacturing method is an aggregation coalescence method, the yellow pigment is dispersed in the binder resin by preparing a yellow pigment dispersion, agglomerating this with binder resin particles, etc., and granulating it to the toner particle size. Toner particles are obtained.

[Other ingredients]
The toner particles may contain other components as necessary.
Other ingredients include colorants other than yellow pigments (e.g. pigments, dyes), mold release agents (e.g. hydrocarbon waxes; natural waxes such as carnauba wax, rice wax, candelilla wax; synthetic waxes such as montan wax). or mineral/petroleum waxes; ester waxes such as fatty acid esters and montanic acid esters).

The toner according to the present embodiment may contain a colorant other than the yellow pigment as long as the visibility of the image is not impaired.
The content of the colorant in the toner particles is preferably 1.0% by mass or less based on the entire toner particles, and from the viewpoint of improving the transparency of the toner, the smaller the content, the more preferable it is.
More specifically, the total content of colorants other than the yellow pigment is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 0 ppm, that is, not contained.

-Structure of toner particles-
The internal structure of the toner particles is preferably a sea-island structure.
The sea-island structure is preferably a sea-island structure having a sea phase containing one of two or more binder resins and an island phase containing the other binder resin dispersed in the sea phase. From the viewpoint of easy phase transition due to pressure, more specifically, a sea-island structure having a sea phase containing a specific styrene resin and an island phase containing a specific (meth)acrylic acid ester resin dispersed in the sea phase. is preferred. Details of the specific styrene resin contained in the sea phase and the (meth)acrylic acid ester resin contained in the island phase are as described above. Note that an island phase not containing a (meth)acrylic acid ester resin may be dispersed in the sea phase.

When the toner particles have a sea-island structure, the average diameter of the island phase is preferably 200 nm or more and 500 nm or less. If the average diameter of the island phase is 500 nm or less, the toner particles are likely to undergo phase transition due to pressure, and if the average diameter of the island phase is 200 nm or more, the mechanical strength required for the toner particles (for example, stirring in the developing device) It has excellent strength and does not easily deform when exposed to heat. From these viewpoints, the average diameter of the island phase is more preferably 220 nm or more and 450 nm or less, and even more preferably 250 nm or more and 400 nm or less.

As a method for controlling the average diameter of the island phase of the sea-island structure within the above range, for example, in the toner particle manufacturing method described below, the amount of the specific (meth)acrylic acid ester resin relative to the amount of the specific styrene resin is increased or decreased. , increasing or decreasing the time for maintaining the high temperature in the process of fusing and coalescing the aggregated resin particles.

Confirm the sea-island structure and measure the average diameter of the island facies using the following method.
The toner is embedded in epoxy resin, sections are prepared using a diamond knife, etc., and the sections are stained with osmium tetroxide or ruthenium tetroxide in a desiccator. Observe the stained section with a scanning electron microscope (SEM). The ocean phase and the island phase of the sea-island structure are distinguished by the light and shade caused by the degree of staining of the resin with osmium tetroxide or ruthenium tetroxide, and this is used to confirm the presence or absence of the sea-island structure. 100 island facies are randomly selected from the SEM image, the long axis of each island facies is measured, and the average value of the 100 long axes is taken as the average diameter.

The toner particles may have a single layer structure or may have a core-shell structure having a core portion and a shell layer covering the core portion. From the viewpoint of suppressing fluidization of the toner in a non-pressurized state, it is preferable that the toner particles have a core-shell structure.

When the toner particles have a core-shell structure, the core portion preferably contains a specific styrene resin and a specific (meth)acrylic acid ester resin from the viewpoint of easy phase transition due to pressure. Furthermore, from the viewpoint of suppressing fluidization of the toner in a non-pressurized state, it is preferable that the shell layer contains a specific styrene resin.

When the toner particles have a core-shell structure, it is preferable that the core portion has a sea phase containing a specific styrene resin and an island phase containing a specific (meth)acrylic acid ester resin dispersed in the sea phase. The average diameter of the island phase is preferably within the range described above. Furthermore, in addition to the core having the above structure, it is preferable that the shell layer contains a specific styrene resin. In this case, the sea phase in the core portion and the shell layer have a continuous structure, and the toner particles are likely to undergo phase transition due to pressure.

Examples of the resin contained in the shell layer include polystyrene; non-vinyl resins such as epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, and modified rosin; and the like.
These resins may be used alone or in combination of two or more.

The average thickness of the shell layer is preferably 120 nm or more, more preferably 130 nm or more, even more preferably 140 nm or more from the viewpoint of suppressing deformation of the toner particles, and preferably 550 nm or less from the viewpoint that the toner particles easily undergo phase transition due to pressure. The thickness is more preferably 500 nm or less, and even more preferably 400 nm or less.

The average thickness of the shell layer is measured by the following method.
The toner is embedded in epoxy resin, sections are prepared using a diamond knife, etc., and the sections are stained with osmium tetroxide or ruthenium tetroxide in a desiccator. Observe the stained section with a scanning electron microscope (SEM). Randomly select 10 toner particle cross sections from the SEM image, measure the thickness of the shell layer per toner particle at 20 locations, calculate the average value, and calculate the average value of the 10 toner particles as the average thickness. do.

From the viewpoint of ease of handling the toner particles, the volume average particle diameter (D50v) of the toner particles is preferably 4 μm or more, more preferably 5 μm or more, and even more preferably 6 μm or more, and the entire toner particles are likely to undergo phase transition due to pressure. From the viewpoint, the thickness is preferably 12 μm or less, more preferably 10 μm or less, and even more preferably 9 μm or less.

The volume average particle diameter (D50v) of the toner particles is measured using Coulter Multisizer II (manufactured by Beckman Coulter) and an aperture with an aperture diameter of 100 μm. 0.5 mg to 50 mg of toner particles are added to 2 mL of a 5% by mass aqueous solution of sodium alkylbenzenesulfonate, dispersed, and then mixed with 100 mL to 150 mL of an electrolytic solution (ISOTON-II, manufactured by Beckman Coulter) using an ultrasonic dispersion machine. Perform dispersion treatment for 1 minute, and use the resulting dispersion as a sample. Measure the particle size of 50,000 particles with a particle size of 2 μm or more and 60 μm or less in the sample. The particle size that cumulatively accounts for 50% in the volume-based particle size distribution starting from the small diameter side is defined as the volume average particle size (D50v).

[External additive]
Examples of external additives include inorganic particles. Inorganic particles include SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO _{2 , CeO 2 ,} Fe ₂ O ₃ , MgO, BaO, CaO, K ₂ O, Na ₂ O, ZrO ₂ , CaO・SiO ₂ , _K2O .( _TiO2 )n, _Al2O3.2SiO2 , _{CaCO3 , MgCO3} , _BaSO4 , _MgSO4, and the like _.

The surface of the inorganic particles used as the external additive is preferably subjected to a hydrophobic treatment. The hydrophobization treatment is performed, for example, by immersing the inorganic particles in a hydrophobization treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminum coupling agents, and the like. These may be used alone or in combination of two or more. The amount of the hydrophobizing agent is, for example, 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the inorganic particles.

External additives include resin particles (resin particles such as polystyrene, polymethyl methacrylate, and melamine resin), cleaning active agents (for example, metal salts of higher fatty acids such as zinc stearate, and particles of fluorine-based polymers). etc. can also be mentioned.

The external additive amount is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.01% by mass or more and 2.0% by mass or less, based on the toner particles.

[Toner characteristics]
The toner according to the present embodiment has at least two glass transition temperatures; one of the glass transition temperatures is presumed to be derived from one of two or more types of binder resins, and the other is a glass transition temperature of two or more types of binder resins. It is presumed that the glass transition temperature originates from the other of the above binder resins. As mentioned above, when the binder resin contains a specific styrene resin and a specific (meth)acrylic acid ester resin, one of the glass transition temperatures is assumed to be that of the specific styrene resin, and the other is the glass transition temperature of the specific styrene resin. One is presumed to be the glass transition temperature of the specific (meth)acrylic ester resin.

Although the toner according to the present embodiment may have three or more glass transition temperatures, it is preferable that the number of glass transition temperatures is two. A form in which the number of glass transition temperatures is two is a form in which the resin contained in the toner is only a specific styrene resin and a specific (meth)acrylic acid ester resin; a specific styrene resin and a specific (meth)acrylic acid ester resin; A form in which the content of other resins other than ester resins is small (for example, a form in which the content of other resins is 5% by mass or less based on the entire toner);

The toner according to the present embodiment has at least two glass transition temperatures, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30° C. or more. The difference between the lowest glass transition temperature and the highest glass transition temperature is more preferably 40° C. or higher, still more preferably 50° C. or higher, and still more preferably 60° C., from the viewpoint that the toner easily undergoes a phase transition due to pressure. That's all. The upper limit of the difference between the lowest glass transition temperature and the highest glass transition temperature is, for example, 140°C or less, 130°C or less, and 120°C or less.

The lowest glass transition temperature exhibited by the toner according to the present embodiment is preferably 10°C or lower, more preferably 0°C or lower, and -10°C or lower, from the viewpoint that the toner easily undergoes a phase transition due to pressure. More preferably, the temperature is -90°C or higher, more preferably -80°C or higher, and -70°C or higher, from the viewpoint of suppressing fluidization of the toner in an unpressurized state. It is more preferable that

The highest glass transition temperature exhibited by the toner according to this embodiment is preferably 30°C or higher, and preferably 40°C or higher, from the viewpoint of suppressing fluidization of the toner in an unpressurized state. The temperature is more preferably 50°C or higher, and from the viewpoint that the toner easily undergoes a phase transition due to pressure, the temperature is preferably 70°C or lower, more preferably 65°C or lower, and 60°C or lower. More preferred.

In the present disclosure, the glass transition temperature of the toner is determined from a differential scanning calorimetry curve (DSC curve) obtained by performing differential scanning calorimetry (DSC). More specifically, it is determined according to the "extrapolated glass transition start temperature" described in the method for determining the glass transition temperature of JIS K7121:1987 "Method for measuring transition temperature of plastics".

The toner according to this embodiment is a toner that undergoes a phase transition under pressure, and satisfies the following formula 1.
Formula 1...10℃≦T1-T2
In Equation 1, T1 is a temperature at which the viscosity is 10,000 Pa·s under a pressure of 1 MPa, and T2 is a temperature at which the viscosity is 10,000 Pa·s at a pressure of 10 MPa.

The temperature difference (T1-T2) is 10°C or higher, preferably 15°C or higher, and more preferably 20°C or higher, from the viewpoint that the toner is likely to undergo a phase transition due to pressure, and the toner is fluidized without being pressurized. From the viewpoint of suppressing this, the temperature is preferably 120°C or lower, more preferably 100°C or lower, and even more preferably 80°C or lower.

The value of temperature T1 is preferably 140°C or less, more preferably 130°C or less, even more preferably 120°C or less, and even more preferably 115°C or less. The lower limit of temperature T1 is preferably 80°C or higher, more preferably 85°C or higher.
The value of temperature T2 is preferably 40°C or higher, more preferably 50°C or higher, and even more preferably 60°C or higher. The upper limit of temperature T2 is preferably 85°C or less.

As an index indicating that the toner is likely to undergo a phase transition due to pressure, the temperature difference (T1-T3) between temperature T1 at which the viscosity is 10,000 Pa·s under a pressure of 1 MPa and temperature T3 at which the viscosity is 10,000 Pa·s under a pressure of 4 MPa (T1-T3 ), and the temperature difference (T1-T3) is preferably 5°C or more. In the toner according to the present embodiment, the temperature difference (T1-T3) is preferably 5° C. or more, more preferably 10° C. or more, from the viewpoint that phase transition occurs easily due to pressure.
The temperature difference (T1-T3) is generally 25°C or less.

In the toner according to the present embodiment, from the viewpoint that the temperature difference (T1-T3) is 5°C or more, it is preferable that the temperature T3 at which the viscosity is 10000 Pa·s under a pressure of 4 MPa is 90°C or less, and preferably 85°C or less. It is more preferable that the temperature be 80° C. or lower. The lower limit of temperature T3 is preferably 60°C or higher.

