JPS61243462A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To obtain a toner scarcely scratching a photosensitive body, not causing deformation of a latent image even under high temp. and high humidity, being easy in cleaning operation, and stable in quality by using a specified polyalkylene. CONSTITUTION:The toner to be used for developing an electrostatic charge image formed in electrophotography contains a polyalkylene having a weight average mol.wt. (Mw) to a number average mol.wt. (Mn) ratio of 2.0-10.0, preferably, 5.0-8.0, and a kinetic friction coefft. of 0.15-0.65, preferably, 0.20-0.50. As the cleaning method when this toner is used, a blade cleaning method using a cleaner blade 8 in contact with the surface of the photosensitive body 1 is preferred, thus permitting offset of the toner to a heat fixing roller to be prevented, scratching of the photosensitive body 1 to be prevented by giving suitable kinetic friction coefft. to the toner, and attachment of low resistance materials and the toner 2 to the surface of the photosensitive body 1, and deformation of the latent image due to said attachment and poor cleaning to be both prevented by the grinding action of the toner itself in combination with the blade 8.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical field to which the invention pertains] The present invention relates to a toner used for developing electrostatic images formed in electrophotography, electrostatic printing, electrostatic recording, and the like.

[Description of prior art]

Image forming methods conventionally known as electrophotography, electrostatic printing, electrostatic recording, etc. all include the step of visualizing the formed electrostatic image using colored fine powder called toner. I'm here. For example, electrophotography is described in US Pat. No. 2,297,691, Japanese Patent Publication No. 42
Although various methods are known, as described in Japanese Patent Publication No. 23910 and Japanese Patent Publication No. 43-24748,
Generally, an electrostatic charge image is formed on the surface of a photoreceptor using a photoconductive substance by a seed method, and then the electrostatic charge image is developed with toner, and the toner image is transferred to a transfer material such as paper as necessary. After the image is transferred, it is fixed by heating, pressure, etc. to obtain a copy.

Among these devices, in the case of an apparatus having a transfer process, it is usual to remove residual toner on the photoreceptor that has not been transferred to the transfer sheet and use the photoreceptor repeatedly.

Methods for removing residual toner on the photoreceptor include blade cleaning method, fur brush cleaning method,
Generally, cleaning is carried out by bringing an IJ-ning member into contact with the photoreceptor, such as by using a magnetic brush cleaning method. In this case, since the voice leaning member is pressed against the photoreceptor with an appropriate pressure, the photoreceptor may be scratched or the toner may stick during repeated use. '・t
In order to avoid this phenomenon of toner sticking to the photoreceptor,
Japanese Patent Laid-Open No. 48-47345 proposes adding both a friction-reducing substance and an abrasive substance to the toner. Although this method is certainly effective in avoiding the toner sticking phenomenon, it has the following problems.

That is, if a friction-reducing substance is added to an extent that can avoid the toner sticking phenomenon, it becomes difficult to remove low electrical resistance substances such as paper dust and ozone adducts that are generated or adhered to the surface of the photoreceptor due to repeated use. In particular, there is a problem in that the latent image on the photoreceptor is significantly damaged by the low electrical resistivity in an environment of high temperature and high humidity. Furthermore, the amounts of the friction-reducing substance and the abrasive substance to be added are delicate, making it difficult to obtain a toner with stable characteristics.

On the other hand, various methods and devices have been developed for the final step of fixing the toner image on a sheet such as paper. The most common method at present is the compression heating method using a heated roller.

The pressure heating method using a heating roller performs fixing by passing the toner image surface of the sheet to be fixed under pressure while contacting the surface of a heating roller whose surface is made of a material that has releasability for toner. It is. In this method, the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, so the thermal efficiency when fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be carried out quickly. It is very effective in high-speed electrophotographic copying machines. However, in the above method, since the surface of the heat roller and the toner image contact each other under pressure in a molten state, a portion of the toner image adheres to and transfers to the surface of the fixing roller, and this is transferred again to the next sheet to be fixed. This causes the so-called offset phenomenon,
It may stain the sheet to be fixed.

Preventing toner from adhering to the surface of the heat fixing roller is considered to be one of the essential conditions for the heat roller fixed fixing method.

For this reason, toners that are constantly worn on a roller have been proposed in Japanese Patent Application Laid-Open Nos. 49-65231, 50-27546, and 55-153944.

However, after studying various toners containing polyallene, which are effective in preventing offset when fixed on a hot roller, the present inventors found that they had some of the problems with cleaning mentioned above, namely, that the photoconductor It has been found that the toner is easily damaged, the toner tends to stick on the photoreceptor, the latent image on the photosensitive plate is easily disturbed, etc., which become more noticeable when the toner contains a certain type of polyalkylene.

