JPH02287363A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To prevent the welding of the toner in the form of stripes on the surface of a photosensitive body by using the combinated metal salt of fatty acid and silicone oil as the additives of the toner contg. a binder resin, coloring agent and the additives. CONSTITUTION:The combinated metal salt of the fatty acid and the silicone oil are used as the additives of the toner. The fatty acid of the combinated metal salt of the fatty acid is exemplified by combinations of >=2 kinds of the fatty acids such as stearic acid, and >=1 kinds of the metal salts thereof such as zinc salt cadmium salt, barium salt, lead salt and nickel salt and the fatty acids to be combined are selected like 10 to 19C fatty acid and 20 to 25C fatty acid. The amts. of the metal salt of the fatty acid and the silicone oil to be added are preferably respectively 1 to 10wt.% of the binder resin. The welding of the toner in the form of stripes on the surface of the photosensi tive body is thus prevented.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a toner for developing electrostatic images.

[Prior Art] Various methods such as a blade method, a brush method, and a web method are used to clean residual toner on a photoreceptor drum in an electrophotographic copying machine or a printer. As the process continues, toner that cannot be removed by these cleaning methods gradually accumulates on the surface of the photoreceptor, causing problems such as so-called poor cleaning or toner filming.

In order to deal with this phenomenon and improve the cleaning performance of residual toner on the photoreceptor drum, it is known to be effective to externally add zinc stearate, a metal soap, to the surface of the photoreceptor. . However, fine particles such as zinc stearate film on the photoreceptor, and when the photoreceptor is made of amorphous selenium, they promote crystallization of selenium, deteriorating the characteristics of the photoreceptor, and as a result, reducing image quality. be.

Therefore, in order to eliminate such adverse effects, for example,
No. 9-228887 proposes adding copper stearate together with zinc stearate to prevent crystallization of selenium. However, this method not only does not completely prevent the promotion of selenium crystallization, but also charges occur between the carrier, toner, and lubricant.
In particular, since zinc stearate has the same positive chargeability as the toner, the charging of the toner becomes extremely unstable, resulting in a problem that the image is distorted.

[Problems to be Solved by the Invention] The present invention has been made in view of the above problems, and even when a photoreceptor having an organic photoconductor is used as a photoreceptor, toner may form streaks on the surface of the photoreceptor. For electrostatic image development, which prevents fusing and protects the photoreceptor, and allows high-quality copy images to be formed over a long period of time without deteriorating the photoreceptor's photosensitive characteristics or toner developer characteristics. The purpose is to obtain toner.

[Means for Solving the Problems] The present invention provides a toner containing a binder resin, a colorant, and an additive, in which a fatty acid complex metal salt and a silicone oil are used as the additives. This toner solves the above-mentioned conventional problems.

Electrostatic charge 1 of the present invention having the above configuration! j! According to the developing toner, the addition of the fatty acid complex metal salt and the silicone oil has an excellent effect of preventing filming, particularly filming on a photoreceptor having an organic photosensitive layer. Further, at the same time as protecting the photoreceptor layer, it is possible to prevent toner from being fused in the form of streaks on the surface of the photoreceptor during cleaning. Furthermore, the image created using the toner of the present invention has the effect that even if a vinyl chloride sheet or the like is placed over the image and stored, the toner image will not be transferred to the vinyl chloride sheet and will not stain it. The present invention will be explained in detail below.

As the binder resin, styrene polymer, acrylic polymer, styrene-acrylic copolymer, polyethylene, chlorinated polyethylene, polypropylene, olefin polymer such as ionomer, polyvinyl chloride, polyester,
Polyamide, polyurethane, epoxy resin, diallyl phthalate resin, silicone resin, ketone resin, polyvinyl butyral resin, phenolic resin, rosin-modified phenolic resin, xylene resin, rosin-modified maleic acid resin,
Examples include various polymers such as rosin ester and petroleum resin.