The method for determining temperature T1, temperature T2, and temperature T3 is as follows.
Compress the toner to create a pellet sample. A pellet-shaped sample is set in a flow tester (manufactured by Shimadzu Corporation, CFT-500), the applied pressure is fixed at 1 MPa, and the viscosity with respect to temperature at 1 MPa is measured. From the obtained viscosity graph, the temperature T1 at which the viscosity becomes 10 ⁴ Pa·s at an applied pressure of 1 MPa is determined. Temperature T2 is determined in the same manner as the method related to temperature T1, except that the applied pressure is changed from 1 MPa to 10 MPa. Temperature T3 is determined in the same manner as the method related to temperature T1, except that the applied pressure is changed from 1 MPa to 4 MPa. A temperature difference (T1-T2) is calculated from temperature T1 and temperature T2. A temperature difference (T1-T3) is calculated from temperature T1 and temperature T3.

[Toner manufacturing method]
The toner according to the present embodiment is obtained by externally adding an external additive to the toner particles after manufacturing the toner particles.

The toner particles may be manufactured by either a dry manufacturing method (eg, kneading and pulverizing method) or a wet manufacturing method (eg, aggregation coalescence method, suspension polymerization method, dissolution/suspension method, etc.). There are no particular restrictions on these manufacturing methods, and known manufacturing methods may be employed. Among these, it is preferable to obtain toner particles by an agglomeration method.

Hereinafter, a method for manufacturing toner particles containing a specific styrene resin and a specific (meth)acrylic acid ester resin as a binder resin by an aggregation coalescence method will be described as an example.
When producing toner particles by an agglomeration method, for example,
a step of preparing a styrenic resin particle dispersion in which styrenic resin particles containing a specific styrenic resin are dispersed (styrenic resin particle dispersion preparation step);
A step of polymerizing a specific (meth)acrylic acid ester resin in a styrene resin particle dispersion to form composite resin particles containing a specific styrene resin and a specific (meth)acrylic acid ester resin (composite resin particle formation process) and
A step of preparing a yellow pigment dispersion liquid in which a yellow pigment is dispersed (yellow pigment dispersion preparation step);
A step of mixing a composite resin particle dispersion in which composite resin particles are dispersed and a yellow pigment dispersion, and aggregating the composite resin particles and yellow pigment to form agglomerated particles (agglomerated particle forming step);
Toner particles are manufactured through a step of heating an agglomerated particle dispersion liquid in which agglomerated particles are dispersed, and fusing and coalescing the agglomerated particles to form toner particles (fusion/coalescence step).

When toner particles are produced by the agglomeration method as described above, toner particles with excellent adhesive properties may be obtained due to the presence and function of the yellow pigment. Although the details of the mechanism are unknown, it is thought that the presence of the yellow pigment acts to increase the average diameter of the island phase of the sea-island structure.
In the agglomerated particle formation process, the yellow pigment becomes unevenly distributed on the surface of the composite resin particles, but if there is a negative charge derived from acrylic acid on the composite resin particle, the nitrogen atoms contained in the yellow pigment function to cancel out the negative charge. do. As a result, when the composite resin particles are fused and unified, the repulsion to the cohesive force due to negative charges is suppressed, and toner particles having island phases with a large average diameter are produced.

The details of each step will be explained below.
In the following description, a method for obtaining toner particles that do not contain a release agent will be described. A mold release agent and other additives may be used as necessary.
When toner particles contain a release agent, in the agglomerated particle forming step, a composite resin particle dispersion, a colorant particle dispersion, and a release agent particle dispersion are mixed, and the composite resin particles, yellow pigment, and What is necessary is to aggregate the mold release agent to form aggregated particles.
The release agent particle dispersion can be prepared, for example, by mixing a release agent and a dispersion medium and then performing a dispersion treatment using a known dispersion machine.

-Styrenic resin particle dispersion preparation process-
In the styrenic resin particle dispersion preparation step, a styrenic resin particle dispersion in which styrenic resin particles containing a specific styrenic resin are dispersed is prepared.
The styrenic resin particle dispersion is, for example, a dispersion in which styrene resin particles are dispersed in a dispersion medium using a surfactant.

Examples of the dispersion medium include aqueous media such as water and alcohols. These may be used alone or in combination of two or more.

Examples of the surfactant include anionic surfactants such as sulfate ester salts, sulfonate salts, phosphate esters, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; polyethylene glycol Examples include nonionic surfactants such as surfactants based on surfactants, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Nonionic surfactants may be used in combination with anionic surfactants or cationic surfactants. Among these, anionic surfactants are preferred. One type of surfactant may be used alone, or two or more types may be used in combination.

As a method for dispersing styrenic resin particles in a dispersion medium, for example, a specific styrenic resin and a dispersion medium are mixed, and the mixture is stirred and dispersed using a rotary shear type homogenizer, a ball mill with media, a sand mill, a dyno mill, etc. There are several methods.

Another method for dispersing styrene resin particles in a dispersion medium is emulsion polymerization. Specifically, after mixing the polymerization component of a specific styrenic resin with a chain transfer agent or a polymerization initiator, an aqueous medium containing a surfactant is further mixed and stirred to prepare an emulsion. Inside, styrene resin is polymerized. At this time, it is preferable to use dodecanethiol as a chain transfer agent.

The volume average particle diameter of the styrene resin particles dispersed in the styrene resin particle dispersion is preferably 100 nm or more and 250 nm or less, more preferably 120 nm or more and 220 nm or less, and even more preferably 150 nm or more and 200 nm or less.
The volume average particle size of the resin particles contained in the resin particle dispersion is determined by measuring the particle size using a laser diffraction particle size distribution analyzer (for example, Horiba LA-700), and calculating the volume-based particle size starting from the small diameter side. The particle size that cumulatively accounts for 50% in the distribution is defined as the volume average particle size (D50v).

The content of styrenic resin particles contained in the styrenic resin particle dispersion is preferably 30% by mass or more and 60% by mass or less, and 40% by mass or more and 50% by mass or less, based on the total mass of the styrenic resin particle dispersion. is more preferable.

-Composite resin particle formation process-
In the composite resin particle forming step, a specific (meth)acrylic acid ester resin is polymerized in a styrene resin particle dispersion to form composite resin particles containing a specific styrene resin and a specific (meth)acrylic acid ester resin. do.
In the composite resin particle forming step, a styrene resin particle dispersion and a polymerization component of a specific (meth)acrylic ester resin are mixed, and the specific (meth)acrylic ester resin is polymerized in the styrene resin particle dispersion. Then, composite resin particles containing the specific styrene resin and the specific (meth)acrylic acid ester resin are formed.

The composite resin particles are preferably resin particles containing a specific styrene resin and a specific (meth)acrylic acid ester resin in a microphase-separated state. The resin particles can be produced, for example, by the method described below.

A polymerization component of a specific (meth)acrylic acid ester resin (a monomer group containing at least two types of (meth)acrylic acid esters) is added to the styrene resin particle dispersion, and an aqueous medium is added as necessary. Next, while stirring the dispersion liquid slowly, the temperature of the dispersion liquid is heated to a temperature higher than the glass transition temperature of the specific styrenic resin (eg, 10 to 30° C. higher than the glass transition temperature of the specific styrenic resin). Next, while maintaining the temperature, an aqueous medium containing a polymerization initiator is slowly added dropwise, and stirring is further continued for a long time in the range of 1 hour to 15 hours. At this time, it is preferable to use ammonium persulfate as a polymerization initiator.

Although the detailed mechanism is not necessarily clear, when the above method is adopted, the monomer and polymerization initiator are impregnated into the styrene resin particles, and the specific (meth)acrylic ester is produced inside the styrenic resin particles. It is assumed that it will polymerize. As a result, the specific (meth)acrylic acid ester resin is contained inside the styrene resin particles, and the specific styrene resin and the specific (meth)acrylic acid ester resin are in a state of microphase separation inside the particles. It is presumed that composite resin particles formed by this method can be obtained.

The volume average particle diameter of the composite resin particles dispersed in the composite resin particle dispersion is preferably 140 nm or more and 300 nm or less, more preferably 150 nm or more and 280 nm or less, and even more preferably 160 nm or more and 250 nm or less.

The content of the composite resin particles contained in the composite resin particle dispersion is preferably 20% by mass or more and 50% by mass or less, more preferably 30% by mass or more and 40% by mass or less, based on the total mass of the composite resin particle dispersion. .

-Yellow pigment dispersion preparation process-
In the yellow pigment dispersion preparation step, a yellow pigment dispersion in which a yellow pigment is dispersed is prepared.
The method for preparing the yellow pigment dispersion is not particularly limited. For example, similar to the styrene resin particle dispersion preparation step, the yellow pigment can be prepared by dispersing the yellow pigment together with a surfactant in a dispersion medium by mechanical impact or the like. A dispersion is prepared. For dispersion of the yellow pigment by mechanical impact, for example, a media-type dispersion machine such as a rotary shear type homogenizer, a ball mill, a sand mill, an attritor, a high-pressure opposing collision type dispersion machine, etc. are used. The yellow pigment may be dispersed using a dispersing machine such as a homogenizer using a polar surfactant.
The volume average particle size, dispersion medium, dispersion method, and content of particles (i.e., yellow pigment) in the yellow pigment dispersion are the same as in each of the styrenic resin particle dispersions, and are preferred. The aspects are also similar.

-Agglomerated particle formation process-
In the aggregated particle forming step, a composite resin particle dispersion in which composite resin particles are dispersed and a yellow pigment dispersion are mixed, and the composite resin particles and yellow pigment are aggregated to form aggregated particles.
Here, in the aggregated particle forming step, the composite resin particles and the yellow pigment are aggregated to form aggregated particles having a diameter close to that of the target toner particles.

Concerning the agglomerated particle forming step, specifically, for example, an aggregating agent is added to a mixture of a composite resin particle dispersion and a yellow pigment dispersion, and the pH of the composite resin particle dispersion is adjusted to an acidic state (for example, pH 2 or more and 5 or less). ), and if necessary, add a dispersion stabilizer, then heat the glass to a temperature close to the glass transition temperature of the specific styrenic resin (specifically, for example, the glass transition temperature of the specific styrene resin - 30°C or higher). transition temperature -10° C. or lower) to aggregate the composite resin particles and the yellow pigment to form aggregated particles.

In the agglomerated particle forming step, a flocculant is added to the mixed liquid of the composite resin particle dispersion and the yellow pigment dispersion at room temperature (e.g. 25°C) while stirring with a rotary shear type homogenizer, and the pH of the composite resin particle dispersion is adjusted. The mixture may be heated after adjusting it to be acidic (for example, pH 2 or more and 5 or less) and adding a dispersion stabilizer if necessary.

Examples of the flocculant include a surfactant having a polarity opposite to that of the surfactant contained in the composite resin particle dispersion, an inorganic metal salt, and a divalent or higher-valent metal complex. When a metal complex is used as the flocculant, the amount of surfactant used is reduced and charging characteristics are improved.
Along with the flocculant, an additive that forms a complex or similar bond with the metal ion of the flocculant may be used as necessary. A chelating agent is preferably used as this additive.

Examples of inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate; inorganic metal salts such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Polymer; etc. are mentioned.
As the chelating agent, a water-soluble chelating agent may be used. Examples of the chelating agent include oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid; aminocarboxylic acids such as iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA); It will be done.
The amount of the chelating agent added is preferably 0.01 parts by mass or more and 5.0 parts by mass or less, more preferably 0.1 parts by mass or more and less than 3.0 parts by mass, based on 100 parts by mass of the resin particles.

-Fusion/unification process-
In the fusion/coalescence step, the agglomerated particle dispersion liquid in which the agglomerated particles are dispersed is heated, and the agglomerated particles are fused/coalesced to form toner particles.
In the fusion/coalescence step, the agglomerated particle dispersion in which the agglomerated particles are dispersed is heated, for example, to a temperature higher than the glass transition temperature of the specific styrenic resin (for example, at a temperature 10 to 30° C. higher than the glass transition temperature of the specific styrenic resin). Heating fuses and coalesces the aggregated particles to form toner particles.

