JPH0713764B2 - Toner for electrostatic image development - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a toner for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, and the like, and particularly to a toner suitable for heat roller fixing.

[Conventional technology]

Conventionally, as the electrophotographic method, as described in U.S. Pat.No. 2,297,691 specification, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748, many methods are known, but in general, A photoconductive substance is used to form an electrical latent image on the photoconductor by various means, and then the latent image is developed with toner, and the toner image is transferred to a transfer material such as paper as necessary. After that, it is fixed by heating, pressure or solvent vapor to obtain a copy.

Various methods and devices have been developed for the final step of fixing the toner image on a sheet such as paper. The most popular method at present is a pressure heating method using a heating roller.

The pressure-bonding heating method using a heating roller performs fixing by allowing the toner image surface of the sheet to be fixed to pass under pressure while contacting the surface of a heating roller whose surface is formed of a material having releasability for toner. . In this method, since the surface of the heat roller and the toner image on the sheet to be fixed are brought into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image on the sheet to be fixed is extremely good, and rapid fixing is possible. It is possible and very effective in a high speed electrophotographic copying machine. However, in the above method, since the heat roller surface and the toner image are in contact with each other in a molten state under pressure, a part of the toner image adheres to and transfers to the fixing roller surface, and re-transfers to the next sheet to be fixed. The so-called offset phenomenon occurs,
It may stain the sheet to be fixed. Preventing toner from adhering to the surface of the heat fixing roller is one of the essential conditions of the heat roller fixing method.

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 from the toner, such as silicone rubber or fluorine-based resin, and further, the surface is prevented from being offset and the roller surface is In order to prevent fatigue, the roller surface is coated with a thin film of a liquid having a good releasing property such as silicone oil. However, this method is extremely effective in preventing toner offset, but has a problem that the fixing device becomes complicated because an apparatus for supplying the offset preventing liquid is required. . Therefore, it is unfavorable to prevent the offset by supplying the offset preventing liquid, and it is the current situation that development of a toner having a wide fixing temperature range and high offset resistance is desired. Therefore, in order to increase the releasability of the toner, a method of adding a wax such as low molecular weight polyethylene or polypropylene that is sufficiently melted when heated is also used, but it is effective for preventing offset, but the toner has a cohesive property. Further, the charging characteristics become unstable, and the durability is likely to be lowered. Therefore, as other methods, various attempts have been made to improve the binder resin.

For example, JP-B-51-23354 proposes a toner using a crosslinked polymer as a binder resin. According to that method, the offset resistance and the anti-sticking property are remarkably improved, but the cross-linking degree increases the fixing point, and the fixing temperature is sufficiently low, and the offset resistance and the anti-sticking property are low. Good satisfactory fixing properties have not been obtained. Generally, in order to improve the fixing property, it is necessary to lower the softening point by lowering the molecular weight of the binder resin, which is contrary to the measures for improving the offset resistance, and in order to achieve the low softening point. Inevitably, the glass transition point of the resin is lowered, and the toner during storage is blocked, which is an undesirable phenomenon. Therefore, a toner was proposed in which a polymer having a low molecular weight and a cross-linked polymer were blended in order to satisfy low-temperature fixing and offset resistance, but the cross-linked polymer has poor compatibility with other polymers and has a good fixing property. Further, a toner satisfying the developing property has not been obtained. In the further crosslinked polymer, a pigment which is a component added to the toner,
There is a problem that it is difficult to disperse the charge control agent, the release agent and the like, and there is a problem that it is difficult to obtain good developing characteristics as a toner.

The number average molecular weight is 10 to improve pulverizability and fixability.
It has been proposed that a high polymer of 0,000 to 500,000 and other monomer components are mixed and then polymerized to obtain a uniform polymer, which is used as a binder resin.However, in this method, offset resistance and fixing in the resin component were proposed. It is not possible to include a component in the high cross-linking region that satisfies the non-wrapping property on the roller, and even if a part of the component is formed, it cannot be uniformly contained because the compatibility between the polymers is poor, and the toner binder In the present situation, the dispersibility of the additive is poor and a toner satisfying the developing property and fixing property is not obtained.

[Object of the Invention]

However, the present invention provides a toner in which the above problems are remarkably improved.

The objects of the present invention are listed below.

(1) An object of the present invention is to provide a dry toner suitable for a heat roll fixing method that does not apply oil.

(2) The object of the present invention is to use a resin composition containing a high-crosslinking component and a low-molecular weight component, which are uniformly mixed and dispersed, so that fixing is sufficiently performed at a lower temperature, and offset and winding are sufficiently performed. It is to provide a toner that is prevented and has a wide fixing temperature range.

(3) The object of the present invention is to have an acceptable agglomeration temperature,
The object is to provide a toner that does not cause blocking during storage and use.

(4) The object of the present invention is to use a resin composition having excellent dispersibility of an additive such as a pigment, a charge control agent, a release agent, etc. to obtain a clear image having a sufficient image density and a high resolution. To provide a toner having excellent developing characteristics.

(5) It is an object of the present invention to provide a toner having excellent durability against repeated use and capable of stably maintaining the high quality image described in the preceding paragraph.

