JP7086583B2 - Toner and toner manufacturing method - Google Patents

Description

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

In recent years, with the development of computers and multimedia, there is a demand for a means for outputting higher-definition full-color images in a wide range of fields from offices to homes. Therefore, the usage and storage environment of users is wide-ranging, and the environmental stability characteristics required for toner are also required to be stricter. On the other hand, there is a high demand for higher speed due to an increase in print volume, and it is necessary to expand the fixing area as a toner.
For that purpose, it is necessary to improve the fixing property on the low temperature side (cold offset resistance) and the fixing property on the high temperature side (hot offset resistance), but these have an affinity between the binder resin and the release agent. It can be achieved by controlling it. However, in order to improve the hot offset resistance, it is generally known to lower the affinity between the binder resin and the release agent, that is, to increase the polarity of the binder resin. The fact is that it cannot be said that the compatibility with the charge stability in a high humidity environment is sufficient.
Patent Document 1 discloses a toner that is excellent in hot offset resistance and suppression of fog (charge stability) under high temperature and high humidity. The polyester resin, which is easy to increase in molecular weight but has high hydrophilicity, enhances hot offset resistance, and the crystalline composite resin, which has high hydrophobicity, and hydrocarbon wax are used in combination to improve the dispersibility of the toner resin surface. It is hydrophobic to. As a result, by suppressing fog in a high temperature and high humidity environment, both hot offset resistance and charge stability in a high temperature and high humidity environment are achieved.

Further, in a fixing method such as a thermal roller or a film, there is a method of controlling the molecular weight distribution of the resin in the toner in order to improve the adhesiveness to the transfer material.
As a method for controlling the molecular weight distribution of the resin, α-methylstyrene dimer (MSD) or a mercaptan-based chain transfer agent is used in a method for producing a toner by polymerizing a polymerizable monomer in an aqueous medium to obtain toner particles. It has been proposed to control it. However, with respect to these chain transfer agents, the former has a problem that the conversion rate of the polymerizable monomer decreases depending on the amount of addition. On the other hand, the latter has an odor caused by a mercapto group, and has a problem that an odor is generated at the time of heat fixing. To solve the latter problem, Patent Document 2 proposes a method of suppressing an odor by adding a deodorant during a cleaning step.

Japanese Unexamined Patent Publication No. 2016-114626 Japanese Unexamined Patent Publication No. 2002-108015

However, the technique of Patent Document 1 requires a complicated resin design, and it is difficult to control the localization of each resin in the toner because the functions are separated by a plurality of resins. It is considered that the compatibility with the charge stability in a high temperature and high humidity environment is not sufficient.
Further, although the technique described in Patent Document 2 solves the problem of odor, it takes a long time to clean by providing a special process. In addition, it has a heavy load on the treatment of wastewater used as a cleaning liquid, and there is still room for improvement.
A first object of the present invention is to solve the above problems. That is, it provides a toner having excellent hot offset resistance and excellent charge stability in a high temperature and high humidity environment.
A second object of the present invention is to provide a method for producing a toner, which can obtain a binder resin having a uniform molecular weight and suppress an odor without lowering the conversion rate.

The first aspect of the present invention is a toner having toner particles containing a binder resin and a wax.
The solubility parameter SP of the binder resin is _9.4 or more and 10.0 or less.
The binder resin contains a resin having a structure represented by the following formula (1) containing a keto group at the end of the main chain.
Equation (1) * -CO-R
(In the formula (1), R indicates a phenyl group or a derivative thereof. * Indicates a bond with the resin backbone.)
The solubility parameter _SW of the wax is 8.1 or more and 9.0 or less.
It relates to a toner characterized in that SP and _{SW satisfy} the formula (2).
Equation (2) | SP _{- SW} |> 0.5

The second aspect of the present invention is a method for producing a toner having toner particles containing a binder resin.
A polymerizable monomer composition containing a polymerizable monomer, a polymerization initiator and a chain transfer agent capable of producing the binder resin is dispersed in an aqueous medium, and a liquid of the polymerizable monomer composition is dispersed. The process of forming droplets and
It comprises a step of polymerizing the polymerizable monomer in the droplet to generate toner particles.
The polymerizable monomer contains at least one selected from the group consisting of styrene, acrylic acid ester, and methacrylic acid ester.
The chain transfer agent relates to a method for producing a toner, which is a vinyl ether type addition cleavage type chain transfer agent represented by the formula (3).
(In the formula (3), R ₂ represents -COOR ₁ or a phenyl group or a derivative thereof, R ₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₃ represents a benzyl group or a carbon number of carbon atoms. Indicates a secondary or tertiary alkyl group of 4-8.)

According to the first aspect of the present invention, a toner having excellent hot offset resistance and excellent charge stability in a high temperature / high humidity environment can be obtained.
According to the second aspect of the present invention, it is possible to provide a method for producing a toner in which a binder resin having a uniform molecular weight and an odor is suppressed without lowering the conversion rate.

In the present invention, the description of "○○ or more and XX or less" and "○○ to XX" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified.
In order to improve the hot offset resistance at the time of fixing, it is preferable to reduce the affinity between the binder resin and the wax, that is, to introduce a polar group into the binder resin. However, increasing the polarity of the binder resin causes destabilization of charge stability in a high temperature and high humidity environment.
Based on the above, the present inventors have made diligent studies focusing on the molecular structure of the binder resin and the relationship between the solubility parameters of the binder resin and the wax. As a result, a specific structure was contained as the molecular structure of the binder resin, and a correlation could be found between the values of the solubility parameters of the binder resin and the wax, which led to the present invention.
That is, in the toner having toner particles containing a binder resin and wax, the solubility parameter SP of the binder resin is _9.4 or more and 10.0 or less, and the binder resin has the following formula at the end of the main chain. When the resin having the structure represented by (1) is contained, the solubility parameter SW of the _wax is 8.1 or more and 9.0 or less, and SP and _{SW satisfy} the condition of the formula (2). It was found that both hot offset resistance at the time of fixing and charge stability in a high temperature and high humidity environment can be achieved.

The solubility parameter is a parameter indicating that those having similar values are likely to be compatible with each other, and the solubility parameter used in the present invention is the commonly used Fedors method [Poly. Eng. Sci. , 14 (2) 147 (1974)], it can be calculated from the type and molar ratio of the constituent monomers.
The unit of the SP value in the present invention is (cal / cm ³ ) ^1/2 , but by 1 (cal / cm ³ ) ^1/2 = 2.046 × 10 ³ (J / m ³ ) ^1/2 ( J / m ³ ) Can be converted to ^1/2 unit.

Equation (1) * -CO-R
(In the formula (1), R indicates a phenyl group or a derivative thereof, or -COOR ₁ (R ₁ : an alkyl group having 1 to 4 carbon atoms). * Indicates a bond with the resin backbone.)
Equation (2) | SP _{- SW} |> 0.5
The present inventors consider the reason why the effect of the present invention can be obtained by using a toner satisfying the above conditions as follows. The present invention is characterized in that the binder resin contains a resin having a polar group represented by the formula (1) at the end of the main chain. It is known that the polymer constituting the resin has a characteristic called a terminal group effect, which greatly affects the thermal characteristics of the resin depending on the structure of the main chain terminal group. It is considered that this is because the terminal portion of the main chain has higher mobility than the side chain and easily interacts with other polymer chains.
In the present invention, the hot offset resistance is improved by including the binder resin having the terminal group structure and the wax, because the solubility parameter difference between the binder resin and the wax is the above formula (2). In addition to the wax release effect due to such a relationship, it is considered that the above-mentioned terminal group effect has a large effect.