The unsaturated monomers used in the above polymer include styrene monomers such as styrene, 0-methylstyrene, 0-methylstyrene, p-methylstyrene, p-methoxystyrene, p-chlorostyrene, nialic acid, Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, -octyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, stearyl acrylate, cyclohexyl acrylate, phenyl acrylate, acrylic 2-hydroxyethyl acid,
2-hydroxypropyl acrylate, glycidyl acrylate, diethylaminoethyl acrylate, acrylamide, acrylonitrile, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 〇-octyl methacrylate, Acrylics such as 2-ethylhexyl methacrylate, dodecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, diethylaminoethyl methacrylate, etc. or methacrylic monomers; carboxylic acids with unsaturated double bonds such as maleic acid, fumaric acid, crotonic acid, itaconic acid, or their alkyl esters, or their alkyl esters; olefinic monomers such as ethylene, propylene, butadiene, etc. Examples include vinyl acetate, vinyl chloride, vinylidene chloride, vinylpyrrolidone, and vinylnaphthalene. The above monomers are used in -i or in a mixture of two or more.

Among the above polymers, those whose main component is a styrene-based polymer, an acrylic polymer, or a styrene-acrylic copolymer are preferred. These polymers have a weight average molecular weight of ao, ooo to 200,000, especially 50,000 to
It is preferably in the range of 150,000, and one type or a mixture of two or more types can be used.

Among the above polymers, rosin esters, rosin-modified phenolic resins, rosin maleic acid resins, epoxy resins, polyesters, cellulose polymers, polyether resins, etc. are useful for improving the triboelectric properties of toner. Useful.

Further, when the toner is a heat fixable toner, the above polymer has a softening point of 50 to 200°C, preferably a softening point of 70 to 1
Preferably, the temperature is 70°C.

When the toner is a pressure fixable toner, polymers that are easily plastically deformed such as olefinic polymers such as polyethylene and polypropylene, and polyamides are mainly used. This polymer can be used with other polymers, such as polyvinyl acetate, ethylene-vinyl acetate copolymer, hydrogenated polystyrene, hydrogenated rosin ester, aliphatic, alicyclic or aromatic petroleum resins, etc. may contain.

In addition, examples of the coloring agent include carbon black, lamp black (C, 1, No, 77268), chromium yellow (C, 1, No, 14090), Hansa yellow (C, 1, No, 11 ( ifiO111680
etc.), benzidine yellow (1, No., 21100 etc.)
, Suren Yellow G (C, 1, No, 70800),
Quinoline Yeo-(C, 1, No.

47005), Permanent Orange GTR (C,
1, No.

12305), pyrazolone orange (C, 1, No, 2
1110), Palkan Orange (C, 1, No. 211)
60), Watch Young Red (C, 1, No, !5
865), Permanent Red (C, 1, No, 12
310 etc.), brilliant carmine 3 B (C,1,
No. 18105), Brilliant Carmine 6B (
C,! , No. 15850) DuPont Oil Red (C, 1, No. 28105) Pyrazolone Red (
C, 1, No. 21120), Lysole Red (C,
1, No.

15630), Rhodamine B Lake (C, 1, No. 4
5170), Rake Red C (C, 1, No. 1558)
5) , O's Bengal (C, 1, No, 45435)
, Aniline Blue (C11, No. 50405),
Ultramarine Blue (C, 1, No.

77103), Calco Oil Blue (C, 1, No, a
zoecBlue 3) Methylene blue chloride (C,I.

No. 52015), Phthalocyanine Blue (C, 1
,No.

74180), Phthalocyanine Green (C, 1, No.
.

74260), malachide green oxalate (C2
1, No. 42000) etc., C, 1,5olvcn
t Yellow 80, C.

1.5olvcnt Red 27, C, 1,5olv
Examples include oil-soluble dyes such as ENT Blue 35 and the like. These colorants may be used alone or in a mixture of two or more, and should be used in an amount that provides sufficient toner image density, for example,
It is used in an amount of 1 to 30% by weight, preferably 2 to 20% by weight.

