JPH06194874A - Binder resin containing releasing agent for toner and electrostatic charge image developing toner using that - Google Patents

Abstract

PURPOSE:To obtain a binder resin to produce a toner excellent in offset resistance, fluidity, electrification property and storage stability by adding crystalline acrylate polymer to polymerizable monomers when polymerizable monomers are polymerized. CONSTITUTION:In the matrix 1 of the binder resin, crystalline acrylate polymer having 5000-500000 weight average mol.wt. and/or crystalline methacrylate polymer are included as domains 2. Namely, when these polymers are added to polymerizable monomers, these polymers are dissolved and uniformly mixed in the polymerizable monomers in the initial stage of polymn. and further precipitate in the binder resin matrix 1 to form domains 2 having clear boundaries from the binder resin during polymn. Thereby, these polymers are easily dispersed in the binder resin with high dispersibility and uniformity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a releasing agent-containing toner binder resin and an electrostatic charge developing toner using the same. More specifically, the present invention relates to electrophotography,
The present invention relates to a release agent-containing toner binder resin used for producing a toner for developing an electrostatic latent image formed in an electrostatic recording method, an electrostatic printing method or the like.

[0002]

2. Description of the Related Art In electrophotography, a heating roller fixing method is widely used as a method for permanently fixing a toner image formed on an image receiving sheet on the sheet. In this method, since the surface of the heating roller and the image surface of the sheet to be fixed are in pressure contact with each other, thermal efficiency at the time of thermally welding the toner image to the sheet to be fixed is excellent, and quick fixing can be performed. Very suitable. However, although the method has the advantages as described above, it has a serious problem of occurrence of an offset phenomenon. This is a phenomenon in which part of the toner forming an image during fixing adheres to the surface of the heat roller, and this transfers to the next sheet to be fixed and stains the image.

As a measure to prevent the offset phenomenon,
In addition to selecting the roller material, apply silicone oil or the like to the heat roller as a release agent, or include a low softening point wax such as low molecular weight polypropylene, low molecular weight polyethylene or paraffin wax in the toner as a release agent. Measures are taken such as widening the molecular weight distribution in order to increase the cohesive force between the melted toners.

In recent years, there has been a demand for low power consumption and high-speed fixing in the heating roller fixing method, and it is said that lowering the Tg of the toner binder resin and lowering the melt viscosity are effective. There is. However, the decrease in Tg of the toner binder resin results in a decrease in storage stability such as blocking,
Further, it causes a decrease in the fluidity of the toner, and the low melt viscosity makes the offset phenomenon more remarkable.

In order to solve these problems, for example,
Japanese Patent Application Laid-Open No. 2-5071 discloses that a crystalline acrylic acid ester or a crystalline methacrylic acid oligomer containing a monomer such as stearyl acrylate or stearyl methacrylate as a constituent unit is added to a toner composition. Proposed. US Patent No. 4
No. 514487 similarly discloses a toner obtained by polymerizing a polymerizable monomer that constitutes a binder resin in the presence of an oligomer of stearyl acrylate or an oligomer of stearyl acrylate-containing copolymer.

Certainly, such an oligomer such as a crystalline acrylic acid ester or a crystalline methacrylic acid ester has a low melting point and a low melt viscosity, so that it is possible to lower the minimum fixing temperature of the obtained toner. . However, at the time of toner production, when these oligomers are added to the toner binder resin and melt-kneaded, there is a large difference in melt viscosity between the toner binder resin and the oligomer. The dispersion of the oligomer becomes insufficient, and the domain of the oligomer existing in the matrix of the toner binder resin becomes relatively large. As described above, when the dispersion domain of the oligomer in the toner particles is large, the offset resistance is not sufficiently exhibited due to the presence of the oligomer, and the fluidity and the blocking resistance are deteriorated. However, problems such as a slow rise of charging of the toner occur as the fluidity decreases.

[0007]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a novel release agent-containing toner binder resin and an electrostatic charge developing toner using the same. Another object of the present invention is to provide a method for producing a release agent-containing toner binder resin used for obtaining an electrostatic charge development toner excellent in offset resistance, fluidity, chargeability and storage stability. To do.

