JP3176297B2 - Toner for developing electrostatic images - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic image developing toner used for electrophotography, electrostatic recording and the like.

[0002]

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

For example, various methods and apparatuses have been developed for fixing a toner image on a sheet such as paper. For example, there are a pressure bonding heating method using a heat roller and a heat fixing method in which a pressing member is brought into close contact with a heating member via a film.

In a heat roller fixing method or a heat fixing method using a film, a toner image surface of a sheet to be fixed is brought into contact with a heat roller or a film surface formed of a material having a releasing property to toner. The fixing is carried out by allowing the sheet to pass through. In this method, since the surface of the heat roller or the film comes into contact with the toner image of the sheet to be fixed, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. Very effective in electrophotographic copiers or printers. However, in the above-described method, a part of the toner image adheres to the fixing roller or the film surface because the heat roller or the surface of the film and the toner image come into contact in a molten state, and is transferred to the next sheet to be fixed. As a result, an offset phenomenon may occur, and the sheet to be fixed may be soiled. It is important for the heat fixing method to prevent the toner from adhering to the heat fixing roller and the film surface.

Conventionally, for the purpose of preventing toner from adhering to the surface of a fixing roller, the roller surface is formed of a material having excellent releasability (for example, silicone rubber or fluorine-based resin) with respect to the toner, and the surface of the roller is further offset. In order to prevent this and to prevent the roller surface from being fatigued, the roller surface is coated with a thin film of a liquid having good releasability such as silicone oil. However, although this method is extremely effective in preventing toner offset, it has a problem in that a fixing device is required because a device for supplying an anti-offset liquid is required.

This is in the opposite direction to miniaturization and weight reduction, and the silicone oil may evaporate due to heat and contaminate the inside of the machine. Therefore, instead of using a silicone oil supply device, instead of supplying the anti-offset liquid during heating from the toner, a method of adding a release agent such as low molecular weight polyethylene or low molecular weight polypropylene to the toner has been proposed. ing.

[0007] In order to improve the fixability and the anti-offset property, it has been proposed to incorporate wax in the following toner. JP-A-52-3304, JP-A-52-33
05, JP-A-57-52574, JP-A-6-52
-324513, JP-A-7-36210 and the like. These waxes are used to improve the offset resistance of the toner at low and high temperatures. However, these properties could not be improved at the same time, the blocking resistance was lowered, and the developability was lowered.

Further, toners containing two or more types of wax in order to exhibit the effect of adding wax from a low temperature region to a high temperature region are disclosed in JP-B-52-3305, JP-A-58-215659, JP-A-62-2
No. 100775, JP-A-4-124676,
JP-A-4-299357, JP-A-4-35815
9, JP-A-4-362953, JP-A-6-36295
No. 130714, JP-A-6-332244, and the like.

However, these toners have some problems. For example, the high-temperature offset resistance is excellent, but the low-temperature fixing property is one step away, or the low-temperature offset resistance and the low-temperature fixing property are excellent, but the blocking resistance is slightly inferior and the developing property is deteriorated. There is an adverse effect, the offset resistance at the time of low temperature and the offset resistance at the time of high temperature cannot be compatible, and a copying machine or a printer using electrophotography has been systematized and enhanced in function. Toner is required to have not only characteristics at the time of melting at the time of fixing but also various characteristics of a fixed image after cooling and solidification.

[0010] For example, images are often rubbed by passing through the inside of the apparatus body many times in double-sided, multiplexed, reduced edition, and the like. For this reason, the members that come into contact when the paper is passed may be stained, or other images may be stained. Further, when the member is stained by passing the paper, another image passing therethrough may be stained.

[0011] The same problem is likely to occur when the obtained image is set as a document on a document feeder.
As described above, in addition to systematization and high functionality, there is a long-awaited need for a toner that can provide an image that can withstand heavy duty associated with speeding up and multiplication.

[0012]

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

An object of the present invention is to provide a toner for developing an electrostatic image, which is excellent in fixing property and anti-offset property.

It is a further object of the present invention to provide a toner for developing an electrostatic charge image which can provide an image having excellent releasability and releasability from a member and does not cause contamination of the member in contact with the toner image. is there.

It is a further object of the present invention to provide a toner for developing an electrostatic image capable of imparting lubricity to a toner image, preventing image stains due to rubbing and peeling of the toner from the image, and obtaining an image having excellent image storability. Is to provide.

[0016]

In a toner for developing an electrostatic charge image having a resin composition containing at least a binder resin and a wax component, the wax component has a melt viscosity at 120 ° C. measured by an E-type viscometer. Wax A of less than 22 mPa · s and a melt viscosity at 120 ° C. of 22 to
A wax B of 100 mPa · s, and the wax A
Is a paraffin wax, and the wax B is a Fischer-Tropsch wax.

[0017]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, the wax A
Is paraffin wax, and the wax B is Fischer-Tropsch wax.

