JPH03206465A - Toner for heat fixing - Google Patents

Abstract

PURPOSE:To obtain the toner for heat fixing which allows low-temp. fixing and is wide in a fixing temp. range by forming A and B, which constitute a block copolymer, or styrene/methacryl copolymers and copolymerizing a vinyl monomer contg. a carboxyl group in at least either of the A and B. CONSTITUTION:The A and B which constitute the block copolymer are the copolymers synthesized from the styrene and methacryl monomers and the vinyl monomer contg. the carboxyl group is copolymerized in at least either of the A and B. A resin having at least >=2 points of glass transition points between 25 and 90 deg.C is used for the block copolymer. The toner for heat fixing which allows the low-temp. fixing and is wide in the fixing temp. range is obtd. in this way.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to everything from monochrome copying machines to full-color copying machines for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. The present invention relates to a toner for dry electrophotography.

[Prior Art] Conventionally, as an electrophotographic method, U.S. Patent No. 2,297,6
Although many methods are known, as described in Japanese Patent Publication No. 91, Japanese Patent Publication No. 42-23910, and Japanese Patent Publication No. 43-24748, etc., various methods are generally used using photoconductive substances. An electrical latent image is formed on the photoreceptor by a means, and then the latent image is developed using toner, and if necessary, the toner image is transferred to a transfer material such as paper, and then heated, pressure, solvent vapor, etc. It is used to fix images and obtain copies.

Various methods and techniques have been developed for the above-mentioned final step, which is the 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 heating roller.

The pressure heating method using a heating roller performs fixing by passing the toner image surface of the sheet to be fixed under pressure on the surface of a heating roller whose surface is made of a material that has releasability to the toner. . In this method, the surface of the heating roller and the toner image on the sheet to be fixed come into contact under pressure, so the thermal efficiency when fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be carried out quickly. , which is very effective in high-speed electrophotographic copying machines. However, in the above method, since the surface of the heating roller 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 surface of the fixing roller, 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. Preventing toner from adhering to the surface of the heating roller is considered to be one of the essential conditions for the heating roller fixed fixing method.

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.

Furthermore, many studies and practical applications have been made on two-color copying machines and full-color copying machines. For example, “Journal of Electrophotography Society J.
Vol 22, Nol (1983) and “Journal of Electrophotography Society J Vol 25, Nol, P. 52 (19
There are also reports on the color reproducibility and gradation reproducibility of 86).

However, unlike television, photographs, and color printed matter, they cannot be directly compared with the real thing, and for people who are used to seeing color images that are more beautifully processed than the real thing, the full-color electrophotographic images that are currently in practical use are not necessarily It has not been a satisfying experience.

In color electrophotography, which requires multiple development steps and the overlapping of several toner layers of different colors on the same support, the following conditions are necessary for the binder resin for color toners: It will be done.

(1) The fixed toner needs to be almost completely melted to such an 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.

In this way, for monochrome copiers, the fixing temperature range. It is desired to develop a binder resin for toner that has a wide range of offset resistance, and for full-color copiers, it not only has a wide fixing temperature range, but also the transparency of the resin and the flatness of the fixing surface when fixed. is required.

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 binder resin for toner is required that is capable of low-temperature fixing, has a wide fixing area, has excellent transparency, and has a flat fixing surface when fixed. be.

A method using pressure-fixed toner can also be considered, but in this method, when used as a full-color toner that reproduces colors by overlapping three or four colors, the binder resin does not dissolve, resulting in poor color mixing. The image becomes dull and desaturated.

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 toner binder resin solely for the purpose of low-temperature fixing.

For example, there is a method of lowering the molecular weight or glass transition point of the resin, but this method deteriorates the storage stability of the toner and causes phenomena such as blocking of the toners with each other and fusion to the developing drum or the like.

In addition, for the purpose of expanding the fixing temperature of conventional vinyl polymers, Japanese Patent Laid-Open No. 58-14148 and Japanese Patent Laid-Open No. 58-7294
8, JP-A-59-174855~6, JP-A-60-123855, JP-A-52-3304~
Publication No. 5, Special Publication No. 57-52574, Special Publication No. 5g
Although a method using an offset preventive agent is disclosed in Japanese Patent No. 8505, etc., it is an auxiliary agent, and the transparency of the toner is impaired especially when used as a mono-force toner, and when used as a full-force slurry toner, color mixing is impaired. Deteriorate.

