JPH04366176A - Toner for thermal fixation and resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition which can give a thermal fixation toner of low-temperature fixation, excellent in storage stability, flow and chargeability and desirable for full color copy. CONSTITUTION:A resin composition formed from domain particles and a matrix, wherein the mean particle size of the domain particles dispersed in the matrix is 5mum or below, the resin P1 constituting the domain particles is an acid- modified polymer prepared by effective an addition reaction of a polymer of a vinyl monomer with an acid and has a glass transmission point Tg1 of 0-60 deg.C, the resin P2 constituting the matrix is a polymer synthesized from a vinyl monomer and has a glass transition point Tg2 of 40-90 deg.C and Tg2 is higher than Tg1 by at least 10 deg.C.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a heat-fixing toner and its resin composition for use in everything from monochrome copying machines to full-color copying machines for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. It is about things.

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 generally,
An electrical latent image is formed on a photoreceptor by various means using a photoconductive substance, and then the latent image is developed using toner, and the toner image is transferred to a transfer material such as paper as necessary. After that, it is fixed by heating, pressure, or solvent vapor to obtain a copy.

Various methods and techniques have been developed for the above-mentioned final step of fixing the toner image on a sheet such as paper. The most common method at present is a compression heating method using a heated roller.

[0004] In the pressure heating method using a heating roller, fixing is carried out by passing the toner image surface of the sheet to be fixed under pressure while contacting the surface of the heating roller whose surface is made of a material that has releasability for the toner. It is something. In this method, the heating roller surface and the toner image on the fixing sheet come into contact under pressure, so the thermal efficiency when fusing the toner image onto the fixing sheet is extremely good, and the fixing can be performed quickly. , which is very effective in high-speed electrophotographic copying machines. However, in the above method, since the heating roller surface and the toner image contact each other under pressure in a molten state, a part of the toner image adheres to and transfers to the fixing roller surface, and this is transferred again to the next sheet to be fixed. A so-called offset phenomenon may occur, and the sheet to be fixed may be stained. One of the essential conditions for the heating roller fixing method is to prevent toner from adhering to the surface of the heating roller fixing roller.

That is, there is currently a demand for the development of a binder resin for toners that has a wide fixing temperature range and is highly resistant to offset.

Further, many studies and practical applications have been made on two-color copying machines and full-color copying machines. for example"
"Journal of Electrophotography Society" Vol 22, No. 1 (1983
) and “Journal of Electrophotography Society” Vol. 25, No. 1,5
There are also reports on color reproducibility and gradation reproducibility, such as 2-(1986).

However, unlike television, photographs, and color printed matter, there is no immediate comparison with the real thing, and people who are accustomed to seeing processed color images that are more beautiful than the real thing may find it difficult to use full-color electronic images that are currently in practical use. Photographic images are not always satisfactory.

[0008] In full-color electrophotography, development is performed multiple times and several toner layers of different colors are required to be superimposed on the same support. Conditions include the following: (1) The fixed toner must be almost completely melted to the extent that the shape of the toner particles cannot be discerned so that it does not diffusely reflect light and interfere with color reproduction. (2) The binder resin must have transparency that does not interfere with toner layers of different tones below the toner layer.

As described above, for mono-color copying machines, it is desired to develop a toner binder resin with a wide fixing temperature range and high offset resistance, and for full-color copying machines,
In addition to having a wide fixing temperature range, it is also required that the resin be transparent and that the fixing surface be flat when fixed. The transparency of the resin and the smoothness of the fixing surface are important not only when fixing it on paper etc. and viewing the reflected image, but also when using OH
This has a great effect on the quality of the transmitted light image fixed on a P sheet or the like.

[0010] Furthermore, in recent years, from monochrome to full-color copying machines, there have been many demands such as higher speeds, shorter heating roller heat-up times, and lower power consumption.

In order to satisfy these requirements, a toner binder that is capable of low-temperature fixing, has a wide fixing area, has excellent transparency, and has a flat fixing surface when fixed is needed. Requires resin.

[0012] A method of using a pressure-fixed toner may also be considered, but in this method, when used as a full-color toner that reproduces colors by overlapping three or four colors, color mixing is poor because the binder resin does not dissolve. Unfortunately, the result is a dull and desaturated image. Therefore, in the fixing step, it is necessary to apply enough heat to melt the binder resin and mix colors.

It is possible to lower the melt viscosity of a binder resin for toner solely for the purpose of low-temperature fixing. For example, one possibility is to lower the molecular weight of the resin or lower the glass transition point, but this method results in poor storage stability of the toner, causing toner particles to block each other, and damage to the developing drum, etc.
This causes phenomena such as fusion.

[0014] Furthermore, for the purpose of increasing the fixing temperature of conventional vinyl polymers, Japanese Patent Laid-Open Nos. 14148-1982, 72948-1980, 174855-1983~
Publication No. 6, Japanese Unexamined Patent Publication No. 123855/1983, Japanese Patent Application Publication No. 1983
2-3304-5, Japanese Patent Publication No. 57-52574, Japanese Patent Publication No. 58-8505, etc., disclose methods of using offset inhibitors, but these are supplementary and are not suitable for monocolor toners in particular. The transparency of the toner is impaired, and when used as a full-color toner, color mixing properties become poor.

[0015] Also, Japanese Patent Application Laid-open No. 56-158340,
JP-A-58-86558, JP-A-58-2034
No. 53, JP-A-59-88748, JP-A-Sho. 5
9-226358, JP 60-45259, JP 60-45261, JP 60-46
In Publication No. 566, Special Publication No. 60-2411, etc.,
A binder resin for toner having a low molecular weight component and a high molecular weight component is disclosed. By using these resins, it has become possible to widen the fixing temperature to some extent, but due to the presence of high molecular weight components such as gels, the pulverizability decreases and the melt viscosity during hot kneading becomes too high. Moreover, when used as a full-color toner, the smoothness of the fixing surface is impaired, resulting in poor color mixing.

In other words, it is extremely difficult to fix at a low temperature, expand the fixing temperature range, and simultaneously satisfy the toner properties of storage stability, fluidity, durability, transparency, and smoothness of the fixing surface. difficult.

[0017]

SUMMARY OF THE INVENTION An object of the present invention is to provide a new resin composition and a heat-fixing toner that solve these problems.

That is, an object of the present invention is to provide a heat-fixing toner that can be fixed at a low temperature and has a wide fixing temperature range, and a resin composition suitable for the toner.

Another object of the present invention is to provide a heat-fixing toner that has excellent storage stability and fluidity, does not cause aggregation, and has excellent impact resistance, and a resin composition suitable for the toner. .

