JPH10239906A - Electrophotographic toner and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a high definition and high quality image and to ensure superior durability and anti-offsetting property by incorporating a binder resin, a colorant and a polymer of a polyvinyl phenol deriv. contg. a reactive functional group. SOLUTION: This electrophotographic toner contains at least a binder resin, a colorant and a polymer of a polyvinyl phenol deriv. contg. a reactive functional group. The toner particles are formed by dissolving at least a monomer compsn. for synthesizing a polymer and the polyvinyl phenol deriv. polymer in a solvent which dissolves the monomer compsn. but does not dissolve it after polymn. and polymerizing the monomer compsn. in the solvent. Since the polyvinyl phenol deriv. polymer contains protonic acid, satisfactory electrostatic chargeability is imparted to the toner particles, and because of the presence of phenyl groups excellent in hydrophobic property, the reduction of the absolute value of the quantity of triboelectric charges at high temp. and humidity is suppressed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic toner capable of providing a high-quality electrophotographic image used in a method for visualizing an electrostatic latent image, and a method for producing the same. .

[0002]

2. Description of the Related Art In order to visualize an electric or magnetic latent image on a recording medium, an image is formed by adsorbing electroconductive or magnetically sensitive fine particles such as toner onto the latent image to form a visible image. There is a way. A representative example is electrophotography, and many methods are known, for example, as described in US Pat. No. 2,297,691. In this electrophotography, a photoconductive substance is generally used to form an electric latent image on a photoreceptor by various means, and then the latent image is developed using toner to form a toner image. After transferring the toner image to a transfer material such as paper as required, a copy is obtained by fixing the toner image to the transfer material using heat, pressure or solvent vapor.

[0003] The toner used in the above-mentioned printers and copiers is a fine particle mainly composed of a resin and a magnetic substance, a colorant such as carbon black, a dye and a pigment, and waxes. １５15 μm. Toner is generally mixed with a coloring agent composed of a dye or pigment or a magnetic material in a thermoplastic resin, melted, uniformly dispersed, and then pulverized and classified to obtain a toner having a desired particle diameter. Being manufactured. This method is relatively stable as a technology, and the management of each material and each process can be performed relatively easily. However, since the contents are exposed to the fracture surface, the above-mentioned wax for lowering the melting point such as wax is used. The components and the components for mold release cannot be contained sufficiently enough to be effective, and there is a drawback that sufficient low-temperature fixing cannot be achieved. Further, since the toner obtained by the above-described pulverization method has a different shape and a relatively wide particle size distribution, frictional charging is not uniformly performed when a predetermined charge is applied to the toner, There is a disadvantage that the printing characteristics become unstable.

In recent years, a method for producing a toner by a polymerization method has been proposed as an improvement over the above-mentioned disadvantages. These are disclosed, for example, in JP-B-36-10231 and JP-B-51.
No. -14895, JP-A-53-17735,
JP-A-53-17736 and JP-A-53-177.
No. 37. The above-mentioned method uses a coloring agent such as a binder resin, a dye or a pigment, for example, a substance to be included in the toner, such as a magnetic substance, carbon black, a charge controlling agent, a release agent such as wax or silicone oil, as needed. The polymerizable monomer is dissolved or dispersed in a polymerizable monomer together with a polymerization initiator and a dispersant to form a polymerizable composition, and dispersed in an aqueous continuous phase containing a dispersion stabilizer using a dispersing apparatus to form a dispersion of fine particles. This dispersion is polymerized and solidified to obtain toner particles having a desired particle size and composition.

The above-mentioned method is expected to have effects such as energy saving, improvement in process yield, and cost reduction since there is no kneading and pulverizing steps. There was a problem that the particle size distribution fluctuated. In addition, since the polymerization of the polymerizable composition is carried out by a solid-phase reaction as described above, the polymerization reaction cannot be completely advanced, and unreacted monomers and oligomers remaining in the toner particles may cause the toner durability and triboelectric charging. There was a problem that had a bad effect on sex. Further, it has been difficult to stably obtain a desired toner particle size required for obtaining a high-quality, high-definition copy image.

On the other hand, with respect to the above-mentioned polymerization method, there has been proposed a polymerization method for producing toner particles by using a solvent in which the monomer constituting the binder resin is dissolved but the polymer compound is not dissolved. For example, it is described in JP-B-6-52432 and JP-A-61-19602. The toner particles formed by this polymerization method are characterized in that toner particles having a small particle size and a narrow particle size distribution can be obtained, and sufficiently high image quality is expected.

However, in the above polymerization method, it is known that the polymer dispersion stabilizer remains on the surface of the toner particles. However, the dispersion stabilizer is required for the toner such as environmental stability and triboelectric charging property of the toner. In some cases, there is a problem that the performance deteriorates.

Further, it is difficult to contain a component for mold release or a component for lowering the melting point, such as a gel component, a graft copolymer, or a wax, and to maintain a narrow particle size distribution with good reproducibility.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrophotographic toner which has excellent environmental stability and triboelectric chargeability and has good fixability, and a method for producing the same.

[0010] Another object of the present invention is to provide a small particle size toner which provides high definition and high quality images, and has excellent durability,
An object of the present invention is to provide an electrophotographic toner having offset resistance and a method for producing the same.