[0008]

[Means for Solving the Problems]
Weight average molecular weight of 5,000 to 5,000 in the binder resin matrix.
The present invention is achieved by a release agent-containing toner binder resin characterized in that 500000 crystalline acrylic acid ester-based polymers and / or crystalline methacrylic acid ester-based polymers are present in the form of domains. Further, a polymer having a sea-island-sea structure in which the binder resin exists in the domains of the crystalline acrylic acid ester-based polymer and / or the crystalline methacrylic acid ester-based polymer has a higher dispersion control. It is a toner binder resin containing a release agent.

In the toner binder resin containing the releasing agent of the present invention, the crystalline acrylic ester polymer and / or
Alternatively, the crystalline methacrylic acid ester-based polymer preferably has a melt viscosity of 50 cP or more at 140 ° C. Further, the binder resin is preferably a styrene polymer or a styrene / acrylic polymer.

The above-mentioned various purposes are to add the above-mentioned crystalline acrylic acid ester-based polymer and / or crystalline methacrylic acid ester-based polymer to a polymerizable monomer that forms a binder resin by polymerization, and to keep the temperature below the polymerization temperature. It can also be achieved by a method for producing a toner binder resin containing a release agent, which comprises dissolving the crystalline polymer at a temperature and performing polymerization by solution polymerization, bulk polymerization, suspension polymerization or the like.

Further, the above-mentioned various objects include that the release agent-containing toner binder resin or the release agent-containing toner binder resin having a sea-island-sea structure is used as at least a part of the binder resin component. It is also achieved by the characteristic electrostatic charge developing toner.

In the toner for electrostatic charge development of the present invention, the content of the crystalline acrylic acid ester polymer and / or the crystalline methacrylic acid ester polymer in the toner composition is 0.5 to 30% by weight. desirable.

[0013]

When the polymerizable monomer is polymerized by bulk polymerization or suspension polymerization, the release agent-containing toner binder resin of the present invention contains a crystalline acrylic acid ester-based polymer and a polymerizable acrylic ester-based polymer in the polymerizable monomer. And / or is obtained by adding a crystalline methacrylic acid ester polymer. The crystalline acrylic acid ester-based polymer and /
Alternatively, the crystalline methacrylic acid ester-based polymer is dissolved in a polymerizable monomer that forms a binder resin by polymerization, for example, a styrene-based monomer, a styrene / acrylic-based monomer or the like in the polymerization temperature range or a temperature range lower than that, Further, it has substantially no compatibility with the binder resin after the polymerization, and particularly when the degree of polymerization of the binder resin exceeds a predetermined level, it is rapidly precipitated. For this reason, when these crystalline acrylic acid ester-based polymers and / or crystalline methacrylic acid ester-based polymers are added to the polymerizable monomer, they are dissolved in the polymerizable monomer at the start of polymerization and uniformly mixed. Are dispersed in the matrix of the binder resin as the polymerization progresses to form domains having clear boundaries with the binder resin, making it easy to disperse in the binder resin and its dispersibility and uniformity. Will be high. The release agent-containing toner binder resin thus obtained has the crystalline acrylic ester polymer and / or crystalline methacrylic ester in the matrix 1 of the binder resin as shown in FIG. It has a structure in which domain 2 of the polymer is formed. Depending on the polymerization method, as shown in FIG. 2, the crystalline acrylic acid ester-based polymer and / or the crystalline methacrylic acid ester-based resin is further included in the matrix 1 of the binder resin, and the binder resin is included in the domain 3 in the domain 2. To have a sea-island-sea structure. Although the mechanism by which such a sea-island-sea structure is formed is not clear,
In any case, the dispersibility of the crystalline acrylic acid ester-based polymer and / or the crystalline methacrylic acid ester-based polymer in the release agent-containing toner binder resin according to the present invention is good.

The electrostatic charge developing toner according to the present invention comprises the toner binder resin containing the releasing agent as described above as at least a part of the binder resin component. The release agent-containing toner binder resin as described above is melt-kneaded with a colorant and / or a magnetic material, and optionally other additives to be added, cooled, pulverized, and classified to obtain a toner. In the charge developing toner, the crystalline acrylic acid ester-based polymer and / or the crystalline methacrylic acid ester-based polymer dispersedly contained in the toner binder resin is bound even after the melt-kneading process. It is one in which fine domains are uniformly dispersed in a resin matrix.