[Purpose of the invention]

The present invention was completed as a result of intensive research to solve various problems associated with conventional toners.The main purpose of the present invention is to provide a toner that is less likely to damage a photoreceptor. It is in.

Another object of the present invention is to provide a toner that does not cause disturbance of latent images even under high temperature and high humidity environments.

Another object of the present invention is to provide a stable toner that allows easy cleaning of toner remaining on a photoreceptor after transfer. Still another object of the present invention is to provide a toner that prevents toner from adhering to and fusing to a photoreceptor and does not cause streak-like or dot-like contamination on copied images.

Another object of the invention is to prevent contamination of the developer sleeve;
To provide a toner that does not cause a decrease in image density even when a large number of copies are made in succession.

Still another object of the present invention is to provide a toner that exhibits good fixing properties and excellent anti-offset properties, especially when used in a hot roller constant fixing system.

[Structure of the invention]

The present inventors continued intensive research to achieve the above-mentioned purpose, and as a result, by using a specific polyalkylene,
It has been discovered that a toner can be obtained that overcomes the problems of conventional toners containing polyalkylene.

That is, the toner of the present invention is characterized by containing a polyalkylene having a weight average molecular weight (4)/number average molecular weight (2) in the range of 20 to +0.0.

The toner of the present invention has a dynamic friction coefficient of 0.15 to 0.
It is characterized by being 65.

The reason why the toner of the present invention can overcome the various problems associated with the conventional toner described above is that the polyalkylene used in the present invention imparts an appropriate coefficient of kinetic friction to the toner particles, imparts abrasive force to the toner, This is because the abrasive power of the abrasive material makes it possible to remove low-resistance substances, paper powder, and the like on the photoreceptor without damaging the surface of the photoreceptor, which has an appropriate surface hardness. Furthermore, by appropriately combining the surface hardness of the photoreceptor and the coefficient of dynamic friction of the toner used in the present invention, appropriate non-adhesion can be achieved through interaction between the photoreceptor and the toner, thereby preventing scratches on the surface of the photoreceptor. This is also because it makes it possible to sufficiently remove toner remaining after transfer without causing any damage, and prevents toner from firmly adhering and fusing onto the photoreceptor. Furthermore, the combination of the dynamic friction coefficient of the toner used in the present invention and the surface hardness of the photoreceptor allows the amount of additives added to impart abrasiveness or lubricity to be zero or very small. This is also because it is effective in preventing the toner or additives from forming on the surface. Furthermore, the abrasive toner of the present invention has the effect of preventing sleeve contamination upon contact with the developing sleeve and stabilizing image density during continuous copying of a large number of sheets.

The value of weight average molecular weight (4)/number average molecular weight (-) of the polyalkylene contained in the toner of the present invention is from 2.0 to
10.0, preferably 5.0 to &0.

The use of polyalkylene prevents offset to the heat fixing roller and gives the toner an appropriate coefficient of kinetic friction, thereby preventing scratches on the photoconductor, and further improving the abrasive effect imparted to the toner particles themselves. This is because the cleaner blade can remove low-resistance substances and adhered toner on the photoreceptor, thereby preventing disturbance of the latent image and poor cleaning.

Here, the dynamic friction coefficient of the toner of the present invention is 0.15 to 0.6.
5, preferably from 0.20 to 0.50.

However, the above friction coefficient is defined by the value measured as follows. That is, for example, HEIDON + 4
OPC is placed on the sample stand of the mold surface property measuring machine (made by Shinan Kagaku).
A flat film made of styrene-methyl methacrylate resin having a hardness of 20 g and corresponding to the surface layer of the photoreceptor is fixed. A polyurethane rubber blade (thickness 2 xx x width 10 sq. x length 50 m) held at an angle of 45° was placed on a flat membrane with an upward sill.
Applying an OOg load and moving the sample stage at a speed of 50 mm/-, 0.50 g of toner placed on the flat membrane is uniformly applied onto the flat membrane.

Next, a vertical load of 100 g was applied to the above toner layer through a quartz disk with a diameter of 15 mm, and the sample stage was set at 5011 mm.
It is moved at a speed of m/jw, the static and dynamic frictional resistance forces generated at this time are measured, and the static and dynamic friction coefficients are calculated.

In particular, weight average molecular weight/number average molecular weight (Mac/Mn) is used as a component of the toner that provides a friction coefficient within the above range.
It is important to contain a polyalkylene having a value of 20 to IO, preferably 5.0 to 5.0 g,O. As mentioned above, the inclusion of a specific polyalkylene in a toner is described in several patent documents and is well known.