Further, when the toner is a magnetic toner, a magnetic material is used together with or in place of the colorant. The above-mentioned magnetic material may be any material that exhibits magnetism or is magnetizable, such as iron such as ferrite and magnetite, metals or alloys that exhibit ferromagnetism such as cobalt, nickel, and manganese, or these metals. Examples include compounds containing the following. These magnetic materials have an average particle size of 0.1~
It has a size of about 1 μm and is used singly or in combination of two or more, usually 20 to 75%, preferably 40 to 70%.
% by weight is used.

Note that, in order to control the charge of the toner for developing an electrostatic image, the toner may contain a charge control agent as another additive. Examples of the charge control agent include nigrosine dye (C,1,N).

, 50415B), oil black (C, 1, No. 2
8150), oil-soluble dyes such as Subiron Black, metal soaps such as naphthenic acid, salicylic acid, octylic acid, fatty acids mentioned below, and metal salts of fatty acids such as manganese, iron, cobalt, lead, zinc, cerium, calcium, and nickel. Alternatively, metal-containing azo dyes, pyrimidine compounds, alkyl salicylic acid metal chelates, etc. are exemplified, and the strength of the binder resin is 0.
Preferably, the content is 1 to 5% by weight.

A fatty acid complex metal salt is added to the above-mentioned toner in order to protect the photoreceptor, prevent the formation of sushi-like toner on the surface of the photoreceptor, and produce high-quality images without deteriorating the developer properties. has been done.

The fatty acids of the fatty acid complex metal salts mentioned above include zinc salts, cadmium salts, barium salts, lead salts, iron salts, nickel salts, cobalt salts, copper salts, strontium salts, calcium salts or magnesium salts of stearic acid, and zinc salts of oleic acid. ,
Manganese, iron, cobalt, copper, lead or magnesium salts, zinc, cobalt, copper, magnesium, aluminum or calcium salts of palmitic acid, zinc or cadmium salts of ricinoleic acid, Known salts such as lead salts of caprylic acid, lead salts of caproic acid, and zinc salts of behenic acid include combinations of two or more types of fatty acids and one or more metal salts thereof. In particular, the fatty acids to be combined are selected to have 10 to 19 carbon atoms and 20 to 25 carbon atoms.

The use of the fatty acid complex salt of the present invention has the following advantages over conventional fatty acid metal salts used alone.

In other words, when used as a lubricant, using a longer-chain linear saturated fatty acid with carbon atoms of 20 or more improves dispersibility and improves the lubricity imparted to the toner. The amount can be reduced and the cost will be advantageous.

However, when used alone, although it does increase the lubricity imparted to toner particles, there is a risk that the lubricity may be impaired during high temperature drying or significant discoloration may occur.

Therefore, by combining it with a relatively short straight chain saturated fatty acid having 10 to 19 carbon atoms, the lubricity is not lost.
Moreover, the stability as a lubricant is maintained.

Examples of such combinations include metal salts of behenic acid and stearic acid, metal salts of behenic acid and nonadecanoic acid, and metal salts of behenic acid and stearic acid and isostearic acid.

For example, in an aliphatic complex metal salt containing behenic acid, the amount of behenic acid may be 50 to 90''LL and 96,
Preferably it is 60 to 80% by weight. This is because behenic acid is a linear saturated fatty acid with 22 carbon atoms, which improves dispersibility and improves the lubricity imparted to toner particles. The effect is reduced to the same extent as when zinc stearate is dispersed. However, when behenic acid is used in an amount exceeding 90% by weight, it is true that the lubricity imparted to the toner particles increases, but there is a risk that the lubricity may be lost or significant discoloration may occur during high temperature drying.

In the present invention, the amount of fatty acid metal salt and silicone oil added is preferably 1 to 10% by weight, respectively, based on the binding resin.