Specifically, an object of the present invention is to contain a gel component in an amount of 0.1 to 60% by weight, and in a GPC chromatogram of a tetrahydrofuran-soluble component, have a main peak value in the region of a molecular weight of 1000 to 25000, and have a molecular weight of Having at least one sub-peak or sub-shoulder in the region of 3000 to 150,000, 1% by weight or more of the A component in the region of molecular weight of 500,000 or more, and 10 to 60 weight of the B component in the region of molecular weight of 30,000 to 500,000. % And a C-component having a molecular weight of 30,000 or less in the range of 20 to 90% by weight of a vinyl polymer, a toner for developing an electrostatic image is provided.

The gel component in the present invention refers to the weight ratio of the polymer component in the resin composition that has been crosslinked and becomes insoluble in the solvent, and is used as a parameter indicating the degree of crosslinking of the resin composition containing the highly crosslinked component. be able to. What is a gel component?
It is defined by the value measured as follows.

That is, when the sample is resin only, weigh 0.5-1.0 g of a certain amount of resin (W ₁ g) and use cylindrical filter paper (Toyo Roshi Kaisha No. 86
R) and put on a Soxhlet extractor, and extracted with 100 to 200 ml of chloroform as a solvent for 6 hours, and the soluble component extracted by the solvent is evaporated, and then 100 ° C.
After vacuum drying for several hours, weigh the soluble resin component (W ₂ g),
Calculate according to the following formula.

Gel component content = (W ₁ −W ₂ ) / W ₁ × 100 (%) When the sample is toner, the series of extraction operations is the same as for resin, but for non-magnetic toner the sample toner weight For magnetic toner, calculate the pigment weight from the sample toner weight minus the pigment and magnetic material weight (W ₃ g) and the solvent-soluble component weight (W ₄ g) in the toner according to the following formula. can do.

Gel component content _{= (W 3 -W 4) /} W 3 × 100 (%) or more of dryness of the solvent-soluble component obtained in operation THF
Dissolve it in (tetrahydrofuran) and let it pass through a sample processing filter to obtain a GPC sample.

In the present invention, the peak of chromatogram by GPC (gel permeation chromatography) and / or the molecular weight of the shoulder is measured under the following conditions.

That is, the column was stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) as a solvent was flowed through the column at this temperature at a flow rate of 1 ml / min to prepare a resin having a sample concentration of 0.05 to 0.1% by weight. THF sample solution
Inject 50 to 200 μl and measure. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value and the count number of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemica
l Co. or Toray Soda Kogyo Co., Ltd. has a molecular weight of 6 × 10 ² ,
2.1 x 10 ³ , 4 x 10 ³ , 1.75 x 10 ⁴ , 5.1 x 10 ⁴ , 1.1 x 10 ⁵ , 3.9 x 1
It is appropriate to use those of 0 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ and to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

As the column, a plurality of commercially available polystyrene gel columns are preferably combined in order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ⁶ , for example, μ-styv manufactured by Watevs.
agel500,10 ^3, 10 ^4, 10 ⁵ combination and, sho of Showa Denko Co., Ltd.
dex KF-80M, KF-802,803,804,805 combination, KA-80
A combination of 2,803,804,805 or TSKgel made by Toyo Soda
G1000H, G2000H, G2500H, G3000H, G4000H, G5000H, G6000H, G
A combination of 7000H and GMH is desirable.

The resin composition in the toner of the present invention contains a high molecular weight polymer component containing a crosslinking component and a low molecular weight polymer component, both of which are one or more selected from styrenes, acrylic acids, methacrylic acids and their derivatives. Those obtained by polymerizing the above monomer are preferable from the viewpoint of development characteristics and charging characteristics, and examples of the monomer that can be used include styrene as styrene, α-methylstyrene, vinyltoluene,
Chlorostyrene, etc., and acrylic acids, methacrylic acids and their derivatives include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate,
Butyl acrylate, octyl acrylate, acrylic acid 2
-Acrylic acid esters such as ethylhexyl, n-tetradecyl acrylate, n-hexadecyl acrylate, lauryl acrylate, cyclohexyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl acrylate, and the like, as well as methacrylic acid and methacrylic acid. Methyl, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, methacrylic acid Phenyl, 2-methacrylic acid
Examples thereof include methacrylic acid esters such as hydroxyethyl, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, and stearyl methacrylate. Further, the high molecular weight polymer component containing a cross-linked region in the resin component of the present invention, and the low molecular weight polymer component, in addition to the above-mentioned monomers, a small amount of other monomers within the range in which the object of the present invention can be achieved, for example, acrylonitrile. , 2-vinyl pyridine, 4-vinyl pyridine, vinyl carbazole, vinyl methyl ether, butadiene,
Isoprene, maleic anhydride, maleic acid, maleic acid monoesters, maleic acid diesters, vinyl acetate and the like may be used.

Examples of the cross-linking agent used to form the cross-linking component of the resin component of the toner of the present invention include divinylbenzene, bis (4acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, and the like. 1,3-brylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexane glycol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol Diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 each diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate (MANDA Honkakusuri), and all that the place of methacrylate or acrylate,
Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and its methacrylate, 2.2-bis (4-methacryloxy, polyethoxyphenyl) Examples thereof include propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, and diaryl chlorendate.