[0011]

The present invention provides at least (i) a binder resin, (ii) a colorant and (ii)
i) An electrophotographic toner comprising a polymer of a polyvinyl phenol derivative having a reactive functional group.

Further, the present invention relates to a method for dissolving a monomer composition for synthesizing a polymer, but not dissolving a polymer obtained by polymerizing the monomer composition. A process for dissolving a polymer of a polyvinyl phenol derivative having a functional functional group and polymerizing the monomer composition in the solvent to form toner particles, the method for producing an electrophotographic toner. .

Since the polymer of the polyvinyl phenol derivative containing a reactive functional group contains a protonic acid, good negative chargeability can be imparted to the toner particles, and a phenyl group having excellent hydrophobicity can be provided. Due to the presence, the decrease in the absolute value of the triboelectric charge amount under high temperature and high humidity can be improved.

Further, the polymer of the polyvinylphenol derivative containing a reactive functional group contains a molecular chain having a complicated molecular structure such as a graft copolymer. It is possible to design a binder resin exhibiting good fixability with low viscosity and softening point.

Further, the high molecular weight polymer of polyvinyl phenol may have a problem that if it is mixed in a large amount at a high temperature such as a softening point of about 200 ° C. to 250 ° C., the fixability of the toner is deteriorated. By using a polymer of a polyvinyl phenol derivative containing a functional functional group, a sufficient amount of vinyl phenol units can be added to the toner while solving the problem that the fixing property of the toner is deteriorated by containing high molecular weight polyvinyl phenol. It becomes possible to make it contain in.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned polyvinylphenol derivative containing a reactive functional group used in the present invention refers to one end, both ends, of polyvinylphenol or a copolymer of vinylphenol and another vinyl monomer. A polymer having a unit having a reactive functional group bonded between the polymer chains, a polymer having a reactive functional group in a part of the hydroxyl group of the polymer chain, or a mixture thereof. Specifically, for example, it is represented by the following general formula (1).

[0017]

Embedded image

The degree of polymerization of the polyvinyl phenol chain is preferably in the range of 10 or more and 1000 or less, more preferably 20 or more and 800 or less, and further preferably 30 or more and 500 or less. If the degree of polymerization is less than 10, the particle size distribution becomes broad, and it is difficult to obtain sufficient environmental stability. If the degree of polymerization exceeds 1,000, the particle size becomes on the order of submicrons, making it difficult to handle as a single particle, increasing the softening point, making it difficult to achieve both good fixability and offset resistance, which is not preferable.

The polymer of the polyvinylphenol derivative having a reactive functional group may be any polymer that can be bonded by the reactive functional group, and specifically, a vinyl polymer compound, a polyester compound, and a polyether compound. , Polyolefin-based compounds and polyamide-based compounds. These may be singular or plural.

As the binder resin in the present invention, any resin can be used as long as it is a generally known resin. Specifically, compounds such as vinyl polymer-based compounds, polyester-based compounds, polyether-based compounds, and polyolefin-based compounds are included. These may be singular or plural.

In the present invention, the polymer of the polyvinylphenol derivative containing a reactive functional group preferably contains a monomer unit constituting the binder resin.

By containing a polymer in which a polyvinylphenol derivative containing a reactive functional group and a part of a binder resin are combined, the compatibility between the binder resin and the polymer in toner particles is improved. The polymer can be dispersed throughout the particles without localization. Therefore, the toner particles can be frictionally charged uniformly, and the environmental stability can be uniformly improved.

Further, since the polymer is uniformly dispersed in the toner particles, it is possible to design a binder resin exhibiting good fixability with low viscosity and softening point at the time of melting while maintaining excellent offset resistance. Becomes

Further, in the present invention, the toner TH
In the molecular weight distribution by GPC of the F-soluble component,
It is preferable that the content of the component of 000 or less is 10% by weight or less.

If unreacted monomers or oligomers such as components having a molecular weight of 1000 or less remain in the toner in an amount of more than 10% by weight based on the weight of the toner, the image quality is degraded by destabilizing the triboelectric charging property. This causes a problem and a problem that durability is remarkably reduced.

Therefore, by removing components having a molecular weight of 1,000 or less in the toner, the instability of the triboelectric charge of the toner can be improved, and the durability can be improved.

The content of the component having a molecular weight of 1,000 or less is as follows:
It is preferably 5% by weight or less, more preferably 3% by weight or less, further preferably 1% by weight or less, and still more preferably 0.5% by weight or less based on the total weight of the toner.

In the present invention, the molecular weight is measured by Shodex GPCSYSTEM-11 manufactured by Showa Denko KK
Using a mold, the column was KF-80MX2, the column temperature was 40 ° C., and tetrahydrofuran (TH
The measurement was performed using F). At this time, the elution time was calibrated using polystyrene as a standard for the molecular weight.

The extraction of the THF-soluble component from the toner was performed under the following conditions to prepare a measurement sample.

A sample of 60 mg is weighed into a sample bottle, and 15 ml of THF is further added. Extraction condition is initial 3hrs
Is left at room temperature for 24 hrs with shaking every 30 minutes. Further, ultrasonic waves are applied for 15 minutes to sufficiently perform extraction. After insoluble matter is sedimented by centrifugation (500 rpm / 20 min), the supernatant is filtered using a membrane filter (regenerated cellulose, 0.45 μm: manufactured by Toyo Filter Paper) to obtain a measurement sample.