In the present invention, the molecular weight distribution of the toner measured by gel permeation chromatography (GPC) is such that 20% or more of the components having a molecular weight of 10,000 or less and 100% or more of the components having a molecular weight of 100,000 or more. It is preferably at least 5%.

Hereinafter, the present invention will be described in detail.

In the toner, various actions are exhibited by dissolving the wax component in the binder resin, so that the toner can take various behaviors. When the wax component is melted, its effect is low unless the melt viscosity is low. If the melt viscosity decreases at an appropriate temperature in accordance with the fixing of the toner, the wax component can move through the binder resin, exhibiting a plasticizing effect or appearing on the surface of the toner particles to exert an interfacial effect. become. At the time of melting the toner, a plasticizing effect, a releasing effect and a peeling effect appear,
It is possible to improve the fixing property, prevent offset and contamination of the fixing member, and avoid troubles such as wrapping around the fixing device and paper jam. Further, at the time of cooling and solidification, the toner image is given a slippery property, and the durability of the image is obtained, so that the contamination of the image and members can be reduced.

A wax having a melt viscosity at 120 ° C. of 100 mPa · s or less, preferably 90 mPa · s or less, particularly 80 mPa · s or less at 120 ° C. as measured by an E-type viscometer, is formed when the toner is melted. When dissolved in the resin, it moves quickly and easily exhibits a plasticizing effect, and easily emerges on the surface of the toner particles.
Easy to get a sliding effect. Further, it is preferable to use paraffin wax, Fischer-Tropsch wax, or polyethylene wax, which is structurally a hydrocarbon structure, in order to make the effect more remarkable.

The present invention relates to an E-type viscometer for measuring 120
Characterized by having wax A having a melt viscosity at 22 ° C. of less than 22 mPa · s, more preferably 20 mP
When the pressure is not more than a · s, particularly preferably 1 to 15 mPa · s, a large plasticizing effect can be obtained, which works to improve fixability.
On the other hand, since the melt viscosity is low, the wax film on the surface of the toner particles is weak, and cannot exhibit the releasing effect. Furthermore, since there is a lot of this wax near the surface of the toner particles,
The plasticizing effect on the surface of the toner particles becomes larger, the viscosity of the toner decreases, and does not contribute much to the offset resistance. In addition, the action can be further enhanced when the paraffin wax is structurally an n-paraffin structure.

Further, the present invention relates to a method for measuring the viscosity of an E-type viscometer.
It is characterized by having a wax B having a melt viscosity at 20 ° C. of 22 to 100 mPa · s, more preferably 25 to 90 mPa · s, and particularly preferably 30 to 80 mPa · s.
When the pressure is Pa · s, the wax film on the surface of the toner particles has an appropriate melt viscosity, so that the strength of the wax film on the surface of the toner particles is improved, and an excellent releasing effect and peeling effect can be obtained. Further, since the wax near the surface of the toner particles does not separate into the toner particles due to phase separation, when the toner image is cooled and solidified, the wax layer is present, so that it has excellent slipperiness and durability against image rubbing. Properties and no contamination of members or other images. For this reason, wax B does not have such a large plasticizing effect, and does not contribute much to a large improvement in fixability.
Further, the effect can be further enhanced by using a Fischer-Tropsch wax structurally containing a little i-paraffin structure.

The present invention relates to an E-type viscometer which measures 120
A combination of wax A having a melt viscosity at 22 ° C. of less than 22 mPa · s and wax B having a melt viscosity of 22 to 100 mPa · s, preferably 20 mPa · s or less.
S or less and 25 to 90 mPa · s, especially 15 m
At a Pa · s or less and 30 to 80 mPa · s, a plasticizing effect, a releasing effect, a peeling effect, and a sliding effect can be combined. Further, since a large amount of wax A is present in the vicinity of the toner particle surface, a wax film of wax B is efficiently formed, so that even with a small amount of addition, excellent releasing, peeling and sliding effects can be obtained. Can be done. As a result, these effects can be sufficiently exerted with a small amount of the wax component. Therefore, it is necessary to prevent the wax component from deteriorating in developing property, blocking resistance, cleaning trouble caused by poor dispersion, drum fusion, and the like. Can be done. Further, it is preferable that the wax A is a paraffin wax and the wax B is a Fischer-Tropsch wax structurally in order to enhance the effect.

In order to exert the above combined effect more strongly, both waxes are measured with an E-type viscometer.
The difference in melt viscosity at ° C is preferably 10 mPa · s or more, more preferably 15 mPa · s or more, and particularly preferably 15 to 70 mPa · s.

The plasticizing effect in the present invention not only lowers the melt viscosity of the toner and increases the fixability of the toner, but also
In the present invention, since the plasticizing effect near the surface of the toner is larger, the melt viscosity of the toner near the surface is further reduced, and the anchor effect on the recording medium works, which greatly contributes to the improvement of the fixing property.

