JPH03217848A - Toner for thermal fixing - Google Patents

Abstract

PURPOSE:To extend the fixing temp. range of a toner as well as to enable fixing at low temp. by using a specified ABA block copolymer as a binding resin and copolymerizing a vinyl monomer contg. a carboxyl group. CONSTITUTION:A (ABA)n block copolymer (n=1-20) is ocomposed of a copolymer A synthesized from styrene and methacrylic monomers and a copolymer B synthesized from styrene and acrylic monomers and a vinyl monomer contg. a carboxyl group is copolymerized with at least one of the copolymers A, B. Both the anti-offsetting property of the segment A at high temp. and the fixability of the segment B at low temp. can be ensured. The fixability of the block copolymer is improved by copolymerizing the vinyl monomer contg. a carboxyl group.

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 heat fixing.

[Prior Art] Conventionally, as an electrophotographic method, U.S. Patent No. 2,297,69
Although many methods are known, as described in Japanese Patent Publication No. 1, Japanese Patent Publication No. 42-23910, and Japanese Patent Publication No. 43-24748, etc., they generally utilize photoconductive substances and perform various methods. forming an electrical latent image on the photoreceptor by means;
Next, the latent image is developed using toner, and if necessary, the toner image is transferred to a transfer material such as paper, and then fixed by heat, pressure, solvent vapor, or the like to obtain a copy.

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 hole.

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 heating roller surface and the toner image come into contact with each other under pressure in a molten state, a portion of the toner image adheres to the fixing roller surface and is transferred to the next sheet to be fixed. This may cause a so-called offset phenomenon and stain the sheet to be fixed. 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.

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 J Vol 22, Not (1983) Journal of Electrophotography Society J Vol 25, Nol, P.52 (
There are also reports on color reproducibility and gradation reproducibility, such as (1986).

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 is not satisfactory.

In full-color electrophotography, development is performed multiple times and several toner layers of different colors are superimposed on the same support.For color electrophotography, the binder resin for color toners must have the necessary conditions. Examples include the following:

(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.

As described above, for mono-color copying machines, it is desirable to develop toner binder resins with a wide fusing temperature range and high offset resistance. It is required that the fixing surface be flat when it is fixed.

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, it is necessary to use a toner binder resin that is capable of low-temperature fixing, has a wide fixing area, has excellent transparency, and has a flat fixing surface when fixed, as mentioned above. It is.

A method of using pressure-fixed toner is also 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 properties. 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 of the resin or the glass transition point, but this method deteriorates the storage stability of the toner and causes phenomena such as toner blocks together or 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. 58
-8505, etc., discloses a method of using an anti-offset agent, but it is an auxiliary agent, and the transparency of the toner is impaired, especially when used as a mono-color toner, and when used as a full-color toner, color mixing properties are poor. Become.

Also, JP-A-56-158340, JP-A-58=
No. 88558, Japanese Patent Application Laid-open No. 58-203453,
JP-A-59-88748, JP-A-59-2263
No. 58, JP-A-60-45259, JP-A-6
Binder resins for toners having a low molecular weight component and a high molecular weight component are disclosed in Japanese Patent Publication No. 0-45261, Japanese Patent Application Laid-Open No. 60-4656fi, Japanese Patent Publication No. 60-2411, and the like. 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,
In addition, especially when used as a full color toner, the smoothness of the fixing surface is impaired when it is fixed, 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 heat-fixing toner 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.

Still another object is to provide a toner for heat fixing that, when used as a full color toner, can form a smooth fixing surface so that the fixed toner does not diffusely reflect light and interfere with color reproduction. There is a particular thing.

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

[Means and actions for solving problems] (ABA). 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 polymer synthesized from a vinyl-based 1000 polymer, the block copolymer constitutes A is a copolymer synthesized from styrene and methacrylic monomers, and B constituting the block copolymer is a copolymer synthesized from styrene and acrylic monomers, and at least one of A and B. The object of the present invention can be achieved by copolymerizing a vinyl monomer containing a carboxyl group with.

A resin whose block copolymer has a glass inversion point of at least two points between 25 and 95° C. is used.

The present inventors have concluded 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 an ABA type block copolymer, A forms the sea and B forms the island.

For example, in Japanese Patent Publication No. 57-6585, as resins for pressure fixing toners, component A is a soft polymer with a glass inversion point of less than 20°C, and component B is a tenacious polymer with a glass inversion point of more than 50°C. A method using an ABA type block copolymer 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 requirements for blocking have also become stricter. 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 for heat fixing is narrow.

