JP2020181187A - toner - Google Patents

Abstract

To provide toner that can both improve the amount of charge and suppress contamination of parts.SOLUTION: A toner contains toner particles. The toner particles contain toner core particles, and organosilicon polymer covering the surface of toner core particles. The organosilicon polymer has a structure represented by R4-SiO3/2 (R4 are independently phenyl groups or alkyl groups having 1 to 6 carbon atoms). Toner core particles contain resin A. The resin A has a substituted or unsubstituted silyl group in the molecule. The substituent of the substituted silyl group is selected from at least one of the group consisting of an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, a hydroxy group, a halogen atom and an aryl group having 6 or more carbon atoms. The content of silicon atoms in resin A is 0.02 to 10.00% by mass. The silicon atom content is 30 to 50% by mass in the organosilicon polymer.SELECTED DRAWING: None

Description

The present disclosure relates to toners for developing electrostatic charge images (electrostatic latent images) used in image forming methods such as electrophotographic and electrostatic printing.

The electrophotographic method is a printing method consisting of the following processes, to give a general example.
First, a photoconductor using a photoconducting substance is uniformly charged, and an electrostatic latent image is formed by exposure. Next, the toner charged by friction with a charging member such as a blade carrier is developed on the photoconductor. Finally, after the toner image is transferred to a medium such as paper, the toner image is fixed on the medium by heating, pressurizing, or the like. If necessary, the toner remaining on the photoconductor after transfer is removed by a cleaning member. By going through this series of processes again, continuous printing can be performed.
In the above process, toner is involved in almost all processes. Therefore, toner is required to have various properties such as fluidity, chargeability, and thermophysical properties (heat-resistant storage property and fixability). Above all, control of toner charging characteristics is important for obtaining printed matter with good image quality. Specifically, the toner charging characteristics are the speed of charging by friction (charging rising property), the magnitude of the amount of charging generated by friction, and the stability independent of temperature and humidity. Among such charging characteristics, improving the charging amount of toner is important for establishing the electrophotographic process.

In order to improve the charge amount of the toner, an external additive (inorganic particles such as silica, titania, and alumina) is often attached or fixed to the surface of the toner particles.
However, the external additive easily contaminates each member in the developing tank, and it is difficult to use it well. Furthermore, in recent years, the speed and life of machines have been increasing, and it is even more difficult to improve the amount of charge and suppress the contamination of parts. Under these circumstances, it has been desired to establish a technique capable of both improving the charge amount of toner and suppressing contamination of members.

As an example of a method for solving these problems, a technique that does not use an external additive has been developed. Specifically, a method of coating a polymer of alkoxysilane on the surface of toner particles by using a sol-gel process is known.
Patent Document 1 discloses a toner in which the surface of toner particles is coated with a polymer of tetraalkoxysilane in order to solve problems such as desorption and burial of a conventional external additive.
Patent Document 2 discloses a toner in which a polymer of dialkoxysilane is coated on the surface of toner core particles made of a polyvinyl-based thermoplastic resin having a dialkoxysilyl group in order to suppress hot offset in the toner fixing process. ing.
Patent Document 3 discloses a toner in which the surface of toner particles is coated with a polymer of trialkoxysilane as a main component in order to improve the wear resistance of the developing unit.

Japanese Unexamined Patent Publication No. 2013-120251 Japanese Unexamined Patent Publication No. 9-269611 Japanese Unexamined Patent Publication No. 2018-194837

It was found that the method described in Patent Document 1 had an insufficient amount of charge. The reason for this is thought to be the charge leak that occurs on the toner surface. This will be described in detail below.
The coating layer on the surface of the toner particles in the method described in Patent Document 1 mainly contains silicon dioxide. However, depending on the conditions, the polymerization of tetraalkoxysilane is insufficient to completely form silicon dioxide, and there are cases where a large amount of silanol groups are present. Since the silanol group has high hygroscopicity, it lowers the resistance value of the toner, and it is considered that a charge leak occurs.
Further, it was found that the method described in Patent Document 1 is also insufficient in suppressing member contamination. It is considered that the reason for this is that the coating layer becomes brittle because the proportion of silicon dioxide completely formed as described above is small and the crosslinked network of siloxane bonds is small.

It was also found that the method described in Patent Document 2 also has an insufficient amount of charge in the toner. The reason for this is also considered to be the charge leak that occurs on the toner surface. This will be described in detail below.
The coating layer on the surface of the toner particles in the method described in Patent Document 2 mainly contains a polydimethylsilicone compound. Since the polydimethylsilicone compound has high flexibility, it is presumed that it is difficult to retain the generated charge in place. As a result, it is probable that a charge leak occurred.

Further, it was found that the method described in Patent Document 2 is also insufficient in suppressing member contamination. It is considered that the reason for this is that there are many free components and the free components easily adhere to the member.
The details are as follows. Patent Document 2 discloses that polydimethylsilicone is covalently bonded by a resin containing bifunctional silane contained in the toner particles, but the proportion of polydimethylsilicone covalently bonded to the surface of the toner particles is small. .. Therefore, it is considered that the free component increases and the free component easily adheres to the member.

It was found that the method described in Patent Document 3 has a higher charge amount of toner than the methods described in Patent Documents 1 and 2. It is considered that the reason for this is that the charge leakage that occurs on the toner surface as described above is suppressed. This will be described in detail below.
The polymer of trialkoxysilane, which is the main component of the toner particle coating layer described in Patent Document 3, has higher hydrophobicity than the polymer of tetraalkoxysilane and is harder than the polymer of polydimethylsilicone, as described above. This is thought to be due to the suppression of charge leakage.
However, in the faster process, it was found that the charge amount was insufficient even if the charge leak occurring on the toner surface could be suppressed.

Further, it was found that the method described in Patent Document 3 suppresses member contamination as compared with the method described in Patent Documents 1 and 2. It is considered that the reason is that the wear resistance is strengthened by using the organosilicon polymer having a predetermined Martens hardness.
However, it was found that the amount of charge was insufficient for the reasons mentioned above. Therefore, in order to secure a sufficient amount of charge, it was examined to use an external additive such as hydrotalcite particles, but it was difficult to suppress the contamination of members by the external additive.

As described above, there is a trade-off relationship between the improvement of toner chargeability and the suppression of member contamination, and it has been difficult to solve the problem by the prior art.
The present disclosure provides a toner that solves the problems of the prior art. That is, the present disclosure provides a toner that can both improve the charge amount of the toner and suppress the contamination of members.

The present disclosure is a toner containing toner particles.
The toner particles
Toner core particles and
An organosilicon polymer that coats the surface of the toner core particles and
Contains,
The organosilicon polymer has a structure represented by the following formula (A) and has a structure represented by the following formula (A).
The toner core particles contain resin A and
The resin A has a substituted or unsubstituted silyl group in the molecule and has.
The substituent of the substituted silyl group is selected from the group consisting of an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, a hydroxy group, a halogen atom and an aryl group having 6 or more carbon atoms. One and
The content of silicon atoms in the resin A is 0.02% by mass to 10.00% by mass.
The present invention relates to a toner characterized in that the content of silicon atoms in the organosilicon polymer is 30% by mass to 50% by mass.

(In the formula (A), R ⁴ independently represents an alkyl group or a phenyl group having 1 to 6 carbon atoms.)

According to the present disclosure, it is possible to provide a toner that can both improve the charge amount of the toner and suppress the contamination of members.

It is a schematic diagram of a Faraday cage.

Unless otherwise specified, the description of "XX or more and YY or less" or "XX to YY" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points.
As a result of diligent studies to solve the above-mentioned problems of the prior art, the present inventors have found that it is possible to improve the charge amount of the toner and suppress the contamination of members by adopting the following configuration.
In particular,
Toner containing toner particles
The toner particles
Toner core particles and
An organosilicon polymer that coats the surface of the toner core particles and
Contains,
The organosilicon polymer has a structure represented by the following formula (A) and has a structure represented by the following formula (A).
The toner core particles contain resin A and
The resin A has a substituted or unsubstituted silyl group in the molecule and has.
The substituent of the substituted silyl group is selected from the group consisting of an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, a hydroxy group, a halogen atom and an aryl group having 6 or more carbon atoms. One and
The content of silicon atoms in the resin A is 0.02% by mass to 10.00% by mass.
The toner is characterized in that the content of silicon atoms in the organosilicon polymer is 30% by mass to 50% by mass.

(In the formula (A), R ⁴ independently represents an alkyl group or a phenyl group having 1 to 6 carbon atoms.)

The inventors speculate as follows about the mechanism by which the amount of charge is significantly increased as compared with the conventional toner and the contamination of members can be suppressed.
First, the mechanism for improving the amount of charge will be described.
Toner charging is a phenomenon in which electric charge is applied to the toner surface by friction between the toner surface and a charging member such as a charging roller, a charging blade, and a carrier. At this time, if the resistance of the toner surface is high, the charge is maintained on the toner surface, so that the toner can be charged. However, the amount of charge is low because the charge can be applied only to the rubbed part.
On the other hand, when the resistance of the toner surface is low, a phenomenon (charge leak) occurs in which electric charges are transmitted through the toner surface and escape. As a result, the amount of charge decreases.
Specifically, the conventional toners described in Patent Documents 1 and 2 have a large charge leak on the toner surface and therefore have a low charge amount.
On the other hand, the conventional toner described in Patent Document 3 has a small charge leak on the toner surface, so that the charge amount is improved although it is not sufficient. However, since the generated charge is retained on the toner surface and the charge on the toner surface is immediately saturated, the charge amount is insufficient in the accelerated process.
As described above, the conventional toner cannot achieve a high charge amount due to the triboelectric charge on the toner surface and the charge leakage relationship.

On the other hand, in the toner of the present disclosure, it is considered that a high charge amount can be realized because the charge on the toner surface is diffused inside the toner core particles and can be charged in the entire toner particles.
The diffusion of electric charge inside the toner core particles is caused by the resin A inside the toner core particles.
More specifically, the silyl group in the resin A tends to be negatively charged. On the other hand, the portion of the resin A other than the silyl group is likely to be positively charged. Therefore, charge transfer occurs between the structure represented by the above formula (A) contained in the organosilicon polymer coating the surface of the toner core particles and the silyl group of the resin A inside the toner core particles. As a result, electric charge is propagated from the toner surface to the inside of the toner core.
Since the charge on the toner surface is reduced by the propagation of the charge, the toner surface can be further charged by friction, and as a result, high charge can be achieved as the toner.

Next, the mechanism for suppressing member contamination will be described.
It has been found that the film of the organosilicon polymer in the toner described in Patent Document 3 is hard and has strong wear resistance, but the adhesion to the toner core particles is insufficient, and the members may be contaminated when printing a large number of sheets. ..
On the other hand, in the present disclosure, by allowing the resin A to be present in the toner core particles, it has become possible to suppress member contamination. The present inventors consider that this is because the polarities of the resin A in the toner core particles and the organosilicon polymer are close to each other, so that the adhesion between the toner core particles and the organosilicon polymer is improved.
As described above, by coating the toner core particles containing the resin A with the organosilicon polymer containing the structure represented by the formula (A), it is the first time to improve the charge amount and suppress the contamination of members, which have been problems. I was able to achieve both.

Hereinafter, the constituent requirements of the present disclosure will be described in detail.
<Resin A>
The toner core particles contain resin A. The resin A has (i) a substituted or unsubstituted silyl group in the molecule, and (ii) the substituent of the substituted silyl group is an alkyl group having 1 or more carbon atoms and 1 or more carbon atoms. It is at least one selected from the group consisting of an alkoxy group, a hydroxy group, a halogen atom and an aryl group having 6 or more carbon atoms.
The number of carbon atoms of the alkyl group is preferably 1 to 20, and more preferably 1 to 4.
The number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably 1 or 2.
The aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
Examples of the resin A are not limited as long as they satisfy the above (i) and (ii), but are not limited to the resin to which a silane coupling agent or the like is chemically bonded, and the weight of the organosilicon compound. Examples thereof include coalescence and hybrid resins thereof. More specifically, a resin obtained by modifying a polyester resin, a vinyl resin, a polycarbonate resin, a polyurethane resin, a phenol resin, an epoxy resin, a polyolefin resin or a styrene acrylic resin with a silane coupling agent and / or a silicone oil or the like can be mentioned. ..

The content of silicon atoms in the resin A is 0.02% by mass to 10.00% by mass. Within this range, it is possible to improve the adhesion between the toner core particles and the organosilicon polymer while propagating the electric charge inside the toner core, so that it is possible to improve the charge amount and suppress the member contamination at the same time.
The content of silicon atoms in the resin A is preferably 0.10% by mass to 5.00% by mass, and more preferably 0.15% by mass to 2.00% by mass.
The content of silicon atoms in the resin A can be controlled by adjusting the amount of the silicon compound used in the production of the resin A.
The content of the resin A in the toner core particles is preferably 0.1% by mass to 100.0% by mass, and more preferably 0.3% by mass to 30.0% by mass.

The resin A preferably has a structure represented by the following formula (1).

(In the formula (1), P ¹ represents a polymer moiety, L ¹ represents a single bond or a divalent linking group, and R ^{1 to} R ³ independently represent hydrogen atoms, halogen atoms, and carbon atoms. one or more alkyl groups, the carbon atom number of 1 or more alkoxy groups, represents a carbon atom number of 6 or more aryl group or a hydroxy group, m represents a positive integer, where m is 2 or more, a plurality of L ¹ , A plurality of R ¹ , a plurality of R ² and a plurality of R ³ may be the same or different, respectively.)

