JPH04299357A - Heat fixable toner - Google Patents

Abstract

PURPOSE:To obtain the heat fixable toner which is fixed at a low temp. and has excellent offset resistance in a wide temp. range by incorporating specific graft-denatured polyalkylene and polyalkylene into a release agent. CONSTITUTION:The release agent of the heat fixable toner contg. at least a binder resin and the release agent contains the graft-denatured polyalkylene having <=3,000 number average mol.wt., <=12,000 weight average mol.wt., <=4.0 weight average mol.wt./number average mol.wt., and 60 to 150 deg.C m. p., and the polyalkylene having <=40cal/g melting heat quantity. Then, the excellent offset resistance and fixability are obtd. and the unequal presence and liberation of the release agent component into the toner are lessened. The generation of fusion filming, etc., to photosensitive members, developing members, etc., is obviated and the stable image densities are maintained. Bright images free from fogging are thus obtd.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing electrostatic latent images and magnetic latent images in electrophotography, electrostatic printing, magnetic recording, and the like. More specifically, the present invention relates to a heat-fixable toner that is used in a heat-fixing method such as heat roller fixing.

0002

[Prior Art] Conventionally, as an electrophotographic method, US Pat.
, 297,691, Japanese Patent Publication No. 42-23910, Japanese Patent Publication No. 43-24748, etc., many methods are known, but in general, they utilize a photoconductive substance, An electrical latent image is formed on the photoreceptor by various means, then the latent image is developed using toner, and if necessary, the toner image is transferred to a transfer material such as paper, followed by heating, pressure, or heating. Copies are obtained by fixing under pressure or solvent vapor, and the toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above-mentioned steps are repeated.

In recent years, such copying devices have begun to be used not only as office copy machines for copying original documents, but also as printers for computer output or as personal copies for individuals. .

[0004] Therefore, smaller size, lighter weight, higher speed, and higher reliability are being strictly pursued, and machines are being constructed of simpler elements in various respects. As a result, the performance required of toner has become more advanced, and it has become impossible to create better machines unless the performance of toner can be improved.

For example, various methods and devices have been developed for the process of fixing toner images on sheets such as paper.
The most common method at present is the compression heating method using a heated roller.

[0006] In the pressure heating method using a heated roller, fixing is carried out by passing the toner image surface of the sheet to be fixed under pressure while contacting the surface of a heated roller whose surface is made of a material that has releasability for the toner. It is something. 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 performed 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 come into contact with each other under pressure in a molten state, a part 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, so-called. This may cause an offset phenomenon and stain the fixing sheet. One of the essential conditions for the heat roller fixing method is to prevent toner from adhering to the surface of the heat fixing roller.

Conventionally, in order to prevent toner from adhering to the surface of the fixing roller, the roller surface is made of a material that has excellent releasability for toner, such as silicone rubber or fluorine resin, and is further coated with anti-offset and other materials. In order to prevent fatigue on the roller surface, the roller surface is coated with a thin film of a liquid having good mold releasability, such as silicone oil. However, although this method is extremely effective in preventing toner offset, it requires a device to supply the offset prevention liquid, resulting in problems such as the complexity of the fixing device. .

[0008] This is in the opposite direction to miniaturization and weight reduction, and moreover, silicone oil and the like may evaporate due to heat and contaminate the inside of the machine. Therefore, instead of using a silicone oil supply device, the idea was to supply an anti-offset liquid from the toner during heat fixing, and a method of adding a release agent such as low molecular weight polyethylene or low molecular weight polypropylene to the toner was developed. Proposed. If such additives are added in large quantities to produce sufficient effects, they may cause filming on the photoreceptor or contaminate the surface of toner carriers such as carriers and sleeves, resulting in image deterioration and impractical use. This poses a problem. Therefore, we have developed a cleaning device that adds a small amount of release agent to the toner to the extent that it does not deteriorate the image, supplies a small amount of release oil, or uses a device that uses a winding type member such as a web to clean the offset toner. They are used together.

However, in view of recent demands for smaller size, lighter weight, and higher reliability, it is necessary to eliminate even these auxiliary devices. Therefore, it is necessary to further improve toner properties such as fixing properties and offset resistance, and it is difficult to achieve this without further improvements in toner binder resins, mold release agents, and the like.

[0010] It is known that polyalkylenes are contained as a release agent in toner, for example, as disclosed in Japanese Patent Application Laid-Open No.
It is disclosed in JP-A-52574, JP-A-52-3304, JP-A-52-3305, and the like.

Furthermore, in order to expand the non-offset temperature range and improve wrapping of transfer paper around heating rollers, etc.
Several techniques have been disclosed for incorporating more than one type of polyalkylene into a toner, which are classified into the following (1), (2), and (3).

(1) A toner containing two types of polyalkylene having different softening points. For example, JP-A-58-
215659, JP-A-60-151650, etc.

(2) A toner containing two types of polyalkylene having different melt viscosities. For example, JP-A-62-
There is a publication No. 100775.

(3) A toner in which both a polyalkylene modified with a specific monomer and an unmodified polyalkylene are contained in the toner, so that the two types have different compatibility with the binder resin. For example, JP-A-60-934
56, JP-A No. 60-93457, and JP-A No. 63-34550.