The crystalline acrylic acid ester-based polymer and / or crystalline methacrylic acid ester-based polymer used in the present invention has a relatively low melting point and also has a long-chain alkyl group, so that it is high. It has releasability, and the offset resistance of the toner becomes good. Further, as described above, in the toner particles for electrostatic charge development according to the present invention, the crystalline acrylic acid ester-based polymer and / or the crystalline methacrylic acid ester-based polymer has good dispersibility and its domain is sufficiently small. Therefore, there is almost no influence of the crystalline acrylic acid ester-based polymer and / or the crystalline methacrylic acid ester-based polymer on the fluidity of the toner particles,
The fluidity is good, and thus the rise of charging is good.

Hereinafter, the present invention will be described in more detail based on the embodiments. Examples of the crystalline acrylic acid ester polymer and / or the crystalline methacrylic acid ester polymer used in the release agent-containing toner binder resin of the present invention include, for example, a monomer represented by the following general formula (I) as a constitutional unit. Contained, preferably 100 to 50 mol%, more preferably 100 to 60 mol%, and further preferably 100 to
The thing containing 70 mol% is mentioned.

[0017]

[Chemical 1]

Specific examples of the monomer represented by the general formula (I) include stearyl acrylate, stearyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, heptadecyl acrylate, heptadecyl methacrylate, nonadecyl acrylate. , Nonadecyl methacrylate, aralkyl acrylate, aralkyl methacrylate, behenyl acrylate, behenyl methacrylate, pentasil acrylate, pentasil methacrylate, heptasil acrylate, heptacil methacrylate, nonacyl acrylate, nonacyl methacrylate, doteracyl acrylate, methacryl Acid doteriacil. Of these, particularly preferred are stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate,
Examples include pentasil acrylate and pentasil methacrylate.

Examples of the monomer copolymerizable with the monomer represented by the general formula (I) include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and α. -Methylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, p
-Styrene-based monomers such as chlorostyrene; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, α-chloro. Methyl acrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid n-
Acrylic ester-based or amorphous methacrylic ester-based monomers such as butyl, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate; acrylonitrile, methacrylonitrile, acrylamide, etc. Acrylic acid type monomers; vinyl ether type monomers such as vinyl methyl ether, vinyl isobutyl ether, vinyl ethyl ether; vinyl ketone type monomers such as vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N
-N-vinyl compound-based monomers such as vinylindole and N-vinylpyrrolidone; and various vinyl-based monomers such as ethylene, propylene, butylene, vinyl chloride and vinyl acetate.

The weight average molecular weight of such crystalline acrylic acid ester polymer and / or crystalline methacrylic acid ester polymer is 5,000 to 50.
0000, more preferably 15000 to 450,000,
More preferably, it is about 35,000 to 400,000.

When the so-called oligomer having a weight average molecular weight of less than 5000 has a low melting point and a low melt viscosity, there is a large difference in melt viscosity between the toner binder resin and the oligomer. When the above-mentioned oligomer is simply melt-kneaded into the toner binder resin, its dispersion becomes insufficient. However, as will be described later, in the polymerizable monomer that forms the toner binder resin, When the oligomer is added and dissolved and then polymerized, the domain of the oligomer present in the matrix of the binder resin is sufficiently small, and the domain forms a sea-island-sea structure depending on the polymerization method. Also shows good dispersibility. When a toner for electrostatic charge development is produced by a pulverizing method using such a binder resin containing an oligomer,
Even in the toner particles, the oligomer can maintain a finely dispersed state in the binder resin. However, in order to obtain a better dispersibility of the crystalline acrylic acid ester polymer and / or the crystalline methacrylic acid ester polymer in the toner particles, the polymerization average molecular weight is desired to be 5000 or more. On the other hand, if the weight average molecular weight exceeds 500000, the melt viscosity becomes too high and the offset resistance is likely to be low.

The melt viscosity of the crystalline acrylic acid ester polymer and / or crystalline methacrylic acid ester polymer at 140 ° C. is 50 cP or more, more preferably 70 to 50,000 cP or more, and most preferably 100 to 40,000 cP. Is desirable. In addition,
The melt viscosity is the viscosity at 140 ° C. measured by a B-type viscometer.