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 aforementioned problems.

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 B points (TgA, Tga), and 25°C≦TgB<TgA≦95°C. That is. 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 presence of A, which is a sea of continuous phase, it is important for blocking resistance.
Achieved by segments.

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 effect of the sea-island structure, the polarity of the binder resin is increased by copolymerizing the vinyl-based 1000 polymer containing carboxyl groups, which improves its affinity for paper and improves its fixing properties. This will improve the results. Therefore, it becomes possible to increase the T'g (glass transition point) of the binder resin, and the block 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 Tgl! If l 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 point (TgA, Tga) of A and H in the block copolymer is 25°C≦Tga<
It is desirable that TgA≦95°C, more preferably 30°C≦Tga<TgA≦90°C. More preferably, TgA and Tga are separated by 10° C. or more.

Here, 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>. type block copolymer used in the present invention) is made of the following styrenic and/or acrylic and/or methacrylic monomers and/or vinyl monomers containing carboxyl groups. be synthesized.

Examples of the styrenic polymer include styrene, 0-methylstyrene, I-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, l)-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-chlor Styrene, 3
．． Examples include styrene derivatives such as 4-dichlorostyrene, I-nitrostyrene, 0-nitrostyrene, and p-nitrostyrene.

Acrylic monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, probyl acrylate, n-cutyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, and acrylic. Examples include acrylic acid esters such as 2-chloroethyl acid and phenyl acrylate.

The composition ratio in the copolymer B is styrene/acrylic = 95/5 to 50/50 (preferably 90/10)
It is desirable that the ratio be in the range of ~60/40.

Examples of methacrylic monomers include methyl methacrylate,
Examples include methacrylic acid esters such as 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 monomers used in the present invention include acrylic acid, metalliclic 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 monomer composition ratio in the copolymer A is styrene/methacrylic = 98/2 to 35/65, preferably 95/5
It is desirable that it be in the range of ~45/65. However, it is also possible to copolymerize other monomers within a range that does not affect the present invention.

The above monomers may be copolymerized in an amount of 1 to 30% by weight, preferably 2 to 20% by weight, based on the ABA block polymer. Furthermore, either A or B may be copolymerized to one side, or both A and B may be copolymerized. When copolymerizing with both A and B, A and B
They may be added in different amounts or may be used in the same amount. In addition, copolymerization of other monomers is not prohibited.

The binder resin used in the present invention may contain (ABA) type block copolymer, but in order to more effectively exhibit the properties of the block copolymer, it is necessary to include The block copolymer is at least 30 wt% or more,
It is desirable that the content is preferably 50 wt% or more.

On the other hand, as the reactive metal compound used when crosslinking a carboxyl group and a metal compound by heat or the like, those containing the following metal ions can be used. Suitable monovalent metal ions include Na''', Li'', Cs''
, Ag", Hg", Cu+, etc., and divalent metal ions include 13e24. Mg”, Ca”, }
{g"Sn2""Pb"Fe24Co",
Ni"Zn", etc. In addition, as trivalent ions, Ap3" Sc3+Fe 3 + , Co
3 + , N 1 3 + . C r 3 ”.
There are Y3 etc. Among the compounds containing metal ions as mentioned above, the more decomposable the compound, the better the results. This is presumed to be because metal ions in the decomposable compounds more easily bond to carboxyl groups in the polymer through thermal decomposition.

Among the reactive metal compounds, organometallic compounds have excellent compatibility and dispersibility with the polymer, and crosslinking by reaction with the metal compound proceeds more uniformly in the polymer, giving better results.

Among the above-mentioned reactive organometallic compounds, those containing organic compounds with high vaporizability and sublimation properties as ligands and counterions are particularly useful.

Examples of organic compounds that form ligands and counterions with metal ions and have the above properties include salicylic acid, salicylamide, salicylamine, salicylaldehyde, salicyrosalicylic acid, ditertiarybutylsalicylic acid, Salicylic acid and its derivatives such as, for example, β-diketones such as acetylacetone, probione acetone, etc., for example, low molecular weight carboxylic acid salts such as acetate and brobionic acid.

It is also possible to impart charge controllability to the toner particles to the metal complex. Examples of such metal complexes include azo metal complexes represented by the following general formula [I].