The materials used in the present invention will be described below.
<Bundling resin>
The binder resin is characterized by containing a resin having a structure represented by the following formula (1) at the end of the main chain.
Equation (1) * -CO-R
(In the formula (1), R indicates -COOR ₁ (R ₁ : an alkyl group having 1 to 4 carbon atoms), or a phenyl group or a derivative thereof. * Indicates a bond with the resin backbone.)

Among the structures of R, examples of R ₁ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and a t-butyl group.
Examples of the derivative of the phenyl group include a phenyl group having a substituent, and examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and an i-butyl group. At least one selected from the group consisting of a group, a t-butyl group, a methoxy group, an ethoxy group and the like can be mentioned. The structure of R is preferably -COOCH ₃ or a phenyl group.

Further, it is preferable that the abundance rate of the structure represented by the formula (1) in the binder resin is 5% or more and 100% or less.
The abundance rate of the structure represented by the formula (1) here is 100%, that is, at least one of the main chain terminal structures in the binder resin is a structure represented by the formula (1) (keto group). Refers to being.
The solubility parameter SP of the binder resin is 9.4 or more and 10.0 or less, the solubility parameter _SW of the _wax is 8.1 or more and 9.0 or less, and _SP and _SW are the above formulas (2). ), When the abundance of the structure represented by the formula (1) is within the above range, the ratio of the binder resin having a polar group terminal to the binder resin is the terminal of the polar group. The amount is sufficient to obtain the wax seepage effect derived from the basic effect.
Further, the abundance rate of the main chain terminal structure represented by the formula (1) in the binder resin is more preferably 5% or more and 70% or less. This improves charge stability.

In order to keep the abundance rate of the structure represented by the formula (1) in the above range, it is preferable to use a polymer reaction, a polymerization termination reaction, or a chain transfer reaction as a method for introducing the main chain terminal structure. ..
When a polymer reaction is used, the main chain end of the binder resin is made into a highly reactive hydroxyl group or carboxyl group in advance, and then the reaction is carried out with a compound having a structure represented by the formula (1). The structure represented by (1) can be introduced.
When a polymerization terminator reaction or a chain transfer reaction is used, a polymerization terminator or a chain transfer agent having a structure represented by the formula (1) after the reaction is used during the polymerization of the binder resin. The structure represented by the formula (1) can be introduced.

Among these introduction methods, when the binder resin is produced by radical polymerization, it is preferable to use a chain transfer agent reaction. In the case of a chain transfer reaction, the conversion rate does not decrease depending on the type of chain transfer agent used and the molecular structure. Furthermore, the chain transfer reaction rate can be controlled by the value of the chain transfer coefficient of the chain transfer agent used. An efficient formula can be obtained by combining the type and structure of the chain transfer agent and the chain transfer coefficient according to conditions such as the type of polymerizable monomer used in the production of the binder resin, the type of radical polymerization used, and the presence or absence of a solvent. It is possible to introduce the structure represented by (1).

Further, the present invention is characterized in that the solubility parameter SP of the binder resin is _9.4 or more and 10.0 or less. The present inventors have a hot offset resistance particularly when the binder resin contains a resin having a structure represented by the above formula (1) at the end of the main chain and the SP of the binder _resin is in the above range. It was found that it is excellent in charge stability in a high temperature and high humidity environment. As described above, in order to efficiently exhibit the terminal group effect due to having a highly polar keto group terminal, it is necessary that the SP of the binder _resin is in the above range.

The fact that the solubility parameter SP of the binder resin is in the range of _9.4 or more and 10.0 or less indicates that the resin has properties close to hydrophobicity. That is, it is preferable that the binder resin has a resin structure mainly composed of styrene, acrylic acid, methacrylic acid, etc., which exhibit hydrophobicity. The SP is more preferably _9.4 or more and 9.8 or less.
As described above, by having the keto group structure represented by the formula (1) at the end of the main chain of the binder resin and setting the solubility parameter SP of the binder resin to _9.4 or more and 10.0 or less. The balance between the hydrophobicity of the binder resin, which contributes to the affinity between the binder resin and the wax, and the polarity of the binder resin, which contributes to the charge stability in a high temperature and high humidity environment, is improved. As a result, it exhibits excellent effects of hot offset resistance and charge stability in a high temperature and high humidity environment.

The binder resin preferably contains a vinyl-based resin. That is, it is preferable that the main chain of the resin having the structure represented by the formula (1) at the end is a vinyl resin. Vinyl-based resin is a general term for resins obtained by using a known radical polymerization method for a polymerizable monomer having a vinyl group, and is a styrene resin, an acrylic resin, a methacrylic resin, a styrene-acrylic resin, and a styrene-methacrylic. Examples include resin.
As the polymerizable monomer constituting the vinyl resin, a monofunctional polymerizable monomer having one vinyl group is used alone or in combination of two or more, or the monofunctional polymerizable monomer and vinyl are used. The polyfunctional polymerizable monomer having a plurality of groups may be combined, the polyfunctional polymerizable monomer may be used alone, or two or more kinds may be combined.
As long as the effect of the present invention is not impaired, a resin other than the resin having the structure represented by the above formula (1) at the end of the main chain may be used as the binder resin.

Examples of the monofunctional polymerizable monomer include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and pn-. Butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, And styrene derivatives such as p-phenylstyrene;
Methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate. , N-Nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and acrylic acid esters such as 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 phosphate ethyl methacrylate, and methacrylic acid esters such as dibutyl phosphate ethyl methacrylate;

Examples of the polyfunctional polymerizable monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and tripropylene glycol. Diacrylate, Polypropylene Glycol Diacrylate, 2,2'-Bis (4- (Acryloxidiethoxy) phenyl) Propane, Trimethylol Propane Triacrylate, Tetramethylol Methan Tetraacrylate, Ethylene Glycol Dimethacrylate, Diethylene Glycol Dimethacrylate, Triethylene Glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (Methyloxydiethoxy) phenyl) propane, 2,2'-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethanetetramethacrylate, divinylbenzene, divinylnaphthalin, And divinyl ether.
The polymerizable monomer is preferably at least one selected from the group consisting of styrene, acrylic acid ester, and methacrylic acid ester.

<Wax>
The present invention is characterized in that the solubility parameter SW of the _wax is 8.1 or more and 9.0 or less. The present inventors have a wax having a solubility parameter _SW in the above range and a _keto group structure represented by the above formula (1) at the end of the main chain of the binder resin in which SP is in the above range. It has been found that the inclusion of the resin improves the affinity balance between the wax and the binder resin, and makes it possible to improve the wax seepage effect at the time of fixing. As long as the solubility parameter is in the above range, a known wax can be used without particular limitation, but a hydrocarbon wax or an ester wax is preferable. The _SW is preferably 8.3 or more and 8.9 or less.

The following can be used as the hydrocarbon wax. Polycarbonates that produce low molecular weight by-products obtained during high molecular weight polyolefin polymerization; Polycarbonates polymerized using catalysts such as Cheegler catalysts and metallocene catalysts; Paraffin wax, Fishertroph wax; Gintall method using coal gas or natural gas as raw materials, Synthetic hydrocarbon wax synthesized by the hydrocol method and the age method; synthetic wax using a compound having one carbon atom as a monomer; hydrocarbon wax having a functional group such as a hydroxyl group and a carboxyl group; having a hydrocarbon wax and a functional group Examples include a mixture with a hydrocarbon wax. In addition, these waxes have a sharp molecular weight distribution using methods such as press sweating method, solvent method, recrystallization method, vacuum distillation method, supercritical gas extraction method, fusion liquid crystal analysis method, etc., and low molecular weight solids. A substance from which fatty acids, low molecular weight solid alcohols, low molecular weight solid compounds and other impurities have been removed may be used.