There are no particular restrictions on the method of adding the fatty acid complex metal salt, and the toner can be prepared by mixing it with each component constituting the toner using a conventional method. Alternatively, for example, a binder resin may be produced by a suspension polymerization method. In this case, it is also possible to polymerize the 7-mer together with a coloring agent in the presence of a fatty acid metal salt, and then mix the silicone oil.

In this case, the fatty acid complex metal salt is added internally to the toner particles and is further exuded onto the surface of the toner particles to impart lubricity to the toner particles themselves, so that all toner particles have uniform lubricity. Therefore, while achieving good cleaning properties, it is also possible to prevent adhesion to the surface of the photoreceptor and deterioration of the characteristics of the photoreceptor as in the case of external additives, and also to improve charging characteristics. It becomes stable because it is due to the charge between the two.

At this time, the amount of aliphatic complex metal salt is 1-
10% by weight, preferably 2 to 5% by weight, and the film thickness of the aliphatic composite metal salt on the surface of the toner particles is 0.001%.
The thickness is preferably about 0.5 μm.

If the amount is less than 96% by weight based on the monomer, the cleaning performance will not be sufficient, while if it is more than 10Ifm%, the slipperiness will be excessive, and the fluidity of the developer will be too good, causing it to easily slip from the developing sleeve, resulting in poor development. Things won't go well.

Here, the suspension polymerization method will be explained.

Examples of polymerizable monomers applicable to the polymerized toner used in the present invention include styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, and p-chlorostyrene. , 3.
4-dichlorostyrene, p-ethylstyrene, 2.4-
dimethylstyrene, p-n-butylstyrene, p-tc
rt-butylstyrene, p-n-hexylstyrene, p
-n-octylstyrene, p-n-nonylstyrene, p
- Styrene and its derivatives such as n-decylstyrene and p-n-dodecylstyrene; Ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; Vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, etc. Vinyl halides: vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate: methyl methacrylate, ethyl methacrylate, propyl methacrylate, -butyl methacrylate, isobutyl methacrylate, -octyl methacrylate , dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate,
α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate Methyl diacrylate, ethyl acrylate, -〇-butyl acrylate, isobutyl acrylate, propyl acrylate, -〇- acrylate Acrylic acid esters such as octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether: Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone;
- N-vinyl compounds such as vinylcarbazole, N-vinylindole, N-vinylpyropyrrolidone: vinylnaphthalenes: acrylonitrile, methacrylonitrile,
There are vinyl monomers such as acrylic acid or methacrylic acid reading conductors such as acrylamide. These may be used alone or in combination. Furthermore, a polymer of these polymerizable monomers may be added to the funeral composition. above l
Among the total t-mers, styrene or styrene having a substituent such as an alkyl group, or a combination of styrene and other monomers is preferred in consideration of the developability and durability of the polymerized toner.

Further, a charge control agent, various coloring agents, and fluidity modifiers may be added to the monomer composition as necessary. Charge control agents include alloy metal dyes, nigrosine, etc., and colorants include conventionally known dyes, carbon black, pigments such as grafted carbon black whose surface is coated with resin, and iron. It is possible to use ferromagnetic metals such as , cobalt, and nickel, or magnetic powders of alloys and compounds such as magnetite, hematite, and ferrite. Further, for the purpose of increasing the amount, a filler such as calcium carbonate or finely powdered silica may be added to the toner in an amount of 0.5 to 201 R%. Further, a fluidity improver such as fine Teflon powder may be added in order to prevent toner particles from coagulating with each other and improve fluidity.

Furthermore, for the purpose of lowering the fixing temperature and/or fixing pressure of the polymerized toner, a low softening point material such as solid paraffin or low molecular weight polyolefin, which has shape retention properties at room temperature, is added to the monomer composition. A large amount of the compound may be added. The low softening point compound in the present invention refers to the ring and ball method (JIS
K2531 etc.) has a softening point determined by itP+ of 40~
It has a temperature of 130°C, preferably 50 to 120°C. If the softening point is 40° C. or lower, the blocking resistance and shape retention of the toner will be insufficient, and if the softening point is 130° C. or higher, there will be little effect in lowering the constant dilution temperature or fixing pressure.