[I] (In the formula, M represents a coordination center metal, such as Cr, Go, Ni. , ffil group. In this case, substituents include a nitro group, a halogen group, a carboxyl group, an anilide group, and an alkyl group having 1 to 18 carbon atoms, an alkoxy group, etc. X, X' , Y, Y'
-(:0- -NH- -NR- ( R
is an alkyl group having 1 to 4 carbon atoms). K@ represents hydrogen, sodium, potassium, ammonium, or aliphatic ammonium. ) Next, specific examples of the complex will be shown.

(Left below) Or the following general formula [I! The basic organic acid metal complexes shown in ] can also be used in the present invention.

[　II　] (In the formula, M represents a coordination center metal, Coordination number 6 Cr, C0 Ni Mn, Examples include Fe.

A represents an alkyl or alkenyl group having a substituent such as an atomyl group (X is a hydrogen atom, a halogen atom, or a nitro group). Examples of Y6 include hydrogen, sodium, potassium, ammonium, and aliphatic ammonium. Z is 101 or n Next, specific examples of the complex will be shown.

Complex [H]-1 Complex [II-2 Complex [11-3 Complex [11]-4 Complex [+1]-5 Complex [11]-6 Complex [111-7 Complex [11]-8 Complex [11] ]-9 Complex [11] -10 These metal complexes can be used alone or in combination of two or more.

The amount of the metal complex added to the toner particles varies depending on the type of toner binder, whether a carrier is used in combination, the pigment that colors the toner, and the reactivity of the metal complex with the binder. The content is 0.01 to 20% by weight, preferably 0.1 to 10% by weight, based on 100% by weight of the binder.

In addition, by reacting with the binder during melt-kneading, the metal complex has higher decomposition and reactivity than when added during binder synthesis, and has excellent compatibility with the binder or dispersibility in the binder, and can be used in toner. It has the advantage of providing stable charging properties.

In the present invention, the photographic toner can be used in one-component and two-component toners, and two-component toners can be widely applied from monocolor to full-color toners.

However, in order to fully exhibit the toner characteristics of the present invention,
When used for full color, the number average molecular weight (M n ) is 1500 ~ 30
000 preferably 2500 to 20000, weight average molecular weight (Mw) 4000 to 50000 preferably 6
It is desirable that it is 000-35000. In addition, when used as a one-component system or monocolor, the number average molecular weight (Mn) of the binder resin is preferably 2,500 to 40,000, preferably 3,500 to 20,000, and the weight average molecular weight (M
w) is 20,000 to 500,000, preferably 3,500
It is desirable that it is 0 to 350,000.

Also, (ABA). Repetition number n of type block copolymer
is preferably 1 to 20. When n exceeds 20, it becomes similar to a random or alternating copolymer,
This is because the properties of the block copolymer are lost. Therefore, for full color applications with low molecular weight, it is more preferable that n=
It is in the range of 1 to 10, and when used for a one-component system with a high molecular weight or a monocolor system, it is more desirable that n=1 to 15 because it exhibits the properties of the block copolymer described above.

The following vinyl-based monomers can be used to form the binder resin mixed and used in the present invention.

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, brobylene, butylene, and isobutylene; butadiene, Unsaturated diolefins such as isobrene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate, and vinyl benzoate; methacrylic acid and methacrylic acid Methyl, ethyl methacrylate, probyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, methacrylic acid-
α-methylene aliphatic monocarboxylic acid esters such as 2-ethylhexyl, stearyl methacrylate, phenyl methacrylate; acrylic acid and methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, probyl acrylate, Acrylic acid esters such as n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate;
Maleic acid, maleic acid half ester; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone,
Vinyl ketones such as vinylhexyl ketone and methyl isobrobenyl ketone; N-vinyl compounds such as N-vinylpyrol, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone; vinylnaphthalenes;
Acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylic nitrile, acrylamide, etc.; polymerized products using one or more types of acrylic acid compounds are used.

The glass transition point of the polymer synthesized from vinyl monomers other than the block copolymer in this binder resin or the mixture of these polymers is 45°C to 85°C in order to exhibit the properties of the block copolymer. The temperature is preferably 55 to 70°C.

Polymers synthesized from vinyl-based polymers can be obtained by generally known methods, such as solution or suspension polymerization using peroxides as initiators.