The toner particles obtained through the above steps usually have a sea-island structure having a sea phase containing a specific styrene resin and an island phase containing a specific (meth)acrylic acid ester resin dispersed in the sea phase. have In the composite resin particles, the specific styrenic resin and the specific (meth)acrylic acid ester resin were in a state of microphase separation, but during the fusion/coalescence process, the specific styrene resins gathered together to form a sea phase. It is presumed that the specific (meth)acrylic acid ester resins gather together to form an island phase.

The average diameter of the island phase of the sea-island structure can be determined, for example, by increasing or decreasing the amount of the styrene-based resin particle dispersion liquid or the amount of at least two types of (meth)acrylic acid esters used in the composite resin particle forming process, or by fusion/coalescence. It can be controlled by increasing or decreasing the time for maintaining the high temperature in the process.

Toner particles with a core-shell structure are, for example,
After obtaining the aggregated particle dispersion liquid (hereinafter also referred to as the first aggregated particle dispersion liquid in which the first aggregated particles are dispersed) in the above-mentioned aggregated particle forming step, the aggregated particle dispersion liquid and the styrene-based resin particle dispersion liquid are combined. A step of further mixing and aggregating the styrene resin particles to further adhere to the surface of the agglomerated particles to form second agglomerated particles (second agglomerated particle forming step);
A step of heating the second agglomerated particle dispersion in which the second agglomerated particles are dispersed to fuse and coalesce the second agglomerated particles to form toner particles having a core-shell structure (core-shell structure formation). process) and
Manufactured through.
The toner particles having a core-shell structure obtained through the above steps have a shell layer containing a specific styrene resin.
A shell layer containing another type of resin may be formed using a resin particle dispersion in which other types of resin particles are dispersed instead of the styrene resin particle dispersion.
In addition, in the agglomerated particle forming step described above, agglomerated particles containing no yellow pigment are formed without using the yellow pigment dispersion, and in the second agglomerated particle forming step, together with the styrene resin particle dispersion. A shell layer containing a yellow pigment and a specific styrene resin may be formed using a yellow pigment dispersion.

After the fusion/coalescence process is completed, the toner particles formed in the liquid are subjected to a known washing process, solid-liquid separation process, and drying process to obtain dry toner particles.
In the washing step, from the viewpoint of chargeability, it is preferable to perform sufficient displacement washing with ion-exchanged water. In the solid-liquid separation step, suction filtration, pressure filtration, etc. are preferably performed from the viewpoint of productivity. From the viewpoint of productivity, the drying process is preferably carried out by freeze drying, flash drying, fluidized drying, vibrating fluidized drying, or the like.

The toner according to the present embodiment is manufactured, for example, by adding and mixing external additives to the obtained dry toner particles.
Mixing may be performed using, for example, a V-blender, Henschel mixer, Loedige mixer, or the like.
Furthermore, if necessary, coarse toner particles may be removed using a vibrating sieve, a wind sieve, or the like.

<Electrostatic image developer>
The electrostatic image developer according to this embodiment contains at least the toner according to this embodiment.
The electrostatic image developer according to the present embodiment may be a one-component developer containing only the toner according to the present embodiment, or a two-component developer containing a mixture of the toner according to the present embodiment and a carrier. It's okay.

There are no particular limitations on the carrier, and known carriers may be used. Examples of carriers include coated carriers in which the surface of a core material made of magnetic powder is coated with resin; magnetic powder-dispersed carriers in which magnetic powder is dispersed in a matrix resin; porous magnetic powder impregnated with resin. and resin-impregnated carriers. The magnetic powder-dispersed carrier and the resin-impregnated carrier may be carriers in which the constituent particles of the carrier are used as a core material and the surface thereof is coated with a resin.

Examples of the magnetic powder include magnetic metals such as iron, nickel, and cobalt; magnetic oxides such as ferrite and magnetite; and the like.

Examples of coating resins and matrix resins include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid. Examples include ester copolymers, straight silicone resins containing organosiloxane bonds or modified products thereof, fluororesins, polyesters, polycarbonates, phenolic resins, and epoxy resins. The coating resin and matrix resin may contain other additives such as conductive particles. Examples of the conductive particles include particles of metals such as gold, silver, and copper, carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate.

The surface of the core material can be coated with a resin by a method of coating with a coating layer forming solution in which a coating resin and various additives (used as necessary) are dissolved in an appropriate solvent. The solvent is not particularly limited, and may be selected in consideration of the type of resin used, suitability for coating, etc.
Specific resin coating methods include a dipping method in which the core material is immersed in a solution for forming a coating layer; a spray method in which the solution for forming a coating layer is sprayed onto the surface of the core material; and a method in which the core material is suspended in fluidized air. Examples include a fluidized bed method in which a coating layer forming solution is sprayed; a kneader coater method in which a carrier core material and a coating layer forming solution are mixed in a kneader coater, and then the solvent is removed; and the like.

The mixing ratio (mass ratio) of toner and carrier in the two-component developer is preferably toner:carrier = 1:100 to 30:100, more preferably 3:100 to 20:100.

<Printed matter manufacturing equipment, printed matter manufacturing method>
The apparatus for manufacturing printed matter according to the present embodiment includes a placement means that stores a developer containing the toner according to the present embodiment and disposes the toner on a recording medium using an electrophotographic method, and folds and presses the recording medium. or crimping means for overlapping and crimping the recording medium and another recording medium.

The printed matter manufacturing method according to the present embodiment is carried out by the printed matter manufacturing apparatus according to the present embodiment.

The method for producing printed matter according to the present embodiment includes a step of disposing the toner on a recording medium by an electrophotographic method using a developer containing the toner according to the present embodiment, and folding and pressing the recording medium. or a press-bonding step of overlapping and press-bonding the recording medium and another recording medium.

The arrangement means included in the printed matter manufacturing apparatus according to the present embodiment includes, for example,
A photoreceptor,
Charging means for charging the surface of the photoreceptor;
an electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged photoreceptor;
a developing unit containing an electrostatic image developer according to the present embodiment, and developing an electrostatic image formed on the surface of the photoreceptor as a toner image by the electrostatic image developer;
a transfer means for transferring the toner image formed on the surface of the photoreceptor to the surface of a recording medium;
Equipped with.
Preferably, the arrangement means further includes a fixing means for fixing the toner image transferred to the surface of the recording medium.

The arrangement step included in the printed matter manufacturing method according to the present embodiment includes, for example,
a charging step of charging the surface of the photoreceptor;
an electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged photoreceptor;
A developing step of developing the electrostatic image formed on the surface of the photoreceptor as a toner image using the electrostatic image developer according to the present embodiment;
a transfer step of transferring the toner image formed on the surface of the photoreceptor to the surface of a recording medium;
including.
Preferably, the arrangement step further includes a fixing step of fixing the toner image transferred to the surface of the recording medium.

The arrangement means may be, for example, a direct transfer type device that directly transfers the toner image formed on the surface of the photoreceptor onto the recording medium; or a device that primarily transfers the toner image formed on the surface of the photoreceptor onto the surface of the intermediate transfer member. , an intermediate transfer type device that secondarily transfers the toner image transferred to the surface of the intermediate transfer member to the surface of the recording medium; a device equipped with a cleaning means that cleans the surface of the photoreceptor before charging after the toner image is transferred; An apparatus including a static eliminating means for irradiating static neutralizing light onto the surface of a photoconductor to eliminate static electricity after a toner image is transferred and before charging.
When the arrangement means is an intermediate transfer type device, the transfer means includes, for example, an intermediate transfer body onto which a toner image is transferred, and a primary transfer system that transfers the toner image formed on the surface of a photoreceptor onto the surface of the intermediate transfer body. and a secondary transfer means that secondarily transfers the toner image transferred onto the surface of the intermediate transfer member onto the surface of the recording medium.

The arrangement means may have a cartridge structure (so-called process cartridge) in which a portion including the developing means is attached to and removed from the arrangement means. As the process cartridge, for example, a process cartridge that is equipped with a developing means for accommodating the electrostatic image developer according to the present embodiment and that can be attached to and detached from a printed matter manufacturing apparatus is suitably used.

The pressure bonding means included in the printed matter manufacturing apparatus according to the present embodiment applies pressure to the recording medium on which the toner according to the present embodiment is placed. As a result, the toner according to this embodiment becomes fluidized on the recording medium and exhibits adhesive properties.
The pressure applied by the pressure bonding means to the recording medium for the purpose of fluidizing the toner according to the present embodiment is preferably 20 MPa or more and 100 MPa or less, more preferably 40 MPa or more and 90 MPa or less, and even more preferably 50 MPa or more and 80 MPa or less.

The toner according to this embodiment may be placed on the entire surface of the recording medium, or may be placed on a part of the recording medium. The toner according to this embodiment is arranged in one layer or in multiple layers on the recording medium. The toner layer according to this embodiment may be a continuous layer in the surface direction of the recording medium, or may be a discontinuous layer in the surface direction of the recording medium.

The amount of toner according to the present embodiment on the recording medium is, for example, 0.5 g/m ² or more and 50 g/m ² or less, and 1 g/m ² or more and 40 g/m ² or less in the area where it is arranged, It is 1.5 g/m ² or more and 30 g/m ² or less.
The layer thickness of the toner (preferably transparent toner) according to the present embodiment on the recording medium is, for example, 0.2 μm or more and 25 μm or less, 0.4 μm or more and 20 μm or less, and 0.6 μm or more and 15 μm or less.

Examples of the recording medium that can be used in the printed matter manufacturing apparatus according to this embodiment include paper, coated paper whose surface is coated with resin, cloth, nonwoven fabric, resin film, and resin sheet.
The recording medium may previously have images on one or both sides.

An example of the printed matter manufacturing apparatus according to the present embodiment will be shown below, but the present embodiment is not limited thereto.

FIG. 1 is a schematic configuration diagram showing an example of a printed matter manufacturing apparatus according to the present embodiment. The printed matter manufacturing apparatus shown in FIG. 1 includes an arrangement means 100 and a pressure bonding means 200 arranged downstream of the arrangement means 100. The arrow indicates the direction of rotation of the photoreceptor or the direction of conveyance of the recording medium.

The placement unit 100 is a direct transfer type device that uses a developer containing the toner of the present embodiment to place the toner of the present embodiment onto the recording medium P using an electrophotographic method. Images are previously formed on one or both sides of the recording medium P.

The arrangement means 100 has a photoreceptor 101 . Around the photoconductor 101, there is a charging roll (an example of charging means) 102 that charges the surface of the photoconductor 101, and an exposure device (static charge image) that exposes the charged surface of the photoconductor 101 to a laser beam to form an electrostatic charge image. (an example of a charge image forming means) 103; a developing device (an example of a developing means) 104 that supplies toner to an electrostatic charge image to develop the electrostatic charge image; a transfer roll (transfer roll) that transfers the developed toner image onto a recording medium P; A photoconductor cleaning device (an example of a cleaning device) 106 for removing toner remaining on the surface of the photoconductor 101 after transfer is arranged in this order.

An operation in which the placement means 100 places the toner according to this embodiment on the recording medium P will be described.
First, the surface of the photoreceptor 101 is charged by the charging roll 102 . The exposure device 103 irradiates the surface of the charged photoconductor 101 with a laser beam according to image data sent from a control unit (not shown). As a result, an electrostatic charge image of the toner arrangement pattern according to this embodiment is formed on the surface of the photoreceptor 101.

The electrostatic charge image formed on the photoreceptor 101 rotates to a developing position as the photoreceptor 101 travels. Then, at the developing position, the electrostatic charge image on the photoreceptor 101 is developed and visualized by the developing device 104 to become a toner image.

The developing device 104 accommodates a developer containing at least the toner and carrier according to the present embodiment. The toner according to the present embodiment is triboelectrically charged by being stirred together with the carrier inside the developing device 104, and is held on the developer roll. As the surface of the photoconductor 101 passes through the developing device 104, toner electrostatically adheres to the electrostatic charge image on the surface of the photoconductor 101, and the electrostatic charge image is developed with the toner. The photoconductor 101 on which the toner image of the toner is formed continues to travel, and the toner image developed on the photoconductor 101 is conveyed to a transfer position.

When the toner image on the photoconductor 101 is conveyed to the transfer position, a transfer bias is applied to the transfer roll 105, and electrostatic force from the photoconductor 101 toward the transfer roll 105 acts on the toner image, and the toner on the photoconductor 101 is transferred. The image is transferred onto the recording medium P.

