JP3015225B2 - Electrostatic image developing toner and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image suitable for heat fixing used in electrophotography, electrostatic recording and magnetic recording, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Many methods are known as described in Japanese Patent Publication No. JP-A-Heisei, 43-24878 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means. Forming and then developing the latent image with toner,
After transferring the toner image to a transfer material such as paper as necessary,
The toner is fixed by heating, pressure, heat and pressure, or solvent vapor to obtain a copy, and the toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated.

Further, a general method of forming a full-color image will be described. The photosensitive member of a photosensitive drum is uniformly charged by a primary charger, and image exposure is performed by a laser beam modulated to a magenta image signal of a document. To form an electrostatic latent image on the photosensitive drum, and develop the electrostatic latent image by a magenta developing device having magenta toner to form a magenta toner image. Next, the developed magenta toner image is transferred onto the photosensitive drum by a transfer charger onto the transferred transfer material.

On the other hand, the photosensitive drum after the development of the electrostatic latent image is neutralized by a static eliminator, cleaned by a cleaning unit, and charged again by a primary charger. The formation of the cyan toner image and the transfer of the cyan toner image to the transfer material on which the magenta toner image has been transferred are performed, and the same process is performed in the same manner as for the yellow color and the black color to transfer the four color toner images to the transfer material. A full-color image is formed by fixing the transfer material having the four color toner images by the action of heat and pressure by a fixing roller.

In recent years, such copying apparatuses have begun to be used not only as office work copying machines for simply copying original documents, but also as printers as personal computer outputs or personal copies for individuals. .

[0006] In addition to the field represented by such a laser beam printer, the development to a plain paper fax using a basic engine is also rapidly developing.

For this reason, smaller, lighter, faster, higher quality, and higher reliability have been strictly pursued, and machines have been constructed from simpler elements in various respects. . As a result, the performance required of the toner has become higher, and if the performance of the toner cannot be improved, a better machine cannot be realized.

In recent years, with the need for various copying,
The factors for color copying are also increasing rapidly, and higher quality, higher resolution, and the like are desired to copy original color images more faithfully.

From these viewpoints, the toner used in the color image forming method needs to have good melting property and color mixing property when heat is applied to the toner, have a low softening point, and have a low melt viscosity. It is preferable to use a toner having a low sharpness and a high sharp melt property.

That is, by using such a sharp melt toner, the color reproduction range of a copy can be widened and a color copy faithful to the original image can be obtained.

However, such a color toner having a high sharp melt property generally has a high affinity with a fixing roller, and tends to be easily offset to the fixing roller during fixing.

Particularly, in the case of a fixing device in a color image forming apparatus, since a plurality of toner layers of magenta, cyan, yellow, and black are formed on a transfer material, offset tends to occur particularly due to an increase in toner layer thickness. It is in.

Conventionally, for the purpose of preventing toner from adhering to the surface of the fixing roller, for example, the roller surface is formed of a material having excellent releasability to the toner, such as silicone rubber or a fluorine-based resin. In order to prevent the roller surface from being fatigued, the roller surface is coated with a thin film of a highly releasable liquid such as silicone oil or fluorine oil. However, this method is extremely effective in preventing toner offset, but has a problem that a fixing device is complicated because a device for supplying an anti-offset liquid is required. Needless to say, this oil application causes delamination between the layers constituting the fixing roller, and consequently has a disadvantage that the life of the fixing roller is shortened. As a transfer material for fixing a toner image using these fixing devices, various papers, coated papers, plastic films and the like are generally used. In particular, the necessity of a transparency film (OHP) using an overhead projector for presentation has recently attracted attention. In particular, OHP differs from paper in that it has a low oil absorbing ability, so that the currently obtained copy OHP is inevitably greasy due to oil application, and a large problem remains in the quality of the obtained image. In addition, there is a great possibility that silicone oil and the like will evaporate due to heat and contaminate the inside of the machine, and there will be problems such as treatment of collected oil. Therefore, instead of using a silicone oil supply device, instead of supplying the anti-offset liquid during heating from the toner, low-molecular-weight polyethylene,
A method of adding a release agent such as low molecular weight polypropylene has been proposed. If a large amount of such an additive is added in order to obtain a sufficient effect, filming on a photoreceptor or contamination of the surface of a toner carrier such as a carrier or a sleeve will cause deterioration of an image and pose a practical problem. Therefore, a small amount of release agent is added to the toner to the extent that the image is not deteriorated, and a small amount of release oil is supplied or the offset toner is wound up using a device such as a web-type member or a cleaning pad. In addition, a cleaning device is used in combination.

However, in view of recent demands for miniaturization, weight reduction, and high reliability, it is necessary and preferable to remove even these auxiliary devices. Therefore, if there is no further performance improvement such as toner fixing and offset,
It is difficult to realize this without further improvement of the binder resin of the toner, the release agent and the like.

Further, especially in full-color separation,
By including a release agent, when OHP is used as the transfer material, the transparency and haze of the image after fixing are slightly reduced due to factors such as high crystallization of the release agent and a difference in the refractive index of the resin. A problem arises.

It is known that a wax is contained in a toner as a release agent. For example, Japanese Patent Publication No. 52-330
No. 4, JP-B-52-3305, JP-A-57-305.
The technology is disclosed in, for example, Japanese Patent No. 52574.

Also, JP-A-3-50559, JP-A-2-79860, JP-A-1-109359, JP-A-62-14166, and JP-A-61-27
3554, JP-A-61-94092, JP-A-61-138259, and JP-A-60-25236
No. 1, Japanese Unexamined Patent Publication No. 60-252360, Japanese Unexamined Patent Publication No.
Japanese Patent Application Laid-Open No. 0-217366 discloses a technique for containing waxes.

Waxes are used to improve the anti-offset property of toner at low and high temperatures and to improve the fixability at low temperature. For example, when the toner is left for a long period of time, the wax migrates to the surface of the toner to deteriorate the developability.

None of the conventional toners satisfies all of these aspects, causing some problems. For example, high-temperature offset and developability are excellent, but low-temperature fixability is just one step away, or low-temperature offset and low-temperature fixability are excellent, but blocking resistance is slightly inferior, and developability decreases when the temperature rises in the machine. And the offset resistance at low and high temperatures cannot be compatible, and the transparency of OHP has been extremely poor.

With respect to the transparency of OHP, in particular, Japanese Patent Application Laid-Open Nos. 4-149559 and 4-107467 disclose the addition of a crystallization nucleating agent or the like to the wax in order to reduce the crystallization of the wax itself. Proposals using a material having a low crystallinity are disclosed in Japanese Patent Application Nos. Hei 3-091108 and Hei 3-242397 and a substance having good compatibility with a binder and having a lower melt viscosity than a binder. To improve the surface smoothness of the toner layer after fixing (JP-A-3-21265).
No. 2).

One of the releasing agents having relatively good transparency and low-temperature fixing performance is montan wax, which is a mineral wax.

The following structural formula is used as the montan wax.

[0023]

[Outside 1] [Wherein, R represents a hydrocarbon group having 28 to 32 carbon atoms,
n represents an integer] It is possible to use a wax having a molecular weight of 800 represented by JP-A-1-185660, JP-A-1-185661, JP-A-1-185662, JP-A-1-185661. JP-A-1-23
No. 8672 proposes a proposal.

However, these are all OHP
Is not fully satisfactory in terms of transparency and haze.

[0025]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic image and a method for producing the same, which solves the above-mentioned problems.