Furthermore, methods for synthesizing (ABA) n-type block copolymers are disclosed in JP-A-63-278910 and JP-A-64.
-6013, JP-A No. 64-28619, and other methods in which a radically polymerizable vinyl monomer is subjected to bulk polymerization or solution polymerization using light using a polymerization initiator having a dithiocarbamate group. .

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.

Another ingredient. Regardless of the two-component toner, carbon black, titanium white, or any other pigment and/or dye can be used as the colorant.

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. r. Mordant Blue-7, C. I. Direct Green 6, C. I. Basic Green 4, C. I. basic green 6
etc. Pigments include yellow lead and cadmium yellow.
Mineral Fast Yellow Navel Yellow Naphthol Yellow S1 Hansa Yellow G1 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 B1 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
1 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 l, 2, 3, 4, 5, 6, 7, 8, 9
, 10, 11, 12, 13, 14, 15,
16, 17. 1B, 19, H, 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, 2
09. C. I. Pigment Violet}-19, C
．． l. Bat Red 1, 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, 3
0, 49, 81, 82, 83, 84, 100
, 109, 121. C. I. Dispersed Red 9. C. I. Solvent violet8. 1
3. 14, 21, 27, C. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic red 1, 2, 9, 12, 13, 14, 15, 1
7, 18, 22, 23, 24, 27, 29
, 32.34.35, 36. 37, 38, 3
9, 40. C. I. Basic violet 1,
3, 7, 10. 14, 15, 21, 25.
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 cyanine pigment having a structure represented by the formula (1) in which 1 to 5 phthalimidomethyl groups are substituted on the cyanine skeleton.

(Hereinafter, blank space) U n = 1 to 5 As a coloring pigment for yellow, C.I. I. Pigment Yeo
-1. 2, 3, 4, 5, 6, 7, 10.
11, 12, 13, 14, 15, 16, 1
7, 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.

Furthermore, the toner in the present invention is not limited to either negatively chargeable or positively chargeable, but when producing a negatively chargeable toner, a charge control agent may be added especially for the purpose of stabilizing the negative chargeability. It is preferable. 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 tertiary butyl salicylic 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 moR%, preferably 1 to 30 moR% of positively chargeable aminocarboxylic acid esters such as dimethylaminomethyl methacrylate are used
A binder resin containing R% 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 the positive charge control agent include structural formula (A). Examples include quaternary ammonium salts represented by (B).

Structural formula (A) Structural formula (B) Structural formula (A) and (B) Quaternary ammonium represented by Among the salts, structural formula (A)-1, 12 Structural formula (B)-1 in The use of positive charge control agents expressed in It is preferable because it shows good chargeability with less dependence. stomach.

Structural formula (A)-1 Structural formula (A)-2 Structural formula (B)-1 In addition, as a resin component of a binder resin in a 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 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 characteristics, is not used as a resin component in a positively chargeable toner, the amount of the positive charge control agent is 0.00 parts by weight 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 100 parts by weight of the binder resin as necessary in order to provide good chargeability with less environmental dependence. 0 to 10 parts by weight, preferably 0 to 10 parts by weight
It is desirable to use 8 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 powders, such as vinylidene fluoride fine powder, polytetrafluoride fine ethylene powder, etc.; or fatty acid metal salts, such as zinc stearate, calcium stearate, lead stearate, etc.; or metal oxides, such as zinc oxide powder; Alternatively, there are finely powdered silica, that is, wet-processed silica, dry-processed silica, and treated silica in which these silicas are surface-treated with a silane coupling agent, a titanium coupling agent, silicone oil, or the like.

A preferred flow improver is a fine powder produced by vapor phase oxidation of a silicon halide compound, so-called dry process silica or fume 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.

SrCR4+ 2 H2+ 02→Si02+ 4
}1cj' 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 preferably within the range of 0.001 to 2μ, particularly preferably 0.00μ.
It is preferable to use silica fine powder within the range of 2 to 0.2 microns.

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.) 200 300 380 TT600 MOX170 MOX 80 COK 84 Ca-0-SiL (CABOT Co.) M- 5 MS- 7 MS-75 HS- 5 EH- 5 Wacker HDK N 20 (WACKER
-CHEMIE GMBH) V15 N20E T30 T40 D-C Fine Silica (Dow Corning Co.) Fransol (Fransil) Furthermore, the silica fine powder produced by gas phase oxidation of the silicon halogen compound was subjected to hydrophobization treatment. It is more preferable to use fine silica powder.

