JPH0833681B2 - Toner composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a toner composition, and more particularly, to developing an electrostatic charge image formed in an electrophotographic method, an electrostatic printing method, an electrostatic recording method or the like. Toner composition.

<Prior Art> Conventionally, in a copying machine using electrophotography, a colorant and a binder resin are used to visualize an electrostatic charge image formed on a photoconductor having selenium, an organic photosensitive layer, etc. by a dry development method. Various toners containing the like are used.

In the dry developing method, an electrostatic charge image formed on the photoreceptor by charging and exposure is developed with the toner, and the developed toner image is transferred to a support such as transfer paper, and a heating roller or a pressure roller is used. The toner image is fixed on a support by the above, and the electrostatic charge image is visualized. Further, after the toner image is transferred to the support, the residual toner on the photoconductor is scraped off by a cleaning blade in order to clean the toner remaining on the photoconductor. When this cleaning process is repeated, the toner is fused to the photoconductor and gradually grows due to frictional heat between the photoconductor surface and the cleaning blade. In particular, if the photoconductor is not smooth or there are protrusions or holes on the photoconductor, the damage to the photoconductor becomes large, and the toner is likely to be fused on the streaks on the surface of the photoconductor. Together
There is a problem that streaks of toner are generated on the copied image and the quality of the copied image is deteriorated.

In order to solve the above problems, it is known that the toner is added with a fatty acid metal salt for protecting the photoconductor and improving the cleaning property, and a polishing substance such as hydrophobic silica (Japanese Patent Publication No. 54/54). -16220, JP 58-1
25045 publication).

<Problems to be Solved by the Invention> However, although the photoconductor can be protected by the addition of the fatty acid metal salt, particularly when the photoconductor has an organic photosensitive layer, the fatty acid metal salt Since the affinity with the photoconductor is large, the fatty acid metal salt is easily filmed on the surface of the photoconductor. When the fatty acid metal salt is formed into a film, the filmed fatty acid metal salt functions as an insulating layer, and the surface potential of the photoconductor having the organic photosensitive layer is generally low, so that the quality of a copied image or the like is improved. There was a problem of lowering. Further, in order to improve image characteristics such as gradation, if a large amount of the above fatty acid metal salt is added, not only the above-mentioned filming occurs, but also the electric resistance of the toner and the developer becomes small, and the solid portion of the image is reduced. There is a problem that bleeding of toner occurs in the vicinity and the quality of a copied image or the like deteriorates. Furthermore, since the organic photosensitive layer of the photoreceptor is softer than the photosensitive layer such as selenium, when a toner to which a polishing substance such as hydrophobic silica is added is used, the organic photosensitive layer is polished by the polishing substance. As a result, there is a problem that it becomes unusable at an early stage.

<Purpose> The present invention has been made in view of the above problems, and even when a photoconductor having an organic photosensitive layer is used as the photoconductor, it protects the photoconductor and causes toner streaks on the surface of the photoconductor. To prevent it from fusing in the shape of
An object of the present invention is to provide a toner composition capable of forming a high quality image by adjusting the electric resistance of the toner and the developer without deteriorating the characteristics of the toner and the developer.

<Means and Actions for Solving Problems> The present invention is based on 100 parts by weight of a powder toner containing a binder resin, a colorant and other additives, and the addition parts by weight x
Is a fatty acid metal salt satisfying the following relational expression: 0 <x ≦ 0.01 (parts by weight) 0.05 to 0.3 parts by weight of an abrasive substance based on 100 parts by weight of the powder toner, and 100 parts by weight of the powder toner. 0.05 to 0.3
The above-mentioned conventional problems are solved by a toner composition to which a weight part of an electric resistance adjusting agent is added.