Another object of the present invention is to provide a heat-fixing toner that has good charging characteristics and is always stable during use, and provides clear and fog-free images, and a resin composition suitable for the toner. It's about providing things.

[0021]Furthermore, another object of the present invention is to use heat fixing to form a smooth fixing surface so that when used as a full-color toner, the fixed toner does not diffusely reflect light and interfere with color reproduction. It is an object of the present invention to provide a toner for use with a toner and a resin composition suitable for the toner.

Another object of the present invention is to provide a heat-fixing toner having color mixing properties that do not interfere with toner layers of different tones below the toner layer when used as a full-color toner, and a resin suitable for the toner. An object of the present invention is to provide a composition.

[0023]

[Means and effects for solving the problem] A resin composition formed of domain particles and a matrix, in which the average particle size of the domain particles dispersed in the matrix is 5 μm or less, and the domain particles constitute the domain particles. The resin P1 is an acid-modified polymer synthesized from a vinyl monomer and then added with an acid, and has a glass transition point Tg1 of 0 to 60.
The resin P2 constituting the matrix is a polymer synthesized from vinyl monomers, and its glass transition point Tg2 is 40 to 90°C, and the glass transition point Tg2 of the resin P2 is the same as that of the resin P1. The object of the present invention is achieved by a resin composition characterized by having a glass transition point Tg1 higher than Tg1 by 10° C. or more, and a toner for heat fixing using this resin composition as a binder resin.

[0024] Further, the resin composition is formed of domain particles and a matrix, and the average particle size of the domain particles dispersed in the matrix is 5 μm or less,
The resin P1 constituting the domain particles is an acid-modified polymer having an unsaturated double bond synthesized from a vinyl monomer and then added with an acid, and its glass transition point Tg1 is 0 to 0.
The resin P2 constituting the matrix is a polymer having unsaturated double bonds synthesized from vinyl monomers, and its glass transition point Tg2 is 40 to 90°C.
and the glass transition point Tg2 of the resin P2 is higher than the glass transition point Tg1 of the resin P1 by 10°C or more, and the resin P1
The object of the present invention is achieved by a resin composition characterized in that the unsaturated double bonds of the resin P2 and the resin P2 are partially chemically bonded to each other, and a toner for heat fixing using this resin composition as a binder resin. is achieved.

The present inventors have found that the reason for this is as follows.

[0026] This has a structure in which resins with high Tg are the sea, and resins having carboxyl groups and low Tg are the islands. Since they are present individually, they have excellent low-temperature fixing properties and excellent blocking resistance. Furthermore, since a monomer having an unsaturated double bond that can be modified with an acid is used, when used in a toner, it has excellent elasticity and fixing properties. Furthermore, since the carboxyl group has a structure in which it is encapsulated in islands, it can be used not only as a negatively chargeable toner but also as a positively chargeable toner. Furthermore, by chemically bonding a portion of the resin constituting the sea and the islands, the islands can be fixed while being finely dispersed, and therefore exhibit excellent blocking resistance over a long period of time.

Regarding toners in which the binder resin has domain particles and a matrix (so-called sea-island structure), for example, in Japanese Patent Publication No. 57-6586, the islands have a Tg3
It is a soft and deformable polymer with a Mn of 500 to 50,000 at <0℃>, and the sea is an amorphous polymer with a Tg<50℃ and a Tm
A method of controlling the island diameter by adding a dispersant such as a graft or a block polymer to a crystalline polymer having a temperature of <40° C. and a tenacious polymer having an Mn of <1500 is disclosed. In this method, as shown in the example substances described in the main text, the polymers forming the sea and islands are completely incompatible materials, and the addition of grafts and block polymers is essential to form the sea-island structure. . Therefore, it seems that a special method for controlling sea islands is adopted by the spray drying method-coacervation method. Although the toner obtained by this method can certainly be fixed at low temperatures, the particle size distribution of the toner produced by the spray drying method is broad, resulting in poor image quality due to fogging, toner scattering, etc. becomes. Furthermore, in the spray drying method, the sea, island, and dispersant resins are dissolved in a mutual solvent, and a non-solvent (selective solvent for matrix components with a boiling point higher than that of the mutual solvent) is added, and then spray-dried. This method first removes the mutual solvent, precipitates the soft polymer component, and then removes the solvent from the matrix formed around the soft polymer component, but this method limits the combinations of resin and solvent. (e.g., the resin is soluble in the first solvent but not in the next solvent added, the boiling point of the solvent must be low for spray drying, etc.) For example, changing the molecular weight of the resin or changing the composition. That cannot be done easily. Furthermore, it is also very difficult to use resins with similar compositions in order to selectively precipitate them. In addition, (2) the polarity of the graft or block polymer that acts as a dispersant for the formed domains is not very strong, so the domains become larger during long-term storage, resulting in poor blocking resistance.

There is also a method of blending a condensation resin such as polyester or epoxy resin for the purpose of low-temperature fixing with a vinyl resin for the purpose of improving high-temperature offset.
It is disclosed in Japanese Patent Publication No. 59-50060. In this method, when a vinyl resin with a weight average molecular weight of 500,000 or more and not very strong polarity is mixed with a condensation resin such as polyester or epoxy resin by melt-kneading, grafts and block polymers are also added. Even if a domain were formed, it would be extremely difficult to control the domain diameter, and furthermore, the domain would grow larger with long-term storage, and therefore the blocking resistance would be affected. It's going to get worse. In addition, as a method of blending resins having different Tg, molecular weight and/or composition, JP-A-56-159340 and JP-A-58-
106552, JP 63-214760, JP 63-217360-3, JP 1-2
Although disclosed in Japanese Patent No. 04061, etc., in these methods, domains are not formed, or even if domains are formed, the particle size is large. If it is lower, the blocking resistance will be very poor.

[0029] Therefore, as a result of intensive study, the present inventors found that
The inventors have now invented a resin and toner with excellent low-temperature fixing properties that do not cause the above-mentioned problems. The binder resin in the present invention includes domain particles having a Tg of 0 to 60°C, an acid value of 15 or more, and having carboxyl groups, and a matrix having a Tg of 40 to 90°C, an acid value of 10 or less and having substantially no carboxyl groups. The toner according to the present invention uses the binder resin. With this configuration, a toner with excellent low-temperature fixing and blocking resistance can be obtained with a Tg of 10% higher than that of the matrix resin.
This is because domain particles having a low temperature and carboxyl groups associate with each other through carboxyl groups to form micelles, so that they are dispersed very finely and stably.