According to studies conducted by the present inventors, it is difficult to homogeneously disperse polyalkylenes, which basically have poor compatibility with binder resins, in toner by means such as heating and kneading. When using two or more types of polyalkylene with different melting properties as in 2), in a series of steps such as heating kneading, pulverization, and classification during toner production,
The polyalkylene component tends to be unevenly distributed and liberated, and the liberated polyalkylene particles have charging characteristics different from those of ordinary toners, causing image stains such as fog. Furthermore, the polyalkylene contained in the toner as a release agent is mainly a low molecular weight wax, and such free wax can cause filming and contamination on the photoreceptor, developing member, carrier, etc. . At the same time, some toner particles containing almost no polyalkylene component are generated, which may cause the toner to fuse to the above-mentioned member.

In the case of (3) above, by incorporating a modified polyalkylene with a specific modified monomer species into the toner, the compatibility with the binder resin is improved, the fluidity of the toner is improved, and the unmodified polyalkylene is improved. This is an attempt to suppress the drawbacks due to polyalkylene content. However, according to studies conducted by the present inventors, when the polyalkylene wax is completely miscible with the binder resin, the powder fluidity of the toner is certainly improved, but at the same time, the mold release effect is impaired. There is a drawback that the original effect of containing a mold release agent is lost.

Moreover, in modified polyalkylene wax produced by a single modified species, the compatibility differs depending on the polymer type of the binder resin or the molecular weight, etc., and it is not compatible with various thermoplastic resins conventionally used as binder resins for toners. There is no universal fit.

As described above, the technology of incorporating two or more types of polyalkylene into a toner is not sufficient at present.

[0019] The release agent used in the toner is as follows:
Low molecular weight polyalkylene waxes are the mainstream, and they themselves have a glass transition point below room temperature, and toners produced by conventional pulverization tend to deteriorate blocking properties during storage and toner powder fluidity. Therefore, it is difficult to incorporate a large amount of a release agent into a toner, and until now, the amount added to the binder resin has been limited to at most 20 parts by weight per 100 parts by weight of the binder resin. The emergence of a mold release agent that exhibits excellent properties is desired.

[0020]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-fixable toner that solves the above-mentioned problems.

That is, the present invention fixes at a low temperature,
Another object of the present invention is to provide a heat-fixable toner having excellent offset resistance over a wide temperature range from low to high temperatures.

Another object of the present invention is that even in high-speed systems, filming and fusing onto photoreceptors and developing members are possible.
Another object of the present invention is to provide a heat-fixing toner that does not generate heat even after long-term use.

A further object of the present invention is to provide a heat-fixable toner that does not cause a decrease in image density over time due to image stains such as fog or contamination of a charging member.

A further object of the present invention is to provide a heat-fixable toner having excellent anti-blocking properties.

Furthermore, the present invention is capable of homogeneously dispersing the release agent contained in the toner in the kneading step during toner production, and the fine powder and coarse powder having a particle size outside the predetermined size obtained in the subsequent pulverization and classification step. The purpose of the present invention is to provide a heat-fixable toner that can be reused and that can be efficiently and continuously produced without any quality problems.

[0026]

Means for Solving the Problems The heat-fixable toner of the present invention has toner particles containing at least a binder resin and a release agent, in which the release agent contains at least (A) a number average Molecular weight (Mn) is 3.0
00 or less, and the weight average molecular weight (Mw) is 12,00
0 or less, and the weight average molecular weight/number average molecular weight (Mw/
(B) a graft-modified polyalkylene A having a Mn) of 4.0 or less and a melting point of 60 to 150°C; and (B) a polyalkylene B having a heat of fusion of 40 cal/g or less. Achieve your purpose.

The present invention will be explained in detail below.

The present inventors have conducted extensive research and found that in order to achieve low-temperature fixability and excellent offset resistance over a wide temperature range from low to high temperatures, the binder resin must have a specific molecular weight distribution. , and a graft-modified polyalkylene having a specific relatively low melting point and a specific polyalkylene having a relatively small heat of fusion that can be melted in an instant heating time and exhibit mold release properties especially in a high-speed system. It has been found that by incorporating at least two types of polyalkylene into the toner as release agents, the above object can be achieved to a high degree because both polyalkylenes are homogeneously dispersed in the toner as sufficiently small segments.

[0029] In addition to the conventional heat roll fixing machine, in order to heat and fix the toner image on the recording material, it is possible to use a fixedly supported heating body and a film that is pressed against the heating body. It has been found that this toner is suitable for a fixing method in which a visible image of the toner is heated and fixed onto a recording material by using a pressure member that brings the recording material into close contact with the heating body through a heat-fixing method.

The specific graft-modified polyalkylene having a relatively low melting point contained as a release agent in the heat-fixable toner of the present invention has a number average molecular weight (Mn
) is 3,000 or less, the weight average molecular weight (Mw) is 12,000 or less, the weight average molecular weight/number average molecular weight (Mw/Mn) is 4.0 or less, and the melting point is 60 to 1
A graft-modified polyalkylene having a temperature of 50°C, preferably having a number average molecular weight (Mn) of 2,500 or less and a weight average molecular weight (Mw) of 7,000 or less,
Weight average molecular weight/number average molecular weight (Mw/Mn) is 3.0
or less, and the melting point is 60 to 120°C.