The releasing effect of the toner of the present invention increases the releasability of the toner and naturally improves the anti-offset property. In the present invention, even if the toner adheres to the heating roller, the cleaning member Is cleaned neatly. Further, there is no occurrence of image contamination due to roller contamination due to re-transfer from the cleaning member. Also,
When the toner is not sufficiently cleaned on the photosensitive drum, when the toner is rubbed by the cleaning blade, a part of the toner is melted and fusion occurs. At this time, in the toner of the present invention, the wax film works effectively and exhibits excellent releasability, so that the fusion can be removed by a cleaning blade and the fusion can be eliminated. Become. Therefore, in the toner of the present invention, even if fusion occurs, before it appears as an image defect,
Will be resolved.

The peeling effect of the toner of the present invention is excellent in peelability from the fixing roller, and the recording medium is easily separated from the fixing roller. Therefore, the sheet is separated from the fixing roller without relying on the sheet discharge separation claw, so that the separation claw is not stained, the separation claw does not stain other images, and the recording medium is caught by the separation claw and fixed. No paper jam occurs.

The sliding effect of the toner of the present invention is that the fixed toner image becomes stronger against rubbing, so that the members that come into contact with the image are less likely to be stained, and contamination of other images caused by these stains is prevented. Can be done. With the systemization of copiers and printers, the chances of rubbing the image increase with the speeding up, and the strength also increases, so the burden on the toner image increases, and durability against rubbing is required. Since the toner of the present invention has excellent slipperiness, it can withstand high performance and high speed of the machine. For example, double-sided function, multiplexing function, reduction editing function, curl removal mechanism, back discharge function, sort function, paper folding function,
The opportunity for the image to be strongly wrung with the binding function, steeple function, and other finisher functions has been increasing, and a toner capable of obtaining an image that can withstand these functions has been required. Toners meet these demands. In addition, the obtained image is used as a document and is often applied to an automatic document feeder, and some documents are passed many times. At this time, if the member that comes in contact with the original is soiled, other originals are stained, or the original is soiled. The toner of the present invention can be safely used as a document without causing stains on members even when the image is used as a document. That is, the toner of the present invention can back up full automation of electrophotographic equipment.

The following can be used as the wax used in the present invention.

Preferred waxes include polyolefins obtained by radical polymerization of olefins under high pressure;
Polyolefin obtained by purifying low-molecular-weight by-products obtained during the polymerization of high-molecular-weight polyolefin; polyolefin polymerized using a catalyst such as a Ziegler catalyst or a metallocene catalyst at a low pressure; polyolefin polymerized using radiation, electromagnetic waves, light, or the like; A low molecular weight polyolefin obtained by thermally decomposing a high molecular weight polyolefin; a paraffin wax, a microcrystalline wax, a Fischer-Tropsch wax; a synthetic hydrocarbon wax synthesized by a Zintall method, a hydrocoll method, an Age method, etc .; Synthetic wax as a monomer, a hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group; a mixture of a hydrocarbon wax and a hydrocarbon wax having a functional group.

Further, these waxes may be obtained by sharpening the molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, a molten liquid crystal deposition method, or a low molecular weight solid. Fatty acids, low molecular weight solid alcohols,
Low molecular weight solid compounds and those from which other impurities have been removed are preferably used.

Particularly preferably used are a paraffin wax, a Fischer-Tropsch wax, a melt viscosity at 120 ° C. of 22 mPa ·
A wax having a melt viscosity of less than 22 mPa · s at 120 ° C. measured by an E-type viscometer and a Fischer-Tropsch wax having a melt viscosity of 22 to 100 mPa · s are preferred.

The melt viscosity is measured using an E-type rotational viscometer. As a viscometer, for example, VT-500 (HAAK)
E company) can be used. In the embodiment, VT-50
0, the measurement temperature was adjusted to 120 ° C by an oil bath with a temperature regulator, and PK1,0.
The measurement was performed at a shear rate of 6,000 s ^-1 using 5 °.

According to the molecular weight distribution of the toner according to the present invention, the component having a molecular weight of 10,000 or less is 20%.
The above is preferable from the viewpoint of improving the fixing property. Components having a molecular weight of 10,000 or less have low viscosity, so that the wax effect of the present invention is more remarkably exhibited. It is preferably 20 to 55%, more preferably 25 to 50%, since the plasticizing effect can be sufficiently exhibited without any adverse effect. If it exceeds 55%, the plasticizing effect becomes too large and the blocking resistance may be poor.

It is preferable that the content of the component having a molecular weight of 100,000 or more is 5% or more from the viewpoint of improving releasability and slipperiness. Since the component having a molecular weight of 100,000 or more has elasticity, it can help the wax releasing effect and effectively form a wax film. Since the wax film is effectively formed as described above, the releasing effect, the peeling effect, and the sliding effect are also improved. Preferably 5-35
%, More preferably 5 to 30%, particularly 7 to 25%, the release effect and the sliding effect are more remarkably exhibited. 35
%, The elasticity is increased, the plasticizing effect is less likely to appear, and improvement in fixability may be hindered.

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

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

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

The styrenic polymer or styrenic copolymer may be cross-linked or a mixed resin.