The binder resin as a matrix used in the toner binder resin containing the releasing agent of the present invention is as follows:
The polymerizable monomer is capable of dissolving the crystalline acrylic acid ester-based polymer and / or the crystalline methacrylic acid ester-based polymer as described above in the polymerization temperature range, and substantially does not dissolve them in the polymer state after polymerization. It is desirable that they are not compatible with each other,
A homopolymer or a copolymer of the vinyl monomer as described above, particularly a styrene resin or a styrene / acrylic resin is preferable.

The release agent-containing toner binder resin having a domain structure in the binder resin matrix or the release agent-containing toner binder resin having a sea-island-sea fine structure according to the present invention is polymerized to form the binder. In the polymerizable monomer forming the resin, the crystalline acrylic acid ester-based polymer and / or crystalline methacrylic acid ester-based polymer is added, the crystalline polymer is dissolved at a temperature not higher than the polymerization temperature, It is obtained by carrying out polymerization. As the polymerization method, methods such as bulk polymerization and suspension polymerization are desirable. In solution polymerization, there is a possibility that the above-mentioned fine structure may not be obtained depending on the type and amount of the solvent.

For example, when the release agent-containing toner binder resin of the present invention is to be obtained by the suspension polymerization method, the above-mentioned polymerizable monomer forming the binder resin is added to the above-mentioned polymerizable monomer. A crystalline acrylic acid ester-based polymer and / or a crystalline methacrylic acid ester-based polymer is added, and the mixture is heated to a polymerization initiation temperature or a temperature lower than that, if necessary, to give a crystalline acrylic acid ester-based polymer and / or a crystalline A methacrylic acid ester-based polymer is dissolved in the polymerizable monomer, and then the mixture is suspended in an aqueous medium to carry out polymerization. The suspension polymerization reaction is usually 30 to 15
0.5-at a temperature in the range of 0 ° C, preferably 50-90 ° C.
It is carried out for 30 hours, preferably 2 to 10 hours.

As the polymerization initiator used for the polymerization, oil-soluble peroxide type or azo type initiators usually used in suspension polymerization can be used. As an example, for example, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide,
Orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide,
Peroxide initiators such as t-butyl hydroperoxide and diisopropylbenzene hydroperoxide,
2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2
′ -Azobis-2,3-dimethylbutyronitrile, 2,
2'-azobis- (2-methylbutyronitrile), 2,
2'-azobis-2,3,3-trimethylbutyronitrile, 2,2'-azobis-2-isopropylbutyronitrile, 1,1'-azobis- (cyclohexane-1-carbonitrile), 2,2 ' -Azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile, 4,4'-azobis-
4-Cyanovaleric acid, dimethyl-2,2'-azobisisobutyrate and the like are available. The polymerization initiator is contained in an amount of 0.01 to 20% by weight, and particularly 0.1 to 1 with respect to the polymerizable monomer.
It is preferably used in the range of 0% by weight.

As the stabilizer used in suspension polymerization, polyvinyl alcohol, starch, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose,
Water-soluble polymers such as sodium polyacrylate and sodium polymethacrylate; surfactants such as anionic surfactants, cationic surfactants, zwitterionic surfactants, nonionic surfactants, etc., and sulfuric acid barium,
Calcium sulfate, barium carbonate, magnesium carbonate, calcium phosphate, talc, clay, diatomaceous earth, metal oxide powder and the like are used.

Examples of the anionic surfactant include fatty acid salts such as sodium oleate and potassium castor oil, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylnaphthalene. Examples thereof include sulfonate, alkane sulfonate, dialkyl sulfosuccinate, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxyethylene alkylphenyl ether sulfate ester salt, polyoxyethylene alkyl sulfate ester salt and the like.

As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine; glycerin fatty acid ester, There are oxyethylene-oxypropylene block polymers and the like.

Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.

Examples of the zwitterionic surfactant include lauryl dimethylamine oxide. When the polymerizable monomer component is thus suspension polymerized to obtain resin fine particles, a known additive such as a chain transfer agent for adjusting the degree of polymerization may be appropriately added.