Of R ^{1 to} R ³ in the formula (1), at least one preferably represents an alkoxy group or a hydroxy group having 1 or more carbon atoms. More preferably, R ^{1 to} R ³ in the above formula (1) independently represent an alkoxy group or a hydroxy group having 1 or more carbon atoms.
Of the above substituents, the alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 4 carbon atoms. The number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably 1 or 2. Further, the number of carbon atoms of the aryl group is preferably 6 to 14, and more preferably 6 to 10.

When at least one of R ^{1 to} R ^{3 in} the formula (1) represents an alkoxy group or a hydroxy group having one or more carbon atoms, the structure represented by the formula (1) has a Si—O— bond. Have.
The toner core particles having a Si—O— bond have an increased affinity with the Si—O— bond in the organosilicon polymer on the surface of the toner particle, so that the efficiency of propagating the charge into the toner core is improved and the amount of charge is increased. At the same time, the adhesion between the toner core particles and the organosilicon polymer is further improved.
Further, by improving the adhesion of the surface of the toner particles to the organosilicon polymer, the resistance to thermal deformation is increased, and the heat-resistant storage stability of the toner is also improved.

In order to make one or more of R ^{1 to} R ³ in the formula (1) a hydroxy group, the resin A in which one or more of R ^{1 to} R ³ is an alkoxy group is hydrolyzed, and the alkoxy group is hydroxy. It may be converted to a group.
Any method may be used for hydrolysis, and for example, there are the following methods.
Resin A in which one or more of R ^{1 to} R ³ in the formula (1) is an alkoxy group is dissolved or suspended in an appropriate solvent (may be a polymerizable monomer), and the pH is adjusted using an acid or an alkali. To be acidic, mix and hydrolyze.
Further, hydrolysis may occur during the production of toner particles.

The P ¹ in the formula (1) is not particularly limited, and examples thereof include a polyester moiety, a vinyl moiety, a styrene acrylic moiety, a polyurethane moiety, a polycarbonate moiety, a phenol resin moiety, and a polyolefin moiety.
Among these, from the viewpoint of charge rising property, it is preferable that P ¹ contains a polyester moiety or a styrene acrylic moiety. For example, it may be a hybrid site of polyester and styrene acrylic. It is more preferable that P ¹ represents a polyester moiety or a styrene acrylic moiety, and it is particularly preferable that P ¹ represents a polyester moiety.
The reason for this can be considered as follows. Since the electric charge is transferred between the silicon atom in the resin represented by the formula (1) and the ester bond in P ¹ , the electric charge generated on the toner surface by triboelectric charging diffuses to the entire toner. Due to this diffusion, not only the surface of the toner but also the inside of the toner can contribute to charging, so that the charging rising property is improved.
The weight average molecular weight (Mw) of the resin A is preferably 3,000 to 100,000, more preferably 3,000 to 30,000, from the viewpoint of charge rising property and storage stability. Various control methods can be mentioned for Mw of the resin A depending on the type of resin contained. For example, when a polyester resin is contained, it can be controlled by adjusting the charging ratio of the monomers dialcohol and dicarboxylic acid, adjusting the polymerization time, and the like. When the styrene acrylic resin is contained, it can be controlled by adjusting the ratio of the vinyl monomer which is the monomer and the polymerization initiator and adjusting the reaction temperature.

The polyester resin is not particularly limited, but is preferably a condensate of a dialcohol and a dicarboxylic acid. For example, a polyester resin having a structure represented by the following formula (6) and at least one structure (s) selected from the group consisting of structures represented by the following formulas (7) to (9). Is preferable. Alternatively, a polyester resin having a structure represented by the following formula (10) can be mentioned.

(In formula (6), R ⁹ represents an alkylene group, an alkenylene group, and an arylene group. In formula (7), R ¹⁰ represents an alkylene group and a phenylene group. In formula (8), R ¹⁸ represents an ethylene group or an ethylene group. Represents a propylene group. X and y are respective integers of 0 or more, and the average value of x + y is 2 to 10. In the formula (10), R ¹¹ represents an alkylene group or an alkenylene group.)

Examples of the alkylene group (preferably having 1 to 12 carbon atoms) in R ⁹ in the above formula (6) include the following. Methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, neopentylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, 1,3- Cyclopentylene, 1,3-cyclohexylene, 1,4-cyclohexylene group.
Examples of the alkenylene group (preferably having 1 to 4 carbon atoms) in R ⁹ in the above formula (6) include a vinylene group, a propenylene group, and a 2-butenylene group.
Examples of the arylene group (preferably having 6 to 12 carbon atoms) in R ⁹ in the above formula (6) include 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 2, Examples thereof include a 6-naphthylene group, a 2,7-naphthylene group and a 4,4′-biphenylene group.
R ⁹ in the above formula (6) may be substituted with a substituent. In this case, examples of the substituent include a methyl group, a halogen atom, a carboxy group, a trifluoromethyl group and a combination thereof.

Examples of the alkylene group (preferably having 1 to 12 carbon atoms) in R ¹⁰ in the above formula (7) include the following. Methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, neopentylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, 1,3- Cyclopentylene, 1,3-cyclohexylene, 1,4-cyclohexylene group.
Examples of the phenylene group in R ¹⁰ in the above formula (7) include a 1,4-phenylene group, a 1,3-phenylene group, and a 1,2-phenylene group.
R ¹⁰ in the above formula (7) may be substituted with a substituent. In this case, examples of the substituent include a methyl group, an alkoxy group, a hydroxy group, a halogen atom and a combination thereof.

Examples of the alkylene group (preferably having 1 to 12 carbon atoms) in R ¹¹ in the above formula (10) include the following. Methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, neopentylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, 1,4- Cyclohexylene group.
Examples of the alkenylene group (preferably having 1 to 40 carbon atoms) in R ¹¹ in the above formula (10) include the following. Vinylene group, propenylene group, butenylene group, butazienylene group, pentenylene group, hexenylene group, hexadienylene group, heptenylene group, octanylene group, decenylene group, octadecenylene group, eicosenylene group, triacontenylene group. These alkenylene groups may have any linear, branched, or cyclic structure. Further, the position of the double bond may be any position, and it is sufficient that it has at least one or more double bonds.
R ¹¹ in the above formula (10) may be substituted with a substituent. In this case, examples of the substituent which may be substituted include an alkyl group, an alkoxy group, a hydroxy group, a halogen atom and a combination thereof.

The vinyl resin is not particularly limited and known ones can be used. For example, the following monomers can be used.
Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene Styrene-based monomers such as styrene and derivatives thereof.
Methyl acrylate, ethyl acrylate, -n-butyl acrylate, isobutyl acrylate, propyl acrylate, -n-octyl acrylate, dodecyl acrylate, -2-ethylhexyl acrylate, stearyl acrylate, -2- acrylate Acrylic acid esters such as chlorethyl and phenylacrylic acid.
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -n-octyl methacrylate, dodecyl methacrylate, -2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic Methacrylic acid esters such as dimethylaminoethyl acid acid, diethylaminoethyl methacrylate.

Amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl-based compounds containing nitrogen atoms such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, metaacrylonitrile and acrylamide. monomer.
Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, silicic acid; and Vinyl-based monomers containing carboxy groups such as these acid anhydrides.

When the compound containing a carboxy group contains a vinyl resin, the method for incorporating the carboxy group in the vinyl resin is not particularly limited, and a known method can be used. For example, it is preferable to use a vinyl-based monomer containing a carboxy group such as acrylic acid and methacrylic acid.
The vinyl resin is preferably a polymer of at least one selected from the group consisting of an acrylic acid ester and a methacrylic acid ester, a styrene-based monomer and a vinyl-based monomer containing a carboxy group.

The divalent linking group that can be represented by L ¹ in the formula (1) includes, for example, structures represented by the following formulas (2) to (5), but is not particularly limited thereto. ..

(R ⁵ in the formula (2) represents a single bond, an alkylene group or an arylene group. (*) Represents a binding site to P ¹ in the formula (1), and (**) represents the above formula (1). ) Represents the binding site to the silicon atom. R ⁶ in the formula (3) represents a single bond, an alkylene group or an arylene group. (*) Represents the binding site to P ¹ in the formula (1). (**) represents a binding site to a silicon atom in the above formula (1). R ⁷ and R ⁸ in the formulas (4) and (5) are independently alkylene groups and arylene groups, respectively. , (*) Represents the binding site to P ¹ in the above formula (1), and (**) represents the binding site to the silicon atom in the formula (1).

The structure represented by the formula (2) is a divalent linking group containing an amide bond.
The linking group can be formed, for example, by reacting a carboxy group in a resin with an aminosilane.
The aminosilane is not particularly limited, but for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β. (Aminoethyl) γ-aminopropylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N -6- (Aminohexyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethylsilane, 3-aminopropylsilicon and the like can be mentioned.
The alkylene group (preferably having 1 to 12 carbon atoms) in R ⁵ is not particularly limited, but may be, for example, an alkylene group containing a -NH- group.
R in ⁵ (preferably 6 to 12 carbon atoms) arylene groups include, but are not limited to, for example, it may be an arylene group having a hetero atom.

The structure represented by the formula (3) is a divalent linking group containing a urethane bond.
The linking group can be formed, for example, by reacting a hydroxy group in a resin with isocyanatesilane.
The isocyanate silane is not particularly limited, but for example, 3-isocyanate propyltrimethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropyldimethylmethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-. Examples thereof include isocyanate propylmethyl diethoxysilane and 3-isocyanate propyl dimethyl ethoxysilane.
The alkylene group (preferably having 1 to 12 carbon atoms) in R ⁶ is not particularly limited, but may be, for example, an alkylene group containing a -NH- group.
The arylene group (preferably having 6 to 12 carbon atoms) in R ⁶ is not particularly limited, but may be, for example, an arylene group containing a hetero atom.

The structure represented by the formula (4) or (5) is a divalent linking group containing a bond grafted to an ester bond in the resin.
The linking group is formed, for example, by an insertion reaction of epoxysilane.
The epoxy silane insertion reaction refers to a reaction including a step of inserting an epoxy group of epoxy silane into an ester bond contained in a main chain in a resin. Further, the insertion reaction referred to here is described as, for example, "Insert reaction of an epoxy compound into an ester bond in a polymer chain" in Synthetic Organic Chemistry, Vol. 49, No. 3, p. 218, 1991. Refers to the reaction that occurs.
The reaction mechanism of the epoxy silane insertion reaction can be represented by the model diagram below.

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

Since there are α-cleavage and β-cleavage in the ring opening of the epoxy group in the figure, two kinds of compounds are formed. The component excluding the epoxy part is a compound grafted on the resin.
The epoxy silane is not particularly limited, but for example, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl. Examples thereof include diethoxysilane.
The alkylene group (preferably having 1 to 12 carbon atoms) in R ⁷ and R ⁸ is not particularly limited, but may be, for example, an alkylene group containing a -NH- group.
The arylene group (preferably having 6 to 12 carbon atoms) in R ⁷ and R ⁸ is not particularly limited, but may be, for example, an arylene group containing a hetero atom.
The oxyalkylene group (preferably having 1 to 12 carbon atoms) in R ⁷ and R ⁸ is not particularly limited, but may be, for example, an oxyalkylene group containing a -NH- group.

<Organosilicon polymer having a structure represented by the formula (A)>
The organosilicon polymer has at least a structure represented by the following formula (A).

(In the formula (A), R ⁴ independently represents an alkyl group or a phenyl group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms)).

About four valence electrons of Si atom in the structure represented by formula (A), 1 piece is involved in binding to R ^4, 3 pieces rest is involved in binding to O atoms. The O atom constitutes a state in which both of the two valences are bonded to Si, that is, a siloxane bond (Si—O—Si). Considering the Si atom and the O atom as the organosilicon polymer, since two Si atoms have three O atoms, it is expressed as −SiO _3/2 .
The organosilicon polymer having the structure represented by the formula (A) has a high hardness because the concentration of the siloxane bond contained in the structure is close to that of silicon dioxide (SiO ₂ ). Further, since the R ⁴ is bound, the structure is highly hydrophobic. The toner of the present disclosure has a higher charge amount than the conventional toner because the leakage of electric charge on the toner surface can be suppressed by these.
The composition of the organosilicon polymer may be controlled so that the hardness and hydrophobicity of the organosilicon polymer having the structure represented by the formula (A) are within desired ranges. Specifically, the type and amount of the organosilicon compound used for producing the organosilicon polymer, and the reaction temperature, reaction time, reaction solvent and pH of hydrolysis, addition polymerization and condensation polymerization at the time of forming the organosilicon polymer. Can be controlled by changing.

The content of silicon atoms in the organosilicon polymer thus obtained is 30% by mass to 50% by mass, preferably 33% by mass to 40% by mass. The content of silicon atoms in the organosilicon polymer can be determined by changing the type of organosilicon compound at the time of production and polycondensing, adjusting the mixing ratio of different types of organosilicon polymers, or polycondensing. It can be controlled by a method such as polycondensation after adjusting (or adjusting) the pH.
Further, in the measurement of ²⁹ Si-NMR of the tetrahydrofuran insoluble portion of the toner particles, the ratio of the peak area of the structure represented by the formula (A) to the total peak area of the organosilicon polymer is preferably 30% to 30%. It is 100%. Further, in order to significantly improve the charge amount and suppress the contamination of members, the ratio of the peak area of the structure represented by the formula (A) is more preferably 50% to 100%. It is more preferably 50% to 90%. The ratio of the peak area of the structure represented by the formula (A) is polycondensed by changing the type of the organosilicon compound at the time of production, or by adjusting the mixing ratio of different types of organosilicon polymers. Alternatively, it can be controlled by a method such as polycondensation after adjusting (or adjusting) the temperature and pH.
In the organosilicon polymer containing the structure represented by the formula (A), R ⁴ in the formula (A) is defined from the viewpoint of keeping the hardness and hydrophobicity of the organosilicon polymer within an appropriate range. It is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms, and more preferably R ⁴ is a hydrocarbon group having 1 to 3 carbon atoms. From the viewpoint of charge retention, more preferably R ⁴ is a methyl or ethyl group, particularly preferably a methyl group.