Further, as the ester wax, it is sufficient that one molecule has at least one ester bond, and either natural wax or synthetic wax may be used.
Examples of synthetic ester waxes include esters of linear aliphatic acids and linear aliphatic monoalcohols, preferably monoester waxes synthesized from long-chain linear saturated fatty acids and long-chain linear saturated monoalcohols. Can be mentioned. The long-chain linear saturated fatty acid is represented by the general formula Cn H ( _{2n + 1)} COOH, and those with n = 5 to 28 are preferably used. Further, as the long-chain linear saturated monoalcohol, those represented by C _n H _{(2n + 1)} OH and n = 5 to 28 are preferably used.
Specific examples of long-chain linear saturated fatty acids include capric acid, undesic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, pentadecyl acid, heptadecanoic acid, tetradecanoic acid, stearic acid, nonadecanoic acid, araquinic acid and behenic acid. , Lignoseric acid, cellotic acid, heptacosanoic acid, montanic acid and melicic acid.
Specific examples of long-chain linear saturated monoalcohols include amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, and myristyl alcohol. Examples thereof include pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecil alcohol, eicosyl alcohol, ceryl alcohol and heptacosanol.

The ester wax having two or more ester bonds in one molecule is an ester wax having 2 to 8 ester bonds, that is, an ester of an alcohol having a valence of 2 to 8 and an aliphatic monocarboxylic acid, or a divalent one. Examples thereof include esters of carboxylic acids having a valence of 8 or more and aliphatic monoalcohols.
Specifically, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecanediol-bis-stearylate, etc .; polyalkanol ester. (Tristearyl trimellitic acid, distearyl maleate) can be mentioned.

The molecular weight of the wax is preferably 2500 or less, more preferably 2000 or less. When the molecular weight of the wax is in the above range, the molecular size (spread of the molecular chain) does not become too large, so that the diffusion rate can be maintained above a certain level, and the wax easily seeps out during fixing. The lower limit is not particularly limited, but is preferably 300 or more.
The wax content in the toner particles is preferably 1% by mass or more and 30% by mass or less. When the wax content is in the above range, the proportion of the wax in the entire toner becomes appropriate, so that good fixing results can be easily obtained when fixing the toner.
The melting point of the wax is preferably 60 ° C. or higher and 120 ° C. or lower, more preferably 65 ° C. or higher and 100 ° C. or lower.
As the toner, only one type of wax may be used, or a plurality of types may be used in combination.

In the present invention, the solubility parameter SP of the binder resin and the solubility parameter _SW of the wax _satisfy the formula (2).
Equation (2) | SP _{- SW} |> 0.5
When _SP and _SW are set in the above range and the absolute value of the difference between _SP and _SW is set in the above range, a good wax seeping effect is likely to be obtained at the time of fixing.
This generally ensures that the balance of affinity between the binder resin and the wax is not too biased towards the affinity in order to produce the wax release effect during toner fixation, that is, the absolute difference in solubility parameter. This is because the value needs to be equal to or higher than a certain value.
| SP _{- SW} | is preferably 1.0 or more. On the other hand, the upper limit is not particularly limited, but is preferably 2.0 or less, and more preferably 1.5 or less.

<Other additives>
In addition to the binder resin and wax, various additives may be added to the toner particles as needed. Typical examples of these additives are described below.

<Colorant>
A colorant may be used as the toner. As the black colorant, carbon black, a magnetic material, and a black colorant using the following yellow / magenta / cyan colorants are used.
Examples of the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, Examples thereof include 155, 168, 180, 185, 214 and the like.
Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221 238, 254, 269, C.I. I. Pigment Violet 19 and the like can be exemplified.

Examples of the cyan colorant include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds and the like. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like.
These colorants can be used alone or in the form of a solid solution. The colorant is selected in terms of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner. The amount of the colorant added is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or the binder resin capable of producing the binder resin.

It is also possible to contain a magnetic material as a colorant to obtain a magnetic toner. In this case, the magnetic material can also serve as a colorant. Magnetic materials include the following iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel, or these metals with aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, and berylium. , Bismus, cadmium, calcium, manganese, selenium, titanium, tungsten, alloys with metals such as vanadium, and mixtures thereof.
The magnetic material is more preferably a surface-modified magnetic material. When the magnetic toner is prepared by a polymerization method, it is preferably hydrophobized with a surface modifier that does not inhibit polymerization. Examples of such a surface modifier include a silane coupling agent and a titanium coupling agent.
The number average particle diameter of these magnetic materials is preferably 2 μm or less, more preferably 0.1 μm or more and 0.5 μm or less. The content in the toner particles is preferably 20 parts by mass or more and 200 parts by mass or less, and more preferably 40 parts by mass or more and 150 parts by mass with respect to 100 parts by mass of the polymerizable monomer or the binder resin capable of producing the binder resin. It is less than a part.

<Charge control agent>
A charge control agent may be added to the toner in order to stabilize the charge characteristics. As the charge control agent, known ones can be used, and 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 is produced by the direct polymerization method, a charge control agent having low polymerization inhibitory property and substantially no solubilized product in the aqueous dispersion medium is particularly preferable.
Specific examples include metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, and dicarboxylic acid as negative charge control agents, metal salts or metal complexes of azo dyes or azo pigments, and boron compounds. , Silicon compounds, Calix Arene. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer-type compound having the quaternary ammonium salt in the side chain, a guanidine compound, a niglocin-based compound, and an imidazole compound.
The amount of these charge control agents used is determined by the type of binder resin, the presence or absence of other additives, and the toner production method including the dispersion method, and is not uniquely limited. In the case of internal addition, it is preferably 0.1 part by mass or more and 10 parts by mass or less, and more preferably 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the binder resin or the polymerizable monomer. In the case of external addition, it is preferably 0.005 part by mass or more and 1.0 part by mass or less, and more preferably 0.01 part by mass or more and 0.3 part by mass or less with respect to 100 parts by mass of the toner particles.

<Chain transfer agent>
Further, the present inventors have prepared a polymerizable monomer composition containing a vinyl ether type addition cleavage type chain transfer agent represented by the formula (3), a polymerizable monomer and a polymerization initiator in the production of the above toner. It has been found that the method including the step of polymerizing and obtaining the binder resin improves the hot offset resistance at the time of fixing and the charge stability in a high temperature and high humidity environment.

(In the formula (3), R ₂ represents -COOR ₁ or a phenyl group or a derivative thereof, R ₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₃ represents a benzyl group or a carbon number of carbon atoms. Indicates a secondary or tertiary alkyl group of 4-8.)
The chain transfer agent is a chain transfer agent having a vinyl ether as a skeleton as shown in the formula (3). In order to exhibit an efficient chain transfer reaction in a radical polymerization field, _R2 in the formula (3) is -COOR ₁ ( _R1 : an alkyl group having 1 to 4 carbon atoms), or a phenyl group or a derivative thereof. It is necessary to be. With the above structure, an efficient chain transfer reaction is exhibited with respect to the polymerizable monomer.
Examples of R ₁ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group and a t-butyl group.
Examples of the derivative of the phenyl group include a phenyl group having a substituent, and examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and an i-butyl group. At least one selected from the group consisting of a group, a t-butyl group, a methoxy group, an ethoxy group and the like can be mentioned.
R ₂ is more preferably -COOCH ₃ , or a phenyl group or a derivative thereof.

The chain transfer agent is an addition-cleaving type chain transfer agent. Efficient addition of the initiator radical generated after addition cleavage to the polymerizable monomer makes it difficult for the polymerization conversion rate to decrease.
For that purpose, R ₃ needs to be a benzyl group and a secondary or tertiary alkyl group having 4 to 8 carbon atoms. Examples of the secondary or tertiary alkyl group having 4 to 8 carbon atoms include an iso-butyl group, a tert-butyl group, and a tert-amyl group.
R3 is more preferably a benzyl group _, an iso-butyl group, or a tert-butyl group.