According to the toner composition of the present invention having the above constitution,
The addition amount of the fatty acid metal salt is small, and it is possible to suppress the filming of the fatty acid metal salt on the photoreceptor surface. Since the film is polished and cleaned, the photoconductor can be protected and the toner can be prevented from fusing in the form of streaks on the surface of the photoconductor even when the photoconductor is cleaned. Further, since the amount of the fatty acid metal salt added is small, the electric resistance of the toner and the developer is hardly reduced,
It does not adversely affect the toner characteristics and image characteristics. Also,
The addition of the abrasive substance not only improves the fluidity of the toner, and thus the charging characteristics and image characteristics of the toner, but the addition of an electric resistance adjuster can adjust the electric resistance of the toner and the developer. The properties are improved.

 The present invention will be described in detail below.

The toner composition of the present invention comprises a powdery toner containing a binder resin, a colorant and other additives, a fatty acid metal salt, an abrasive substance and an electric resistance modifier added to the toner.

Examples of the binder resin include styrene polymers, acrylic polymers, styrene-acrylic copolymers, polyethylene, chlorinated polyethylene, polypropylene, olefin polymers such as ionomers, polyvinyl chloride, polyesters, polyamides, polyurethanes. Examples include various polymers such as epoxy resin, diallyl phthalate resin, silicone resin, ketone resin, polyvinyl butyral resin, phenol resin, rosin-modified phenol resin, xylene resin, rosin-modified maleic acid resin, rosin ester, and petroleum resin.

Examples of the unsaturated monomer used in the polymer include styrene, α-methylstyrene, o-methylstyrene, p-
Styrene-based monomers such as methylstyrene, p-methoxystyrene, p-chlorostyrene; acrylic acid, methyl acrylate, ethyl acrylate, -n-butyl acrylate,
Isobutyl acrylate, -n-octyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate,
Stearyl acrylate, cyclohexyl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, diethylaminoethyl acrylate, acrylamide, acrylonitrile, methacrylic acid, methyl methacrylate, methacrylic acid Ethyl, methacrylic acid-n-
Butyl, isobutyl methacrylate, methacrylic acid-n-
Octyl, 2-ethylhexyl methacrylate, dodecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, phenyl naphthalate, glycidyl methacrylate, 2-hydroxyethyl methacrylate,
Acrylic or methacrylic monomers such as 2-hydroxypropyl methacrylate and diethylaminoethyl methacrylate; carboxylic acids having unsaturated double bonds such as maleic acid, fumaric acid, crotonic acid, itaconic acid or alkyl esters thereof, or Examples thereof include alkyl esters; olefinic monomers such as ethylene, propylene and butadiene; vinyl acetate; vinyl chloride; vinylidene chloride; vinylpyrrolidone; vinylnaphthalene. The above monomers are used alone or in combination of two or more.

Among the above polymers, those having a styrene polymer, an acrylic polymer, a styrene-acrylic copolymer, or the like as a main component are preferable. These polymers preferably have a weight average molecular weight of 30,000 to 200,000, and particularly preferably 50,000 to 150,000, and are used alone or in combination of two or more.

Among the above-mentioned polymers, rosin ester, rosin-modified phenol resin, rosin maleic acid resin, epoxy resin, polyester, fibrin-based polymer, polyether resin and the like are used for improving the triboelectric charging property of the toner. It is useful.

When the toner is a heat-fixing toner, the above polymer preferably has a softening point of 50 to 200 ° C, and more preferably 70 to 170 ° C.

When the toner is a pressure-fixing toner, a polymer that is easily plastically deformed, such as an olefin polymer such as polyethylene or polypropylene, is mainly used. This polymer is another polymer, for example, polyvinyl acetate, ethylene-hinyl acetate copolymer, hydrogenated polystyrene, polymer such as hydrogenated rosin ester, aliphatic, alicyclic or aromatic petroleum. It may contain a resin and the like.