Further, in the present invention, the peak of the molecular weight distribution of the THF-soluble component is preferably from 3,000 to 100,000.

The fixability of the toner greatly depends on the softening temperature of the binder resin and the viscosity in the molten state. By setting the peak of the molecular weight distribution of the THF-soluble component of the toner in the range of 3,000 to 100,000, the viscosity of the binder resin in a molten state can be reduced, and as a result, the fixing property of the toner can be significantly improved.

The peak of the molecular weight distribution of the THF-soluble component is 30.
When the ratio is less than 00, environmental stability is deteriorated, and further, the problem of offset at the time of fixing occurs. 100000 peak
If the ratio exceeds the above range, a problem of poor fixing occurs, and stable triboelectric charging cannot be obtained.

The peak of the molecular weight distribution of the THF-soluble component is:
It is preferably 3000 or more and 80000 or less, more preferably 5000 or more and 50000 or less, and still more preferably 700 or less.
It is preferable that it is in the range of 0 to 30,000.

In the present invention, the number average particle diameter (D ₁ )
The content of toner particles having a particle diameter equal to or less than 1/2 ((D ₁ ) / 2) is preferably 10% by number or less.

The toner particles having a very small particle diameter ((D ₁ ) / 2) or less of the particle diameter ((D ₁ ) / 2) of the number average particle diameter (D ₁ ) have a significantly higher triboelectric charge than the toner having the center particle diameter. With. These toner particles are not developed,
The phenomenon that the image is not transferred even if it is developed causes deterioration in image quality. For this reason, by removing the toner particles having the fine particle diameter so as to be 10% by number or less, it is possible to obtain a high-quality and high-definition image.

The content of toner particles having a particle diameter ((D ₁ ) / 2) or less which is _１ ／ of the number average particle diameter (D ₁ ) is preferably 6 number% or less, more preferably 3 number% or less. More preferably, it is in the range of 1% by number or less.

In the present invention, the number average particle diameter (D
₁ ) and GALAI's C for measurement of volume average particle diameter (D ₃ )
Model IS-100 was used.

In the present invention, the content of toner particles having a particle diameter ((D ₃ ) × 2) or more twice the volume average particle diameter (D ₃ ) is preferably 10% by volume or less.

Large toner particles having a particle diameter (D ₃ ) × 2 or more twice as large as the volume average particle diameter (D ₃ )
It has a low triboelectric charge compared to toner having a central particle size.
If these toners are present in an amount of more than 10% by volume, there is a problem that image quality is deteriorated due to fogging and scattering. By removing these large-sized toner particles, it is possible to obtain a high-quality and high-definition image.

The content of toner particles having a particle diameter ((D ₃ ) × 2) or more twice the volume average particle diameter (D ₃ ) is preferably 6% by volume or less, more preferably 3% by volume or less. Preferably, it is in the range of 1% by volume or less.

On the other hand, according to the method for producing a toner of the present invention, at least the monomer composition for synthesizing the polymer is dissolved in a solvent in which the polymer obtained by polymerizing the monomer composition is not dissolved. It is characterized in that toner particles are formed by dissolving a polymer of a monomer composition and a polyvinylphenol derivative containing a reactive functional group, and polymerizing the monomer composition in the solvent.

According to the method of the present invention, the production of a polymer of a polyvinylphenol derivative containing a reactive functional group and a part of a binder resin and the formation of toner particles can be performed at a time. Further, the polymer can be dispersed not only in the vicinity of the surface of the toner particles but also in the particles. Further, by using a polyvinylphenol derivative containing a reactive functional group, the amount of the polymer contained in the toner particles can be uniformly stabilized, so that the triboelectric charging property and environmental stability are uniformly improved. Can be done. Also,
Since a polymer of a polyvinylphenol derivative having a reactive functional group and a part of the binder resin stably forms toner particles in a liquid, reproducibility is improved, and polymerization of a vinylphenol chain of the derivative is performed. Since the degree can be reduced as compared with the related art, the problem that the fixability of the toner particles is deteriorated is solved.

The amount of the polyvinylphenol derivative containing a reactive functional group is from 0.01% to 30% by weight, preferably from 0.1% to 10% by weight, based on the organic solvent or the mixed liquid. And more preferably in the range of 0.5% by weight or more and 5% by weight or less. It can also be used by mixing with other dispersion stabilizers.
If the amount used is less than 0.01% by weight, particles will aggregate during polymerization, resulting in poor monodispersibility. If the content is more than 30% by weight, the particle size becomes too small, so that micron-sized particles cannot be obtained, resulting in poor fixability as a toner.

In the present invention, the content of the reactive functional group of the polyvinyl phenol derivative containing the reactive functional group is 0.001 to 20 mol% based on the monomer unit of the vinyl phenol derivative. Is preferred.

The content of the reactive functional group in the derivative is preferably from 0.01 mol% to 10 mol%, more preferably from 0.05 mol% to 8 mol%, based on the monomer unit of the vinylphenol derivative. More preferably, 0.
The range is preferably from 05 mol% to 5 mol%, more preferably from 0.05 mol% to 3 mol%.