[0031] The low-temperature fixability and low-temperature properties of the toner are affected in any case where the number average molecular weight (Mn) exceeds 3,000, when the weight average molecular weight (Mw) exceeds 12,000, or when the melting point exceeds 150°C. If the offset resistance is poor and the melting point is less than 60° C., problems such as a decrease in the blocking resistance of the toner or deterioration of the powder cohesiveness of the toner occur.

The graft-modified polyalkylene is graft-modified with a styrene derivative and an unsaturated fatty acid derivative, and the amount of modification is 5 to 20% relative to the polyalkylene.
It is preferably 7 to 15 parts by weight, more preferably 7 to 15 parts by weight.
Parts by weight are preferred. Further, the weight ratio of the styrene derivative to the unsaturated fatty acid derivative is preferably 1:9 to 9:1, more preferably 7:3 to 3:7 parts by weight. When the ratio is from 1:9 to 9:1, the graft-modified polyalkylene is appropriately and homogeneously dispersed in the binder resin of the toner, resulting in better offset resistance, low-temperature fixing properties, and the like. Furthermore, even when other polyalkylene is used as a release agent in addition to the graft-modified polyalkylene, uneven distribution and release of the other polyalkylene in the toner can be suppressed, resulting in image stains such as fog, Filming and adhesion to the photoreceptor and developing member does not occur or is reduced.

[0033] If the amount of graft modification of the graft-modified polyalkylene is less than 5 parts by weight per 100 parts by weight of the polyalkylene, the compatibility of the binder resin will be extremely reduced and phase separation will occur on a macro level. The above-mentioned problems caused by dispersion are likely to occur particularly in systems in which other mold release agents are used in combination. On the other hand, if the amount of graft modification exceeds 20 parts by weight, the compatibility of the graft modified polyalkylene with the binder resin becomes excessive, which may actually lead to a decrease in the offset resistance of the toner or the blocking resistance of the toner. This will lead to a decline in sexuality. As the graft-modified species of the graft-modified polyalkylene according to the present invention, when a styrene-based derivative and an unsaturated fatty acid-based derivative are simultaneously grafted, the above-mentioned objectives are highly achieved. It is insufficient if it is modified only with a derivative or only with an unsaturated fatty acid derivative, or if the modification ratio thereof is outside the range of 1:9 to 9:1. Furthermore, a combination of modified species that is preferably used includes styrene and unsaturated dibasic acid esters.

Furthermore, as another type of polyalkylene contained in the heat-fixable toner of the present invention together with the specific graft-modified polyalkylene having a relatively low melting point as a release agent, when the heat of fusion is 40 cal/g or less, It is possible to realize a heat-fixable toner having excellent offset resistance in a wide temperature range from low to high temperatures without causing the problems caused by dispersion as described above. If the heat of fusion exceeds 40 cal/g, the polyalkylene may not be sufficiently melted during the instantaneous heating time, especially during high-speed fixing, and the offset resistance of the toner may deteriorate. Also in fixing, so-called high temperature offset tends to occur.

The polyalkylene has a heat of fusion of 40c.
al/g or less and preferably 30 cal/g
Although it is preferable that the following is true and there is no particular limitation,
Polyalkylene having polypropylene as the main structural unit is preferred. Further, if necessary, the polyalkylene may be graft-modified with a specific modified species in the same manner as the above-mentioned graft-modified polyalkylene.

In the present invention, the molecular weight distribution of the mold release agent is G
It is measured by PC (gel permeation chromatography) under the following conditions.

(GPC measurement conditions) Equipment: GPC-150C (Waters) Column: Showdex KF-80M 2 series (Showa Denko) Temperature: 135°C Solvent: O-dichlorobenzene (0.1% ionol added) Flow rate :1.0ml/min Sample: Inject 0.4ml of 0.15% sample

[0038]
Measurement is performed under the above conditions, and a molecular weight calibration curve prepared using a monodisperse polystyrene standard sample is used to calculate the molecular weight of the sample.

The melting point and heat of fusion of the mold release agent according to the present invention are measured using DSC-7 (PerkinElmer) at a heating rate of 10° C./min according to ASTM (D3418).
-82) according to the temperature setting pattern.

The melting point of the mold release agent is the temperature at which the peak top of the highest melting temperature is located, as shown in FIG. The amount of heat (calories) to be measured is expressed as the weight of the test sample (g
).

In the present invention, a specific graft modification having a relatively low melting point has a heat of fusion of 40 cal/g with a polyalkylene.
The content of the following polyalkylenes in the toner is 0.5 to 10 parts by weight (more preferably 1 to 8 parts by weight) based on 100 parts by weight of the binder resin, and the content ratio of both polyalkylenes is grafted. The content ratio of modified polyalkylene is 1/10 to 9/1 of the total weight of polyalkylene contained.
The content is preferably 10 (more preferably 4/10 to 8/10).

If the total content of graft-modified polyalkylene and polyalkylene is less than 0.5 parts by weight based on 100 parts by weight of the binder resin, the addition effect will be small, and if it exceeds 10 parts by weight, it will have a particularly low melting point. However, when a binder resin having a low glass transition point is used, the blocking resistance of the toner decreases. If the content ratio of the graft-modified polyalkylene in the total polyalkylene is less than 1/10, the effect of adding the two types of release agents will be small, and the polyalkylene component in the toner will likely be unevenly distributed and liberated.
Furthermore, when the ratio exceeds 9/10, the effect of adding the two types of mold release agents will be reduced.