The resin composition in the toner of the present invention needs to be uniformly mixed from the high molecular weight polymer including the cross-linking region component to the low molecular weight polymer. Since the high molecular weight polymer containing the cross-linking region component is insoluble in the solvent, it is difficult to bring the high molecular weight polymer and the low molecular weight polymer into a mixed state in a solution state, and even if they are apparently mixed, It is not a truly homogeneous mixture. Furthermore, this high molecular weight polymer
The method of thermally melting and mechanically mixing with the low molecular weight polymer does not mean that the mixture is truly uniform. Therefore, in order to uniformly mix the low molecular weight component effective for low-temperature fixing and dispersibility of the additive and the cross-linking region component effective for offsetting and wrapping, the low-molecular weight component and the cross-linking region component are connected. The presence of high-molecular-weight components in the non-crosslinked state is effective. Further, it has been found that the medium- and high-molecular-weight components have a great effect not only on the role of connection between the molecular weight and the ratio, but also on such points as low-temperature fixing, offset, and toner pulverizability. Therefore, in order to obtain a resin composition in which a high molecular weight polymer having a cross-linking region component and a low molecular weight polymer are uniformly mixed, a monomer component which gives a medium or high molecular weight polymer in advance with the low molecular weight polymer together with a crosslinking agent. A method of obtaining a high-molecular-weight polymer having a cross-linking region component by dissolving or mixing in, and polymerizing again after the second stage polymerization is preferable.

The low molecular weight polymer in the resin composition used in the present invention can be obtained by a commonly used polymerization method such as a bulk polymerization method or a solution polymerization method.

In the bulk polymerization method, a low molecular weight polymer can be obtained by polymerizing at a high temperature to stop the termination reaction rate.
There is a problem that it is difficult to control the reaction. In that respect, in the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in radical chain transfer between solvents and by adjusting the amount of the initiator and the reaction temperature. It is preferable to obtain a low-molecular weight substance in the resin composition used in. Incidentally, it is difficult to synthesize a resin containing a required amount of gel component only by the solution polymerization method. This low molecular weight polymer is re-polymerized with the monomer that gives the high molecular weight polymer among the above-mentioned crosslinking agent and the components in the crosslinking region, but the gel component in the crosslinking region until it becomes an insoluble component in the solvent is formed. As a polymerization method to be obtained, an emulsion polymerization method or a suspension polymerization method is preferable.

Taking the suspension polymerization method as an example, a vinyl-based monomer containing a low molecular weight polymer in a suspended state is polymerized together with a crosslinking agent, so that the resin composition has a pearl-like shape and a low molecular weight. From the polymer to the high molecular weight polymer including the crosslinking component, it can be obtained in a uniformly mixed and preferable state. The resin composition used in the toner of the present invention thus obtained has a gel component of 0.1 to 60% by weight, preferably 1 to 55% by weight, particularly preferably 10 to 50% by weight, and GPC of other solvent-soluble components. In the chromatogram, the molecular weight is 1000 to 25000, preferably 1500 to 18000, and particularly preferably 2000 to 15000, having a main peak value (the value at which the highest peak is located in the GPC chromatogram), and having a molecular weight of 3000 to 150000. , Preferably 5,000 to 100,000, particularly preferably 8,000 to 80,000, having a sub-peak value (a value at which a peak having a height next to the main peak is located) or a sub-shoulder value.

The above-mentioned resin composition is contained as a main component in the toner of the present invention, but 60% by weight or more, preferably 80% by weight, particularly preferably 90% by weight or more is good with respect to the total amount of the binder resin.

Furthermore, in the GPC molecular weight distribution, the chromatogram was divided into three at the molecular weight boundaries of 30,000 and 500,000, and from the high molecular weight side, the A component (the region of 500,000 or more) and the B component (30,000 to 500,000 respectively). Area) and C component (area of 30,000 or less), and the respective composition ratios to the entire chromatogram are divided into three parts by cutting the chromatogram or the integrated value of the chromatogram, and calculating the ratio by each weight. When the weight ratio is calculated by the weight method, the component ratio of the component A is 1% or more, preferably 1 to 20%, more preferably 1 to 15%, and still more preferably 1 to 0, as described in the synthesis column described later. 10%; B component 10 to 60%, preferably 15 to 55%,
More preferably 20 to 50%; C component 20 to 90%, preferably
It is preferably from 35 to 80%, more preferably from 40 to 70%.

The reason for these is that when the gel component in the resin composition exceeds 60%, the melting temperature of the crosslinking component causes the fixing temperature to rise, and the additive dispersion becomes worse when used in a toner. Become. Further, the components in the high cross-linking region are likely to be cut during the kneading of the resin, which causes a trouble in the design of the toner. If the gel content is less than 0.1%, it tends to wrap around the offset and the roller, and the gel content is 0.1%.
When it is less than the above range and the high molecular weight range is large, the pulverizability is significantly deteriorated.

When the molecular weight of the solvent-soluble component does not have a main peak value at 1000 to 25000, and the main peak value is 25000 or more, the fixing temperature of the created toner rises and the fixing temperature range becomes narrower.
The pulverizability also deteriorates, leading to a decrease in production efficiency. When the molecular weight of the main peak value is 1000 or less, the toner produced has a markedly poor offset resistance and winding around a roller, and may cause problems in blocking. The molecular weight of the sub-peak or sub-shoulder value is not in the range of 3000 to 150,000. When the value is 150,000 or more, the dispersibility of the additive is poor, the fixing temperature is remarkably increased, and the pulverizability is remarkably deteriorated. The molecular weight of the subpeak or subscaler value is 30
When it is less than 00, the toner produced has poor offset resistance and poor winding around the roller, which may cause blocking problems. In the toner of the present invention, the above problems are remarkably improved, and a toner having excellent offset resistance and roller wrapping, a wide fixing temperature range, excellent developing characteristics and good pulverizability can be obtained.