Also, JP-A-56-158340 5 JP-A-58-8
6558, JP 58-203453, JP 59-88748, JP 59-22635
Publication No. 8, JP-A-60-45259, JP-A-60-Sho.
-45261 publication, Japanese Patent Application Laid-Open No. 60-46566,
Japanese Patent Publication No. 60-2411 discloses a toner binder resin having a low molecular weight component and a high molecular weight component. By using these resins, it has become possible to expand the fixing temperature to a certain extent, but due to the presence of high molecular weight components such as gels, the grindability may deteriorate and the melt viscosity during hot kneading may become too high. There is a problem, and
In particular, when used as a full strength toner, the smoothness of the fixing surface upon fixing is impaired, resulting in poor color mixing properties.

That is, 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.

[Problems to be Solved by the Invention] An object of the present invention is to provide a new toner for electrophotography that improves these problems.

That is, an object of the present invention is to provide a toner for heat fixing that is capable of low temperature fixing and has a wide fixing temperature range.

Still another object is to provide a toner for heat fixing that has excellent storage stability and fluidity, does not cause aggregation, and has excellent impact resistance.

Still another object is to provide a heat-fixing toner that has good charging properties and is always stable during use, and provides clear and fog-free images.

Another object of the present invention is to provide a heat fixing toner that, when used as a full strength toner, can form a smooth fixing surface so that the fixed toner does not diffusely reflect light and interfere with color reproduction. It's about doing.

Yet another object is to provide a heat-fixing toner which, when used as a full-strength toner, has color mixing properties that do not interfere with toner layers of different tones underlying the toner layer.

[Means and actions for solving problems] (ABAAl n
In a toner containing a binder resin containing a type block copolymer (n = 1 to 20) or a mixture of the block copolymer and a vinyl polymer, A and B constituting the block copolymer are The object of the present invention is achieved by a copolymer synthesized from styrene-based and methacrylic-based monomers, in which a vinyl monomer containing a carboxyl group in at least one of A and H is copolymerized.

Here, the block copolymer used is a resin having at least two glass transition points between 25 and 90°C.

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

It is known that conventional block copolymers have a so-called sea-island structure. Naturally, the largest component is the ocean, and the smallest component is the island. Therefore, in the ABA type block copolymer, A
B forms an island in the ocean.

For example, in Japanese Patent Publication No. 57-6585, the glass transition point of the A segment is 20 as a resin for pressure fixing toner.
A method using an ABA type block copolymer, which is a soft polymer with a temperature lower than 50°C and a tough polymer with a B segment glass transition point higher than 50°C, is disclosed.

The most common fixing method today is the heating method. In particular, the pressure heating method using a heated roller performs fixing by passing the toner image surface of the sheet to be fixed under pressure while contacting the surface of a heated roller whose surface is made of a material that has releasability for toner. It is. In this method, the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, so the thermal efficiency when fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. It is very effective in electrophotographic copying machines.

However, the temperature inside the machine may rise due to heat during fixing. For this reason, an undesirable phenomenon of blocking of the toner during storage may occur, and there has been a significant demand for blocking. In such heat fixing, toner obtained using a resin having a soft polymer with a glass transition point lower than 20° C. as component A tends to block in the device, and as a result, the fluidity of the powder is poor and a good image cannot be obtained. difficult to obtain.

Furthermore, although fixing is possible as described in heat fixing, high temperature offset occurs because a soft polymer with a glass transition point lower than 20°C occupies the sea part of the sea/island structure. Therefore, the fixing temperature range becomes narrow when the heat roller is used constantly.

Therefore, as a result of intensive research, the present inventors have found that, in the sea/island structure of (ABA) n-type block copolymer (n = 1 to 20), by making the sea and islands have a certain configuration, the above-mentioned We have now invented a toner with excellent low-temperature fixing properties that does not cause the problems described above.

In other words, in the sea/island structure, the A segment, which is the sea, provides blocking resistance and high temperature offset resistance, and the B segment provides low temperature fixing property. That is, for the purpose of functional separation, the monomer composition ratio of the A segment and the B segment is changed, and the A segment and the B segment have different glass transition points (TgA.Tg+i), and 25°C≦Tgll<TgA≦95℃ It is something to do.