As the crosslinking agent for the binder resin, a compound having two or more polymerizable double bonds may be mainly used. For example, aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene and the like; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate and the like; Divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide and divinyl sulfone; and 3
Compounds having at least two vinyl groups are used alone or as a mixture.

The method for synthesizing the styrene copolymer may be any of a bulk polymerization method, a solution polymerization method, a suspension polymerization method and an emulsion polymerization method.

In the bulk polymerization method, a polymer having a low molecular weight can be obtained by increasing the termination reaction rate by polymerizing at a high temperature, but there is a problem that the reaction is difficult to control.
In the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in radical chain transfer depending on the solvent and by adjusting the amount of the initiator and the reaction temperature.
It is preferable to obtain a low molecular weight polymer having a maximum molecular weight in a molecular weight range of 5,000 to 100,000 in the chromatogram of C.

As the solvent used in the solution polymerization, xylene, toluene, cumene, cellosolve acetate, isopropyl alcohol, benzene and the like are used. In the case of a styrene monomer mixture, xylene, toluene or cumene is preferred. It is appropriately selected depending on the polymer to be polymerized.

The reaction temperature varies depending on the solvent used, the initiator and the polymer to be polymerized.
It is better to carry out at 0 ° C. In solution polymerization, solvent 100
It is preferable to carry out with 30 parts by weight to 400 parts by weight of the monomer based on parts by weight.

Further, it is preferable to mix another polymer in the solution at the end of the polymerization, and several kinds of polymers can be mixed well.

Further, as a polymerization method for obtaining a high molecular weight polymer or a crosslinked polymer having a maximum value of the molecular weight in a region having a molecular weight of 100,000 or more in a chromatogram of GPC,
Emulsion polymerization and suspension polymerization are preferred.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. . In this method, it is easy to control the heat of reaction, and since the phase in which the polymerization is carried out (the oil phase composed of the polymer and the monomer) and the aqueous phase are different, the termination reaction rate is small, and as a result, the polymerization rate is large. , With a high degree of polymerization.
Furthermore, because the polymerization process is relatively simple and the polymerization product is fine particles, it is easy to mix with a colorant, a charge control agent, and other additives in the production of a toner. This is advantageous as compared with other methods as a method for producing a binder resin for a toner.

However, the resulting polymer tends to be impure due to the added emulsifier, and an operation such as salting out is required to take out the polymer. Therefore, suspension polymerization is a simple method.

In the suspension polymerization, 100 parts by weight or less of the monomer (preferably 1 part by weight) is added to 100 parts by weight of the aqueous solvent.
(0 to 90 parts by weight). Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate, and the like. There is an appropriate amount in terms of the amount of a monomer relative to an aqueous solvent, and generally 0.05 to 1 based on 100 parts by weight of an aqueous solvent. Used in parts by weight. The polymerization temperature is suitably from 50 to 95 ° C., but should be appropriately selected depending on the polymerization initiator used and the target polymer. Further, any kind of polymerization initiator can be used as long as it is insoluble or hardly soluble in water.

The polymerization initiator used in these polymerization methods includes t-butylperoxy-2-ethylhexanoate, cumin perpivalate, t-butylperoxylaurate, benzoyl peroxide, lauroyl peroxide, Octanoyl peroxide, di-t
-Butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 1,1-bis (t-butylperoxy) cyclohexane, 1,4-bis (t-butylperoxycarbonyl) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl 4,4 -Screw (t-
Butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, 1,3-bis (t-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexane, 2,
5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di-t-butyldiperoxyisophthalate, 2,2 -Bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutarate, di-t-butylperoxyhexa Hydroterephthalate, di-t-butylperoxyazelate, 2,5-dimethyl-2,5-di (t-
Butyl peroxy) hexane, diethylene glycol
Bis (t-butylperoxycarbonate), di-t-
Butyl peroxytrimethyl adipate, tris (t-
(Butylperoxy) triazine, vinyltris (t-butylperoxy) silane, etc., which can be used alone or in combination.

The amount of use is 0.05 parts by weight or more (preferably 0.1 to 15 parts by weight) with respect to 100 parts by weight of the monomer.

Next, the composition of the polyester resin will be described.

Examples of the dihydric alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol and 1,5-pentanediol. , 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-
Hexanediol, hydrogenated bisphenol A, bisphenol represented by the formula (A) and derivatives thereof;

[0055]

[Outside 1] (Wherein R is an ethylene or propylene group, x,
y is an integer of 0 or more, respectively, and the average value of x + y is 0 to 10).

Diols represented by the formula (B):

[0057]

[Outside 2] Where x 'and y' are integers of 0 or more, and x '
The average value of + y 'is 0 to 10. ).

As the divalent acid component, for example, phthalic acid,
Benzenedicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides and lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides and lower alkyl esters; n- Alkenyl succinic acids or alkyl succinic acids such as dodecenyl succinic acid, n-dodecyl succinic acid, or anhydrides and lower alkyl esters thereof; fumaric acid, maleic acid, citraconic acid, unsaturated dicarboxylic acids such as itaconic acid or anhydrides, lower acids And dicarboxylic acids such as alkyl esters; and derivatives thereof.