It is another object of the present invention to provide a toner for developing an electrostatic image, which is excellent in low-temperature fixability to a transfer material and anti-offset property, and a method for producing the same.

Still another object of the present invention is to provide a toner for developing electrostatic images which can be fixed without using a large amount of oil or without applying any oil, and a method for producing the same. .

Still another object of the present invention is to provide a full-color toner capable of obtaining a high-quality full-color OHP excellent in transparency and a method for producing the same.

[0029]

According to the present invention, there is provided a toner for developing an electrostatic image, comprising a binder resin, a colorant and a monofunctional ester compound having tertiary and / or quaternary carbon. About. Further, the present invention provides a method of melting and kneading a mixture having a binder resin, a colorant, and a monofunctional ester compound having a tertiary or / and quaternary carbon, cooling,
The present invention relates to a method for producing a toner for developing an electrostatic image, which comprises pulverizing and classifying toner particles.

Further, the present invention provides a method for producing toner particles directly by polymerizing a mixture having a polymerizable monomer, a colorant and a monofunctional ester compound having a tertiary or / and quaternary carbon. The present invention relates to a method for producing a toner for developing an electrostatic image, which is a feature of the invention.

The following is a detailed description using specific examples.

As typical examples of the monofunctional ester compound having a tertiary and / or quaternary carbon used in the present invention,
The compound mainly represented by the following structural formula [1] is exemplified.

[0033]

[Outside 2] [Wherein, R ₁ represents an organic group having ₁ to 35 carbon atoms, and Y _{1 and} Y
₂ and Y ₃ are the same or different groups, and represent a hydrogen atom,
X represents a halogen atom or an organic group, X represents an oxygen atom or a sulfur atom, Z represents an oxygen atom or a sulfur atom, and m represents zero or an integer of 1 or more. However, when m is zero, Y _1, Y ₂ and Y ₃ represents an organic group. ] More specifically, the following monofunctional compounds can be mentioned.

[0034]

[Outside 3]

The monofunctional ester compound used in the present invention has a low affinity for the binder resin in order to exhibit good low-temperature fixability, is highly hydrophobic, and has a low melting point. It is.

Further, as a result of intensive studies, the present inventors have found that, in order to further impart the function of transparency, which is the object of the present invention, the structure of the release agent itself for inhibiting crystallization of the release agent itself. Has been found to be necessary to break the symmetry of tertiary or tertiary carbon.

The monofunctional polyester compound is preferably used in an amount of 1 to 40 parts by weight (preferably 2 to 30 parts by weight) based on 100 parts by weight of the binder resin of the toner.

The amount of the monofunctional ester to be added depends on the binder resin,
In a dry toner production method in which a mixture having a colorant and a monofunctional ester of the present invention is melt-kneaded, cooled, pulverized, and then classified to obtain toner particles, 1 to 10 parts by weight, more preferably 100 parts by weight, per 100 parts by weight of a binder resin is more preferable. It is preferred to use 2-5 parts by weight.

In a polymerization toner production method in which toner particles are directly obtained by polymerizing a mixture having a polymerizable monomer, a colorant and a monofunctional ester compound,
It is preferable to use 10 to 40 parts by weight, more preferably 15 to 30 parts by weight, based on 100 parts by weight of the polymerizable monomer.

Polymerization method compared to dry toner production method In a toner production method, a generally used release agent is lower in polarity than a binder resin. Therefore, in a polymerization method in an aqueous medium, a large amount of the release agent is encapsulated inside toner particles. In general, a large amount of a release agent can be used as compared with a dry toner production method, and the effect of preventing offset during fixing is particularly effective.

When the addition amount is less than the lower limit, the offset prevention effect tends to decrease, and when the addition amount exceeds the upper limit, the anti-blocking effect is reduced, the offset resistance effect is adversely affected, and the drum fusion and sleeve fusion are easily caused. Further, in the case of a polymerization toner, a toner having a wide particle size distribution tends to be generated.

In order to obtain a sufficiently transparent OHP image with a low heat capacity of the fixing device, it is most important to lower the crystallinity of the release agent usually contained in the toner. However, in order to impart more sufficient transparency as a secondary effect, there are some undissolved toner grain boundaries that were not dissolved even after fixing, or the crystallinity of the release agent layer is caused by irregular reflection of light. In this case, the effective light transmittance is reduced, and as a result, haze is reduced. Further, even if the components mixed in the toner are sufficiently dissolved at the time of fixing, if the difference in the refractive index between the dissolved toner layer and the release agent layer formed between the fixing members is large, this is also the case of light. It is not preferable because it causes irregular reflection.

The increase in the irregular reflection of light leads to a decrease in the brightness of the projected image and a decrease in the sharpness of the color. In particular, when a transmission type overhead projector is used, this problem is further increased than when a reflection type overhead projector is used.

That is, in order to reduce the crystallinity of the release agent, it is important to lower the crystallinity of the release agent alone. Further, in order to prevent unmelted toner grain boundaries from being present in the toner fixing layer, the glass transition temperature (T
A material having a small melting enthalpy (ΔH), which is the latent heat of the release agent, is particularly preferable in order to make g) and the melting point (mp) of the release agent as close as possible and to quickly dissolve it with a low energy amount. It is preferable that the difference in solubility parameter (SP) between the binder resin and the release agent is appropriately adjusted in order for the molten release layer to quickly move between the binder resin layer and the fixing member and form an anti-offset layer. .

Preferred examples of the present invention from such a viewpoint will be described in detail below.

The monofunctional ester compound release agent used in the present invention generally uses a polyester resin, a styrene-acrylic resin, an epoxy resin or a styrene-butadiene resin as a binder resin of the toner. Therefore, those having a refractive index close to those of these resins are preferable.

As a method of measuring the refractive index, first, the vertical (2
0-30) x width (8) x thickness (3-10) to make a solid sample, then apply a small amount of bromonaphthalene to the prism surface to improve the adhesion to the prism surface.
A method of mounting a solid sample thereon and measuring the refractive index is exemplified. Further, as the measuring instrument, for example, an Appe refractometer 2T manufactured by Atago Co., Ltd. may be mentioned.

The difference in refractive index between the binder resin and the monofunctional ester compound at a temperature of 25 ° C. is 0.18 or less, more preferably 0.10 or less. Introduction of a heteroester in which the ester group is replaced by a hetero element such as sulfur or phosphorus is also effective for adjusting the refractive index. If the refractive index difference exceeds 0.18, the transparency of the OHP image is likely to be reduced, and particularly, a halftone projected image is not preferable because the brightness becomes low.

The melting point of the monofunctional ester compound used in the present invention is preferably from 30 to 120 ° C., more preferably from 50 to 100 ° C. Melting point
When the temperature is lower than 30 ° C., the blocking resistance of the toner, the suppression of sleeve contamination and the prevention of contamination of the photoconductor at the time of copying a large number of sheets are apt to be reduced. If the melting point exceeds 120 ° C., excessive energy is required for uniform mixing with the binder resin in the production of the toner by the pulverization method, and the use of a high-boiling solvent in the production of the toner by the polymerization method. And a pressure-resistant reaction vessel under high pressure is required, and the apparatus becomes extremely complicated, which is not preferable.

The solubility parameter (SP) value is determined by the method of Fedors using the additivity of atomic groups [Polym.
Eng. Sci. , 14 (2) 147 (1974)].