With this configuration, a toner with excellent low-temperature fixing properties can be obtained because the A segment is a sea and the B segment is an island. Due to the existence of the A segment, which is a sea of continuous phase, anti-blocking properties are achieved.

On the other hand, during heating during fixing, low-temperature fixability is provided by the action of the B segment.

Here, since the A segment and the B segment are connected to each other, unlike the case where each exists separately, such as in a polymer blend, the A segment and the B segment interact with each other. It is presumed that the high-temperature offset resistance of the segment and the low-temperature fixing property of the B segment are compatible.

In order to further satisfy the object of the present invention, the present inventors have made extensive studies and found that even better results can be obtained by copolymerizing a vinyl monomer containing a carboxyl group.

In other words, in addition to the effects of the sea and island structure, the polarity of the binder resin increases by copolymerizing vinyl monomers containing carboxyl groups, resulting in improved affinity for paper and improved fixing properties. It is something to do.

Therefore, it becomes possible to increase the Tg (glass transition point) of the binder resin, and the blocking resistance is further improved.

Furthermore, such a binder resin makes it possible to utilize the crosslinking reaction between the metal compound and the carboxyl group, making it possible to control the viscosity during hot melting and further improving fixing properties and offset properties.

Here, if Tga is lower than 25° C., blocking occurs even if TgA is increased, and if TgA exceeds 95° C., toner fixability deteriorates.

Furthermore, the glass transition points (Tga, Tgs) of A and B in the block copolymer are 25°C≦Tga<
It is desirable that TgA≦95°C, more preferably 30°C≦Tga<TgA≦90°C. More preferably, TgA and TgB are separated by 10° C. or more.

Note that the heat fixing method refers to a method of fixing by heating, such as a pressure heating method using a heat roller, a method of fixing by pressing the recording member against the heating member and bringing the recording member into close contact with the heating member via a film, etc. There is.

The copolymer A or B constituting the (ABA) n-type block copolymer used in the present invention is synthesized from the following styrenic and methacrylic monomers and/or vinyl monomers containing carboxyl groups.

Examples of styrenic monomers include styrene, O-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,
4-dimethylstyrene, p-n-butylstyrene, p-
tert-butylstyrene, I)-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-chlor Styrene, 3.
Examples include styrene derivatives such as 4-dichlorostyrene, m-nitrostyrene, 0-nitrostyrene, and p-nitrostyrene.

Examples of methacrylic monomers include methyl methacrylate,
Examples of methacrylic acid esters include ethyl methacrylate, probyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, and phenyl methacrylate. It will be done.

The carboxyl group-containing vinyl monomer used in the present invention includes acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, maleic anhydride, fumaric acid, maleic acid and their methyl, ethyl, butyl,
There are 2-ethylhexyl monoesters, and one or more of these may be used. Among these, methacrylic acid, maleic anhydride, and cinnamic acid are particularly preferred in consideration of the hygroscopicity of the polymer.

The above monomer is (ABA). It may be copolymerized in an amount of 1 to 30% by weight, preferably 2 to 20% by weight, based on the type block copolymer.

Further, it may be copolymerized with either A or B or with both.

When copolymerizing both A and B, the amounts added may be the same or different for A and B.

In addition, the monomer composition ratio in the copolymer of A is styrene/
Methacrylic type = 98/2 to 35/65 preferably 95
/5 to 45/65, and the monomer composition ratio in the cobolimer B is styrene/methacrylic = 9575 to
It is desirable that the ratio be in the range of 30/70, preferably 90/10 to 40/60. However, it is also possible to copolymerize other monomers within a range that does not affect the present invention.

The binder resin used in the present invention only needs to contain an ABAln type block copolymer, but in order to more effectively exhibit the properties of the block copolymer, it is necessary to contain the block copolymer in the binder resin. It is desirable that the copolymer is contained in an amount of at least 30% by weight, preferably 50% by weight or more.

In addition, the glass transition point of a polymer synthesized from a vinyl monomer other than the block copolymer in the binder resin or a mixture of such polymers is 45°C to 85°C in order to exhibit the properties of the block copolymer. It is desirable that the temperature is preferably 55 to 70°C.

Furthermore, the glass transition point of A and B in the block copolymer (
TgA, Tg++) is 25℃≦TgB< as mentioned above.
It is desirable that TgA≦90°C, more preferably 30°C≦Tgi<TgA≦85°C.