The reason for this is that in a resin composition in which a high molecular weight polymer component including a crosslinked region to a low molecular weight polymer component is uniformly mixed, high molecular weight and low molecular weight segments are mixed together in the crosslinked region. It is considered that the high molecular weight component containing cross-linking prevents a decrease in cohesive force and excessive fluidity as a matrix at the time of heat melting, while the low molecular weight component exhibits heat melting property, resulting in heat melting at low temperature. However, it is considered that it exhibits excellent heat-melting properties such that the cohesive force is reduced and excessive flow is suppressed even at high temperatures. The polymer uniformly mixed from the low molecular weight component to the highly crosslinked component in the present invention means that when a toner is prepared by using the polymer, the image density due to repeated use which occurs in the case of a nonuniformly mixed polymer. It means that the deterioration of fogging does not actually occur.

Regarding the grindability, the components in the high molecular weight region other than the cross-linking region impart toughness to the composition while the components in the cross-linking region impart brittleness, and the low-molecular weight component further imparts easiness to be pulverized, thereby improving overall It is considered that the crushing characteristics necessary for improving the excellent production efficiency are generated.

As the charge control agent used in the toner of the present invention, a conventionally known positive or negative charge control agent is used. Charge control agents known in the art today include the following:

(1) The following substances are used to control the toner to be positively charged.

Nigrosine, azine dyes containing alkyl groups having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), basic dyes (eg CI
Basic Yellow 2 (CI41000), CIBasic Yellow 3,
CIBasic Red 1 (CI45160), CIBasic Red 9 (C.
I.42500), CIBasic Violet 1 (CI, 42535), CIBa
sic Violet 3 (CI42555), CIBasic Violet 10 (C.
I.45170), CIBasic Violt 14 (CI42510), CIBa
sic Blue 1 (CI42025), CIBasic Blue 3 (CI510
05), CIBasic Blue 5 (CI42140), CIBasic Blu
e 7 (CI42595), CIBasic Blue 9 (CI52015),
CIBasic Blue 24 (CI52030), CIBasic Blue 25
(CI52025), CIBasic Blue 26 (CI44045), C.
I.Basic Green 1 (CI42040), CIBasic Green 4
(CI42000) and the like, lake pigments of these basic dyes, (as the laking agent, phosphotungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.) , CISovent Black 3 (CI2615
0), Hansa Yellow G (CI11680), CIMordlant B
lack 11, CI Pigment Black 1, Gilsonite, Asfarto, etc.

Alternatively, for example, benzolmethyl-hexadecylammonium chloride, decyl-trimethylammonium chloride, or dialkyltin compounds such as dibutyl and dioctyl, metal salts of higher fatty acids, glass, mica, inorganic fine powder such as zinc oxide, EDTA, metal complexes of acetylacetone. Etc., polyamine resins such as vinyl polymers containing amino groups and condensation polymers containing amino groups.

(2) The following substances control the toner to be negatively charged. Japanese Patent Publication No. 41-20153, No. 43-27596, No. 44-63
Metal complex salts of monoazo dyes described in 97 and 45-26478.

Nitrohumic acid and its salts or dyes and pigments such as CI14645 described in JP-A-50-133338, JP-B-55-427.
No. 52, Japanese Patent Sho 58-41508, Japanese Patent Sho 58-7384, Japanese Patent Sho 5
9-7385 etc. salicylic acid, naphthoic acid, metal complexes of dicarboxylic acid such as Co, Cr, Fe, sulfonated copper phthalocyanine pigment, nitro group, halogen-introduced styrene oligomer, chlorinated paraffin, etc. .

In addition, the toner of the present invention gives good results even when an additive is mixed as necessary. Examples of the additives include lubricants such as Teflon and zinc stearate, or abrasives such as cerium oxide, silicon carbide, and strontium titanate, or fluidity-imparting agents such as colloidal silica and aluminum oxide, anti-caking agents, or carbon. There are conductivity-imparting agents such as black, zinc oxide, antimony oxide and tin oxide, fixing aids such as low molecular weight polyethylene, low molecular weight polypropylene and various waxes, or offset resistant agents. In addition, a small amount of reverse polarity white fine particles and black fine particles can be used as a developing property improver.

Further, when the toner of the present invention is used as a two-component developer, it is used as a mixture with carrier powder. In this case, the mixing ratio of the toner and the carrier powder is 0.1 to 50% by weight, preferably 0.5 to 10% by weight, and more preferably 3 to 5% by weight as the toner concentration.

As the carrier that can be used in the present invention, all known carriers can be used, for example, iron powder, ferrite powder, magnetic powder such as nickel powder, glass beads, etc., and their surfaces treated with a resin or the like. Something is included.

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 also serves as a coloring agent. Examples of the magnetic material contained in the magnetic toner of the present invention include iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel; or aluminum, cobalt and copper of these metals;
Examples thereof include alloys of metals such as lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof.