Examples of the colorant include carbon black, lamp black (CINo.77266), chrome yellow (CINo.14090), and Hansa yellow (CINo.11660, 11).
680, etc.), Benzidine Yellow (CI No. 21100, etc.),
Slene Yellow G (CINo.70600), Quinoline Yellow (CINo.47005), Permanent Orange GTR (CINo.
12305), Pyrazolone Orange (CINo.21110), Balkan Orange (CINo.21160), Watch Young Red (CINo.15865), Permanent Red (CINo.12310)
Etc.), Brilliant Carmine 3B (CINo.16105), Brilliant Carmine 6B (CINo.15850), DuPont Oil Red (CINo.26105), Pyrazolone Red (CINo.2).
1120), Resole Red (CINo.15630), Rhodamine B Rake (CINo.45170), Rake Red C (CINo.1)
5585), Rose Bengal (CINo.45435), Aniline Blue (CINo.50405), Ultramarine Blue (CIN)
o.77103), Calco Oil Blue (CINo.azoec Blue
3), Methylene Blue Chloride (CINo.52015), Phthalocyanine Blue (CINo.74160), Phthalocyanine Green (CINo.74260), Malachide Green Oxalate (CINo.42000), or CISolvent Yellow.
Oil-soluble dyes such as 60, CISolvent Red 27 and CISolvent Blue 35 are exemplified. These colorants are used in one kind or in a mixture of two or more kinds, and are used in such an amount that a sufficient toner image density is obtained, for example, 1 to 30% by weight, preferably 2
Used up to 20% by weight.

When the toner is a magnetic toner, a magnetic substance is used together with the colorant or in place of the colorant. The magnetic substance may be any material that exhibits magnetism or is magnetizable. For example, ferrite, magnetite, and other iron, cobalt, nickel, manganese, and other ferromagnets, alloys, or these metals. Examples thereof include compounds containing. These magnetic materials have an average particle size of 0.1 to
It has a size of 1 μm, and is used generally in one or two or more kinds, and is usually used in an amount of 20 to 75% by weight, preferably 40 to 70% by weight.

In order to control the charge of the electrostatic image developing toner,
The toner, as other additives, charge control agents, for example, nigrosine dye (CINo.50415B), oil black (CINo.26150), oil-soluble dyes such as spirone black, naphthenic acid, salicylic acid, octylic acid, The below-mentioned binder resin is a fatty acid, a resin acid such as manganese, iron, cobalt, lead, zinc, cerium, calcium, nickel, a metal soap such as a metal salt, a metal-containing azo dye, a pyrimidine compound, an alkylsalicylic acid metal chelate, or the like. Per 0.1
What is contained is preferably about 5% by weight.

Further, in order to prevent the toner from adhering to the fixing roller, the above-mentioned toner includes an offset preventing agent, for example, various waxes such as low molecular weight polypropylene, low molecular weight polyethylene, and paraffin wax, and an olefin unit having 4 or more carbon atoms. A low molecular weight olefin polymer, a fatty acid amide, a silicone oil, and the like are preferably contained in an amount of 0.5 to 15% by weight based on the toner.

A fatty acid metal salt is added to the powder toner in order to protect the photoconductor and to obtain a high-quality image without deteriorating the developer characteristics.

Examples of the fatty acid of the fatty acid metal salt include saturated or unsaturated fatty acids having 8 to 36 carbon atoms, such as caprylic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, behenic acid, Lignoceric acid, cerotic acid, montanic acid, oleic acid,
Examples thereof include elaidic acid, linoleic acid, linolenic acid, erucic acid, ricinoleic acid, dihydroxystearic acid, cyclic fatty acids, dibasic acids, and dimer acids which are dimers of the above unsaturated fatty acids. Of the above fatty acids, saturated fatty acids, especially stearic acid, are preferred.

Further, as the metal of the fatty acid metal salt, zinc, lead,
Iron, copper, tin, cadmium, aluminum, calcium,
Various metals such as magnesium, nickel, cobalt, manganese, lithium and barium can be exemplified. Of the above metals, zinc is preferred. Among the aliphatic metal salts, the zinc stearate is particularly preferable because it has about 5 times the effect of aluminum stearate.