The toner for electrophotography according to 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 synthesized from the (ABA) n-type block copolymer and/or vinyl monomer or the mixture of the polymers used as the binder resin is l500~30000
Preferably 2500 to 20000, weight average molecular weight (
Mw) is 4,000 to 50,000, preferably 6,000 to 3
It is desirable that it is 5000. In addition, when used as a one-component system or monocolor, the number average molecular weight (Mn) of the binder resin is 2,500 to 40,000, preferably 3,500.
~20000, weight average molecular weight (Vi w) is 200
00-500000 preferably 35000-35000
It is desirable that it be 0.

Also, (ABA). It is desirable that the repeating number n of the type block copolymer is 1 to 20. This is because when n exceeds 20, the properties of the block copolymer are lost, similar to random or alternating copolymers. Therefore,
For full color applications with low molecular weight, more preferably n=1
-lO, and when used as a one-component system with a high molecular weight or a monocolor system, it is more desirable that n=1 to 15, since the above-mentioned properties of the block copolymer can be exhibited.

The vinyl monomers constituting the binder resin mixed and used in the present invention include the following.

For example, styrene, 0-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
- Styrene derivatives such as chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, 0-nitrostyrene, p-nitrostyrene, and ethylene and unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; Unsaturated diolefins such as butadiene and isobrene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl acetate,
Vinyl esters such as vinyl blobionate and vinyl benzoate; methacrylic acid and methyl methacrylate, ethyl methacrylate, probyl methacrylate, methacrylic acid n
-butyl, isobutyl methacrylate, n- methacrylate
Octyl, dodecyl methacrylate, 2-methacrylate
α-methylene aliphatic monocarboxylic acid esters such as ethylhexyl, stearyl methacrylate, phenyl methacrylate; acrylic acid and methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, probyl acrylate, acrylic acid n-octyl,
Dodecyl acrylate, 2-ethylhexyl acrylate,
stearyl acrylate, 2-chloroethyl acrylate,
Acrylic acid esters such as phenyl acrylate; maleic acid, maleic acid half ester; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isobropenyl ketone N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrolidone; vinylnaphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; acrolein, etc. One type or a combination of two or more types can be used.

Polymers synthesized from vinyl monomers can be obtained by commonly known methods, such as solution or suspension polymerization using peroxides as initiators.

Also (ABA). Methods for synthesizing type block copolymers are disclosed in JP-A-63-278910 and JP-A-64-
Examples include the method of bulk polymerizing or solution polymerizing a radically polymerizable vinyl monomer with light using a polymerization initiator having a dithiocarbamate group, which is disclosed in JP-A No. 6013, JP-A No. 64-26619, and the like.

The toner for electrophotography according to the present invention can be applied to either one-component or two-component toner. Therefore, 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.

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

For example, when the toner of the present invention is used as a magnetic 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 l5, C. L. 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 S1 Hansa Yellow G, permanent yellow NCG, tartrazine lake, red yellow lead, molybdenum orange, permanent orange GTR, virazolone orange, benzidine orange G1 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
First Sky Blue, Indance Blue BC,
Chrome green, chromium oxide, pigment green B,
There are 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 a coloring pigment for magenta, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9
, 10, 11, 12, 13, 14, 15,
16, 17, 18, 19, 21, 22,
23, 30, 31, 32, 37, 38, 39
, 40, 41, 48, 49, 50, 51,
52, 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 l, 2, 10, 13. 15,
23, 29. 35, etc.

Although a pigment may be used alone, it is more preferable to use a dye and a pigment in combination to improve the clarity from the viewpoint of image quality of a full-color image.

As magenta dye, C. I. solvent red l
, 3, 8, 23, 24, 25, 27
, 30, 49, 81, 82, 83, 84,
100, 109, 121; C. I. Dispersed Red 9, c. r. Solvent Violet 8, 13
, 14, 21, 27. C. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic red l, 2, 9, 12, 13, 14, 15,
17, 18, 22, 23, 24, 27, 2
9, 32, 34, 35, 36, 37. 3g,
39, 40; C. I. basic violet 1
, 3, 7, 10, 14, 15, 21, 2
5, 26, 27. Examples include basic dyes such as No. 28.

As a coloring pigment for cyan, 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 formula (1) substituted with 1 to 5 phthalimidomethyl groups.

n=1 to 5 (blank below) 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, 83; C. I
．． Bat yellow 1, 3. 20, etc.