Examples of low softening point compounds include paraffins, waxes, low molecular weight polyolefins with softening points within the above range, modified waxes having aromatic groups, hydrocarbon compounds having alicyclic groups, natural waxes, and long chains with 12 or more carbon atoms. Hydrocarbon chain [0113(C)+2) u or (CH2) 12
Examples include long-chain carboxylic acids having the above aliphatic carbon chains, esters thereof, and the like. A mixture of different low softening point compounds may be used. Specifically, paraffin wax (manufactured by Nippon Oil), paraffin wax (manufactured by Nippon Seizan), micro wax (manufactured by Nippon Oil), microcrystalline wax (manufactured by Nippon Seizan), hard paraffin wax (manufactured by Nippon Seizan), PE-130 (manufactured by Hoechst), Mikata no Iwax II0P (manufactured by Mikata Petrochemicals), Mikata No. 1 Iwax 220P (manufactured by Mikata Petrochemicals), Mikata No. 1 Iwax 860P (manufactured by Mikata Petrochemicals) ), Mikata I\Iwatsux 210P (manufactured by Mikata Petrochemicals) Mikata\Iwatux 320P (manufactured by Mikata Petrochemicals), Mikata\Iwatsux 410P (manufactured by Mikata Petrochemicals) Mikata/% Iwatsux 4
20P (manufactured by Mikata Petrochemical) No1 L/T'7 T
-100X (Mikata Petrochemical), Highlets T-200
X (Mikata Petrochemical), Highlets T-300X (
Mikata Petrochemical): Vetrogin 80 (Mikata Petrochemical)
, Vetrogin 100 (Mikata Petrochemical), Vetrogin 1
20 (manufactured by Mikata Petrochemical), Tac Ace ^-100 (manufactured by Mikata Petrochemical), Tac Ace P-1oo (manufactured by Mikata Petrochemical), Tac Ace B-60 (manufactured by Mikata Petrochemical)
, modified wax JC-1141 (manufactured by Mikata Petrochemical), modified wax jC-2130 (manufactured by Mikata Petrochemical), modified wax JC-4020 (manufactured by Mikata Petrochemical), modified wax JC-1142 (manufactured by Mikata Petrochemical) Modified wax JC-5020 (manufactured by Mikata Petrochemical): beeswax, carnauba wax, montan wax, etc.

In addition, when using a low softening point compound having a softening point of 100° C. or higher, it may be preferable to carry out dispersion and granulation under pressure while raising the temperature of the aqueous medium to 100° C. or higher.

The low softening point compound contains 10% of the polymerizable monomer in order to lower the fixing temperature and/or fixing pressure of the ff1 toner.
50 to 3000 parts by weight are mixed with 0 parts by weight. In particular, it is preferable to mix 70 to 1000 parts by weight. 50
If it is less than 3,000 parts by weight, it is insufficient to lower the fixing temperature or fixing pressure of the fixed roller, and if it exceeds 3,000 parts by weight, there is a strong tendency for the blocking resistance and durability to decrease.

Furthermore, the polymerization initiator used in the present invention is soluble in the polymerizable monomer, and is used in the amount range normally used (2 to 5 parts by weight of the polymerization initiator per 100 parts by weight of the monomer). . Examples of the polymerization initiator that can be used in the present invention include 2.2'-azobis-(2,4-dimethylvaleronitrile);
2'-azobisisobutyronitrile, t,t'-azobis(cyclohexane-1-carbonitrile), 2.2
“-azobis-4-methoxy-2,4-dimethylvaleronitrile, other azobisisobutyronitriles (Al
Azo or diazo polymerization initiators such as 13N): peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, isopropyl peroxy carbonate, cumene hydroperoxide, 2,4-dichlorylbenzoyl peroxide, and lauroyl peroxide. Examples include polymerization initiators. Also, two or more of these may be used in combination.