[0030] Here, the Tg of the domain particles is 0°C.
If the Tg is lower, blocking will occur even if the Tg of the matrix resin is increased, and if the Tg of the domain particles exceeds 60° C., the fixing properties of the toner will deteriorate. Further, when the acid value of the domain particles is less than 15, the dispersion stability of the domain particles is poor, and therefore, the blocking resistance is poor. Furthermore, if the Tg of the matrix resin is lower than 40°C, blocking will occur, and if it exceeds 90°C, the toner fixing properties will deteriorate. In addition, the acid value of the matrix resin is 10
If it exceeds this, the compatibility with the domain particles increases and the dispersion stability of the domain particles worsens, resulting in poor blocking resistance. Therefore, the glass transition point Tg1 of the domain particles constituting this binder resin is more preferably 15 to 50°C, and the glass transition point Tg1 of the matrix resin is more preferably 15 to 50°C.
g2 is more preferably 55 to 80°C. Furthermore, in order to further exhibit the effect of the present invention, it is desirable that Tg2 is higher than Tg1 by 10°C or more.

The weight ratio of the matrix resin to the resin forming the domain particles is preferably 5 to 300 parts by weight of the resin forming the domain particles per 100 parts by weight of the matrix resin. This is because if the amount of resin forming the domain particles is less than 5 parts by weight, there is no effect of lowering the fixing temperature.
This is because if more than 100 parts by weight is mixed, the blocking resistance may be poor.

In the binder resin used in the present invention, the vinyl monomers constituting the matrix resin include the following.

For example, styrene, o-methylstyrene,
m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p- n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o -Nitrostyrene, p-
Styrene derivatives such as nitrostyrene; Ethylene and unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; Unsaturated diolefins such as butadiene and isoprene; Vinyl chloride, vinylidene chloride,
Vinyl halides such as vinyl bromide and vinyl fluoride;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methacrylic acid and methyl methacrylate, ethyl methacrylate, propyl methacrylate,
α-methylene aliphatic monocarboxylic acid esters such as n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate; acrylic acid and methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-acrylate
Acrylic acid esters such as chloroethyl and phenyl acrylate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-vinylpyrrole, N-vinyl compounds such as N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone; vinylnaphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; one or two types of acrolein, etc. Polymerization using the above methods is used.

In particular, when an acid-modified polymer having an unsaturated double bond is used as the matrix resin, at least a polymer having an acid-modifiable unsaturated double bond such as unsaturated diolefins such as butadiene and isoprene is used. Use monomers. The amount of the monomer having an unsaturated double bond used in the matrix resin and domain resin is 0.1 to 0.1, respectively.
It is desirable that the amount is 70 wt%, preferably 0.3 to 55 wt%.

In the binder resin used in the present invention, as the vinyl monomer constituting the domain resin, those having a matrix structure can be similarly used, but the domain resin is acid-modified. Acids for acid modification include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride, fumaric acid, maleic acid, and their methyl, ethyl, butyl, 2-ethylhexyl, octyl, dodecyl, hexadecyl, Examples include monoesters such as stearyl, and after synthesizing one or more of these with a vinyl monomer, it is added to an unsaturated double bond by heat treatment in a solvent or the like.

[0036] The amount of acid for modifying the domain resin in the binder resin used in the present invention is such that the domain particle size is 5 μm.
m or less in the polymer forming the domain.
It is desirable that the amount is 1 to 50 wt%, preferably 1 to 30 wt%.

Furthermore, in order to chemically bond the matrix resin and the domain resin, it is necessary to leave some double bonds in the domain resin. Therefore, the amount of acid for modifying the domain resin is desirably 95 mol % or less based on the amount of unsaturated diolefin monomer.

The heat fixing toner of the present invention can be used as a one-component toner or a two-component toner, and the two-component toner can be widely applied from monocolor to full color.

However, in order to fully exhibit the toner characteristics of the present invention, when used for full color, the number average molecular weight (Mn) of the polymer of the domain particles used as the binder resin is preferably 1,500 to 40,000. is 3
500 to 30,000, weight average molecular weight (Mw) is 300
0 to 300,000, preferably 5,000 to 100,000
It is desirable that Further, the number average molecular weight (Mn) of the matrix resin is 1500 to 20000, preferably 3000 to 10000, and the weight average molecular weight (Mw) is 30.
00 to 50,000, preferably 6,000 to 30,000. In addition, when used as a one-component system or monocolor, the number average molecular weight (Mn) of the polymer of the domain particles used as the binder resin is 300.
0 to 150,000, preferably 5,000 to 100,000
, weight average molecular weight (Mw) is 6,000 to 1,000,000
, preferably 10,000 to 700,000. In addition, the number average molecular weight (Mn
) is 3000-50000, preferably 6000-30
000, weight average molecular weight (Mw) is 6000-2500
00, preferably 10,000 to 150,000.

Polymers synthesized from vinyl monomers can be obtained by generally known methods, such as solution or suspension polymerization using a peroxide as an initiator.

[0041] As a method for making the binder resin take a domain-matrix (sea-island) structure using the resins for matrix and domain obtained respectively by this method, it is not possible to simply dry blend and melt-knead. It is extremely difficult to create a uniform and fine sea-island structure.

As a result of intensive studies, the present inventors succeeded in creating a uniform and fine sea-island structure using the following method.

[0043] Each polymerized resin is dissolved in a non-polar solvent (even if a polar solvent is used, a sea-island structure can be formed, but the domain diameter becomes larger), and the solution is heated and stirred vigorously. and blend. In the present invention, it is very important to control the domain diameter to be small. Therefore, in the case of blending, although it is effective to increase the stirring power during blending, the compatibility between the matrix resin and domain resin can be increased by increasing the temperature, and therefore it is possible to further reduce the domain diameter. Can be done. By removing the solvent in this state and rapidly cooling it, it became possible to create a uniform and fine sea-island structure.

[0044] Furthermore, if the domain resin is polymerized using a nonpolar solvent, then acid is added, and the matrix resin is polymerized in the presence of the domain resin, the domain resin is blended in a micro-dispersed state. Therefore, the domain diameter can be made very small.

Further, contrary to this method, it is also possible to first polymerize the resin for the matrix, then polymerize the resin for the domain, and then add acid.

Furthermore, as a method for chemically bonding resins P1 and P2, after dissolving the acid-added resins P1 and P2 in a suitable solvent, for example, using only a peroxide such as benzoyl peroxide, residual carbon is removed. In addition to methods of crosslinking heavy bonds with each other, or methods of crosslinking using peroxides such as benzoyl peroxide or other radical polymerization initiators and vinyl monomers or divinyl crosslinking monomers (e.g., divinylbenzene, etc.), When melting and kneading resins, colorants, magnetic powders, etc., peroxides such as benzoyl peroxide and/or
Alternatively, a method may be used in which a vulcanizing agent and/or a vulcanization accelerator for ordinary rubber or plastics are mixed in advance and crosslinked during melt-kneading.