<Method for producing an organosilicon polymer having a structure represented by the formula (A)>
The organosilicon polymer is not particularly limited, but is preferably a polycondensation polymer of an organosilicon compound (trifunctional silane) having a structure represented by the following formula (11).

In formula (11), R ¹⁴ is synonymous with R ⁴ in formula (A).
In the formula (11), R ^{15 to} R ¹⁷ independently represent a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group (hereinafter, these are collectively referred to as a reactive group). By hydrolyzing, addition polymerization and polycondensation of these reactive groups to form a crosslinked structure, contamination of members can be further suppressed.
From the viewpoint of mild hydrolyzability at room temperature, precipitation of toner particles on the surface, and coating property, R ^{15 to} R ¹⁷ are independently alkoxy groups having 1 to 3 carbon atoms. It is preferably a methoxy group or an ethoxy group, more preferably. Further, the hydrolysis, addition polymerization and condensation polymerization of R ^{15 to} R ¹⁷ can be controlled by changing the reaction temperature, reaction time, reaction solvent and pH.

In order to obtain an organosilicon polymer, it is preferable to use one or a combination of trifunctional silanes.
Specific examples of the trifunctional silane include the following.
Methyltrimethoxysilane, Methyltriethoxysilane, Methyldiethoxymethoxysilane, Methylethoxydimethoxysilane, Methyltrichlorosilane, Methylmethoxydichlorosilane, Methylethoxydichlorosilane, Methyldimethoxychlorosilane, Methylmethoxyethoxychlorosilane, Methyldiethoxychlorosilane, Methyl Triacetoxysilane, Methyldiacetoxymethoxysilane, Methyldiacetoxyethoxysilane, Methylacetoxydimethoxysilane, Methylacetoxymethoxyethoxysilane, Methylacetoxydiethoxysilane, Methyltrihydroxysilane, Methylmethoxydihydroxysilane, Methylethoxydihydroxysilane, Methyldimethoxy Trifunctional methylsilanes such as hydroxysilanes, methylethoxymethoxyhydroxysilanes, methyldiethoxyhydroxysilanes.
Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltri Trifunctional such as methoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane Sexual silane.
Trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

Further, an organosilicon polymer obtained by using the following compounds in combination with the trifunctional silane may be used to the extent that the effects of the present disclosure are not impaired.
An organic silicon compound having four reactive groups in one molecule (tetrafunctional silane), an organic silicon compound having two reactive groups in one molecule (bifunctional silane), and one reactive group in one molecule. the organosilicon compound (monofunctional silane), the trifunctional silane R ⁴ has a substituent. Specific examples of these compounds include the following.
Dimethyldimethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxy Silane, 3- (2-aminoethyl) aminopropyltriethoxysilane.
Three such as vinyltriisocyanatesilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinylethoxydihydroxysilane, vinyldimethoxyhydroxysilane, vinylethoxymethoxyhydroxysilane, vinyldiethoxyhydroxysilane, etc. Functional vinylsilane.

Further, the content of the organosilicon polymer in the toner particles is preferably 0.1% by mass to 20.0% by mass, and more preferably 1.0% by mass to 10.0% by mass.
When the content of the organosilicon polymer is 0.1% by mass or more, it is possible to suppress the generation of member contamination and fog. When it is 20.0% by mass or less, it is possible to make it difficult for charge-up to occur. The content of the organosilicon polymer changes the type and amount of the organosilicon compound used for producing the organosilicon polymer, the method for producing the toner particles when forming the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent and the pH. It can be controlled by doing.

Examples of the method for producing the organosilicon polymer include, but are not limited to, the following methods.
First, core particles of a toner containing a binder resin and, if necessary, a colorant are produced and dispersed in an aqueous medium to obtain a core particle dispersion liquid. Next, an organosilicon compound is added to the core particle dispersion and polycondensed to form an organosilicon polymer that covers the surface of the toner core particles.
As a method of adding the organosilicon compound, the organosilicon compound may be added as it is. Alternatively, it may be added after being mixed with an aqueous medium in advance and hydrolyzed.
Organosilicon compounds undergo a polycondensation reaction after being hydrolyzed. The optimum pH for the hydrolysis reaction and the optimum pH for the polycondensation reaction may differ. Therefore, the organosilicon compound and the aqueous medium are mixed in advance, hydrolyzed at a pH suitable for the hydrolysis reaction, and then polycondensed at the optimum pH for the polycondensation reaction to effectively react. Can be advanced.

<About binding resin>
The resin contained in the toner core particles may be only the resin A described above, but may also have a binder resin if necessary.
When the toner core particles contain a binder resin, the content of the resin A with respect to 100 parts by mass of the binder resin is preferably 0.1 part by mass to 20.0 parts by mass, and 0.3 parts by mass to 5. More preferably, it is 0 parts by mass.
The binder resin is not particularly limited, and conventionally known ones can be used, but for example, vinyl-based resin, polyester resin and the like are preferable. Examples of the vinyl-based resin, polyester resin, and other binder resin include the following resins or polymers.

Monopolymers of styrene such as polystyrene and polyvinyltoluene and their substitutes;
Styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, Styrene-octyl acrylate copolymer, dimethylaminoethyl styrene-acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-methacryl Dimethylaminoethyl acid acid copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene -Styrene-based copolymers such as maleic acid copolymer and styrene-maleic acid ester copolymer;
Polymethylmethacrylate, polybutylmethacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinylbutyral, silicone resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic hydrocarbons Hydrocarbon resin and aromatic petroleum resin.
These binder resins can be used alone or in combination of two or more.

From the viewpoint of chargeability, the binder resin preferably contains a carboxy group, and is preferably a resin produced by using a polymerizable monomer containing a carboxy group. Specific examples of the polymerizable monomer containing a carboxy group include, but are not limited to, the following polymerizable monomers.
(Meta) acrylic acids such as α-ethylacrylic acid and crotonic acid, and α-alkyl derivatives or β-alkyl derivatives; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid; monoacryloyloxysuccinate Unsaturated dicarboxylic acid monoester derivatives such as ethyl ester, succinic acid monoacryloyloxyethylene ester, phthalic acid monoacryloyloxyethyl ester, and phthalic acid monomethacryloyloxyethyl ester.

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

Further, the polyester resin may be a polyester resin containing a urea group. It is preferable not to cap the carboxy group existing at the end of the polyester resin or the like.
The binder resin may have a polymerizable functional group for the purpose of improving the change in the viscosity of the toner at a high temperature. Examples of the polymerizable functional group include a vinyl group, an isocyanato group, an epoxy group, an amino group, a carboxy group and a hydroxy group.

<Crosslinking agent>
In order to control the molecular weight of the binder resin, a cross-linking agent may be added during the polymerization of the polymerizable monomer.
As the cross-linking agent, for example, the following compounds can be used, but the cross-linking agent is not limited thereto.
Ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, divinylbenzene, bis (4-acrylate) Loxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl Glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate and polyester type diacrylate (MANDA Nihonkayaku) and the above acrylate changed to methacrylate.
The amount of the cross-linking agent added is preferably 0.001 part by mass to 15.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

<Release agent>
The toner core particles may contain wax.
As the wax, for example, the following waxes can be used, but the wax is not limited thereto.
Monovalent alcohols and aliphatic monocarboxylic acid esters such as behenyl behenyl, stearyl stearate, palmityl palmitate, or esters of monovalent carboxylic acid and aliphatic monoalcohol; dibehenyl sebacate, hexanediol dibehenate, etc. Divalent alcohol and aliphatic monocarboxylic acid ester, or divalent carboxylic acid and aliphatic monoalcoyl acid ester; trivalent alcohol such as glycerin tribehenate and aliphatic monocarboxylic acid ester, or 3 Esters of valent carboxylic acids and aliphatic monoalcohols; tetravalent alcohols and aliphatic monocarboxylic acid esters such as pentaerythritol tetrastearate, pentaerythritol tetrapalmitate, or tetravalent carboxylic acids and aliphatic monoalcohols Esters; hexavalent alcohols and aliphatic monocarboxylic acid esters such as dipentaerythritol hexastearate and dipentaerythritol hexapalmitate, or hexavalent carboxylic acids and aliphatic monocarboxylic acid esters; polyglycerin behenate and the like. Polyvalent alcohol and aliphatic monocarboxylic acid ester, or ester of polyvalent carboxylic acid and aliphatic monoalcolate; natural ester wax such as carnauba wax and rice wax; petroleum wax such as paraffin wax, microcrystallin wax and petrolatum. And derivatives thereof; hydrocarbon waxes and derivatives thereof according to the Fisher Tropsch method; polyolefin waxes such as polyethylene wax and polypropylene wax and derivatives thereof; higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid; acid amide wax.
The content of wax in the toner particles is preferably 0.5% by mass to 20.0% by mass.

<Colorant>
The toner core particles may contain a colorant. The colorant is not particularly limited, and for example, the known colorants shown below can be used.
Examples of the yellow pigment include condensed azos such as yellow iron oxide, navels yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartradin lake. Compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, for example, the following can be mentioned.
C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180.
Examples of the orange pigment include the following.
Permanent Orange GTR, Pyrazolone Orange, Balkan Orange, Benzidine Orange G, Indus Rembrilliant Orange RK, Indus Rem Brilliant Orange GK.
Examples of the red pigment include Bengala, Permanent Red 4R, Resole Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Lake Red D, Brilliant Carmine 6B, Brilliant Carmin 3B, Eosin Lake, Rhodamin Lake B, Alizarin Lake and the like. Examples thereof include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, base dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. In particular,
For example, the following can be mentioned.
C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221 and 254.
Examples of blue pigments include copper phthalocyanine compounds such as alkaline blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, and induslen blue BG and their derivatives, anthraquinone compounds, and basic dyes. Examples include rake compounds. Specifically, for example, the following can be mentioned.
C. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.
Examples of the purple pigment include Fast Violet B and Methyl Violet Lake.
Examples of the green pigment include Pigment Green B, Malachite Green Lake, and Final Yellow Green G.
Examples of the white pigment include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of the black pigment include carbon black, aniline black, non-magnetic ferrite and magnetite, and those colored black by using the above-mentioned yellow colorant, red colorant and blue colorant.
These colorants may be used alone or in combination of two or more. Moreover, these colorants can be used in the state of a solid solution.
If necessary, the surface treatment of the colorant may be performed with a substance that does not inhibit polymerization.
The content of the colorant in the toner particles is preferably 3.0% by mass to 15.0% by mass.

<Charge control agent>
The toner core particles may contain a charge control agent. The charge control agent is not particularly limited, and known ones can be used. In particular, a charge control agent having a high charging speed and capable of stably maintaining a constant charge amount is preferable. Further, when the toner core particles are produced by a direct polymerization method, a charge control agent having low polymerization inhibitory property and substantially no solubilized product in an aqueous medium is particularly preferable.
Examples of the charge control agent that controls the toner core particles in a load-electricity manner include the following.
Examples of the organic metal compound and the chelate compound include a monoazo metal compound, an acetylacetone metal compound, an aromatic oxycarboxylic acid, an aromatic dicarboxylic acid, an oxycarboxylic acid and a dicarboxylic acid-based metal compound. Others include aromatic oxycarboxylic acids, aromatic monos and polycarboxylic acids and their metal salts, anhydrides or esters, phenol derivatives such as bisphenols and the like. Further, urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthoic acid-based compounds, boron compounds, quaternary ammonium salts, and calix arenes are mentioned.

On the other hand, examples of the charge control agent for controlling the toner core particles to be positively charged include the following.
Niglosin modifications due to niglosin and fatty acid metal salts; guanidine compounds; imidazole compounds; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, and these. Onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and their lake pigments (as lake agents include phosphotung acid, phosphomolybdic acid, phosphotungene molybdic acid, tannic acid, Lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); Metal salts of higher fatty acids; Resin-based charge control agents.
These charge control agents can be used alone or in combination of two or more. The content of these charge control agents in the toner particles is preferably 0.01% by mass to 10% by mass.

<External agent>
Toner particles can be used as toner without external addition, but in order to improve fluidity, chargeability, cleanability, etc., so-called external additives such as fluidizing agent and cleaning aid are added externally. It may be used as toner.
Examples of the external additive include inorganic oxide fine particles composed of silica fine particles, alumina fine particles, titanium oxide fine particles, inorganic stearic acid compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, or strontium titanate and titanium. Examples thereof include fine particles of an inorganic titanate compound such as zinc acid. These can be used alone or in combination of two or more.
It is preferable that these inorganic fine particles are gloss-treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil, or the like in order to improve heat resistance and storage stability and environmental stability. BET specific surface area of the external additive ^is preferably 10m ² / g~450m 2 / g.