These ferromagnetic materials have an average particle size of 0.1 to 2 μm, preferably 0.1 to μm, and the amount contained in the toner is about 20 to 200 parts by weight, and particularly preferably the resin is 100 parts by weight of the resin component. 40 to 150 parts by weight is preferable for 100 parts by weight of the component.

Further, a colorant may be added to the toner of the present invention if necessary.

Any appropriate pigment or dye is used as the colorant used in the toner of the present invention. Toner colorants are well known and include, for example, pigments such as carbon black, alinine black, acetylene black, naphthol yellow,
There are Hansa Yellow, Rhodamine Lake, Alizarin Lake, red iron oxide, phthalocyanine blue, indanthrene blue and so on. These are used in an amount necessary and sufficient to maintain the optical density of the fixed image, and can withstand 100 parts by weight of resin.
The amount added is 0.1 to 20 parts by weight, preferably 2 to 10 parts by weight. Further, a dye is further used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, methine dyes, etc.
The addition amount of 20 parts by weight, preferably 0.3 to 3 parts by weight is good.

To prepare the toner for developing an electrostatic image according to the present invention, the resin composition and the charge control agent according to the present invention, if necessary, a magnetic material and a pigment or dye as a colorant, an additive and the like are added to a ball mill and other materials. After thoroughly mixing with a mixer, use a heat kneader such as a heating roll, kneader, or extruder to melt, knead, and knead the meat to make the resins compatible with each other, and then disperse or dissolve the pigment or dye. After cooling and solidification, pulverization and classification can be performed to obtain a toner having an average particle size of 5 to 20 μm.

Alternatively, a method in which the material is dispersed in a binder resin solution and then spray-dried, or a predetermined material is mixed with a monomer that constitutes the binder resin to form an emulsion, a suspension and then polymerization is performed. Polymerization method of obtaining a toner by a method or a method of forming a capsule toner composed of a core and a shell can be applied.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. All parts in the following formulations are parts by weight.

[Synthesis Example 1] A mixed solution of 70 parts of styrene, 20 parts of n-butyl acrylate, 10 parts of α-methylstyrene and 6 parts of benzoyl peroxide was added dropwise to 200 parts of toluene at a boiling point over 5 hours, and thereafter. , Keep it at the boiling point for 3 hours to polymerize,
After vacuum drying, toluene was removed to obtain a low molecular weight polymer-1. Next, a homogeneous mixture of 70 parts of low molecular weight polymer-1, 75 parts of styrene, 24 parts of n-butyl acrylate, 1 part of divinylbenzene and 4 parts of benzoyl peroxide was dissolved in 0.8 part of polyvinyl alcohol partially saponified water to prepare 300 parts of water. Parts in a solution and polymerized for 15 hours at a polymerization temperature of 80 ° C. to obtain a pearl-like resin composition in which a high molecular weight polymer including a gel component and a low molecular weight polymer are uniformly mixed, and dried under reduced pressure. To obtain a resin composition-1.

About 0.5 g of Resin Composition-1 was precisely weighed, put in a cylindrical filter paper (Toyo Roshi Kaisha No.86R), and subjected to Soxhlet extraction for 6 hours using 180 ml of chloroform as a solvent, and the medium in the extracted soluble component. Evaporate to remove, then at 100 ℃ 1
After vacuum drying for 2 hours, the amount of soluble resin component was weighed. From the sample weight and this value, the gel component weight (degree of crosslinking) was determined according to the above equation. Further, this soluble resin component was dissolved in THF to prepare a sample having a concentration of 0.1% by weight, which was passed through a non-aqueous sample pretreatment filter to prepare a GPC sample. Using Shodex KF-80M as a GPC measurement column, it was installed in a 40 ° C heat chamber of a GPC measurement device (Waters 150C ALC / GPC), THF flow rate was 1 ml / min, and the detector was RI at 200 μl. GPC was measured by injection. As a calibration curve for molecular weight measurement, the molecular weight is 0.5 × 10 ³ , 2.35 × ³ , 10.2
× 10 ³ , 35 × 10 ³ , 110 × 10 ³ , 200 × 10 ³ , 470 × 10 ³ , 1200 × 1
0 ^3, (manufactured by Waters Co.) 2700 × 10 ^3, 8420 × 10 ³ of 10 monodisperse polystyrene standard substance using THF solution.

The resin composition-1 had a gel component weight of 33% by weight, and an eluting component had a molecular weight main peak value of 6000 and a subpeak value of 51,000. The chromatogram by GPC is shown in FIG.

[Synthesis Example 2] In suspension polymerization, 120 parts of a low molecular weight polymer, 0.5 part of divinylbenzene, and t-butylperoxy- as a polymerization initiator.
A pearl-like resin composition-2 was obtained in the same manner as in Synthesis Example 1 except that 2 parts of 2-ethylhexanoate was used.
The weight of the gel component of the resin composition was 5% by weight, the main peak value of the molecular weight of the eluted component was 5,000, and the shoulder value was 82,000.

[Synthesis Example 3] A pearl-like resin composition-3 was obtained in the same manner as in Synthesis Example 1 except that 1.4 parts of divinylbenzene and 4.5 parts of benzoyl peroxide were used as an initiator in the suspension polymerization.
The gel component of the resin composition was 45%, the main peak value of the molecular weight of the eluted component was 5,000, and the shoulder value was 31,000.