The graft-modified polyalkylene monomer used in the present invention includes ethylene, propylene,
Butene-1, Pentene-1, Hexene-1, Heptene-1
1. Straight chain α-olefins such as octene-1, nonene-1, deron-1, branched α-olefins with branched moieties at the end, and the positions of these unsaturated groups. These homopolymerized olefins or copolymerized olefins thereof are exemplified. In the present invention, weight average molecular weight/number average molecular weight (M
w/Mn) is 4.0 or less, and a fairly sharp molecular weight distribution is required, so it is recommended to use monomers with 5 or less carbon atoms or linear α-olefins as monomers. preferable.

[0044] The heat of fusion used in the present invention is 40 cal/
As the monomer of the polyalkylene having a weight of less than g, the same monomers as the above-mentioned graft-modified polyalkylene can be used. In addition, this material may be subjected to graft modification, other modification, modification, etc. or may remain unmodified as long as the heat of fusion is 40 cal/g or less.

[0045] More preferably, the polyalkylene contains 85% by weight or more of propylene structural units, from the viewpoint of offset resistance and blocking resistance when used as a toner.

Examples of styrene derivatives as modified species of the graft-modified polyalkylene used in the present invention include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethyl Styrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n
-hexylstyrene, p-n-octylstyrene, p-
n-nonylstyrene, p-n-decylstyrene, p-n
-dotecylstyrene, p-methoxysterene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, etc., and one or more of these may be used simultaneously. Among them, it is preferable to use styrene.

Examples of unsaturated fatty acid derivatives as another modified species of the graft-modified polyalkylene used in the present invention include methacrylic acid and methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, dodecyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate , methacrylates such as glycidyl methacrylate; for example, acrylic acid and methyl acrylate, ethyl acrylate, propyl acrylate,
n-butyl acrylate, isobutyl acrylate, n
-Octyl acrylate, lauryl acrylate, stearyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, 2-
Acrylates such as chloroethyl acrylate, 2-hydroxyethyl acrylate, cyclohexyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dibutylaminoethyl acrylate, 2ethoxy acrylate, 1,4-butanediol diacrylate; maleic acid; fumaric acid; itaconic acid; citraconic acid; and, for example, monoethyl maleate, diethyl maleate, monopropyl maleate, dipropyl maleate, monobutyl maleate, dibutyl maleate, di-2-ethylhexyl maleate, monoethyl fuma rate, diethyl fumarate, dibutyl fumarate, di-2
Ethylhexyl fumarate, monoethyl itaconate,
Examples include unsaturated dibasic acid esters such as diethyl itaconate, monoethyl citraconate, and diethyl citraconate, and one or two of these may be used.
More than one species can be used at the same time, and among them, unsaturated dibasic acid esters are preferred, and among these, dibutyl fumarate is particularly preferred.

[0048] As a method for graft modification, conventionally known methods can be used. For example, grafting can be achieved by heating and reacting the polyolefin with a styrene derivative monomer and an unsaturated fatty acid derivative monomer in a molten state or in a solvent, in the atmosphere or under pressure in the presence or absence of a radical initiator. A modified polyolefin is obtained. Grafting with a styrene derivative monomer and an unsaturated fatty acid derivative monomer may be performed simultaneously or individually.

[0049] As the initiator used for the grafting reaction,
For example, benzoyl peroxide, dichlorobenzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl perphenylacetate, cumin perpivalate, azobis-isobutyronitrile, dimethylazoisobutyrate,
Dicumyl peroxide and the like can be mentioned.

The binder resin of the toner used in the present invention includes styrene and its substituted substances such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, and vinyltoluene; acrylic acid; Methyl, ethyl acrylate, n-butyl acrylate,
Acrylic esters such as t-butyl acrylate; methyl methacrylate, ethyl methacrylate, n methacrylate
-butyl, t-butyl methacrylate, 2- methacrylate
Methacrylic acid esters such as ethylhexyl and cyclohexyl methacrylate; acrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; unsaturated carboxylic acids and unsaturated carboxylic acid esters such as maleic acid and maleic esters; ethylene, propylene, and ptadine Examples include olefins and diolefins. Monopolymers of these monomers, copolymers of two or more types of monomers, and polyesters, nonlinear polyesters, polyethers, polyamides, epoxy resins, polyamides, terpene resins, and phenolic resins alone Alternatively, they can be used in combination.

The monomers mentioned above can be polymerized in the presence of an initiator and in the presence or absence of a crosslinking agent.

As the initiator, di-t-butyl peroxide, benzoyl peroxide, lauroyl peroxide, t-butyl peroxylaurate, 2,2'
-Azobisisobutyronitrile, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,4-bis(t-butylperoxy)cyclohexane, 1,4-bis(t-butylperoxy)cyclohexane, -butylperoxycarbonyl)cyclohexane, 2,2-bis(t-butylperoxy)octane, n-butyl 4,4-bis(t-butylperoxy)valylate, 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-
3,2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di-t-butyldiperoxyisophthalate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl) Propane, di-t-butylperoxy α-methyl succinate, di-t-butylperoxydimethylglutarate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, 2,5 -dimethyl-2,5-di(t-butylperoxy)-hexane, diethylene glycol bis(t-butylperoxycarbonate), di-t-butylperoxyotrimethyladipate, tris(t-
butylperoxy)triazine, vinyltris(t-butylperoxy)silane, etc., and these can be used alone or in combination.