In order to use the toner of the present invention as a one-component toner, it may contain magnetic powder. As such magnetic powder, a substance that is magnetized when placed in a magnetic field is used, and includes powders of ferromagnetic metals such as iron, cobalt, and nickel, and alloys and compounds such as magnetite, hematite, and ferrite. The content of this magnetic powder is 15 to 70% by weight based on the weight of the toner.

In addition, carbon black, titanium white, and any other pigments and/or dyes can be used as the coloring agent, regardless of whether the toner is one-component or two-component.

For example, when the toner of the present invention is used as a magnetic color toner, C.I. I. Direct Red 1, C. I. Direct Red 4, C. I
．． Acid Red 1, C. I. Basic red 1, C
．． I. Modern Tread 30, C. I. Direct Blue 1, C. I. Direct Blue 2, C. I. Acid Blue 9, C. I. Acid Blue 15, C. I. Basic Blue 3, C. I. Basic Blue 5, C. I
．． Mordant Blue 7, C. I. direct green 6
,C. I. Basic Green 4, C. I. There is a basic green 6th grade. Pigments include yellow lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, red yellow lead, molybdenum orange, permanent orange GTR,
Pyrazolone Orange, Benzidine Orange G, Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Deep Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake , Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, Chrome Green, Chromium Oxide, Pigment Green B, Malachite Green Lake, Final Yellow Green G, etc.

Further, when the toner of the present invention is used as a two-component full color toner, the following can be mentioned.

As the coloring pigment for magenta, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 1
0, 11, 12, 13, 14, 15, 16, 17, 18
,19,21,22,23,30,31,32,37,
38, 39, 40, 41, 48, 49, 50, 51, 5
2, 53, 54, 55, 57, 58, 60, 63, 64
,68,81,83,87,88,89,90,112
,114,122,123,163,202,206,
207, 209;C. I. pigment violet 19
,C. I. Bat Red 1, 2, 10, 13, 15, 2
3, 29, 35, etc.

[0052] Although such a pigment may be used alone, it is more preferable from the viewpoint of the image quality of a full-color image to use a combination of a dye and a pigment to improve the clarity. Such magenta dyes include C.I. I. Solvent red 1,3
,8,23,24,25,27,30,49,81,8
2,83,84,100,109,121,C. I. Disperse Red 9, C. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic red 1, 2, 9, 12, 13, 14, 15, 17, 18, 2
2, 23, 24, 27, 29, 32, 34, 35, 36
, 37, 38, 39, 40, C. I. Basic violet 1, 3, 7, 10, 14, 15, 21, 25, 2
Examples include basic dyes such as 6, 27, and 28.

Other coloring pigments such as cyan coloring pigments include C.I. I. pigment blue 2, 3, 15,
16, 17, C. I. Bat Blue 6, C. I. Acid Blue 45 or a copper phthalocyanine pigment having a phthalocyanine skeleton having a structure represented by the following formula (1) substituted with 1 to 5 phthalimidomethyl groups, etc.

[0054]

[Chemical Formula 1] As a coloring pigment for yellow, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12,
13, 14, 15, 16, 17, 23, 65, 73, 8
3;C. I. Bat Yellow 1, 3, 20, etc. can be mentioned.

The amount of the colorant used is 0.1 to 60 parts by weight, preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the binder resin.

[0056] Furthermore, the toner in the present invention has negative chargeability,
Although the toner is not limited to positive chargeability, when producing a negatively chargeable toner, it is preferable to add a charge control agent especially for the purpose of stabilizing the negative chargeability. Examples of negative charge control agents include organometallic complexes such as metal complexes of alkyl-substituted salicylic acids (eg, chromium complexes or zinc complexes of di-tert-butylsalicylic acid).

When producing a positively chargeable toner, nigrosine, triphenylmethane compounds, rhodamine dyes, polyvinylpyridine, and the like may be used as charge control agents exhibiting positive chargeability. In addition, when producing a color toner, 0.1 to 40 mol% of positively chargeable aminocarboxylic acid esters such as dimethylaminomethyl methacrylate as a monomer, preferably 1 to 3 mol%.
A binder resin containing 0 mol % may be used, or a colorless or light-colored positive charge control agent that does not affect the color tone of the toner may be used. Examples of positive charge control agents include quaternary ammonium salts represented by structural formulas (A) and (B).

[0058]

[Case 2]

[0059]

[Chemical formula 3] Among the quaternary ammonium salts represented by structural formulas (A) and (B), positive charge control agents represented by structural formulas (A)-1, -2 and structural formula (B)-1 are used. This is preferable because it shows good charging properties with little environmental dependence.

[0060]

[C4]

[0061]

[C5]

[0062]

[Chemical 6] Also, as a resin component of the binder resin in positively chargeable toner,
When using an aminocarboxylic acid ester such as dimethylaminomethyl methacrylate that exhibits positive charge characteristics, a positive charge control agent or a negative charge control agent is used as necessary.

In the case of a negatively chargeable toner, the amount of the negative charge control agent used is 0.1 to 15 parts by weight based on 100 parts by weight of the binder resin.
Parts by weight, preferably 0.5 to 10 parts by weight.

[0064] When an aminocarboxylic acid ester such as dimethylaminomethyl methacrylate, which exhibits positive charging properties, is not used as a resin component in a positively chargeable toner, a positive charge control agent is added to 100 parts by weight of the binder resin. te 0.1~15
It is desirable to use 0.5 to 10 parts by weight, preferably 0.5 to 10 parts by weight. In addition, when using aminocarboxylic acid esters, a positive charge control agent and/or a negative charge control agent may be added to 100 parts by weight of the binder resin, if necessary, in order to provide good chargeability with less environmental dependence. It is desirable to use 0 to 10 parts by weight, preferably 0 to 8 parts by weight.

Furthermore, in the toner of the present invention, a fluidity improver may be added for the purpose of improving the fluidity of the toner.

[0066] The flow improver used in the present invention is as follows:
Any substance can be used as long as it can increase the fluidity by comparing before and after addition by adding it to the colorant-containing resin particles.

For example, fluororesin powder, ie, vinylidene fluoride fine powder, polytetrafluoroethylene fine powder, etc.; or fatty acid metal salt, ie, zinc stearate, etc.
Calcium stearate, lead stearate, etc.; or metal oxides, i.e. zinc oxide powder, etc.; or fine powder silica, i.e. wet process silica, dry process silica, these silicas with silane coupling agents, titanium coupling agents, silicone oil, etc. There are treated silicas that have undergone surface treatment.

