JP2021047350A - toner - Google Patents

Abstract

To provide a toner which aims at reducing the size and increasing the life of a cartridge, offers improved coloring power, and yet is capable of forming good toner images without fogging and regulation faults.SOLUTION: A toner is provided, comprising toner particles containing a binder resin and a pigment, and an external additive A. Defining Aps as a proportion of area occupied by the pigment in a surface layer range from a surface to a depth of 0.1 μm of a toner particle, as observed in a cross-sectional observation of the toner using a transmission electron microscope, each toner particle has Aps in a range of 2.5 to 5.5%, inclusive. The external additive A consists of silica particles having a work function Ws of 5.70 eV or less. A coverage of the external additive A on a toner surface is in a range of 1.0 to 15.0%, inclusive.SELECTED DRAWING: None

Description

The present invention relates to toners used in image forming methods for visualizing electrophotographic and electrostatic charge images.

In recent years, methods such as electrophotographic methods for visualizing image information via electrostatic latent images have been used in various fields, and not only in terms of performance such as higher image quality and higher speed, but also in miniaturization of copiers, printers, and cartridges. Evolution in terms of usability such as longevity and longevity is also required.
As one means for reducing the size and life of the cartridge, a method of improving the coloring power of a single toner grain to reduce the amount of toner consumed during printing can be considered. Specifically, a method of increasing the amount of pigment contained in the toner, a method of mechanically improving the pigment dispersion in the toner (Patent Document 1), and a method of improving the pigment dispersion in the toner by using a pigment dispersant or the like (Patent Document 1). Patent Document 2) and the like have been reported.
On the other hand, when these methods are used, the amount of pigment present in the vicinity of the toner surface inevitably increases, so that the uniformity of chargeability on the toner surface is impaired, and image defects such as fog and poor regulation are likely to occur. I have a problem.

Japanese Patent No. 04665900 Japanese Unexamined Patent Publication No. 2015-10175

As described above, in the conventional technique, when the coloring power of the toner is improved, fog and improper regulation become trade-offs, and it has not been possible to achieve both at a high level.
That is, an object of the present invention is to provide a toner capable of forming a good toner image without fogging or improper regulation even if the toner has improved coloring power with the aim of reducing the size and extending the life of the cartridge. That is.

As a result of diligent studies to solve the above problems, the present inventors have found that the following toners can be used.
That is, the present invention is a toner particle containing a binder resin and a pigment, and a toner containing an external additive A.
In the cross-sectional observation of the toner using a transmission electron microscope, the toner particles have an Aps of 2 when the ratio of the area occupied by the pigment in the surface layer region from the surface of the toner particles to a depth of 0.1 μm is Aps. 5.5% or more and 5.5% or less,
The external additive A is a silica particle having a work function Ws of 5.70 eV or less.
The toner is characterized in that the coverage of the external additive A on the surface of the toner is 1.0% or more and 15.0% or less.

According to the present invention, it is possible to obtain a toner capable of forming a good toner image without fogging or improper regulation even if the toner has improved coloring power with the aim of reducing the size and extending the life of the cartridge.

Hereinafter, the present invention will be described in detail.

The toner of the present invention is a toner particle containing a binder resin and a pigment, and a toner containing an external additive A.
In the cross-sectional observation of the toner using a transmission electron microscope, the toner particles have an Aps of 2 when the ratio of the area occupied by the pigment in the surface layer region from the surface of the toner particles to a depth of 0.1 μm is Aps. 5.5% or more and 5.5% or less,
The external additive A is a silica particle having a work function Ws of 5.70 eV or less.
The coating ratio of the external additive A on the surface of the toner is 1.0% or more and 15.0% or less.

The toner particles used in the toner of the present invention are toner particles that have been subjected to techniques such as increasing the amount of pigment added and strengthening pigment dispersion in order to increase the coloring power.

Aps can be mentioned as one index for evaluating the presence state of the pigment in the toner particles. Aps is the ratio of the area occupied by the pigment in the surface layer region from the surface of the toner particles to a depth of 0.1 μm in the cross-sectional observation of the toner using a transmission electron microscope. It is essential that the toner particles of the present invention have an Aps of 2.5% or more and 5.5% or less. When Aps is within the above range, it is possible to obtain a toner in which the coloring power, which is the object of the present invention, and fog and improper regulation are compatible. When Aps is less than 2.5%, the pigment is agglomerated in the toner particles, or the pigment is unevenly distributed in the center of the toner particles, and a pigment-free shell layer is present on the toner surface. In any case, it tends to be inferior in coloring power. On the other hand, when Aps is larger than 5.5%, it means that the pigments are extremely unevenly distributed near the surface of the toner particles, or that the amount of pigments in the toner particles is excessive. Even in this case, the charge uniformity is remarkably inferior, so that it is difficult to make the charge uniform with an external additive as in the present invention.

A more preferable range of Aps is 3.2% or more and 5.0% or less.

The toner particles used in the toner of the present invention are known methods such as a pulverization method, an emulsion aggregation method, a dissolution suspension method, and a suspension polymerization method as long as the above-mentioned Aps is 2.5% or more and 5.5% or less. Can be manufactured using. Above all, it is preferable to produce by a production method including a step of granulating in an aqueous medium such as a suspension polymerization method and a dissolution suspension polymerization method because Aps control is easy.

The toner particles of the present invention produced by the suspension polymerization method are produced, for example, as follows. A polymerizable monomer composition is prepared by mixing a colorant composition, a polymerizable monomer, a wax, a polymerization initiator and the like. Next, the polymerizable monomer composition is dispersed in an aqueous medium to granulate the particles of the polymerizable monomer composition. Then, the polymerizable monomer in the particles of the polymerizable monomer composition is polymerized in an aqueous medium to obtain toner particles.

As the polymerizable monomer, a vinyl-based polymerizable monomer capable of radical polymerization is used. As the vinyl-based polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Examples of the monofunctional polymerizable monomer include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p. Styrene derivatives such as −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 Acrylic-based polymerizable properties such as -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 2-benzoyloxyethyl acrylate. Monomer; 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, Methacrylic polymerizable monomers such as n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl butyrate, benzoate Vinyl esters such as vinyl acid acid and vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone can be mentioned.

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- (acryloxy diethoxy) phenyl) propane, trimethylpropan triacrylate, tetramethylolmethanetetraacrylate, 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- (methacryloxy diethoxy) phenyl) propane, 2,2'-bis (4- (methacryloxy polyethoxy) phenyl) propane, trimethyl propanetrimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalin, divinyl ether, etc. Can be mentioned.

The monofunctional polymerizable monomer is used alone, in combination of two or more, or in combination with the polyfunctional polymerizable monomer. The polyfunctional polymerizable monomer can also be used as a cross-linking agent.

The polymerizable monomer composition in the above step is prepared by mixing a dispersion liquid in which the above-mentioned colorant composition is dispersed in a first polymerizable monomer with a second polymerizable monomer. Is preferable. That is, the pigment is better dispersed by sufficiently dispersing the colorant composition with the first polymerizable monomer and then mixing it with the second polymerizable monomer together with other toner materials. Can be present in the toner particles in the state.

As the polymerization initiator used in the polymerization of the polymerizable monomer, an oil-soluble initiator and / or a water-soluble initiator is used. Examples of the oil-soluble initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), and 2 , 2'-Azobis-4-methoxy-2,4-dimethylvaleronitrile and other pigment dispersants; acetylcyclohexylsulfonyl peroxide, diisopropylperoxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide , Acetyl peroxide, t-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, t-butyl peroxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl hydroperoxide. , Di-t-butyl peroxide, cumene hydroperoxide and other peroxide-based initiators.

Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) hydrochloride, and 2,2'-azobis (2-aminodinopropane) hydrochloric acid. Examples thereof include salts, azobis (isobutylamidine) hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.

Further, in order to control the degree of polymerization of the polymerizable monomer, a chain transfer agent, a polymerization inhibitor and the like can be further added and used.

The concentration of the polymerization initiator is preferably in the range of 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer, and more preferably 0.1 parts by mass or more and 10 parts by mass or less. If it is in the range of. The type of the above-mentioned polymerizable initiator is slightly different depending on the polymerization method, but it is used alone or in combination with reference to the 10-hour half temperature.