After the suspension polymerization is completed, the polymerized toner particles present in the aqueous medium are separated from the aqueous medium and dried.
When separating from the aqueous medium, an aggregating agent may be used to perform an aggregating treatment, if necessary.

Examples of the aggregating agent include inorganic acids such as hydrochloric acid, organic acids such as acetic acid, these acids and alkaline earth metals,
Known coagulant of water-soluble metal salt composed of aluminum or the like,
Alternatively, an organic solvent which is a non-solvent for the water-insoluble fine particles and / or the binder resin as described in Japanese Patent Application No. 3-199146 can be used.

When the release agent-containing toner binder resin of the present invention is to be obtained by a bulk polymerization method, the above-mentioned crystal is added to the polymerizable monomer forming the binder resin after polymerization as described above. Crystalline acrylic acid ester-based polymer and / or crystalline methacrylic acid ester-based polymer is added, and the mixture is heated to a polymerization initiation temperature or a temperature lower than that as necessary to give a crystalline acrylic acid ester-based polymer and / or crystalline methacrylic acid polymer. Polymerization is carried out after the acid ester polymer is dissolved in the polymerizable monomer.

The bulk polymerization reaction is usually 120 to 250 ° C.
Preferably 0.1 to 2 at a temperature in the range of 140 to 200 ° C
It is carried out for 0 hours, preferably for 0.5 to 10 hours. The polymerization rate is 30 to 100%, more preferably 5
It is preferably about 0 to 100%.

Polymerization initiators used as necessary during polymerization include the above-mentioned oil-soluble peroxide type and azo type initiators, and known additives such as chain transfer agents are appropriately added. You may.

The toner for electrostatic charge development according to the present invention contains a release agent having a desired domain structure, which is blended with the crystalline acrylic acid ester polymer and / or the crystalline methacrylic acid ester polymer thus obtained. A toner binder resin is used as at least a part of the binder resin component, and together with a colorant and / or a magnetic material, and other additives such as a charge control agent which is optionally blended inside the toner particles, Melt kneading, cooling, crushing,
It can be obtained by classifying.

The melt-kneading temperature in such a pulverizing method varies depending on the kind of the binder resin used and the like, but is, for example, 100 to 200 ° C., more preferably 1
About 20 to 180 ° C. is suitable, and various kneaders, extruders and the like can be used. Also,
The pulverization can also be performed using a known pulverizer such as a cutter mill or a jet mill. The average particle size of the toner is, for example, 3 to 15 μm, preferably 5 by classification.
It is about 12 μm. It is also possible to subject the toner obtained by such a pulverization method to a spheroidizing treatment such as a heating treatment. Finally, the toner particles thus obtained are subjected to, for example, an adhesion treatment of an additive such as a fluidizing agent which is added to the surface portion of the toner particles, if necessary.

In the toner for electrostatic charge development of the present invention, the above-mentioned crystalline acrylic acid ester polymer and / or crystalline methacrylic acid ester-based polymer is contained in the toner composition in an amount of 0.5 to 30% by weight, and more preferably 0.5 to 30% by weight. Is 1
˜15% by weight. If the blending amount is less than 0.5% by weight, it is difficult to sufficiently improve the offset resistance of the obtained toner, while the blending amount is 30% by weight.
If it exceeds the range, there is a great possibility that the heat fixing property, the fluidity, the charging rise of the toner and the like are deteriorated.

In the electrostatic charge developing toner of the present invention, as the binder resin which can be blended with the release agent-containing toner binder resin, various resins conventionally used in such toner can be used. The homopolymers or copolymers of the above-mentioned polymerizable monomers, polyester resins and the like are preferable, and particularly styrene resins or styrene /
Acrylic resin is desirable. The blending amount is not particularly limited as long as the blending amount of the crystalline acrylic acid ester polymer and / or the crystalline methacrylic acid ester polymer is within the above-mentioned predetermined range.

The colorant used in the toner for electrostatic charge development of the present invention may be any of dyes and pigments well known to those skilled in the art, and may be organic or inorganic. Specific examples thereof include carbon black, nigrosine dye, aniline blue, chalco oil blue, chrome yellow, ultramarine blue,
DuPont Oil Red, Quinoline Yellow, Methylene Blue Chloride, Phthalocyanine Blue, Malachide Green Oxalate, Lamp Black, Oil Black,
Azo oil black, rose bengal, etc. are mentioned, and if necessary, two or more of them may be used in combination.