A preferred flow improver is a fine powder produced by vapor phase oxidation of a silicon halide compound, so-called dry process silica or fumed silica, which is produced by conventionally known techniques. It is. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl4+2H2+O2→SiO2+4HClAlso,
In this manufacturing process, it is also possible to obtain a composite fine powder of silica and other metal oxides by using other metal halide compounds such as aluminum chloride or titanium chloride together with the silicon halide compound, and these are also included.

The particle size is 0.0 as the average primary particle size.
It is desirable to use fine silica powder within the range of 0.01 to 2μ, particularly preferably within the range of 0.002 to 0.2μ.

Commercially available fine silica powder produced by vapor phase oxidation of a silicon halogen compound used in the present invention includes, for example, those sold under the following trade names.

AEROSIL (Japan Aerosil Co., Ltd.)
130

200


300

380

TT600

M
OX170

MOX80

COK84
Ca-O-SiL (CABOT Co.)
M-5

MS-7

M.S.
-75

HS-5

EH-5 Wack
er HDK N 20
V15 (WACKER
-CHEMIE GMBH) N2
0E

T30

T40 D-C Fi
ne Silica (Dow Corning Co.)
Further, it is more preferable to use treated silica fine powder obtained by hydrophobicizing silica fine powder produced by vapor phase oxidation of the silicon halogen compound. Among the treated silica fine powders, it is particularly preferred that the silica fine powders be treated so that the degree of hydrophobicity as measured by a methanol titration test is in the range of 30 to 80.

Hydrophobicity can be imparted by chemical treatment with an organosilicon compound that reacts with or physically adsorbs fine silica powder.

In a preferred method, fine silica powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allyl phenyldichlorosilane, benzyl Dimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxy Silane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and terminals with 2 to 12 siloxane units per molecule. There are dimethylpolysiloxanes containing one hydroxyl group bonded to Si in each unit located at . These may be used alone or in a mixture of two or more.

The particle size of the treated silica fine powder is 0.
．． It is preferable to use one in the range of 0.003 to 0.1 μm. Commercially available products include Taranox-500 (Talco Co., Ltd.) and AEROSIL R-972 (Nippon Aerosil Co., Ltd.).

[0077] Regarding the positively chargeable toner, positively chargeable silica fine particles may be used in order not only to improve its fluidity but also to obtain good chargeability with little environmental dependence.

In order to obtain such positively charged silica fine particles, it is preferable to treat them with a coupling agent or silicone oil containing an amino group. Examples of such processing agents include:

[0079]

[C7]

[0080]

[Chemical formula 8]

[0081]

[Chemical formula 9] There are aminosilane coupling agents such as

As the silicone oil, amino-modified silicone oil having a partial structure having an amino group in the side chain of the following formula is generally used.

[0083]

embedded image (Here, R1 represents hydrogen, an alkyl group, an aryl group, or an alkoxy group, R2 represents an alkylene group or a phenylene group, and R3 and R4 represent hydrogen, an alkyl group, or an aryl group. However, The above alkyl group, aryl group, alkylene group, and phenylene group may contain an amine, or may have a substituent such as a halogen within a range that does not impair chargeability. m and n are positive Integers are shown.) Examples of such silicone oils having amino groups include the following.

[0084] Product name
Viscosity at 25°C (cps) Amine equivalent SF
8417 (manufactured by Torre Silicone) 12
00 3500KF393 (manufactured by Shin-Etsu Chemical)
60 360KF857 (manufactured by Shin-Etsu Chemical)
70 830KF860
(Manufactured by Shin-Etsu Chemical)
250 7600KF861
(Manufactured by Shin-Etsu Chemical)
3500 2000KF862 (
(manufactured by Shin-Etsu Chemical)
750 1900KF864 (
(manufactured by Shin-Etsu Chemical)
1700 3800KF865 (manufactured by Shin-Etsu Chemical)
90 4400KF369 (
(manufactured by Shin-Etsu Chemical)
20 320KF38
3 (manufactured by Shin-Etsu Chemical)
20 320X-
22-3680 (manufactured by Shin-Etsu Chemical)
90 8800X-22-
380D (manufactured by Shin-Etsu Chemical) 230
0 3800X-22-3801C
(Manufactured by Shin-Etsu Chemical) 3500
3800X-22-3810B (manufactured by Shin-Etsu Chemical) 1300 1
700 Note that the amine equivalent is the equivalent per amine (g/eqiv), which is the value obtained by dividing the molecular weight by the number of amines per molecule.

[0085] It is preferable to use silica fine particles treated with a coupling agent or silicone oil containing these amino groups, which are further subjected to hydrophobization treatment with the above-mentioned organosilicon compound.

When the toner of the present invention is used as a two-component toner, the carrier used during development also plays an important role in order to fully exhibit its effects.

Examples of carriers used in the present invention include surface oxidized or unoxidized iron, nickel, copper, zinc,
Metals such as cobalt, manganese, chromium, and rare earths, their alloys or oxides, and ferrites can be used. Moreover, there are no special restrictions on the manufacturing method.

Further, a system in which the surface of the carrier is coated with a resin or the like is particularly preferred in the J/B development method. As a method for this, any conventionally known method can be applied, such as a method in which a coating material such as a resin is dissolved or suspended in a solvent and applied and adhered to the carrier, or a method in which a powder is simply mixed.

Substances that adhere to the carrier surface vary depending on the toner material, but include, for example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin,
Metal complexes of ditertiary butylsalicylic acid, styrene resins, acrylic resins, polyacids, polyvinyl butyral, nigrosine, aminoacrylate resins, basic dyes and their lakes, silica fine powder, alumina fine powder, etc. are used singly or in combination. is suitable, but is not necessarily limited to this.

The amount of the above compound to be treated may be appropriately determined so that the carrier satisfies the above conditions, but generally the total amount is 0.1 to 30% by weight (preferably 0.5 to 20% by weight) based on the carrier of the present invention. weight%) is desirable.

[0091] The average particle size of these carriers is 10 to 100
[mu], preferably 20 to 70[mu].

[0092] As a particularly preferred embodiment, Cu-Zn-
It is a ternary Fe ferrite, and its surface is made of a combination of resins such as fluorine resin and styrene resin, such as polyvinylidene fluoride and styrene-methyl methacrylate resin; polytetrafluoroethylene and styrene-methyl methacrylate resin, A mixture of a fluorine copolymer and a styrene copolymer in a ratio of 90:10 to 20:80, preferably 70:30 to 30:70, preferably 0.01 to 5% by weight. Examples include coated ferrite carriers coated with 0.1 to 1% by weight and having the average particle diameter as described above and containing 70% by weight or more of carrier particles having a 250 mesh pass and a 400 mesh on. As the fluorine-based copolymer, vinylidene fluoride
Tetrafluoroethylene copolymer (10:90-90:
10) is exemplified, and the styrene-based copolymer is styrene-2-ethylhexyl acrylate (20:80-80).
:20), styrene-2-ethylhexyne acrylate-
Methyl methacrylate (20-60:5-30:10-5
0) is exemplified.