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 reaction with fine silica powder or chemical treatment 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, triorganosilylmercabutane, trimethylsilylmercabutane, triorganosilane Silyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane,
Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and siloxane units containing 2 to 12 siloxane units per molecule, one each for the terminally located unit. St
Examples include dimethylborisiloxane containing a hydroxyl group bonded to . 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 1 μm.

As a commercially available product, Taranotsuku 500 (Talco Co., Ltd.)
, AEROSIL R-972 (Japan Aerosil Co., Ltd.), etc.

Furthermore, positively chargeable silica fine particles may be used for the positively chargeable toner in order to not only 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. As such a treatment agent, for example, H2NCH2CHzCHxSi (OC+{3) 3H
2NCR2CH2CH2S1 (OC2HS) 3CH
3 H2NG82CH2CH2Si (OCH3)2HJC
ONHC}l2c}l2cLsi (0(:2}15)
! fhNc}l2cHJHc}l2cLclhsi(O
CH3) 3LNCH2CFlalDICH2CHzN
HCH2CH2CHzSi(OCHs) 3H3C20
COCH2CHJ}ICH2CH2CH2Si(QC}
+3) 3H5C20COCH2CH2NHCH2CH
2NHC}I2CLCH2Sj(QC}+3)383C
OCOCH2CH2NHCHzCH2NHCH2C}l
2cH2st (OCI{3) 3H,C2 \ N-C}IzC}12c}l2si (OCR3) 3/ H51;2 HOC82CH2 \ N-CH2CHzClbSi (OCH3) 3/ HOCH2(;}+2 (}12 co) 3sic}I2CH2CH2- NHC
}I2(H2CO) 3sicH2cHzcH2-NH
C}I2(H5C20)3SIC}12CH2CH2\NH HzCNHCH2CHzClhSi (OC2HS)
3}12N(CH2CH2NH) 2cl{2c82c
}I2Si (QC}+3)3FI3C-NHCONH
There are aminosilane coupling agents such as C3HaSi(OCH3)3.

As silicone oils, amino-modified silicone oils that have a partial structure with an amino group in the side chain of the following formula are generally used. (Here, Rl represents hydrogen, an alkyl group, an aryl group, or an alkoxy group, and R2
represents an alkylene group or a phenylene group, R,, R4
represents 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 represent positive integers. ) Examples of such silicone oils having amino groups include the following.

(manufactured by Toray Silicone) KF393 (manufactured by Shin-Etsu Chemical) κF857 (manufactured by Shin-Etsu Chemical) KF860 (manufactured by Shin-Etsu Chemical) KF861 (manufactured by Shin-Etsu Chemical) κF862 (manufactured by Shin-Etsu Chemical) KF864 (manufactured by Shin-Etsu Chemical) κF8 [15 (manufactured by Shin-Etsu Chemical Co., Ltd.) KF369 (manufactured by Shin-Etsu Chemical Co., Ltd.) KF383 (manufactured by Shin-Etsu Chemical Co., Ltd.) X-22-3680 (manufactured by Shin-Etsu Chemical Co., Ltd.) X-22-3
800 (manufactured by Shin-Etsu Chemical Co., Ltd.) X-22-3801C (
(manufactured by Shin-Etsu Chemical) 320 8800 3800 3800 l700 What is amine equivalent? , equivalent per amine (g/
eqiv) is the value obtained by dividing the molecular weight by the number of amines per molecule.

It is preferable to use silica-like 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 stick to the carrier surface vary depending on the toner material, but examples include polytetrafluoroethylene, monochrome trifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, metal complex of ditertiary butyl salicylic acid, and styrene resin. , acrylic resin, boriacid, polyvinyl butyral, nigrosine, aminoacrylate resin, basic dye and its lake, fine silica powder, fine alumina powder, etc. may be used singly or in combination, but are not necessarily limited to these. .

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 diameter of these carriers is preferably 10 to 100μ, preferably 20 to 70μ.

A particularly preferred embodiment is a ternary ferrite of Cu-Zn-Fa, whose surface is coated with a combination of resins such as fluororesin and styrene resin, such as polyvinylidene fluoride and styrene-methyl methacrylate resin; Fluorine-based ethylene 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 average particle size as described above and containing 70% by weight or more of carrier particles having a 250 mesh pass and a 400 mesh on. Examples of the fluorine-based copolymer include vinylidene fluoride-tetrafluoroethylene copolymer (10:90 to 90:10), and examples of the styrene-based copolymer include styrene-2-ethylhexyl acrylate (20:80). ~80:20) and styrene-2-ethylhexyne acrylate-methyl methacrylate (20-60; 5-30:10-50).