The suspension polymerization reaction is usually carried out at a polymerization temperature of 50° C. or higher, and the upper limit temperature is set in consideration of the decomposition rate of the polymerization initiator. If the set polymerization temperature is too high, the polymerization initiator will be rapidly decomposed, which is not preferable. Therefore, if the softening point of the low softening point compound used is high (usually 70°C or higher), granulation at a temperature suitable for polymerization cannot be carried out because the viscosity of the monomer composition increases, so the aqueous dispersion medium After first granulating the monomer composition without adding a polymerization initiator while maintaining the temperature above this softening point, the temperature of the dispersion system is lowered to a temperature range below the upper limit temperature suitable for polymerization. A special procedure is then required to add the polymerization initiator into the aqueous medium.

The suspension method involves dispersing a color toner in a low softening point compound and dispersing the polymerizable monomer, additives, etc. uniformly into a 11Q body composition, which is then dispersed in a 11Q composition in an amount of 0.1 to 50% by weight. % dispersant (e.g. poorly soluble inorganic dispersant) (e.g. 5°C or higher than the polymerization temperature, preferably 10°C or higher)
(heated to a temperature higher than ℃) using an ordinary stirrer, homomixer, homogenizer, etc. Preferably the monomer droplets have the desired toner particle size;
Generally 30μm or less (e.g. volume average particle size 0.1-20μm)
The stirring speed, time, and temperature of the aqueous medium are adjusted to have a magnitude of μI++). Thereafter, the temperature of the aqueous medium is lowered to the polymerization temperature while stirring is performed to the extent that sedimentation of the particles is prevented so that this state is substantially maintained by the action of the dispersant. Polymerization temperature is 50°C or higher, preferably 55°C or higher
set at a temperature of 80°C, particularly preferably 60-75°C,
A polymerized toner is obtained by adding a substantially water-insoluble polymerization initiator while stirring, recovering by an appropriate method such as washing, filtration, decantation, centrifugation, etc., and drying. In the suspension polymerization method, 200 to 3000 parts by weight of water is usually used as an aqueous dispersion medium per 100 parts by weight of polymerizable IL fi1.

The method of manufacturing toner particles by suspension polymerization in the presence of the fatty acid complex metal salt of the present invention has been described above. However, as mentioned above, the present invention also includes various components of the toner such as pre-prepared setting resin. A toner can also be prepared by mixing.

In that case, the amount of the fatty acid complex metal salt is 0.00% in 100 parts by weight of the toner. It is preferable that all of O1 to Q and 4i[1 can be added, and the film thickness on the toner surface of the fatty acid complex metal salt based on this amount is about 0.001 to 0.5 μm. 0.4!1 for toner! If it is above the Q portion, filming will occur on the surface of the photoreceptor and blurring of the image will occur, which is not preferable.

If it is less than 0.01ff1m part, the smoothness of the toner will be significantly impaired.

The above toner has a particle size of 1 to 30 μm, preferably 5 to 20 μm.
It is preferable to have a diameter of μm. The electrostatic image developing toner of the present invention is useful as either a -component toner or a two-component toner. Alternatively, it can also be used as a liquid toner. Note that when used as a -component toner, the toner containing the above magnetic material alone is used as a developer,
When used as a two-component toner, it is mixed with a carrier such as iron powder or glass beads to form a developer. The above-mentioned carrier may be an uncoated carrier such as glass beads or oxidized or unoxidized iron powder, or a magnetic material such as iron, nickel, cobalt, or ferrite, or a magnetic material such as acrylic polymer, fluorine polymer, or polyester. Coated carriers coated with polymers are used and usually have a particle size of 50 to 2000 μm. Further, when using a developer consisting of the above-mentioned toner and carrier, the toner is usually used in an amount of 2 to 10% by weight.