Therefore, the present inventors believe that the polyalkylene-containing toner described in those patent documents is
It has been found that there are serious practical problems in the various points mentioned above related to Ni-Kaji leaning. Furthermore, the already specified physical property values (for example, weight average molecular weight, softening point, etc.) of these polyalkylenes do not provide any suggestions for controlling the friction coefficient of toner within a desired range, which is the main objective of the present invention. It turned out that it wasn't a thing.

That is, the polyalkylene conventionally contained in toners was selected for the purpose of improving fixing properties and preventing offset, and no consideration was given to problems related to cleaning properties and contamination of the 3S photoconductor. .

The present inventors focused on the relatively high molecular weight component of polyalkylene, which was conventionally thought not to contribute to improving fixing properties or preventing offset, and aimed to broaden the molecular weight distribution of polyalkylene within a specific range. It has been found that the above-mentioned problems can be overcome. In other words, by incorporating a specific polyalkylene high molecular weight component into the toner, it is possible to control the dynamic friction coefficient of the toner, and it is possible to provide the toner with an appropriate abrasive force depending on the surface hardness of the photoreceptor. .

The high molecular weight distribution of polyalkylene can be expressed by the value of weight average molecular weight/number average molecular weight (Ma+/Mn).

There are various methods for measuring the above-mentioned weight average molecular weight (2) and number average molecular weight (2), resulting in slight differences. Therefore, the measurement method used in the present invention will be explained.

When the number of molecules of molecular weight Mi is Ni, the number average molecular weight door is the value obtained by adding the product of the number fraction N i/P i of molecular weight Mi and Mi from O to ψ for i, that is, defined by the formula . This is an average over the number of molecules. On the other hand, the weight average molecular weight i, which emphasizes the contribution of high molecular weight substances to the average molecular weight, is defined as 1, y:MiNt 1=1.

By the way, in general, when dealing with polymers having large molecular weights of hundreds of thousands or millions, it is not important that M takes discrete values in units of monomer molecular weights; Even if M is considered to change continuously, no errors will occur in the mathematical results. Not only that, but the mathematical treatment is often simpler. On the other hand, the molecular weight is M and M+d
Let the ratio of the number of molecules between M be n(M)dM. It is assumed that n(M) satisfies the number distribution interval number regarding molecular weight, and the number average molecular weight is given by the formula. Similarly, the weight average molecular weight is as follows.

On the other hand, Kölpermeation chromatography (GP)
From the chromatogram of C), the differential weight molecular weight distribution ω(MX
=Mn(M)) can be obtained.

Therefore, the above number average molecular weight and weight average molecular weight are
It is possible to calculate simultaneously from the PC chromatogram.

In the present invention, in the gel permeation chronigraph,
At a temperature of 135°C, 0-dichlorobenzene (α
Using ionol addition), 400 μm of a sample solution with a concentration α1 weight is injected at a flow rate of 1.0 −. A calibration curve prepared using a monodisperse polystyrene standard sample is used to measure the molecular weight of the sample. The column to be used is not limited in any way, but examples include A-80M manufactured by Shodex. To the present invention □
The values of weight average molecular weight and number average molecular weight are
□The polystyrene equivalent values were used as they were.

The present inventors have a weight average molecular weight in a specific range and a weight average molecular weight/number average molecular weight (Ms
/Mn) is 2.0 to 10.0, preferably 5.0 to
We found that polyalkylene with g, in the range of 0 is preferable, and that by controlling the value of M (V~n), it is possible to eliminate various problems related to cleaning while achieving the purpose of preventing offset. Heading: This completes the present invention.

The polyalkylene contained in the toner of the present invention has a weight average molecular weight Mω of 3.000 to go, ooo and a value of weight average molecular weight/number average molecular weight (Mw'Mn) of 2θ
~10.0, and in particular, in order to exhibit the above-mentioned effects, the weight average molecular weight Mω is preferably 5.000 to 60.
．． 000 and weight average molecular weight/number average molecular weight (Mφ~n
) The above polyalkylenes include polyethylene, polypropylene, polybutene, polyhexene, etc., ethylene-propylene copolymers, ethylene-butene copolymers, etc.
There are terpolymers of these and hexene, as well as thermally modified products of these. Particularly effective are polypropylene and thermally modified products thereof. These polyalkylenes are contained in an amount of 1 to 20 parts by weight, preferably 1 to 20 parts by weight, based on the resin component.
It is preferable to contain up to 10 parts by weight. This is because by incorporating polyalkylene in an amount within this range into the toner, the unevenness and hardness of the toner surface can be made appropriate, the photoreceptor will not be damaged, and the toner can maintain appropriate abrasiveness. This is because the aforementioned disturbance of the latent image and image contamination due to deposits on the photoreceptor can be prevented.