The magnetic powder used to obtain the magnetic toner is, for example, powder of a ferromagnetic metal such as iron, cobalt, nickel, magnetite, hematite, or the like.
Examples thereof include powders of metal compounds such as ferrite. Since these magnetic powders also function as colorants, they may be used alone, but of course they can be used in combination with the colorants described above.

The amount of the colorant and / or the magnetic powder added may be in a wide range depending on the type of the colorant and / or magnetic powder used and the type of electrostatic charge developing toner to be obtained. , Preferably 1 to 70 in the toner composition
%, More preferably 1 to 60% by weight.

In the electrostatic charge developing toner of the present invention,
Further, conventionally well-known toner additives such as a charge control agent, a fluidizing agent, and waxes can be added to the inside or outside surface portion of the toner particles, if necessary.

Examples of the charge control agent include nigrosine, monoazo dye, zinc, hexadecyl succinate,
Alkyl ester or alkyl amide of naphthoic acid,
Examples thereof include nitrohumic acid, N, N-tetramethyldiamine benzophenone, N, N-tetramethylbenzidine, triazine, and metal salicylate complex.

Examples of the fluidizing agent include silica, aluminum oxide, titanium oxide, magnesium fluoride and the like.

As the waxes, the cyclic method softening point of 80 to
Polymers at 180 ° C., high melting point paraffin wax having a melting point of 60 to 70 ° C., fatty acid esters, and partially saponified products thereof, higher fatty acids, fatty acid metals, higher alcohols, and the like, among which polyethylene, polypropylene Polyolefin waxes such as However, when such waxes are added to the toner for electrostatic charge development of the present invention, if the amount of the waxes added is large, the fluidity of the toner and the characteristics such as charging rise may be greatly impaired. The amount of addition is 100% by weight or less, more preferably 50% by weight or less, based on the amount of the crystalline acrylic acid ester-based polymer and / or crystalline methacrylic acid ester-based polymer blended in the toner. desirable.

[0048]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, all "parts" and "%" are by weight unless otherwise specified.

Example 1 A 0.4% aqueous solution of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) 130.2 was placed in a flask equipped with a stirrer, an inert gas introducing tube, a reflux condenser and a thermometer.
The department was set up. 80 parts of styrene, n-acrylic acid
To a polymerizable monomer component consisting of 20 parts of butyl and 0.2 part of divinylbenzene, stearyl polyacrylate (melting point (DS
C method peak temperature) 53.8 ° C., Mw = 11400, Mn
= 5600, melt viscosity (140 ° C.) 532 cP) 6 parts,
A mixture in which 1 part of azoisobutyronitrile and 2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) were dissolved was added and stirred to obtain a uniform suspension.

Next, nitrogen gas was heated to 80 ° C. while blowing nitrogen gas, and the polymerization reaction was carried out by continuing stirring at this temperature for 5 hours, followed by cooling, washing, dehydration, and drying processes, and then Tg = 65 ° C. Mw = 158000, Mn = 4100
A toner binder resin (1) for electrostatic charge development containing the above stearyl polyacrylate was obtained.

The disperse state of the stearyl polyacrylate in the electrostatic charge developing toner binder resin (1) was observed by using a transmission electron microscope (TEM) photograph. As shown in FIG. The crystalline stearyl acrylate domain 2 is formed in the binder resin matrix 1,
Furthermore, the dispersed state of the sea-island-sea structure in which the domain 2 includes the domain 3 of the binder resin was confirmed.

Example 2 A flask similar to that of Example 1 was charged with a polymerizable monomer consisting of 80 parts of styrene and 20 parts of n-butyl acrylate and stearyl polymethacrylate (melting point (peak temperature by DSC method) 37.
5 parts of 8 ° C., Mw = 256000, Mn = 19900 and melt viscosity (140 ° C.) of 6800 cP) were charged and heated to 140 ° C. while blowing nitrogen, and stirring was continued at this temperature for 4 hours to carry out bulk polymerization. The polymerization rate at this time is 81%
Met.