The SP value of the monofunctional ester compound used in the present invention is preferably in the range of 7.5 to 9.7. The monofunctional ester having an SP value of less than 7.5 has poor compatibility with the binder resin to be used, and as a result, it is difficult to obtain a good dispersion in the binder resin. The compound easily adheres to the developing sleeve, and the charge amount of the toner tends to change. Further, the density fluctuates easily at the time of ground fog and toner supply.

When a monofunctional ester compound having an SP value exceeding 9.7 is used, blocking between toners is likely to occur when the toner is stored for a long time. Further, since the compatibility with the binder resin is too good, it is difficult to form a sufficient releasable layer between the fixing member and the toner binder resin layer at the time of fixing, and the offset phenomenon is easily caused.

The melt viscosity of the monofunctional ester compound used in the present invention is measured at 130 ° C. using a cone-plate type rotor (PK-1) with VP-500 manufactured by HAAKE. The melt viscosity at 130 ° C. is preferably from 1 to 300 cps, more preferably a monofunctional ester compound having from 3 to 50 cps. When the melt viscosity is lower than 1 cps, when a thin layer of the toner layer is coated on the sleeve with a blade or the like in a non-magnetic one-component developing method, the sleeve is easily contaminated by mechanical shearing force. Further, in the two-component developing method, when a toner is developed using a carrier, damage due to a shear force between the toner and the carrier is apt to occur, and external additives are easily buried and the toner is crushed.
When the toner has a melt viscosity of more than 300 cps, the viscosity of the dispersoid is too high when producing a toner using a polymerization method, and it is not easy to obtain a toner having a small particle size having a uniform particle size. The toner tends to have a wide distribution.

The hardness of the monofunctional ester compound is measured, for example, by using a Shimadzu Dynamic Ultra Micro Hardness Tester (DUH-200).
Is used. The measurement conditions were as follows. After displacing 10 μm at a load speed of 9.67 mg / sec under a load of 0.5 g using a Vickers indenter, holding for 15 seconds, and analyzing the dents on the sample, the Vickers hardness was determined. . As the sample, a sample previously melted using a mold having a diameter of 20 mmφ is formed into a column having a thickness of 5 mm. The hardness of the release agent used in the present invention is 0.3 to 5.0.
Is preferable, and a more preferable Vickers hardness is 0.1.
5-3.0 is particularly effective.

A toner containing a monofunctional ester compound having a Vickers hardness lower than 0.3 is liable to be crushed at a cleaning portion of a copying machine in copying a large number of sheets, easily causing toner fusion on a drum surface, and consequently an image. Black streaks are likely to occur on the top. Further, when multiple image samples are stored while being stacked, the toner is transferred to the surface and so-called show-through tends to occur, which is not preferable. A toner containing a monofunctional ester compound having a Vickers hardness of more than 5.0 requires an unnecessarily high pressurizing force for a fixing device used at the time of heat fixing, and requires an unnecessarily high strength design for the fixing device. If a fixing device with a normal pressing force is used, the offset resistance tends to decrease, which is not preferable.

The crystallinity of the monofunctional ester compound is 1
The content is preferably 0 to 50%, more preferably 20 to 35%.

When the crystallinity is less than 10%, the toner storability and fluidity tend to deteriorate, and when it exceeds 50%, the transparency of the OHP image tends to deteriorate.

The degree of crystallinity in the present invention is measured by the following formula from the area ratio between the amorphous scattering peak and the crystal scattering peak without using a calibration curve.

[0059]

[Outside 4]

As a measuring device, for example, Rotorflex RU300 (Cu target, point focus, output 50 Kv / 250 mA) manufactured by Rigaku Denki Co., Ltd. can be mentioned.

The transmission method-rotation method is used for the measurement, and the measurement angle is 2θ = 5 to 35 °.

The number average molecular weight of the monofunctional ester compound in the present invention is measured by a vapor pressure osmotic pressure (VPO) method.

The measurement conditions are as follows.

Apparatus: Model 115 Hitachi molecular weight measuring apparatus Temperature: 61 ° C. Solvent: toluene (special grade reagent) Standard sample: benzyl (special grade reagent) The number average molecular weight is calculated from the following equation. The sample concentration is
The average molar concentration is calculated from the charged amount, and the average molar concentration is read from the ΔR obtained in the sample measurement using a ΔR-average molar concentration calibration curve prepared with benzyl.

[0065]

[Outside 5]

The number average molecular weight (Mn) of the monofunctional ester compound is preferably from 200 to 2,000. More preferably, Mn is from 500 to 1,000.

If the number average molecular weight is less than 200, the melting point tends to be too low and the blocking resistance tends to deteriorate.

When Mn exceeds 2,000, the releasing effect and OHP transparency tend to decrease.

The method for producing the monofunctional ester compound used in the present invention includes, for example, a synthesis method by an oxidation reaction,
Synthesis from carboxylic acids and derivatives thereof, ester group introduction reactions typified by Michael addition reactions, and the like are generally used. A particularly preferred method for producing the monofunctional esters used in the present invention is a method using a dehydration condensation reaction from a carboxylic acid compound and an alcohol compound from the versatility of the raw materials and the ease of the reaction, or a method using an acid halide and an alcohol compound. Reactions are particularly preferred.

[0070]

[Outside 6]

In order to transfer the above-mentioned ester equilibrium reaction to the production system, a large excess alcohol is used, or the reaction is carried out in an aromatic organic solvent capable of azeotropic distillation with water using a Dean-Stark water separator. . Further, a method of synthesizing an ester by using an acid halide compound and adding a base as an acceptor of an acid by-produced in an aromatic organic solvent can also be used.

As the binder resin used in the toner of the present invention, the following binder resins can be used.

For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene and their substituted products; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene Copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-
Styrene such as vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer -Based copolymer; polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin , Xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, petroleum resin and the like can be used. Preferred binders include styrene copolymers or polyester resins.

Examples of comonomers for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and the like.
Double such as dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc. A monocarboxylic acid having a bond or a substituted product thereof;
For example, dicarboxylic acids having a double bond such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate and the like;
Vinyl esters such as vinyl acetate and vinyl benzoate; ethylene-based olefins such as ethylene, propylene and butylene; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; vinyl methyl ether; Vinyl monomers such as vinyl ethyl ether and vinyl isobutyl ether; alone or in combination of two or more.

The number average molecular weight of the THF-soluble component of the binder resin of the present invention is preferably from 3,000 to 1,000,000.

The styrene-based polymer or styrene-based copolymer may be crosslinked, or may be a resin mixture thereof.

As the crosslinking agent for the binder resin, a compound having two or more polymerizable double bonds may be mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; Carboxylic acid esters having two double bonds such as glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butadiol dimethacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone; and 3
Compounds having at least two vinyl groups are used alone or as a mixture. The amount of the polymerizable monomer 1
0.001 to 10 parts by weight is preferable with respect to 00 parts by weight.

The toner of the present invention may contain a charge control agent.

The following substances control the toner to be negatively charged.

For example, organic metal compounds and chelate compounds are effective, and examples thereof include monoazo metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid-based metal compounds. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

Further, urea derivatives, metal-containing salicylic acid compounds, quaternary ammonium salts, calixarenes, silicon compounds, styrene-acrylic acid copolymers, styrene-
Examples include methacrylic acid copolymer, styrene-acryl-sulfonic acid copolymer, and nonmetal carboxylic acid compounds.

The following substances control the toner to be positively charged.