The fatty acid metal salt is an amount in which x satisfies the following relational expression, where x is the addition weight part of the fatty acid metal salt to 100 parts by weight of the powder toner, 0 <x ≦ 0.01 (parts by weight), preferably 0.001 ~ 0.01 parts by weight is added. If the fatty acid metal salt is not added, the photoreceptor cannot be sufficiently protected, and the fusion of the toner on the surface of the photoreceptor causes streaks on the copied image or the like, which deteriorates the image quality. On the other hand, if it exceeds 0.01 parts by weight, the fatty acid metal salt is filmed on the surface of the photoconductor and image blurring is likely to occur, which is not preferable.

Further, a polishing substance is added to the toner.
As the above-mentioned polishing substance, when a film of the fatty acid metal salt is produced, the film is polished so as to clean the photoreceptor, and as long as it does not adversely affect the characteristics of the toner, the photoreceptor and the image. Those that can be used, for example, talc, kaolin, barium sulfate and the like may be used, but aluminum silicate, surface-treated aluminum silicate, titanium dioxide, calcium carbonate, antimony trioxide, barium titanate, calcium titanate,
Strontium titanate, magnesium oxide, calcium silicate, zinc oxide, zirconium oxide and the like are preferable,
Particularly, colloidal silica and surface-treated hydrophobic silica are preferable. By adding the above-mentioned abrasive substance, particularly hydrophobic silica, the fluidity of the toner and the developer is improved, and the charging characteristics and image characteristics of the toner are improved. The polishing substance preferably has an average particle size of 5 to 100 mμ, particularly 10 to 30 mμ. If the particle size of the abrasive substance is out of the above range, the above effects are reduced, which is not preferable.

A preferred specific example of the above polishing material is "Aerosil R972" (average particle size: 16 m, manufactured by Nippon Aerosil Co., Ltd.).
μ) and the like can be exemplified.

The polishing material is added to 0.05 to 0.3 parts by weight based on 100 parts by weight of the powder toner. If the amount of the abrasive substance added is less than 0.05 parts by weight, the fluidity of the toner will be poor, and if it exceeds 0.3 parts by weight, the photoreceptor will be easily damaged.

Further, an electric resistance adjusting agent is added to the powder toner in order to adjust the electric resistance of the toner and the developer, and eventually the image characteristics such as gradation and density, and obtain a high quality image. There is.

As the electric resistance adjusting agent, any one can be used as long as it can adjust the electric resistance of the toner and does not adversely affect the characteristics of the toner, the photoreceptor and the image, and examples thereof include carbon black. However, aluminum oxide, which can finely adjust the electric resistance, is preferable.

The electric resistance adjuster preferably has a particle size similar to that of the polishing substance, and is, for example, Nippon Aerosil Co., Ltd.
"Aluminum oxide C" (average particle size 20 mμ) and the like can be exemplified.

The electric resistance adjusting agent is added in an amount of 0.05 to 0.3 parts by weight based on 100 parts by weight of the powder toner. If the amount of the electrical resistance adjusting agent added is less than 0.05 parts by weight, it becomes difficult to finely adjust the electrical resistance. On the other hand, if the amount exceeds 0.3 parts by weight, image blurring tends to occur.

In addition, in order to improve the fluidity of the toner, the toner surface may be treated with a compound having a low surface tension such as a silane coupling agent or silicone or a fluorine compound. Further, if desired, the powder toner may be heat-treated to smooth the corners of the toner in order to improve the fluidity of the toner.

The above powder toner has a particle size of 1 to 30 μm, preferably 5 to 30 μm.
It has a thickness of ~ 25 μm.