The coated ferrite carrier has a sharp particle size distribution, provides favorable triboelectric charging properties for the toner of the present invention, and has the effect of improving electrophotographic properties.

When preparing a two-component developer by mixing with the toner of the present invention, the mixing ratio is 2% to 15% by weight, preferably 4% to 13% by weight, as the toner concentration in the developer. % usually gives good results. If the toner concentration is less than 2%, the image density will be too low to be practical, and if it is more than 15%, foreign fog and in-machine scattering will increase, and the useful life of the developer will be shortened.

The measurement method according to the present invention will be described below.

(1) Measurement of glass transition temperature Tg In the present invention, a differential thermal analysis measurement device (DSC measurement device), D
Measurement is performed using SC-7 (manufactured by PerkinElmer).

[0097] The sample to be measured is 5 to 20 mg, preferably 10 mg.
Accurately weigh mg.

[0098] Place this in an aluminum pan, use an empty aluminum pan as a reference, and measure the temperature range from 30°C to 2.
Measurement is performed between 00°C and a temperature increase rate of 10°C/min at normal temperature and normal humidity.

[0099] During this temperature raising process, a main endothermic peak in the temperature range of 40 to 100°C is obtained.

[0100] The intersection of the line between the baselines before and after the endothermic peak appears and the differential thermal curve is defined as the glass transition temperature Tg in the present invention.

(2) Measurement of Molecular Weight In the present invention, the molecular weight of a chromatogram by GPC (gel permeation chromatography) is measured under the following conditions.

That is, the column was stabilized in a heat chamber at 40°C, and THF (tetrahydrofuran) was flowed as a solvent through the column at this temperature at a flow rate of 1 ml per minute, so that the sample concentration was 0.05 to 0.6 wt. Measurement is performed by injecting 50 to 200 μl of a THF sample solution of the resin adjusted to %. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithm value and the count number of a calibration curve prepared using several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for creating a calibration curve, for example, Pressure Chemica
l Co. or manufactured by Toyo Soda Kogyo Co., Ltd. with a molecular weight of 6 x 102, 2.1 x 103, 4 x 103, 1.75.
×104, 5.1×104, 1.1×105, 3.9×
105, 8.6×105, 2×106, 4.48×10
It is appropriate to use at least 10 standard polystyrene samples. Also, the detector has R
An I (refractive index) detector is used.

[0103] As for the column, 103 to 2 x 10
In order to accurately measure the molecular weight range of 6, it is recommended to combine multiple commercially available polystyrene gel columns.
μ-styragel 500,1 manufactured by aters
Combinations of 03, 104, 105, and sh made by Showa Denko
odex KF-80M, KF-801, 803,
Combination of 804, 805, KA-802, 803, 80
4,805 combination or TSKge manufactured by Toyo Soda
l G1000H, G2000H, G2500H, G
3000H, G4000H, G5000H, G6000
A combination of H, G7000H, and GMH is preferred.

(3) Acid value The acid value is important as it accurately indicates the progress of esterification in a short time. Generally, the esterification check starts at an acid value of about 80 and ends at an acid value of about 20 to 50, if necessary.

The acid value is defined as the number of milligrams of caustic potash required to neutralize the carboxyl groups contained in 1 g of resin. Therefore, the acid value indicates the number of terminal groups. The measurement method is as follows.

[0106] “2 to 10 g of sample
Weigh into a 1-liter Erlenmeyer flask, methanol:toluene = 3
Approximately 50 ml of a 0:70 mixed solvent is added to dissolve the resin. If the solubility is poor, a small amount of acetone may be added. N/1 was pre-standardized using a mixed indicator of 0.1% bromothymol blue and phenol red.
Titrate with a 0-potassium to alcohol solution, and calculate the acid value from the amount of alcoholic potash consumed using the following calculation.

Acid value = KOH (number of ml) x N x 56.1/sample weight (N is a factor of N/10KOH) (4) Average particle size of domain particles In the present invention, the average particle size of domain particles For example,
Measure under the following conditions. Approximately 0.1 g of the binder resin is placed on a glass plate and melted on a hot plate. After dissolving the binder resin, add 2 to 3 drops of rhodamine dye dissolved in ethanol. Immediately after applying the dye, place a cover glass on top and press it down to create a thin layer of binder resin/rhodamine. (As mentioned above, the resin forming the domain particles is a polymer having carboxyl groups. Therefore, the rhodamine dye dissolved in ethanol is attracted to the carboxyl groups and selectively colors the domain particles.) Observe with a microscope and randomly
Photograph at least four fields of view. The particle sizes of particles that can be visually identified in these photographs are measured. The average value of the particle diameters measured by the above method is determined (number average) and is taken as the average particle diameter of the domain particles.

[0108] If the domain cannot be seen using this method, the domain can be dyed in the same manner as described above using osmic acid or ruthenic acid as the dye. After this, there is also a method of making a thin section, observing the dispersion state of the domains with a transmission electron microscope, and measuring the average particle size of the domains using the same method as described above.

[0109]

[Examples] The present invention will be explained in detail below with reference to Examples.

Resin production example 1 (Resin solution blend) Polymerized styrene for domain resin
140g butadiene
60
gbenzoyl peroxide
15g toluene
A polymerization reaction was carried out at 80° C. for 16 hours using 500 g. After the reaction, 20 g of maleic anhydride was added to cause an addition reaction to the butadiene unsaturated portion. Thereafter, the ring was opened with a small amount of water. As a result, Mn5000, Mw12000, Tg35.
A copolymer at 0°C was obtained. (Resin A) Polymerized styrene for matrix resin
240g n-butyl acrylate
60g benzoyl peroxide
24g toluene
Using 750g, 85℃×
The polymerization reaction was carried out for 16 hours. As a result, Mn5300,
A copolymer having a Mw of 17,000 and a Tg of 58.5°C was obtained. (
Resin B) Next, the ratio of (Resin A) and (Resin B) is 3:7.
The polymer/toluene solutions after the polymerization reaction were each weighed so that (resin A) and (resin B) were mixed, strongly stirred, and then dried to obtain binder resin (I).

[0111] The acid value of the domain resin is 40.0, the acid value of the matrix resin is 0, and the domain average particle size is 2.
．． It was 0 μm.

Resin Production Example 2 (Polymerization in the Presence of Resin) After polymerizing the matrix resin using the same amount of monomer as in Resin Production Example 1, the domain resin was added in a 50/50 ratio.
Polymerization was carried out in the presence of After the polymerization reaction is complete,
20 g of maleic anhydride was added and an addition reaction was performed to open the ring in the same manner as in Resin Production Example 1 to obtain a binder resin (II).