[Synthesis Example 4] A pearl-shaped resin composition-4 was prepared in the same manner as in Synthesis Example 1 except that 60 parts of a low molecular weight polymer, 1.9 parts of divinylbenzene, and 4.5 parts of benzoyl peroxide were used as an initiator in suspension polymerization. Got The resin composition has a gel component of 55%, an elution component has a main peak molecular weight of 5000, and a shoulder value of 3
It was 3000.

[Synthesis Example 5] A pearl-shaped resin composition-5 was obtained in the same manner as in Synthesis Example 1 except that 1 part of triethylene glycol diacrylate was used as a crosslinking agent in suspension polymerization instead of divinylbenzene. The gel component of the resin composition is 27%, the main peak value of the molecular weight of the eluted component is 5800, and the sub peak value is 4
It was 8,000.

[Synthesis Example 6] In the synthesis of the low molecular weight polymer, except that carbon tetrachloride was added to the solvent and 65 parts of styrene, 15 parts of α-methylstyrene and 7 parts of benzoyl peroxide were used, a low molecular weight polymer-1 was prepared. Low molecular weight polymer-2 was obtained in the same manner as in the synthesis. Next, a pearl-like resin composition-6 was obtained in the same manner as in Synthesis Example 1 except that 70 parts of the low molecular weight polymer-2, 8 parts of α-methylstyrene and 5 parts of benzoyl peroxide were used. . The gel component of the resin composition was 30%, the molecular weight main peak value of the eluted component was 900, and the Cjorder value was 13000.

[Synthesis Example 7] In the synthesis of the low molecular weight polymer, α-methylstyrene was not used, the amount of styrene was increased by that amount, and 3 parts of benzoyl peroxide was used.
Low molecular weight polymer-3 was obtained in the same manner as in the synthesis example of. Then, a pearl-like resin composition was prepared in the same manner as in Synthesis Example 1 except that 70 parts of the low molecular weight polymer-3 and 0.8 part of t-butylperoxy 2-ethylhexanoate were added as an initiator. Got 7. The gel component of the resin composition is 36%, the molecular weight main peak value of the eluted component is 28,000, and the sub peak value is 98.
It was 000.

[Synthesis Example 8] In suspension polymerization, 15 parts of low molecular weight polymer-1, 2.2 parts of divinylbenzene, and t-butylperoxy-2- as an initiator
A pearl-like resin composition-8 was obtained in the same manner as in Synthesis Example 1 except that 2 parts of ethylhexanoate was added. The gel component of the resin composition was 76%, the main peak value of the molecular weight of the eluted component was 8000, and the sub-beak value was 86000.

[Synthesis Example 9] In the synthesis of the low molecular weight polymer, the same procedure as in the synthesis of the low molecular weight polymer-1 was carried out except that α-methylstyrene was not used, styrene was increased by that amount, and 2.5 parts of benzoyl peroxide was used. , Low molecular weight polymer-4 was obtained. Next, except using 70 parts of low molecular weight polymer-4 and 0.6 part of t-butylperoxy 2-ethylhexanoate as an initiator,
All in the same manner as in Synthesis Example 1, pearl-shaped resin composition-9
Got The main peak value of the gel component of the resin composition was 32% and the molecular weight of the eluted component was 113,000 and the sub peak value was 27,000.

[Synthesis Example 10] In the synthesis of the low molecular weight polymer, the low molecular weight polymer-1 was used except that α-methylstyrene was not used, the amount of styrene was increased by that amount, and 3 parts of benzoyl peroxide was used.
Low molecular weight polymer-5 was obtained in the same manner as in the synthesis of. Next, a pearl-like resin composition was prepared in the same manner as in Synthesis Example-1 except that 70 parts of low molecular weight polymer-5 and 0.5 part of t-butylperoxy 2-ethylhexanoate were added as an initiator. I got -10. The gel component 40% of the resin composition, the main peak value of the molecular weight of the eluted component is 23000, the sub-peak value is
It was 195,000.

[Synthesis Example 11] In suspension polymerization, 20 parts of low molecular weight polymer-1 and 1.3 parts of divinylbenzene, benzoyl peroxide as an initiator
A pearl-like resin composition-11 was obtained in the same manner as in Synthesis Example 1 except that 4.5 parts were used. The gel component of the resin composition is 45%, the main peak value of the molecular weight of the eluted component is 25,000,
The shoulder value was 5000.

[Synthesis Example 12] A pearl-shaped resin composition-12 was obtained in the same manner as in Synthesis Example 1 except that 1.3 parts of triethylene glycol diacrylate and 4.5 parts of benzoyl peroxide were used as an initiator in suspension polymerization. It was Gel component 41 of the resin composition
%, The main peak value of the molecular weight of the eluted component was 5000, and the Cjorder value was 36000.

[Synthesis Example 13] A low molecular weight polymer-5 was obtained in the same manner as the synthesis of the low molecular weight polymer-1 except that 15 parts of 2-ethylhexyl acrylate and 75 parts of styrene were used in the synthesis of the low molecular weight polymer. Next, a pearl-like resin composition-13 was obtained in the same manner as in Synthesis Example 1 except that 70 parts of this low molecular weight polymer-5 was used. The gel component of the resin composition was 29%, the molecular weight main peak value of the eluted component was 5500, and the sub peak value was 48000.