Next, as the crosslinking agent, it is possible to mainly use a compound having two or more polymerizable double bonds. For example, aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene: ethylene glycol diacrylate, triethylene glycol diacrylate,
Carboxylic acid esters having two double bonds such as bisphenol diethylene glycol diacrylate; divinyl compounds such as divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups may be used alone or as a mixture.

[0054] In the present invention, as the binder resin, styrene-acrylic acid ester copolymer, styrene-
Methacrylic acid ester copolymers and polyester resins are preferred in terms of appropriate affinity with the two types of polyalkylene waxes of the present invention, and crosslinked styrene-acrylic acid ester copolymers are preferred in terms of offset resistance and durability. , a crosslinked styrene-methacrylic acid ester copolymer, and a non-linear polyester resin are preferred, and in terms of achieving both offset resistance and low-temperature fixing properties, it is preferred that the molecular weight distribution of the resin has at least two or more peaks. For example, the above-mentioned resins include a mixed system of a low-molecular resin and a polymer resin, a mixed system of a low-molecular resin and a crosslinked resin, and a two-stage polymerization system using monomers constituting the resin.

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

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

Nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 1627/1983), basic dyes (for example, C.I. Basic Yellow
2 (C.I.41000), C.I. I. Basic
Yellow 3,C. I. Basic Red
1 (C.I.45160), C.I. I. Basic
Red 9 (C.I.42500), C.I. I. Bas
ic Violet 1 (C.I.42535),
C. I. Basic Violet 3 (C.I.
42555), C. I. Basic Violet
10 (C.I.45170), C.I. I. Basic
Violet 14 (C.I.42510), C.I.
I. Basic Blue 1 (C.I.4202
5), C. I. Basic Blue3 (C.I.5
1005), C. I. Basic Blue 5 (
C. I. 42140), C. I. Basic Blue
e 7 (C.I.42595), C. I. Bas
ic Blue 9 (C.I.52015),
C. I. BasicBlue 24 (C.I.5
2030), C. I. Basic Blue 25
(C.I.52025), C.I. I. Basic BL
ue 26 (C.I.44025), C. I. Bas
ic Green 1 (C.I.42040)
,C. I. Basic Green 4 (C.
I. 42000) and other basic dye lake pigments (lake-forming agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), C. I. Sovento Black
k3 (C.I.26150), Hansa Yellow G (
C. I. 11680), C. I. Mordlant
Black11,C. I. Pigmento Bl
ask1 etc.

Alternatively, for example, benzolmethyl-hexadecyl ammonium chloride, decyl-trimelyl ammonium chloride, dialkyltin compounds such as dibutyl and dioctyl, metal salts of higher fatty acids, inorganic fine powders such as glass, mica, and zinc oxide, EDTA, acetylacetone Polyamine resins such as metal complexes, vinyl polymers containing amino groups, condensation polymers containing amino groups, etc. In particular, from the viewpoint of dispersibility, nigrosine, metal salts of higher fatty acids, vinyl polymers having amino groups, etc. are preferable.

(2) The following substances can be used to control the negative chargeability of toner. Special Publication No. 41-20153,
Publication No. 42-27596, Publication No. 44-6397,
Examples include metal complex salts of monoazo dyes described in JP-A No. 45-26478 and the like.

[0060] Nitrohumic acid and its salts or C.I. I. 14
Dyes and pigments such as 645, Japanese Patent Publication No. 55-42752,
Special Publication No. Sho 58-41508, Special Publication No. Sho 58-7384
Zn of salicylic acid, naphthoic acid, dicarboxylic acid described in Japanese Patent Publication No. 59-7384, etc.
Metal complexes such as Al, Co, Cr, and Fe, sulfonated copper phthalocyanine pigments, nitrile groups, styrene oligomers with halogens introduced, chlorinated paraffins, etc. In particular, from the viewpoint of dispersibility, metal complexes of monoazo dyes, metal complexes of salicylic acid, alkylsalicylic acid, naphthoic acid, and dicarboxylic acid are preferred.

Good results can also be obtained with the toner of the present invention when additives are mixed therein as required. As an additive,
For example, lubricants such as Teflon, zinc stearate, and polyvinylidene fluoride are preferred, with polyvinylidene fluoride being preferred. Alternatively, abrasives such as cerium oxide, silicon carbide, and strontium titanate, among which strontium titanate is preferred. Alternatively, fluidity imparting agents such as colloidal silica and aluminum oxide, particularly hydrophobic colloidal silica, are preferred. It is also possible to use anti-caking agents; conductivity imparting agents such as carbon black, zinc oxide, antimony oxide, and tin oxide; and various polar waxes such as carnauba wax, amide wax, and higher alcohol wax. Further, a small amount of white fine particles and black fine particles of opposite polarity can be used as a developing property improving agent.

Furthermore, when the toner of the present invention is used as a two-component developer, it is mixed with carrier powder. In this case, the mixing ratio of toner and carrier powder is 0.1 to 50% by weight in terms of toner concentration, preferably 0.1 to 50% by weight.
The content is preferably 5 to 15% by weight, more preferably 3 to 5% by weight.

[0063] Known carriers can be used in the present invention, such as magnetic powders such as iron powder, ferrite powder, and nickel powder, glass beads, etc., and their surfaces coated with fluorine resin or Examples include those whose surface has been treated with acrylic resin or silicone resin.