Modified products such as nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate;
And onium salts such as phosphonium salts, which are analogs thereof, and their lake pigments, triphenylmethane dyes, and these lake pigments (as the lake-forming agent, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid) , Lauric acid, gallic acid, ferricyanide, ferrocyanide) metal salts of higher fatty acids: diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide: dibutyltin borate, dioctyltin borate, dicyclohexyltin borate, etc. Diorganotin borates; these can be used alone or in combination of two or more. Of these, charge control agents such as nigrosine and quaternary ammonium salts are particularly preferably used.

These charge controlling agents are used in an amount of 0.01 to 20 parts by weight (preferably 0.5 to 20 parts by weight) based on 100 parts by weight of the resin component.
-10 parts by weight).

Examples of the colorant for the toner include black pigments such as carbon black, alline black, and acetylene black.

Examples of pigments for magenta include red lead graphite, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G, cadmium red, permanent red 4R, watching red calcium salt, eosin lake, and brilliant carmine 3.
B, carmine 6B, manganese purple, fast violet B, methyl violet lake, rhodamine lake, alizarin lake, bengara, quinacridone, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9,
10, 11, 12, 13, 14, 15, 16, 17, 1
8, 19, 21, 22, 23, 30, 31, 32, 3,
7, 38, 39, 40, 41, 48, 49, 50, 5,
1, 52, 53, 54, 55, 57, 58, 60, 6
3, 64, 68, 81, 83, 87, 88, 89, 9
0, 112, 114, 122, 123, 163, 20
2, 206, 207, 209: C.I. I. Pigment Violet 19, C.I. I. Butt Red 1, 2, 10, 1
3, 15, 23, 29, 35 and the like.

Examples of cyan pigments include C.I. I. Pigment Blue 2, 3, 15, 16, 17; I. Bat blue 6; I. Acid Blue 45, Indanthrene Blue, Navy Blue, Cobalt Blue, Alkaline Blue Lake, Vicryable Lake, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, Chrome Green, Chromium Oxide, Pigment Green B, Malachite Green Lake, Final Yellow green G
And the like.

Examples of the yellow pigments include naphthol yellow, Hiza yellow, graphite, cadmium yellow, mithral fast yellow, navel yellow, permanent yellow NCG and tartrazine lake; I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5, 73, 83, 97, 120, 127, 174, 17
6, 180, 181, 191; I. Bat Yellow 1, 3, 20 and the like.

These pigments are used in an amount necessary to maintain the optical density of the fixed image, and 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, per 100 parts by weight of the resin. The addition amount is preferred.

Examples of the dye used as the colorant include the following.

Examples of magenta dyes include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 3
0, 49, 81, 82, 83, 84, 100, 109,
121; I. Disperred 9; C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I.
I. Disperse Violet 1; I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 1
8, 22, 23, 24, 27, 29, 32, 34, 3
5, 36, 37, 38, 39, 40; I. Basic violet 1, 3, 7, 10, 14, 15, 21,
C. 25, 26, 27, 28; I. Direct red 1, 4; I. Acid Red 1, C.I. I. Modant Red 30 and the like.

Cyan dyes include C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Azide Blue 9, C.I. I. Ajid 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.
Basic Green 6 and the like.

The amount of these dyes is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the resin.

Further, the toner of the present invention can be used as a magnetic toner by further containing a magnetic material. In this case, the magnetic material can also serve as a colorant. In the present invention, the magnetic material contained in the magnetic toner includes iron oxide such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and aluminum, cobalt, copper, lead, magnesium, and tin of these metals. ,
Examples include alloys of metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

The ferromagnetic material preferably has an average particle size of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount contained in the toner is preferably 20 to 200 parts by weight, more preferably 40 to 150 parts by weight, based on 100 parts by weight of the resin component.

The magnetic characteristics when 10K Oersted is applied are as follows: coercive force (Hc) 20 to 300 Oersted, saturation magnetization (σs) 50 to 200 emu / g, residual magnetization (σr)
Those having 2 to 20 emu / g are preferred.

The additive for imparting various toner properties should have a particle diameter of 1/5 or less of the volume average diameter of the toner particles from the viewpoint of durability when added to the toner or when added to the toner. Is preferred. The particle size of the additive means an average particle size obtained by observing the surface of the toner particles with an electron microscope. As additives for imparting these properties, for example, the following are used.

Examples of the fluidity-imparting agent include metal oxides (such as silicon oxide, aluminum oxide, and titanium oxide), carbon black, and carbon fluoride. Those subjected to a hydrophobic treatment are more preferable. As an abrasive, metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.)
-Nitride (such as silicon nitride) and carbide (such as silicon carbide) metal salts (such as calcium sulfate, barium sulfate, and calcium carbonate).

Examples of the lubricant include fluororesin powder (vinylidene fluoride, polytetrafluoroethylene, etc.) and fatty acid metal salts (zinc stearate, calcium stearate, etc.).

Examples of the charge control particles include metal oxides (such as tin oxide, titanium oxide, zinc oxide, silicon oxide, and aluminum oxide) and carbon black.

These additives are used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner particles. These additives may be used alone or in combination of two or more.

The toner of the present invention can be used as a one-component or two-component developer in any developer.

For example, in the case of a magnetic toner in which a magnetic substance is contained in a toner as a one-component developer, there is a method in which a magnet incorporated in a developing sleeve is used to convey and charge the magnetic toner. . When a non-magnetic toner containing no magnetic substance is used, there is a method in which the toner is conveyed by forcibly frictionally charging the developing sleeve with a blade and a fur brush and causing the toner to adhere to the sleeve.

On the other hand, when used as a commonly used two-component developer, a carrier is used as a developer together with the toner of the present invention. The carrier used in the present invention is not particularly limited, but is mainly composed of a single ferrite and a composite ferrite composed of iron, copper, zinc, nickel, cobalt, manganese, and chromium. Carrier shape is also important from the viewpoint that saturation magnetization and electric resistance can be controlled in a wide range. For example, it is preferable to select a spherical shape, a flat shape, an irregular shape, and the like, and to further control a fine structure of a carrier surface state, for example, surface unevenness. . Generally, the above inorganic oxide is calcined,
A method of coating the resin after forming carrier core particles in advance by granulation is used.However, from the viewpoint of reducing the load on the toner of the carrier, the inorganic oxide and the resin are kneaded and then pulverized. , A method of obtaining a low-density dispersion carrier by classification, and a method of directly obtaining a polymerized carrier for obtaining a spherical dispersion carrier by suspension-polymerizing a kneaded product of an inorganic oxide and a monomer in an aqueous medium are also used. It is possible to

A system in which the surface of the carrier is coated with a resin or the like is particularly preferable. As the method, any conventionally known method such as a method of dissolving or suspending a coating material such as a resin in a solvent, coating and adhering to a carrier, and a method of simply mixing with a powder can be applied.

The substance fixed to the carrier surface varies depending on the toner material. Examples thereof include polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, a metal compound of ditersharry butylsalicylic acid, and styrene-based compounds. Resin, acrylic resin, polyacid, polyvinyl butyral, nigrosine, amino acrylate resin, basic dyes and lakes thereof, silica fine powder, alumina fine powder, etc. are suitable for use alone or in combination, but are not necessarily limited to this. Not done.

The treatment amount of the above compound is generally preferably 0.1 to 30% by weight (preferably 0.5 to 20% by weight) based on the total amount of the carrier of the present invention.

The average particle size of these carriers is 10 to 100.
μ, preferably 20 to 50 μ.