The BET specific surface area is determined by a low-temperature gas adsorption method based on a dynamic constant pressure method according to the BET method (preferably the BET multipoint method). For example, by using a specific surface area measuring device (trade name: Gemini 2375 Ver.5.0, manufactured by Shimadzu Corporation) to adsorb nitrogen gas on the sample surface and measuring using the BET multipoint method. The BET specific surface area (m ² / g) is calculated.
The total amount of these various external additives added is preferably 0.05 parts by mass to 10 parts by mass, and more preferably 0.1 parts by mass to 5 parts by mass with respect to 100 parts by mass of the toner particles. is there. Further, as the external additive, various combinations may be used.

<Developer>
The toner can be used as a magnetic or non-magnetic one-component developer, but may be mixed with a carrier and used as a two-component developer.
As the carrier, magnetic particles made of known materials such as metals such as iron, ferrite and magnetite, and alloys of these metals with metals such as aluminum and lead can be used. Among these, it is preferable to use ferrite particles. Further, as the carrier, a coat carrier in which the surface of the magnetic particles is coated with a coating agent such as a resin, a resin dispersion type carrier in which the magnetic fine powder is dispersed in a binder resin, or the like may be used.
The carrier preferably has a volume average particle diameter of 15 μm to 100 μm, and more preferably 25 μm to 80 μm.

<Manufacturing method of toner core particles>
As a method for producing the toner core particles, a known means can be used, and a kneading and pulverizing method or a wet production method can be used. From the viewpoint of uniform particle size and shape controllability, a wet production method can be preferably used. Further, examples of the wet production method include a suspension polymerization method, a dissolution suspension method, an emulsion polymerization aggregation method, and an emulsion aggregation method.
Here, the suspension polymerization method will be described. In the suspension polymerization method, resin A and, if necessary, other additives such as polymerizable monomers and colorants for producing a binder resin are added to a disperser such as a ball mill or an ultrasonic disperser. May have a step of preparing a polymerizable monomer composition in which these are uniformly dissolved or dispersed using the above (preparation step of a polymerizable monomer composition). At this time, if necessary, a polyfunctional monomer, a chain transfer agent, a wax as a release agent, a charge control agent, a plasticizer, and the like can be appropriately added.
As the polymerizable monomer in the suspension polymerization method, the vinyl-based polymerizable monomer shown below can be preferably exemplified.
Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene; methylacrylate, Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n- Acrylic polymerizable monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n -Propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl Methacrylate-based polymerizable monomers such as phosphate ethyl methacrylate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl formate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone.

In the suspension polymerization method, the above-mentioned polymerizable monomer composition is put into a prepared aqueous medium, and the polymerizable monomer composition is used by a stirrer or a disperser having a high shearing force. It may have a step (granulation step) of forming the droplets to a desired toner particle size.
It is preferable that the aqueous medium in the granulation step contains a dispersion stabilizer in order to control the particle size of the toner particles, sharpen the particle size distribution, and suppress the coalescence of the toner particles in the manufacturing process. Dispersion stabilizers are generally classified into polymers that exhibit repulsive force due to steric hindrance and poorly water-soluble inorganic compounds that stabilize dispersion by electrostatic repulsive force. Since the fine particles of the poorly water-soluble inorganic compound are dissolved by an acid or an alkali, they can be dissolved and easily removed by washing with an acid or an alkali after polymerization, and thus are preferably used.
As the dispersion stabilizer of the poorly water-soluble inorganic compound, those containing any one of magnesium, calcium, barium, zinc, aluminum and phosphorus are preferably used. More preferably, it contains any of magnesium, calcium, aluminum and phosphorus. Specifically, for example, the following can be mentioned.
Sodium phosphate, magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, chloride Calcium, hydroxyapatide.
Organic compounds such as polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, and starch may be used in combination with the dispersion stabilizer.
These dispersion stabilizers are preferably used in an amount of 0.01 parts by mass to 2.00 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
Further, in order to make these dispersion stabilizers finer, a surfactant of 0.001 part by mass to 0.1 part by mass may be used in combination with 100 parts by mass of the polymerizable monomer. Specifically, a commercially available nonionic surfactant, a commercially available anionic surfactant, and a commercially available cationic surfactant can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate,
Potassium stearate, calcium oleate and the like are preferably used.

In the suspension polymerization method, a step of obtaining a toner mother particle dispersion liquid by polymerizing the polymerizable monomer contained in the polymerizable monomer composition, preferably set to a temperature of 50 ° C. to 90 ° C. ( It may have a polymerization step). The polymerization step may be performed after the granulation step, or may be performed while performing the granulation step.
In the polymerization step, it is preferable to perform a stirring operation so that the temperature distribution in the container becomes uniform. When the polymerization initiator is added, it can be carried out at any timing and required time. Further, the temperature may be raised in the latter half of the polymerization reaction for the purpose of obtaining a desired molecular weight distribution, and further, in the latter half of the reaction or the end of the reaction in order to remove unreacted polymerizable monomers, by-products, etc. from the system. Later, a partial aqueous medium may be distilled off by a distillation operation. The distillation operation can be performed under normal pressure or reduced pressure.
As the polymerization initiator used in the suspension polymerization method, an oil-soluble initiator is generally used. For example, the following can be mentioned.
2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4 -Azo compounds such as methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropyl peroxy carbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, tert- Butylperoxy-2-ethylhexanoate, benzoyl peroxide, tert-butylperoxyisobutyrate, cyclohexanone peroxide, methylethylketone peroxide, dicumyl peroxide, tert-butylhydroperoxide, di-tert-butylper Peroxide-based initiators such as oxide, tert-butylperoxypivalate, and cumenehydroperoxide.
As the polymerization initiator, a water-soluble initiator may be used in combination as needed, and examples thereof include the following.
Ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) hydrochloride, 2,2'-azobis (2-aminodinopropane) hydrochloride, azobis (isobutylamidin) Hydrochloride, 2,2'-azobisisobutyronitrile sodium sulfonate, ferrous sulfate or hydrogen peroxide.
These polymerization initiators can be used alone or in combination of two or more, and a chain transfer agent, a polymerization inhibitor, or the like can be further used in combination in order to control the degree of polymerization of the polymerizable monomer.

In the step of coating the surface of the toner core particles with the organosilicon polymer, when the toner core particles are formed in the aqueous medium, the organosilicon compound is hydrolyzed as described above while performing the polymerization step in the aqueous medium. A liquid can be added to form the surface layer. Further, the dispersion liquid of the toner particles after the polymerization may be used as the core particle dispersion liquid, and the hydrolysis liquid of the organosilicon compound may be added to form the surface layer.
Further, in cases other than the aqueous medium such as the kneading and pulverizing method, the obtained toner particles are dispersed in the aqueous medium and used as the core particle dispersion, and the hydrolyzate of the organosilicon compound is added as described above, and the surface layer Can be formed.

The particle size of the toner particles is preferably 3.0 μm to 10.0 μm in weight average from the viewpoint of obtaining a high-definition and high-resolution image. The weight average particle size of the toner can be measured by the pore electric resistance method. For example, "Coulter Counter Multisizer
3 ”(manufactured by Beckman Coulter Co., Ltd.) can be used for measurement. The toner particle dispersion liquid thus obtained is sent to a filtration step for solid-liquid separation of the toner particles and the aqueous medium.
Solid-liquid separation for obtaining toner particles from the obtained toner particle dispersion can be performed by a general filtration method, and then in order to remove foreign substances that could not be completely removed from the surface of the toner particles, reslurry or washing water. It is preferable to perform further washing by washing with a toner. After sufficient washing, solid-liquid separation is performed again to obtain a toner cake. Then, it is dried by a known drying means, and if necessary, a group of particles having a particle size other than a predetermined size is separated by classification to obtain toner particles. At this time, the separated particle swarms having a non-predetermined particle size may be reused in order to improve the final yield.

The method for measuring each physical property value is described below.
<Preparation method for tetrahydrofuran insoluble matter of toner particles (extraction of organosilicon polymer)>
First, when the surface of the toner particles is treated with an external additive or the like, the external additive is removed by the following method to obtain toner particles.
Add 160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) to 100 mL of ion-exchanged water and dissolve it with a hot water bath to prepare a sucrose concentrate. 31 g of the above sucrose concentrate in a centrifuge tube (capacity 50 mL), and 10 of a neutral detergent for cleaning precision measuring instruments with a pH of 7 consisting of Contaminone N (nonionic surfactant, anionic surfactant, and organic builder). Add 6 mL of a mass% aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a dispersion. 1.0 g of toner is added to this dispersion, and the toner lumps are loosened with a spatula or the like.
The centrifuge tube is shaken on a shaker at 350 spm (strokes per min) for 20 minutes. After shaking, the solution is replaced with a glass tube for a swing rotor (capacity: 50 mL), and separated by a centrifuge (manufactured by Kokusan Co., Ltd., H-9R) at 3500 rpm for 30 minutes. By this operation, the toner particles and the detached external additive are separated. Visually confirm that the toner and the aqueous solution are sufficiently separated, and collect the separated toner in the uppermost layer with a spatula or the like. The collected toner is filtered through a vacuum filter and then dried in a dryer for 1 hour or more to obtain toner particles. Perform this operation multiple times to secure the required amount.

Next, the tetrahydrofuran (THF) insoluble content of the toner particles is prepared as follows.
10.0 g of toner particles are weighed, placed in a cylindrical filter paper (No. 84 manufactured by Toyo Filter Paper), and subjected to a Soxhlet extractor. Extract for 20 hours using 200 mL of THF as a solvent. Then replace with 200 mL of new THF and extract for 20 hours. Finally, the mixture is replaced with 200 mL of new THF and extracted for 20 hours (total amount of THF used is 600 mL, total extraction time is 60 hours).
The filtrate in the cylindrical filter paper is vacuum-dried at 40 ° C. for several hours to obtain a tetrahydrofuran insoluble matter. The tetrahydrofuran insoluble component includes "an organosilicon polymer having a structure represented by the formula (A)".
Further, if necessary, insoluble components such as pigments are removed from the insoluble components in tetrahydrofuran, and the above-mentioned external preparation is removed in order to isolate "an organosilicon polymer having a structure represented by the formula (A)". The same method as the operation may be performed ("tetrahydrofuran insoluble" is used instead of the above "toner". The organosilicon polymer is often isolated in the lower layer after centrifugation).

<Preparation method for tetrahydrofuran-soluble components of toner particles (removal of resin A)>
The resin A in the toner particles is taken out by separating the extract using tetrahydrofuran (THF) by the solvent gradient elution method. The preparation method is shown below.
10.0 g of toner particles are weighed, placed in a cylindrical filter paper (No. 84 manufactured by Toyo Filter Paper), and subjected to a Soxhlet extractor. The solid obtained by extracting with 200 mL of THF as a solvent for 20 hours and removing the solvent from the extract is a THF-soluble component. The THF-soluble component contains resin A. This is done multiple times to obtain the required amount of THF soluble.
For the solvent gradient elution method, gradient preparative HPLC (LC-20AP high-pressure gradient preparative system manufactured by Shimadzu Corporation, SunFire preparative column 50 mm φ250 mm manufactured by Waters) is used. The column temperature is 30 ° C., the flow rate is 50 mL / min, acetonitrile is used as a poor solvent for the mobile phase, and THF is used as a good solvent. A sample obtained by dissolving 0.02 g of a THF-soluble component obtained by extraction in 1.5 mL of THF is used as a sample for separation. The mobile phase starts with a composition of 100% acetonitrile, and 5 minutes after the sample injection, the ratio of THF is increased by 4% per minute, and the composition of the mobile phase is adjusted to 100% THF over 25 minutes. The components can be separated by drying the obtained fraction. As a result, the resin A can be obtained. Which fraction component is the resin A can be determined by measuring the content of silicon atoms and ¹³ C-NMR measurement described later.

<Method for measuring the content of silicon atoms in resin A or organosilicon polymer>
For the measurement of the silicon content in the resin A or the organic silicon polymer, the wavelength dispersive fluorescent X-ray analyzer "Axios" (manufactured by PANalytical) and the attached dedicated software for setting the measurement conditions and analyzing the measurement data. "SuperQ ver. 4.0F" (manufactured by PANalytical) is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).
As a measurement sample, resin A or 4 g of a tetrahydrofuran-soluble component obtained by the above-mentioned preparation method, or 4 g of an organosilicon polymer or a tetrahydrofuran-insoluble component is placed in a special aluminum ring for pressing and flattened to form a tablet. Using a compressor "BRE-32" (manufactured by Maekawa Testing Machine Mfg. Co., Ltd.), pressurize at 20 MPa for 60 seconds to use pellets molded to a thickness of 2 mm and a diameter of 39 mm.
Binder particles [trade name: Spectro Blend, components: C81.0% by mass, O2.9% by mass, H13.5% by mass, N2.6% by mass, chemical formula: C ₁₉ H ₃₈ ON, shape: powder (44 μm) ); Made by Rigaku Co., Ltd.] SiO ₂ particles (hydrophobic fumed silica) [trade name: AEROSIL NAX50, specific surface area: 40 ± 10 m ² / g, carbon content: 0.45%, based on 100 parts by mass. ~ 0.85%; manufactured by Nippon Aerosil Co., Ltd.] Add 0.5 parts by mass and mix well using a coffee mill. Similarly, the SiO ₂ particles are mixed with the binder particles so as to be 5.0 parts by mass and 10.0 parts by mass, respectively, and these are used as a sample for the calibration curve.
For each sample, pellets of the sample for the calibration curve were prepared as described above using a tablet molding compressor, and when PET was used for the spectroscopic crystal, the diffraction angle (2θ) = 109.08 ° was observed. The count rate (unit: cps) of Si-Kα rays is measured. At this time, the acceleration voltage and current value of the X-ray generator are set to 24 kV and 100 mA, respectively. A calibration curve having a linear function is obtained with the obtained X-ray count rate on the vertical axis and the amount of SiO ₂ particles added in each calibration curve sample on the horizontal axis.