The residual monomer of this polymer was heated to a temperature of 140.
C., removed under vacuum of -730 mmHg, Tg = 63.
A toner binder resin (2) for electrostatic charge development containing poly (stearyl methacrylate) at 2 ° C., Mw = 280,000 and Mn = 14,700 was obtained.

The disperse state of poly (stearyl methacrylate) in this electrostatic charge developing toner binder resin (2) was confirmed by TEM photography, and the same dispersion of sea-island-sea structure as in Example 1 was observed. Was given.

Example 3 Toner binder resin for electrostatic charge development (1) 100 parts Carbon black 10 parts (MA-600, manufactured by Mitsubishi Kasei Co., Ltd.) Spylon Black TRH 2 parts (Hodogaya Chemical Co., Ltd.) 7.) The above mixture was kneaded by a Labo Plastomill at 160 ° C. for 15 minutes, coarsely crushed to 1 mm or less, further finely pulverized by a jet mill, and then classified by an air classifier to obtain an average particle diameter of 7.
Toner raw powder (1) for electrostatic charge development having a size of 5 μm was obtained.

Raw toner powder for electrostatic charge development (1) 100
0.3 part of hydrophobic Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) was added to parts by weight and uniformly dispersed to obtain a toner (1) for electrostatic charge development.

The electrostatic charge developing toner (1) was subjected to an image output test with a commercially available copying machine Leodry 7610 (manufactured by Toshiba Corp.), and as a result, no offset phenomenon was observed and a stable and good image was obtained. Was obtained.

The disperse state of the stearyl polyacrylate in the toner (1) for electrostatic charge development was confirmed by a TEM photograph. As a result, very fine domains having a size of about 0.5 μm or less were formed and toner particles were formed. It was confirmed that they were uniformly dispersed in the inside.

Example 4 Toner Binder Resin for Electrostatic Development (2) 85 parts Low molecular weight styrene / n-butyl acrylate copolymer 20 parts (Tg = 68 ° C., Mw = 11000, Mn = 2300) Mapico BL-200 60 parts (manufactured by Titanium Industry Co., Ltd.) Bontron E-82 2.5 parts (manufactured by Orient Chemical Industry Co., Ltd.) The above mixture was kneaded with a Labo Plastomill at 160 ° C. for 10 minutes and then crushed to 1 mm or less After fine pulverization with a jet mill, classification with an air classifier, average particle size 1
Toner raw powder (2) for electrostatic charge development having a particle size of 1.0 μm was obtained.

This electrostatic charge developing toner raw powder (2) 100
0.4 part of hydrophobic Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) was added to parts by weight and uniformly dispersed to obtain a toner (2) for electrostatic charge development.

The electrostatic charge developing toner (2) was subjected to an image output test with a commercially available copying machine NP-5000 (manufactured by Canon Inc.). As a result, no offset phenomenon was observed and a stable and good image was obtained. was gotten.

The dispersion state of poly (stearyl methacrylate) in this electrostatic charge developing toner (2) was confirmed by the same method as in Example 1. The dispersion state was the same as in Example 1. Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that the stearyl polyacrylate was removed, and after the steps of cooling, washing, dehydration and drying, Tg 65 ° C., Mw = 165000, Mn = 4.
000 comparative electrostatic charge developing toner binder resins (a) were obtained.

Comparative electrostatic charge developing toner binder resin (a) 100 parts Carbon black 10 parts (MA-600, manufactured by Mitsubishi Kasei Co., Ltd.) Spiron Black TRH 3 parts (Hodogaya Chemical Co., Ltd.) The above mixture was kneaded in the same manner as in Example 3, further pulverized and classified. As a result, the average particle diameter is 8.0 μm.
Comparative electrostatic charge developing toner raw powder (a) was obtained. To 100 parts by weight of this comparative electrostatic charge developing toner raw powder (a), 0.3 part of hydrophobic Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) was added and uniformly dispersed to obtain a comparative electrostatic charge developing toner (a). .

The comparative electrostatic charge developing toner (a) was subjected to an image output test with a commercially available copying machine Leodry 7610 (manufactured by Toshiba Corp.). As a result, an offset occurred from the second sheet and the toner was continuously excellent. I couldn't get the image.