Toner remaining on the photoconductor 101 is removed and collected by a photoconductor cleaning device 106. The photoreceptor cleaning device 106 is, for example, a cleaning blade, a cleaning brush, or the like. The photoreceptor cleaning device 106 is preferably a cleaning brush from the viewpoint of suppressing the phenomenon in which the toner according to the present embodiment remaining on the surface of the photoreceptor becomes fluidized by pressure and adheres to the surface of the photoreceptor in a film form. .

The recording medium P onto which the toner image has been transferred is conveyed to a fixing device (an example of fixing means) 107. The fixing device 107 is, for example, a pair of fixing members (roll/roll, belt/roll). Although the arrangement unit 100 does not need to include the fixing device 107, it is preferable to include the fixing device 107 from the viewpoint of suppressing the toner according to the present embodiment from falling off the recording medium P. The pressure that the fixing device 107 applies to the recording medium P may be lower than the pressure that the pressure device 230 applies to the recording medium P2, and specifically, preferably 0.5 MPa or more and 10 MPa or less.

The fixing device 107 may or may not have an internal heat source (for example, a halogen heater) for heating the recording medium P.
When the fixing device 107 has an internal heat source, the surface temperature of the recording medium P when heated by the heat source is preferably 80° C. or more and 200° C. or less, more preferably 110° C. or more and 180° C. or less, and 130° C. or more. More preferably, the temperature is 175°C or lower. Note that the fact that the fixing device 107 does not have an internal heat source does not exclude the possibility that the temperature inside the fixing device 107 becomes higher than the environmental temperature due to heat generated by a motor or the like included in the placement means 100.

By passing through the arrangement means 100, the recording medium P becomes a recording medium P1 on which the toner according to the present embodiment is applied on the image. The recording medium P1 is conveyed toward the pressure bonding means 200.

In the printed matter manufacturing apparatus according to the present embodiment, the arrangement means 100 and the pressure bonding means 200 may be located close to each other or may be separated from each other.
When the arrangement means 100 and the pressure bonding means 200 are separated from each other, the arrangement means 100 and the pressure bonding means 200 are connected, for example, by a conveyance means (for example, a belt conveyor) that conveys the recording medium P1.

The pressing means 200 includes a folding device 220 and a pressing device 230, and is a means for folding and pressing the recording medium P1.

The folding device 220 folds the recording medium P1 passing through the device to produce a folded recording medium P2.
The recording medium P2 may be folded, for example, in half, in three, or in four, and only a portion of the recording medium P2 may be folded. The recording medium P2 is in a state in which the toner according to the present embodiment is disposed on at least a portion of at least one of the two opposing surfaces.

The folding device 220 may include a pair of pressure members (for example, roll/roll, belt/roll) that apply pressure to the recording medium P2. The pressure applied to the recording medium P2 by the pressure member of the folding device 220 may be lower than the pressure applied to the recording medium P2 by the pressure device 230, and specifically, preferably 1 MPa or more and 10 MPa or less.

The pressure bonding means 200 may include a stacking device for stacking the recording medium P1 and another recording medium instead of the folding device 220.
The overlapping form of the recording medium P1 and another recording medium is, for example, one overlapping another recording medium on the recording medium P1, one overlapping another recording medium at multiple locations on the recording medium P1, etc. For example, they overlap each other. The other recording medium may be a recording medium on which an image is previously formed on one or both sides, a recording medium on which no image is formed, or a pressure-bonded printed matter prepared in advance.

The recording medium P2 that has exited the folding device 220 (or the stacking device) is conveyed toward the pressing device 230.

The pressure device 230 includes a pair of pressure members (namely, pressure rolls 231 and 232). The pressure roll 231 and the pressure roll 232 are in contact with each other at their outer peripheral surfaces and press against each other to apply pressure to the recording medium P2 passing therethrough. The pair of pressure members included in the pressure device 230 is not limited to a combination of a pressure roll and a pressure roll, but may be a combination of a pressure roll and a pressure belt, or a combination of a pressure belt and a pressure belt.
Further, the pair of pressure members in the pressure device 230, for example, allow the recording medium P2 to pass through a gap between a pair of spaced apart pressure members (roll/roll, etc.) and apply pressure to the passing recording medium P2. It may be an aspect.

When pressure is applied to the recording medium P2 passing through the pressure device 230, the toner according to this embodiment is fluidized on the recording medium P2 by the pressure and exhibits adhesive properties. The pressure applied by the pressure device 230 to the recording medium P2 is preferably 20 MPa or more and 100 MPa or less, more preferably 40 MPa or more and 90 MPa or less, and even more preferably 50 MPa or more and 80 MPa or less.

The pressurizing device 230 may or may not have a heat source (for example, a halogen heater) for heating the recording medium P2 inside.
When the pressure device 230 has a heat source inside, the surface temperature of the recording medium P2 when heated by the heat source is preferably 40°C or more and 80°C or less, more preferably 50°C or more and 70°C or less, and 55°C. The temperature is more preferably 65°C or less.
Note that the fact that the pressurizing device 230 does not have a heat source inside does not exclude the possibility that the temperature inside the pressurizing device 230 becomes equal to or higher than the environmental temperature due to heat generated by a motor or the like included in the pressurizing device 230.

When the recording medium P2 passes through the pressure device 230, the folded surfaces are adhered to each other by the fluidized toner according to the present embodiment, and a pressure-bonded printed matter P3 is produced.
In the produced pressure-bonded printed matter P3, opposing surfaces are partially or completely adhered to each other.

The completed pressure-bonded printed matter P3 is carried out from the pressure device 230.

The first form of the pressure-bonded printed material P3 is a pressure-bonded printed material in which folded recording media are adhered on opposing surfaces with the toner according to the present embodiment.
The pressure-bonded printed matter P3 of this embodiment is manufactured by a printed matter manufacturing apparatus including a folding device 220.

The second form of the pressure-bonded printed matter P3 is a pressure-bonded printed matter in which a plurality of overlapping recording media are adhered on opposing surfaces with the toner according to the present embodiment.
The pressure-bonded printed matter P3 of this embodiment is manufactured by a pressure-bonded printed matter manufacturing apparatus that includes a stacking device.

The printed matter manufacturing apparatus according to this embodiment is not limited to an apparatus that continuously conveys the recording medium P2 from the folding device 220 (or stacking device) to the pressing device 230.
The printed matter manufacturing apparatus according to the present embodiment stores the recording medium P2 that has come out of the folding device 220 (or stacking device), and after the stored amount of the recording medium P2 reaches a predetermined amount, the printing medium P2 is It may be a device that is conveyed to the pressurizing device 230.

In the printed matter manufacturing apparatus according to the present embodiment, the folding device 220 (or the stacking device) and the crimping device 230 may be close to each other or may be separated from each other. When the folding device 220 (or the stacking device) and the pressure bonding device 230 are separated from each other, the folding device 220 (or the stacking device) and the pressure bonding device 230 are, for example, a conveying means ( For example, they are connected by a conveyor belt).

The printed matter manufacturing apparatus according to the present embodiment may include a cutting device that cuts the recording medium into predetermined dimensions. The cutting means is, for example, disposed between the arrangement means 100 and the pressure bonding means 200, and cuts off an area of the recording medium P1 where the toner according to the present embodiment is not arranged; a folding device 220; A cutting device disposed between the pressurizing device 230 and cutting off an area of the recording medium P2 in which the toner according to the present embodiment is not arranged; a cutting means for cutting off a part of the area that is not adhered by the toner according to the present embodiment; and the like.
Note that, according to the cutting means, a part of the area where the toner according to the present embodiment is arranged may be cut off.

The printed matter manufacturing apparatus according to this embodiment is not limited to a single-fed type apparatus. The printed matter manufacturing apparatus according to the present embodiment performs a placement process and a pressure bonding process on a long recording medium to form a long pressed printed matter, and then cuts the long pressed printed matter into predetermined dimensions. It may also be a device that does this.

The printed matter manufacturing apparatus according to the present embodiment may further include a colored image forming means that forms a colored image on a recording medium by electrophotography using a colored electrostatic image developer.
The colored image forming means is, for example,
a photoreceptor;
Charging means for charging the surface of the photoreceptor;
an electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged photoreceptor;
a developing means that contains a colored electrostatic image developer and develops the electrostatic image formed on the surface of the photoreceptor as a colored toner image with the colored electrostatic image developer;
a transfer means for transferring the colored toner image formed on the surface of the photoreceptor to the surface of a recording medium;
and a heat fixing means for heat fixing the colored toner image transferred to the surface of the recording medium.

A method of manufacturing a printed matter according to the present embodiment using the manufacturing apparatus configured as described above, further comprising a colored image forming step of forming a colored image on a recording medium by an electrophotographic method using a colored electrostatic image developer. A manufacturing method is performed. Specifically, the colored image forming process is as follows:
a charging step of charging the surface of the photoreceptor;
an electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged photoreceptor;
a developing step of developing the electrostatic image formed on the surface of the photoreceptor as a colored toner image using a colored electrostatic image developer;
a transfer step of transferring the colored toner image formed on the surface of the photoreceptor to the surface of a recording medium;
The method includes a heat fixing step of heat fixing the colored toner image transferred to the surface of the recording medium.

The colored image forming means included in the printed matter manufacturing apparatus according to the present embodiment is, for example, a direct transfer type device that directly transfers a colored toner image formed on the surface of a photoreceptor to a recording medium; An intermediate transfer type device that primarily transfers the colored toner image transferred to the surface of an intermediate transfer member, and secondarily transfers the colored toner image transferred to the surface of the intermediate transfer member to the surface of a recording medium; a colored toner image A device equipped with a cleaning means for cleaning the surface of the photoreceptor before charging after transferring a colored toner image; a device equipped with a static eliminating means for removing static electricity by irradiating the surface of the photoreceptor with neutralizing light after transferring a colored toner image and before charging. It is a device such as ;
When the colored image forming means is an intermediate transfer type device, the transfer means includes, for example, an intermediate transfer body onto which a colored toner image is transferred, and a colored toner image formed on the surface of a photoconductor onto the intermediate transfer body. and a secondary transfer means that performs secondary transfer of the colored toner image transferred onto the surface of the intermediate transfer member onto the surface of the recording medium.

In the printed matter manufacturing apparatus according to the present embodiment, when the developer arrangement means including toner according to the present embodiment and the colored image forming means adopt an intermediate transfer method, the arrangement means and the colored image forming means are , the intermediate transfer body and the secondary transfer means may be shared.

In the printed matter manufacturing apparatus according to the present embodiment, the toner-containing image developer arrangement means and the colored image forming means according to the present embodiment may share a heat fixing means.

Hereinafter, an example of a printed matter manufacturing apparatus according to the present embodiment including a colored image forming means will be shown, but the present embodiment is not limited thereto. In the following explanation, the main parts shown in the figures will be explained, and the explanation of the others will be omitted.

FIG. 2 is a schematic configuration diagram showing an example of a printed matter manufacturing apparatus according to the present embodiment. The printed matter manufacturing apparatus shown in FIG. 2 includes a printing unit 300 that simultaneously places toner on a recording medium and forms a colored image according to the present embodiment, and a pressure bonding unit 200 disposed downstream of the printing unit 300. Equipped with

The printing unit 300 is a 5-tandem printing unit and an intermediate transfer printing unit. The printing unit 300 includes a unit 10T for disposing toner (T) according to the present embodiment, and units 10Y and 10M for forming images of each color of yellow (Y), magenta (M), cyan (C), and black (K). , 10C and 10K. The unit 10T is an arrangement unit that arranges the toner according to the present embodiment on the recording medium P using a developer containing the toner according to the present embodiment. The units 10Y, 10M, 10C, and 10K are means for forming a colored image on the recording medium P using a developer containing colored toner, respectively. Units 10T, 10Y, 10M, 10C and 10K employ an electrophotographic method.

The units 10T, 10Y, 10M, 10C, and 10K are arranged in parallel and spaced apart from each other in the horizontal direction. The units 10T, 10Y, 10M, 10C, and 10K may be process cartridges that can be attached to and detached from the printing means 300.