Next, the resin A to be analyzed or the tetrahydrofuran-soluble component obtained by the above-mentioned preparation method, or the organosilicon polymer or the tetrahydrofuran-insoluble component was pelleted as described above using a tablet molding compressor, and the Si- Measure the count rate of Kα rays. Then, the content of silicon atoms in the resin A or the soluble content in tetrahydrofuran, or the organosilicon polymer or the insoluble component in tetrahydrofuran is determined from the above calibration curve.

<Method of confirming the structure represented by the formula (A)>
The structure represented by the formula (A) in the organosilicon polymer contained in the toner particles is confirmed by the following method.
Alkyl group represented by ^{R 4} in formula ^(A), confirmed by 13 C-NMR.
( ¹³ C-NMR (solid) measurement conditions)
Equipment: JEM-ECX500II manufactured by JEOL RESONANCE
Sample tube: 3.2 mmφ
Sample: Tetrahydrofuran insoluble content 150 mg obtained by the above preparation method
Measurement temperature: Room temperature Pulse mode: CP / MAS
Measurement nuclear frequency: 123.25 MHz ( ¹³ C)
Reference substance: Adamantane (external standard: 29.5 ppm)
Sample rotation speed: 20 kHz
Contact time: 2ms
Delay time: 2s
Number of integrations: 2000 to 8000 times Methyl group (Si-CH ₃ ), ethyl group (Si-C ₂ H ₅ ), propyl group (Si-C ₃ H ₇ ), which are bonded to silicon atoms by the method. Depending on the presence or absence of a signal due to a butyl group (Si-C ₄ H ₉ ), a pentyl group (Si-C ₅ H ₁₁ ), a hexyl group (Si-C ₆ H ₁₃ ) or a phenyl group (Si-C ₆ H ₅ ) confirms alkyl group represented by ^{R 4} in formula (a).

<Method of calculating the ratio of the peak area of the partial structure represented by the formula (A) to the total peak area of the organosilicon polymer>
²⁹ Si-NMR (solid) measurement of the tetrahydrofuran insoluble content of the toner particles is performed under the following measurement conditions.
( ²⁹ Si-NMR (solid) measurement conditions)
Equipment: JEM-ECX500II manufactured by JEOL RESONANCE
Sample tube: 3.2 mmφ
Sample: Tetrahydrofuran insoluble content of toner particles for NMR measurement 150 mg
Measurement temperature: Room temperature Pulse mode: CP / MAS
Measurement nuclear frequency: 97.38 MHz ( ²⁹ Si)
Reference substance: DSS (external standard: 1.534 ppm)
Sample rotation speed: 10 kHz
Contact time: 10ms
Delay time: 2s
Accumulation number: 2000-8000 times

After the above measurement, a plurality of silane components having different substituents and bonding groups in the THF insoluble component of the toner particles are peak-separated into the X1 structure, X2 structure, X3 structure, and X4 structure in the following figure by curve fitting. Calculate the peak area for each.
X1 structure: (R _i ) (R _j ) (R _k ) SiO _1/2
X2 structure: (R _g ) (R _h ) Si (O _1/2 ) ₂
X3 structure: R _m Si (O _1/2 ) ₃
X4 structure: Si (O _1/2 ) ₄

(In the above figure, R _i , R _j , R _k , R _g , R _h , and R _m in the X1 to X3 structures are alkyl groups having 1 to 6 carbon atoms, which are independently bonded to silicon. Indicates an organic group such as, halogen atom, hydroxy group, acetoxy group or alkoxy group.)
Then, the ratio of the X3 structure is calculated, and the ratio of the structure represented by the formula (A) to the total peak area of the organosilicon polymer is calculated.
When it is necessary to confirm the structure represented by the above formula (A) in more detail, it may be identified by the measurement result of ¹ H-NMR together with the measurement results of ¹³ C-NMR and ²⁹ Si-NMR. ..

<Identification of the structure represented by equation (1)>
The polymer sites P ¹ , L ¹ and R ^{1 to} R ³ in the structure represented by the formula (1) are ¹ H-NMR analysis, ¹³ C-NMR analysis, ²⁹ Si-NMR analysis and FT-IR. Perform using analysis. As the analysis sample, the tetrahydrofuran-soluble component obtained by the above-mentioned preparation method or the separately synthesized resin A is used.
When L ¹ contains an amide bond as represented by the above formula (2), it can be identified by ^{1 1} H-NMR analysis. Specifically, it can be identified by the chemical shift value of the proton of the NH site of the amide group, and the amide group can be quantified by calculating the integral value.
When R ^{1 to} R ³ in the structure represented by the formula (1) contain an alkoxy group or a hydroxy group, the alkoxy is carried out by the same method as in the above-mentioned " ²⁹ Si-NMR (solid) measurement conditions". It is possible to determine the valence of a group or hydroxy group for a silicon atom. As the analysis sample, the tetrahydrofuran-soluble component obtained by the above-mentioned preparation method, the separately synthesized resin A, or the like is used.
Specifically, the valence can be calculated by calculating the ratio of the X1 to X4 structures in the measurement data and calculating the ratio of the peak area derived from the alkoxy group or the hydroxy group.

<Measurement method of weight average molecular weight (Mw)>
The weight average molecular weight (Mw) of the resin is measured by gel permeation chromatography (GPC) as follows.
First, the sample is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshori Disc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is prepared so that the concentration of the component soluble in THF is about 0.8% by mass. This sample solution is used for measurement under the following conditions.
Equipment: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation)
Columns: Shodex KF-801, 802, 803, 804, 805, 806, 80
7 7 stations (manufactured by Showa Denko)
Eluent: tetrahydrofuran (THF)
Flow velocity: 1.0 mL / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL
In calculating the molecular weight of the sample, standard polystyrene resin (trade name "TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10," A molecular weight calibration curve prepared using F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) is used.

<Measurement method of acid value Av of resin>
The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of the resin is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure.
(1) Preparation of Reagents 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), and ion-exchanged water is added to make 100 mL to obtain a phenolphthalein solution.
Dissolve 7 g of special grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide, leave it for 3 days, and then filter it to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container.
As for the factor of the potassium hydroxide solution, 25 mL of 0.1 mol / L hydrochloric acid was placed in a triangular flask, several drops of the phenolphthaline solution were added, titrated with the potassium hydroxide solution, and the hydroxylation required for neutralization was performed. Obtained from the amount of potassium solution. As the 0.1 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test 2.0 g of the crushed sample is precisely weighed in a 200 ml Erlenmeyer flask, 100 ml of a mixed solution of toluene / ethanol (2: 1) is added, and the mixture is dissolved over 5 hours. Then, a few drops of the phenolphthalein solution are added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) Substitute the obtained result into the following formula to calculate the acid value.
A = [(CB) x f x 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (ml), C: addition amount of potassium hydroxide solution in this test (ml), f: potassium hydroxide Solution factor, S: mass (g) of sample.

<Measurement method of hydroxyl value OHv of resin>
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when acetylating 1 g of a sample. The hydroxyl value of the resin is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure.
(1) Preparation of Reagents 25 g of special grade acetic anhydride is placed in a 100 mL volumetric flask, pyridine is added to make the total volume 100 mL, and the mixture is sufficiently shaken to obtain an acetylation reagent. The obtained acetylation reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide, etc.
Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume) and add ion-exchanged water to make 100 mL to obtain a phenolphthalein solution.
Dissolve 35 g of special grade potassium hydroxide in 20 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide, leave it for 3 days, and then filter it to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container.
As for the factor of the potassium hydroxide solution, take 25 mL of 0.5 mol / L hydrochloric acid in an Erlenmeyer flask, add a few drops of the phenolphthaline solution, titrate with the potassium hydroxide solution, and neutralize the potassium hydroxide solution. Obtained from the amount of. As 0.5 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test 1.0 g of the crushed sample is precisely weighed into a 200 mL round bottom flask, and 5.0 mL of the acetylation reagent is accurately added to this using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylation reagent, a small amount of special grade toluene is added to dissolve the sample.
A small funnel is placed on the mouth of the flask, and about 1 cm of the bottom of the flask is immersed in a glycerin bath at about 97 ° C. and heated. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with thick paper having a round hole.
After 1 hour, remove the flask from the glycerin bath and allow to cool. After allowing to cool, add 1 mL of water from the funnel and shake to hydrolyze acetic anhydride. The flask is heated again in a glycerin bath for 10 minutes for further complete hydrolysis. After allowing to cool, wash the funnel and flask walls with 5 mL of ethyl alcohol.
A few drops of the phenolphthalein solution are added as an indicator and titrated with the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used.
(3) Substitute the obtained result into the following formula to calculate the hydroxyl value.
A = [{(BC) x 28.05 x f} / S] + D
Here, A: hydroxyl value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (mL), C: addition amount of potassium hydroxide solution in this test (mL), f: potassium hydroxide The factor of the solution, S: the mass (g) of the sample, D: the acid value of the sample (mgKOH / g).

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

<Synthesis of polyester (A-1)>
Polyester (A-1) was synthesized by the following procedure.
The following materials were placed in an autoclave equipped with a decompression device, a water separator, a nitrogen gas introduction device, a temperature measuring device, and a stirring device, and the reaction was carried out under a nitrogen atmosphere at normal pressure at 200 ° C. for 5 hours.
・ Bisphenol A-propylene oxide 2.1 mol adduct: 39.6 parts ・ Terephthalic acid: 8.0 parts ・ Isophthalic acid: 7.6 parts ・ Tetrabutoxytitanate: 0.1 parts Then, trimellitic acid 0.01 A part and 0.12 part of tetrabutoxytitanate were added and reacted at 220 ° C. for 3 hours, and further reacted under reduced pressure of 10 mmHg to 20 mmHg for 2 hours to obtain polyester (A-1).
The acid value of the obtained polyester (A-1) was 6.1 mgKOH / g, the hydroxyl value was 33.6 mgKOH / g, and Mw = 10200.

<Synthesis of polyester (A-2)>
In the synthesis of the polyester (A-1), the polyester was similarly modified except that 39.6 parts of the 2.1 mol adduct of bisphenol A-propylene oxide was changed to 33.2 parts of the 2 mol adduct of bisphenol A-ethylene oxide. (A-2) was obtained.
The acid value of the obtained polyester (A-2) was 5.8 mgKOH / g, the hydroxyl value was 34.3 mgKOH / g, and Mw = 10800.

<Synthesis of polyester (A-3)>
Polyester (A-3) was synthesized by the following procedure.
The following materials were placed in an autoclave equipped with a decompression device, a water separator, a nitrogen gas introduction device, a temperature measuring device, and a stirring device, and the reaction was carried out under a nitrogen atmosphere at normal pressure at 200 ° C. for 5 hours.
・ Bisphenol A-propylene oxide 2 mol adduct: 21.0 parts ・ Ethylene glycol: 2.1 parts ・ Isosorbide: 0.6 parts ・ Terephthalic acid: 14.8 parts ・ Tetrabutoxytitanate: 0.1 parts Then tri 1.1 parts of meritic acid and 0.1 part of tetrabutoxytitanate were added, and the mixture was reacted at 220 ° C. for 3 hours and further reacted under reduced pressure of 10 mmHg to 20 mmHg for 2 hours to obtain polyester (A-3).
The acid value of the obtained polyester (A-3) was 6.0 mgKOH / g, the hydroxyl value was 32.4 mgKOH / g, and Mw = 10400.

<Synthesis of polyester (A-4)>
A polyε-caprolactone [polyester (A-4)] having a stearyl ester terminal as a carboxylic acid was synthesized by the following procedure.
The following materials were charged in a reaction vessel equipped with a nitrogen gas introduction device, a temperature measuring device, and a stirring device, and the reaction was carried out at 100 ° C. for 5 hours in a nitrogen atmosphere.
-Stearyl alcohol: 3.0 parts-ε-caprolactone: 38.2 parts-Titanium (IV) tetraisopropoxide: 0.5 parts Dissolve the obtained resin in chloroform, add this solution to methanol and re-drop. Polyester (A-4) was obtained by precipitation and filtration.
The acid value of the obtained polyester (A-4) was 0.0 mgKOH / g, the hydroxyl value was 30.3 mgKOH / g, and Mw = 8300.

<Synthesis of polyester (A-5)>
Polylactic acid [polyester (A-5)] was synthesized by the following procedure.
The following materials were charged in an autoclave equipped with a decompression device, a water separator, a nitrogen gas introduction device, a temperature measuring device, and a stirring device, and the reaction was carried out under a nitrogen atmosphere at normal pressure at 200 ° C. for 5 hours.
-Lactic acid: 100.0 parts-Tetrabutoxytitanate: 0.1 parts After that, 0.1 parts of tetrabutoxytitanate was added and reacted at 220 ° C. for 3 hours, and further reacted under reduced pressure of 10 mmHg to 20 mmHg for 2 hours. It was. The obtained resin was dissolved in chloroform, and this solution was added dropwise to ethanol, reprecipitated and filtered to obtain polyester (A-5).
The acid value of the obtained polyester (A-5) was 3.5 mgKOH / g and Mw = 30,000.