The toner composition of the present invention is useful as either a one-component toner or a two-component toner. When used as a one-component toner, the toner containing the magnetic material is used alone as a developer, and when used as a two-component toner, mixed with a carrier such as iron powder or glass beads to be used as a developer. . As the carrier, glass beads, an uncoated carrier such as oxidized or unoxidized iron powder, or a magnetic substance such as iron, nickel, cobalt, or ferrite is used as an acrylic polymer, a fluoropolymer, a polyester, or the like. Coated carriers coated with coalescence are used, usually 50-2000
It has a particle size of μm. When a developer comprising the above toner and carrier is used, the toner is usually 2 to 15
% By weight.

As the photoreceptor, selenium, selenium-tellurium, zinc oxide, cadmium sulfide, amorphous silicon and the like can be used, but organic photoreceptors, for example, selenium-polyvinylcarbazole (PVK) composite photoreceptor, polyvinylcarbazole. And a photoreceptor containing 2,4,7-trinitrofluorenone or tetracyano-p-quinodimethane (TCNQ), or a photoreceptor containing a photosensitive organic compound having a heterocyclic ring, a condensed ring, or the like in a polymer. The toner composition of the present invention is particularly suitable when an organic photoreceptor is used.

The toner composition is obtained by a conventionally known developing method, for example,
When it is a one-component toner, it is developed by a hair brush developing method, a magnetic brush developing method, a powder cloud developing method, and when it is a two-component toner, it is developed by a cascade developing method, a magnetic brush developing method and the like.

Hereinafter, one method for producing the toner composition of the present invention will be briefly described. First, a powder toner containing a binder resin, a colorant and the like is manufactured. This powder toner is obtained by a conventionally known method, for example, by using the binder resin and the colorant on a heat roll,
Mix and disperse using a heating mixer such as an extruder,
While crushing with a crusher such as a hammer mill or jet mill, a mechanical crushing method of classifying with a classifier to obtain a predetermined particle size, or dispersing the colorant or the like in a solution of the binder resin to obtain a predetermined particle size. It can be produced by a spray drying method or the like in which the particles are spray dried. Then, a predetermined amount of the fatty acid metal salt, the polishing substance, and the electric resistance adjusting agent are added to the toner, and the mixture is uniformly mixed using an appropriate mixing machine such as a ball mill or a V-type mixing machine. The composition can be manufactured.

<Example> Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 Using 90% by weight of styrene-acrylic copolymer as a binder resin, 7.5% by weight of carbon black as a colorant, 1.5% by weight of polypropylene as an anti-offset agent, and 1.0% by weight of nigrosine dye as a charge control agent. A powder toner having an average particle size of 5 to 20 μm was prepared by a conventional method. To 100 parts by weight of this toner, zinc stearate was added at a ratio shown in Table 1, and hydrophobic silica (“Aerosil R972”, manufactured by Nippon Aerosil Co., Ltd.) 0.2
By weight, 0.2 part by weight of aluminum oxide (“aluminum oxide C”, manufactured by Nippon Aerosil Co., Ltd.) was added and uniformly mixed to prepare a toner composition.

Further, the toner composition is 4.5% by weight, and the average particle size is 50 to 8
A 05.5 μm ferrite carrier and 95.5% by weight were uniformly mixed in a ball mill to prepare a developer.

Then, using the above-mentioned developer, the developing characteristics were examined with a copying machine equipped with a photoreceptor having an organic photosensitive layer (a modified DC-111 model manufactured by Mita Kogyo Co., Ltd.), and the results shown in Table 1 were obtained. Obtained.

As is clear from the results shown in Table 1, when zinc stearate is not added, the toner is fused to the photoconductor, and when the addition amount is 0.03 parts by weight or more, filming on the photoconductor is caused. Occurs. On the other hand, when the amount of zinc stearate added was 0.01 parts by weight or less, it was found that toner fusion to the photoconductor, filming, and image blurring did not occur. When the toner was fused to the photoreceptor, black streaks due to the fused toner were seen in the image.