When the content of the reactive functional group is as small as less than 0.001 mol% with respect to the monomer unit of the vinylphenol derivative, there is a problem that the effect of including the reactive functional group is not sufficiently exhibited. May occur. If the amount exceeds 20 mol%, the content of the gel component becomes excessive due to complex binding with the binder resin, which may cause a problem that the fixability of the toner is deteriorated.

According to the present invention, materials required for a normal toner, such as a colorant, a magnetic substance, a charge control agent, and a release agent, can be internally or externally added to the toner particles as needed.

The polymerization reaction may be carried out after dispersing or dissolving these materials in a liquid for dissolving the above-mentioned polyvinyl phenol derivative having a reactive functional group and the monomer composition for providing the binder resin before polymerization. These materials may be added after the polymerization. After being taken out as particles, these materials may be incorporated by kneading or the like.

The polymerizable monomers used in the binder resin of the present invention include styrene, o-methylstyrene, m-methylstyrene, p-methoxystyrene, p-ethylstyrene and p-tert-butylstyrene. Styrene monomers such as acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, n-propyl acrylate, isobutyl acrylate, octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, acrylic Acrylic esters such as stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and n-methacrylate -Octyl, dodecyl methacrylate , 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate,
Methacrylic esters such as dimethylaminomethyl methacrylate and diethylaminoethyl methacrylate; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide and the like, and vinyl derivatives, specifically, for example, methyl Vinyl ether, ethyl vinyl ether,
Alkyl vinyl ethers such as propyl vinyl ether, n-butyl ether and isobutyl ether; β-chloroethyl vinyl ether, phenyl vinyl ether, p
And diene compounds such as -methylphenyl ether, p-chlorophenyl ether, p-bromophenyl ether, p-nitrophenyl vinyl ether, p-methoxyphenyl vinyl ether, and butadiene.

These monomers can be used alone or as a mixture, and a suitable polymer composition that can obtain preferable characteristics can be selected.

The melt viscosity of the toner of the present invention can be adjusted as required by incorporating a high molecular weight component or a gel component. The introduction of such a component is achieved by using a crosslinking agent having two or more polymerizable double bonds per molecule. Specific examples of the crosslinking agent include, for example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate,
Tetraethylene glycol dimethacrylate, 1,3-
Butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6
-Hexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate,
Examples thereof include compounds such as pentaerythritol tetramethacrylate, glycerol acroxydimethacrylate, N, N-divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone, and two or more compounds may be appropriately mixed and used. . Such a crosslinking agent can be previously mixed with the polymerizable mixture, or can be appropriately added during the polymerization as needed.

When forming the toner of the present invention, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconate, monobutyl maleate, a phosphoric acid-containing monomer, Are acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate, sulfonic acid group-containing monomers, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, acroyl morpholine, 2-
Vinyl pyridine, 3-vinyl pyridine, 4-vinyl pyridine, N-vinyl pyrrolidone, 2-vinyl imidazole, N-methyl-2-vinyl imidazole, N-vinyl imidazole, or copolymers of the above-mentioned salts and the like are charged. Can also be adjusted.

When forming a polymerized toner by the method of the present invention, fine particles are generated as the reaction proceeds. The obtained fine particles are repeatedly washed with a reaction solvent or another suitable solvent. At this time, a separating means such as a centrifugal separator may be used to improve the washing efficiency.

After washing, the obtained toner is separated by filtration, dried,
Fine particles are obtained by crushing, and a predetermined additive is appropriately added to obtain the toner of the present invention. On this occasion,
As a means for separation and drying, a spraying method such as spray drying can also be used.

As the polymerization medium used in the present invention, a liquid in which the binder resin is precipitated as the polymerization proceeds is used. Specifically, for example, methanol, ethanol,
-Propanol, 2-propanol, 1-butanol,
2-butanol, isobutyl alcohol, tertiary butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol,
Isopentyl alcohol, tertiary pentyl alcohol, 1-hexanol, 2-methyl 1-pentanol, 4-methyl-2-pentanol, 2-ethylbutanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol Linear or branched aliphatic alcohols such as, 2-ethyl 1-hexanol; pentane, 2-methylbutane, n-hexane, cyclohexane, 2-methylpentane, 2,2-dimethylbutane;
2,3-dimethylbutane, heptane, n-octane, isooctane, 2,2,3-trimethylpentane, decane, nonane, cyclopentane, methylcyclopentane,
In addition to aliphatic hydrocarbons such as methylcyclohexane, ethylcyclohexane, p-menthane, and bicyclohexyl,
Examples thereof include aromatic hydrocarbons, halogenated hydrocarbons, ethers, fatty acids, esters, sulfur-containing compounds, and water. These substances may be used alone or as a mixture.