Furthermore, the toner of the present invention can further contain a magnetic material and be used as a magnetic toner. In this case, the magnetic material also serves as a coloring agent. The magnetic materials contained in the magnetic toner of the present invention include iron oxides such as magnetite, hematite, and ferrite, or compounds of divalent metals and iron oxides; metals such as iron, cobalt, and nickel, or aluminum of these metals; Examples include alloys of metals such as cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

These ferromagnetic materials have an average particle size of 0.1 to 2
It is preferably about 0.1 to 0.5 μm. The amount of resin component contained in the toner is 100%
It is preferably about 20 to 200 parts by weight, particularly preferably 40 to 180 parts by weight, based on 100 parts by weight of the resin component.

Furthermore, a coloring agent may be added to the toner of the present invention, if necessary.

[0067] Any suitable pigment or dye can be used as the colorant used in the toner of the present invention. Toner colorants are well known, and examples include pigments such as carbon black, aniline black, acetylene black, naphthol yellow, Hansa yellow, rhodamine lake, alizarin lake, red iron, phthalocyanine blue, and indanthrene blue. These are used in a necessary and sufficient amount to maintain the optical density of the fixed image, and should be added in an amount of 0.1 to 20 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the binder resin. Also, for the same purpose,
Additionally, dyes are used. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, methine dyes, etc., and the amount added is preferably 0.1 to 20 parts by weight, preferably 0.3 to 3 parts by weight, per 100 parts by weight of the binder resin.

To prepare the toner for developing an electrostatic image according to the present invention, the specific polyalkylene and resin composition according to the present invention, a charge control agent, a magnetic material as necessary, a pigment or dye as a coloring agent, Additives, etc. are thoroughly mixed using a ball mill or other mixer, then heated rolls, kneaders, etc.
Pigments or dyes are dispersed or dissolved in the resin by melting, mixing, and kneading using a heat kneader such as an extruder to make the resins compatible with each other, and after cooling and solidifying, the particles are crushed and classified to obtain particles with an average particle size of 3 to 3. A toner of 20 μm can be obtained.

[0069]

[Examples] The present invention will be specifically explained below using Examples, but these are not intended to limit the invention in any way. Note that the parts in the following formulations are parts by weight.

Production Example of Graft-Modified Polyalkylene Production Example 1 400 parts of cumene was placed in a reactor, and the temperature was raised to around the reflux temperature (approximately 150°C) under a nitrogen atmosphere.
Add 100 parts of unmodified low molecular weight polyethylene at 0°C,
It took about 1 hour for complete dissolution. To this, 6 parts of styrene monomer, 6 parts of dibutyl coumarate, di-tert
-Butyl peroxide (hereinafter abbreviated as DTBPO)1.
0 part was added dropwise over about 4 hours. Furthermore, at 147℃, about 1
．． The reaction was allowed to proceed for 5 hours. Next, cumene was removed, and the mixture was further degassed by vacuum drying to completely remove remaining volatile components.

When the obtained graft-modified polyethylene was analyzed by proton (H1) and carbon (C13)-NMR (JEOL Ltd. 400MH, JUM EM-400 type was used), it was found that polyethylene wax 100
parts, styrene was 5.95 parts and dibutyl fumarate was 5.90 parts. Also, the number average molecular weight (Mn) by GPC is 1300, the weight average molecular weight (Mw) is 2.8
90, the weight average molecular weight/number average molecular weight (Mw/Mn) was 2.2, and the melting point by DSC was 115.2°C.

[0072] When the obtained graft-modified polyethylene was separated into three parts according to molecular weight by the above GPC and each of the obtained products was analyzed by the above NMR in the same manner as above, it was found that all of them were polyethylene wax. The amount of modification of styrene and dibutyl fumarate was within ±5%, consistent with the above results, and from this it was confirmed that almost all the polymer chains of polyethylene were graft modified.

Production Example 2 100 parts of unmodified low molecular weight polypropylene with a melting point of 125°C was placed in a reactor and melted at 160°C under a nitrogen atmosphere. Next, 10 parts of styrene monomer, 5 parts of dipentyl fumarate, and 1.0 part of DTBPO were gradually and continuously fed over about 4 hours, and then the reaction was continued by heating for about 1.5 hours. Vacuum drying was carried out in the molten state, sufficient deaeration treatment was performed to remove volatile components, and the mixture was then cooled.

The obtained graft-modified polypropylene was
When subjected to proton (H1) and carbon (C13) and -NMR in the same manner as in Production Example 1, it was found that styrene was 9.0 parts and dipentyl fumarate was 3.5 parts based on 100 parts of polypropylene.

In addition, the number average molecular weight (Mn) by GPC was 2,300, the weight average molecular weight (Mw) was 6,900, the weight average molecular weight/number average molecular weight (Mw/Mn) was 3.0, and the melting point was determined by DSC. was 142.5°C.

[0076] Similarly to Production Example 1, the protons (H
1) and carbon (C13)-NMR analysis results show that the amount of modification of styrene and dipentyl fumarate to polypropylene is ±10% of the above results before fractionation.
It was confirmed that most of the polymer chains of polypropylene were graft-modified.

Following the graft modification method of Production Example 1, graft-modified polyalkylenes as shown in Production Examples 3 to 6 in Table 1 were synthesized.