Further, in the present invention, a cross-linking agent can be used at the time of synthesizing the vinyl polymer in order to enhance the stress resistance of the toner particles and control the molecular weight of the particle constituent molecules.

As the cross-linking agent, a compound having two or more polymerizable double bonds is used. Specifically, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylic rate, and dimethacrylate such as 1,3-butanediol dimethacrylate. Examples include carboxylic acid esters having two double bonds; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.

In terms of toner fixability and offset resistance, these cross-linking agents preferably have a range of 0.05 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass, based on 100 parts by mass of the monomer. It is preferable to use in the range of mass part or more and 5 parts by mass or less.

The polymerizable monomer and the cross-linking agent are used alone or in an appropriate mixture so that the theoretical glass transition temperature (Tg) is in the range of 40 ° C. or higher and 75 ° C. or lower. When the theoretical glass transition temperature is 40 ° C or higher, problems are unlikely to occur in terms of toner storage stability and stress resistance, while when it is 75 ° C or lower, transparency and low-temperature fixability in the case of full-color image formation of toner. Does not decrease.

The aqueous medium used in the suspension polymerization method is preferably an aqueous medium containing a dispersion stabilizer. As the dispersion stabilizer, known inorganic and organic dispersion stabilizers can be used. Examples of the inorganic dispersion stabilizer include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, and calcium sulfate. , Barium sulfate, bentonite, silica, alumina and the like.

Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like. It is also possible to use nonionic, anionic and cationic surfactants. 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 can be mentioned.

Among the above dispersion stabilizers, in the present invention, it is preferable to use a poorly water-soluble inorganic dispersion stabilizer that is soluble in acid. Further, in the present invention, when a poorly water-soluble inorganic dispersion stabilizer is used to prepare an aqueous dispersion medium, these dispersion stabilizers are 0.2 parts by mass with respect to 100 parts by mass of the polymerizable monomer. It is preferable to use at a ratio so as to be in the range of 2.0 parts by mass or less. This is because the use in a ratio within such a range improves the droplet stability of the polymerizable monomer composition in an aqueous medium. Further, in the present invention, it is preferable to prepare an aqueous medium using water in the range of 300 parts by mass or more and 3000 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer composition.

In the present invention, when preparing an aqueous medium in which the poorly water-soluble inorganic dispersion stabilizer is dispersed, a commercially available dispersion stabilizer may be used as it is for dispersion. However, in order to obtain dispersion stabilizer particles having a fine and uniform particle size, it is preferable to prepare the above-mentioned poorly water-soluble inorganic dispersion stabilizer by producing it under high-speed stirring in water. For example, when calcium phosphate is used as a dispersion stabilizer, a preferable dispersion stabilizer can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring to form fine particles of calcium phosphate.

As the colorant for the toner particles of the present invention, the following black, yellow, magenta and cyan pigments can be used. In addition, a dye can be used together if necessary.

As the black colorant, a known black colorant can be used, but carbon black is particularly preferable.

The carbon black is not particularly limited, and for example, carbon black obtained by a production method such as a thermal method, an acetylene method, a channel method, a furnace method, or a lamp black method can be used.

The average primary particle size of carbon black used in the present invention is not particularly limited, but it is preferable that the average primary particle size is 14 nm or more and 80 nm or less. When the average primary particle size is 14 nm or more, the toner does not exhibit redness and is preferable as black for forming a full-color image. When the average primary particle size of carbon black is 80 nm or less, it is preferable that the carbon black is well dispersed and the coloring power is not too low.

The average primary particle size of carbon black can be measured by taking an enlarged photograph with a scanning electron microscope.

The carbon black may be used alone or in combination of two or more.

These may be crude pigments, or may be prepared pigment compositions as long as they do not significantly impair the effects of the present invention.

As the yellow colorant, a known yellow colorant can be used.

As the pigment-based yellow colorant, compounds typified by condensed polycyclic pigments, isoindolinone compounds, anthraquinone compounds, azometal complex methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110 , 111, 117, 123, 128, 129, 138, 139, 147, 148, 150, 155, 166, 168, 169, 177, 179, 180, 181, 183, 185, 191: 1, 191, 192, 193. 199 can be mentioned.

As the magenta colorant, a known magenta colorant can be used.

As the magenta colorant, condensed polycyclic pigments, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds are used. 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 Violet19 can be mentioned.

As the cyan colorant, a phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound are used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

The colorant can be used alone or in a mixed state and further in a solid solution state.

The amount of the pigment added is preferably such that the mass% of the pigment in the toner particles is 4.8% by mass or more and the Aps is 5.5% or less from the viewpoint of coloring power.

As a method for dispersing the pigment in the toner, a known pigment dispersion method can be used, and by using these methods alone or in combination, Aps can be controlled within the above range.

Specifically, a method of increasing the physical strength of the dispersion in the step of dispersing the above-mentioned colorant composition in the first polymerizable monomer, a method of adding a pigment dispersant to the toner constituent material, and the like are used. is there.

Above all, a method using a pigment dispersant is preferable from the viewpoint of improving the coloring power and controlling Aps. As the pigment dispersant that can be used, a widely known pigment dispersant can be used, and a pigment dispersant having a polymer component and an adsorption component that adsorbs to the pigment, and the adsorption component has a partial structure represented by the following general formula (1) It is more preferable from the viewpoint of adsorption efficiency to the pigment and suppression of pigment reaggregation in the toner manufacturing process.

［前記一般式（１）中、Ｒ₄、Ｒ₅及びＡｒのいずれかは、単結合又は連結基を介してポリマー成分が結合する構造を有する。
Ｒ₄は、アルキル基、フェニル基、ＯＲ₈基又はＮＲ₉Ｒ₁₀基を表し、Ｒ₈〜Ｒ₁₀は、それぞれ独立して、水素原子、アルキル基、フェニル基又はアラルキル基を表す。Ｒ₄がポリマー成分と結合する場合、単結合又は連結基を介して結合し、Ｒ₄に結合する連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ₆−及び−ＮＨＣＨ（ＣＨ₂ＯＨ）−からなる群より選ばれる二価の連結基であり、Ｒ₆は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。
Ｒ₅は、アルキル基、フェニル基、ＯＲ₄₂基又はＮＲ₄₃Ｒ₄₄基を表し、Ｒ₄₂〜Ｒ₄₄は、それぞれ独立して、水素原子、アルキル基、フェニル基又はアラルキル基を表す。Ｒ₅がポリマー成分と結合する場合、連結基を介して結合し、Ｒ₅に結合する連結基は、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ₁₁−、−ＮＨＣＯＣ（ＣＨ₃）₂−及び−ＮＨＣＨ（ＣＨ₂ＯＨ）−からなる群より選ばれる二価の連結基であり、Ｒ₁₁は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。
Ａｒは、アリール基を表し、Ａｒがポリマー成分と結合する場合、単結合又は連結基を介して結合し、Ａｒに結合する連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ₆−及び−ＮＨＣＨ（ＣＨ₂ＯＨ）−からなる群より選ばれる二価の連結基であり、Ｒ₆は、水素原子、アルキル基、フェニル基又はアラルキル基を表す。
前記単結合又は連結基が、Ｒ₄、Ｒ₅、又はＡｒに結合する場合は、Ｒ₄、Ｒ₅、又はＡｒの水素原子と置換して結合する。］

[In the general formula (1), any of R ₄ , R ₅ and Ar has a structure in which a polymer component is bonded via a single bond or a linking group.
R ₄ represents an alkyl group, a phenyl group, an OR ₈ group or an NR ₉ R ₁₀ group, and R _{8 to} R ₁₀ independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R ₄ is bonded to the polymer component, it is bonded via a single bond or a linking group, and the linking group bonded to R ₄ is an amide group, an ester group, a urethane group, a urea group, an alkylene group, a phenylene group, -O. It is a divalent linking group selected from the group consisting of −, −NR ₆ − and −NHCH (CH _{2 OH) −, and R 6} represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
R ₅ represents an alkyl group, a phenyl group, an OR ₄₂ group or an NR ₄₃ R ₄₄ group, and R _{42 to} R ₄₄ independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. If R ₅ is bound to the polymer component, bonded through a linking group, the linking group attached to R ₅ is an alkylene group, a phenylene _{group, -O -, - NR 11 -} , - NHCOC (CH 3) 2 - It is a divalent linking group selected from the group consisting of −NHCH (CH _{2 OH) −, and R 11} represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
Ar represents an aryl group, and when Ar is bonded to a polymer component, it is bonded via a single bond or a linking group, and the linking group bonded to Ar is an amide group, an ester group, a urethane group, a urea group, or an alkylene group. , A phenylene group, a divalent linking group selected from the group consisting of _{−O−, −NR 6−} and −NHCH (CH _{2 OH) −, where R 6} is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. Represents.
The single bond or a linking group, R _4, R _5, or when attached to Ar is, R _4, R _5, or bonded substituted with Ar hydrogen atoms. ]