In a particularly preferred embodiment, Cu—Zn—
Fe ternary ferrite whose surface is a combination of a resin such as a fluorine resin and a styrene resin, for example, polyvinylidene fluoride and styrene-methyl methacrylate resin: polytetrafluoroethylene and styrene-methyl methacrylate resin, A mixture of a fluorine-based copolymer and a styrene-based copolymer in a ratio of 90:10 to 20:80, preferably 70:30 to 30:70, and 0.01 to 5% by weight, preferably 0.1-1% by weight
Coated ferrite carriers having the above-mentioned average particle size, which are coated and have a 250 mesh pass, 400 mesh on carrier particles of 70% by weight or more, may be mentioned. As the fluorine-based copolymer, a vinylidene fluoride tetrafluoroethylene copolymer (10:90 to 90: 1)
0). Examples of the styrene copolymer include styrene-2-ethylhexyl acrylate (20:80 to 80:
20), styrene-2-ethylhexyne acrylate-methyl methacrylate (20-60: 5-30: 10-5)
0) is exemplified.

The coated ferrite carrier has a sharp particle size distribution, provides favorable triboelectrification to the toner of the present invention, and has the effect of improving electrophotographic properties.

When a two-component developer is prepared by mixing with the toner of the present invention, the mixing ratio is 2 to 15% by weight, preferably 4% by weight, as the toner concentration in the developer.
Good results are usually obtained with １３13% by weight. When the toner density is 2% or less, the image density is low and cannot be used practically.
If it is 15% or more, fog and scattering in the machine are increased, and the useful life of the developer is shortened.

Further, the following are preferred as the carrier magnetic characteristics.

The magnetization intensity (σ ₁₀₀₀ ) at 1000 Oe after magnetic saturation is 100 to 300.
It is required to be emu / cm ³ . In order to achieve higher image quality, preferably 100 to 250 e
It is preferably mu / cm ³ . 300 emu / cm ³
If it is larger, it becomes difficult to obtain a high quality toner image. If it is less than 100 emu / cm ³ , the magnetic binding force is reduced, and carrier adhesion is likely to occur.

Further, as for the shape of the carrier, it is preferable that SF1 indicating the degree of roundness is 180 or less and SF2 indicating the degree of unevenness is 250 or less. Note that SF1, SF
2 is defined by the following formula, and is made by Nileco LVZEXI.
It was measured at II.

[0115]

[Outside 7]

The method for producing the pulverized toner in the present invention is as follows.
The binder resin, the monofunctional ester compound of the present invention, a pigment or dye as a colorant, a dye, a magnetic substance, a charge control agent, if necessary, and other additives are sufficiently mixed with a mixer such as a Henschel mixer or a ball mill. After mixing, melt and knead using a hot kneader such as a heating roll, kneader, extruder to make the resins compatible with each other, disperse or dissolve the metal compounds, pigments, dyes, and magnetic substances, and cool and solidify. After the pulverization and classification, the toner according to the present invention can be obtained.

Further, if necessary, desired additives are sufficiently mixed with a mixer such as a Henschel mixer to obtain the toner for an electrostatic image developer according to the present invention.

Further, the polymerized toner used in the present invention is obtained by the following method. That is, a monomer system in which a monofunctional ester compound, a colorant, a charge control agent, a polymerization initiator, and other additives are added to a polymerizable monomer, and the mixture is uniformly dissolved or dispersed with a homogenizer or an ultrasonic disperser. Is dispersed in a dispersion medium containing a dispersion stabilizer or an emulsifier by a stirrer, a homomixer, a homogenizer, or the like, and granulated. Thereafter, by the action of the dispersion stabilizer, stirring may be performed to such an extent that the monomer-based particle state is maintained and the sedimentation of the monomer-based particles is prevented. The polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. Further, the temperature may be raised in the latter half of the polymerization reaction,
Furthermore, the latter half of the reaction to remove unreacted polymerizable monomers and by-products that cause odor at the time of fixing the toner, or
After the completion of the reaction, a part of the aqueous medium may be distilled off. After the completion of the reaction, the generated toner particles are washed, collected by filtration, and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer system.

The particle size of the toner was 0.1 to 12 μm in weight average particle size in Coulter Counter Model TA-II (manufactured by Coulter Electronics Co., Ltd.), and the particle size distribution was
It is preferable that the coefficient of variation in the weight average diameter is 8 to 40%.
0 <SF1 <150, SF2 representing the degree of unevenness is 10
It is preferable that 0 <SF2 <200.

When a toner is directly obtained by a polymerization method, the polymerizable monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methylstyrene.
Styrene monomers such as methoxystyrene and p-ethylstyrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-acrylate
-Propyl, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, acrylates such as phenyl acrylate, methyl methacrylate,
Ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, Examples include methacrylic esters such as diethylaminoethyl methacrylate and the like, and monomers such as acrylonitrile, methacrylonitrile, and acrylamide. These monomers can be used alone or as a mixture.

Further, a polymer or a copolymer having a polar group as an additive may be added to the monomer system of the polymerization method toner of the present invention for polymerization.

The polar polymers and copolymers that can be used in the present invention are exemplified below.

Polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, copolymers with styrene-unsaturated carboxylic esters, etc., nitrile monomers such as acrylonitrile, vinyl chloride Halogen-containing monomers, acrylic acid, unsaturated carboxylic acids such as methacrylic acid, and other unsaturated dibasic acids,
Examples thereof include polymers such as unsaturated dibasic acid anhydrides and nitro monomers or copolymers with styrene monomers, polyesters, epoxy resins and the like.

Examples of the polymerization initiator include, for example, 2,2'-
Azobis- (2,4-dimethylvaleronitrile), 2,
2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2 '
Azo- or diazo-based polymerization initiators such as azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropylopyryl peroxycarbonate, cumene hydroperoxide, t -Butyl hydroperoxide, di-t-butyl peroxide, dixyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis (4,
4-tert-butylperoxycyclohexyl) propane,
A peroxide initiator such as tris (t-butylperoxy) triazine, a polymer initiator having a peroxide in a side chain, a persulfate such as potassium persulfate and ammonium persulfate, hydrogen peroxide, and the like are used. You. The polymerization initiator is preferably added in an amount of 0.5 to 20 parts by weight of the polymerizable monomer, and may be used alone or in combination.

In the present invention, known crosslinking agents and chain transfer agents may be added in order to control the molecular weight. The preferred addition amount is 0.001 to 15 parts by weight.

In the present invention, any suitable stabilizer may be used as a dispersion medium for producing a polymerization toner by emulsion polymerization, dispersion polymerization, suspension polymerization, seed polymerization, polymerization using salting out, or the like. use. For example, as inorganic compounds, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate , Bentonite, silica, alumina and the like. As organic compounds, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salts, starch polyacrylamide, polyethylene oxide, poly (hydroxystearic acid-g-methacryl) For example, an acid-methyl-eu-methacrylic acid) copolymer or a nonionic or ionic surfactant is used.

When the emulsion polymerization method is used, an anionic surfactant, a cationic surfactant, an amphoteric ionic surfactant and a nonionic surfactant are used. These stabilizers, based on 100 polymerized parts of the polymerizable monomer,
It is preferred to use from 0.2 to 30 parts by weight.

When an inorganic compound is used among these stabilizers, a commercially available one may be used as it is, but in order to obtain fine particles, the inorganic compound may be formed in a dispersion medium.