The photoreceptor may include selenium, selenium-tellurium,
Photoreceptors such as zinc oxide, cadmium sulfide, and amorphous silicon can also be used, but organic photoreceptors such as selenium
Polyvinylcarbazole (PVK) composite photoreceptor, polyvinylcarbazole and 2.4.7-trinitrofluorenone or tetranitrocyano-p-quinodimethane (
T CN Toners are particularly suitable.

The toner for developing an electrostatic image can be developed by a conventionally known developing method, for example, when it is a -component toner, it is developed by a bristle brush development method, magnetic brush development method, or powder cloud development method, and when it is a two-component toner, it is developed by a cascade method. Developed by a developing method, magnetic brush developing method, etc.

A method for producing the toner for developing an electrostatic image according to the present invention will be briefly described below. First, a powder toner containing a binder resin, a colorant, etc. is manufactured. This powder toner is produced by a conventionally known method, for example, by mixing and dispersing the binder resin and a tinting agent using a heated mixer such as a hot roll or an extruder, and then using a pulverizer such as a hammer mill or jet mill. It can be produced by pulverizing and classifying with a classifier to obtain a predetermined particle size, or by a spray drying method in which the coloring agent, etc. is dispersed in a solution of the noble resin and spray-dried to obtain a predetermined particle size. I can do it. Then, a predetermined amount of the fatty acid metal salt is added to the toner and mixed uniformly using an appropriate mixer such as a ball mill or a V-type mixer, thereby producing the toner for developing an electrostatic image of the present invention. be able to.

[Example] The present invention will be explained in more detail by giving examples below.

Styrene-butyl acrylate copolymer as a binder resin: 90% by weight: 96% Carbon black as a young coloring agent: 9%
．． 0% by weight, 1.0 nigrosine dye as charge control agent
A powder toner having an average particle size of 5 to 20 μm was prepared by a conventional method using % by weight.

To 100 ffi parts of this toner, 0.2 parts of silicone oil and a fatty acid complex metal salt were added and mixed to prepare a toner for developing an electrostatic image.

A developer was prepared by uniformly mixing 3.5% by weight of the electrostatic image developing toner and 95.5% by weight of a ferrite carrier having an average particle size of 50 to 80 μm in a ball mill.

Then, an image was produced using a copying machine, Recopy 4060, and the image was evaluated.

Example 1 A fatty acid complex metal salt was composed as follows, and the amount added was 0.1 parts by weight, zinc salt of behenic acid, 80w1%, copper salt of stearic acid, 15wt%, aluminum salt of nonadecanoic acid, 25vt%, and the electrical resistance of the developer was determined. is 4. It was as high as lX 109Ω (500 VolL applied). Further, toner fusion to the photoreceptor, filming of the photoreceptor, and image blurring did not occur. Further, even when 50,000 sheets were continuously copied under high humidity, no filming on the photoreceptor or blurring of the images occurred.

However, without the addition of silicone oil, the offset resistance and PVC resistance deteriorated.

Example 2 Fatty acid complex metal salt was composed as follows, and the amount added was 0.2 parts by weight Zinc salt of behenic acid 80w1% Calcium salt of valmitic acid 20ν[% Copper salt of lauric acid
When the developer was set at 20V L%, the electrical resistance of the developer was as high as 3.6×1.09Ω (500 VolL applied). Further, toner fusion to the photoreceptor, filming of the photoreceptor, and image blurring did not occur. Further, even when 50,000 sheets were continuously copied under high humidity, no filming on the photoreceptor or blurring of the images occurred.

Example 3 A fatty acid complex metal salt was composed as shown below, and the amount added was 0.1 parts by weight, calcium salt of behenic acid, 70 wt%, copper salt of myristic acid, 30 vt%, and the electrical resistance of the developer was 4.3 x 109Ω (500 Volt applied). ) was high. Further, toner fusion to the photoreceptor, filming of the photoreceptor, and image blurring did not occur. Also, even when copying 50,000 copies continuously under high humidity, filming of the photoreceptor,
No blurring of images occurred.