The Clark Evans Index (CEI) is an index for evaluating the pigment dispersion state in the toner particles. CEI is when the average of the distances between the closest centers of gravity of all the pigment particles is r and the expected value of the distances between the closest centers of gravity of the pigment particles having a Poisson distribution is E (r) in the cross-sectional observation of the toner particles. , CEI is defined as CEI = r / E (r). When the CEI is less than 1, it is a concentrated distribution (the degree of aggregation is large), when the CEI is equal to 1, it is a Poisson distribution (random distribution), and when the CEI is larger than 1, it is a regular distribution (distributed at regular intervals). Become. The limit value of CEI is about 2.1. The toner particles of the present invention preferably have a CEI of 0.70 or more and 1.30 or less. When the CEI is in the above range, a toner having good coloring power can be obtained.

Further, as another index for evaluating the pigment dispersion state in the toner particles, the dispersed pigment particle size in the toner particles can be mentioned. In the cross-sectional observation of the toner particles, the value obtained by multiplying the observed circle-equivalent diameter (mean value) of the pigment particles by 4 / π is the dispersed pigment particle size. The dispersed pigment particle size is calculated not only for the primary particles but also for agglomerated pigment lumps as one particle size unit. Therefore, the better the dispersion in the primary particles, the lower the numerical value of the dispersed pigment particle size. The toner particles of the present invention preferably have a dispersed pigment particle size of 30 nm or more and 130 nm or less. When the dispersed pigment particle size is in the above range, a toner having good coloring power can be obtained.

The toner particles of the present invention preferably contain one or more waxes. The total amount of wax contained in the toner is preferably 2.5 parts by mass or more and 25.0 parts by mass or less in 100 parts by mass of the toner particles. The total amount of wax contained in the toner is more preferably 4.0 parts by mass or more and 20 parts by mass or less, and further preferably 6.0 parts by mass or more and 18.0 parts by mass or less.

Examples of the wax include the following. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystallin wax, Fishertropush wax, paraffin wax; oxides of aliphatic hydrocarbon waxes such as polyethylene oxide wax, or block copolymers thereof. Waxes mainly composed of fatty acid esters such as carnauba wax and montanic acid ester wax, and deoxidized fatty acid esters such as carnauba wax partially or wholly deoxidized; palmitic acid, stearic acid, montanic acid, etc. Saturated linear fatty acids; unsaturated fatty acids such as brush diic acid, eleostearic acid, parinaphosphoric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, ceryl alcohol, melicyl alcohol; sorbitol Polyhydric alcohols such as; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid amide, etc. Saturated fatty acid bisamides; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N'diorail adipic acid amide, N, N'diorail sebacic acid amide; m-xylene bisstea Aromatic bisamides such as acid amides, N, N'dystearyl isophthalic acid amides; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally referred to as metal soap); Waxes obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylic acid; a partial esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; obtained by hydrogenation of vegetable fats and oils, etc. Examples thereof include methyl ester compounds having a hydroxyl group.

For the toner particles of the present invention, a charge control agent may be used in order to keep the chargeability of the toner stable regardless of the environment.

Examples of the load-electric charge control agent include the following. Monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acid-based metal compounds, aromatic oxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, Examples thereof include phenol derivatives such as anhydrides, esters and bisphenols, urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthoic acid-based compounds, boron compounds, quaternary ammonium salts, calix arene, and resin-based charge control agents.

Examples of the positively charged charge control agent include the following. Nigrosine modified products with niglosin and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and their analogs. Onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and their lake pigments (as lake agents, phosphoric acid, phosphoric acid, phosphorus tungsten molybdic acid, tannic acid, lauric acid, galvanic acid) Acids, ferricyanides, ferrocyanides, etc.); Metal salts of higher fatty acids; Diorganosin oxides such as dibutyltin oxide, dioctylstinoxide, dicyclohexylstinoxide; Diorganosins such as dibutyltinborate, dioctylstinborate, dicyclohexylstinborate Borates; Resin-based charge control agents can be mentioned.

These can be used alone or in combination of two or more.

Among them, as the charge control agent other than the resin-based charge control agent, a metal-containing salicylic acid-based compound is preferable, and a metal containing aluminum or zirconium is particularly preferable. A particularly preferred control agent is an aluminum salicylate compound.

As the resin-based charge control agent, it is preferable to use a polymer or copolymer having a sulfonic acid group, a sulfonic acid base or a sulfonic acid ester group, a salicylic acid moiety, and a benzoic acid moiety.

The preferable blending amount of the charge control agent is 0.01 part by mass or more and 20.00 parts by mass or less, more preferably 0.05 part by mass or more and 10.00 parts by mass or less with respect to 100.00 parts by mass of the polymerizable monomer. Is.

In the toner particles of the present invention, a resin may be added for various purposes in addition to the above-mentioned polymerizable monomer. Examples of the resin that can be added are described below, but other resins may be used. For example, polyester resin, polycarbonate resin, phenol resin, epoxy resin, polyamide resin, cellulose resin and the like can be mentioned.

The toner of the present invention is a toner obtained by externally adding an external additive A to the toner particles.

The external additive A used in the toner of the present invention is essential to be silica particles having a work function Ws controlled to 5.70 eV or less. By externally adding the silica particles to the toner particles whose Aps are controlled, it is possible to achieve both the coloring power and the fog and poor regulation, which are the objects of the present invention.

Although the detailed reason why such an effect can be obtained with the toner obtained from the present invention is not clear, the present inventors consider as follows.

Generally, the work function of the pigment used for the toner is smaller than the work function of the binder resin preferably used for the toner such as polyester and styrene acrylic resin. Therefore, in the case of triboelectric charging, the portion where the pigment is present near the surface is more positively charged, and the portion where the pigment is not present near the surface is more negatively charged, resulting in uneven charging in one toner particle. .. Therefore, as described above, the toner with high control of Aps and aiming at high coloring power tends to be inferior in fog and improper regulation.

According to the present invention, even with a toner aiming at high coloring power by controlling such Aps at a high level, it is possible to make uneven charging uniform by externally adding silica particles having a defined work function. Is. The silica particles whose work function Ws is controlled to be as low as 5.70 eV or less have an ability to transfer the acquired charge to another substance when it is triboelectrically charged. The toner in which the silica particles are externally attached to the toner particles having a high Aps causes an electric charge to be transferred from the silica particles to a pigment in the vicinity of the surface in the vicinity of the silica particles. The silica particles that have lost their charge as a result are triboelectrically charged again. After that, the electric charge is transferred from the recharged silica particles to the pigment again. Since this charge transfer process is repeated until the unevenness of charge in the toner particles is made uniform, the authors think that it is possible to obtain a toner capable of forming a good toner image without fogging or improper regulation. ..

When the work function Ws of the external agent A exceeds 5.70 eV, the electric charge is not transferred from the external agent A to the pigment, the unevenness of the electric charge is not made uniform, and the effect of the present invention is exhibited. do not do.

A more preferable range of the work function Ws of the external preparation A is 5.35 eV or more and 5.70 eV or less. When the work function is in the above range, the amount of electric charge held by the external additive A is finally increased, so that image defects such as fog are less likely to occur.

Further, when the work function of the pigment used in the toner of the present invention is Wp, the difference between the work function of the pigment and the external agent A Ws-Wp is 0 eV <Ws-Wp <1.0 eV, which is more regulated. It is preferable from the viewpoint that it can be suppressed. When 0 eV <Ws-Wp, the transfer of electric charge from the external additive A to the pigment is not excessive, and the overcharge of the toner can be suppressed. When Ws-Wp <1.0 eV, the backflow of electric charge from the pigment to the external preparation A can be suppressed, and the unevenness of electric charge is further improved.