In the present invention, together with the polyvinyl phenol having a reactive functional group at the time of polymerization, an organic solvent used for the polymerization reaction or a dispersion stabilizer that dissolves in a mixed solution with water can be used. Specifically, for example,
Polystyrene, polymethyl methacrylate, phenol novolak resin, cresol novolak resin, styrene-acryl copolymer, polymethyl vinyl ether, polyethyl vinyl ether, polybutyl vinyl ether, vinyl ether copolymer such as polyisobutyl vinyl ether, polyvinyl alcohol, polyvinyl acetate, styrene -Butadiene copolymer, ethylene-vinyl acetate copolymer, polyvinylpyrrolidone, polyhydroxystyrene, vinyl chloride, polyvinyl acetal, cellulose,
Cellulose acetate, cellulose nitrate, alkylated cellulose, hydroxyalkylated cellulose, specifically hydroxymethyl cellulose, hydroxypropyl cellulose, saturated alkyl polyester resin, aromatic polyester resin, polyamide resin, polyacetal, polycarbonate resin, or copolymers thereof And other known surfactants, and mixtures thereof.

As the polymerization initiator used in the present invention, any of those known as radical initiators can be used. Specific examples of the polymerization initiator include, for example, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, and 1,1′-azobis- (cyclohexane -1-carbonitrile), 2,2'-azobis-4-methoxy2,
Azo or diazo polymerization initiators such as 4-dimethylvaleronitrile; 2,2′-azobis (2-aminodipropane) dihydrochloride, 2,2′-azobis (N,
Amidine compounds such as N'-dimethyleneisobutylamidine) and 2,2'-azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide And 2,2,4-dichlorobenzoyl peroxide, lauroyl peroxide, and the like, and peroxide mixtures such as potassium persulfate and ammonium persulfate, and mixtures of the above-mentioned initiators.

In the present invention, known chain transfer agents, specifically, carbon tetrachloride, carbon tetrabromide, ethyl dibromide acetate, ethyl tribromide acetate, ethyl dibromide benzene, ethane dibromide, Halogenated hydrocarbons such as ethane dichloride; hydrocarbons such as diazothioether, benzene, ethylbenzene, and isopropylbenzene; mercaptans such as tertiary decyl mercaptan and n-dodecyl mercaptan; and disulfides such as diisopropyl zantogen disulfide are added. You can also.

The concentration of the polymerization initiator used for obtaining the toner of the present invention can be appropriately adjusted in consideration of the molecular weight, yield, and the like of the polymer to be produced. 0.01% by weight or more of the total amount of monomers 20
% By weight, more preferably from 0.1% by weight to 10% by weight, even more preferably from 1% by weight to 8% by weight.

As the colorant used in the present invention, specifically, in addition to carbon black, an organic colorant, for example, C.I. I. Direct Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I.
I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6; cadmium yellow, mineral first yellow, navel yellow, naphthol yellow S,
Hansa Yellow G, Permanent Yellow NCG, Tartrazine Lake, Molybdenum Orange GTR, Benzidine Orange G, Cadmium Red 4R, Watching Red Calcium Salt, Brilliant Carmine 3B, Fast Violet B, Methyl Violet Lake, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Pigments such as lake, quinacridone, rhodamine lake, phthalocyanine blue, fast sky blue, pigment green B, malachite green lake, and final yellow green G; I. Solvent Yellow 6, C.I. I. Solvent Yellow 9, C.I. I. Solvent Yellow 17, C.I. I. Solvent Yellow 31,
C. I. Solvent Yellow 35, C.I. I. Solvent Yellow 100, C.I. I. Solvent Yellow 102,
C. I. Solvent Yellow 103, C.I. I. Solvent Yellow 105, C.I. I. Solvent Orange 2,
C. I. Solvent Orange 7, C.I. I. Solvent Orange 13, C.I. I. Solvent Orange 14, C.I.
I. Solvent Orange 66, C.I. I. Solvent Red 5, C.I. I. Solvent Red 16, C.I. I. Solvent Red 17, C.I. I. Solvent Red 18, C.I.
I. Solvent Red 19, C.I. I. Solvent Red 22, C.I. I. Solvent Red 23, C.I. I. Solvent Red 143, C.I. I. Solvent Red 145,
C. I. Solvent Red 146, C.I. I. Solvent Red 149, C.I. I. Solvent Red 150, C.I.
I. Solvent Red 151, C.I. I. Solvent Red 157, C.I. I. Solvent Red 158, C.I. I.
Solvent Violet 31, C.I. I. Solvent Violet 32, C.I. I. Solvent violet 33,
C. I. Solvent Violet 37, C.I. I. Solvent Blue 22, C.I. I. Solvent Blue 63, C.I.
I. Solvent Blue 78, C.I. I. Solvent Blue 83, C.I. I. Solvent Blue 84, C.I. I. Solvent Blue 85, C.I. I. Solvent Blue 86, C.I.
I. Solvent Blue 104, C.I. I. Solvent Blue 191, C.I. I. Solvent Blue 194, C.I. I.
Solvent Blue 195, C.I. I. Solvent Green 24, C.I. I. Solvent Green 25, C.I. I. Solvent Brown 3, C.I. I. Dyes such as Solvent Brown 9 are preferred. Commercially available dyes include, for example, Mitsubishi Kasei's Diaresin: Yellow-3G, Yellow-F, Y
yellow-H2G, Ye1low-HG, Ye1lo
w-HC, Ye1low-HL, Orange-HS,
Orange-G, Red-GG, Red-S, Red
-HS, Red-A, Red-K, Red-H5B, V
iolet-D, Blue-J, Blue-G, Blue
e-N, Blue-K, Blue-P, Blue-H3
G, Blue-4G, Green-C, Brown-A
Ya-Hodogaya Chemical's indigo dye SOT dye: Yellow-
1, Yellow-3, Yellow-4, Orange
e-1, Orange-2, Orange-3, Sca
rlet-1, Red-1, Red-2, Red-3,
Brown-2, Blue-1, Blue-2, Vio
let-1, Green-1, Green-2, Gre
en-3, Black-1, Black-4, Blac
k-6, Black-8 and sudan dyes of BASF: Yellow-146, Yellow-150, O
range-220, Red-290, Red-38
0, Red-460, Blue-670, orient black, oil black, oil color: Yellow
w-3G, Yellow-GR, Yellow- # 10
5, Orange-PS, Orange-PR, Ora
nge- # 201, Scarlet- # 308, Red
-5B, Brown-GR, Brown- # 416, G
green-BG, Green- # 502, Blue-B
OS, Blue-IIN, Black-HBB, Bla
ck- # 803, Black-EB, Black-E
X, Sumiplast of Sumitomo Chemical: Blue GP, Blue OR, Red-FB, Red-3B, Yellow FL7
G, Yellow GC, Nippon Kayaku Kayaron, Polyester Black EX-SF300, Kayaset Red
B, blue A-2R and the like.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples.
All parts used in the examples are parts by weight.