[0078]

[Table 1]

The amount of modification of the graft-modified polyalkylene in Table 1 is based on the proton (H1) and carbon (H1) in Production Example 1.
C13) - As a result of NMR analysis, the amount of modified species purchased was 9.
It was confirmed that the polymer had been modified by 0% by weight or more, and that most of the polymer chains had been evenly modified by grafting.

Example 1 Styrene-n-butyl acrylate copolymer 100 parts Magnetic powder EPT-500 (Magnetite manufactured by Toda Kogyo Co., Ltd.)
60 parts Salicylic acid metal complex 2 parts Graft modified polyethylene wax of Production Example-1
3 parts, low molecular weight propylene-ethylene copolymer wax (copolymerization weight ratio 90:10) 2 parts

The weight average molecular weight Mw of the above styrene-n-butyl acrylate copolymer is approximately 370,000, and moreover, it has two peaks in the gel permeation chromatogram. [However, in measuring the molecular weight distribution of the binder resin, the solvent was tetrahydrofuran (THF) under the GPC conditions.
), solvent temperature was 40°C, column configuration was Showa Denko's Showdex KF-801, KF-802, KF-8.
03, KF-804, KF-805, KF-806, K
A combination of 7 series of F-807 is adopted. ]

[0082] Also,
The heat of fusion of the above low molecular weight propylene-ethylene copolymer wax was 28 cal/g.

[0083] After premixing the above materials, they are melt-kneaded using a twin-screw extruder, cooled, pulverized using a pneumatic pulverizer, classified using an air classifier, and cut into fine powder (F powder). A black fine powder (M powder) with an average particle size of 11.5 μm was obtained.

At this time, when the ratio of the mold release agent content in the F powder to the mold release agent content in the M powder (F/M ratio) was measured using DSC-7, the F/M ratio was 1. 02, and it was confirmed that there was substantially no uneven distribution or release of the mold release agent.

Next, 0.5 part of hydrophobic colloidal silica was dry mixed with 100 parts of the M powder to obtain a one-component magnetic toner.

[0086] This toner was used in a Canon copier NP-6.
650 was used for evaluation. Even after 100,000 sheets of paper were passed, no filming fusion was observed on the developer carrier, photoreceptor, etc., and no image defects such as fog or a decrease in image density were observed.

During this period, the offset property was also good and no stains on the back surface were observed.

Furthermore, regarding offset property, NP-6
The temperature was set at 230° C., which is higher than the fixing temperature of the 650 machine, and 1,000 sheets were fed intermittently, but the offset property was good and no back stains were observed. Regarding fixability, NP-
The set temperature of the fixing device of 6650 was lowered by 20° C. to produce an image, and the image was rubbed back and forth 10 times with Silbon paper under a load of 50 g/cm 2 and evaluated based on the rate of decrease in solid image density. As a result, the concentration reduction rate was 6%, which was very good.

Example 2 A toner was obtained in the same manner as in Example 1 except that the binding binder resin was a non-linear polyester resin and the amount of the salicylic acid metal complex was changed to 3 parts.

However, the above polyester resin is polycondensed by containing 6 mol% of trimellitic anhydride as a network agent in all the constituent monomers, and there is almost no THF-insoluble content at 40°C. GP similar to example 1
The number average molecular weight Mn under C conditions was about 4,200, the weight average molecular weight Mw was about 12,000, and the acid value of the resin after synthesis was 15 KOHmg/g.

The F/M ratio measured in the same manner as in Example 1 was 1.01, confirming that there was substantially no uneven distribution of release agent.

[0092] This toner was used in the Canon Co., Ltd. copier NP-6.
650 was used for evaluation. Even after 100,000 sheets of paper were passed, no filming fusion was observed on the developer carrier, photoreceptor, etc., and no image defects such as fog or a decrease in image density were observed.

During this period, the offset property was also good and no stains on the back surface were observed.

Furthermore, regarding offset property, NP-6
The temperature was set at 230°C, which is higher than the set temperature of the fixing device of a 650 machine, and 1,000 sheets were fed intermittently, but the offset property was good and no back stains were observed. NP in terms of fixability
-6650, the set temperature of the fixing device was lowered by 20° C. to produce an image, and the image was rubbed back and forth 10 times with Silbon paper loaded with a load of 50 g/cm 2 to evaluate the rate of decrease in solid image density. As a result, the concentration reduction rate was 4%, which was very good.

Example 3 - Binder resin of Example 1 100 parts - Carbon black 5 parts - Nigrosine dye 2 parts - Graft modified polypropylene wax of Production Example-2
2 parts - Low molecular weight polypropylene wax (Sanyo Kasei Co., Ltd., Viscoll 660p) 3 parts The heat of fusion of the above low molecular weight polypropylene wax is 18
It was cal/g.

[0096] As an external additive for toner using the above material,
A toner was obtained in the same manner as in Example 1 except that 1.0 part of acyno-modified silicone oil-treated silica was used.

[0097]F/M measured in the same manner as in Example 1
The ratio was 1.03, and it was confirmed that there was substantially no uneven distribution of waxes.

[0098] The above toner and a resin autoferrite carrier were dry mixed (toner concentration 10%) to obtain a developer using the above toner as a starting agent and the above toner as a replenishing agent.