In order to obtain the effect of the present invention, it is essential that the coverage of the external additive A on the toner surface is 1.0% or more and 15.0% or less. When the coverage is less than 1.0%, the amount of the external additive A is small, so that the probability of being close to the pigment is reduced, and uneven charging cannot be made uniform. If the coverage is greater than 15.0%, fixation inhibition by the external additive will occur.

Examples of the silica particles serving as the external additive A include solgel silica particles, aqueous colloidal silica particles, alcoholic silica particles, fumed silica particles obtained by the vapor phase method, molten silica particles, and explosive silica particles. Among them, sol-gel silica particles are preferable because of the ease of controlling the work function. The work function of the sol-gel silica particles can be adjusted by controlling the particle size of the silica particles and controlling the amount of surface functional groups.

The surface of the external additive A is preferably hydrophobized. The hydrophobizing treatment is performed, for example, by immersing inorganic particles in a hydrophobizing agent. The hydrophobizing agent is not particularly limited, and examples thereof include known organic silicon compounds having an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.). Examples thereof include silane coupling agents of silane compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylchlorosilane and trimethylmethoxysilane; hexamethyldisilazane; tetramethyldisilazane and the like). Among them, hexamethyldisilazane is preferable. The work function of the silica particles can also be controlled by the treatment amount of this hydrophobizing agent.

The degree of hydrophobization of the external preparation A is preferably 40% or more and 65% or less. When the degree of hydrophobicity of the external additive A is within the above range, it is possible to achieve both suppression of poor regulation and suppression of fog at a higher level.

The average circle equivalent diameter of the external additive A is preferably 10 nm or more and 80 nm or less. When the average circle equivalent diameter of the external additive A is 80 nm or less, the adhered state of the external additive A on the toner surface becomes uniform, and the effect of the present invention can be obtained more efficiently.

As a method of externally adding the external additive A to the toner particles, a widely known method can be used.

Further, apart from the external additive A, another external additive may be externally added as long as the present invention is not impaired. Examples of the external additive that can be used include metal oxides such as aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, and zinc oxide; nitrides such as silicon nitride; carbides such as silicon carbide. Carbides; inorganic metal salts such as calcium sulfate, barium sulfate and calcium carbonate; fatty acid metal salts such as zinc stearate and calcium stearate; silica and the like.

The weight average particle size (D4) of the toner of the present invention is preferably 4.0 μm or more and 9.0 μm or less. More preferably, it is 5.0 μm or more and 7.5 μm or less.

When the weight average particle size of the toner is 4.0 μm or more, the fluidity of the toner is good, and it is difficult to cause adverse effects such as fog, scattering, and thin image density. In addition, the cleanability of the transfer residual toner remaining on the photoconductor and the intermediate transfer body is improved, and the photoconductor, the intermediate transfer body, and the charging member are less likely to be contaminated. Further, when it is 9.0 μm or less, it becomes difficult to cause deterioration of fine line reproducibility of fine characters and the like and deterioration of image scattering, and it is possible to provide a high-quality image which is desired these days.

Hereinafter, methods for measuring various physical properties according to the present invention will be described.

<Measurement of Aps>
The pigment distribution state in the toner is evaluated by observing the cross section of the toner particles with a transmission electron microscope, calculating Aps from the cross-sectional area of the domain formed by the pigment, and using the average value of 100 arbitrarily selected toners.

Specifically, the toner is embedded in a visible light curable embedding resin (D-800, manufactured by Nissin EM), cut to a thickness of 60 nm by an ultrasonic ultramicrotome (EM5, manufactured by Leica), and a transmission electron electron is used. Observation is performed with a microscope (H7500, manufactured by Hitachi, Ltd.) at an acceleration voltage of 120 kV. Select 100 toner cross sections to be observed within ± 2.0 μm from the weight average particle size and take a picture. Image processing software (Photoshop 5.0, manufactured by Adobe) is used for the obtained image to clarify the distinction between the pigment domain and the binder resin region. In detail, the pigment domains can be distinguished as follows. The captured TEM image is binarized according to the brightness with image processing software. At this time, the toner pigment and the photocurable resin D800 are bright areas, and the areas other than the toner pigment are dark areas. The outline of the toner can be distinguished by the brightness of the toner and the light and darkness of the photocurable resin.

Masking is performed on the cross section of the toner particles, leaving the surface layer region from the surface of the toner particles (outline of the cross section) to a depth of 0.1 μm (including the boundary of 0.1 μm). Specifically, a line is drawn from the center of gravity of the toner particle cross section with respect to a point on the contour of the toner particle cross section. On the line, a position 0.1 μm in the direction of the center of gravity is specified from the contour. Then, this operation is performed for one round of the contour of the toner particle cross section to clearly indicate the surface layer region from the contour of the toner particle cross section to 0.1 μm. The occupied area percentage of the pigment domain in the area of the obtained surface layer region was calculated and used as Aps.

<Measurement of Clark Evans Index (CEI)>
The average r of the distances between the closest centers of gravity of all the pigment particles was calculated from the images analyzed by the above-mentioned measurement method of Aps. Next, from r, the expected value E (r) of the distance between the closest centers of gravity of the pigment particles in the case of Poisson distribution was calculated. The CEI was calculated from the formula CEI = r / E (r).

<Measurement of dispersed pigment particle size>
The average value of the circle-equivalent diameters of the pigments was calculated from the images analyzed by the above-mentioned Aps measurement method. The dispersed pigment particle size was calculated by multiplying this value by 4 / π.

<Measurement of the equivalent circle diameter of the external additive>
The primary particles of the silica particles were calculated as follows.

Toner is photographed using a Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation). Subsequently, the captured toner image is taken into image processing software (Photoshop 5.0, manufactured by Adobe), the area of each particle is measured by image analysis of the primary particles, and the equivalent circle diameter is calculated from this area value. This circle-equivalent diameter was calculated for 100 silica particles, and the average thereof was taken as the average circle-equivalent diameter.

<Measurement of coverage>
The coverage of the external additive A on the surface of the toner particles was calculated as follows.

First, the toner is photographed using a Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation). Subsequently, the photographed toner surface image was obtained from the image analysis software ImAge-Pro Plus ver. Analysis was performed using 5.0 (Nippon Roper Co., Ltd.), and the coverage was calculated.

The image capturing conditions of S-4800 are as follows.

(1) Sample preparation A thin layer of conductive paste is applied to a sample table (aluminum sample table 15 mm x 6 mm), and toner is sprayed onto the sample table. Further air blow to remove excess toner from the sample table and allow it to dry sufficiently. Set the sample table in the sample holder and adjust the sample table height to 36 mm with the sample height gauge.

(2) S-4800 Observation condition setting When measuring the adhesion rate, elemental analysis is performed in advance by the above-mentioned energy dispersive X-ray analysis (EDS), and the measurement is performed after distinguishing the external additive A on the surface of the toner particles. ..

Inject liquid nitrogen into the anti-contamination trap attached to the housing of S-4800 until it overflows, and leave it for 30 minutes. Start up "PC-SEM" of S-4800 and perform flushing (cleaning of FE chip which is an electron source). Click the acceleration voltage display part of the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Confirm that the flushing intensity is 2, and execute. Confirm that the emission current due to flushing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position.

Click the acceleration voltage display to open the HV setting dialog, and set the acceleration voltage to [1.1 kV] and the emission current to [20 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select [Up (U)] and [+ BSE] for the SE detector, and select [+ BSE] in the selection box to the right of [+ BSE]. L. A. 100] is selected to set the mode for observing with a reflected electron image. Similarly, in the [Basic] tab of the operation panel, set the probe current of the electro-optical system condition block to [NormAl], the focus mode to [UHR], and the WD to [4.5 mm]. Press the [ON] button on the acceleration voltage display of the control panel to apply the acceleration voltage.

(3) Calculation of Number of Toners Average Particle Size (D1) Drag the inside of the magnification display section of the control panel to set the magnification to 5000 (5k) times. Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the focus is adjusted to some extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles. Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and focus with autofocus. This operation is repeated twice more to focus.

Then, the particle size of 300 toners is measured to obtain the number average particle size (D1) of the toners. The particle size of each particle is the maximum diameter when the toner particles are observed.

(4) Focus adjustment For particles with an average particle size of toner (D1) of ± 0.1 μm obtained in (3), the magnification is displayed on the control panel with the midpoint of the maximum diameter aligned with the center of the measurement screen. Drag the inside of the part to set the magnification to 10000 (10k) times.

Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the focus is adjusted to some extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles.

Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and focus with autofocus. After that, the magnification is set to 50,000 (50k) times, the focus is adjusted using the focus knob and the STIGMA / ALIGNMENT knob in the same manner as above, and the focus is adjusted again by autofocus. Repeat this operation again to focus.

Here, if the inclination angle of the observation surface is large, the measurement accuracy of the coverage tends to be low, so by selecting the one that focuses on the entire observation surface at the same time when adjusting the focus, select the one with the least inclination of the surface. And analyze.

(5) Image saving Perform brightness adjustment in ABC mode, take a picture with a size of 640 x 480 pixels, and save it. The following analysis is performed using this image file. One photograph is taken for each toner to obtain an image of 25 toner particles.

(6) Image analysis Using the following analysis software, the fixation rate is calculated by binarizing the image obtained by the above method. At this time, the above screen is divided into 12 squares and each is analyzed.

Image analysis software ImAge-Pro Plus ver. The analysis conditions for 5.0 are as follows. However, when the average particle size of the added external additives is unknown, the measurement target is excluded according to the particle size as shown below. If silica particles having a particle size of less than 10 nm and more than 40 nm are contained in the divided compartment, the adhesion rate is not calculated in that compartment.

Select "Measurement"-"Count / Size"-"Options" on the toolbar and set the binarization conditions. Select 8 concatenations in the object extraction options and set the smoothing to 0. In addition, pre-selection, filling holes, and inclusive lines are not selected, and "exclude borders" is set to "none". Select "measurement items" from the "measurement" in the toolbar, type 2-10 ⁷ to screen the range of the area.

The sticking rate is calculated by enclosing a square area. At this time, the area (C) of the area is set to 24,000 to 26,000 pixels. "Treatment"-Automatically binarizes by binarization, and calculates the total area (D) of the area without the external additive A.

From the total area D of the area C of the square area and the area without the external agent A, the area where the external agent A exists can be obtained by the following formula.
Coverage with external additive A (%) = 100- (D / C x 100)

The arithmetic mean value of all the obtained data was used as the coverage ratio.

<Separation of external additive A>
When the external additive A separated from the surface of the toner is used as the measurement sample, the external additive A is separated from the toner according to the following procedure.

160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved while boiling to prepare a sucrose concentrate. In a centrifuge tube, 31 g of the sucrose concentrate and 6 mL of Contaminone N (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder) , Wako Pure Chemical Industries, Ltd.) to prepare a dispersion. 1 g of toner is added to this dispersion, and the toner lumps are loosened with a spatula or the like.

The centrifuge tube is set in "KM ShAker" (model: VSX) manufactured by Iwaki Sangyo Co., Ltd., and shaken for 20 minutes under the condition of 350 reciprocations per minute. After shaking, the solution is replaced with a glass tube for a swing rotor (50 mL), and centrifugation is performed with a centrifuge at 3500 rpm for 30 minutes.

In the glass tube after centrifugation, the toner is present in the uppermost layer, and the external additive is present in the aqueous solution side of the lower layer. The aqueous solution of the lower layer is collected and centrifuged to separate sucrose and the external additive. If necessary, centrifuge is repeated, and after sufficient separation, the dispersion is dried and the external additive is collected.

From this collected external additive, the external additive A and the external additive B are selected by using a centrifugation method. When an external additive other than the external additive A is added, the mixture is similarly sorted by the centrifugation method.

If the external preparation A before the external addition is available, various physical properties can be measured and calculated by the following method with the external addition alone.

<Measurement of work function>
The work functions of the pigment and the external additive A were measured using a photoelectron spectrometer (AC-2 manufactured by RIKEN Keiki Co., Ltd.). The sample is uniformly spread and placed on the device measurement holder, a deuterium lamp is used as a UV light source for exciting the sample, and the irradiation light amount is set to 500 mW. In addition, monochromatic light is selected by a spectroscope, and the sample is irradiated with a spot size of 4 mm square, an energy scanning range of 3.4 to 6.2 eV, and a measurement time of 10 sec / 1 point. Then, the photoelectrons emitted from the sample surface are detected, and the work function meter software is used to perform arithmetic processing. The work function is measured with a repetition accuracy (standard deviation) of 0.02 eV.

<Measurement of hydrophobicity>
The degree of hydrophobization of the external additive A was measured by a powder wettability tester "WET-100P" (manufactured by Reska).

A fluororesin-coated spindle-shaped rotor having a length of 25 mm and a maximum body diameter of 8 mm was placed in a cylindrical glass container having a diameter of 5 cm and a thickness of 1.75 mm. After putting 70 ml of a hydrous methanol solution consisting of 50% by volume of methanol and 50% by volume of water in the cylindrical glass container, 0.5 g of metal titanate fine particles were added and set in a powder wettability tester. Methanol was added to the liquid at a rate of 0.8 mL / min through the powder wettability tester while stirring at a rotation speed of 3.3 times / sec using a magnetic stirrer. The transmittance was measured with light having a wavelength of 780 nm, and the value represented by the volume percentage of methanol (= (volume of methanol / volume of mixture) × 100) when the transmittance reached 50% was defined as the degree of hydrophobicity. .. The volume ratio of initial methanol to water is adjusted as appropriate according to the degree of hydrophobization of the sample.

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited by the following examples.

<Production example of pigment dispersant 1>
(Production example of polymer component (P-1) of pigment dispersant)
100 parts by mass of propylene glycol monomethyl ether is heated while replacing with nitrogen and refluxed at a liquid temperature of 120 ° C. or higher, and 156 parts by mass of styrene, 7.2 parts by mass of acrylic acid, 9.6 parts by mass of butyl acrylate, and acrylic acid are added thereto. 48.7 parts by mass of stearyl (styrene / acrylic acid / butyl acrylate / stearyl acrylate = 60/4/30/6 [mol ratio]), and tert-butylperoxybenzoate [organic peroxide-based polymerization initiator, A mixture of 1.25 parts by mass of [Purbutyl Z] manufactured by Nichiyu Co., Ltd. was added dropwise over 3 hours. After completion of the dropping, the solution is stirred for 3 hours, distilled at atmospheric pressure while raising the liquid temperature to 170 ° C., and after the liquid temperature reaches 170 ° C., the solution is distilled at 1 hPA under reduced pressure for 1 hour to remove the solvent, and the resin solid is removed. Obtained. The solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was filtered off to obtain a polymer component (P-1).

(Production example of pigment adsorbing component (B-1))
Subsequently, the pigment adsorbing component (B-1) described in the general formula (1) was produced according to the following scheme.

First, 3.11 parts by mass of 4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 30 parts by mass of chloroform, and the mixture was ice-cooled to 10 ° C. or lower to add 1.89 parts by mass of diketene (manufactured by Tokyo Chemical Industry Co., Ltd.). added. Then, the mixture was stirred at 65 ° C. for 2 hours. After completion of the reaction, the mixture was extracted with chloroform and concentrated to obtain compound (27).

Next, 40.00 parts by mass of methanol and 5.29 parts by mass of concentrated hydrochloric acid were added to 4.25 parts by mass of dimethyl 2-aminoterephthalate (manufactured by Merck Group), and the mixture was ice-cooled to 10 ° C. or lower. To this solution, 2.10 parts by mass of sodium nitrite dissolved in 6.00 parts by mass of water was added, and the mixture was reacted at the same temperature for 1 hour. Then, 0.990 parts by mass of sulfamic acid was added, and the mixture was further stirred for 20 minutes (diazonium salt solution). 4.51 parts by mass of compound (27) was added to 70.00 parts by mass of methanol, ice-cooled to 10 ° C. or lower, and the diazonium salt solution was added. Then, 5.83 parts by mass of sodium acetate dissolved in 7.00 parts by mass of water was added, and the mixture was reacted at 10 ° C. or lower for 2 hours. After completion of the reaction, 300.00 parts by mass of water was added and the mixture was stirred for 30 minutes, and then the solid was separated by filtration and purified by the recrystallization method from N, N-dimethylformamide to obtain compound (28). Next, 8.58 parts by mass of compound (28) and 0.40 parts by mass of palladium-activated carbon (palladium 5%) were added to 150.00 parts by mass of N, N-dimethylformamide under a hydrogen gas atmosphere (reaction pressure). 0.1 to 0.4 MPa), stirred at 40 ° C. for 3 hours. After completion of the reaction, the solution was filtered off and concentrated to give compound (B-1).