[0063]

【Example】

(Toner Production Example 1) As a polyvinyl phenol derivative containing a reactive functional group, a compound represented by the following compound 1 was synthesized by living anion polymerization.

[0064]

Embedded image

The average polymerization degree (sum of x and y in the formula) of the polyvinylphenol chain of the compound shown in Compound 1 was 58. The content of the reactive functional group was 0.08 mol%.

In a reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a mechanical stirrer, 300 parts of methanol 8 parts of carbon black 3 parts of compound 1 80 parts of styrene 20 parts of n-butyl acrylate 20 parts of 2,2'- A mixture consisting of 6 parts of azobisisobutyronitrile was charged into the reaction vessel and mixed well while flowing nitrogen gas. The reactor was heated in a 75 ° C. oil bath under a nitrogen atmosphere and refluxed for 12 hours.

After cooling to room temperature, solid-liquid separation and washing of the dispersion were repeated.

[0068] The obtained powder was dried, number average particle size 3.68Myuemu, the ratio of the volume average particle diameter (D ₃₎ to a number average particle diameter _{(D 1) (D 3 /} D 1) is 1. 03 polymer particles A were obtained.

The content of particles having a particle diameter half that of D ₁ is 0.0
It was 1% by number. The content of particles having a particle size twice as large as D ₃ was 0.03% by volume.

When the content of carbon black in the polymer particles A was measured by TGA measurement, it was found that 5.8% by weight of the carbon black was contained in the polymer particles A.

After dissolving the polymer particles A in THF, the mixture was centrifuged.
Carbon black was removed using a separator. This solution
Pour into a large amount of methanol to collect the precipitate,
Dried. This is dissolved in deuterated chloroform, C¹³
-NMR measurement was performed. Launched vinyl phenol unit
The presence of a benzene ring with a hydroxyl group attached
Is the existence of a double bond due to a reactive functional group not confirmed?
Was. Polymerization of the compound represented by Compound 1 on the polymer particles A
The presence of the object was confirmed.

To 7 parts of the above-mentioned polymer particles A, 0.14 parts of crushed titanium oxide having a BET value of 350 m ² / g was mixed with a Henschel mixer, and finely divided titanium oxide was externally added to obtain toner A. .

The toner A is dissolved in THF, and the soluble component GP
C measurement was performed. Maximum peak of molecular weight distribution is 18300
The component having a molecular weight of 1,000 or less was 0.015% by weight based on the toner A.

(Production Example 2 of Toner) As a polyvinyl phenol derivative having a reactive functional group, a compound represented by the following compound 2 was synthesized by living anion polymerization.

[0075]

Embedded image

The average polymerization degree (m in the formula) of the polyvinylphenol chain of the compound shown in Compound 2 was 60, and the average polymerization degree of the methyl methacrylate chain (n in the formula) was 20. Further, the content of the reactive functional group was 1.25 mol%.

In a reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen inlet, and a mechanical stirrer, 300 parts of methanol, 2 parts of compound 2, 90 parts of styrene, 10 parts of n-ethylhexyl acrylate, 10 parts of 2,2'-azobisisobutyi A mixture consisting of 6 parts of lonitrile was charged into the reaction vessel and mixed well in a nitrogen stream. The reactor was heated in a 75 ° C. oil bath under a nitrogen atmosphere and refluxed under a nitrogen atmosphere for 14 hours. After separating half (dispersion-1), a mixture consisting of 3 parts of oil black and 100 parts of methanol was further charged into the reaction vessel, and the reactor was further heated in an oil bath at 75 ° C. under a nitrogen atmosphere, and the reaction was continued for 2 hours. The mixture was refluxed under a nitrogen atmosphere (dispersion liquid-2).

After cooling to room temperature, solid-liquid separation and washing of the dispersion liquid 2 were repeated.