In order to finely disperse these stabilizers,
A surfactant of 0.001 to 0.1 polymerization part may be used. This is to promote the desired action of the dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, and lauryl acid. Sodium, potassium stearate, calcium oleate and the like.

In the present invention, it is necessary to pay attention to the polymerization inhibitory property and the water phase migration property of the colorant used for the polymerization toner in the present invention. It is better to perform a hydrophobic treatment without inhibiting polymerization. In particular, many dyes and carbon blacks have polymerization inhibitory properties, so care must be taken when using them. As a preferable method for surface-treating the dye system, a method in which a polymerizable monomer is previously polymerized in the presence of these dyes is mentioned, and the obtained colored polymer is added to the monomer system. The carbon black may be treated with a substance that reacts with the surface functional group of the carbon black, for example, a polyorganosiloxane, in addition to the same treatment as the above dye.

In the present invention, fixability, offset resistance,
The evaluation method of the mixed color region and the transparency is as follows.

1) Fixing Property, Offset Resistance, and Color Mixing Area First, an appropriate amount of the above external additive is externally added to a toner containing the monofunctional ester compound of the present invention to obtain a developer.
An unfixed image of the obtained developer is prepared by a commercially available copying machine.

When the toner is a black toner, the fixing property and the anti-offset property are evaluated by a heat roller external fixing device having no oil application function.

Further, in the case of a mono-color toner or a full-color toner, in addition to a heat roller external fixing device having no oil application function, a commercially available full-color copying machine such as CLC
-500 (manufactured by Canon Inc.), a small amount of oil is uniformly applied to the fixing roller (for example, 0.02 g / A4
Size), and evaluate the fixability, the anti-offset property, and the color mixture area, and obtain a fixed image for evaluating the transparency.

As the roller material at this time, a fluorine-based material is used for both the upper and lower parts. The fixing conditions include a nip of 7.0 mm when the transfer material is SK paper (manufactured by Nippon Paper Co., Ltd.), and a process speed of 80 mm / sec.
When the transfer material is an OHP sheet (Pictorico Trapen for copier / made by Asahi Glass Co., Ltd.), the nip is set to 7.0 mm, the process speed is set to 15 mm / sec,
The temperature control is performed every 5 ° C. within a temperature range of 0 ° C.

The fixing property was determined by applying a load of 50 g / cm ² to a fixed image (including a low-temperature offset image) and applying a load to silbon paper [Lenz Cleaning Paper “das”.
per (R) "(Ozu Paper Co. Ltd.
d)], the temperature at which the density reduction rate before and after rubbing is less than 10% is defined as the fixing start point.

The offset resistance is determined by setting the temperature at which the offset disappears visually as the low-temperature offset starting point, and raising the temperature.
The highest temperature without offset is defined as the hot offset end point.

Further, in the mixed color area, the image in the non-offset area is converted to a handy gloss meter gloss checker IG-310.
(Manufactured by Horiba, Ltd.), and the gloss value was 7
The area is determined by defining the area as the maximum value.

2) Regarding Transparency The transmittance and the haze (haze) of the obtained fixed image with respect to each toner amount per unit area were measured, and the numerical value at a toner weight of 0.75 mg / cm ² per unit area was measured. And the transparency was evaluated. The method for measuring the transmittance and haze is described below.

The transmittance was measured using a Shimadzu self-recording spectrophotometer UV.
Using 2200 (manufactured by Shimadzu Corporation), the transmittance of the OHP film alone was set to 100%, and the transmittance at the maximum absorption wavelength at magenta toner: 650 nm for cyan toner: 500 nm for yellow toner: 600 nm was measured. I do.

The haze was measured using a haze meter NDH.
It measured using -300A (made by Nippon Shikara Kogyo Co., Ltd.). The test results are shown in Tables 1 and 2.

Tables 1 and 2 show the fixing start temperature, low temperature offset start point, high temperature offset end point, non-offset area,
The values of the low temperature start point, the high temperature end point, the color mixing area, the transmittance, and the haze are described.

In the DSC measurement in the present invention, since the exchange of heat of the monofunctional ester compound is measured and its behavior is observed, it is necessary to measure with a high-precision internal heating input compensation type differential scanning calorimeter from the measurement principle. There is. For example, DSC-7 manufactured by PerkinElmer can be used.

The measuring method is as described in ASTM, D3418-82.
Perform according to. As the DS curve used in the present invention, a DSC curve measured when the temperature is raised once, a pre-history is taken, and then the temperature is lowered and raised at a temperature rate of 10 ° C./min.

For the FT-IR measurement, for example, the kBr method is employed, and FTS60A manufactured by Bio-Rad is used.

The NMR measurement is carried out, for example, using a 400 MHz EX400 manufactured by JEOL Ltd.

The present invention will be described in detail with reference to a method for synthesizing a monofunctional ester compound, toner examples and comparative examples.

Synthesis method of monofunctional ester compound-1 In a 4-liter four-necked flask equipped with a Dimroth condenser and a Dean-Stark water separator, 2 l of benzene, 720 g of montanic acid, 200 g of 2,2-dimethyloctanol
g, p-toluenesulfonic acid was further added, and the mixture was sufficiently stirred and dissolved. After refluxing for 7 hours, the valve of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the residue was sufficiently washed with sodium hydrogen carbonate, dried, and the solvent was distilled off. The obtained compound was recrystallized, washed and purified.

The physical properties are shown below.

DSC (peak value) 62 ° C. (ΔH) 115 J / g Refractive index 1.488 SP value 8.1 Hardness 2.8 Crystallinity 20 Viscosity 13 cps Number average molecular weight (measured by VPO method) 535

In the present invention, the molecular weight distribution of the chromatogram of the monofunctional ester compound by HPLC using chloroform as a solvent was measured under the following conditions. That is,
Chloroform as a solvent was flowed through the column at room temperature at a flow rate of 3.5 ml / min, and about 3.5 ml of a chloroform sample solution was injected for measurement. An RI (refractive index) detector was used as a detector. As the column, a plurality of commercially available polystyrene gel columns are preferably combined, and examples thereof include JAIGEL 1H and 2H manufactured by Nippon Kagaku Kogyo. The sample concentration was 1%.

HP of conventional natural wax and synthetic wax
The LC spectrum was broad, even if produced by distillation. On the other hand, the HPLC spectrum of the monofunctional ester compound synthesized as described above was very sharp and high purity was obtained.

Synthesis method of monofunctional ester compound -2 2 l of benzene, 530 g of behenic acid, 200 ml of 2,2-diethylhectanol were placed in a 4 l four-necked flask equipped with a Dimroth condenser and a Dean-Stark water separator.
g, p-toluenesulfonic acid was further added, and the mixture was sufficiently stirred and dissolved, and then refluxed for 6 hours. Otherwise, the procedure was the same as in Synthesis method-1.

Thus, the monofunctional ester compound N
o. Compound 2 was synthesized.

The physical properties are shown below.

DSC (peak value) 59 ° C. (ΔH) 109 J / g Refractive index 1.488 SP value 8.4 Hardness 1.9 Crystallinity 29 Viscosity 17 cps Number average molecular weight (measured by VPO method) 530

Synthesis method of monofunctional ester compound-3 In a 4-liter four-necked flask equipped with a Dimroth condenser and a Dean-Stark water separator, 2 l of benzene, 540 g of stearic acid, 200 g of 4-ethylhectanol,
Further, p-toluenesulfonic acid was added, sufficiently stirred and dissolved, and then refluxed for 7 hours. Other procedures were performed in the same manner as in Synthesis method-1.