The amount of coloring agent used is 0.00 parts by weight per 100 parts by weight of the binder resin.
The amount is 1 to 60 parts by weight, preferably 0.5 to 50 parts by weight.

Further, the toner in the present invention is not limited to negatively chargeable or positively chargeable, but when producing a negatively chargeable toner,
In particular, it is preferable to add a charge control agent for the purpose of stabilizing the negative charge characteristics. As a negative charge control agent, for example, a metal complex of alkyl-substituted salicylic acid (for example, Z-tert
-organometallic complexes such as chromium complexes or zinc complexes of 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 mo1%, preferably 1 to 30 mof, of positively chargeable aminocarboxylic acid esters such as dimethylamine methyl methacrylate are used as monomers.
% of the binder resin is used, or a colorless or light-colored positive charge control agent that does not affect the color tone of the toner may be used. As a positive charge control agent, for example, structural formula (A
)n(B) and the like.

Structural formula (A) Structural formula (B) Among the quaternary ammonium salts represented by structural formulas (A) and (B), structural formulas (A)-1, -2. Structural formula (B)-
It is preferable to use the positive charge control agent represented by 1 because it exhibits good charging properties with little environmental dependence.

Structural formula (A)-1 Structural formula (A)-2 Structural formula (B)-1 In addition, dimethylamine methyl methacrylate, which exhibits positive charging characteristics, can be used as a resin component of the binder resin in positively charging toner. When using aminocarboxylic acid esters, 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 preferably 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin.

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, the amount of the positive charge control agent is 0.0% per 100 parts by weight of the binder resin. It is desirable to use 1 to 15 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 the binder resin 1 as necessary in order to provide good chargeability with less environmental dependence.
It is desirable to use O-10 parts by weight, preferably O-8 parts by weight, per 00 parts by weight.

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

As the fluidity improver used in the present invention, any fluidity improver 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 thearate, lead stearate, etc.; or metal oxides, i.e., zinc oxide powder, etc.; or finely powdered silica, i.e., wet process silica,
There are dry-processed silica, and treated silica that is surface-treated with silane coupling agents, titanium coupling agents, silicone oil, etc.

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. 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.

StCI! 4+ 2 H2+ O■→SiO■+4 H
Cj) Also, 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, These are also included.

The average primary particle size of the particles is desirably within the range of 0.001 to 2μ, particularly preferably o. o
It is preferable to use fine silica powder within the range of oz to 0.2μ.

Commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds used in the present invention include those commercially available under the following trade names, for example.

AEROSIL 130
(Japan Aerosil Co., Ltd.) 200 300 380 TT600 MOXl70 MOX 80 COK 84 Ca-0-SiL
M-5 (CABOT Co.) MS-7MS-75 HS-5 EH-5 CHEMIE GMBH) T30 T40 D-C Fine Silica (Dow Corning Go.) Fransol (Franzil) Furthermore, it is more preferable to use treated silica fine powder obtained by hydrophobicizing silica fine powder produced by gas 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 reacting with fine silica powder or chemically treating with an organosilicon compound that physically adsorbs it.

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, benzyldimethylchlorosilane, promomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmerbutane, trimethylsilylmercabutane, Organosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane,
Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and siloxane units having 2 to 12 siloxane units per molecule, each having l units at the terminal position. Examples include dimethylborisiloxane containing a hydroxyl group bonded to Si. These may be used alone or in a mixture of two or more.

? The particle size of the treated silica fine powder is 0.003-0.
It is preferable to use one in the range of 1μ.

Commercially available products include Taranox 500 (Talco),
Examples include Aerosil R-972 (Nippon Aerosil Co., Ltd.).