(Production Example of Pigment Dispersant 1)
Next, the amino group of the compound (B-1) having an azo skeleton partial structure and the carboxyl group of the polymer component (P-1) were bonded by amidation to produce a pigment dispersant 1 according to the following scheme.

［上記構造式中で、「ｃｏ」とは、共重合体を構成する各単量体単位の配列が無秩序であることを示す記号である。］

[In the above structural formula, "co" is a symbol indicating that the arrangement of each monomer unit constituting the copolymer is disordered. ]

First, 1.98 parts by mass of compound (B-1) was added to 500.00 parts by mass of tetrahydrofuran, and the mixture was heated to 80 ° C. and dissolved. After dissolution, the temperature is lowered to 50 ° C., 37.50 parts by mass of the polymer component (P-1) is added and dissolved, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide / hydrochloride (EDC / HCl) 1 After adding .96 parts by mass and stirring at 50 ° C. for 5 hours, the liquid temperature was gradually returned to room temperature, and the reaction was completed by stirring overnight. After completion of the reaction, the solution was filtered, concentrated, and purified by reprecipitation with methanol to obtain a pigment dispersant 1.

<Production example of polyester resin A>
20 parts by mass of propylene oxide-modified bisphenol A (2 mol adduct), 80 parts by mass of propylene oxide-modified bisphenol A (3 mol adduct), 20 parts by mass of terephthalic acid in a reactor equipped with a stirrer, a thermometer, and an outflow cooler. 20 parts by mass of isophthalic acid and 0.50 parts by mass of tetrabutoxytitanium were added, and the esterification reaction was carried out at 190 ° C. Then, 1 part by mass of trimellitic anhydride (TMA) was added, the temperature was raised to 220 ° C., the pressure inside the system was gradually reduced, and a polycondensation reaction was carried out at 150 Pa to obtain a polyester resin A. The acid value of the polyester resin A was 12 mg / KOH, and the softening point was 110 ° C.

<Pigment>
As for the pigments, those shown in Table 1 were used.

<Manufacturing of toner particles 1>
(Preparation of aqueous medium)
-Ion-exchanged water 1000.0 parts by mass-Sodium phosphate 14.0 parts by mass-10% hydrochloric acid 4.5 parts by mass K. A mixture was obtained by stirring at 12000 rpm using a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.). The resulting mixture was kept warm at 65 ° C. for 60 minutes while purging with nitrogen. Next, an aqueous solution of calcium chloride in which 8 parts by mass of calcium chloride was dissolved in 10 parts by mass of ion-exchanged water was collectively added to the mixture to prepare an aqueous medium containing a dispersant. The pH of the prepared aqueous medium was 5.5.

(Preparation of Pigment Dispersion Solution 1: Pigment Dispersion Step)
・ Styrene 60.0 parts by mass ・ Pigment 1 (carbon black) 8.0 parts by mass ・ Charge control agent (manufactured by Orient Chemical Industries Co., Ltd .: Bontron E-88) 0.5 parts by mass ・ Pigment dispersant 1 0.8 parts by mass The above materials and zirconia particles having a mass of 1.7 mm were put into an attritor (Mitsui Miike Kakoki Co., Ltd.) and mixed at 220 rpm for 5 hours to disperse a colorant and a charge control agent in styrene. After the dispersion, the zirconia particles were separated to prepare a pigment dispersion liquid 1.

(Preparation of Polymerizable Monomer Composition 1)
15.0 parts by mass of styrene ・ 25.0 parts by mass of n-butyl acrylate (n-BA) ・ 6.0 parts by mass of polyester resin A The above materials were mixed and stirred for 2 hours to dissolve the polyester resin A. A polymerizable monomer composition 1 was obtained.

(Preparation of Polymerizable Monomer Composition 2)
After mixing the pigment dispersion 1 and the polymerizable monomer composition 1, the following materials were added.
-Hydrocarbon wax (melting point: 77 ° C) 10.0 parts by mass-Divinylbenzene 0.02 parts by mass

After the addition, it was heated to 65 ° C. while mixing. While keeping warm at 65 ° C. for 30 minutes, T.I. K. A polymerizable monomer composition 2 was obtained by uniformly dissolving at 500 rpm using a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.).

(Granulation / polymerization process)
The obtained polymerizable monomer composition 2 was put into the above-mentioned aqueous medium. Next, 10.0 parts by mass of the polymerization initiator t-butylperoxypivalate (25% toluene solution) was added, and T.I. K. The mixture was stirred with a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.) at 10000 rpm for 5 minutes, and granulated at pH 5.5. Then, the temperature was raised to 70 ° C. while stirring with a paddle stirring blade, and the reaction was carried out for 5 hours while stirring.

(Distillation process)
After completion of the polymerization reaction, the temperature inside the container was raised to 100 ° C. and distilled for 4 hours.

(Washing / drying / classification / external addition process)
After completion of the distillation step, the reaction vessel was cooled to 30 ° C. at 5 ° C./min, 10% hydrochloric acid was added, and the dispersant was dissolved with stirring for 2 hours at a pH of 2. The obtained emulsion was pressure-filtered and further washed with 2000 parts by mass or more of ion-exchanged water. The obtained cake was returned to 1000 parts by mass of ion-exchanged water, added with 10% hydrochloric acid, and rewashed with stirring at a pH of 1 or less for 2 hours.

The emulsion obtained in the same manner as above is pressure-filtered, further washed with 2000 parts by mass or more of ion-exchanged water, sufficiently aerated, dried and wind-classified, and toner particles having a weight average particle size of 7.0 μm. I got 1.

<Manufacturing of toner particles 2 to 15>
Toner particles 2 to 15 were obtained by the same production method as that of toner particles 1 except for the changes as shown in Table 2.

<Manufacturing of toner particles 16>
(Production example of resin fine particle dispersion liquid 1)
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 100.0 parts by mass of the obtained polyester resin, 45.0 parts by mass of methyl ethyl ketone, and 45.0 parts by mass of tetrahydrofuran were charged and heated to 80 ° C. And dissolved.

Next, under stirring, 300.0 parts by mass of ion-exchanged water at 80 ° C. was added and dispersed in water, and then the obtained aqueous dispersion was transferred to a distillation apparatus and distilled until the fraction temperature reached 100 ° C. It was.

After cooling, ion-exchanged water was added to the obtained aqueous dispersion to adjust the resin concentration in the dispersion to 20%. This was designated as the resin fine particle dispersion liquid 1. The average particle size of the polyester resin A in the obtained resin particle dispersion 1 was 48 nm.

In the method for producing the toner particles 1, 35 parts by mass (7 parts by mass of solid content) of the resin fine particle dispersion liquid 1 is added to the emulsion after completion of distillation, and the pH of the emulsion is 7.0% so as to be 8.0. An aqueous sodium carbonate solution was added, and the mixture was kept at 80 ° C. for 1 hour.

Then, the treatment was carried out in the same manner as in the method for producing the toner particles 1, to obtain the toner particles 16.

When the cross section of the toner particles 16 was observed with a transmission electron microscope, it was found that the resin fine particles of polyester A had a core-shell structure in which the resin fine particles were adhered to the surface of the toner particles.

<Manufacturing of toner particles 17>
(Preparation of resin particle dispersion liquid 2)
-Polyester resin A 200.0 parts by mass-Charge control agent (manufactured by Orient Chemical Industries Co., Ltd .: Bontron E-88) 1.0 parts by mass-Ion-exchanged water 500.0 parts by mass Put the above material in a stainless steel container and take a hot bath. Heat and melt to 95 ° C. below, and add 0.1N sodium hydrogen carbonate to make the pH higher than 7.0 while sufficiently stirring at 7800 rpm using a homogenizer (manufactured by IKA: Ultratarax T50). Then, a mixed solution of 3 parts by mass of sodium dodecylbenzenesulfonate and 297 parts by mass of ion-exchanged water was gradually added dropwise to emulsify and disperse the mixture to obtain a resin particle dispersion liquid 2. When the particle size distribution of the polyester resin particle dispersion 2 was measured using a particle size measuring device (LA-920, manufactured by Horiba Seisakusho), the average particle size of the contained polyester resin particle dispersion was 0.20 μm. Also, no coarse particles larger than 1 μm were observed.