Further, it is preferable to use a trivalent or higher valent alcohol component and a trivalent or higher valent acid component which also function as a crosslinking component.

The trihydric or higher polyhydric alcohol component includes
For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol,
1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,
3,5-trihydroxybenzene and the like.

In the present invention, the trivalent or higher polyvalent carboxylic acid component includes, for example, trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid,
2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,2
5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-
Octanetetracarboxylic acid, empol trimer acid, and anhydrides and lower alkyl esters thereof;

[0062]

[Outside 3] (Wherein X is an alkylene group or alkenylene group having 5 to 30 carbon atoms having at least one side chain having 3 or more carbon atoms), such as tetracarboxylic acids, and anhydrides and lower alkyl esters thereof. And polyvalent carboxylic acids and derivatives thereof.

The alcohol component used in the present invention is 40 to 60 mol%, preferably 45 to 55 mol%.
%, 60 to 40 mol% as an acid component. Preferably 5
It is preferably from 5 to 45 mol%.

The polyvalent component having a valence of 3 or more is preferably 1 to 60 mol% of all components.

The polyester resin can also be obtained by generally known condensation polymerization.

In the toner according to the present invention, in addition to the above-mentioned binder resin component, the following compounds may be contained at a ratio smaller than the content of the binder resin component. For example, silicone resin, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, rosin, modified rosin,
Examples include terpene resins, phenolic resins, and copolymers of two or more α-olefins.

The glass transition point (Tg) of the binder resin is preferably from 45 to 80 ° C., more preferably from 50 to 70 ° C.

In the present invention, the binder resin and the toner G
The molecular weight distribution of the chromatogram by PC is measured under the following conditions.

That is, the column was stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) as a solvent was passed through the column at this temperature at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution was injected. Measure. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK is used.
It is appropriate to use about 0 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
As the column, a plurality of commercially available polystyrene gel columns are preferably combined, and for example, showex GPC KF-801, 802, 80 manufactured by Showa Denko KK
3,804,805,806,807,800P or TSKgelG1000H (H
_{XL), G2000H (H XL)} , G3000H (H XL),
_{G4000H (H XL), G5000H (} H XL), G60
00H (H _XL ), G7000H (H _XL ), TSKgua
rdcolumn can be mentioned.

A sample is prepared as follows.

After placing the sample in THF and leaving it to stand for several hours, it is shaken sufficiently, mixed well with THF (until the sample is no longer united), and left still for 12 hours or more. Then T
The time of leaving in HF is set to 24 hours or more.
After that, the sample processing filter (pore size 0.45
０．５0.5 μm, for example, Myshodisk H-25-
5, a product made by Tosoh Corporation, an Exiclodisc 25CR, a product made by Germanic Science Japan, etc.) can be used as a GPC sample. The sample concentration is
The resin component is adjusted to be 0.5 to 5 mg / ml.

The binder resin used in the present invention has a weight average molecular weight (Mw) of 4,000 to 5 as measured by GPC.
It becomes a low molecular weight resin of 000 (preferably 5,000 to 30,000) and a high molecular weight resin having Mw of 100,000 or more (preferably 150,000 or more) or a tetrahydrofuran (THF) insoluble component (gel component). It is preferable to use both a resin having a crosslinking component and a resin having a gel component. The low molecular weight resin and the high molecular weight resin or the gel component-containing resin may be wet-mixed in a solvent, or may be dry-mixed during the production of the toner. Furthermore,
A resin having a gel component or a resin having a gel component dispersed in a low molecular weight resin may be used. Further, a high molecular weight resin, a gel component-containing resin, and a gel component may be synthesized in the presence of a low molecular weight resin. Alternatively, a low molecular weight resin may be synthesized in the presence of a high molecular weight resin, a gel-containing resin, and a gel component. Also,
It may be used as a mixture with a resin having another molecular weight.

The toner of the present invention preferably contains a charge control agent.

The following substances control the toner to be positively charged.

Modified products such as nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-vitroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate;
Onium salts such as phosphonium salts, which are analogs thereof, and their lake pigments, triphenylmethane dyes and these lake pigments Acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.) metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin borate Diorganotin borates; guanidine compounds, imidazole compounds; These can be used alone or in combination of two or more. Among these, a triphenylmethane compound and a quaternary ammonium salt whose counter ion is not halogen are preferably used. The general formula (1)

[0076]

[Outside 4] [Wherein, R ₁ represents H or CH ₃ , and R ₂ and R ₃ represent a substituted or unsubstituted alkyl group (preferably, C ₁ -C 3
₄ )] Monomer of monomer represented by the following formula: A copolymer with a polymerizable monomer such as styrene, acrylate or methacrylate described above can be used as a positive charge control agent. In this case, these charge control agents also act as (all or part of) the binder resin.

Particularly, a compound represented by the following general formula (2) is preferable in the constitution of the present invention.