Thus, the monofunctional ester compound N
o. 3 was synthesized.

The physical properties are shown below.

DSC (peak value) 62 ° C. (ΔH) 122 J / g Refractive index 1.48 SP value 9.2 Hardness 2.2 Crystallinity 31 Viscosity 18 cps Number average molecular weight (measured by VPO method) 450

Synthesis method of monofunctional ester compound -4 In a 3 l four-necked flask equipped with a Dimroth condenser and a Dean-Stark water separator, 2 l of benzene, 580 g of behenic acid, 200 g of 6-propanehectanol, and p- Add toluene sulfonic acid, stir well and dissolve,
The mixture was refluxed for 6 hours. Other procedures were performed in the same manner as in Synthesis method-1.

Thus, the monofunctional ester compound N
o. 4 was created.

The physical properties are shown below.

DSC (peak value) 55 ° C. (ΔH) 111 J / g Refractive index 1.49 SP value 8.5 Hardness 2.7 Crystallinity 36 Viscosity 22 cps Number average molecular weight (measured by VPO method) 510

[0165]

【Example】

Example 1 Styrene-butyl acrylate-divinylbenzene copolymer (copolymer weight ratio = 80: 16: 4) (weight average molecular weight = about 50,000) 1000 parts by weight Magnetic iron oxide (average particle size = 0.25 μm) (Saturation magnetization = 60 emu / g residual magnetization = 10K under 10K Oersted)
emu / g coercive force = 120 Oe) 800 parts by weight Di-t-butylsalicylic acid metal compound 20 parts by weight Monofunctional ester compound No. 140 parts by weight After the above materials were preliminarily mixed, melt kneading was performed by a biaxial kneading extruder set at 130 ° C. After cooling, the kneaded material was coarsely pulverized, finely pulverized by a pulverizer using a jet stream, and further classified using an air classifier to obtain a magnetic toner having a weight average particle size of 8.1 μm. This magnetic toner 10
0 parts by weight and 0.7 parts by weight of hydrophobic colloidal silica fine powder were mixed (externally added) to obtain a magnetic toner having colloidal silica fine powder on the surface of toner particles.

Using this magnetic toner, an unfixed image was obtained using a commercially available electrophotographic copying machine NP-8582 (manufactured by Canon Inc.), and the fixability and the offset resistance were evaluated by the above evaluation methods.

The results and measured values are shown in Table 1.

Example 2 Styrene-butyl acrylate-divinylbenzene copolymer (copolymer weight ratio = 80: 16: 4) (weight average molecular weight = about 50,000) 1000 parts by weight Magnetic iron oxide (average particle size = 0) .25 μm) (saturation magnetization = 60 emu / g under 10K Oersted residual magnetization = 10
emu / g coercive force = 120 Oe) 800 parts by weight Di-t-butylsalicylic acid metal compound 20 parts by weight Monofunctional ester compound No. After premixing the above materials, a magnetic toner was obtained in the same manner as in Example 1, and a fixing test was performed. The weight average particle diameter of the obtained magnetic toner was 8.2 μm.

Table 1 shows the results.

Example 3 Styrene-butyl acrylate-divinylbenzene copolymer (copolymerization weight ratio = 80: 16: 4) (weight average molecular weight = about 50,000) 1,000 parts by weight Magnetic iron oxide (average particle size = 0) .25 μm) (saturation magnetization = 60 emu / g under 10K Oersted residual magnetization = 10
emu / g coercive force = 120 Oe) 800 parts by weight Di-t-butylsalicylic acid metal compound 20 parts by weight Monofunctional ester compound No. 340 parts by weight After the above materials were preliminarily mixed, a developer was obtained and a fixing test was carried out in the same manner as in Example 1. The weight average particle diameter of the obtained magnetic toner was 8.3 μm.

Table 1 shows the results.

Example 4 Styrene-butyl acrylate-divinylbenzene copolymer (copolymer weight ratio = 80: 16: 4) (weight average molecular weight = about 50,000) 1000 parts by weight Magnetic iron oxide (average particle size = 0) .25 μm) (saturation magnetization = 60 emu / g under 10K Oersted residual magnetization = 10
emu / g coercive force = 120 Oe) 800 parts by weight Di-t-butylsalicylic acid metal compound 20 parts by weight Monofunctional ester compound No. 440 parts by weight After premixing the above materials, a magnetic toner was obtained and a fixing test was performed in the same manner as in Example 1. The weight average particle diameter of the obtained magnetic toner was 8.4 μm.

Table 1 shows the results.

Example 5 Polyester resin (bisphenol A-based diol-terephthalic acid-trimellitic acid condensate) (monomer mixture weight ratio = 50: 45: 5) (weight average molecular weight = about 5000)
0) 1000 parts by weight Copper phthalocyanine pigment 40 parts by weight Monoazo metal compound 20 parts by weight Monofunctional ester compound No. After preliminarily mixing the above materials, a cyan color toner having a weight average particle size of 8.0 μm was obtained in the same manner as in Example 1. 1.2 parts by weight of hydrophobic titanium oxide fine powder was externally added to 100 parts by weight of the toner to obtain a cyan color having fine particles of titanium oxide on the surface of toner particles.

94 parts by weight of a ferrite carrier coated with an acrylic resin was mixed with 6 parts by weight of the externally added toner to obtain a two-component developer.

Table 1 shows the results.

Example 6 To 708 parts by weight of ion-exchanged water, 452 parts by weight of an aqueous 0.1 M Na ₃ PO ₄ solution were added, and the mixture was heated to 60 ° C., and then heated using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). ) And stirred at 12000 rpm.
To this, 69 parts by weight of a 1.0 M CaCl ₂ aqueous solution was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ . On the other hand, styrene 165 parts by weight n-butyl acrylate 35 parts by weight Magnetic iron oxide (average particle size = 0.25 μm) (saturation magnetization = 60 emu / g residual magnetization = 10 K under 10 K Oersted)
emu / g coercive force = 120 oersted) 95 parts by weight styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = about 57)
000) 9 parts by weight Divinylbenzene 2 parts by weight Metal di-t-butylsalicylate 2 parts by weight Monofunctional ester compound No. 140 parts by weight The above material was heated to 60 ° C., and was uniformly dissolved and dispersed at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). Into this, 10 parts by weight of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition. The polymerizable monomer composition was charged into the aqueous medium, and the mixture was subjected to 10,000 rpm with a TK homomixer at 60 ° C. in an N ₂ atmosphere.
Then, the mixture was stirred at m for 20 minutes to granulate the polymerizable monomer composition.
Thereafter, the temperature was raised to 80 ° C. while stirring with a paddle stirring blade,
The reaction was performed for 10 hours.

After the completion of the polymerization reaction, the mixture was cooled, hydrochloric acid was added to dissolve calcium phosphate, and then filtered, washed with water and dried to obtain polymer particles.

To 100 parts by weight of the obtained magnetic toner particles, 0.8 part by weight of hydrophobic silica having a specific surface area of 200 m ² / g by the BET method was externally added to obtain a suspension polymerization toner. The weight average particle diameter of the obtained magnetic toner was 8.1 μm.

Using this magnetic toner, a fixing test was performed in the same manner as in Example 1.

The results are shown in Table 1.