The proportions of A component, B component and C component of the vinyl polymer obtained in each synthesis example are shown in Table 1 below.

[Example 1] The above materials were well mixed with a blender and then kneaded with two rolls heated to 150 ° C. After allowing the kneaded product to cool naturally, it is crushed with a cutter mill, crushed with a fine crusher using a jet air stream, and further classified with an air classifier to obtain a black fine powder with an average particle size of 11-12 μm. Obtained. Wet-produced silica was mixed with this using a Henschel mixer to obtain a toner. When this toner was subjected to continuous 3000-sheet durability using a Canon NP-3525 copying machine using an OPC photoconductor, a clear image with an image density of 1.2 to 1.3 and high resolution without fog was obtained. Further, the temperature of the fixing roller was changed by using the NP-3525 fixing device, and the offset, fixing property test, and winding were examined.
The offset did not occur from 0 ° C to 230 ° C, the fixing property at 150 ° C was good, and the winding on the roller did not occur.
It was also found that this toner is excellent in pulverizability and blocking resistance at 50 ° C. for 1 day.

Example 2 Example 1 except that 100 parts of Resin Composition-2 was used.
A toner was created in the same manner as in, and was subjected to continuous 3000 sheet durability using a Canon NP-3525 copier.
3. A clear image with high resolution without fog was obtained. Furthermore, when the offset roller fixing temperature was changed using the NP-3525 fixing device and the offset fixing property test and wrapping were examined, as shown in Table 2, no offset occurred from 145 ° C to 230 ° C, and the fixing property at 150 ° C was also good. No wrapping around the roller occurred. Grindability of this toner and 50 ℃
The blocking resistance in one day was also good.

[Example 3] A toner was prepared in the same manner as in Example 1 except that 100 parts of Resin Composition-3 was used, and 3,000 continuous images were made using a Canon NP-3525 copying machine. Concentration 1.
From 25 to 1.35, a clear image with high resolution without fog was obtained. In addition, the offset fixing test was conducted by changing the fixing roller temperature using the NP-3525 fixing device and the winding was examined. As shown in Table 2, the offset did not occur from 140 ° C to 230 ° C and the fixing property at 150 ° C was good. No wrapping around the roller occurred. Further, it was found that there was no problem with the blocking property at 50 ° C. for 1 day and the pulverizability of the toner was excellent.

[Example 4] 100 parts of Resin Composition-4, 60 parts of magnetite, 4 parts of low molecular weight polypropylene, and 2 parts of chromium salicylate complex compound were mixed well with a blender and then kneaded with two rolls heated to 150 ° C. After allowing the kneaded product to cool naturally, it is roughly crushed with a cutter mill and then crushed with a fine crusher using a jet air stream, and further classified with an air classifier, and the average particle size of deposition is 11 to 12μ.
m black fine powder was obtained. Hydrophobic dry silica was mixed with this with a Henschel mixer to prepare a toner. This toner is a Canon NP that uses an amorphous silicon photoconductor.
When 3,000 sheets were continuously run using a −7550 copier, a clear image with an image density of 1.2 to 1.3 and high resolution without fog was obtained. Further, the temperature of the fixing roller was changed by using the NP-7550 fixing device, and the offset, fixing test, and winding were examined, and as shown in Table-2, 140 ° C to 230 ° C
Upset did not occur, the fixing property at 150 ° C was relatively good, and winding around the roller did not occur. Also
It was found that there was no problem in the blocking property of the toner at 50 ° C. for 1 day, and this toner was also excellent in pulverizability.

[Example 5] Example 1 was repeated except that the resin composition-5 was used.
Toner was created in the same manner as above, and was subjected to continuous 3000-sheet durability with a Canon NP-3525 copier, resulting in an image density of 1.15 to 1.3,
A clear image with high resolution and no fog was obtained. NP-35
When the fixing roller temperature was changed by using a 25 fixing device, the offset, fixing property, and wrapping were examined.
As shown in Fig. 3, the offset did not occur from 140 ° C to 230 ° C, the fixing property at 150 ° C was relatively good, and the winding around the roller did not occur. Further, it was found that the toner of the present invention has no problem in the blocking property at 50 ° C. for one day, and the pulverizability of the toner is excellent.

[Example 6] A toner was prepared in the same manner as in Example 1 except that 100 parts of Resin Composition-11 was used, and the toner was continuously run for 3000 sheets on a Canon NP-3525 copying machine. Concentration 1.2
~ 1.3, high resolution and clear image without fog was obtained.
Using the NP-3525 fixing device, we examined the offset, fixing property, and wrapping while changing the fixing roller temperature.
As shown in Table 2, the offset did not occur up to 140 ° C to 230 ° C, the fixing property at 150 ° C was relatively good, and the winding around the roller did not occur. Further, there was no problem in the blocking property at 50 ° C. for 1 day, and the pulverizability of the toner was almost satisfactory.