[0078]

[Outside 5] [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are each a hydrogen atom which may be the same or different, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl. Represents a group. R ⁷ , R ⁸ and R ⁹ each represent a hydrogen atom, a halogen atom, which may be the same or different,
Represents an alkyl group or an alkoxy group. A ^- is an anion such as sulfate ion, nitrate ion, borate ion, phosphate ion, hydroxide ion, organic sulfate ion, organic sulfonate ion, organic phosphate ion, carboxylate ion, organic borate ion, and tetrafluoroborate. Is shown).

The following substances control the toner to be negatively charged.

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

An azo metal complex represented by the following general formula (3) is preferred.

[0082]

[Outside 6] [Wherein, M represents a coordination center metal, and Sc, Ti, V,
Examples include Cr, Co, Ni, Mn, and Fe. Ar is an aryl group, such as a phenyl group or a naphthyl group, and may have a substituent. Examples of the substituent in this case include a nitro group, a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms and an alkoxy group. X, X ', Y, Y' are -O-, -CO-,-
NH- and -NR- (R is an alkyl group having 1 to 4 carbon atoms).

[0083]

[Outside 7] Represents hydrogen, sodium, potassium, ammonium, aliphatic ammonium or none].

In particular, the central metal is preferably Fe or Cr, the substituent is preferably a halogen, an alkyl group or an anilide group, and the counter ion is preferably hydrogen, alkali metal ammonium or aliphatic ammonium. Also, a mixture of complex salts having different counter ions is preferably used.

Alternatively, a basic organic acid metal complex represented by the following general formula (4) also gives negative chargeability and can be used in the present invention.

[0086]

[Outside 8]

In particular, Fe, Cr, S
i, Zn, and Al are preferred, and the substituent is preferably an alkyl group, an anilide group, an aryl group, or a halogen; and the counter ion is preferably hydrogen, ammonium, or aliphatic ammonium.

As a method for incorporating the charge control agent into the toner, there are a method of adding the charge control agent inside the toner and a method of externally adding the charge control agent. The use amount of these charge control agents is determined by the type of the binder resin, the presence or absence of other additives, the toner manufacturing method including the dispersion method, and is not limited to a specific one. It is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the binder resin.

In the toner of the present invention, charging stability,
In order to improve developability, fluidity and durability, it is preferable to add silica fine powder.

The silica fine powder used in the present invention is BE
The specific surface area by nitrogen adsorption measured by the T method is 20 m ² / g
Those within the above range (particularly 30 to 400 m ² / g) give good results. It is preferable to use 0.01 to 8 parts by weight, preferably 0.1 to 5 parts by weight of silica fine powder with respect to 100 parts by weight of the toner.

The silica fine powder has a silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, a silane coupling agent, and a functional group, if necessary, for the purpose of hydrophobization, charge control and the like. It is also preferable that the treatment is performed with a treating agent such as a silane coupling agent or another organosilicon compound, or in combination with various treating agents.

It is also preferable to add the following inorganic powder in order to improve developability and durability. Magnesium, zinc, aluminum, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin,
Metal oxides such as antimony; composite metal oxides such as calcium titanate, magnesium titanate and strontium titanate; metal salts such as calcium carbonate, magnesium carbonate and aluminum carbonate; clay minerals such as kaolin;
Phosphate compounds such as apatite; silicon compounds such as silicon carbide and silicon nitride; and carbon powders such as carbon black and graphite. Among them, zinc oxide, aluminum oxide, cobalt oxide, manganese dioxide, strontium titanate, magnesium titanate and the like are preferable.

Further, the following lubricant powder can be added. Fluorine resins such as Teflon and polyvinylidene fluoride; fluorine compounds such as carbon fluoride; fatty acid metal salts such as zinc stearate; fatty acid derivatives such as fatty acids and fatty acid esters; molybdenum sulfide, amino acids and amino acid derivatives.

The toner of the present invention can be used as a two-component developer in combination with a carrier. When the toner is used in the two-component developing method, any known carrier can be used. Specifically, particles having an average particle size of 20 to 300 [mu] m, such as metals such as iron, nickel, cobalt, manganese, chromium, and rare earths, and their alloys and oxides, whose surface is oxidized or not oxidized, are used.

Further, those obtained by attaching or coating a substance such as a styrene resin, an acrylic resin, a silicone resin, a fluorine resin or a polyester resin on the surface of the carrier particles are preferably used.

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

These ferromagnetic substances preferably have an average particle diameter of 2 μm or less, preferably 0.1 to 0.5 μm.
The amount contained in the toner is preferably about 20 to 200 parts by weight, particularly preferably 40 to 150 parts by weight, per 100 parts by weight of the resin component.

The colorant that can be used in the toner of the present invention includes any suitable pigment or dye. As a colorant of the toner, for example, carbon black as a pigment,
Examples include aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengalara, phthalocyanine blue, and indanthrene blue. These are used in an amount necessary and sufficient to maintain the optical density of the fixed image, and 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, per 100 parts by weight of the resin.
Good addition amount by weight. A dye is further used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes.
0.1 to 20 parts by weight, preferably 0.3 to parts by weight
The addition amount of 10 to 10 parts by weight is good.