<Synthesis of polyester (A-6) and (A-7)>
In the synthesis of the polyester (A-1), the polyesters (A-6) and (A-7) were prepared in the same manner except that the reaction pressure, the reaction temperature, and the reaction time were adjusted so as to obtain the desired molecular weight. Synthesized.
The physical properties of the obtained polyesters (A-6) and (A-7) are shown in Table 1.

<Styrene acrylic resin (A-8) synthesis>
A styrene acrylic resin (A-8) was synthesized as follows.
100.0 parts of propylene glycol monomethyl ether was heated while substituting with nitrogen, and the mixture was refluxed at a liquid temperature of 120 ° C. or higher. There, 80.2 parts of styrene, 20.1 parts of butyl acrylate, 5.0 parts of acrylic acid, and tert-butyl peroxybenzoate [organic peroxide-based polymerization initiator, manufactured by Nichiyu Co., Ltd., trade name. : A mixture of 1.0 part of perbutyl Z] was added dropwise over 3 hours.
After completion of the dropping, the solution was stirred for 3 hours and then distilled at atmospheric pressure while raising the liquid temperature to 170 ° C. After the liquid temperature reached 170 ° C., the pressure was reduced to 1 hPa, and the mixture was distilled for 1 hour to remove the solvent to obtain a resin solid. The resin solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was filtered off to obtain a styrene acrylic resin (A-8).
The acid value of the obtained styrene acrylic resin (A-8) was 36.6 mgKOH / g and Mw = 22000.

<Styrene acrylic resin (A-9) synthesis>
A styrene acrylic resin (A-9) was synthesized as follows.
100.0 parts of propylene glycol monomethyl ether was heated while substituting with nitrogen, and the mixture was refluxed at a liquid temperature of 120 ° C. or higher. There, 72.9 parts of styrene, 21.6 parts of acrylic acid, and 1.0 part of tert-butyl peroxybenzoate [organic peroxide-based polymerization initiator, manufactured by NOF CORPORATION, trade name: perbutyl Z]. Was added dropwise over 3 hours.
After completion of the dropping, the solution was stirred for 3 hours and then distilled at atmospheric pressure while raising the liquid temperature to 170 ° C. After the liquid temperature reached 170 ° C., the pressure was reduced to 1 hPa, and the mixture was distilled for 1 hour to remove the solvent to obtain a resin solid. The resin solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was filtered off to obtain a styrene acrylic resin (A-9).
The acid value of the obtained styrene acrylic resin (A-9) was 154.6 mgKOH / g, Mw =
It was 22000.

<Synthesis of acrylic resin (A-10)>
Acrylic resin (A-10) was synthesized as follows.
100.0 parts of propylene glycol monomethyl ether was heated while substituting with nitrogen, and the mixture was refluxed at a liquid temperature of 120 ° C. or higher. There, 30.0 parts of methyl methacrylate, 50.4 parts of acrylic acid, and tert-butyl peroxybenzoate [organic peroxide-based polymerization initiator, manufactured by NOF CORPORATION, trade name: perbutyl Z] 1.0. The mixture of parts was added dropwise over 3 hours.
After completion of the dropping, the solution was stirred for 3 hours and then distilled at atmospheric pressure while raising the liquid temperature to 170 ° C. After the liquid temperature reached 170 ° C., the pressure was reduced to 1 hPa, and the mixture was distilled for 1 hour to remove the solvent to obtain a resin solid. The resin solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was filtered off to obtain an acrylic resin (A-10).
The acid value of the obtained acrylic resin (A-10) was 351.8 mgKOH / g and Mw = 8700.

<Synthesis of resin A (R-1)>
The carboxy group in the polyester (A-1) and the amino group in the aminosilane were amidated, and the resin A (R-1) was synthesized as follows.
50.0 parts of polyester (A-1) was dissolved in 200.0 parts of N, N-dimethylacetamide, 1.2 parts of 3-aminopropyltriethoxysilane, and DMT-MM (4- (4, 4,) as a condensing agent. 1.7 parts of 6-dimethoxy-1,3,5-triazine-2-yl) -4-methylmorpholinium chloride) was added, and the mixture was stirred at room temperature for 5 hours. After completion of the reaction, this solution was added dropwise to methanol, reprecipitated and filtered to obtain resin A (R-1).
Table 2 shows the physical properties of the obtained resin A (R-1).

<Synthesis of resins A (R-2), (R-3), and (R-13) to (R-16)>
In the synthesis of the resin A (R-1), the same applies except that 1.2 parts of 3-aminopropyltriethoxysilane was changed to "type and amount of modified silicon compound" shown in Table 1. Then, each of the resins A (R-2), (R-3), and (R-13) to (R-16) was synthesized.
Table 2 shows the physical properties of these obtained resins A.

<Synthesis of Resins A (R-7), (R-9), (R-17) to (R-21), (R-23), and (R-24)>
In the synthesis of (R-1), the polyester (A-1) was changed to each of the "types of the base raw material resin" shown in Table 1, and the amount of 3-aminopropyltriethoxysilane added was changed. The amount of DMT-MM added was changed from 1.2 parts to each of the "addition amount of modified silicon compound" shown in Table 1, and the addition amount of DMT-MM was changed from 1.7 parts to "condensation agent (DMT-)" shown in Table 1. Resins A (R-7), (R-9), (R-17) to (R-21), (R-23), and resin A (R-7), (R-9), (R-17) to (R-21), and (R-23), in the same manner except that each of the "addition amount of MM)" was changed. , (R-24) were synthesized.
Table 2 shows the physical properties of these obtained resins A.

<Synthesis of resin A (R-4)>
Resin A (R-4) having a urethane bond formed by reacting a hydroxy group in polyester (A-1) with an isocyanate group in isocyanate silane was synthesized as follows.
50.0 parts of polyester (A-1) is dissolved in 500.0 parts of chloroform, and 1.3 parts of 3-isocyanatepropyltriethoxysilane and 0.5 parts of titanium (IV) tetraisopropoxide are added under a nitrogen atmosphere. It was added and stirred at room temperature for 5 hours. After completion of the reaction, this solution was added dropwise to methanol, reprecipitated and filtered to obtain resin A (R-4).
Table 2 shows the physical properties of the obtained resin A (R-4).

<Synthesis of resin A (R-8)>
In the synthesis of the resin A (R-4), the polyester (A-1) was changed to the polyester (A-4), and the amount of 3-isocyanatepropyltriethoxysilane added was 1.3 to 6.6 parts. Resin A (R-8) was synthesized in the same manner except that it was changed to.
Table 2 shows the physical properties of the obtained resin A (R-8).

<Synthesis of resin A (R-5)>
Resin A (R-5) forming a linking group represented by the formula (4) or the formula (5) by an insertion reaction with an epoxy group in the epoxy silane with respect to the ester bond in the polyester (A-1) Was synthesized.
50.0 parts of polyester (A-1) is dissolved in 100.0 parts of anisole, 2.9 parts of 5,6-epoxyhexyltriethoxysilane and 10.0 parts of tetrabutylphosphonium bromide are added, and the atmosphere is nitrogen. , Heated and stirred at about 140 ° C. for 5 hours. After allowing to cool, the reaction mixture was dissolved in 200 ml of chloroform, added dropwise to methanol, reprecipitated and filtered to obtain resin A (R-5).
Table 2 shows the physical properties of the obtained resin A (R-5).

<Synthesis of resin A (R-6)>
In the synthesis of the resin A (R-5), the polyester (A-1) was changed to the polyester (A-2), and 2.9 parts of 5,6-epoxyhexyltriethoxysilane was added to (3-glycidoxy). Resin A (R-6) was synthesized in the same manner except that it was changed to 12.2 parts of propyl) trimethoxysilane.
Table 2 shows the physical properties of the obtained resin A (R-6).

<Synthesis of resin A (R-10)>
400.0 parts of pure water was mixed and stirred in a solution prepared by dissolving 10.0 parts of the resin A (R-1) in 90.0 parts of toluene. After stirring, the pH was adjusted to 5.0 using dilute hydrochloric acid, and the mixture was stirred at room temperature for 2.4 hours, then the stirring was stopped and the mixture was transferred to a separating funnel to extract the oil phase. The oil phase was concentrated and reprecipitated with methanol to obtain resin A (R-10) in which one alkoxy group was hydrolyzed.
Table 2 shows the physical properties of the obtained resin A (R-10).

<Synthesis of resin A (R-11)>
In the synthesis of the resin A (R-10), the alkoxy group was obtained in the same manner except that the pH was changed from 5.0 to 4.0 and the stirring time was changed from 2.4 hours to 3.8 hours. Two hydrolyzed resin A (R-11) was obtained.
Table 2 shows the physical properties of the obtained resin A (R-11).

<Synthesis of resin A (R-12)>
In the synthesis of the resin A (R-11), the resin A (R-12) in which three alkoxy groups were hydrolyzed was obtained in the same manner except that the stirring time was changed from 3.8 hours to 10.8 hours. Obtained.
Table 2 shows the physical properties of the obtained resin A (R-12).

* 1: Content of silicon atoms in resin A (mass%)

<Production example of toner mother particle dispersion 1>
(Production example of water-based medium 1)
390.0 parts of ion-exchanged water and 14.0 parts of sodium phosphate (12-hydrate) [manufactured by Lhasa Industry Co., Ltd.] were added to the reaction vessel, and the mixture was kept warm at 65 ° C. for 1.0 hour while purging nitrogen. did.
T. K. A calcium chloride aqueous solution in which 9.2 parts of calcium chloride (dihydrate) is dissolved in 10.0 parts of ion-exchanged water while stirring at 12,000 rpm using a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.). Was put in all at once to prepare an aqueous medium containing a dispersion stabilizer.
Further, 10% hydrochloric acid was added to the aqueous medium to adjust the pH to 6.0 to obtain an aqueous medium 1.
(Production Example of Polymerizable Monomer Composition 1)
-Styrene 60.0 parts-Colorant (CI Pigment Blue 15: 3) 6.5 parts The above material was put into an attritor (manufactured by Nippon Coke Industries Co., Ltd.), and zirconia particles with a diameter of 1.7 mm were further added. The dispersion liquid 1 in which the colorant was dispersed was prepared by dispersing the particles at 220 rpm for 5.0 hours.
The following materials were added to the dispersion liquid 1.
・ 20.0 parts of styrene ・ 20.0 parts of n-butyl acrylate ・ 3.0 parts of resin A (R-1) ・ 5.0 parts of polyester (A-1) ・ Fischer-Tropsch wax (melting point: 78 ° C) 7 .0 parts This was kept warm at 65 ° C. K. A polymerizable monomer composition 1 was prepared by uniformly dissolving and dispersing at 500 rpm using a homomixer.
(Granulation process)
While maintaining the temperature of the water-based medium 1 at 70 ° C. and the rotation speed of the stirrer at 12,000 rpm, the polymerizable monomer composition 1 was charged into the water-based medium 1 and the polymerization initiator, t-butylperoxypi. 9.0 parts of the polymer was added. Granulation was carried out for 10 minutes while maintaining 12,000 rpm with the stirring device as it was.
(Polymerization process)
Change from a high-speed stirrer to a stirrer equipped with a propeller stirring blade, carry out polymerization at 70 ° C. for 5.0 hours while stirring at 150 rpm, then raise the temperature to 85 ° C. and heat for 2.0 hours. The polymerization reaction was carried out in 1 to obtain a toner mother particle dispersion liquid 1.
Further, the toner mother particle dispersion liquid 1 was adjusted by adding ion-exchanged water so that the toner mother particle concentration in the dispersion liquid became 20.0%.

<Production Examples of Toner Mother Particle Dispersion Liquids 2-6, 8-21, 28, and 29>
In the production example of the toner mother particle dispersion liquid 1, the resin A (R-1) is used as the resins A (R-2) to (R-6), (R-8) to (R-21), (R-21). Toner mother particle dispersions 2 to 6, 8 to 21, 28, and 29 were produced in the same manner except that they were changed to 23) and (R-24), respectively.

<Production example of toner mother particle dispersion 7>
In the production example of the toner mother particle dispersion liquid 1, the same applies except that the resin A (R-1) is changed to the resin A (R-7) and the polyester (A-1) is changed to the polyester (A-3). The toner mother particle dispersion liquid 7 was produced.

<Production example of toner mother particle dispersion 22>
In the production example of the toner mother particle dispersion liquid 1, the toner mother particle dispersion liquid 22 was produced in the same manner except that polyester (A-1) was not used.

<Production example of toner mother particle dispersion 23>
In the production example of the toner mother particle dispersion liquid 1, the toner mother particle dispersion liquid 23 was produced in the same manner except that the resin A (R-1) was not used.

<Production example of toner mother particle dispersion liquid 24>
In the production example of the toner mother particle dispersion liquid 1, the toner mother particle dispersion liquid 24 was produced in the same manner except that the resin A (R-1) was changed to 3-aminopropyltrimethoxysilane.