Comparative Example 2 Comparative electrostatic charge developing toner binder resin (a) 100 parts Low molecular weight polypropylene wax 5 parts (Viscor 660P, Sanyo Chemical Industry Co., Ltd.) Carbon black 10 parts (MA-600, Mitsubishi Kasei) Industrial Co., Ltd. Spiron Black TRH 2 parts (Hodogaya Chemical Co., Ltd.) Using the above mixture in the same manner as in Example 3, a comparative electrostatic charge developing toner stock having an average particle diameter of 7.8 μm is prepared. A powder (b) was obtained.

This comparative electrostatic charge developing toner raw powder (b)
0.3 part of hydrophobic Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) was added to 100 parts by weight and uniformly dispersed to obtain a comparative electrostatic charge developing toner (b).

The comparative electrostatic charge developing toner (a) was subjected to an image output test using a commercially available copying machine Leodry 7610 (manufactured by Toshiba Corp.). As a result, no offset phenomenon was observed, but the image density was stable. No good image could not be obtained continuously.

When the dispersion state of the wax in this comparative electrostatic charge developing toner (b) was confirmed by a TEM photograph, the wax domain was large and the dispersion was insufficient.

[0069]

As described above, the toner binder resin containing the releasing agent of the present invention has a weight average molecular weight of 5,000 to 50,000.
No. 0 crystalline acrylic acid ester-based polymer and / or crystalline methacrylic acid ester-based polymer, and the crystalline polymer is present in the matrix of the binder resin in the form of domains. In the toner for electrostatic charge development obtained by using this release agent-containing toner binder resin, the crystalline polymer forms fine domains and becomes uniformly and sufficiently dispersed. It has offset resistance, good fluidity, storage stability and charging characteristics.

[Brief description of drawings]

FIG. 1 is a cross-sectional view schematically showing a fine structure of an embodiment of a toner binder resin containing a release agent of the present invention,

FIG. 1 is a sectional view schematically showing a fine structure of another embodiment of a release agent-containing toner binder resin of the present invention.

[Explanation of symbols]

1 ... Binder resin matrix, 2 ... Domain of crystalline acrylic acid ester-based polymer and / or crystalline methacrylic acid ester-based polymer, 3 ... Domain of binder resin.

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[Procedure amendment]

[Submission date] January 17, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 is a cross-sectional view schematically showing a fine structure of an embodiment of a toner binder resin containing a release agent of the present invention,

FIG. 2 is a cross-sectional view schematically showing a fine structure of another embodiment of the release agent-containing toner binder resin of the present invention.

[Description of Reference Signs] 1 ... Binder resin matrix, 2 ... Domain of crystalline acrylic acid ester-based polymer and / or crystalline methacrylic acid ester-based polymer, 3 ... Domain of binder resin.

Claims (7)

[Claims] 1. A separation characterized in that a crystalline acrylic acid ester-based polymer and / or a crystalline methacrylic acid ester-based polymer having a weight average molecular weight of 5,000 to 500,000 is present in the binder resin matrix in the form of domains. Toner binder resin containing mold agent. 2. The toner binder resin containing a release agent according to claim 1, wherein the crystalline acrylic acid ester-based polymer and / or the crystalline methacrylic acid ester-based polymer has a melt viscosity of 50 cP or more at 140 ° C. 3. A sea in which domains of a crystalline acrylic acid ester-based polymer and / or a crystalline methacrylic acid ester-based polymer are present in a matrix of a binder resin, and the binder resin is present in the domains to form domains. The release agent-containing toner binder resin according to claim 1, having an island-sea structure. 4. The toner binder resin containing a release agent according to claim 1, wherein the binder resin is a styrene polymer or a styrene / acrylic polymer. 5. The crystalline acrylic acid ester-based polymer and / or the crystalline methacrylic acid ester-based polymer is added to a polymerizable monomer that forms a binder resin by polymerization, and the temperature is lower than the polymerization temperature. A method for producing a toner binder resin containing a release agent, which comprises dissolving a crystalline polymer and performing polymerization. 6. A toner for electrostatic charge development, wherein the release agent-containing toner binder resin according to claim 1 is used as at least a part of a binder resin component. 7. The content of the crystalline acrylic acid ester-based polymer and / or the crystalline methacrylic acid ester-based polymer in the toner composition is 0.5 to 30% by weight.
7. The toner for electrostatic charge development according to claim 6, which is