[0113] As a result of sampling and measuring a small amount of the matrix resin at this time, Mn5400, Mw180
00, Tg 59.0°C, acid value 0. In addition, as a result of polymerization under the same conditions as the domain resin at this time, M
n4900, Mw11000, Tg33℃, acid value 43.
It was 5.

[0114] The average domain particle size of this binder resin (II) was 0.3 μm.

[0115] Hereinafter, by changing the amount of initiator and the ratio of monomer amount,
Resins (III) and (IV) were synthesized. Comparative resins (A) to (F) were also synthesized and shown in Tables 1 and 2, respectively.

[0116]

[Table 1]

[0117]

[Table 2]

Example 1 Binder resin (I)
100
Part aluminum complex of di-tert-butylsalicylic acid 4.0 parts Copper phthalocyanine pigment having the structure represented by formula (1)
5.0 parts were melt-kneaded in a roll mill, cooled, coarsely pulverized, finely pulverized, classified, and further treated with hexamethyldisilazane as a fluidity improver to obtain a classified product of 100 parts.
0.5 parts per part, 0.2 parts of aluminum oxide fine powder
% was added externally to prepare a toner.

[0119] As a carrier, styrene-acrylic 2
-C coated with 0.5% by weight of ethylhexyl-methyl methacrylate (copolymerization weight ratio 50:20:30)
u-Zn-Fe based ferrite carrier (average particle size 45μ
m, 250 mesh pass 400 mesh on 87% by weight
) was used to prepare a developer so that the toner concentration was 6.0% by weight.

Using these developer and toner, an unfixed image was obtained by developing and transferring it using a full color copying machine CLC-500 manufactured by Canon Co., Ltd., and a fixing test was performed using an external fixing device.

As a result, the fixing temperature range in which colors can be mixed is 12.
The temperature was 5-220°C.

[0122] Using these developers and toners, CLC
An image reproduction test was conducted at -500.

As a result, even after printing 20,000 sheets in monochrome mode, there was no offset to the fixing roll, and a full-color image faithfully reproducing the original color chart without fogging was obtained. Furthermore, the toner transportability within the copying machine was good and stable image density was obtained.

Even when an OHP film was used, the toner permeability was very favorable.

[0125] Also, leave it in a hot air dryer at 45°C for one day.
When the blocking state of the toner was observed, no change was observed, and the toner had good fluidity.

Example 2 The same procedure as Example 1 was carried out except that the resin was changed to II, and Table 3
I got the result.

Comparative Examples 1 to 3 The same procedure as in Example 1 was carried out except that the resins were changed to A to C, and the results shown in Table 3 were obtained.

[0128]

[Table 3]

Example 3 Resin III of Resin Synthesis Example
100 parts magnetic iron oxide

Part 70 Nigrosine

2 parts were melt-kneaded in a roll mill, cooled, coarsely pulverized, finely pulverized, and classified. Further, 0.6 parts of hydrophobized dry silica was added as a fluidity improver to 100 parts of the classified product.
A one-component magnetic toner was prepared by externally adding 100% of the total amount.

[0130] With this toner, Canon copier NP-48
An unfixed image was obtained using No. 35, and a fixing test was performed using an external fixing device. As a result, the fixable area is 120 to 24
It was 0°C. Furthermore, an image reproduction test was conducted using this toner and a copying machine. As a result, even after printing 100,000 sheets, there was no offset to the fixing roll, and a good image without fogging or scattering was obtained.

[0131] Also, the blocking resistance was checked in the same manner as in Example 1 and was found to be good.

Example 4 The same procedure as Example 3 was carried out except that the resin was changed to IV, and the results shown in Table 4 were obtained.

Comparative Examples 4 to 6 The same procedure as in Example 3 was carried out except that the resins were changed to D to F, and the results shown in Table 4 were obtained.

[0134]

[Table 4]

Resin production example 3 (Crosslinking in resin solution) Polymerization of resin for domain Styrene
140g butadiene
60g benzoyl peroxide 15
g Toluene
Using 500g,
Polymerization reaction was carried out at 85°C for 10 hours. After the reaction, 15 g of maleic anhydride was added to cause an addition reaction to the butadiene unsaturated portion. Thereafter, the ring was opened with a small amount of water. As a result, Mn4
600, Mw 13500, Tg 30.0°C, acid value 30.
A copolymer of 0 was obtained. (Resin G) Polymerization of matrix resin Styrene
170g butadiene
30g benzoyl peroxide 15
g Toluene
Using 500g,
Polymerization reaction was carried out at 85° C. for 16 hours. As a result, Mn6
000, Mw 17000, Tg 59.0°C, and acid value 0 copolymer was obtained. (Resin H) Next, (Resin G) and (Resin H
) The polymer/toluene solution after the polymerization reaction was weighed, and (resin G) and (resin H) were solution-mixed so that the ratio of benzoyl peroxide was 3:7. Add 1g and raise the temperature of the mixed solution to 80℃.
hr reaction. After the reaction, the mixture was dried to obtain a binder resin (V).

[0136] In this binder resin (V), the domain average particle size was 3.0 μm.

Resin production example 4 (resin for crosslinking during kneading)
In Resin Production Example 1, the solution blend without crosslinking was dried to obtain a binder resin (VI). This binder resin (VI
) was 2.0 μm.

[0138] Hereinafter, by changing the amount of initiator and the ratio of monomer amount,
Resins (VII) and (VIII) were synthesized, and comparative resins (G) to (L) were also synthesized, and are shown in Tables 5 and 6, respectively.

[0139]

[Table 5]

[0140]

[Table 6]

Example 5 Binder resin (V)
100
Part aluminum complex of di-tert-butylsalicylic acid 4.0 parts Copper phthalocyanine pigment having the structure represented by formula (1)
5.0 parts were melt-kneaded in a roll mill, cooled, coarsely pulverized, finely pulverized, classified, and further treated with hexamethyldisilazane as a fluidity improver to obtain a classified product of 100 parts.
0.5 parts per part, 0.2 parts of aluminum oxide fine powder
% was added externally to prepare a toner.

Thereafter, a developer was prepared in the same manner as in Example 1, and a fixing test was conducted.

As a result, the fixing temperature range in which colors can be mixed is 13.
The temperature was 0 to 220°C.

[0144] Using these developers and toners, CLC
An image reproduction test was conducted at -500.

As a result, even after printing 20,000 sheets in monochrome mode, there was no offset to the fixing roll, and a full-color image faithfully reproducing the original color chart without fogging was obtained. Further, the toner transportability within the copying machine was good and stable image density was obtained.