<Production example of toner mother particle dispersion liquid 25>
660.0 parts of ion-exchanged water and 25.0 parts of a 48.5% sodium dodecyldiphenyl ether disulfonate aqueous solution were mixed, and T.I. K. An aqueous medium 2 was prepared by stirring at 10000 rpm using a homomixer.
The following material was added to 500.0 parts of ethyl acetate and dissolved at 100 rpm with a propeller-type stirrer to prepare a solution.
100.0 parts of styrene / butyl acrylate copolymer (copolymerization mass ratio: 80/20)
-Resin A (R-1) 3.0 parts-Polyester (A-1) 5.0 parts-Colorant (CI Pigment Blue 15: 3) 6.5 parts-Fischer-Tropsch wax (melting point: 78 ° C) ) 9.0 parts 150.0 parts of the aqueous medium 2 was put into a container, and T.I. K. Using a homomixer, the mixture was stirred at a rotation speed of 12,000 rpm, 100.0 parts of the solution was added thereto, and the mixture was mixed for 10 minutes to prepare an emulsified slurry.
After that, 100.0 parts of the emulsified slurry was placed in a flask equipped with a degassing pipe, a stirrer and a thermometer, and the mixture was aged at 45 ° C. for 4 hours under reduced pressure at 30 ° C. for 12 hours while stirring at 500 rpm. To obtain a solvent-free slurry.
After the solvent-free slurry was filtered under reduced pressure, 300.0 parts of ion-exchanged water was added to the obtained filtered cake, and T.I. K. After mixing and redispersing with a homomixer (rotation speed 12,000 rpm for 10 minutes), the mixture was filtered.
The obtained filtered cake was dried at 45 ° C. for 48 hours in a dryer, and sieved toner matrix particles 25 were obtained with a mesh having a mesh size of 75 μm.

390.0 parts of ion-exchanged water and 14.0 parts of sodium phosphate (12-hydrate) [manufactured by Lhasa Industry Co., Ltd.] were put into the container, and kept warm at 65 ° C. for 1.0 hour while purging nitrogen. did.
T. K. Using a homomixer, while stirring at 12,000 rpm, a calcium chloride aqueous solution in which 9.2 parts of calcium chloride (dihydrate) was dissolved in 10.0 parts of ion-exchanged water was added all at once to add a dispersion stabilizer. An aqueous medium containing the mixture was prepared.
Further, 10% hydrochloric acid was added to the aqueous medium to adjust the pH to 6.0 to obtain an aqueous medium 3.
200.0 parts of the toner mother particles 25 were put into the aqueous medium 3, and T.I. K. Using a homomixer, the mixture was dispersed for 15 minutes while rotating at a temperature of 60 ° C. and 5,000 rpm. Ion-exchanged water was added to adjust the concentration of toner matrix particles in the dispersion to 20.0% to obtain a toner particle dispersion 25.

<Production example of toner mother particle dispersion liquid 26>
(Production example of resin particle dispersion)
The following materials were weighed, mixed and dissolved.
・ 82.6 parts of styrene ・ 9.2 parts of n-butyl acrylate ・ 1.3 parts of acrylic acid ・ 3.0 parts of resin A (R-1) ・ 0.4 parts of hexanediol diacrylate ・ n-lauryl mercaptan 3 .2 parts A 10% aqueous solution of Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to the obtained solution and dispersed. An aqueous solution prepared by dissolving 0.15 parts of potassium persulfate in 10.0 parts of ion-exchanged water was added while stirring slowly for 10 minutes. After nitrogen substitution, emulsion polymerization was carried out at a temperature of 70 ° C. for 6.0 hours. After completion of the polymerization, the reaction solution was cooled to room temperature and ion-exchanged water was added to obtain a resin particle dispersion having a solid content concentration of 12.5% and a volume-based median diameter of 0.2 μm.
(Production example of wax particle dispersion)
The following materials were weighed and mixed.
・ Ester wax (melting point: 70 ° C) 100.0 parts ・ Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 15.0 parts ・ Ion-exchanged water 385.0 parts Wet jet mill JN100 (Co., Ltd.) A wax particle dispersion was obtained by dispersing for 1 hour. The solid content concentration of the wax in the wax particle dispersion was 20.0%.
(Production example of colorant particle dispersion)
The following materials were weighed and mixed.
・ Colorant (CI Pigment Blue 15: 3) 100.0 parts ・ Neogen RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 15.0 parts ・ Ion-exchanged water 885.0 parts Wet jet mill JN100 A colorant particle dispersion was obtained by dispersing for 1 hour using (manufactured by Joko Co., Ltd.).

・ Resin particle dispersion 160.0 parts ・ Wax particle dispersion 10.0 parts ・ Colorant particle dispersion 10.0 parts ・ Magnesium sulfate 0.2 parts Use a homogenizer (manufactured by IKA: Ultratarax T50) as the material. After dispersing using, the mixture was heated to 65 ° C. with stirring.
After stirring at 65 ° C. for 1.0 hour and observing with an optical microscope, it was confirmed that aggregate particles having a number average particle size of 6.0 μm were formed.
After adding 2.2 parts of Neogen RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) to this, the temperature was raised to 80 ° C. and stirred for 2.0 hours to obtain fused spherical toner mother particles.
After cooling, the solid was filtered and filtered and washed with 720.0 parts of ion-exchanged water by stirring for 1.0 hour. The solution containing the toner mother particles was filtered and dried using a vacuum dryer to obtain toner mother particles 26.

390.0 parts of ion-exchanged water and 14.0 parts of sodium phosphate (12-hydrate) [manufactured by Lhasa Industry Co., Ltd.] were put into the container, and kept warm at 65 ° C. for 1.0 hour while purging nitrogen. did.
T. K. Using a homomixer, while stirring at 12,000 rpm, a calcium chloride aqueous solution in which 9.2 parts of calcium chloride (dihydrate) was dissolved in 10.0 parts of ion-exchanged water was added all at once to add a dispersion stabilizer. An aqueous medium containing the mixture was prepared.
Further, 10% hydrochloric acid was added to the aqueous medium to adjust the pH to 6.0 to obtain an aqueous medium 4.
200.0 parts of the toner mother particles 26 were put into the aqueous medium 4, and T.I. K. Using a homomixer, the mixture was dispersed for 15 minutes while rotating at a temperature of 60 ° C. and 5,000 rpm. Ion-exchanged water was added to adjust the concentration of toner matrix particles in the dispersion to 20.0% to obtain a toner particle dispersion 26.

<Production example of toner mother particle dispersion 27>
The following materials were put into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe.
・ 29.0 parts of terephthalic acid ・ Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
80.0 parts ・ Titanium dihydroxybis (triethanolamineate) 0.1 parts Then, the mixture was heated to 200 ° C. and reacted for 9 hours while removing the water produced while introducing nitrogen. Further, 5.8 parts of trimellitic anhydride was added, and the mixture was heated to 170 ° C. and reacted for 3 hours to synthesize polyester (A-11) as a binder resin.
Also,
・ Low density polyethylene (melting point: 100 ° C) 20.0 parts ・ Styrene 64.0 parts ・ n-butyl acrylate 13.5 parts ・ Acrylonitrile 2.5 parts was charged into an autoclave, and the temperature was raised after nitrogen replacement in the system. The temperature was maintained at 180 ° C. with stirring.
50.0 parts of a xylene solution of 2.0% t-butyl hydroperoxide was continuously added dropwise to the system over 4.5 hours, and after cooling, the solvent was separated and removed, and the copolymer was grafted onto polyethylene. The graft polymer was obtained.

・ Polyester resin (A-11) 100.0 parts ・ Resin A (R-1) 3.0 parts ・ Paraffin wax (melting point: 75 ° C) 5.0 parts ・ Graft polymer 5.0 parts ・ C.I. I. Pigment Blue 15: 3 5.0 parts After mixing the materials well with an FM mixer (FM-75 type, manufactured by Nippon Coke Industries Co., Ltd.), a twin-screw kneader (PCM-30 type, Ikegai) set at a temperature of 100 ° C. It was melt-kneaded by Iron Works Co., Ltd.
The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely crushed product.
Next, the obtained pyroclastic material was used as a turbo mill (T-250: RSS rotor / SNB liner) manufactured by Turbo Industries, Ltd. to obtain a finely pulverized material having a size of about 5 μm.
Then, fine powder and coarse powder were cut using a multi-division classifier utilizing the Coanda effect to obtain toner matrix particles 27.

390.0 parts of ion-exchanged water and 14.0 parts of sodium phosphate (12-hydrate) [manufactured by Lhasa Industry Co., Ltd.] were put into the container, and kept warm at 65 ° C. for 1.0 hour while purging nitrogen. did.
T. K. Using a homomixer, while stirring at 12,000 rpm, a calcium chloride aqueous solution in which 9.2 parts of calcium chloride (dihydrate) was dissolved in 10.0 parts of ion-exchanged water was added all at once to add a dispersion stabilizer. An aqueous medium containing the mixture was prepared.
Further, 10% hydrochloric acid was added to the aqueous medium to adjust the pH to 6.0 to obtain an aqueous medium 5.
200.0 parts of the toner mother particles 27 were put into the aqueous medium 5, and T.I. K. Using a homomixer, the mixture was dispersed for 15 minutes while rotating at a temperature of 60 ° C. and 5,000 rpm. Ion-exchanged water was added to adjust the concentration of the toner mother particles in the dispersion to 20.0% to obtain a toner mother particle dispersion 27.

<Production example of toner mother particle dispersion liquid 28>
In the production example of the toner mother particle dispersion liquid 27, the toner mother particle dispersion liquid 28 was produced in the same manner except that the resin A (R-1) was not used.

<Production example of toner mother particle dispersion 29>
In the production example of the toner mother particle dispersion liquid 27, the toner mother particle dispersion liquid 29 was produced in the same manner except that the resin A (R-1) was changed to the resin A (R-22) synthesized below. .. [Synthesis of resin A (R-22)]
・ Toluene 100.0 parts ・ Styrene 70.0 parts ・ Butyl acrylate 30.0 parts ・ 3-Mercaptopropylmethyldimethoxysilane 1.8 parts ・ Azobisisobutyronitrile (AIBN) 1.5 parts four-mouth flask After substitution with nitrogen, polymerization was carried out at 80 ° C. for 8 hours to obtain a toluene solution of the polymer. A toluene solution of this polymer was redisposited with n-hexane to give resin A (R-22). The content of silicon atoms in the obtained resin A (R-22) was 0.21% by mass.

<Production example of toner mother particle dispersion liquid 30>
In the production example of the toner mother particle dispersion liquid 17, the toner mother particle dispersion liquid 30 was produced in the same manner except that the resin A (R-23) was used instead of the resin A (R-17).

<Production example of toner mother particle dispersion 31>
In the production example of the toner mother particle dispersion liquid 21, the toner mother particle dispersion liquid 31 was produced in the same manner except that the resin A (R-24) was used instead of the resin A (R-21).

<Production example of organosilicon compound liquid 1>
-Ion-exchanged water 90.0 parts-Methyltrimethoxysilane 10.0 parts The material was weighed in a beaker and the pH was adjusted to 4.5 with 1 mol / L hydrochloric acid. Then, the mixture was stirred for 1 hour while heating at 60 ° C. in a water bath to prepare an organosilicon compound solution 1.

<Production example of organosilicon compound liquid 2>
In the production example of the organosilicon compound solution 1, 10.0 parts of methyltrimethoxysilane was changed to a mixture of 8.5 parts of methyltriethoxysilane and 1.5 parts of tetraethoxysilane. Compound solution 2 was produced.

<Production example of organosilicon compound liquid 3>
In the production example of the organosilicon compound solution 1, 10.0 parts of methyltrimethoxysilane was changed to a mixture of 9.0 parts of methyltrimethoxysilane and 1.0 part of dimethoxydimethylsilane in the same manner. Compound solution 3 was produced.

<Production example of organosilicon compound liquid 4>
In the production example of the organosilicon compound solution 1, 10.0 parts of methyltrimethoxysilane was changed to a mixture of 9.5 parts of methyltrimethoxysilane and 0.5 part of propyltrimethoxysilane. A silicon compound solution 4 was produced.

<Production example of organosilicon compound liquid 5>
In the production example of the organosilicon compound solution 4, the organosilicon compound solution 5 was produced in the same manner except that propyltrimethoxysilane was changed to hexyltrimethoxysilane.

<Production example of organosilicon compound liquid 6>
In the production example of the organosilicon compound solution 4, the organosilicon compound solution 6 was produced in the same manner except that propyltrimethoxysilane was changed to phenyltrimethoxysilane.

<Production example of organosilicon compound liquid 7>
In the production example of the organosilicon compound solution 1, the organosilicon compound solution 7 was produced in the same manner except that methyltrimethoxysilane was changed to tetramethoxysilane.

<Production example of organosilicon compound liquid 8>
In the production example of the organosilicon compound solution 1, the organosilicon compound solution 8 was produced in the same manner except that methyltrimethoxysilane was changed to dimethyldiethoxysilane.

<Manufacturing example of toner 1>
The following materials were weighed in the reaction vessel and mixed using a propeller stirring blade.
-Organosilicon compound solution 1 20.0 parts-Toner mother particle dispersion 1 500.0 parts Next, after adjusting the pH of the obtained mixed solution to 7.0 and adjusting the temperature of the mixed solution to 50 ° C. The mixture was held for 1 hour while mixing using a propeller stirring blade.
Then, the pH was adjusted to 9.5 using a 1 mol / L NaOH aqueous solution, and the temperature was maintained at 50 ° C. for 2 hours with stirring.
The pH was adjusted to 1.5 with 1 mol / L hydrochloric acid, stirred for 1 hour, filtered while washing with ion-exchanged water, and then dried to obtain toner particles 1.
When the tetrahydrofuran (THF) insoluble content of the toner particles 1 was measured by fluorescent X-ray measurement, the content of silicon atoms in the insoluble content was 35% by mass.
Moreover, when the insoluble matter was measured by ²⁹ Si-NMR, the ratio of the peak of the structure represented by the formula (A) was 71%.
The obtained toner particles 1 were designated as toner 1.