[0099] This developer was applied to the Canon Co., Ltd. copier FC-
2 was used for evaluation. Even after running 10,000 sheets, no filming adhesion was observed on the developer carrier or photoconductor, there was almost no spent on the carrier, and there were no image defects such as fog or a decrease in image density. There wasn't.

During this period, the offset property was also good and no stains on the back were observed.

Furthermore, regarding the offset property, the temperature was set at 220° C. which is higher than the set temperature of the fixing device of the FC2 machine, and 1000 sheets were fed intermittently, but the offset property was good and no stains on the back side were observed. Regarding fixing performance, the set temperature of the fixing device of the FC-2 machine was lowered by 30℃ to produce an image, and the fixing temperature was 50g/c.
The image was rubbed back and forth 10 times with Silbon paper under a load of m2, and evaluated based on the rate of decrease in solid image density. As a result, the concentration reduction rate was 6%, which was very good.

Example 4 Instead of the graft-modified polyethylene wax of Example-1, the graft-modified ethylene-propylene copolymer wax of Production Example 3 (ethylene-propylene copolymerization ratio 9:1) was used.
A toner was obtained in the same manner as in Example 1 except that 3 parts of the following were used.

The F/M ratio measured in the same manner as in Example 1 was 1.02, confirming that there was substantially no uneven distribution or release of waxes.

The above toner was evaluated using a laser beam printer LBP-8II manufactured by Canon Inc.

Even after 5,000 sheets were passed, no filming or fusion was observed on the developer carrier, photoreceptor, etc., and no image defects such as fog or a decrease in image density were observed.

[0106] Furthermore, regarding offset property, LBP-8
The temperature was set at 210° C., which is higher than the setting temperature of the fixing device of II, and 1,000 sheets were fed intermittently, but the offset property was good and no back stains were observed. Regarding fixability, L
The set temperature of the fixing device of BP-8II was lowered by 30℃ to produce an image, and 10
Evaluation was made based on back-and-forth rubbing and the rate of decrease in solid image density. As a result, the concentration reduction rate was 5%, which was very good.

Comparative Example 1 Evaluation was carried out in the same manner as in Example 1 except that the graft-modified polyethylene wax of Production Example 5 used in Example 1 was replaced with the graft-modified polyethylene wax of Production Example 5.

Comparative Example 2 Evaluation was conducted in the same manner as in Example 2 except that the graft-modified polyethylene wax of Production Example 4 used in Example 2 was replaced with the graft-modified polyethylene wax of Production Example 4.

Comparative Example 3 In place of the graft-modified ethylene-propylene copolymer wax of Production Example 3 used in Example 3, unmodified polypropylene wax (manufactured by Sanyo Chemical Co., Ltd., Vilcol 330P) was used.
Evaluation was conducted in the same manner as in Example 3 except that .

Comparative Example 4 Evaluation was carried out in the same manner as in Example 1 except that the graft-modified polyethylene wax of Production Example 6 used in Example 1 was replaced with the graft-modified polyethylene wax of Production Example 6.

Comparative Example 5 Low molecular weight propylene-ethylene copolymer wax used in Example 1 (copolymerization weight ratio 90:10), heat of fusion 28 c
The evaluation was carried out in the same manner as in Example 1, except that a low molecular weight polyethylene wax having a heat of fusion of 54 cal/g was used instead of 54 cal/g.

Binder resin 10 of Comparative Examples 1 to 5 above
The number of parts of mold release agent relative to 0 parts remains unchanged from the respective corresponding examples.

[0113] Table 2 shows the evaluation results for each.

[0114]

[Table 2]

[0115]

Effects of the Invention The heat fixable toner of the present invention has (A) as a release agent a number average molecular weight (Mn) of 3,000 or less, a weight average molecular weight (Mw) of 12,000 or less, and a weight Average molecular weight/number average molecular weight (Mw/Mn) is 4.
0 or less and a graft modified polyalkylene having a melting point of 60 to 150°C and (B) a heat of fusion of 40 cal/g
Since it has the following polyalkylene, it has excellent offset resistance and fixing properties, and furthermore, the release agent component is less unevenly distributed and released in the toner, and as a result, the photosensitive member,
It is possible to maintain stable image density without causing fusion filming on the developing member, etc., and to provide clear images without fog.

[Brief explanation of the drawing]

FIG. 1 is a DSC endothermic peak histogram for explaining the melting point and heat of fusion of a mold release agent according to the present invention.

Claims (3)

[Claims] 1. A heat-fixable toner having toner particles containing at least a binder resin and a release agent, wherein the release agent has at least (A) a number average molecular weight (Mn
) is 3,000 or less, the weight average molecular weight (Mw) is 12,000 or less, the weight average molecular weight/number average molecular weight (Mw/Mn) is 4.0 or less, and the melting point is 60 to 1
Graft modified polyalkylene A and (B) at 50°C
Polyalkylene B having a heat of fusion of 40 cal/g or less
A heat-fixing toner characterized by having the following properties. 2. In the graft-modified polyalkylene A, the graft-modified species is a styrene derivative and an unsaturated fatty acid derivative, and the amount of modification is 5 to 20 parts by weight per 100 parts by weight of the polyalkylene. 2. The heat fixable toner according to claim 1, wherein the weight ratio of the derivative to the unsaturated fatty acid derivative is 1:9 to 9:1. 3. The polyalkylene is polypropylene B
The heat-fixable toner according to claim 1, having as a main structural unit.