Example 7 Styrene 165 parts by weight n-butyl acrylate 35 parts by weight Copper phthalocyanine pigment 14 parts by weight Styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = about 57
000) 9 parts by weight Monoazo metal compound 2 parts by weight Monofunctional ester compound No. Using 140 parts by weight of the polymerizable composition, in the same manner as in Example 6,
A cyan color toner having a weight average particle size of 8.2 μm was obtained.
1.2 parts by weight of hydrophobic titanium oxide fine powder was externally added to 100 parts by weight of the cyan color toner to obtain a cyan color toner having fine particles of titanium oxide on the surface of toner particles. 94 parts by weight of a ferrite carrier coated with an acrylic resin was mixed with 6 parts by weight of the externally added toner to obtain a two-component developer.

The results are shown in Table 1.

[Example 8] Styrene 165 parts by weight n-butyl acrylate 35 parts by weight Copper phthalocyanine pigment 14 parts by weight Styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = approx. 57
000) 9 parts by weight Monoazo metal compound 2 parts by weight Monofunctional ester compound No. 120 parts by weight Using the above polymerizable composition, a developer was obtained in the same manner as in Example 7, and the fixability, the offset resistance, the color mixing region, the OHP transmittance, and the haze were measured. In addition,
The resulting cyan color toner has a weight average particle size of 8.0.
μm.

Table 1 shows the results.

Example 9 Styrene 165 parts by weight n-butyl acrylate 35 parts by weight Quinacridone pigment 16 parts by weight Styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = about 57)
000) 9 parts by weight Monoazo metal compound 2 parts by weight Monofunctional ester compound No. 120 parts by weight After obtaining the polymerizable composition, a developer was obtained in the same manner as in Example 7, and the fixability, the offset resistance, the color mixing area, the OHP transmittance, and the haze were measured. The weight average particle size of the obtained magenta color toner was 8.0.
μm.

Table 1 shows the results.

[Example 10] Styrene 165 parts by weight n-butyl acrylate 35 parts by weight Disazo yellow pigment 13 parts by weight Styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = approx. 57
000) 9 parts by weight Monoazo metal compound 2 parts by weight Monofunctional ester compound No. 120 parts by weight Using the above polymerizable composition, a developer was obtained in the same manner as in Example 7, and the fixability, the offset resistance, the color mixing region, the OHP transmittance, and the haze were measured. In addition,
The weight average particle size of the obtained yellow color toner is 8.
It was 1 μm.

Table 1 shows the results.

Comparative Example 1 Styrene-butyl acrylate-divinylbenzene copolymer (copolymer weight ratio = 80: 16: 4) (weight average molecular weight = about 50,000) 1,000 parts by weight Magnetic iron oxide (average particle size = 0) .25 μm) (saturation magnetization = 60 emu / g under 10K Oersted residual magnetization = 10
emu / g coercive force = 120 oersted) 800 parts by weight Di-t-butylsalicylic acid metal compound 20 parts by weight Low molecular weight polypropylene (Viscose 660P; manufactured by Sanyo Chemical Co., Ltd.) 40 parts by weight In the same manner as described above, a magnetic toner was obtained, and a fixing test was performed. The weight average particle diameter of the obtained magnetic toner was 8.1 μm.

Table 2 shows the results.

[Comparative Example 2] Polyester resin (condensate of bisphenol A-based diol-terephthalic acid-trimellitic acid) (monomer mixture weight ratio = 50:40:10) (weight average molecular weight = about 5500)
0) 1000 parts by weight magnetic iron oxide (average particle size = 0.25 μm) (saturation magnetization = 60 emu / g under 10 K Oersted residual magnetization = 10)
emu / g coercive force = 120 Oersted) 750 parts by weight Monoazo metal compound 20 parts by weight Montan ester wax E (Hoechst) 40 parts by weight After premixing the above materials, a magnetic toner was obtained in the same manner as in Example 1. Then, a fixing test was performed. The weight average particle diameter of the obtained magnetic toner was 8.2 μm.

Table 2 shows the results.

Comparative Example 3 Polyester resin (bisphenol A-based diol-terephthalic acid-trimellitic acid condensate) (monomer mixture weight ratio = 50: 45: 5) (weight average molecular weight = about 5000)
0) 1000 parts by weight Phthalocyanine pigment 40 parts by weight Monoazo metal compound 20 parts by weight Montan ester wax KP (Hoechst) 40
Parts by weight After the above materials were premixed, a toner was obtained and a developer was prepared in the same manner as in Example 5, and the fixability, the offset resistance, the color mixing area, the OHP transmittance, and the haze were measured. Incidentally, the weight average particle size of the obtained color toner,
It was 7.9 μm.

Table 2 shows the results.

Comparative Example 4 Styrene 165 parts by weight n-butyl acrylate 35 parts by weight Magnetic iron oxide (average particle size = 0.25 μm) (saturation magnetization = 60 emu / g residual magnetization = 10 under 10 K Oersted)
emu / g coercive force = 120 oersted) 95 parts by weight styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = about 57)
000) 9 parts by weight Divinylbenzene 2 parts by weight Monoazo metal compound 2 parts by weight Montan ester wax KP (Hoechst) 40
Using parts by weight of the polymerizable composition, in the same manner as in Example 9,
A magnetic toner was obtained and a fixing test was performed. The weight average particle size of the obtained magnetic toner was 8.2 μm.

The results are shown in Table-2.

Comparative Example 5 Styrene 165 parts by weight n-butyl acrylate 35 parts by weight Copper phthalocyanine pigment 14 parts by weight Styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = about 57
000) 9 parts by weight Di-t-butylsalicylic acid metal compound 2 parts by weight Using the above polymerizable monomer composition, a toner was obtained in the same manner as in Example 7, a developer was prepared, and fixing properties and anti-offset properties were obtained. The properties, the color mixing area, the OHP transmittance, and the haze were measured. The weight average particle size of the obtained color toner was 7.9 μm.

The results are shown in Table 2.

Comparative Example 6 Styrene 165 parts by weight n-butyl acrylate 35 parts by weight Copper phthalocyanine pigment 14 parts by weight Styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = about 57
000) 9 parts by weight Monoazo metal compound 2 parts by weight Montan ester wax E (Hoechst) 40 parts by weight Using the above polymerizable monomer composition, a toner is obtained in the same manner as in Example 7, and a developer is prepared. Then, the fixability, the offset resistance, the color mixing area, the OHP transmittance, and the haze were measured. The obtained color toner had a weight average particle size of 8.0 μm.

The results are shown in Table 2.

[0202]

[Table 1]

[0203]

[Table 2]

[0204]

By using the polyfunctional polyester compound of the present invention, it is possible to obtain a toner excellent in low-temperature fixability to a transfer material and offset resistance without applying a small amount of oil or at all. Can be.

Also, high-quality full-color OH with excellent transparency
P can be generated.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Tatehiko Chiba 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-4-156933 (JP, A) JP-A-5 -119509 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/08-9/097

Claims (3)

(57) [Claims] 1. A toner for developing an electrostatic image, comprising a binder resin, a colorant and a monofunctional ester compound having a tertiary and / or quaternary carbon. 2. A method comprising melt-kneading, cooling, pulverizing and classifying a mixture comprising a binder resin, a colorant and a monofunctional ester compound having tertiary or / and quaternary carbon to form toner particles. A method for producing an electrostatic image developing toner. 3. A polymerizable monomer, a colorant and a tertiary or / and
And producing a toner particle directly by polymerizing a mixture having a monofunctional ester compound having a quaternary carbon.