Furthermore, the toner of the present invention has a BET specific surface area of 0.5 to 500 m''/lz, particularly 50 to 400 m''/lz, determined by nitrogen adsorption method.
It is preferable to add a non-magnetic inorganic fine powder f. This is because the addition of such fine powder reduces the aforementioned disturbance of the latent image. This is because such fine powder has a large specific surface area, so that it is possible to remove the low-resistance substance adhering to the drum by adsorbing or adhering it to its surface. Examples of such non-magnetic inorganic fine powder include alumina, titanium dioxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide,
Silica sand, clay, mica, wollastonite, diatomaceous earth, silicon carbide, various inorganic oxide pigments, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, 1φ magnesium oxide, zirconium oxide, sulfuric acid, barium carbonate Examples include powders or particles such as calcium carbonate, fine silica powder, etc., but copper titanate, silicon carbide, cerium oxide, and fine silica powder are particularly preferred.

The silica fine powder is a fine powder having S i -0-8i bonds, and includes both those manufactured by a dry method and those manufactured by a wet method. Various conventionally known methods can be applied to produce fine silica powder by a wet method. For example, the decomposition of sodium silicate with an acid can be expressed as a general reaction formula (the reaction formula is omitted below): Na2O.xSi02+HC1-H (20→5i02.
nH2O-1-NaCLOther decomposition of sodium silicate with ammonia salts or alkali salts, method of generating alkaline earth metal silicate from sodium silicate and then decomposing with acid to produce silicic acid, sodium silicate solution There are methods such as converting it into silicic acid using an ion exchange resin, and using natural silicic acid or silicate.

The silica fine powder mentioned here includes anhydrous silicon dioxide (silica) and aluminum silicate.

Any silicates such as sodium silicate, potassium silicate, magnesium silicate, and zinc silicate can be applied.

The particle size is preferably within the range of 0.01 to 2 μm as an average primary particle size. Further, it is desirable that the material contains 85 weight percent or more of SiO□.

Silica fine powder produced by the dry process is called dry process silica,
It is also called fumed silica, and is produced by conventionally known techniques. For example, this method utilizes a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

5iCA! , +2H, +O, →Sin, +AHC1
In addition, in this manufacturing process, it is also possible to obtain a composite fine powder of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. The present invention also includes them.

The particle size is desirably within the range of α001 to 2μ as an average primary particle size, particularly preferably 0.002μ.
It is preferable to use silica fine powder within the range of ~0.2μ.

Specifically, as these silica fine powders, there are various commercially available silicas, but those having a hydrophobic group on the surface are preferable, such as R-972 (manufactured by Aerosil Corporation), Taranox 5OO (manufactured by Talco Corporation). , and those treated with other silane coupling agents, titanium coupling agents, silicone oils, silicone oils having amines in their side chains, etc. are preferable. In particular, it is preferable to use positively chargeable silica fine powder when the toner is positively chargeable, and to use negatively chargeable silica fine powder when the toner is negatively chargeable. Furthermore, the positively chargeable or negatively chargeable silica fine powder has an absolute value of the tripo charge amount as determined by the following measurement method.
μc/ is preferably 9 or more, and particularly preferably K 30 pc/ or more.

Definitions of the tripocharge value and positive chargeability will be explained below using positively chargeable silica fine powder as an example.

Positively chargeable silica fine powder is defined as follows.

That is, silica fine powder 2f left overnight in an environment of 25°C, 50y, 60% RH and a carrier iron powder that is not coated with resin and has a main particle size of 200 to 300 mesh (for example, BFV200/Nippon Iron Powder Co., Ltd.) 300) IP in an aluminum pot with a volume of approximately 200 CH under the above environment (hold it in your hand and hold it up and down approximately 50 cm).
□Tolipocharge of the fine silica powder is measured by the usual blow-off method using an aluminum cell with a 400 mesh screen. A silica fine powder with a positive trypo charge measured by this method is defined as a positively charged silica fine powder.

In order to obtain such positively charged silica fine powder, it is preferable to treat it with a coupling agent containing an amine or silicone oil. Examples of such treatment agents include, for example, H, NC 8, C 5i (QC).

Peng NC Toku C Toku C Toku 5i (QC, 8).

CH3 ■ Peng NC Toku C Toku C Peng Si (OCH,).

CH.

H2NCH, CH2NHC Toku C Toku C Toku Si (OCH
3).