<Production Examples of Toners 2 to 21, 28 to 31, and Comparative Toners 6 to 7>
In the production example of the toner 1, the toners 2 to 21 and 28 to 31 and the toners for comparison are obtained in the same manner except that the toner mother particle dispersion 1 is changed to the toner mother particle dispersions shown in Table 3, respectively. Each of the toners 6 to 7 was manufactured. The physical properties of these toners are shown in Table 3 below.

<Manufacturing example of toner 22>
In the production example of the toner 1, the toner 22 was prepared in the same manner except that the pH was adjusted to 9.5, the temperature was 50 ° C., and the mixture was held for 2 hours with stirring, but was changed to hold for 18 hours. Obtained. The physical properties of this toner are shown in Table 3 below.

<Manufacturing example of toners 23 to 27>
In the production example of the toner 1, each of the toners 23 to 27 was produced in the same manner except that the organosilicon compound solution 1 was changed to each of the organosilicon compound solutions 2 to 6. The physical properties of these toners are shown in Table 3 below.
<Manufacturing example of toner 32>
The pH was adjusted to 11.5 with respect to 500.0 parts of the toner mother particle dispersion 1 using an aqueous sodium hydroxide solution. This was heated to 60 ° C., and 20.0 parts of the organosilicon compound solution 1 was added with stirring. After the addition, stirring was continued while maintaining the temperature at 60 ° C., and a condensation reaction was carried out for 2 hours.
Then, the pH was adjusted to 1.5 with 1 mol / L hydrochloric acid, stirred for 1 hour, filtered while washing with ion-exchanged water, and then dried to obtain toner particles 32.
When the tetrahydrofuran (THF) insoluble content of the toner particles 32 was measured by fluorescent X-ray measurement, the content of silicon atoms in the insoluble content was 33% by mass.
Moreover, when the insoluble matter was measured by ²⁹ Si-NMR, the ratio of the peak of the structure represented by the formula (A) was 65%.
The obtained toner particles 32 were designated as toner 32.

<Manufacturing example of comparative toner 1>
Assuming Patent Document 1, the comparative toner 1 was manufactured as follows.
In the production example of the toner 1, the comparison toner 1 is obtained in the same manner except that the organosilicon compound liquid 1 is changed to the organosilicon compound liquid 7 and the toner mother particle dispersion liquid 1 is changed to the toner mother particle dispersion liquid 28. Manufactured. The physical properties of this toner are shown in Table 3 below.

<Manufacturing example of comparative toner 2>
Assuming Patent Document 2, the comparative toner 2 was manufactured as follows.
In the production example of the toner 1, the comparison toner 2 is similarly changed except that the organosilicon compound liquid 1 is changed to the organosilicon compound liquid 8 and the toner mother particle dispersion liquid 1 is changed to the toner mother particle dispersion liquid 29. Manufactured. The physical properties of these toners are shown in Table 3 below.

<Manufacturing example of comparative toner 3>
Assuming Patent Document 3, the comparative toner 3 was manufactured as follows.
In the production example of the toner 1, the comparative toner 3 was produced in the same manner except that the toner mother particle dispersion liquid 1 was changed to the toner mother particle dispersion liquid 23. The physical properties of this toner are shown in Table 3 below.

<Manufacturing example of comparative toner 4>
Assuming Patent Document 3, the comparative toner 4 was manufactured as follows.
100 parts of the comparative toner 3 and 0.2 part of hydrotalcite particles [trade name: DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.] were added to SUPERMIXER PICCOLO (manufactured by Kawata Co., Ltd.) at 3000 rpm. Mixing was performed for 10 minutes. After the treatment, the mixture was sieved with a mesh having an opening of 150 μm to obtain a comparative toner 4. The physical properties of this toner are shown in Table 3 below.

<Manufacturing example of comparative toner 5>
In the production example of the toner 1, the comparative toner 5 was produced in the same manner except that the toner mother particle dispersion liquid 1 was changed to the toner mother particle dispersion liquid 24. The physical properties of this toner are shown in Table 3 below.

* 2: Content of silicon atoms in the organosilicon polymer (mass%)
* 3: Ratio (%) of the peak area of the structure represented by the formula (A) to the total peak area of the organosilicon polymer.
The abbreviations in Table 3 are as follows.
MTMS: Methyltrimethoxysilane MTES: Methyltriethoxysilane DMDMS: Dimethyldimethoxysilane DMDES: Didimethyldiethoxysilane TEOS: Tetraethoxysilane TMOS: Tetramethoxysilane PrTMS: Ppropyltrimethoxysilane HTMS: Hexyltrimethoxysilane PhTMS: Phenyltrimethoxy Silane

[Examples 1-32, Comparative Examples 1-7]
The method of evaluation performed for each of the toners 1 to 32 and the comparative toners 1 to 7 will be described below. The evaluation results are shown in Table 4.

<Preparation for toner evaluation>
A modified machine of a commercially available Canon laser beam printer LBP7600C was used. The modification point was that the rotation speed of the developing roller was set to 540 mm / sec by changing the evaluation machine main body and software.
Using this, the following toner charge amount, member contamination, and charge rise were evaluated.

<Evaluation of charge amount (normal temperature and humidity environment)>
200 g of toner was loaded into the toner cartridge of LBP7600C. Then, the toner cartridge was left to stand in an environment of normal temperature and humidity (25 ° C./50% RH; also referred to as N / N) for 24 hours. The toner cartridge after being left for 24 hours in the environment was attached to the LBP7600C.
Twenty solid images were output. The machine was forcibly stopped during the output of the 20th sheet, and the amount of toner charged on the developing roller immediately after passing through the regulation blade was measured. The amount of charge on the developing roller was measured using the Faraday cage shown in the perspective view of FIG. The inside (on the right side of the figure) was decompressed so that the toner on the developing roller was sucked in, and a toner filter 33 was provided to collect the toner. In FIG. 1, reference numeral 31 is a suction unit, and reference numeral 32 is a holder.
The charge amount per unit mass (μC / g) is calculated from the mass M (g) of the collected toner and the charge Q (μC) directly measured by the coulomb meter, and the toner charge amount (Q / M) is calculated. As a result, the evaluation was performed according to the following criteria. The evaluation results are shown in Table 4.
A: Less than -50 μC / g B: -50 μC / g or more and less than -40 μC / g C: -40 μC / g or more and less than -30 μC / g D: -30 μC / g or more and less than -20 μC / g E: -20 μC / g or more

<Evaluation of member contamination (method of measuring the amount of Si on the developing roller)>
After the evaluation of the charge amount was completed, 4000 sheets of 35.0% print rate images were printed out in the horizontal direction on A4 paper under the same environment.
After printing 4000 sheets, the developing roller was taken out from the used cartridge and the toner was removed with a blower. With respect to the portion centered on a point that is 10 cm from one end in the longitudinal direction of the developing roller toward the other end, the surface of the developing roller is cut with a cutter so that the area is 5 mm × 5 mm and the thickness is 1 mm. It was taken and fixed to the sample table with carbon tape. Place the sample table on which the sample is fixed in the sample chamber of Pt ion sputtering (E-1045, manufactured by HITACHI), set the discharge current to 15 mA, the discharge time to 20 seconds, and the distance from the Pt target to the sample surface to 3 cm, and set the degree of vacuum. Pt was deposited at 7.0 Pa. The obtained sample was observed with a scanning electron microscope (JSM-7800, manufactured by JEOL Ltd.). The observation conditions are as follows.
Observation mode: SEM
Detector: LED
Filter: 3
Irradiation current: 8
WD: 10.0mm
Acceleration voltage: 5kV
The observation field of view was adjusted to 500 times, and EDS (NORAN System 7, manufactured by Thermo Fisher Scientific) analysis was performed. The conditions were set as follows, carbon, oxygen, silicon, and platinum were selected in the element settings, and electron beam images over the entire field of view were collected.
Lifetime limit: 30 seconds Time constant: Rate1
Then, the spectrum was quantified, and the ratio (atomic%) of each element of carbon, oxygen, silicon, and platinum was determined. The value obtained by dividing the obtained ratio of silicon (atomic%) by the ratio of platinum (atom%) was defined as the amount of Si on the developing roller in the field of view. The amount of Si on the developing roller was measured for the three fields of view, and the average value was taken as the final amount of Si on the developing roller (atomic%) and evaluated according to the following criteria. The evaluation results are shown in Table 4.
A: Less than 1.0 atomic% B: 1.0 atomic% or more and less than 2.0 atomic% C: 2.0 atomic% or more and less than 3.0 atomic% D: 3.0 atomic% or more and less than 4.0 atomic% E: 4.0 atomic% or more

<Evaluation of charge rise (high temperature and high humidity environment)>
200 g of toner was loaded into the toner cartridge of LBP7600C. Then, the toner cartridge was left to stand in an environment of high temperature and high humidity (35 ° C./80% RH; also referred to as H / H) for 24 hours. The toner cartridge after being left for 24 hours in the environment was attached to the LBP7600C.
First, after printing one solid black sheet, the toner charge amount (Q / M) was measured by the same evaluation as the above charge amount evaluation. The charge amount at this time was defined as the "initial toner charge amount".
Next, 20 sheets of solid white were printed, and the toner charge amount (Q / M) was measured by the same evaluation as the above charge amount evaluation. The charge amount at this time was defined as "toner saturated charge amount".
From the measurement results, the charge rise was calculated from the following formula.
Charge rise (%) = (initial toner charge) / (toner saturated charge) x 100
The charge rising property obtained by the above formula was evaluated according to the following criteria. The evaluation results are shown in Table 4.
A: Charge rise is 90% or more B: Charge rise is 70% or more and less than 90% C: Charge rise is 50% or more and less than 70% D: Charge rise is 30% or more and less than 50% E : Charge rise is less than 30%

<Evaluation of charge retention (high temperature and high humidity environment)>
0.01 g of toner was weighed in an aluminum pan and charged to −600 V using a corona charging device [trade name: KTB-20, manufactured by Kasuga Electric Co., Ltd.]. Subsequently, the change behavior of the surface potential was measured for 30 minutes using a surface electrometer (model 347 manufactured by Trek Japan) in an H / H environment.
From the measurement results, the charge retention rate was calculated from the following formula. The charge retention was evaluated based on the charge retention. The evaluation results are shown in Table 4.
Charge retention after 30 minutes (%) = (surface potential after 30 minutes / initial surface potential) x 100
A: Charge retention rate is 90% or more B: Charge retention rate is 70% or more and less than 90% C: Charge retention rate is 50% or more and less than 70% D: Charge retention rate is 30% or more and less than 50% E: Charge retention rate Is less than 30%

<Evaluation of heat resistance>
About 10 g of toner was placed in a 100 mL poly cup, left at 50 ° C. (normal humidity) for 3 days, and then visually evaluated. The evaluation results are shown in Table 4.
A: No agglutination is seen.
B: A small amount of agglomerates can be seen, but they easily crumble.
C: Aggregates are seen, but easily crumble.
D: Aggregates can be seen, but they collapse when shaken.
E: Aggregates can be grabbed and do not easily collapse.

Claims (10)

Toner containing toner particles
The toner particles
Toner core particles and
An organosilicon polymer that coats the surface of the toner core particles and
Contains,
The organosilicon polymer has a structure represented by the following formula (A) and has a structure represented by the following formula (A).
The toner core particles contain resin A and
The resin A has a substituted or unsubstituted silyl group in the molecule and has.
The substituent of the substituted silyl group is selected from the group consisting of an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, a hydroxy group, a halogen atom and an aryl group having 6 or more carbon atoms. One and
The content of silicon atoms in the resin A is 0.02% by mass to 10.00% by mass.
A toner characterized in that the content of silicon atoms in the organosilicon polymer is 30% by mass to 50% by mass.

(In the formula (A), R ⁴ independently represents an alkyl group or a phenyl group having 1 to 6 carbon atoms.) The resin A has a structure represented by the following formula (1).
The toner according to claim 1.

(In the formula (1), P ¹ represents a polymer moiety, L ¹ represents a single bond or a divalent linking group, and R ^{1 to} R ³ independently represent hydrogen atoms, halogen atoms, and carbon atoms. one or more alkyl groups, the carbon atom number of 1 or more alkoxy groups, represents a carbon atom number of 6 or more aryl group or a hydroxy group, m represents a positive integer, where m is 2 or more, a plurality of L ¹ , A plurality of R ¹ , a plurality of R ² and a plurality of R ³ may be the same or different, respectively.) At least one of R ^{1 to} R ³ in the formula (1) represents an alkoxy group or a hydroxy group having one or more carbon atoms.
The toner according to claim 2. R ^{1 to} R ³ in the formula (1) independently represent an alkoxy group or a hydroxy group having 1 or more carbon atoms.
The toner according to claim 2 or 3. P ¹ in the formula (1) is representative of the polyester portion, or styrene acrylic site,
The toner according to any one of claims 2 to 4. ^{P 1} in the formula (1) is representative of the polyester portion,
The toner according to any one of claims 2 to 5. The weight average molecular weight of the resin A is 3000 to 100,000.
The toner according to any one of claims 1 to 6. In the measurement of ²⁹ Si-NMR of the tetrahydrofuran insoluble portion of the toner particles, the ratio of the peak area of the structure represented by the formula (A) to the total peak area of the organosilicon polymer is 30% to 100%. ,
The toner according to any one of claims 1 to 7. In the measurement of ²⁹ Si-NMR of the tetrahydrofuran insoluble portion of the toner particles, the ratio of the peak area of the structure represented by the formula (A) to the total peak area of the organosilicon polymer is 50% to 90%. ,
The toner according to claim 8. Formula (A) ^{R 4} in represents an alkyl group having 1 to 3 carbon atoms,
The toner according to any one of claims 1 to 9.