However, without the addition of silicone oil, the offset resistance and PVC resistance deteriorated.

Example 4 Fatty acid complex metal salt was composed as follows, and the amount added was 0.2 parts by weight Iron salt of behenic acid 70 vL% Aluminum of stearic acid 30 vt% The electrical resistance of the developer was 3.4X 109Ω (500 Volt applied )
It was expensive. Further, toner fusion to the photoreceptor, filming of the photoreceptor, and image blurring did not occur. Further, even when 50,000 sheets were continuously copied under high humidity, no filming on the photoreceptor or blurring of the images occurred.

However, without the addition of silicone oil, the offset resistance and PVC resistance deteriorated.

Example 5 p-ethylstyrene 80g isobutyl acrylate 30g carbon black (manufactured by Cabot, USA) 0g chromium-containing azo dye 5g low molecular weight polypropylene 2g composite zinc salt of behenic acid/stearic acid/isophthalic acid -H/ 30/ to 5.0g
Add 2300 g of deionized water to a separable flask with an internal volume of 2!2 equipped with a stirrer, thermometer, and gas inlet tube.
After blowing nitrogen gas for 30 minutes to drive out the air in the system, heat it from the outside in a hot water bath and stir, then raise the internal temperature to 50°C and add azobisisonitrile 0.5
g was added.

Polymerization was carried out at the same temperature for 8 hours and at 80°C for 2 hours to complete the reaction.

The composite zinc salt of behenic acid/stearic acid/isostearic acid-〇〇/30/10, which was uniformly dispersed in the monomer, oozed out onto the surface of the toner because it was not dissolved in the polymer. In this way, a toner having a jlL average particle size of 13 μm was obtained.

This toner was classified into 5 to 20 microns. (However, those with a particle size of less than 5μI and more than 20μm are excluded.) This toner 100! Silicone oil was mixed and externally added to the IfB part, mixed with a carrier, and used as a developer for evaluation using this developer in a copying machine (Recopy 4060) that uses amorphous selenium as a photoreceptor material. did. This copying machine has a mechanism in which a positive charge image is formed on a photoconductor, developed using a magnetic brush method, and any toner remaining on the photoconductor is cleaned with a urethane rubber cleaning blade.

The electrical resistance of this developer is approximately 109 Ω (when 500 V is applied), and after continuous copying of ioo and ooo sheets, the cleaning performance was good, the amount of charge did not decrease, and the toner on the photoreceptor was No melting, no filming on the photoreceptor, and no blurring of images occurred. Furthermore, even when 50,000 sheets were continuously copied under high humidity conditions, no filming on the photoreceptor or blurring of the images occurred.

On the other hand, when a toner not mixed with silicone oil was used, the offset resistance was poor, and when the copied image was stored in contact with a vinyl chloride film, it was observed that part of the image was transferred to the vinyl chloride film.

Furthermore, when the fatty acid complex metal salt was composed of only the zinc salt of behenic acid, toner melting onto the photoreceptor occurred, resulting in filming of the photoreceptor and blurring of images during continuous copying of 50,000 sheets under high humidity. The deterioration was significant.

[Effects of the Invention] As explained above, according to the toner for developing electrostatic images of the present invention, by adding a very small amount of fatty acid complex metal salt to the toner, it is possible to prevent filming and protect the photoreceptor. In addition, it is possible to prevent the toner from melting on the surface of the photoreceptor, and furthermore, even if the toner image is stored overlapping with a vinyl chloride film or the like, the vinyl chloride film will not be contaminated.

Claims (2)

[Claims] (1) A toner for developing electrostatic images containing a binder resin, a colorant, and an additive, characterized in that a fatty acid complex metal salt and a silicone oil are used as the additives. (2) The fatty acid complex metal salt according to claim (1), wherein the fatty acid complex metal salt contains at least one selected from fatty acid metal salts having 10 to 19 carbon atoms and at least one selected from fatty acid metal salts having 20 to 25 carbon atoms. Toner for developing electrostatic images.