H2NC0NHCH,CH,CH,S i (QC,H
,)sH2NCH,CH2CH25,CH,CH,S
i (OCH,)sH,NCH,CH,NHCH,CH
,Nl'(CH,CH,CH,S i (0CH3)
.

H,C,0COCH2CH,NHCH,CH,CI,S
i (OCH3)sH,IC,0COCH,CH,NH
CH, CH, NHCH, CH, CH, S i (OCH
,).

H, C2OCOCH2CH2NHCH2CH, NHCH
,CH,NHCH,C)T,Nu(CH8O),SiC
Chicken CH2CH2 H3COCOCH2 (J%NHCH2CH, NHCH,
CM, CH, S i (OCH3).

(H,Co)s8i CH,CH,CH2-NH
CH.

(H2CO)38iCH,CH,CH,-NHCH.

H, CNHCH, CH, CH, 5i (OCd; 14).

H, N (CH, CH2NH), CH, CH2CH25
i (OCH8)aH8C-NHCONHC,H65i
Aminosilane coupling agents such as (OCH8)a and modified silicone oils having an amine in the side chain of the following formula are generally used.

-5i-O- (Here, R1 represents hydrogen, an alkyl group, an aryl group, or an alkoxy group, R1 represents an alkylene group or a phenylene group, and R and lR4 represent hydrogen, an alkyl group, or an aryl group. The above-mentioned alkyl group, aryl group, alkylene group, and phenylene group may contain an amine, or may have a substituent such as ) or rogene within a range that does not impair chargeability. ) Examples of such silicone oils include the following:

5F84i7 () - made by Les Silico Y)
+200 3500KF393 (manufactured by Shin-Etsu Chemical) 60 360KF857
(Manufactured by Shin-Etsu Chemical) 70 830K
Fg60 (Shin-Etsu Chemical 111j)
250 7600KF861 (manufactured by Shin-Etsu Chemical)
3500 2000KFg62 (
(manufactured by Shin-Etsu Chemical) 750 1900 KFg64 (manufactured by Shin-Etsu Chemical) 170
0 3800KFB65 (manufactured by Shin-Etsu Chemical)
90 4400KF361? (Manufactured by Shin-Etsu Chemical Co., Ltd.) 20 320KFB8
3 (manufactured by Shin-Etsu Chemical) 20 3
20X-22-3660 (manufactured by Shin-Etsu Chemical) 90
8800X-22-380D (manufactured by Shin-Etsu Chemical)
2300 3800X-22-380IC (manufactured by Shin-Etsu Chemical) 3500 3800X-22-381
0B (manufactured by Shin-Etsu Chemical Co., Ltd.) 1300 +700 The amine equivalent in the present invention is the equivalent per amine (f/eqiv), which is the value obtained by dividing the molecular weight by the number of amines per molecule.

Preferred positively chargeable or negatively chargeable silica fine powders are:
The degree of hydrophobicity measured by methanol titration test is 30
It is preferable to have a value in the range of -80, but in order to perform hydrophobization treatment in this way, conventionally known hydrophobization methods are used. Granted. A preferred method is to treat fine silica powder with an organosilicon compound after treating it with a treatment agent such as the silane coupling agent described above, or at the same time as treating it with a treatment agent such as a silane coupling agent.

Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane,
Allyl phenylcyclosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane/, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl Acrylate, vinyldimethylacetoxysilane, further dimethylethoxysilane, dimethyldimethoxysilane, diphenyljethoxysilane, hexamethyldisiloxane, 1,3-divinylnato2methyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 1 molecule Hit 2. There are dimethylpolysiloxanes having 12 siloxane units and each unit located at the end containing one hydroxyl group bonded to Si. These may be used alone or in a mixture of two or more.

Note that the methanol titration test here is an experimental test to confirm the degree of hydrophobization of the silica fine powder having a hydrophobized surface.

The methanol titration test specified herein for evaluating the degree of hydrophobization of treated silica fine powder is conducted as follows. Sample silica fine powder 0.2f' in capacity 250m
Add to 50 ml of water in an Erlenmeyer flask. Methanol is titrated from the puret until the entire amount of silica is wetted.

At this time, the solution in the flask is constantly stirred with a magnetic stirrer. The end point is observed by suspending the entire amount of silica fine powder in the liquid, and the degree of hydrophobization is expressed as the percentage of methanol in the liquid mixture of methanol and water when the end point is reached.