For 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 H2NCH2CH■CHzS1(OCHs)sH2NC
H2CH2CH2Si(OC2H5)! HJCONHC
HzCHtCHzSi(oc2ufi)s? 1. NcH
．． (:H■NHCH2CH2CH2S1(OCH3)3
H. NCH. C:H. NHCH. CH2NHCH. CH
．． CH. Si (OCH.). H3CgOCOCHiC
HJHCHaCH2CHiSi (QC}+3) aH
sCzOCOCHxCHJ}ICHzCHJHCHxC
HaCHgSl (OCHs) sHzCOCOCH2
CHxNHCHHzCH2NHCHxCHzCHzS1
(OCHz) aH-C2 \H. N +sr (OCHS) 1 ◎→HCHiCHxCHgSi (OCHs)st{J
CHzCHJHCHz+ CHaCHzSi (OCH
s) sH2NCH2 +CH2CHzSl(OCHa
)3o2NcH2cHJHcH2+CH2CH2Si
(ocl{3). }10CH2CH2 \ (}12co) 3sicHzcH*cHz-Nl{C
H2(82CO)3SiC}{2CH2CH2-NHC
H2 (H゜0・0)・SiCHzCl{zcHz, NH / (H6C20)ssicHzcl{zcHiLc? lI
{cLc}+2cLsi(OCJs)sHaN (CH
2CH-NH) 2cH2CHaCHaSl (OCH
s) sHsC-NHCONHC3HaS1(OCHs
) 3 and other aminosilane coupling agents.

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

(Here, R1 represents hydrogen, an alkyl group, an aryl group, or an alkoxy group, R2 represents an alkylene group or a phenylene group, and Rs and R- represent hydrogen, an alkyl group, or an aryl group. However, the above alkyl group , an aryl group, an alkylene group, and a 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 represent positive integers. ) Examples of such silicone oils having amino groups include the following.

SF84L7 (Toray KF393 KF857 KF860 KF861 KF862 KF864 KF865 ・Manufactured by Silicone Company) (Manufactured by Shin-Etsu Chemical Company) (Manufactured by Shin-Etsu Chemical Company) (Manufactured by Shin-Etsu Chemical Company) (Manufactured by Shin-Etsu Chemical Company) (Manufactured by Shin-Etsu Chemical Company) (Manufactured by Shin-Etsu Chemical Company) (Manufactured by Shin-Etsu Chemical Company) ) (manufactured by Shin-Etsu Chemical) 1200 3500 60 360 70 830 250 7600 3500 2000 750 1900 1700 3800 90 4400 KF369 (manufactured by Shin-Etsu Chemical) 20
320KF383 (manufactured by Shin-Etsu Chemical)
20 320X-22-3680 (manufactured by Shin-Etsu Chemical) 90 8800X-22-380
D (manufactured by Shin-Etsu Chemical) 2300 3800
X-22-3801C (manufactured by Shin-Etsu Chemical) 3500
3800X-22-3810B (manufactured by Shin-Etsu Chemical Co., Ltd.) 1300 1700 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.

It is preferable to use silica fine particles treated with a coupling agent or silicone oil containing these amino groups and 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.

As the carrier used in the present invention, for example, surface-oxidized or unoxidized metals such as iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earths, alloys or oxides thereof, 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 above-mentioned 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, and g-tert-
It is appropriate to use metal complexes of butylsalicylic acid, styrene resins, acrylic resins, boriacid, polyvinyl butyral, nigrosine, aminoacrylate resins, basic dyes and their lakes, fine silica powder, fine alumina powder, etc., singly or in combination. However, it 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 30% by weight) based on the carrier of the present invention.
20% by weight) is desirable.

The average particle size of these carriers is preferably 10 to 100 microns, preferably 20 to 70 microns.

A particularly preferred embodiment is a ternary ferrite of Cu-Zn-Fe, whose surface is coated with a combination of resins such as fluororesin and styrene resin, such as polyvinylidene fluoride and styrene-methyl methacrylate resin; Fluoroethylene and styrene-methyl methacrylate resin, fluorine-based copolymer and styrene-based copolymer;
etc. 90:10 to 20:80, preferably 70:30
~30:70 ratio mixture, 0.01~
Examples include coated ferrite carriers coated with 5% by weight, preferably 0.1 to 1% by weight, and having the above-mentioned average particle size and containing 70% by weight or more of carrier particles of 250 mesh pass and 400 mesh on. Examples of the fluorine-based copolymer include vinylidene fluoride-tetrafluoroethylene copolymer (10:90-90:10), and examples of the styrene-based copolymer include styrene-2-ethylhexyl acrylate (20:80-20:80). 80: 20).
Styrene-2-ethylhexyne acrylate-methyl methacrylate (20-60:5-30:10-50) 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 as the toner concentration in the developer.
% to 15% by weight, preferably 4% to 13% by weight
Usually good results are obtained. Toner concentration is 2%
If it is less than 15%, the image density will be too low to be practical, and if it is more than 15%, fogging 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.