[0079] The obtained powder was dried, number average particle size 4.52Myuemu, the ratio of the volume average particle diameter (D ₃₎ to a number average particle diameter _{(D 1) (D 3 /} D 1) is 1. 04 black polymer particles B were obtained.

The content of particles having a particle diameter half that of D ₁ is 0.0
It was 2% by number. The content of particles having a particle size twice as large as D ₃ was 0.03% by volume.

After the solid-liquid separation and washing of the dispersion liquid 1 were repeated, the dispersion liquid was sufficiently dried to obtain polymer particles B-1. The number average particle diameter of B-1 was 4.33 μm, and D ₃ / D ₁ was 1.04.

This was dissolved in deuterated chloroform, C
¹³-NMR measurement was performed. For vinyl phenol unit
The presence of a hydroxyl group-bonded benzene ring was confirmed.
The presence of a double bond due to the reactive functional group was confirmed.
Did not. Compound 2 was added to polymer particles B-1 and B.
The presence of a polymer of the compound represented by was confirmed.

To 7 parts of the above polymer particles B, 0.14 part of crushed titanium oxide having a BET value of 350 m ² / g was mixed with a Henschel mixer, and fine powder of titanium oxide was externally added to obtain toner B. .

The toner B is dissolved in THF, and the soluble component GP
C measurement was performed. Maximum peak of molecular weight distribution is 26300
The amount of the component having a molecular weight of 1,000 or less was 0.02% by weight based on the toner B.

(Production Example 3 of Toner) In a reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen introducing pipe, and a mechanical stirrer, 300 parts of ethylbenzene 2 parts of compound 2 80 parts of styrene 20 parts of n-butyl acrylate 20 parts 2, A mixture consisting of 10 parts of 2'-azobisisobutyronitrile was charged into the reaction vessel and mixed well in a nitrogen stream. The reactor was heated in a 60 ° C. oil bath under a nitrogen atmosphere and refluxed for 10 hours under a nitrogen atmosphere. After cooling to room temperature, this is poured into a large amount of methanol,
The precipitate was collected and dried sufficiently to obtain Resin 3.

The toner particles were produced by the following method.

Using the apparatus shown in FIG. 1, 1000 parts of ion-exchanged water, 1 part of polyvinyl alcohol, 0.05 part of sodium dodecylbenzenesulfate and 0.05 part of chloroform were added as a continuous phase to a predetermined container, and further, 180 parts of chloroform, 20 parts of resin, and 1 part of oil blue Was thoroughly mixed and then charged into a predetermined container 3. Vibrator 11
And the pressure of nitrogen gas is 0.55 kg.
/ Cm ² to produce particles. After a while, the continuous phase became cloudy, and after 1 hour, after all the dispersed phases were completely injected, the suspension was taken out. After repeating filtration and washing,
After drying sufficiently, powder 1 was obtained.

The powder 1 was further classified by using an elbow jet classifier, and the number average particle diameter was 4.62 μm.
Powder 2 having a ratio (D ₃ / D ₁ ) of 1.09 between the volume average particle diameter (D ₃ ) and the number average particle diameter (D ₁ ) was obtained.

The content of particles having a particle diameter half that of D ₁ is 0.0
7% by number. The content of particles having a particle size twice as large as D ₃ was 0.6% by volume.

The above powder 27 parts was crushed and treated with B
Toner C was obtained by mixing 0.14 parts of titanium oxide having an ET value of 350 m ² / g with a Henschel mixer and externally adding fine titanium oxide powder.

The toner C was dissolved in THF, and GPC measurement was performed. The peak of the molecular weight distribution is 28300, and the component having a molecular weight of 1000 or less is 0.16% by weight based on the toner C.
Met.

(Comparative Toner Production Example 1) Ion-exchanged water 7
The 0.1M-Na ₃ PO ₄ aqueous solution 450 parts were heated to put to 60 ° C. to 10 parts. This was stirred at 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo),
68 g of a 1.0 M CaCl ₂ aqueous solution was gradually added, and C
An aqueous medium containing a ₃ (PO ₄ ) ₂ was obtained.

On the other hand, 180 parts of styrene 20 parts of n-butyl acrylate 20 parts of polyvinyl phenol (degree of polymerization 58) 5 parts of carbon black 10 parts of di-t-butyl salicylic acid metal compound 1 part The above formulation was heated to 60 ° C. And uniformly dissolved and dispersed at 10,000 rpm. Into this, 10 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable composition. The above-mentioned polymerizable monomer composition was charged into the aqueous medium, and the mixture was subjected to 12000 rpm with a TK homomixer at 60 ° C. in a nitrogen atmosphere.
Then, the mixture was stirred at m for 20 minutes to granulate the polymerizable monomer composition.
Then, while stirring with a paddle stirring blade, the temperature was raised to 80 ° C.
The reaction was performed for 0 hours.

Under reduced pressure, a part of the aqueous medium was distilled off, followed by cooling. Hydrochloric acid was added thereto to dissolve calcium phosphate, and then filtration and washing with water were repeated. After drying, polymer particles D having a number average particle diameter of 4.56 μm and a ratio (D ₃ / D ₁ ) of the volume average particle diameter (D ₃ ) to the number average particle diameter (D ₁ ) of 1.38 were obtained.