The chain transfer agent is, for example, α-benzyloxystyrene, i-butyloxystyrene, t-butyloxystyrene, benzyloxyp-methylstyrene, benzyloxyp-methoxystyrene, methyl2-benzyloxyacrylate, ethyl2-benzyloxy. Examples thereof include acrylate, n-butyl 2-benzyloxy acrylate, t-butyl 2-benzyloxy acrylate, methyl 2-i-butyloxy acrylate, and methyl 2-t-butyloxy acrylate.
Further, it is preferable that the chain transfer agent is at least one selected from the group consisting of the formulas (4) to (6).

The amount of the chain transfer agent represented by the formula (3) to be added is preferably 0.1 part by mass or more and 5.0 parts by mass or less with respect to 100.0 parts by mass of the polymerizable monomer, preferably 0.3. It is more preferably more than parts by mass and not more than 4.5 parts by mass. When the addition amount is in this range, it becomes easy to control the polymerization from the viewpoints of the amount of the low molecular weight component and the decrease in the polymerization conversion rate, so that it becomes easy to obtain a resin having a well-balanced molecular weight distribution. Further, when the addition amount is in this range, it is possible to prevent the residual amount of unreacted substances and the like at the time of completion of the polymerization from becoming too large.

<Polymer initiator>
Examples of the polymerization initiator that can be used in the polymerizable monomer composition include known organic peroxide initiators and azo compound initiators. Examples of the organic peroxide initiator include the following.
Alkyl peroxy ester type such as t-butyl peroxypivalate and t-amyl peroxypivalate, peroxymonocarbonate type such as t-amyl peroxyisopropyl carbonate, 1,1-di (t-amyl peroxy) Peroxyketal type such as cyclohexane, dialkyl peroxide type such as dit-butyl peroxide and dit-amyl peroxide, diacyl peroxide type such as diisonanoyl peroxide and diisobutyryl peroxide, bis (4-t- Butylcyclohexyl) Peroxydicarbonate type such as peroxydicarbonate can be mentioned.

Examples of the azo compound initiator include 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, and 1,1'-azobis (cyclohexane-1-carbonitrile). , 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobismethylbutyronitrile, 1,1'-azobis (1-acetoxy-1-)
Phenylethane) and the like.
The polymerization initiator is preferably an alkyl peroxy ester type organic peroxide, a diacyl peroxide type organic peroxide, or an azo compound.
The organic peroxide initiator or the azo compound initiator may be used as it is, or a plurality of types may be mixed and used.

As a method for producing the toner, a polymerizable monomer composition containing a vinyl ether type addition cleavage type chain transfer agent represented by the formula (3), a polymerizable monomer and a polymerization initiator is polymerized to obtain a binder resin. A method including a step of obtaining is preferable. For example, a known production method using a binder resin produced in advance, a known production method for producing toner particles through the radical polymerization step, and the like can be mentioned. Preferred examples thereof include a dry production method, an emulsion aggregation method, a dissolution suspension method, and a suspension polymerization method.

The steps included in the manufacturing method of the present invention will be described below.
<Step of polymerizing the polymerizable monomer composition to obtain a binder resin>
In the method for producing a toner of the present invention, a polymerizable monomer composition containing a vinyl ether type addition cleavage type chain transfer agent represented by the formula (3), a polymerizable monomer and a polymerization initiator is polymerized and bound. It is preferable to include a step of obtaining a resin.
As described above, the use of a chain transfer agent under polymerization makes it possible to efficiently control the backbone terminal structure.
Here, in the vinyl ether type addition cleavage type chain transfer agent represented by the formula (3), the starting radical is cleaved after the radical is added, and at that time, the radical growth end generates a keto group. As described in the section of the chain transfer agent described above, the structure represented by the formula (3) minimizes the decrease in conversion rate during the polymerization of styrene, acrylic or methacrylic polymerizable monomers. It is possible to efficiently introduce the terminal keto group while suppressing it.

In the second aspect of the present invention, the following production method can be preferably used.
A method for producing a toner having toner particles containing a binder resin.
A polymerizable monomer composition containing a polymerizable monomer, a polymerization initiator and a chain transfer agent capable of forming the binder resin is dispersed in an aqueous medium, and a liquid of the polymerizable monomer composition is dispersed. The process of forming droplets and
It comprises a step of polymerizing the polymerizable monomer in the droplet to generate toner particles.
The polymerizable monomer contains at least one selected from the group consisting of styrene, acrylic acid ester, and methacrylic acid ester.
A method for producing a toner, wherein the chain transfer agent is a vinyl ether type addition cleavage type chain transfer agent represented by the above formula (3).

In the method for producing toner particles by the suspension polymerization method, the present inventors show an efficient chain transfer reaction in a suspension polymerization site by using the chain transfer agent represented by the formula (3), and the conversion rate. It was found that a binder resin having a uniform molecular weight can be obtained without lowering the molecular weight. It was also found that the obtained toner particles suppress the odor.
When the chain transfer agent has the above structure, it exhibits an efficient chain transfer reaction with styrene, acrylic acid ester, and methacrylic acid ester. Further, the chain transfer agent is an addition-cleaving type chain transfer agent, and the starting radical generated after the addition-cleavage is efficiently added to the polymerizable monomer, so that the polymerization conversion rate is less likely to decrease.
The chain transfer agent is a chain transfer agent having a vinyl ether as a skeleton. Since this vinyl ether type addition cleavage type chain transfer agent does not have a functional group such as a mercapto group that causes an odor, a binder resin in which the odor is suppressed can be obtained without performing a special step.

Next, the suspension polymerization method will be described.
Polymerizable monomers capable of producing a binder resin, chain transfer agents represented by the formula (3), and, if necessary, other additives such as colorants and waxes, homogenizers, ball mills, colloid mills, super A polymerizable monomer composition is prepared by uniformly dissolving or dispersing with a disperser such as a sonic disperser, and dissolving the polymerization initiator in the disperser. Next, the polymerizable monomer composition is suspended in an aqueous medium containing a dispersion stabilizer to form droplets of the polymerizable monomer composition. Then, the toner particles are produced by polymerizing the polymerizable monomer in the droplets.
The polymerization initiator and the chain transfer agent may be added at the same time as the other additives are added to the polymerizable monomer, or may be mixed immediately before the suspension in the aqueous medium. Further, immediately after granulation and before starting the polymerization reaction, a polymerizable monomer or a polymerization initiator dissolved in a solvent may be added.

The weight average particle size (D4) of the toner particles is preferably 4.0 μm or more and 9.0 μm or less, more preferably 5.0 μm or more and 8.0 μm or less, and further preferably 5.0 μm or more 7 It is 0.0 μm or less.

Hereinafter, the calculation method and the measurement method of each physical property value specified in the present invention will be described.
<Measurement method of wax molecular weight>
The molecular weight of the wax is measured by gel permeation chromatography (GPC) as follows.
Special grade 2,6-di-t-butyl-4-methylphenol (BHT) is added to o-dichlorobenzene for gel chromatograph so as to have a concentration of 0.10% by mass / volume, and the mixture is dissolved at room temperature. The wax and o-dichlorobenzene to which the above BHT is added are placed in a sample bottle and heated on a hot plate set at 150 ° C. to dissolve the wax. When the wax melts, put it in a preheated filter unit and install it in the main body. A GPC sample that has passed through the filter unit is used. The sample solution is adjusted so that the concentration is 0.15% by mass. This sample solution is used for measurement under the following conditions. Equipment: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Detector: RI for high temperature
Column: TSKgel GMHHR-HHT 2 stations (manufactured by Tosoh)
Temperature: 135.0 ° C
Solvent: o-dichlorobenzene for gel chromatograph (BHT 0.10 mass / volume% added) Flow rate: 1.0 ml / min
Injection volume: 0.4 ml
In calculating the molecular weight of the wax, standard polystyrene resin (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-" 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) is used.