(Preparation of wax particle dispersion)
-Ion-exchanged water 500.0 parts by mass-Hydrocarbon wax (melting point: 77 ° C) 250.0 parts by mass Put the above material in a stainless steel container, heat and melt to 95 ° C in a warm bath, and homogenizer (IKA: Ultra). While sufficiently stirring at 7800 rpm using Talux T50), 0.1 N sodium hydrogen carbonate is added to make the pH larger than 7.0. Then, a mixed solution of 5 parts by mass of sodium dodecylbenzenesulfonate and 245 parts by mass of ion-exchanged water was gradually added dropwise to emulsify and disperse. When the particle size distribution of the wax particles contained in this wax particle dispersion was measured using a particle size measuring device (LA-920 manufactured by Horiba Seisakusho), the average particle size of the number of wax particles contained was 0.35 μm. Also, no coarse particles larger than 1 μm were observed.

(Preparation of Colorant Particle Dispersion Solution 1)
-Pigment 1 (carbon black) 100 parts by mass, sodium dodecylbenzenesulfonate 5 parts by mass, ion-exchanged water 400 parts by mass or more were mixed and dispersed using a sand grinder mill. When the particle size distribution of the colorant particles contained in the colorant particle dispersion was measured using a particle size measuring device (LA-920, manufactured by Horiba Seisakusho), the average particle size of the number of the colorant particles contained was 0. No coarse particles were observed that were 2 μm and greater than 1 μm.

(Production example of toner particles 17)
-Resin particle dispersion 2500 parts by mass-Colorant particle dispersion 1 37.5 parts-Wax particle dispersion 30 parts by mass-Sodium dodecylbenzene sulfonate 5 parts by mass Reactor (Volume 1 liter flask, anchor blade with baffle) ) Is charged with the polyester resin particle dispersion 1, the wax particle dispersion and sodium dodecylbenzene sulfonate, and the mixture is uniformly mixed. On the other hand, the colorant particle dispersion is uniformly mixed in a 500 mL beaker and gradually added to the reactor with stirring to obtain a mixed dispersion. While stirring the obtained mixed dispersion, 0.5 parts by mass of an aqueous aluminum sulfate solution was added dropwise to form aggregated particles.

After completion of the dropping, the inside of the system was replaced with nitrogen, and the mixture was kept at 50 ° C. for 1 hour and further at 55 ° C. for 1 hour.

Then, the temperature was raised and the temperature was maintained at 90 ° C. for 30 minutes. Then, the temperature was lowered to 63 ° C. and then kept for 3 hours to form fused particles. The reaction at this time was carried out in a nitrogen atmosphere. After the end of the predetermined time, cooling was performed at a temperature lowering rate of 0.5 ° C. per minute until room temperature was reached.

After cooling, the reaction product was subjected to solid-liquid separation under a pressure of 0.4 MPa with a 10 L volume pressure filter to obtain a toner cake. Then, ion-exchanged water was added to the pressure filter until it was full, and the mixture was washed at a pressure of 0.4 MpA. Further, it was washed in the same manner, and was washed a total of 3 times. This toner cake was dispersed in 1 L of a 50:50 mixed solvent of methanol / water in which 0.15 parts by mass of the nonionic surfactant 1 was dissolved to obtain a surface-treated toner particle dispersion.

The toner particle dispersion was poured into a pressure filter, and 5 L of ion-exchanged water was further added. Then, after solid-liquid separation under a pressure of 0.4 MPa, the fluidized bed was dried at 45 ° C. to obtain toner particles 17.

<Manufacturing of toner particles 18>
In the production example of the toner particles 17, after the step of holding at 90 ° C. for 30 minutes, 35 parts by mass (7 parts by mass of solid content) of the resin fine particle dispersion liquid 1 is added so that the pH of the emulsion becomes 8.0. A 7.0% aqueous sodium carbonate solution was added, and the mixture was kept at 80 ° C. for 1 hour.

Then, the treatment was carried out in the same manner as in the method for producing the toner particles 17, and the toner particles 18 were obtained.

<Manufacturing of toner particles 19>
-Polyester resin A 100 parts by mass-Charge control agent (manufactured by Orient Chemical Industries Co., Ltd .: Bontron E-88) 0.5 parts by mass-Hydrocarbon wax (melting point: 77 ° C) 10.0 parts by mass-Pigment 1 (carbon black) 7.5 parts by mass After premixing the above raw materials with a Henshell mixer FM10C (Mitsui Miike Machinery Co., Ltd.), a twin-screw kneading extruder (PCM-30: manufactured by Ikekai Iron Works Co., Ltd.) set at a rotation speed of 200 rpm. The set temperature was adjusted so that the direct temperature near the outlet of the kneaded product was 155 ° C., and the kneaded product was kneaded. The obtained melt-kneaded product was cooled, and the cooled melt-kneaded product was roughly pulverized with a cutter mill. Then, the obtained coarsely pulverized product was finely pulverized using a turbo mill T-250 (manufactured by Turbo Industries, Ltd.) with a feed amount of 20 kg / hr and an air temperature adjusted so that the exhaust temperature became 38 ° C. The obtained finely pulverized product was classified using a multi-division classifier utilizing the Coanda effect to obtain toner particles 19 having a weight average particle diameter (D4) of 7.3 μm.

表中ＺｎＰＣは亜鉛フタロシアニンを示す。

In the table, ZnPC indicates zinc phthalocyanine.

<Production example of silica particles 1>
To a 1.5 L glass reaction vessel equipped with a stirrer, a dropping nozzle, and a thermometer, 500 parts by mass of methanol was added and 70 parts by mass of water whose pH was adjusted to 5.4 with 10% by mass hydrochloric acid was added and mixed. , A catalytic solution was obtained. After adjusting this catalyst solution to 30 ° C., 100 parts by mass of tetramethoxysilane (TMS) and 20 parts by mass of 8.0% by mass ammonia water are simultaneously added dropwise over 60 minutes with stirring to make hydrophilic silica fine particles. A dispersion was obtained.

Then, the obtained silica particle dispersion was concentrated to a solid content concentration of 40% by mass with a rotary filter R-fine (manufactured by Kotobuki Kogyo Co., Ltd.) to obtain a silica fine particle dispersion.

To 250 parts by mass of the silica particle dispersion, 50 parts by mass of hexamethyldisilazane (HMDS) was added as a hydrophobizing agent, reacted at 130 ° C. for 2 hours, cooled, and then dried by spray drying. Silica particles 1 were obtained. The physical characteristics are shown in Table 3.

<Manufacturing of silica particles 2-4, 6-9>
Silica particles 2 to 4, 6 to 9, which are external additives A, were obtained by the same production method as that of silica particles 1 except for the modification as shown in Table 3.

<Manufacturing of silica particles 5>
In the production example of silica particles 1, the pH of the catalyst solution was adjusted to 8.2 with aqueous ammonia, and the conditions were changed to the methods shown in Table 3, but the same production method as for silica particles 1 was used. Silica particles 5 as agent A were obtained.

<Manufacturing method of toner 1>
Silica particles 1 were externally added as an external additive A to the obtained toner particles 1.
・ Toner particles 1 100.0 parts by mass ・ Silica particles 1 (appendix A) 1.0 parts by mass ・ Hydrophobic silica fine particles 1.5 parts by mass ・ Hydrophobic titanium oxide fine particles 0.3 parts by mass Using Mitsui Miike Kakoki Co., Ltd.), mixing was performed at 3000 rpm for 15 minutes to obtain toner 1.

The hydrophobic silica fine particles were surface-treated with 20% by mass of dimethyl silicone oil with respect to the silica fine particles, and the number average particle size of the primary particles was 7 nm, and the BET specific surface area was 130 m ² / g. The hydrophobic titanium oxide fine particles were surface-treated with 15.0% by mass of isobutyltrimethoxysilane with respect to the titanium oxide fine particles, and the number average particle size of the primary particles was 50 nm.

<Manufacturing method of toners 2 to 30>
Toners 2 to 30 were obtained by the same manufacturing method as that of toner 1 except for the changes as shown in Table 4.

[Examples 1 to 23]
In Examples 1 to 23, the following evaluations were performed using toners 1 to 23 as the toner.