The content of particles having a particle diameter half that of D ₁ is 13.
It was 1% by number. The content of particles having a particle size twice as large as D ₃ was 12.8% by volume.

To 7 parts of the above polymer particles D, 0.14 part of crushed titanium oxide having a BET value of 350 m ² / g was mixed with a Henschel mixer, and fine titanium oxide powder was externally added to obtain toner D. .

The toner D is dissolved in THF, and the soluble component GP
C measurement was performed. The maximum peak of the molecular weight distribution is 68200.
The component having an average molecular weight of 1,000 or less was 11.6% by weight based on the toner D.

(Production Example 2 of Comparative Toner) Polymer particles D were subjected to air classification, and the number average particle diameter of 4.47 μm and the ratio of volume average particle diameter (D ₃ ) to number average particle diameter (D ₁ ) (D ₃ ) / D ₁ )
Of 1.14 was obtained. The content of the particles of the half of the particle size of D ₁ was 0.8% by number. The content of particles having a particle size twice as large as D ₃ was 0.7% by volume.

To 7 parts of the polymer particles D ′, 0.14 part of crushed titanium oxide having a BET value of 350 m ² / g was mixed with a Henschel mixer, and a fine powder of titanium oxide was externally added to prepare toner E. Obtained.

<Examples 1-3, Comparative Examples 1-2> Toner A
~ F on the paper with the same weight, using a modified heat and pressure fixing machine,
By measuring the lower limit fixing temperature under a normal temperature and normal humidity environment, relative evaluation of low temperature fixing property and offset resistance was performed.

7 parts of the toners A to F described above were mixed with 93 parts of a ferrite core having a particle size of 25 μm coated with a styrene-acrylic copolymer to obtain a two-component developer.

[0102] Canon full color laser copying machine CL
Using a C-500 modified machine, a continuous durability test of 10,000 sheets was performed.

Further, under a normal temperature and normal humidity environment (23 ° C., 55% R
H) and in a high-temperature and high-humidity environment (33 ° C., 80% RH), the images of these developers were evaluated.

Table 1 shows the results.

[0105]

[Table 1] The image quality was graded into four levels of ◎, △, Δ, and ×. The practical levels are ◎ and ○.

[0106]

According to the present invention, since a polymer of a polyvinyl phenol derivative containing a reactive functional group is contained, good negative chargeability can be imparted to toner particles, and high temperature and high humidity can be obtained. It is possible to improve the lowering of the absolute value of the triboelectric charge amount below. Further, it is possible to design a binder resin exhibiting good fixability with low viscosity and softening point during melting while maintaining excellent offset resistance.

[Brief description of the drawings]

FIG. 1 is a schematic view of a specific apparatus of a toner manufacturing method of the present invention.

[Description of Signs] 1 Porous body 2 Tubular module 3 Dispersed phase vessel 4 Continuous phase tank 5 Continuous phase vessel 6 Polymerization reaction vessel 7 Nitrogen cylinder 8, 9 Pressure gauge 10 Vibration generator 11 Vibrator 12 Refluxer 21, 22, 23, 24, 25 valves

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[Procedure amendment]

[Submission date] May 20, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Name of invention

[Correction method] Change

[Correction contents]

Patent application title: Toner for electrophotography and method for producing the same

Claims (8)

[Claims] 1. At least (i) a binder resin, (ii)
An electrophotographic toner comprising a colorant and (iii) a polymer of a polyvinylphenol derivative having a reactive functional group. 2. The electrophotographic toner according to claim 1, wherein the polymer of the reactive functional group-containing polyvinyl phenol derivative contains a monomer unit constituting the binder resin. 3. The toner according to claim 1, wherein the content of components having a molecular weight of 1,000 or less is 10% by weight or less based on the weight of the toner in the molecular weight distribution of the THF-soluble portion of the toner by GPC. The toner for electrophotography according to the above. 4. The electrophotographic toner according to claim 1, wherein a peak of a molecular weight distribution of the THF-soluble component of the toner by GPC is from 3,000 to 100,000. 5. The toner according to claim 1, wherein the content of toner particles having a particle diameter ((D ₁ ) / 2) or less, which is 平均 of the number average particle diameter (D ₁ ), is 10 number% or less. 5. The electrophotographic toner according to any one of items 1 to 4. 6. The toner according to claim 1, wherein the content of toner particles having a particle diameter ((D ₃ ) × 2) or more twice the volume average particle diameter (D ₃ ) is 10% by volume or less. 5. The electrophotographic toner according to any one of the above items 5. 7. A solvent for dissolving a monomer composition for synthesizing a polymer but not dissolving a polymer obtained by polymerizing the monomer composition, at least the monomer composition and a reactive functional group. By dissolving a polymer of a polyvinyl phenol derivative containing, and polymerizing the monomer composition in the solvent,
A method for producing an electrophotographic toner, wherein toner particles are formed. 8. The content of the reactive functional group of the polyvinyl phenol derivative containing the reactive functional group is 0.000 based on the monomer unit of the vinyl phenol derivative.
The method for producing an electrophotographic toner according to claim 7, wherein the amount is 1 mol% or more and 20 mol% or less.