To prepare the toner for developing an electrostatic image according to the present invention, a binder resin, a wax, a metal salt or a metal complex, a pigment or dye as a colorant, a magnetic substance, a charge control agent if necessary, Other additives, etc. are mixed thoroughly by a mixer such as Henschel Mickey, ball mill, etc., then heated and melt-kneaded using a hot kneader such as a kneader or extruder while the resins are mixed with each other. Disperse or dissolve metal compounds, pigments, dyes, magnetic materials,
After solidification by cooling, pulverization and classification are performed to obtain the toner according to the present invention.

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

In producing a toner, it is preferable to uniformly disperse waxes in a binder resin in order to obtain the effects of the present invention. When the dispersion state is non-uniform or free waxes are present, the toner performance may not be sufficiently exhibited. In order to achieve such a dispersed state, it is preferable to perform a melt kneading process in the next step using a melt-kneaded wax and a resin as a binder resin before melt-kneading at the time of preparing the toner. Further, it is preferable that the resin is dissolved in a solvent, the wax is wet-mixed in the solvent, the solvent is removed, and then dried and pulverized, and then used as a binder resin to enter a toner melt-kneading step.
It is also preferable to raise the temperature of the solvent when mixing the waxes, and to mix the waxes in a molten state.

[0102]

The present invention will be described below with reference to specific examples.

Table 1 shows the waxes used in the examples.
The viscosity is a value measured at 120 ° C. using an E-type viscometer.

[0104]

[Table 1]

A binder resin was prepared as follows. Styrene-butyl acrylate copolymer A crosslinked with divinylbenzene having a THF insoluble content of 50% by weight by a suspension polymerization method
(St / BA = 75/25, Tg = 60 ° C., THF-soluble component Mw = 200,000) was prepared. Styrene butyl acrylate copolymer B (St / BA = 80/20, Tg = 67 ° C., Mg) using tris (t-butylperoxy) triazine as a polymerization initiator in a suspension polymerization method.
w = 920,000). Then, styrene butyl acrylate copolymer C (St / BA
= 85/15, Tg = 61 ° C, Mw = 15,000). A solution obtained by mixing 30 parts by weight of a copolymer A obtained by pulverizing 70 parts by weight of the copolymer C in a solution was used as a binder resin 1, and 70 parts by weight of the copolymer C and 3 parts of the copolymer B were used.
One obtained by mixing 0 parts by weight in the solution was used as a binder resin 2.
Further, a wax was added thereto, and the mixture was dissolved under heating and mixed. After removing the solvent, the mixture was dried and pulverized to obtain a resin composition. The amount of the wax added is as shown in Table 2. The number of copies is 10
0 parts by weight.

[0106]

[Table 2]

Example 1 Resin Composition 1 100 parts by weight Magnetite (average diameter 0.2 μ) 85 parts by weight Monoazo iron complex 2 parts by weight

After the above materials were premixed with a Henschel mixer, they were kneaded with a twin-screw kneading extruder set at 110 ° C. The obtained kneaded material was cooled and coarsely pulverized by a cutter mill, finely pulverized using a pulverizer using a jet stream, and classified using a multi-partition classifier utilizing the Coanda effect to obtain a weight average diameter of 7. A negatively chargeable magnetic toner of 2 μm was obtained. To 100 parts by weight of this toner, 1.0 part by weight of negatively charged hydrophobic silica was externally added and mixed with a Henschel mixer to obtain Magnetic Toner 1. Table 3 shows data on the molecular weight distribution of the THF-soluble component of the magnetic toner.

Table 4 shows the results of the fixing test, offset test, and image durability test of the magnetic toner 1. As a result, good fixing characteristics and good durability characteristics were obtained, and there was no occurrence of document contamination when a copied image was used as a document.

Fixing property and offset test Electrophotographic copying machine NP-6750 (manufactured by Canon Inc.)
Was used to perform a fixing property test and an offset resistance test.
Turn on the power of the copier that has been sufficiently adapted to the environment at room temperature of 15 ° C., and immediately after the standby mode, copy the A3 image of 90 g / m ² paper to 20
0 sheets were continuously copied. 50 g / cm of the 200th image
^The fixing property was judged from the reduction rate of the image density before and after the rubbing with the silbon paper with the weight of ² reciprocating five times. The smaller the reduction rate, the better the fixing property.

The offset was determined by observing the image during the fixing test and when the fixing device overshot three times after the fixing test, and visually observing the image with toner. A: There is no stain on the image due to the offset phenomenon. B: Slight contamination due to the offset phenomenon occurs on the image. C: Stain due to the offset phenomenon occurs on the image.