The results are shown in Table 5.

[Comparative Examples 1 to 7]
In Comparative Examples 1 to 7, the following evaluations were performed using toners 24 to 30 as the toner.

The results are shown in Table 5.

<Image evaluation>
The image evaluation was carried out by partially modifying a commercially available color laser printer (HP Color LaserJet Enterprise M855). The modification was improved so that it would work just by installing a one-color toner cartridge and an imaging drum. In addition, the process speed was modified to 60 ppm. Furthermore, if necessary, the printing paper was modified so that the printing paper could be taken out with the toner image unfixed. Furthermore, the fuser was modified so that it could be changed to any temperature.

After removing the toner contained in the toner cartridge for black toner and the imaging drum mounted on this color laser printer and cleaning the inside with an air blow, each toner (425 g) is put into the toner cartridge and the imaging drum. Each toner (127 g) was introduced into the color laser printer, and the toner cartridge and the imaging drum refilled with the toner were attached to the color laser printer, and the following image evaluation was performed. The specific image evaluation items are as follows.

[Fog]
In a high temperature and high humidity environment (temperature 33 ° C./humidity 85% RH), a test was conducted in which 30,000 images with a printing rate of 1% were printed out as horizontal lines. After the test was completed, the reflectance (%) of the non-image portion of the image printed out after being left for 48 hours was measured with "REFLECTOMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.). The obtained reflectance was evaluated using a numerical value (%) obtained by subtracting the reflectance (%) of the unused printout paper (standard paper) measured in the same manner. The smaller the value, the more the image fog is suppressed. The evaluation was performed using plain paper (HP Brochure Paper 200 g, Glossy, manufactured by HP, 200 g / m ^{2) in the gloss paper mode.}

(Evaluation criteria)
A: Less than 0.5% B: 0.5% or more and less than 1.5% C: 1.5% or more and less than 3.0% D: 3.0% or more

[Poor regulation]
In a low temperature and low humidity environment (15 ° C, 10% RH), after the printout test of 30,000 and 35,000 images with a print rate of 1% with horizontal lines is completed, the toner load is 0.3 mg / cm ² halftone. The evaluation was made based on the amount of spotted streaks and toner lumps that appeared on the image.
A: Not occurred.
B: There are no speckled streaks, but there are a few small toner lumps.
C: There are some spotted streaks on the edges, or there are 4 or 5 small toner lumps.
D: There are spot-like streaks on the entire surface, or there are 5 or more small toner lumps or obvious toner lumps.

[Coloring power]
The coloring power was evaluated as the amount of toner loaded on the paper at an image density of 1.40.

The smaller the toner loading amount at an image density of 1.40, the higher the coloring power, and the larger the toner loading amount at an image density of 1.40, the lower the coloring power.

A solid image of 10 mm × 10 mm for density measurement was output on the center of A4 plain paper (GF-C081A4: manufactured by Canon Marketing Japan Inc.). The development contrast of a 10 mm × 10 mm solid image for density measurement was adjusted so that the image density measured by the Macbeth reflection densitometer RD918 (manufactured by Macbeth) was 1.40.

The amount of unfixed toner loaded on the paper in the above settings was measured and ranked below.

(Evaluation criteria)
A: Less than 0.35 mg / cm ^2.
B: 0.35mg / cm ² more than 0.43mg / cm less than ^2.
C: 0.43 mg / cm ² or more and less than 0.47 mg / cm ^2.
D: 0.47 mg / cm ² or more.

[Fixability]
Using the above evaluation machine and using businesss 4200 (manufactured by Xerox) with a basis weight of 105 g / m ² as evaluation paper, each temperature control is changed every 5 ° C. in the temperature range from 130 ° C. to 220 ° C. The original image was output at the temperature.

As the original image, a 10 mm square solid patch image (toner loading amount 0.90 mg / cm ² ) was output in which the image was arranged in the center of each of the nine divisions of the paper surface.

Subsequently, the minimum fixable temperature was determined by performing a rubbing resistance test of the fixed image output at each temperature.

The minimum fixable temperature is the average of the density reduction rates obtained by measuring ^{the fixed image density and the image density after rubbing the fixed image with Sylbon paper loaded with a load of 50 g / cm 2 five times in each patch.} It is defined as a fixing state in which the value satisfies 10% or less.

A "Macbeth reflection densitometer RD918" (manufactured by Macbeth) was used for measuring the density.
A: A stable fixed image can be obtained when the minimum fixable temperature is 170 ° C or lower.
B: A stable fixing image can be obtained when the minimum fixable temperature is higher than 170 ° C and 175 ° C or lower.
C: A stable fixed image can be obtained when the minimum fixable temperature is higher than 175 ° C and 180 ° C or lower.
D: The minimum fixable temperature is higher than 180 ° C., or there is no fixable temperature.

Claims (11)

Toner particles containing a binder resin and a pigment, and a toner containing an external additive A.
In the cross-sectional observation of the toner using a transmission electron microscope, the toner particles have an Aps of 2 when the ratio of the area occupied by the pigment in the surface layer region from the surface of the toner particles to a depth of 0.1 μm is Aps. 5.5% or more and 5.5% or less,
The external additive A is a silica particle having a work function Ws of 5.70 eV or less.
A toner characterized in that the coverage of the external additive A on the surface of the toner is 1.0% or more and 15.0% or less. When the toner particles have the work function of the pigment as Wp,
0 <Ws-Wp <1.0
The toner according to claim 1. The toner according to claim 1 or 2, wherein the work function Ws of the external additive A is 5.35 eV or more and 5.70 eV or less. The toner according to any one of claims 1 to 3, wherein the Aps of the toner particles is 3.2% or more and 5.0% or less. The toner according to any one of claims 1 to 4, wherein the mass% of the pigment in the toner is 4.8% by mass or more. The invention according to any one of claims 1 to 5, wherein the index (CEI) of the pigment dispersion state in the cross-sectional image of the toner particles is 0.70 or more and 1.30 or less, and the dispersed pigment particle size is 30 nm or more and 130 nm or less. Toner. The toner according to any one of claims 1 to 6, wherein the pigment is carbon black. The toner according to any one of claims 1 to 7, wherein the outer additive A is silica fine particles having an average circle-equivalent diameter of 10 nm or more and 80 nm or less. The toner according to any one of claims 1 to 8, wherein the degree of hydrophobization of the external additive A is 40% or more and 65% or less. The toner according to any one of claims 1 to 9, wherein the toner particles contain a pigment dispersant. The toner according to claim 10, wherein the pigment dispersant has a polymer component and an adsorption component that adsorbs to the pigment, and the adsorption component of the pigment dispersant has a partial structure represented by the following general formula (1).

[In the formula (1), any of R ₄ , R ₅ and Ar has a structure in which the polymer component is bonded via a single bond or a linking group.
R ₄ represents an alkyl group, a phenyl group, an OR ₈ group or an NR ₉ R ₁₀ group, and R _{8 to} R ₁₀ independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. When R ₄ is bonded to the polymer component, it is bonded via a single bond or a linking group, and the linking group bonded to R ₄ is an amide group, an ester group, a urethane group, a urea group, an alkylene group, a phenylene group, -O. It is a divalent linking group selected from the group consisting of −, −NR ₆ − and −NHCH (CH _{2 OH) −, where R 6} represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. R ₅ represents an alkyl group, a phenyl group, an OR ₄₂ group or an NR ₄₃ R ₄₄ group, and R _{42 to} R ₄₄ independently represent a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
If R ₅ is bound to the polymer component, bonded through a linking group, the linking group attached to R ₅ is an alkylene group, a phenylene _{group, -O -, - NR 11 -} , - NHCOC (CH 3) 2 - It is a divalent linking group selected from the group consisting of and -NHCH (CH _{2 OH) -, and R 11} represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
Ar represents an aryl group, and when Ar is bonded to a polymer component, it is bonded via a single bond or a linking group, and the linking group bonded to Ar is an amide group, an ester group, a urethane group, a urea group, or an alkylene group. , A phenylene group, a divalent linking group selected from the group consisting of _{−O−, −NR 6−} and −NHCH (CH _{2 OH) −, where R 6} is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. Is shown.
The single bond or a linking group, when bound to R _4, R ₅ or Ar, is bonded substituted with R _4, R ₅ or Ar hydrogen atoms. ]