An intermediate transfer belt (an example of an intermediate transfer body) 20 extends below the units 10T, 10Y, 10M, 10C, and 10K through each unit. The intermediate transfer belt 20 is provided so as to be wound around a drive roll 22, a support roll 23, and a counter roll 24 that are in contact with the inner surface of the intermediate transfer belt 20, and is configured to run in a direction from the unit 10T to the unit 10K. . An intermediate transfer body cleaning device 21 is provided on the image holding surface side of the intermediate transfer belt 20 so as to face the drive roll 22 .

The units 10T, 10Y, 10M, 10C and 10K each include developing devices (an example of developing means) 4T, 4Y, 4M, 4C and 4K. The developing devices 4T, 4Y, 4M, 4C, and 4K each contain toner, yellow toner, magenta toner, cyan toner, and black toner according to the present embodiment stored in toner cartridges 8T, 8Y, 8M, 8C, and 8K. Supply is made.

Since the units 10T, 10Y, 10M, 10C, and 10K have the same configuration and operation, the unit 10T for disposing toner on the recording medium according to this embodiment will be described as a representative.

The unit 10T has a photoreceptor 1T. Around the photoconductor 1T, there is a charging roll (an example of charging means) 2T that charges the surface of the photoconductor 1T, and an exposure device (static charge image) that exposes the surface of the charged photoconductor 1T to a laser beam to form an electrostatic charge image. An example of a charge image forming means) 3T, a developing device (an example of a developing means) 4T that supplies toner to an electrostatic charge image to develop the electrostatic charge image, a primary transfer roll that transfers the developed toner image onto the intermediate transfer belt 20 5T (an example of a primary transfer means) and a photoreceptor cleaning device 6T (an example of a cleaning means) for removing toner remaining on the surface of the photoreceptor 1T after the primary transfer are arranged in this order. The primary transfer roll 5T is arranged inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1T.

Hereinafter, the operation of arranging toner and forming a colored image on the recording medium P according to the present embodiment will be described while illustrating the operation of the unit 10T.
First, the surface of the photoreceptor 1T is charged by the charging roll 2T. The exposure device 3T irradiates the surface of the charged photoreceptor 1T with a laser beam according to image data sent from a control section (not shown). As a result, an electrostatic charge image of the toner arrangement pattern according to this embodiment is formed on the surface of the photoreceptor 1T.

The electrostatic charge image formed on the photoreceptor 1T rotates to a developing position as the photoreceptor 1T travels. Then, at the developing position, the electrostatic charge image on the photoreceptor 1T is developed and visualized by the developing device 4T to become a toner image.

The developing device 4T accommodates a developer containing at least the toner and carrier according to the present embodiment. The toner according to the present embodiment is triboelectrically charged by being stirred together with the carrier inside the developing device 4T, and is held on the developer roll. As the surface of the photoconductor 1T passes through the developing device 4T, toner electrostatically adheres to the electrostatic charge image on the surface of the photoconductor 1T, and the electrostatic charge image is developed with the toner. The photoreceptor 1T on which the toner image of the toner is formed continues to travel, and the toner image developed on the photoreceptor 1T is transported to the primary transfer position.

When the toner image on the photoconductor 1T is conveyed to the primary transfer position, a primary transfer bias is applied to the primary transfer roll 5T, and electrostatic force from the photoconductor 1T toward the primary transfer roll 5T acts on the toner image, causing the toner image to move onto the photoconductor. The toner image on 1T is transferred onto the intermediate transfer belt 20. The toner remaining on the photoreceptor 1T is removed and collected by the photoreceptor cleaning device 6T. The photoreceptor cleaning device 6T is, for example, a cleaning blade, a cleaning brush, etc., and is preferably a cleaning brush.

In units 10Y, 10M, 10C, and 10K, the same operation as in unit 10T is performed using developer containing colored toner. The intermediate transfer belt 20 to which the toner image of the toner according to the present embodiment has been transferred in the unit 10T passes through the units 10Y, 10M, 10C, and 10K in sequence, and the toner images of each color are multiple-transferred onto the intermediate transfer belt 20. Ru.

The intermediate transfer belt 20 to which five toner images are multiple-transferred through the units 10T, 10Y, 10M, 10C, and 10K is connected to the intermediate transfer belt 20, the opposing roll 24 in contact with the inner surface of the intermediate transfer belt, and the image of the intermediate transfer belt 20. This leads to a secondary transfer section comprised of a secondary transfer roll (an example of secondary transfer means) 26 disposed on the holding surface side. On the other hand, the recording medium P is fed via the supply mechanism to the gap where the secondary transfer roll 26 and the intermediate transfer belt 20 are in contact with each other, and a secondary transfer bias is applied to the opposing roll 24. At this time, electrostatic force from the intermediate transfer belt 20 toward the recording medium P acts on the toner image, and the toner image on the intermediate transfer belt 20 is transferred onto the recording medium P.

The recording medium P onto which the toner image has been transferred is conveyed to a thermal fixing device (an example of thermal fixing means) 28. The heat fixing device 28 includes a heat source such as a halogen heater, and heats the recording medium P. The surface temperature of the recording medium P when heated by the heat fixing device 28 is preferably 80° C. or more and 200° C. or less, more preferably 110° C. or more and 180° C. or less, and even more preferably 130° C. or more and 175° C. or less. The colored toner image is thermally fixed onto the recording medium P by passing through the thermal fixing device 28 .

The heat fixing device 28 is a device that applies pressure as well as heating, from the viewpoint of suppressing the toner according to the present embodiment from falling off from the recording medium P and from the viewpoint of improving the fixability of the colored image to the recording medium P. For example, the fixing member may be a pair of fixing members (roll/roll, belt/roll) equipped with a heat source inside. When the heat fixing device 28 applies pressure, the pressure that the heat fixing device 28 applies to the recording medium P may be lower than the pressure that the pressure device 230 applies to the recording medium P2, and specifically, It is preferably 0.1 MPa or more and 2 MPa or less.

By passing through the printing means 300, the recording medium P becomes a recording medium P1 to which a colored image and the toner according to the present embodiment are applied. The recording medium P1 is conveyed toward the pressure bonding means 200.

The configuration of the crimping means 200 in FIG. 2 may be the same as the crimping means 200 in FIG. 1, and a detailed explanation of the configuration and operation of the crimping means 200 will be omitted.

In the printed matter manufacturing apparatus according to the present embodiment, the printing means 300 and the pressure bonding means 200 may be close to each other or may be separated from each other. When the printing means 300 and the pressure bonding means 200 are separated from each other, the printing means 300 and the pressure bonding means 200 are connected, for example, by a conveyance means (for example, a belt conveyor) that conveys the recording medium P1.

The printed matter manufacturing apparatus according to this embodiment may include a cutting device that cuts the recording medium into predetermined dimensions. The cutting means is, for example, disposed between the printing means 300 and the pressure bonding means 200, and cuts off an area of the recording medium P1 where the toner according to the present embodiment is not placed; the folding device 220; A cutting device disposed between the pressurizing device 230 and cutting off an area of the recording medium P2 in which the toner according to the present embodiment is not arranged; a cutting means for cutting off a part of the area that is not adhered by the toner according to the present embodiment; and the like.

The printed matter manufacturing apparatus according to this embodiment is not limited to a single-fed type apparatus. The printed matter manufacturing apparatus according to the present embodiment forms a long pressed printed matter by performing a colored image forming process, an arrangement process, and a pressure bonding process on a long recording medium, and then predetermines the long pressed printed matter. It may also be a device that cuts the material to specified dimensions.

<Process cartridge>
A process cartridge according to this embodiment will be described.
The process cartridge according to the present embodiment contains the electrostatic charge image developer according to the present embodiment, and has a developing means for developing the electrostatic charge image formed on the surface of the photoreceptor as a toner image using the electrostatic charge image developer. This is a process cartridge that can be attached to and removed from printed matter manufacturing equipment.

The process cartridge according to the present embodiment may be configured to include a developing means and, if necessary, at least one selected from a photoreceptor, a charging means, an electrostatic image forming means, a transfer means, and the like.

An example of a process cartridge according to the present embodiment will be shown below, but the present embodiment is not limited thereto. In the following explanation, the main parts shown in the figures will be explained, and the explanation of the others will be omitted.

FIG. 3 is a schematic configuration diagram showing an example of a process cartridge according to this embodiment.
The process cartridge 500 shown in FIG. 3 is attached to and removed from, for example, the printed matter manufacturing apparatus shown in FIG. 1 or 2.

The process cartridge 500 includes a photoreceptor 501, a charging roll 502 (an example of a charging means) provided around the photoreceptor 501, a developing device 504 (an example of a developing means), and a photoreceptor cleaning device 506 (an example of a cleaning means). This is a cartridge that is integrated with a housing 517. The housing 517 has an opening 518 for exposure. The housing 517 has a mounting rail 516, through which the process cartridge 500 is mounted on a printed matter manufacturing apparatus.

FIG. 3 also shows an exposure device 503, a transfer device 505, and a recording medium P that are arranged around the process cartridge 500 when the process cartridge 500 is installed in a printed matter manufacturing apparatus.

<Toner cartridge>
The toner cartridge according to the present embodiment is a toner cartridge that accommodates the toner according to the present embodiment and is attached to and detached from a printed matter manufacturing apparatus. The toner cartridge stores replenishment toner to be supplied to a developing means provided in a printed matter manufacturing apparatus.

The printing means 300 shown in FIG. 2 has a configuration in which toner cartridges 8T, 8Y, 8M, 8C, and 8K are attached and detached, and developing devices 4T, 4Y, 4M, 4C, and 4K are provided with toner cartridges 8T, 8Y, respectively. , 8M, 8C, and 8K via toner supply pipes (not shown). An example of the toner cartridge according to the present embodiment is a toner cartridge 8T, which accommodates the toner according to the present embodiment. The toner cartridges 8Y, 8M, 8C, and 8K contain yellow, magenta, cyan, and black toners, respectively. When the amount of toner contained in the toner cartridges becomes low, these toner cartridges are replaced.

Hereinafter, embodiments of the invention will be described in detail with reference to Examples, but the embodiments of the invention are not limited to these Examples at all. In the following description, unless otherwise specified, "parts" and "%" are based on mass.

<<Preparation of toner (T1) and developer (G1)>>
<Preparation of resin particle dispersion for core part>
[Preparation of styrenic resin particle dispersion (A1)]
- Styrene: 440 parts - n-butyl acrylate: 130 parts - Acrylic acid: 20 parts - Dodecanethiol: 10 parts A monomer solution was prepared by mixing and dissolving the above materials.
10 parts of an anionic surfactant (manufactured by Dow Chemical Company, DOWFAX2A1) was dissolved in 250 parts of ion-exchanged water, and the monomer solution was added to disperse and emulsify to obtain an emulsion.

One part of an anionic surfactant (manufactured by Dow Chemical Company, DOWFAX2A1) was dissolved in 555 parts of ion-exchanged water, and the solution was charged into a polymerization flask.
A reflux tube was installed in the polymerization flask, and while injecting nitrogen and stirring slowly, the polymerization flask was heated to 75° C. in a water bath and maintained.
9 parts of ammonium persulfate was dissolved in 43 parts of ion-exchanged water, and the solution was added dropwise into the polymerization flask via a metering pump over 20 minutes, and then the emulsion was added dropwise via the metering pump over 200 minutes.
Thereafter, the polymerization flask was maintained at 75° C. for 3 hours while stirring to complete the first stage polymerization. A styrenic resin particle dispersion (A1) was obtained in which the volume average particle diameter (D50v) of the resin particles was 195 nm, the glass transition temperature was 53° C., and the weight average molecular weight was 32,000.

[Preparation of composite resin particle dispersion (A1)]
Next, after the temperature was lowered to room temperature, 240 parts of 2-ethylhexyl acrylate, 160 parts of n-butyl acrylate, and 1200 parts of ion-exchanged water were added to the polymerization flask and slowly stirred for 2 hours.
Thereafter, the temperature was raised to 70° C. while stirring, and 4.5 parts of ammonium persulfate and 100 parts of ion-exchanged water were added dropwise to the polymerization flask via a metering pump over 20 minutes. Then, stirring was continued for 3 hours to complete the polymerization.
Through the above steps, the composite resin particles with a volume average particle diameter (D50v) of 240 nm, a weight average molecular weight of 133,000, and a number average molecular weight of 18,000 are obtained, and the solid content is adjusted by adding ion-exchanged water. A 30% composite resin particle dispersion (A1) was obtained.
The composite resin particle dispersion liquid (A1) was used as the resin particle dispersion liquid for core part (A1).