<Measurement method of molecular weight of binder resin>
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the binder resin are measured by gel permeation chromatography (GPC) as follows.
First, the binder resin is dissolved in tetrahydrofuran (THF) at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Mysholidisc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. This sample solution is used for measurement under the following conditions.
Equipment: High-speed GPC equipment "HLC-8220GPC" [manufactured by Tosoh Corporation]
Column: LF-604 double eluent: THF
Flow velocity: 0.6 ml / min
Oven temperature: 40 ° C
Sample injection amount: 0.020 ml
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-" 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) is used.

<Measurement method of main chain terminal structure abundance of binder resin>
The method of measuring the abundance rate (%) of the main chain terminal structure of the binder resin is described. Since the main chain terminal structure is a terminal group having different motility and a keto group structure, a known analytical method by nuclear magnetic resonance spectroscopy can be used. Specifically, ¹³ C-NMR measurement is performed using AVANCE-600 (deuterated chloroform used solvent) with an FT-NMR ultra-low temperature probe manufactured by Bruker Biospin Co., Ltd.
In addition, 100 mg of a sample is dissolved in 0.7 ml of a solvent, and a sample solution containing 50 mM of chromium (III) acetylacetonate as a relaxation reagent is used and quantified by a reverse gate decoupling method. A composition analysis was performed, and the integral ratio of the signal of the carbonyl carbon of the terminal keto group to other carbonyl carbon derived from the acrylic structure in the polymer or the phenyl carbon derived from the styrene structure in the polymer was used for each monomer amount. The abundance ratio of the terminal group can be calculated.
On the other hand, since the apparent molecular weight can be calculated from the monomer composition ratio in the polymer assuming that the abundance of the terminal groups is 100%, the abundance of the main chain terminal structure is determined from the ratio between the apparent molecular weight and the number average molecular weight. Can be calculated.
Since the binder resin contained in the toner of the present invention may have a large average molecular weight, a method for measuring the abundance of the main chain terminal structure in that case will be described.
Precipitation fractionation is performed with a good solvent / poor solvent mixed system of the target polymer, or a commercially available fractionation chromatography (fractionation GPC) is used to obtain fractions (fractions) for each of a plurality of molecular weights.
The molecular weight and molecular weight distribution of these distillates are measured by GPC or the like, and the above-mentioned ¹³ C-NMR measurement is performed on a plurality of samples having a small molecular weight, and the abundance of the main chain terminal structure in each sample is calculated. The abundance of the main chain terminal structure can be determined by averaging the abundance of these main chain terminal structures.
Regarding the separation of the binder resin, wax, etc. in the toner, the composition of the toner is analyzed, the types of the binder resin, wax, fixing aid, etc. contained are estimated, and then extraction is performed using each good solvent. be able to. Alternatively, fractionation using the above-mentioned precipitation fractionation method or fractionation GPC is performed, and a fraction of each component is obtained. By analyzing these by known structural analysis methods (nuclear magnetic resonance spectroscopy, infrared spectroscopy, thermal decomposition GC / MS, etc.), the structures of each polymer, wax, and fixing aid can be identified, and the SP value and the like can be determined. Can be calculated. Further, the binder resin can be estimated from the abundance ratio of each polymer species, and the abundance rate of the terminal group can be determined by the method of calculating the abundance rate of the terminal group structure.

<Measurement method of melting point Tm of wax>
The melting point Tm of the wax is measured according to ASTM D3418-82 using a differential scanning calorimeter analyzer "Q1000" (manufactured by TA Instruments).
The melting point of indium and zinc is used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value.
Specifically, 5 mg of wax is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rise rate is 10 ° C. in the measurement temperature range of 30 to 200 ° C. Measure at / min. In the measurement, the temperature is once raised to 200 ° C., then lowered to 30 ° C. at 10 ° C./min, and then raised again at 10 ° C./min. The maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the melting point Tm in the DSC measurement.

<Measuring method of weight average particle size (D4) and number average particle size (D1) of toner>
The weight average particle size (D4) and the number average particle size (D1) of the toner are the precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, Beckman. (Manufactured by Coulter) is used. For measurement condition setting and measurement data analysis, use the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) to measure with 25,000 effective measurement channels and analyze the measurement data. I do.
As the electrolytic aqueous solution used for the measurement, one in which special grade sodium chloride is dissolved in ion-exchanged water so that the concentration becomes 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.
Before performing measurement and analysis, set the dedicated software as follows.
In the "Change standard measurement method (SOM) screen" of the dedicated software, set the total count number of the control mode to 50,000 particles, measure once, and set the Kd value to "Standard particles 10.0 μm" (Beckman Coulter). Set the value obtained using (manufactured by the company). By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check the flash of the aperture tube after measurement.
On the "Pulse to particle size conversion setting screen" of the dedicated software, set the bin spacing to the logarithmic particle size, the particle size bin to the 256 particle size bin, and the particle size range to 2 μm or more and 60 μm or less.

The specific measurement method is as follows.
(1) 200 ml of the electrolytic aqueous solution is placed in a 250 ml round bottom beaker made of glass exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flash" function of the dedicated software.
(2) Put 30 ml of the electrolytic aqueous solution in a 100 ml flat bottom beaker made of glass. Among them, as a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a pH 7 precision measuring instrument consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Is diluted 3 times by mass with ion-exchanged water, and 0.3 ml of the diluted solution is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and are installed in the water tank of the ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is added, and 2 ml of the Contaminone N is added into the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic solution in the beaker is maximized.
(5) With the electrolytic aqueous solution in the beaker of (4) being irradiated with ultrasonic waves, 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. For ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, the electrolytic aqueous solution of (5) in which toner is dispersed is dropped onto the round bottom beaker of (1) installed in the sample stand, and the measured concentration is adjusted to 5%. Then, the measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the particle size is calculated. When the graph / volume% is set in the dedicated software, the "average diameter" on the analysis / volume statistical value (arithmetic mean) screen is the weight average particle size (D4), and the graph / number% is set in the dedicated software. The "average diameter" on the "analysis / number statistical value (arithmetic mean)" screen is the number average particle size (D1).

<Measurement method of polymerization conversion rate>
The polymerization conversion rate is determined by the following method.
A polymerization inhibitor is added to 1 g of the suspension after the completion of the polymerization reaction, and this is dissolved in 4 ml of THF and obtained by gas chromatography under the following conditions from the amount of residual polymerizable monomer by the internal standard method.
G. C. Condition measuring device: Shimadzu GC-15A (with capillaries)
Carrier: N ₂ , 2 kg / cm ² 50 ml / min. split 10ml / 1
3s
Column: ULBON HR-150m x 0.25mm
Temperature rise: 5 min at 50 ° C. Retention → 10 ° C / min. The temperature rises to 100 ° C → 20 ° C / min. The temperature was raised to 200 ° C. and the amount of holding sample: 2 μl.
Standard substance: Toluene

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

<Manufacturing of binder resin 1>
The following materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube.
・ 75.0 parts by mass of styrene ・ 25.0 parts by mass of n-butyl acrylate ・ 1.0 part by mass of α-benzyloxystyrene ・ Perbutyl PV (manufactured by Nippon Yushi) 7.0 parts by mass ・ 100.0 parts by mass of toluene Then After stirring uniformly, nitrogen was bubbled for 10 minutes and then heated to 75 ° C. in a nitrogen flow state. After reacting for 6 hours, methanol was used as a precipitating agent for reprecipitation, purification, and vacuum drying to obtain a binder resin 1.
The composition of the obtained binder resin was styrene: n _- butyl acrylate = 75:25 (mass ratio), and the solubility parameter SP derived from this composition ratio was 9.8. The molecular weight of the binder resin 1 determined by GPC was a weight average molecular weight (Mw) 18900 and a number average molecular weight (Mn) 13100.
The main chain terminal structure of the binder resin was -CO-Ph, and the abundance of the terminal structure calculated by ¹³ C-NMR was 12.5%. Table 1 shows the physical characteristics of the obtained binder resin.