Image durability test 1 Electrophotographic copying machine NP-6750 (manufactured by Canon Inc.)
Using A4 size originals with an image area ratio of 5% on an A4 size 80 g / m ² transfer paper, 50 sheets each on both sides for a total of 10,
000 sheets were printed, and the obtained image was again used as transfer paper to print 10,000 sheets on both sides. This was repeated three more times. The image stain at this time was evaluated. An image for image evaluation was taken for each set, and the image density was measured. A: No stain was generated on the image. B: Some stain was generated on the image. C: Stain was generated on the image.

Image endurance test 2 Following image endurance test 1, A4 size image area ratio 5
% Original and 4i on A4 size 80g / m ² transfer paper
In the n1 reduced layout mode (function of converting four originals into one image by using a multiplexing mechanism), a total of 10,000
0 images are drawn, and the obtained image is used again as transfer paper, and images in the 4-in-1 reduced layout mode are displayed as 10.
000 sheets, and this was repeated three more times. The image stain at this time was evaluated. An image for image evaluation was taken for each set, and the image density was measured. A: No stain was generated on the image. B: Some stain was generated on the image. C: Stain was generated on the image.

Original dirt test Electrophotographic copying machine NP-6750 (manufactured by Canon Inc.)
Using an auto document feeder (1), image contamination was examined when a copy image was used as a document. Fifty double-sided copied images of A4 size with an image area ratio of 20% were passed through an automatic document feeder five times in a single-sided copy mode from a double-sided original, and stains on the original were evaluated. A: No stain was generated on the image. B: Some stain was generated on the image. C: Stain was generated on the image.

Examples 2 to 6, Comparative Examples 1, 5 and 6 In place of the resin composition 1, resin compositions 2 to 7 and 11 to 1
Weight average diameter 7.
Magnetic toners 2 to 7 and 11 to 12 of 0 to 7.5 μm were obtained. Table 3 shows data on the molecular weight distributions of magnetic toners 2 to 7 and 11 to 12 obtained by externally adding silica in the same manner as in Example 1, and Table 4 shows the evaluation results.

Comparative Example 2 A magnetic toner 8 having a weight average diameter of 7.0 μm was obtained in the same manner as in Example 1 except that the resin composition 8 was used instead of the resin composition 1. Magnetic toner 8 obtained in the same manner as in Example 1.
Table 4 shows the evaluation results. The image durability was slightly inferior, and drum fusion occurred during image durability.

Comparative Example 3 A magnetic toner 9 having a weight average diameter of 7.3 μm was obtained in the same manner as in Example 1 except that the resin composition 9 was used instead of the resin composition 1. Magnetic toner 9 obtained in the same manner as in Example 1.
Table 4 shows the evaluation results. Poor offset resistance, causing paper jams.

Comparative Example 4 A magnetic toner 10 having a weight average diameter of 7.5 μm was obtained in the same manner as in Example 1 except that the resin composition 10 was used instead of the resin composition 1. Table 4 shows the evaluation results of the magnetic toner 10 obtained in the same manner as in Example 1. The fixing property was slightly inferior, and drum fusing occurred during image durability.

[0119]

[Table 3]

[0120]

[Table 4]

[0121]

As described above, by using two kinds of low-viscosity waxes as described above, a plasticizing effect, a releasing effect, a peeling effect, and a sliding effect are imparted to the toner, and the toner has excellent fixability, offset resistance, and image durability. The present invention can provide a toner.

It is an object of the present invention to provide a toner capable of providing an image which does not cause a trouble in a document producing operation, which is excellent in developing property, and which can cope with systematization, high speed and high function of a copying machine and a printer. it can.

According to the present invention, it is possible to provide a toner which gives an image which becomes an original which can be used repeatedly.

Continuation of the front page (72) Inventor Hiroyuki Fujikawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-8-234480 (JP, A) JP-A-6-332244 ( JP, A) JP-A-4-153659 (JP, A) JP-A-7-271094 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/08

Claims (4)

(57) [Claims] 1. An electrostatic image developing toner having a resin composition containing at least a binder resin and a wax component, wherein the wax component is measured with an E-type viscometer.
A having a melt viscosity at 22 ° C of less than 22 mPa · s
And the melt viscosity at 120 ° C. is 22 to 100 mPa ·
possess a s wax B, the wax A paraffin wa
And the wax B is Fischer-Tropsch
The toner for developing electrostatic images, wherein the wax der Rukoto. 2. A difference in melt viscosity between the wax A and the wax B at 120 ° C. measured with an E-type viscometer is 10 m.
The toner for developing an electrostatic image according to claim 1, which has a Pa · s or more. 3. In the molecular weight distribution of the toner measured by gel permeation chromatography (GPC), components having a molecular weight of 10,000 or less are 20% or more, and components having a molecular weight of 100,000 or more are 5% or more. the toner according to claim 1 or 2 is. 4. In a molecular weight distribution of the toner measured by GPC, 25 or less components having a molecular weight of 10,000 or less are contained.
５０50%, and components having a molecular weight of 100,000 or more
The toner for developing an electrostatic image according to claim 3 , wherein the content of the toner is from 30% to 30%.