Example 2 100 parts by weight of the powder toner of Example 1 above, 0.01 parts by weight of zinc stearate, and 0.1% of aluminum oxide of Example 1 were used.
A toner composition was prepared by adding 2 parts by weight and the hydrophobic silica of Example 1 at a ratio shown in Table 2. When the image characteristics were examined in the same manner as in Example 1, the results shown in Table 2 were obtained.

As is clear from Table 2, toners having no hydrophobic silica added have poor fluidity of the toner, and when the amount of hydrophobic silica added is 0.4 parts by weight or more, the photoconductor is scratched and I couldn't protect my body. On the other hand, when the addition amount of the hydrophobic silica is 0.05 to 0.3 parts by weight, the fluidity of the toner is good, the photoreceptor can be protected, and there is no fusion of the toner on the surface of the photoreceptor, The image characteristics were also excellent.

Example 3 0.01 parts by weight of zinc stearate and 0.2 parts by weight of the hydrophobic silica of Example 1 were added to 100 parts by weight of the powder toner of Example 1 and the aluminum oxide of Example 1 is shown in Table 3. A toner composition was prepared by adding each of them in a ratio. When the image characteristics were examined in the same manner as in Example 1, the results shown in Table 3 were obtained.

As is clear from Table 3, the toner having no aluminum oxide added has a poor fluidity of the toner, and the addition amount is 0.4
When the amount is more than the amount by weight, the fluidity of the toner is lowered, the photoreceptor is scratched, and image blurring occurs. On the other hand, when the addition amount of aluminum oxide is 0.05 to 0.3 parts by weight, the toner has good fluidity, and the image having excellent gradation is obtained without causing scratches on the photoreceptor and blurring of the image. was gotten. It has been found that the electric resistance of the developer decreases as the amount of aluminum oxide added increases, and the electric resistance of the toner can be adjusted by the amount of aluminum oxide added.

<Effects of the Invention> As described above, according to the toner composition of the present invention, the amount of the fatty acid metal salt added is small, and the fatty acid metal salt is unlikely to form a film on the surface of the photoconductor. Even when filming by the fatty acid metal salt occurs, the film of the fatty acid metal salt is polished and cleaned by the polishing substance, so that the photoconductor can be protected and the surface of the photoconductor can be maintained even when cleaning the photoconductor. Thus, it is possible to prevent the toner from fusing in a stripe shape. Further, since the amount of the fatty acid metal salt added is small, the electric resistance of the toner and the developer is hardly reduced, and the characteristics of the toner and the image characteristics are not adversely affected. Further, the addition of the abrasive substance not only improves the fluidity of the toner, by extension, the charging characteristics and the image characteristics of the toner, but also the addition of the electric resistance adjusting agent can adjust the electric resistance of the toner and the developer. The unique effect of the present invention is that a high quality image can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Riichi Matsui 1-2-2 Tamatsukuri, Higashi-ku, Osaka-shi, Osaka Mita Industry Co., Ltd. (56) References JP-A-53-81127 (JP, A) Kai 59-229567 (JP, A) JP 58-125046 (JP, A) JP 60-262172 (JP, A) JP 56-140356 (JP, A) JP 61-7846 ( JP, A) JP 58-152257 (JP, A) JP 61-188546 (JP, A) JP 61-188549 (JP, A) JP 61-56353 (JP, A)

Claims (4)

[Claims] 1. To 100 parts by weight of a powder toner containing a binder resin, a colorant and other additives, the added weight part x
Is a fatty acid metal salt satisfying the following relational expression: 0 <x ≦ 0.01 (parts by weight) 0.05 to 0.3 parts by weight of an abrasive substance based on 100 parts by weight of the powder toner, and 100 parts by weight of the powder toner. 0.05 to 0.3
A toner composition comprising a part by weight of an electric resistance modifier. 2. The toner composition according to claim 1, wherein the fatty acid metal salt is zinc stearate. 3. The toner composition according to claim 1, wherein the polishing substance is silica. 4. The toner composition according to claim 1, wherein the electric resistance modifier is aluminum oxide.