<Manufacturing of binder resin 2 to 15>
As shown in Table 1, the binder resins 2 to 15 were obtained in the same manner as the binder resin 1 except that the raw materials and the number of added copies were changed. Table 1 shows the physical characteristics of each of the obtained binder resins.

(Example 1)
<Manufacturing of toner 1>
・ Bound resin 1 100.0 parts by mass ・ Hydrocarbon wax (melting point 78 ℃; manufactured by Nippon Seiwa Co., Ltd.) 12.0 parts by mass ・ Copper phthalocyanine pigment (Pigment Blue 15: 3) 4.5 parts by mass ・ Load electric control Agent (Bontron E-88; manufactured by Orient Chemical Co., Ltd.) 0.3 parts by mass After mixing the above materials well with Mitsui Henchel Mixer (“FM-75 type”, manufactured by Mitsui Miike Kakoki Co., Ltd.), the temperature was adjusted to 130 ° C. It was kneaded with the set twin-screw kneader (“PCM-30 type”, manufactured by Ikekai 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. The obtained coarse crushed product was finely pulverized using a collision-type airflow crusher using a high-pressure gas. Next, the particles were classified by a wind power classifier (“Elbow Jet Lab EJ-L3”, manufactured by Nittetsu Mining Co., Ltd.) using the Coanda effect, and fine powder and coarse powder were simultaneously classified and removed to obtain toner particles.
Hydrophobic silica fine powder (primary particle diameter: 7 nm, BET) treated with 20% by mass of dimethyl silicone oil as an external additive with respect to 100.0 parts by mass of the obtained toner particles. Specific surface area: 300 m ² / g) 1.5 parts by mass was mixed with a Mitsui Henchel mixer at a stirring speed of 3000 rpm for 15 minutes to obtain toner 1. The weight average particle size (D4) of the toner 1 was 5.9 μm. Table 2 shows the physical characteristics of the obtained toner.

(Examples 2 to 17)
<Manufacturing of toners 2 to 17>
As shown in Table 2, toners 2 to 17 were obtained by the same manufacturing method as that of toner 1 except that the raw materials and the number of copies added were changed. Table 2 shows the physical characteristics of each of the obtained toners.

(Example 18)
<Manufacturing of toner 18>
(Manufacturing of resin fine particle dispersion liquid 1 for core)
・ Bound resin 10 60.0 parts by mass ・ Anionic surfactant (Neogen RK; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 0.2 parts by mass ・ N, N-dimethylaminoethanol 1.9 parts by mass ・ tetrahydrofuran 200.0 parts by mass The above parts are mixed and dissolved, and the ultra-high-speed stirring device T.I. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primix Corporation). Further, 177.80 parts by mass of ion-exchanged water was added dropwise, and then Tetrahydrofuran was removed using an evaporator to obtain a core resin fine particle dispersion liquid 1. The volume-based particle size of the resin fine particles in the dispersion was 0.22 μm as a result of measurement using a dynamic light scattering type particle size distribution meter (Nanotrack: manufactured by Nikkiso Co., Ltd.).

(Manufacturing of resin fine particle dispersion liquid 1 for shell)
・ Polyester resin A 60.0 parts by mass ・ Anionic surfactant (Neogen RK; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.3 parts by mass ・ N, N-dimethylaminoethanol 1.9 parts by mass ・ tetrahydrofuran 200.0 parts by mass (Polyester resin A is terephthalic acid: isophthalic acid: propylene oxide-modified bisphenol A (2 mol adduct): ethylene oxide-modified bisphenol A (2 mol adduct) = 20:20:44:50 (mass ratio) polycondensation. Object; Mn: 3200, Mw: 7000.)
Using the above, a resin fine particle dispersion for shell 1 was obtained in the same manner as the resin fine particle dispersion for core. The volume-based particle size of the resin fine particles in the dispersion was 0.09 μm.

(Aqueous dispersion of colorant fine particles)
・ Copper phthalocyanine pigment (Pigment Blue 15: 3) 100.0 parts by mass ・ Anionic surfactant (Neogen RK; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 15.0 parts by mass ・ Ion exchange water 885.0 parts by mass or more is mixed. , A high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) was used to disperse for 1 hour to prepare an aqueous dispersion of colorant fine particles in which the colorant was dispersed. The volume-based particle size of the colorant fine particles in the aqueous dispersion of the colorant fine particles was 0.20 μm as a result of measurement using a dynamic light scattering type particle size distribution meter.

(Aqueous dispersion of mold release agent fine particles)
・ Hydrogen wax (melting point 78 ℃; manufactured by Nippon Seiwa Co., Ltd.) 100.0 parts by mass ・ Anionic surfactant (Neogen RK; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 10.0 parts by mass ・ Ion exchanged water 880.0 parts by mass After putting the above part into a mixing container equipped with a stirrer, heat it to 90 ° C. and circulate it to Clairemix W Motion (manufactured by M-Technique) while the rotor outer diameter is 3 cm and the clearance is 0.3 mm. The mixture was stirred under the conditions of a rotor rotation speed of 19000 rpm and a screen rotation speed of 19000 rpm, and after dispersion treatment for 60 minutes, the temperature was 40 ° C. under the cooling treatment conditions of a rotor rotation speed of 1000 rpm, a screen rotation speed of 0 rpm, and a cooling speed of 10 ° C./min. By cooling to, an aqueous dispersion of the release agent fine particles was obtained. The volume-based particle size of the release agent fine particles in the aqueous dispersion of the release agent fine particles was 0.15 μm as a result of measurement using a dynamic light scattering type particle size distribution meter.

(Preparation of core particle dispersion)
・ Resin fine particle dispersion liquid for core 1 40.0 parts by mass ・ Water-based dispersion liquid of colorant fine particles 10.0 parts by mass ・ Aqueous dispersion liquid of mold release agent fine particles 20.0 parts by mass ・ 1% by mass magnesium sulfate aqueous solution 20.0 140.0 parts by mass of ion-exchanged water The above is dispersed using a homogenizer (made by IKA: Ultratalax T50), and then heated to 45 ° C in a heating water bath while stirring with a stirring blade. did. After holding at 45 ° C. for 1 hour, when observed with an optical microscope, it was confirmed that aggregated particles having an average particle size of 5.5 μm were formed. After adding 40 parts by mass of a 5 mass% trisodium citrate aqueous solution, the temperature was raised to 85 ° C. while stirring and held for 120 minutes to fuse the core particles.
Then, while continuing stirring, water was put into the water bath and cooled to 25 ° C. to obtain a core particle dispersion. Further, when the particle size of the core particles in the core particle dispersion was measured by a particle size distribution analyzer (Colter Multisizer III: manufactured by Coulter) by the Coulter method, the weight average particle size (D4) was 4.5 μm. ..