Further, the applied amount of these silica fine powders exhibits an effect when the amount is 0.01 to 20% based on the weight of the developer, and particularly preferably when 0.1 to 3 m is added, excellent stability is obtained. Shows positive or negative chargeability. Regarding the preferred form of addition, it is preferable that treated silica fine powder in an amount of α01 to 3% by weight based on the weight of the developer is attached to the surface of the toner particles. Examples of the resin include monopolymers of styrene and its substituted products such as polystyrene, poly-9-p-chlorostyrene, and polyvinyltoluene: styrene-p-chlorostyrene copolymers, styrene-propylene copolymers,
Styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer Coalescence, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-
Methyl chlormethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-
butadiene copolymer, styrene-isoprene copolymer,
Styrenic copolymers such as styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene , polypropylene, polyester, polyurethane, polyamide, −
Epoxy resin, polyvinyl butyral, polyamide,
Polyacrylic acid resin, rosin, modified rosin, terpene resin, 7-enol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, carnauba wax, etc. alone or in combination. Can be used.

Further, as the coloring material used in the toner of the present invention, conventionally known carbon black, copper phthalocyanine iron black, etc. can be used, and all conventionally known positive or negative load S: control agents can be used in the toner of the present invention. be able to.

Furthermore, when the toner of the present invention is used as a magnetic toner, it may also have the function of a coloring agent, and may contain magnetic fine particles.

As the magnetic particles, a substance that is magnetized by being placed in a magnetic field is used, and powders of ferromagnetic metals such as 5 iron, cobalt, and nickel, or magnetite, γ-Fe, 03
, alloys and chemical compounds such as ferrite can be used.
In order to fully exhibit the effects of the present invention described above, these magnetic fine particles must absorb nitrogen.

BIT specific surface area by method is 2 to 20rrl/l, especially
: 25 to 12 m''/f% Magnetic powder having a Mohs hardness of 5 to 7 is preferred.

The content of the magnetic powder is preferably 10 to 70% by weight based on the weight of the toner. Furthermore, the toner of the present invention may contain lubricants, conductivity imparting agents, fixing aids, etc., such as polytetra Fluoroethylene powder, polyvinylidene fluoride powder, metal salts of higher fatty acids, carbon black, conductive tin oxide, etc. may be added.

Furthermore, the toner of the present invention has a volume resistivity of 100 or more,
In particular, it is preferable that it be larger than 1On sub.

The volume resistivity referred to here is the toner's IOCjK97
It is defined as the value calculated from the current value after 1 minute has elapsed after molding with a pressure of cm2 and applying an electric field of 1 OOV/cm to this.

The toner of the present invention can be mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite powder, etc., if necessary, and used as a so-called two-component developer.

In producing the toner of the present invention, the constituent materials are thoroughly kneaded using a heat kneader such as a hot roll, Niegoo, Nigestruder, etc., and then obtained by mechanical crushing and classification, or by dispersing the materials in a binder resin solution. and then spray drying, or a polymerization method toner production method in which a predetermined material is mixed with a monomer to form a binder resin to form an emulsified suspension and then polymerized to obtain a toner. Each method can be applied.

On the other hand, in order to efficiently achieve the above-mentioned object of the present invention using the toner of the present invention, the surface hardness of the photoreceptor used should be 8f or more, preferably 10 to 10.
It is desirable that it be 100f. If the hardness is low, the photoreceptor is susceptible to scratches, which may cause disturbances in the latent image at high humidity or the generation of toner that is not cleaned. Furthermore, if the hardness is too large, it becomes impossible to remove the low-resistance material formed on the surface of the photosensitive plate, resulting in disturbance of the latent image at high humidity.

The above hardness is measured as follows.

As an example, a case will be described in which an OPC photoreceptor is measured.

The OPC photoreceptor was fixed on the sample stage of a HEIDON l A type surface property measuring machine (manufactured by Shinan Kagaku), and a diamond needle (conical, with a cone angle of 9000 mm) was attached to the OPC photoreceptor.
The tip has a diameter of 0. It has a hemispherical shape of OIm. ), apply a vertical load d and move the sample stage at a speed of Sow/- to scratch the surface of the OPC photoreceptor. The width of this scratch is measured using, for example, a microscope attached to a microhardness meter MVK-F (manufactured by Akashi Seisaku Shin).

The above operation, the load illusion, for example, IO? , 15F.

2Of, 25f, 30t, 35t, 40f, . . . are repeated, and from the relationship of linear regression between the scratch width and the load, the load to create a scratch of 50 μm is calculated and used as the hardness of the OPC photoreceptor. Here, if the OPC photoreceptor is a drum,
It is necessary to set the OPC photoreceptor over the sample so that the scratches are made in the axial direction of the drum.

The toner of the present invention can be applied to various developing methods. For example, special brush development method, cascade development method, method using conductive magnetic toner described in U.S. Pat. Method using toner, Japanese Patent Application Laid-open No. 1983
-42141 publication, 55-18656 publication, 55-18656 publication
Examples include the method described in Japanese Patent Publication No. 4-43027, a fur brush development method, a powder cloud method, an impression development method, and the like.