・Measurement of glass transition temperature Tg In the present invention, a differential thermal analysis measuring device (DSC measuring device), DSC-7 (manufactured by PerkinElmer) is used.
Measure using.

The sample to be measured is accurately weighed in an amount of 5 to 20 mg, preferably 10 mg.

This is placed in an aluminum pan, and using an empty aluminum pan as a reference, measurement is performed at room temperature at a temperature increase rate of 10° C./min within a measurement temperature range of 30° C. to 200° C.

In this temperature raising process, an endothermic peak of the main beak in the temperature range of 40 to 100°C is obtained.

The intersection of the line between the midpoints of the base lines before and after the endothermic peak appears and the differential thermal curve is defined as the glass transition temperature Tg in the present invention.

-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 THE column was added as a solvent to the column at this temperature.
(Tetrahydrofuran) is flowed at a flow rate of 1 mg per minute, and a THF sample solution of the resin adjusted to a sample concentration of 0.05 to 0.6% by weight is injected 50 to 200 times for measurement. 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 boristyrene sample for preparing the calibration cotton, for example, Pressure Chemical Co. Made or
Manufactured by Toyo Soda Kogyo Co., Ltd. with a molecular weight of 6 x 10”, 2.
lX 10", 4 X 103, 1.75X 10'
,5. IX 10', l. IX 10@, 3.9X
10', 8.6X 10', 2 X 10', 4
．． It is appropriate to use a standard polystyrene sample of at least 1O point. or,
An Rl (refractive index) detector is used as a detector.

In addition, in order to accurately measure the molecular weight range of 10'' to 2 x 10', it is recommended to use a combination of commercially available polystyrene gel columns, such as Waters (
μ-styragel (manufactured by Waters)
l) 500. 10", 10', 10" combination, or Showa Denko's shodex
KF-1110M, KF-801, 803, 80
4, 805 combination, KA-802, 803, 80
4, 805 combination or TSKg manufactured by Toyo Soda
elG1000H, G2000H, G2500H,
G3000H, G4000H, G5000H, G
A combination of 6000H, G7000H, and GMH is preferred.

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

In addition, all parts indicate parts by weight.

Resin production example l The first stage of polymerization was placed in a glass reaction vessel, the inside of the vessel was sufficiently replaced with nitrogen, the vessel was tightly sealed, and the vessel was placed 15cm away from the reactor at a 400°C.
A W ultraviolet lamp was placed and the reaction was carried out for 15 hours.

After the reaction, a portion was sampled and its molecular weight was measured by GPC. As a result, it had a number average molecular weight (]!iifn) of 3900 and a weight average molecular weight (Mw) of 8500. Moreover, the glass transition point (Tg) was 42°C.

Thereafter, a second stage polymerization was carried out as follows to obtain an ABA type block copolymer.

After mixing and dissolving these, 15 minutes under the same conditions as above.
Polymerization was carried out by irradiating ultraviolet light for a period of time.

After the reaction, this copolymer was purified by reprecipitation using hexane,
Dry under reduced pressure. The tan of this copolymer by GPC is 1
4000, MW was 31500, and two Tg values were observed: 43°C and 65°C. The ABA type block copolymer obtained here is referred to as resin A.

Resin Production Example 2 The first stage of polymerization was placed in a glass reaction vessel, the interior of the vessel was sufficiently purged with nitrogen, the vessel was tightly sealed, and a 400 W ultraviolet lamp was placed 15 cm away from the reactor for reaction for 15 hours.

After the reaction, a portion was sampled and its molecular weight was measured by GPC. As a result, a number average molecular weight (Mn) of 4200 and a weight average molecular weight (Mw) of 8700 was obtained. Moreover, the glass transition point (Tg) was 44°C.

Thereafter, a second stage polymerization was carried out as follows to obtain an ABA type block copolymer.

After mixing and dissolving these, 15 minutes under the same conditions as above.
Polymerization was carried out by irradiation with ultraviolet light for a period of time. After the reaction, this copolymer was purified by reprecipitation using hexane and dried under reduced pressure.

The Mn of this copolymer by GPC is 12500, MW
was 33,000, and two Tg values were observed: 43°C and 67°C. The ABA type block copolymer obtained here is referred to as resin A. Resin Production Example 3 The first stage of polymerization was placed in a glass reaction vessel, the interior of the vessel was sufficiently purged with nitrogen, the vessel was tightly sealed, and a 400W ultraviolet lamp was placed 15 cm away from the reactor to allow reaction for 15 hours.