[0146] Even when an OHP film was used, the toner permeability was very favorable.

Further, the toner was left in a hot air dryer at 45° C. for one day and the blocking state of the toner was observed, but no change was observed and it had good fluidity.

Example 6 The same procedure as in Example 5 was performed except that the resin was changed to VI, 0.3 parts of benzoyl peroxide and 0.1 part of zinc oxide were added, and crosslinking was performed during kneading, and the results shown in Table 7 were obtained. .

Comparative Examples 7 to 9 The same procedure as in Example 5 was carried out except that the resins were changed to G to I, and the results shown in Table 7 were obtained.

[0150]

[Table 7]

Example 7 Resin VII of Resin Synthesis Example
100 parts magnetic iron oxide

Part 70 Nigrosine

2 parts were melt-kneaded in a roll mill, cooled, coarsely pulverized, finely pulverized, and classified. Further, 0.6 parts of hydrophobized dry silica was added as a fluidity improver to 100 parts of the classified product.
A one-component magnetic toner was prepared by externally adding 100% of the total amount.

[0152] With this toner, Canon copier NP-48
An unfixed image was obtained using No. 35, and a fixing test was performed using an external fixing device. As a result, the fixable area is 130 to 24
It was 0°C. Furthermore, an image reproduction test was conducted using this toner and a copying machine. As a result, even after printing 100,000 sheets, there was no offset to the fixing roll, and good images without fogging or scattering were obtained.

[0153] Also, the blocking resistance was checked in the same manner as in Example 1 and was found to be good.

Example 8 The same procedure as in Example 7 was performed except that the resin was changed to VIII, 0.3 parts of benzoyl peroxide and 0.2 parts of zinc oxide were added, and crosslinking was performed during kneading, and the results shown in Table 8 were obtained. .

Comparative Examples 10 to 12 The same procedure as in Example 7 was carried out except that the resins were changed to J to L, and the results shown in Table 8 were obtained.

[0156]

[Table 8]

[0157]

Effects of the Invention As described above, by using the resin composition of the present invention, low temperature fixing is possible, and storage stability and
A heat-fixing toner having excellent fluidity and charging properties and suitable for full-color copying can be obtained.

Claims (16)

[Claims] Claim 1: A resin composition formed of domain particles and a matrix, wherein the average particle size of the domain particles dispersed in the matrix is 5 μm or less, and the resin P1 constituting the domain particles is a vinyl-based resin composition. It is an acid-modified polymer synthesized from a monomer and then added with an acid, and its glass transition point Tg1 is 0 to 60°C, and the resin P2 constituting the matrix is a polymer synthesized from a vinyl monomer, Its glass transition point Tg2 is 40-9
0° C., and the glass transition point Tg2 of the resin P2 is 10° C. or more higher than the glass transition point Tg1 of the resin P1. 2. The resin composition according to claim 1, wherein the resin P1 has a carboxyl group, and the resin P2 has substantially no carboxyl group. 3. The acid value of the resin P1 is 15 or more,
3. The resin composition according to claim 1, wherein the resin P2 has an acid value of 10 or less. 4. The resin composition according to claim 1, wherein 5 to 300 parts by weight of the resin P1 is blended per 100 parts by weight of the resin P2. 5. A resin composition formed of domain particles and a matrix, wherein the average particle size of the domain particles dispersed in the matrix is 5 μm or less, and the resin P1 constituting the domain particles is a vinyl-based resin composition. It is an acid-modified polymer having an unsaturated double bond that is acid-added after being synthesized from monomers, and its glass transition point Tg1 is 0 to 6.
The resin P2 constituting the matrix is a polymer having unsaturated double bonds synthesized from vinyl monomers, and its glass transition point Tg2 is 40 to 90°C. A resin composition characterized in that the transition point Tg2 is 10° C. or more higher than the glass transition point Tg1 of the resin P1, and the unsaturated double bonds of the resin P1 and the resin P2 are partially chemically bonded to each other. . 6. The resin composition according to claim 5, wherein the resin P1 has a carboxyl group, and the resin P2 has substantially no carboxyl group. 7. The resin P1 has an acid value of 15 or more,
7. The resin composition according to claim 5, wherein the resin P2 has an acid value of 10 or less. 8. The resin composition according to claim 5, wherein 5 to 300 parts by weight of the resin P1 is blended per 100 parts by weight of the resin P2. 9. A toner for heat fixing having a binder resin, wherein the binder resin is formed of a resin composition formed of domain particles and a matrix, and the binder resin includes domain particles dispersed in the matrix. The average particle size of the domain particles is 5 μm or less, and the resin P1 constituting the domain particles is an acid-modified polymer synthesized from a vinyl monomer and then added with an acid, and its glass transition point Tg1 is 0 to 60.
The resin P2 constituting the matrix is a polymer synthesized from vinyl monomers, and its glass transition point Tg2 is 40 to 90°C, and the glass transition point Tg2 of the resin P2 is higher than that of the resin P1. A heat fixing toner characterized by having a glass transition point Tg1 higher than the glass transition point Tg1 by 10°C or more. 10. The heat fixing toner according to claim 9, wherein the resin P1 has a carboxyl group, and the resin P2 has substantially no carboxyl group. 11. The heat fixing toner according to claim 9, wherein the resin P1 has an acid value of 15 or more, and the resin P2 has an acid value of 10 or less. 12. The heat fixing toner according to claim 9, wherein 5 to 300 parts by weight of the resin P1 is blended per 100 parts by weight of the resin P2. 13. In a heat fixing toner having a binder resin, the binder resin is a resin composition formed of domain particles and a matrix, and the average particle size of the domain particles dispersed in the matrix is The resin P1 constituting the domain particles is an acid-modified polymer having an unsaturated double bond synthesized from a vinyl monomer and then added with an acid, and has a glass transition point Tg1 of 0 to 60°C. The resin P2 constituting the matrix is a polymer having unsaturated double bonds synthesized from vinyl monomers, and has a glass transition point Tg2 of 40 to 9.
0°C, and the glass transition point Tg2 of the resin P2 is
1. A toner for heat fixing, characterized in that the unsaturated double bonds of the resin P1 and the resin P2 are partially chemically bonded to each other, the glass transition point Tg1 being 10° C. or more higher than the glass transition point Tg1 of the resin P1. 14. The heat fixing toner according to claim 13, wherein the resin P1 has a carboxyl group, and the resin P2 has substantially no carboxyl group. 15. The heat fixing toner according to claim 13, wherein the resin P1 has an acid value of 15 or more, and the resin P2 has an acid value of 10 or less. 16. The heat fixing toner according to claim 13, wherein 5 to 300 parts by weight of the resin P1 is blended per 100 parts by weight of the resin P2.