(Preparation of toner particles)
1000 parts by mass of the core particle dispersion was placed in a tall beaker and stirred in a heating water bath at 25 ° C. with a stirring blade. Subsequently, 113 parts by mass of the resin fine particle dispersion for the shell was added, and the mixture was stirred for 10 minutes. Further, 200 parts by mass of a 2 mass% calcium chloride aqueous solution was slowly added dropwise. The dispersion liquid at this stage is referred to as dispersion liquid A.
In this state, a small amount of the liquid was extracted at any time, passed through a 2 μm microfilter, and stirring was continued at 25 ° C. until the filtrate became transparent. After confirming that the filtrate became transparent, the temperature was raised to 40 ° C., 133 parts by mass of a 5 mass% trisodium citrate aqueous solution was added, the temperature was raised to 65 ° C., and stirring was performed for 1.5 hours. Then, the obtained liquid was cooled to 25 ° C., filtered and separated into solid and liquid, and then 800 parts by mass of ion-exchanged water was added to the solid content and the mixture was stirred and washed for 30 minutes. After that, filtration and solid-liquid separation were performed again. As described above, filtration and washing were repeated until the electric conductivity of the filtrate became 150 μS / cm or less in order to eliminate the influence of the residual surfactant.
Next, the obtained solid content was dried to obtain core-shell structure type toner particles 18. Since the weight average particle size (D4) of the obtained core-shell structure type toner particles 18 was 6.6 μm, it was determined that the toner particles were obtained without agglomeration.
The obtained toner particles 18 were externally added in the same manner as in the toner 1, to obtain the toner 18. Table 3 shows the physical characteristics of the obtained toner.

(Example 19)
<Manufacturing of toner 19>
・ Bound resin 1 100.0 parts by mass ・ Methyl ethyl ketone 100.0 parts by mass ・ Ethyl acetate 100.0 parts by mass ・ Hydrocarbon wax (melting point 78 ° C; manufactured by Nippon Seiwa Co., Ltd.) 12.0 parts by mass ・ Copper phthalocyanine pigment ( Pigment Blue 15: 3) 6.5 parts by mass, load electrical control agent (Bontron E-88, manufactured by Orient Chemical Co., Ltd.) 1.0 parts by mass Using the above material with an attritor (manufactured by Mitsui Metals Co., Ltd.) for 3 hours. The mixture was dispersed to obtain a colorant dispersion.
On the other hand, 27 parts by mass of calcium phosphate is added to 3000 parts by mass of ion-exchanged water heated to a temperature of 60 ° C., and the mixture is stirred at a stirring speed of 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, an aqueous medium was prepared. The colorant dispersion was added to the aqueous medium and stirred with a TK homomixer at a stirring speed of 12,000 rpm for 15 minutes at a temperature of 65 ° C. and an _N2 atmosphere to granulate the colorant particles. After that, the TK homomixer was changed to a normal propeller stirring device, the stirring speed of the stirring device was maintained at 150 rpm, the internal temperature was raised to 95 ° C. and held for 3 hours to remove the solvent from the dispersion liquid. , A dispersion of toner particles was prepared. Hydrochloric acid was added to the obtained dispersion of toner particles to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve the calcium phosphate salt. The dispersion was filtered and washed with a pressure filter to obtain toner aggregates. Then, the toner agglomerates were crushed and dried to obtain toner particles.
The obtained toner particles were externally added in the same manner as in toner 1 to obtain toner 19. The weight average particle size (D4) of the toner 19 was 6.0 μm. Table 3 shows the physical characteristics of the obtained toner.

(Example 20)
<Manufacturing of toner 20>
To 1300.0 parts by mass of ion-exchanged water heated to a temperature of 60 ° C., 9.0 parts by mass of tricalcium phosphate was added, and the mixture was stirred at a stirring speed of 15,000 rpm using a TK homomixer, and the water system was used. The medium was prepared.
Further, the following binder resin material was mixed with a propeller type stirring device at a stirring speed of 100 rpm to prepare a mixed solution.
・ Styrene 75.0 parts by mass ・ n-butyl acrylate 25.0 parts by mass ・ α-benzyloxystyrene 1.5 parts by mass Next, in the above solution,
・ Copper phthalocyanine pigment (Pigment Blue 15: 3) 6.5 parts by mass ・ Load electric control agent (Bontron E-88, manufactured by Orient Chemical Co., Ltd.) 0.5 parts by mass ・ Hydrocarbon wax (melting point 78 ° C) 12.0 parts by mass After adding the parts, the mixed solution was heated to a temperature of 70 ° C. and then stirred with a TK homomixer at a stirring speed of 10,000 rpm to dissolve and disperse to prepare a polymerizable monomer composition. ..
Subsequently, the polymerizable monomer composition was put into the aqueous medium, 7.0 parts by mass of perbutyl PV was added as a polymerization initiator, and the mixture was stirred at a temperature of 70 ° C. using a TK homomixer. The mixture was stirred at a speed of 15,000 rpm for 20 minutes and granulated.
While transferring to a propeller type stirrer and stirring at a stirring speed of 200 rpm, styrene and n-butyl acrylate, which are polymerizable monomers in the polymerizable monomer composition, are polymerized and reacted at a temperature of 85 ° C. for 5 hours to polymerize the toner. A slurry containing particles was produced. After completion of the polymerization reaction, the slurry was cooled. Hydrochloric acid was added to the cooled slurry to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve the calcium phosphate salt. Then, it was washed with 10 times the amount of water of the slurry, filtered and dried, and then the particle size was adjusted by classification to obtain toner particles. The main chain terminal structure in the binder resin was -CO-Ph, and the abundance rate of the terminal structure calculated by ¹³ C-NMR was 15.2%.
The obtained toner particles were externally added in the same manner as in toner 1 to obtain toner 20. The weight average particle size (D4) of the toner 20 was 5.8 μm. Table 3 shows the physical characteristics of the obtained toner.

表中、－Ｐｈはフェニル基を示す。

In the table, -Ph indicates a phenyl group.

(Comparative Examples 1 to 8)
<Manufacturing of toners 21 to 28>
As shown in Table 4, toners 21 to 28 were obtained by the same manufacturing method as that of toner 1 except that the raw materials and the number of copies added were changed. Table 4 shows the physical characteristics of each toner.

(evaluation)
The performance of each of the obtained toners was evaluated according to the following method.
Image evaluation was performed using a modified machine of LBP-7700C (manufactured by Canon) as an image forming apparatus. The LBP-7700C was modified in the following points.
-The process speed can be set arbitrarily by changing the gear and software of the evaluation machine.
-A cyan cartridge was used as the cartridge used for the evaluation. That is, the product toner was extracted from a commercially available cyan cartridge, the inside was cleaned with an air blow, and then 200 g of the produced toner was filled. The product toner was removed from each of the magenta, yellow, and black stations, and magenta, yellow, and black cartridges with the toner remaining amount detection mechanism disabled were inserted.
-The fixing temperature of the fixing unit can be set manually.

<Hot offset resistance>
Under normal temperature and humidity environment (temperature 23 ° C, relative humidity 50%), the toner mass per unit area should be 0.70 mg / cm ² at the center of the tip of A4 plain paper for copiers (75 g / m ² ). An image having a large number of 10 mm × 10 mm solid images for density measurement adjusted to the above was output. A hot offset (a phenomenon in which a part of the fixing image adheres to the surface of the member of the fixing device and is further fixed on the recording material in the next round) occurs at the rear end of the recording material in the paper passing direction when passing through the fuser. The temperature of the surface of the fixing and heating part at that time was defined as the hot offset generation temperature, and the evaluation was made based on the following evaluation criteria. When outputting the image, the process speed was set to 100 mm / sec.
A: 200 ° C or higher B: 195 ° C or higher and lower than 200 ° C C: 190 ° C or higher and lower than 195 ° C D: 180 ° C or higher and lower than 190 ° C E: less than 180 ° C

<Fog in a high temperature and high humidity environment (temperature 32.5 ° C, relative humidity 80%)>
Under a high temperature and high humidity environment (temperature 32.5 ° C., relative humidity 80%), A4 color laser copy paper (manufactured by Canon, 80 g / m ² ) was used as the evaluation paper, and an image having a white background was output. The reflectance (%) of the white background portion of the output image was measured at 5 points each using a digital white photometer (TC-6D type, manufactured by Tokyo Denshoku Co., Ltd., using an amber filter), and the average value was obtained. Similarly, the reflectance (%) of the white background portion of the evaluation paper before output was measured, and the difference between the average values of the two reflectances (%) was taken as the image fog (%).
It was judged that the lower the image fog difference (%), the better the charge stability of the toner.
A: The image fog difference (%) before and after output is less than 0.5%.
B: The image fog difference (%) before and after output is 0.5% or more and less than 1.0%.
C: The image fog difference (%) before and after output is 1.0% or more and less than 1.5%.
D: The image fog difference (%) before and after output is 1.5% or more and less than 2.0%.
E: The image fog difference (%) before and after output is 2.0% or more.
Table 5 shows the results of the toner performance evaluation.