After drying the composite resin particle dispersion (A1), the thermal behavior of the dried composite resin particles was analyzed using a differential scanning calorimeter (manufactured by Shimadzu Corporation) in the temperature range of -150°C to 100°C. , two glass transition temperatures (Tg1 and Tg2) were observed. Table 2 shows the glass transition temperatures.

[Preparation of composite resin particle dispersions (A2) to (A5)]
The amounts of 2-ethylhexyl acrylate (abbreviated as "2EHA" in Table 2) and n-butyl acrylate (abbreviated as "BA" in Table 2) were changed as shown in Table 2 below, and the volume average of the composite resin particles Composite resin particle dispersions (A2) to (A5) were obtained in the same manner as in the preparation of composite resin particle dispersion (A1), except that the particle size was controlled within the range of 200 nm to 240 nm.
Note that the solid content of the composite resin particle dispersions (A2) to (A5) was all set to 30% using ion-exchanged water.
The composite resin particle dispersions (A2) to (A5) were used as the core part resin particle dispersions (A2) to (A5).

<Preparation of resin particle dispersion for shell layer>
(Preparation of resin particle dispersion liquid (B1) for shell layer)
- Styrene: 450 parts - n-butyl acrylate: 135 parts - Acrylic acid: 10 parts - Dodecanethiol: 10 parts A monomer solution was prepared by mixing and dissolving the above materials.
10 parts of an anionic surfactant (manufactured by Dow Chemical Company, DOWFAX2A1) was dissolved in 250 parts of ion-exchanged water, and the monomer solution was added to disperse and emulsify to obtain an emulsion.

One part of an anionic surfactant (manufactured by Dow Chemical Company, DOWFAX2A1) was dissolved in 555 parts of ion-exchanged water, and the solution was charged into a polymerization flask.
A reflux tube was installed in the polymerization flask, and while injecting nitrogen and stirring slowly, the polymerization flask was heated to 75° C. in a water bath and maintained.
9 parts of ammonium persulfate was dissolved in 43 parts of ion-exchanged water, and the solution was added dropwise into the polymerization flask via a metering pump over 20 minutes, and then the emulsion was added dropwise via the metering pump over 200 minutes.
Thereafter, the polymerization flask was maintained at 75° C. for 3 hours while stirring to complete the first stage polymerization. A resin particle dispersion for a shell layer in which the volume average particle diameter (D50v) of the resin particles is 200 nm, the glass transition temperature is 53°C, the weight average molecular weight is 33,000, and the solid content is adjusted to 30% by mass by adding ion-exchanged water. (B1) was obtained.

<Preparation of release agent particle dispersion>
(Preparation of release agent particle dispersion (1))
・Fischer-Tropsch wax: 270 parts (manufactured by Nippon Seirin Co., Ltd., product name: FNP-0090, melting temperature = 90°C)
・Anionic surfactant: 1.0 part (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK)
- Ion exchange water: 400 parts The above ingredients were mixed, heated to 95°C, dispersed using a homogenizer (IKA, Ultra Turrax T50), and then dispersed for 360 minutes using a Manton-Gorlin high-pressure homogenizer (Gorlin). A mold release agent particle dispersion (1) (solid content 20%) in which mold release agent particles having a volume average particle diameter of 0.23 μm were dispersed was prepared by the treatment.

<Preparation of yellow pigment dispersion>
(Preparation of yellow pigment dispersion (1))
・Yellow pigment (manufactured by Clariant, CIPigment Yellow 74): 50 parts ・Ionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 5 parts ・Ion exchange water: 195 parts Mix the above components, After dispersing for 10 minutes with a homogenizer (IKA Ultra Turrax), dispersion treatment was performed for 15 minutes at a pressure of 250 Mpa using an Ultimizer (counter-impingement type wet grinder: manufactured by Sugino Machine Co., Ltd.), and adjustment was made by adding ion-exchanged water. A yellow pigment dispersion (1) (solid content: 2%) in which a yellow pigment having a volume average particle size of 130 nm was dispersed was prepared.

<Preparation of toner particles (T1)>
・Resin particle dispersion for core part (A1): 600 parts ・Release agent particle dispersion (1): 10 parts ・Colloidal silica aqueous solution: 13 parts (Nissan Chemical Co., Ltd., Snowtex OS)
・Ion exchange water: 1000 parts ・Anionic surfactant: 1 part (manufactured by Dow Chemical Co., Ltd., Dowfax2A1)
The above ingredients were placed in a 3-liter reaction vessel equipped with a thermometer, pH meter, and stirrer, and at a temperature of 25°C, 1.0% nitric acid was added to adjust the pH to 3.0, and then a homogenizer ( Four parts of the prepared 10% polyaluminum chloride aqueous solution was added and dispersed for 6 minutes while dispersing at 5,000 rpm using an Ultra Turrax T50 (manufactured by IKA Japan Co., Ltd.).

After that, a stirrer and a mantle heater were installed in the reaction vessel, and while adjusting the rotation speed of the stirrer so that the slurry was sufficiently stirred, the heating rate was 0.2 °C/min until the temperature reached 40 °C. After the temperature exceeded .degree. C., the temperature was increased at a rate of 0.05.degree. C./min, and the particle size was measured every 10 minutes using Multisizer II (aperture diameter: 50 .mu.m, manufactured by Beckman Coulter). When the volume average particle diameter reached 7.5 μm, the temperature was maintained, and 115 parts of the resin particle dispersion for shell layer (B1) and 0.24 parts of the yellow pigment dispersion (1) were mixed and then mixed for 5 minutes. I put it in. After holding for 30 minutes, the pH was brought to 6.0 using 1% aqueous sodium hydroxide. Thereafter, while adjusting the pH to 6.0 every 5°C in the same manner, the temperature was raised to 90°C at a heating rate of 1°C/min and maintained at 96°C. When observing the particle shape and surface properties using an optical microscope and a scanning electron microscope (FE-SEM), coalescence of the particles was confirmed at 2.0 hours, so the container was heated to 30°C with cooling water for 5 minutes. It was then cooled.

The slurry after cooling was passed through a nylon mesh with an opening of 30 μm to remove coarse powder, and the toner slurry that had passed through the mesh was filtered under reduced pressure using an aspirator. The toner remaining on the filter paper was crushed by hand as finely as possible, poured into ion-exchanged water of 10 times the amount of toner at a temperature of 30° C., and stirred and mixed for 30 minutes. Next, filter the toner under reduced pressure with an aspirator, crush the toner remaining on the filter paper as finely as possible by hand, pour it into ion-exchanged water of 10 times the amount of toner at a temperature of 30°C, stir and mix for 30 minutes, and then reduce the pressure using an aspirator again. It was filtered and the electrical conductivity of the filtrate was measured. This operation was repeated until the electrical conductivity of the filtrate became 10 μS/cm or less to wash the toner. The washed toner was pulverized into fine particles using a wet-dry type sizing machine (Cormill), and then vacuum-dried for 36 hours in a dryer at 25° C. to obtain toner particles (T1).
The obtained toner particles (T1) had a volume average particle diameter of 8.5 μm, a weight average molecular weight of 125,000, and a number average molecular weight of 17,000.

<Preparation of toner (T1)>
100 parts of toner particles (T1) and 1.5 parts of hydrophobic silica (RY50, manufactured by Nippon Aerosil Co., Ltd.) were mixed and mixed for 30 seconds at a rotation speed of 13,000 rpm using a sample mill. The toner (T1) was obtained by sieving with a vibrating sieve having an opening of 45 μm.

The content of yellow pigment in the toner (T1) was measured by the method described above and was found to be 22 ppm.

When the thermal behavior of toner (T1) was analyzed using a differential scanning calorimeter (manufactured by Shimadzu Corporation) in the temperature range of -150°C to 100°C, two glass transition temperatures were observed. Table 3 shows the glass transition temperatures.

The temperature T1 and temperature T2 of the toner (T1) were determined by the measurement method described above, and the temperature difference (T1-T2) was calculated to be 20°C.

When the cross section of the toner (T1) was observed using a scanning electron microscope (SEM), a sea-island structure was observed. Further, the toner (T1) had a core portion in which an island phase existed and a shell layer in which an island phase did not exist.
The sea phase contained a specific styrene resin, and the island phase contained a specific (meth)acrylate ester resin. The average diameter of the island phase was determined using the measurement method described above. Table 3 shows the average diameter of the island facies.

<Preparation of developer (G1)>
10 parts of toner (T1) and 100 parts of the following resin-coated carrier were placed in a V-type blender, stirred for 20 minutes, and then sieved with a vibrating sieve having a mesh size of 212 μm to obtain a developer (G1).

・Mn-Mg-Sr ferrite particles (average particle size 40 μm): 100 parts ・Toluene: 14 parts ・Polymethyl methacrylate: 2 parts ・Carbon black (VXC72: manufactured by Cabot): 0.12 parts The above except for ferrite particles The material and glass beads (diameter 1 mm, same amount as toluene) were mixed and stirred for 30 minutes at a rotation speed of 1200 rpm using a sand mill manufactured by Kansai Paint Co., Ltd. to obtain a dispersion. This dispersion liquid and ferrite particles were placed in a vacuum degassing type kneader, and dried under reduced pressure while stirring to obtain a resin-coated carrier.

≪Preparation of toners (T2) to (T12), (T18) to (T19) and developers (G1) to (G12), (G18) to (G19)≫
Toners (T2) to (T12), (T18) to (T19) were produced. Then, developers (G2) to (G12), (G18) to (G19) was produced.

≪Preparation of toner (T13) to (T14) and developer (G13) to (G14)≫
Toner particles (T1) were prepared in the same manner as toner (T1), except that yellow pigment dispersion (2) or (3) below was used instead of yellow pigment dispersion (1). (T13) to (T14) were produced. Developers (G13) to (G14) were produced in the same manner as developer (G1) except that toners (T13) to (T14) were used.

<Preparation of yellow pigment dispersion>
(Preparation of yellow pigment dispersion (2))
・Yellow pigment (manufactured by Dainichiseika Chemical Co., Ltd., CIPigment Yellow 93): 50 parts ・Ionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 5 parts ・Ion exchange water: 195 parts Mix the above components After dispersing for 10 minutes with a homogenizer (IKA Ultra Turrax), dispersion treatment was performed for 15 minutes at a pressure of 250 Mpa using an Ultimizer (counter-impingement type wet grinder: manufactured by Sugino Machine Co., Ltd.), and ion-exchanged water was added. A yellow pigment dispersion (2) (solid content: 2%) was prepared by dispersing a yellow pigment having a volume average particle size of 180 nm.

(Preparation of yellow pigment dispersion (3))
・Yellow pigment (manufactured by Clariant, CIPigment Yellow 180): 50 parts ・Ionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 5 parts ・Ion exchange water: 195 parts Mix the above components, After dispersing for 10 minutes with a homogenizer (IKA Ultra Turrax), dispersion treatment was performed for 15 minutes at a pressure of 250 Mpa using an Ultimizer (counter-impingement type wet crusher: manufactured by Sugino Machine Co., Ltd.), and adjustment was made by adding ion-exchanged water. Thus, a yellow pigment dispersion (3) (solid content: 2%) was prepared, in which a yellow pigment having a volume average particle size of 150 nm was dispersed.

≪Preparation of toner (T15) to (T-17) and developer (G15) to (G-17)≫
<Preparation of toner particles (T15)>
・Resin particle dispersion for core part (A1): 715 parts ・Release agent dispersion (1): 10 parts ・Yellow pigment dispersion (1): 0.24 parts ・Colloidal silica aqueous solution: 13 parts (Nissan Chemical) Co., Ltd., Snowtex OS)
・Ion exchange water: 1000 parts ・Anionic surfactant: 1 part (manufactured by Dow Chemical Co., Ltd., Dowfax2A1)
The above ingredients were placed in a 3-liter reaction vessel equipped with a thermometer, pH meter, and stirrer, and at a temperature of 25°C, 1.0% nitric acid was added to adjust the pH to 3.0, and then a homogenizer ( Four parts of the prepared 10% polyaluminum chloride aqueous solution was added and dispersed for 6 minutes while dispersing at 5,000 rpm using an Ultra Turrax T50 (manufactured by IKA Japan Co., Ltd.).