In addition, when using the toner of the present invention, cleaning methods such as a blade cleaning method, a fur brush cleaning method, and a magnetic brush cleaning method are used, but as an excellent combination of the toner of the present invention and the photoreceptor, fluorade is used. A cleaning method is preferred.

Further, immediately before the cleaning step, a static elimination step or the like may be provided as necessary to facilitate toner cleaning.

FIGS. 1 and 2 show an example of a cleaning device using a blade cleaning method.

In the figure, numeral 1 indicates a photoreceptor, and this photoreceptor is rotating in the direction indicated by the arrow in the figure. An electrostatic latent image is formed on the surface of the photoreceptor 10 by a well-known method, the latent image is made into a mirror surface by toner, and this mirror image is transferred to a transfer material. In order to remove the toner 2 remaining on the photoreceptor 1 after transfer,
A cleaning device 7 is provided. The cleaning device shown in FIG. 1.2 includes a cleaning member 8 that comes into contact with the surface of the photoreceptor 1 so as to scrape off the toner 2 on the photoreceptor 1, and a cleaning member 8 that captures the toner detached from the photoreceptor 1. A collecting member 9 is provided to collect the water. In general, the collection member 9 is arranged so as to be in contact with the surface of the photoreceptor to prevent the toner scraped off by the cleaning member 8 from scattering outside the cleaning device.

The cleaning member g can be made of urethane rubber or the like with a JI of 8 degrees. The contact pressure at this time is preferably 5 to 209/cd in the case shown in Figure 1, and 30 to 40 t/cd in the case shown in Figure 2 [Example] Below, Examples and The present invention will be explained in more detail using comparative examples, but the present invention is not limited by these K. Note that all parts on each side are parts by weight.

Example 1 7 Tanetite (BET specific surface area 5 rr?/f, Mohs hardness 5.5) 40 parts Lid polypropylene 6% = 15.000%, A = 5.8
) Mix 3 parts and roll mill to 16
Melt and knead at 0°C. After cooling, it is coarsely pulverized using a hammer mill, and then finely pulverized using a jet pulverizer.

Next, the mixture was separated using an air classifier to obtain a black toner having a volume average particle size of about 13 μm. The dynamic friction coefficient of the obtained toner was 028.

On the other hand, a laminated OPC photoreceptor having a charge transport layer made of methyl methacrylate-styrene (weight ratio 9:1) copolymer with a Tg measured by DSC of 80°C or higher was fabricated on a conductive cylinder, and a photosensitive drum was fabricated. Obtained. The hardness of this photoreceptor was 21 g.

The resulting photosensitive drum is uniformly charged by corona discharge of 16 KV at a linear surface velocity of 66 xw/sec, and then an original image is irradiated to form a latent image.

This latent image is generated using a sleeve rotating magnet rotary type developer with a sleeve diameter of 50n1, a sleeve surface magnetic flux density of 700 Gauss, a number of magnetic poles of 12, and a blade-sleeve gap of α5 Mll as shown in FIG. .2tx, apply a bias voltage of 1 + OOV to the sleeve, develop the developer layer formed on the sleeve using the toner by bringing it into contact with the photosensitive drum, and then apply the toner from the back side of the transfer paper. The powder image was transferred while being irradiated with a 7KV corona and fixed using a heating roll.

On the other hand, the toner remaining on the drum after transfer was cleaned using a cleaning device as shown in Figure t42. At this time, the blade is JI8-A hardness 65' urethane rubber.
was brought into contact with the photosensitive drum at a linear pressure of I 5 g/cm.

A running test of 10,000 sheets was conducted in an energized environment, but no cleaning defects were observed, and good images with stable image density and no image disturbance were obtained. After the running test was completed, the entire seat was removed and observed. There was virtually no damage or filming, and the toner that would have remained after the transfer had been sufficiently cleaned and removed.

Furthermore, similar experiments were conducted at 30°C and 90% RH and at 15°C.
Similar good results were obtained when the test was carried out in an environment of lo%RH.

Example 2 Silica fine powder synthesized by dry method (specific surface area approximately 13
0rI? /f): 00 parts by weight of silicone oil having an amine in the side chain (viscosity 7 at 25°C)
Q cps, amine equivalent weight 830) 12 parts by weight were sprayed and the temperature was approx. The hardness of this silica was 6.0 on the Mohs hardness scale.

100 parts by weight of the black fine powder of Example I was treated with the above silicone oil having an amine in its side chain.