Table 6 shows the chain transfer agents used in Examples and Comparative Examples.

<Example 101>
To 1300.0 parts by mass of ion-exchanged water heated to a temperature of 60 ° C., 9.0 parts by mass of tricalcium phosphate was added, and a stirring speed was used using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). An aqueous medium was prepared by stirring at 15,000 rpm.
Further, the following binder resin materials were mixed with a propeller type stirring device at a stirring speed of 100 rpm to prepare a mixed solution.
・ Styrene 75.0 parts by mass ・ n-butyl acrylate 25.0 parts by mass ・ α-BnOSt (α-benzyloxystyrene) 2.0 parts by mass Next, in the above solution,
-Cyan colorant (CI Pigment Blue 15: 3) 6.5 parts by mass-Load electric control agent (Bontron E-88, manufactured by Orient Chemical Co., Ltd.) 0.5 parts by mass-Hydrocarbon wax (Tm = 78 ° C) ) Add 9.0 parts by mass, then heat the mixture to a temperature of 70 ° C., then stir with a TK homomixer at a stirring rate of 10,000 rpm to dissolve, disperse, and polymerize the monomer. The composition was adjusted.
Subsequently, the polymerizable monomer composition was put into the aqueous medium, and 7.0 parts by mass of perbutyl PV (10-hour half-life temperature 54.6 ° C. (manufactured by Nippon Yushi)) was added as a polymerization initiator. Using a TK homomixer at a temperature of 70 ° C., the mixture was stirred at a stirring speed of 15,000 rpm for 20 minutes to granulate.
While transferring to a propeller type stirrer and stirring at a stirring speed of 200 rpm, styrene and n-butyl acrylate, which are polymerizable monomers in the polymerizable monomer composition, are polymerized and reacted at a temperature of 85 ° C. for 5 hours to polymerize the toner. A slurry containing particles was produced. After completion of the polymerization reaction, the slurry was cooled. Hydrochloric acid was added to the cooled slurry to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve the calcium phosphate salt. Then, it was washed with 10 times the amount of water of the slurry, filtered and dried, and then the particle size was adjusted by classification to obtain toner particles.
Hydrophobic silica fine particles (primary particle diameter: 7 nm, BET specific surface area: 130 m) treated with dimethyl silicone oil in an amount of 20% by mass with respect to the silica fine particles as an external additive with respect to 100.0 parts by mass of the toner particles. ² / g) 1.5 parts by mass was mixed with Mitsui Henshell Mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at a stirring speed of 3000 rpm for 15 minutes to obtain toner 101. The evaluation results are shown in Table 8.

<Manufacturing of Examples 102 to 112>
Toners 102 to 112 were obtained by the same manufacturing method as that of toner 101 except that the raw materials and the number of copies added were changed as shown in Table 7. The evaluation results are shown in Table 8.

<Manufacturing of Comparative Example 101>
As shown in Table 7, the toner 113 was produced by the same manufacturing method as the toner 101 except that the raw materials and the number of added copies were changed, but the conversion rate did not increase and the toner 113 could not be obtained.
<Manufacturing of Comparative Examples 102 to 105>
As shown in Table 7, toners 114 to 117 were obtained by the same manufacturing method as the toner 101 except that the raw materials and the number of added copies were changed. The evaluation results are shown in Table 8.

[evaluation]
<Evaluation of polymerization conversion rate>
The polymerization conversion rate was calculated as described above and evaluated according to the following criteria.
(Evaluation criteria)
A: Conversion rate 99.0% or more B: Conversion rate 98.0% or more and less than 99.0% C: Conversion rate 96.0% or more and less than 98.0% D: Conversion rate less than 96.0%

<Evaluation of odor>
The odor of the toner was evaluated by the following method.
After filling 100 g of toner in a 250 cc resin bottle, sealing it with a lid, and leaving it for 2 days,
The presence or absence of odor at the time of opening was performed by sensory evaluation. The presence or absence of odor was evaluated by using 10 evaluators to evaluate the number of people who felt the odor.

<Low temperature fixing evaluation>
The low-temperature fixing evaluation was carried out by partially modifying a commercially available color laser printer [HP Color LaserJet 3525dn]. The modification was improved so that it would work even if only one color process cartridge was installed. In addition, the fuser was modified so that it could be changed to any temperature.
After removing the toner inside from the process cartridge for cyan toner mounted on this color laser printer and cleaning the inside with an air blow, each toner is introduced into the process cartridge and the toner is refilled. Was mounted on a color laser printer and a fixing rubbing test was carried out at a fixing device temperature of 160 ° C.
Under normal temperature and humidity environment (temperature 23 ° C, relative humidity 50%), adjust the amount of toner on the transfer material to 0.5 mg / cm ² , and make 3 vertical 10 mm x 10 mm images for concentration measurement. × 50 images with 9 points of 3 horizontal points were output.
The obtained 50th fixed image was rubbed 5 times with Sylbon paper loaded with a weight of 50 g / cm ² , and evaluated from the rate of decrease in image density after rubbing based on the following. A Macbeth reflection densitometer (manufactured by Macbeth) was used to measure the image density, and the relative density of the white background with a document density of 0.00 was measured with respect to the printout image. Was calculated and evaluated. As the transfer material, plain paper (LETTER size XEROX 4200 paper, manufactured by XEROX, 75 g / m ² ) was used.
(Evaluation criteria)
A: Image density reduction rate is less than 1.0% B: Image density reduction rate 1.0% or more and less than 3.0% C: Image density reduction rate 3.0% or more and less than 5.0% D : Image density reduction rate of 5.0% or more

Claims (6)

A toner having toner particles containing a binder resin and a wax.
The solubility parameter SP of the binder resin is _9.4 or more and 10.0 or less.
The binder resin contains a resin having a structure represented by the following formula (1) containing a keto group at the end of the main chain.
Equation (1) * -CO-R
(In the formula (1), R indicates a phenyl group or a derivative thereof. * Indicates a bond with the resin backbone.)
The solubility parameter _SW of the wax is 8.1 or more and 9.0 or less.
A toner characterized in that SP and _{SW satisfy} the equation (2).
Equation (2) | SP _{- SW} |> 0.5

The toner according to claim 1, wherein the wax has a molecular weight of 2500 or less. The toner according to claim 1 or 2, wherein the binder resin contains a vinyl-based resin. The toner according to any one of claims 1 to 3, wherein the content of the wax in the toner particles is 1% by mass or more and 30% by mass or less. The toner according to any one of claims 1 to 4, wherein the presence rate of the structure represented by the above formula (1) in the binder resin is 5% or more and 100% or less. The method for manufacturing a toner according to any one of claims 1 to 5.
Having a step of polymerizing a polymerizable monomer composition containing a vinyl ether type addition cleavage type chain transfer agent represented by the formula (3), a polymerizable monomer, and a polymerization initiator to obtain the binder resin. A method for producing a toner, which is characterized by.

(In the formula (3), R ₂ represents -COOR ₁ or a phenyl group or a derivative thereof, R ₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₃ represents a benzyl group or a carbon number of carbon atoms. Indicates a secondary or tertiary alkyl group of 4-8.)