After that, a stirrer and a mantle heater were installed in the reaction vessel, and while adjusting the rotation speed of the stirrer so that the slurry was sufficiently stirred, the heating rate was 0.2 °C/min until the temperature reached 40 °C. After the temperature exceeded .degree. C., the temperature was increased at a rate of 0.05.degree. C./min, and the particle size was measured every 10 minutes using Multisizer II (aperture diameter: 50 .mu.m, manufactured by Beckman Coulter). When the volume average particle diameter reached 8.5 μm, the temperature was maintained and the pH was adjusted to 6.0 using a 1% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 6.0 every 5°C in the same manner, the temperature was raised to 90°C at a heating rate of 1°C/min and maintained at 96°C. When observing the particle shape and surface properties using an optical microscope and a scanning electron microscope (FE-SEM), coalescence of the particles was confirmed at 2.0 hours, so the container was heated to 30°C with cooling water for 5 minutes. It was then cooled.
The slurry after cooling was passed through a nylon mesh with an opening of 30 μm to remove coarse powder, and the toner slurry that had passed through the mesh was filtered under reduced pressure using an aspirator. The toner remaining on the filter paper was crushed by hand as finely as possible, poured into ion-exchanged water of 10 times the amount of toner at a temperature of 30° C., and stirred and mixed for 30 minutes. Next, filter the toner under reduced pressure with an aspirator, crush the toner remaining on the filter paper as finely as possible by hand, pour it into ion-exchanged water of 10 times the amount of toner at a temperature of 30°C, stir and mix for 30 minutes, and then reduce the pressure using an aspirator again. It was filtered and the electrical conductivity of the filtrate was measured. This operation was repeated until the electrical conductivity of the filtrate became 10 μS/cm or less to wash the toner. The washed toner was pulverized into small pieces using a wet-dry type sizing machine (Cormill), and then vacuum-dried for 36 hours in a dryer at 25° C. to obtain toner particles (T15).
The obtained toner particles (T1) had a volume average particle diameter of 8.3 μm, a weight average molecular weight of 133,000, and a number average molecular weight of 18,000.

<Preparation of toner (T15) and developer (G15)>
Toner (T15) was produced in the same manner as toner (T1) except that toner particles (T15) were used instead of toner particles (T1). Then, a developer (G15) was produced in the same manner as the developer (G1) except that toner (T15) was used.

<Preparation of toner particles (T16) and (T17)>
Production of toner particles (T15) except that the amount (0.24 parts) of yellow pigment dispersion (1) used during production of toner particles (T15) was changed to 0.44 parts or 0.65 parts, respectively. In the same manner as above, toner particles (T16) to (T17) were produced.
Toners (T16) to (T17) were produced in the same manner as toner (T1) except that toner particles (T16) or (T17) were used instead of toner particles (T1). Developers (G16) to (G17) were produced in the same manner as developer (G1) except that toners (T16) to (T17) were used.

[Evaluation of dirt inside the machine]
The first to fourth developing units are filled with cyan, magenta, yellow, and black colored electrostatic image developers. 1) was accommodated.
Recording paper (OK Prince high-quality paper, basis weight 157 g, manufactured by Oji Paper Co., Ltd.) was set, and the amount of toner (1) applied was 3 g/m ² at a fixing temperature of 170°C and a fixing pressure of 4.0 kg/cm ^{2 .} An image (area density: 30%) containing a mixture of text and photographic images was formed and fixed. As for the order of arrangement of the toner images, the toner image of toner (1) was arranged on top of the colored toner image. Under these conditions, 1,000 sheets were continuously printed.
After printing, remove the fifth developing device and the photoconductor facing the fifth developing device, transfer the dirt on the main body frame directly under the fifth developing device to a tape, attach the tape with the dirt transferred to black paper, and store it inside the machine. Contamination was confirmed and evaluated. Table 4 shows the results.
The evaluation criteria are as follows.
-Evaluation criteria-
A: On the tape attached to black paper, the toner is at an invisible level, and there is almost no dirt inside the machine B: On the tape attached to black paper, there are some visible toner accumulations, but the dirt inside the machine is tolerable. Range C: For tape attached to black paper, toner accumulation is visible on the entire surface of the tape, and dirt inside the machine is noticeable.

[Evaluation of adhesion]
After evaluating the dirt inside the machine, 10 more copies were printed, the 10th image was folded so that the fixing surfaces overlapped, and it was crimped using a modified pressure sealer PRESSELE LEADA (manufactured by Toppan Forms Co., Ltd.) to create a crimped print. was created. Thereafter, the pressure-bonded printed matter was left in an environment of 22° C. and 50% for one day.
The pressure-bonded printed matter was cut to a width of 15 mm in the long side direction, three rectangular test pieces were made, and a 90 degree peel test was performed. Adhesion was evaluated by peel force. The peel speed of the 90 degree peel test was 20 mm/ The load (N) from 10 mm to 50 mm after the start of measurement was taken at intervals of 0.4 mm, the average was calculated, and the loads (N) of the three test pieces were averaged. Table 4 shows the results.

<Preparation of dispersion containing styrene resin particles>
[Preparation of styrenic resin particle dispersion (St1)]
- Styrene: 390 parts - n-butyl acrylate: 100 parts - Acrylic acid: 10 parts - Dodecanethiol: 7.5 parts The above materials were mixed and dissolved to prepare a monomer solution.
8 parts of an anionic surfactant (manufactured by Dow Chemical Company, Dowfax 2A1) was dissolved in 205 parts of ion-exchanged water, and the monomer solution was added to disperse and emulsify to obtain an emulsion.
2.2 parts of an anionic surfactant (manufactured by Dow Chemical Company, Dowfax 2A1) was dissolved in 462 parts of ion-exchanged water, and the solution was charged into a polymerization flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction pipe. The mixture was heated to and held at 73° C. while stirring.
3 parts of ammonium persulfate was dissolved in 21 parts of ion-exchanged water and added dropwise to the polymerization flask over 15 minutes via a metering pump, and then the emulsion was added dropwise over 160 minutes via a metering pump.
Next, the polymerization flask was maintained at 75° C. for 3 hours while slowly stirring, and then returned to room temperature.
As a result, the styrene resin contains styrene resin particles, has a volume average particle diameter (D50v) of 154 nm, a weight average molecular weight of 59 k by GPC (UV detection), a glass transition temperature of 54°C, and a solid content of 42%. A resin particle dispersion (St1) was obtained.

The styrenic resin particle dispersion (St1) was dried, the styrene resin particles were taken out, and the thermal behavior was measured in the temperature range of -150°C to 100°C using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-60A). Upon analysis, one glass transition temperature was observed. Table 5 shows the glass transition temperatures.

[Preparation of styrenic resin particle dispersions (St2) to (St13)]
Styrenic resin particle dispersions (St2) to (St13) were prepared in the same manner as in the preparation of styrenic resin particle dispersion (St1), except that the monomers were changed as shown in Table 5.

In Table 5, monomers are indicated by the following abbreviations.
Styrene: St, n-butyl acrylate: BA, 2-ethylhexyl acrylate: 2EHA, ethyl acrylate: EA, 4-hydroxybutyl acrylate: 4HBA, acrylic acid: AA, methacrylic acid: MAA, 2-carboxy acrylate Ethyl: CEA

<Preparation of dispersion containing composite resin particles>
[Preparation of composite resin particle dispersion (M1)]
・Styrenic resin particle dispersion (St1): 1190 parts (solid content 500 parts)
- 2-ethylhexyl acrylate: 250 parts - n-butyl acrylate: 250 parts - Ion exchange water: 982 parts The above materials were charged into a polymerization flask, stirred at 25°C for 1 hour, and then heated to 70°C.
2.5 parts of ammonium persulfate was dissolved in 75 parts of ion-exchanged water, and the solution was added dropwise to the polymerization flask via a metering pump over 60 minutes.
Next, the polymerization flask was maintained at 70° C. for 3 hours while slowly stirring, and then returned to room temperature.
As a result, a composite resin particle dispersion (M1) containing composite resin particles with a volume average particle diameter (D50v) of 183 nm, a weight average molecular weight of 129 k by GPC (UV detection), and a solid content of 32% was obtained. Ta.

The composite resin particle dispersion (M1) was dried, the composite resin particles were taken out, and the thermal behavior was analyzed in a temperature range of -150°C to 100°C using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-60A). However, two glass transition temperatures were observed. Table 6 shows the glass transition temperatures.

[Preparation of composite resin particle dispersions (M2) to (M21) and (cM1) to (cM3)]
In the same manner as in the preparation of the composite resin particle dispersion (M1), except that the styrene resin particle dispersion (St1) was changed as shown in Table 6, or by polymerization of the (meth)acrylic acid ester resin. Composite resin particle dispersions (M2) to (M21) and (cM1) to (cM3) were prepared by changing the components as shown in Table 6.

[Preparation of composite resin particle dispersions (M22) to (M27)]
Composite resin particle dispersions (M22) to (M27) were prepared in the same manner as in the preparation of composite resin particle dispersion (M1), but by adjusting the amounts of 2-ethylhexyl acrylate and n-butyl acrylate. did.

In Table 6, monomers are indicated by the following abbreviations.
Styrene: St, n-butyl acrylate: BA, 2-ethylhexyl acrylate: 2EHA, ethyl acrylate: EA, 4-hydroxybutyl acrylate: 4HBA, acrylic acid: AA, methacrylic acid: MAA, 2-carboxy acrylate Ethyl: CEA, Hexyl acrylate: HA, Propyl acrylate: PA

<Preparation of toner>
[Preparation of toner (1) and developer (1)]
- Composite resin particle dispersion (M1): 504 parts - Ion exchange water: 710 parts - Anionic surfactant (manufactured by Dow Chemical Company, Dowfax2A1): 1 part

The above materials were placed in a reaction container equipped with a thermometer and a pH meter, and the pH was adjusted to 3.0 by adding 1.0% nitric acid aqueous solution at a temperature of 25°C. 23 parts of a 2.0% aluminum sulfate aqueous solution was added while dispersing at a rotation speed of 5000 rpm using a Lux T50). Next, a stirrer and a mantle heater were installed in the reaction vessel, and the temperature was raised at a rate of 0.2 °C/min until the temperature reached 40 °C, and at a rate of 0.05 °C/min after exceeding 40 °C. The particle size was measured every 10 minutes using Multisizer II (aperture diameter 50 μm, manufactured by Beckman Coulter). When the volume average particle diameter reached 5.0 μm, the temperature was maintained, and 170 parts of the styrene resin particle dispersion (St1) and 0.3 parts of the yellow pigment dispersion (1) were added over 5 minutes. After the addition, the slurry was maintained at 50° C. for 30 minutes, and then a 1.0% aqueous sodium hydroxide solution was added to adjust the pH of the slurry to 6.0. Next, while adjusting the pH to 6.0 every 5°C, the temperature was raised to 90°C at a temperature increase rate of 1°C/min and maintained at 90°C. When observing the particle shape and surface properties using an optical microscope and a field emission scanning electron microscope (FE-SEM), coalescence of the particles was confirmed at 10 hours, so the container was heated to 30°C with cooling water for 5 minutes. It was then cooled.

The slurry after cooling was passed through a nylon mesh with an opening of 15 μm to remove coarse particles, and the slurry that had passed through the mesh was filtered under reduced pressure using an aspirator. The solid content remaining on the filter paper was crushed by hand as finely as possible, poured into ion-exchanged water (temperature: 30°C) of 10 times the amount of solid content, and stirred for 30 minutes. Next, filter it under reduced pressure with an aspirator, crush the solid content remaining on the filter paper as finely as possible by hand, pour it into ion-exchanged water (temperature 30°C) of 10 times the amount of solid content, stir for 30 minutes, and then crush it again with an aspirator. It was filtered under reduced pressure and the electrical conductivity of the filtrate was measured. This operation was repeated until the electrical conductivity of the filtrate became 10 μS/cm or less to wash the solid content.