0.4 parts by weight of the silica fine powder obtained above was added to prepare a toner.

The coefficient of kinetic friction of this toner is 0.30. Ta.

- When a copy image was obtained using the obtained toner in the same manner as in Example 1, a clear image was obtained. Furthermore, we conducted a running test of 10,000 sheets and were able to obtain good images with stable image density and no image disturbance.Similar experiments were conducted in an environment of 30°C, 90% RH, 115°C + 0.96 RH. However, the same good results were obtained.After the test, the light plate was in almost the same clean condition as a new one.

Example 3 Styrene-butyl methacrylate copolymer 100
Nigrosine 3I Carbon Black 5I Polypropylene G loss = 29,0.00 t, , crime bias = 3.6)
A black toner was obtained in the same manner as in Example 1 by mixing #2. The friction coefficient of this toner was measured and found to be 0.39.

10 parts by weight of this toner and iron powder (product name: EFv manufactured by Nippon Iron Powder)
A developer was prepared by mixing 90 parts by weight of 250 to 400), and a commercially available two-component magnetic brush was applied at a developing line pressure of 70 f/cm2.
Other conditions were the same as in Example 1, and a clear image was obtained.A running test of 10,000 sheets was also conducted, and a good image with stable image density and no image disturbance was obtained. A similar experiment was carried out at 30°cqo%RH, 15°CIO
%RH environment, similarly good results were obtained. At this time, the drum after the test was in almost the same clean condition as a new one.

The same procedure as in Example 1 was performed except that a styrene-acrylonitrile copolymer having a Tg of 80°C or higher was used instead of the methyl methacrylate-styrene copolymer in Example 1, and good results were obtained. Obtained. The hardness of this photoreceptor was 5 grade.

Instead of polypropylene in Example 1, fish = 411! ,
000, Mm/Mn=8, O ethylene-propylene 1/7
Example 1 except that a thermally modified copolymer was used.
When the same procedure was carried out, good results were obtained. The dynamic friction coefficient of this toner was 0.20.

``■ Vice 4- Example 2 except that 7 parts of polypropylene was added.
When the same procedure was carried out, the results were good.
``The coefficient of dynamic friction of this toner was α45.

Nira 1st 1st! A photoreceptor using polymethyl methacrylate was used instead of the methyl methacrylate-styrene copolymer of Example 1, and the same procedure as in Example 1 was carried out, and good results were obtained under each different environment. . The hardness of this photoreceptor is 38? Met.

$8 Instead of polypropylene in Example 1, Mω=7200
, Mac/Mn = 5. The same procedure as in Example 1 was performed except that 1 of polypropylene was used, and good results were obtained.

The coefficient of dynamic friction of this toner was 0.21.

[Comparative Example 1] A toner was prepared in Example 1 except that polypropylene was removed. The dynamic friction coefficient of the toner was 0.12.

When a running test was conducted under high temperature and high humidity conditions, significant image disturbance occurred.〇 [Comparative Example 2] Mm = 2800. When polyethylene with Mar/Mn = 1.9 was subjected to a running test under high temperature and high humidity conditions, significant image disturbance occurred. The coefficient of dynamic friction of this toner was 0.14.

[Comparative Example 3] Mal=93. OOO1Mac/Mn = l 2.5
Example 2 was repeated except that 8 parts by weight of polypropylene was used.

The coefficient of dynamic friction of the toner was 0.67.

During a running test under high temperature and high humidity, many scratches occurred on the photoreceptor, resulting in image disturbances.

[Summary of effects of the invention]

In the present invention, since the above-mentioned specific polyalkylene is used as the polyalkylene contained in the toner, when the toner of the present invention is used in a hot roller constant deposition method, the offset phenomenon to the hot roller is prevented. At the same time, by giving the toner an appropriate coefficient of friction,
It does not damage the photoreceptor, and moreover, the abrasive effect imparted to the toner particles themselves is sufficiently exerted to remove dirt and adhering toner, thereby preventing latent image disturbances and poor cleaning.

[Brief explanation of drawings]

1 and 2 are diagrams schematically showing one example of a cleaning device using the toner of the present invention, in which 1
2 represents a photoreceptor, 2 represents toner remaining after transfer, 7 represents a cleaning device, wound represents a cleaning member, and 9 represents a collection member. Patent applicant: Canon Co., Ltd. Figure 1 Figure 2

Claims (2)

[Claims] (1) Weight average molecular weight (@Mω@)/number average molecular weight (@
A toner for developing electrostatic images containing polyalkylene having a Mω@) value of 20 to 10.0. (2) The toner for developing electrostatic images according to claim (1), which has a dynamic friction coefficient of 0.15 to 0.65.