[Example 7] A toner was prepared in the same manner as in Example 1 except that 100 parts of Resin Composition-12 was used, and the toner was continuously used for 3,000 sheets with a Canon NP-3525 copying machine. Concentration 1.15
~ 1.3, high resolution and clear image without fog was obtained.
Using the NP-3525 fixing device, we examined the offset, fixing property, and wrapping while changing the fixing roller temperature.
As shown in Table 2, the offset did not occur up to 140 ° C to 230 ° C, the fixing property at 150 ° C was good, and winding around the roller did not occur at all. Further, it was found that the blocking property at 1 day at 50 ° C. and the pulverizability of the toner were excellent.

[Example 8] A toner was prepared in the same manner as in Example 1 except that 100 parts of Resin Composition-13 was used, and the toner was continuously run for 3000 sheets on a Canon NP-3525 copying machine. Concentration 1.15
~ 1.25, clear image with high resolution without fog was obtained. Using the NP-3525 fuser, we examined the offset, fixability, and wrapping by changing the temperature of the fixing roller. As shown in Table-2, the offset did not occur from 140 ℃ to 230 ℃, and the fixing at 150 ℃ was performed. The property was good, and winding around the roller did not occur. Further, it was found that the blocking property at 1 day at 50 ° C. and the pulverizability of the toner were excellent.

[Comparative Example 1] A toner was prepared in exactly the same manner as in Example 1 except that 100 parts of Resin Composition-6 was used, and the toner was subjected to continuous 3000-sheet durability with a Canon NP-3525 copying machine. 1.2
Although a clear image with no fog was obtained, as shown in Table 3, in the evaluation of offset property, fixability and wrapping using the NP-3525 fixer, there was no problem with the fixability at 150 ° C. On the image, the offset at 140 ° C and the offset at 230 ° C were conspicuous, and winding around the roller occurred. Further, toner blocking was confirmed under the condition of 1 day at 50 ° C.

[Comparative Example 2] A toner was prepared in the same manner as in Example 1 except that 100 parts of Resin Composition-7 was used. This toner is made by Canon
When 3,000 sheets were continuously run on the NP-3525 copier, an image density of 1.1 to 1.2 and a clear image without fog were obtained.
In the evaluation of offset, fixability, and wrapping with the −3525 fixing device, offset and wrapping at 230 ° C. and blocking at 50 ° C. for 1 day did not occur, but as shown in Table 3, the offset occurred at 140 ° C. It was found that the fixability at 150 ° C was poor and the pulverizability was extremely poor.

[Comparative Example 3] A toner was prepared in the same manner as in Example 1 except that 100 parts of Resin Composition-8 was used, and the toner was continuously prepared using Canon NP-3525.
After running 3000 sheets, the image density was as low as 0.95 to 1.15, and only fog-like images were obtained. In the evaluation of offset, fixing property, and wrapping with the NP-3525 fixing device,
There was no problem with blocking at 230 ° C, winding, and blocking resistance at 50 ° C for 1 day, but fixing at 150 ° C, 1
The offset at 40 ° C was poor, and the grindability was not satisfactory.

[Comparative Example 4] A toner was prepared in the same manner as in Example 1 except that 100 parts of Resin Composition-9 was used, and the toner was continuously prepared using Canon NP-3525.
After running 3000 sheets, an image with image density of 1.1 to 1.2 and slightly fog was obtained. The offset, fixing property, and wrapping evaluation of the NP-3525 fuser were 230 ° C and 1 day at 50 ° C. Blocking and winding around the roller did not occur, but the offset at 140 ° C, 1
The fixability at 50 ° C was poor, and the grindability was extremely poor.

[Comparative Example 5] A toner was prepared in the same manner as in Example 1 except that 100 parts of the resin composition-10 was used, and the toner was continuously 3,000 using Canon NP-3525.
When the sheets were subjected to durability test, the image obtained had no fog, but the image density was low at 1.05 to 1.15. Also, NP-3525
In the evaluation of the offset, fixing property, and wrapping by the fixing device, the offset at 230 ° C, the blocking at 50 ° C for 1 day, and the wrapping around the roller did not occur, but the offset at 140 ° C and the fixing property at 150 ° C were not found. The toner grindability was extremely poor.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a chromatogram for Example 1, and FIG. 2 shows a chromatogram for Comparative Example 4.

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Claims (5)

[Claims] 1. A gel component is contained in an amount of 0.1 to 60% by weight, and a tetrahydrofuran-soluble component has a main peak value in a molecular weight range of 1000 to 25,000 and a main peak value in a molecular weight range of 3000 to 150,000 in a GPC chromatogram. At least 1
It has one sub-peak or sub-shoulder, and the amount of A component in the molecular weight range of 500,000 or more is 1% by weight or more and the molecular weight is 30,000-
A toner for developing an electrostatic image, which comprises a vinyl polymer having 10 to 60% by weight of the B component in the range of 500,000 and 20 to 90% by weight of the C component in the range of 30,000 or less. . 2. The toner for developing an electrostatic charge image according to claim 1, wherein the gel component is contained in an amount of 1 to 55% by weight. 3. The toner for developing an electrostatic image according to claim 1, wherein the gel component is contained in an amount of 10 to 50% by weight. 4. The toner for developing an electrostatic charge image according to claim 1, wherein the vinyl polymer is uniformly mixed from a low molecular weight polymer to a high molecular weight polymer among the polymers containing a crosslinking component. 5. The electrostatic charge image developing according to claim 1, wherein the vinyl polymer is prepared by preparing a vinyl monomer containing a low molecular weight polymer in the presence of a crosslinking agent. toner.