After the reaction, a portion was sampled and the molecular weight was measured by GPC, and the number average molecular weight (Mn) was 4100 and the weight average molecular weight (lli (w) was 8500.The glass transition point (Tg) was 44°C. there were.

Thereafter, a second stage polymerization was carried out as follows to obtain an ABA type block copolymer.

After mixing and dissolving these, 15 minutes under the same conditions as above.
Polymerization was carried out by irradiating ultraviolet light for a period of time.

After the reaction, this copolymer was purified by reprecipitation using hexane,
Dry under reduced pressure. The Mn of this copolymer by GPC is 13
000, MW is 33000, Tg is 43℃ and 6
Two points at 6°C were observed. The ABA type block copolymer obtained here is referred to as resin A.

Hereinafter, resins D and E and resin F of Comparative Example 1 were determined by the amount of initiator,
Synthesis was carried out by changing the styrene/n-butyl methacrylate ratio.

(Left below) Using resin production comparative examples 2 and 3, Mn120 was obtained by generally known solution polymerization.
00, Mw 28000, and Tg 57°C. The random copolymer obtained here is referred to as Resin G (Comparative Example 2).

In addition, the amount of penzoyl peroxide was reduced to 5 g and the same reaction was performed to obtain M n 14500 M w 620
00, a random copolymer with a Tg of 65°C was obtained. The resin obtained here is referred to as H (Comparative Example 3).

Example 1 was melt-kneaded in a roll mill, cooled, coarsely pulverized, finely pulverized, and classified, and further treated with hexamethyldisilazane as a fluidity improver. 0.5 part of fine silica powder was added to 100 parts of the classified product. A toner was prepared by externally adding 0.2 part of aluminum oxide fine powder.

As a carrier, styrene-acrylic 2-ethylhexy-methyl methacrylate (copolymerization weight ratio 50:2
0:30) coated with 0.5% by weight of Cu-
Zn-Fe ferrite carrier (average particle size 45pm,
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 which was simply developed and transferred using a Canon full color copying machine CLC-500, and a fixing test was performed using an external fixing device.

As a result, the fixing temperature range where colors can be mixed is 120 to 210 degrees Celsius.
Met.

An image reproduction test was conducted using CLC-500 using these developers and toners.

As a result, even after printing 15,000 sheets in monochrome mode, there was no offset to the fixing roll, and a full-color image that faithfully reproduced 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.

Further, when the toner was left in a hot air dryer at 45° C. for 3 days to check the blocking state of the toner, no change was observed and it had good fluidity.

Examples 2 and 3 and Comparative Examples 1 and 2 The same procedure as in Example 1 was performed except that the resins were changed to B, C, F, and G, and the results shown in the following table were obtained.

(Left below) 10 parts of the glutinous rice paste was melt-kneaded in a roll mill, cooled, coarsely pulverized, finely pulverized, and classified. Furthermore, 0.0% of positively charged hydrophobized dry silica was added as a flow improver to 100 parts of the classified product. A one-component magnetic toner was prepared by externally adding 6 parts.

An unfixed image was obtained using this toner using a Canon copier NP-4835, and a fixing test was performed using an external fixing device. As a result, the fixable range was 120 to 200°C.

Furthermore, an image reproduction test was conducted using this toner and a copying machine. As a result, after printing 10,000 sheets, there was no offset to the 6 fixing rolls, and a good image without fogging or scattering was obtained.

In addition, the blocking resistance was checked in the same manner as in Example 1 and was found to be good.

Example 5 and Comparative Example 3 The same procedure as Example 4 was carried out except that the resins were changed to E and H, and the results shown in the following table were obtained.

Table 3 [Effects of the Invention] According to the present invention, by using a specific ABA type block copolymer as the binder resin, it is possible to achieve both the high temperature offset resistance of the A segment and the low temperature fixing property of the B segment. This toner is suitable for fixing methods.

Claims (1)

[Claims] (1) (ABA)_n-type block copolymer (n=1-2
0), or a toner containing a binder resin containing a mixture of the block copolymer and a vinyl polymer, wherein A and B constituting the block copolymer are styrene-methacrylic copolymers; , A and B are copolymerized with a vinyl monomer containing a carboxyl group, and the block copolymer has at least two glass transition points between 25 and 95°C. Toner for heat fixing.