The washed solid content was finely pulverized using a wet-dry type sizing machine (Cormill) and vacuum-dried in an oven at 25° C. for 36 hours to obtain toner particles (1). Toner particles (1) had a volume average particle diameter of 8.0 μm.

100 parts of toner particles (1) and 1.5 parts of hydrophobic silica (RY50, manufactured by Nippon Aerosil Co., Ltd.) were mixed and mixed for 30 seconds at a rotation speed of 13,000 rpm using a sample mill. The toner (1) was obtained by sieving with a vibrating sieve having an opening of 45 μm.

Using toner (1) as a sample, we analyzed its thermal behavior in the temperature range of -150°C to 100°C using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-60A), and two glass transition temperatures were observed. It was done. Table 7 shows the glass transition temperatures.

When the temperature T1 and temperature T2 of toner (1) were determined by the above-mentioned measuring method, toner (1) satisfied formula 1 "20°C≦T1-T2".

When the cross section of toner (1) was observed using a scanning electron microscope (SEM), a sea-island structure was observed. Further, toner (1) had a core portion in which an island phase existed and a shell layer in which an island phase did not exist.
The sea phase contained a specific styrene resin, and the island phase contained a specific (meth)acrylate ester resin. The average diameter of the island phase was determined using the measurement method described above. Table 7 shows the average diameter of the island facies.
The content of yellow pigment in toner (1) was measured by the method described above and was found to be 26 ppm.

10 parts of toner (1) and 100 parts of the following resin-coated carrier were placed in a V-type blender, stirred for 20 minutes, and then sieved with a vibrating sieve having a mesh size of 212 μm to obtain developer (1).

・Mn-Mg-Sr ferrite particles (average particle size 40 μm): 100 parts ・Toluene: 14 parts ・Polymethyl methacrylate: 2 parts ・Carbon black (VXC72: manufactured by Cabot): 0.12 parts The above except for ferrite particles The material and glass beads (diameter 1 mm, same amount as toluene) were mixed and stirred for 30 minutes at a rotation speed of 1200 rpm using a sand mill manufactured by Kansai Paint Co., Ltd. to obtain a dispersion. This dispersion liquid and ferrite particles were placed in a vacuum degassing type kneader, and dried under reduced pressure while stirring to obtain a resin-coated carrier.

[Preparation of toners (2) to (27) and developers (2) to (27)]
Toners (2) to (27) and developer (2) were prepared in the same manner as toner (1) except that the composite resin particle dispersion and styrene resin particle dispersion were changed as shown in Table 3. ~(27) was prepared.

When the temperature T1 and temperature T2 of toners (2) to (27) were determined by the measurement method described above, all of toners (2) to (27) satisfied formula 1 "10°C ≦T1-T2". .

[Preparation of comparative toners (c1) to (c3) and developers (c1) to (c3)]
Toners (c1) to (c3) and developer (c1) were prepared in the same manner as toner (1) except that the composite resin particle dispersion and styrene resin particle dispersion were changed as shown in Table 3. ~(c3) was prepared.

[Evaluation of pressure-responsive phase transition]
The temperature difference (T1-T3), which is an index indicating that the toner is susceptible to phase transition due to pressure, was determined. Using each toner as a sample, temperature T ₁ and temperature T ₂ were measured using a flow tester (manufactured by Shimadzu Corporation, CFT-500), and the temperature difference (T1-T3) was calculated. Table 7 shows the temperature difference (T1-T3).

[Evaluation of adhesion]
An apparatus shown in FIG. 2 was prepared as a printed matter manufacturing apparatus. That is, it includes a five tandem type and intermediate transfer type printing unit that simultaneously places the toner according to the present embodiment on a recording medium and forms a colored image, and a pressure bonding unit having a folding device and a pressure device. Prepared printed matter manufacturing equipment.
A toner according to the present embodiment (or a comparative toner), a yellow toner, a magenta toner, a cyan toner, and a black toner were respectively placed in five developing devices included in the printing means. As the yellow toner, magenta toner, cyan toner, and black toner, commercially available products manufactured by Fuji Xerox were used.
Postcard paper V424 manufactured by Fuji Xerox Co., Ltd. was prepared as a recording medium.
The image formed on the postcard paper was an image with an area density of 30% in which black characters and full-color photographic images were mixed, and was formed on one side of the postcard paper.
The amount of the toner according to this embodiment (or the toner for comparison) applied to the image forming area of the image forming surface of the postcard paper was 3 g/m ² .
The folding device was a device that folded the postcard paper in half so that the image forming surface was on the inside.
The pressure device was set to have a pressure of 90 MPa.
Using the above-mentioned apparatus and conditions, 10 postcards were successively produced, each of which was folded in half with the image-forming side facing inside and whose image-forming sides were adhered to each other.
The 10th postcard was cut in the long side direction to a width of 15 mm to prepare a rectangular test piece, and a 90 degree peel test was performed. The peeling speed of the 90 degree peel test was 20 mm/min, and after the start of the measurement, the load (N) from 10 mm to 50 mm was sampled at 0.4 mm intervals, the average was calculated, and the load (N) of 3 test pieces was measured. averaged. The load (N) required for peeling was classified as follows. Table 7 shows the results.

A: 1.0N or more B: 0.8N or more and less than 1.0N C: 0.6N or more and less than 0.8N D: 0.4N or more and less than 0.6N E: Less than 0.4N

100 Arranging means 101 Photoreceptor 102 Charging roll (an example of charging means)
103 Exposure device (an example of electrostatic image forming means)
104 Developing device (an example of developing means)
105 Transfer roll (an example of transfer means)
106 Photoreceptor cleaning device (an example of cleaning means)
107 Fixing device (an example of fixing means)
200 Pressure bonding means 220 Folding device 230 Pressure devices 231, 232 Pressure roll P Recording medium P1 Recording medium P2 on which the toner according to the present embodiment is applied on the image Folded recording medium P3 Pressure-bonded printed material

300 Printing means 1T, 1Y, 1M, 1C, 1K Photoreceptor 2T, 2Y, 2M, 2C, 2K Charging roll (an example of charging means)
3T, 3Y, 3M, 3C, 3K exposure device (an example of electrostatic image forming means)
4T, 4Y, 4M, 4C, 4K developing device (an example of developing means)
5T, 5Y, 5M, 5C, 5K Primary transfer roll (an example of primary transfer means)
6T, 6Y, 6M, 6C, 6K Photoconductor cleaning device (an example of cleaning means)
8T, 8Y, 8M, 8C, 8K Toner cartridge 10T, 10Y, 10M, 10C, 10K Unit 20 Intermediate transfer belt (an example of intermediate transfer body)
21 Intermediate transfer member cleaning device 22 Drive roll 23 Support roll 24 Opposing roll 26 Secondary transfer roll (an example of secondary transfer means)
28 Heat fixing device (an example of heat fixing means)

500 Process cartridge 501 Photoreceptor 502 Charging roll (an example of charging means)
503 Exposure device (an example of electrostatic image forming means)
504 Developing device (an example of developing means)
505 Transfer device (an example of transfer means)
506 Photoreceptor cleaning device (an example of cleaning means)
516 Mounting rail 517 Housing 518 Opening for exposure

Claims (24)

comprising two or more binder resins including a styrene resin and a (meth)acrylic acid ester resin , and a yellow pigment,
The content of the yellow pigment is 5 ppm or more and 100 ppm or less, and
A toner for developing an electrostatic image for producing pressure-bonded printed matter , which has at least two glass transition points, and the difference between the lowest glass transition temperature and the highest glass transition temperature is 30° C. or more. The toner for developing an electrostatic image according to claim 1, wherein the yellow pigment is a pigment selected from the group consisting of a monoazo pigment, a disazo pigment, and a benzimidazolone disazo pigment. The yellow pigment is C. I. Pigment Yellow 74, C. I. Pigment Yellow 93 and C.I. I. The toner for developing an electrostatic image according to claim 1 or 2, wherein the toner is a pigment selected from the group consisting of Pigment Yellow 180. The styrenic resin is a styrene resin containing styrene and other vinyl monomers as polymerization components, and the (meth)acrylic ester resin contains at least two types of (meth)acrylic esters as polymerization components, The electrostatic charge image according to any one of claims 1 to 3, which is a (meth)acrylic ester resin in which the mass ratio of (meth)acrylic ester to the entire polymerization component is 90% by mass or more. Toner for development. 5. The toner for developing an electrostatic image according to claim 4, wherein the mass proportion of styrene in the entire polymerization component of the styrenic resin is 60% by mass or more and 95% by mass or less. Among the at least two kinds of (meth)acrylic esters contained as polymerization components in the (meth)acrylic ester-based resin, the mass ratio of the two with the highest mass ratio is 80:20 to 20:80. The toner for developing an electrostatic image according to claim 4 or 5. Of the at least two types of (meth)acrylic esters contained as polymerization components in the (meth)acrylic ester-based resin, the two with the highest mass ratio are (meth)acrylic acid alkyl esters, and the two types are The toner for developing an electrostatic image according to any one of claims 4 to 6, wherein the difference in the number of carbon atoms in the alkyl groups of the (meth)acrylic acid alkyl ester is 1 or more and 4 or less. The toner for developing an electrostatic image according to any one of claims 4 to 7, wherein the other vinyl monomer contained as a polymerization component in the styrene resin contains a (meth)acrylic acid ester. The electrostatic charge according to any one of claims 4 to 8, wherein the other vinyl monomer contained as a polymerization component in the styrenic resin includes at least one of n-butyl acrylate and 2-ethylhexyl acrylate. Toner for image development. The electrostatic image developing device according to any one of claims 4 to 9, wherein the styrene resin and the (meth)acrylic acid ester resin contain the same type of (meth)acrylic acid ester as a polymerization component. toner. The toner for developing an electrostatic image according to any one of claims 4 to 10, wherein the (meth)acrylic acid ester resin contains 2-ethylhexyl acrylate and n-butyl acrylate as polymerization components. The toner for developing an electrostatic image according to any one of claims 1 to 11, wherein the content of the styrene resin is greater than the content of the (meth)acrylate resin. The static resin according to any one of claims 1 to 12, comprising a sea phase containing the styrene resin and an island phase containing the (meth)acrylate resin dispersed in the sea phase. Toner for developing charged images. The toner for developing an electrostatic image according to claim 13, wherein the average diameter of the island phase is 200 nm or more and 500 nm or less. The static resin according to any one of claims 1 to 14, comprising a core portion containing the styrene resin and the (meth)acrylic acid ester resin, and a shell layer covering the core portion. Toner for developing charged images. The toner for developing electrostatic images of printed matter according to claim 15, wherein the shell layer contains the styrene resin. The toner for developing an electrostatic image according to any one of claims 1 to 16, wherein the temperature at which the toner exhibits a viscosity of 10,000 Pa·s under a pressure of 4 MPa is 90° C. or less. An electrostatic image developer comprising the toner for developing an electrostatic image according to any one of claims 1 to 17. A toner cartridge containing the toner for developing an electrostatic image according to any one of claims 1 to 17, which is detachable from a printed matter manufacturing apparatus. A developing device containing the electrostatic charge image developer according to claim 18 and developing an electrostatic charge image formed on the surface of the photoreceptor as a toner image by the electrostatic charge image developer,
A process cartridge that can be attached to and removed from printed matter manufacturing equipment. An electrostatic image developer containing the toner for developing an electrostatic image according to any one of claims 1 to 17 is stored, and the toner for developing an electrostatic image is placed on a recording medium by an electrophotographic method. arrangement means;
crimping means for folding and crimping the recording medium or stacking and crimping the recording medium and another recording medium;
Printed matter manufacturing equipment, including: 22. The printed matter manufacturing apparatus according to claim 21, further comprising a colored image forming means for forming a colored image on a recording medium by an electrophotographic method using a colored electrostatic image developer. Using an electrostatic image developer containing the toner for developing an electrostatic image according to any one of claims 1 to 17, the toner for developing an electrostatic image is placed on a recording medium by an electrophotographic method. placement process,
a crimping step of folding and crimping the recording medium or stacking and crimping the recording medium and another recording medium;
A method of producing printed matter, including: 24. The method for producing a printed matter according to claim 23, further comprising a colored image forming step of forming a colored image on a recording medium by electrophotography using a colored electrostatic image developer.