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 measurement device (OSC measurement device!) is used. Measured using DSC-7 (manufactured by PerkinElmer).

Precisely weigh 5 to 20 mg, preferably 10 mg, of the sample to be measured.

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./mfn within a measurement temperature range of 30° C. to 200° C.

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

The intersection point between the line at the midpoint of the base line before and after the endothermic peak appears and the differential heat 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 THF was added to the column at this temperature as a solvent.
(tetrahydrofuran) was flowed at a flow rate of 1 mR/min, and a THF sample solution of the resin adjusted to a sample concentration of 0.05 to 0.6% by weight was added at a rate of 50 to 200μ! Inject and measure. 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 Chemical Co.
．． or manufactured by Toyo Soda Kogyo Co., Ltd. with a molecular weight of 6 x
10', 2. lx 103,4 x 1031.75
X 10' 5. IX 10' 1. IX
105 3.9X 1058.6'x 10
It is appropriate to use at least 10 standard polystyrene samples of 5.2 x 106 or 4.48 x 106. Further, an RI (refractive index) detector is used as a detector.

In addition, as a column, in order to accurately measure the molecular weight range of 103 to 2 x 106, it is recommended to combine a plurality of commercially available polystyrene gel columns, for example, Water
μ-styragel 500, 103.
10'105 combination, Showa Denko's shodex
κF-80M, KF-801, 803, 804,
805 combination, κA-802, 803, 804,
805 combination or TSKgel manufactured by Toyo Soda
GIOOOH, G2000H, G250DH,
G3000}IG40001{, G5000H, G
A combination of 6000H, G700011, and GMH is preferred.

[Example] Hereinafter, the present invention will be explained in detail with reference to Examples. In addition, all parts indicate parts by weight.

Resin Production Example 1 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 from the reactor to allow 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 4100 and a weight average molecular weight (Mw) of 8800 were obtained. Moreover, the glass transition point (Tg) was 43°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 Mn of this copolymer by GPC is 12
000, Mw is 32000, Tg is 43℃ and 6
Two points at 5°C were observed. 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 replaced with nitrogen, and the vessel was tightly sealed. A 400 W ultraviolet lamp was placed 15 cm from the reactor and the reaction was carried out for 15 hours.

After the reaction, a portion was sampled and its molecular weight was measured by GPC, and it was found to have a number average molecular weight (Mn) of 4,700 and a weight average molecular weight (Mw) of 9,000. Moreover, the glass transition point (Tg) was 45°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 Mn of this copolymer by GPC is 15
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 B.

Resin Production Example 3 The first stage of polymerization was placed in a glass reaction vessel, the interior of the vessel was sufficiently replaced with nitrogen, and the vessel was tightly sealed. A 400 W ultraviolet lamp was placed at a distance of 15 cm from the reactor, and the reaction was carried out for 15 hours.

After the reaction, a portion was sampled and its molecular weight was measured by GPC, and it was found to have a number average molecular weight (Mn) of 4300 and a weight average molecular weight (Mw) of 8700. Moreover, the glass turning point (Tg) was 43°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 Mn of this copolymer by GPC is 13
500, Mw was 32,000, and two Tg values were observed: 43°C and 65°C. The ABA type block copolymer obtained here is referred to as resin C.

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

(Left below) Comparative example of resin production 2. Mn130 using generally known solution polymerization using
00, Mw 32000, and Tg 58°C. The random copolymer obtained here is referred to as Resin G (Comparative Example 2).

In addition, the same reaction was carried out with the amount of penzoyl peroxide reduced to 5 g, and Mn was 24,000 and Mw was 82,000.
, a random copolymer having a Tg of 62°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, laminated, classified, and further treated with hexamethyldisilazane as a flow improver to obtain a classified product 10.
0 parts to 0.5 parts, aluminum oxide fine powder to 0.5 parts.
2 parts were added externally to prepare a toner.

As a carrier, styrene-acrylic 2-ethylhexy-methyl methacrylate (copolymerization weight ratio 50:2
Cu4 coated with 0.5% by weight of 0:30)
n-Fe ferrite carrier (average particle size 45ttm,
A developer was prepared using a 250 mesh bath (400 mesh on, 87% by weight) 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 125 to 205 degrees Celsius.
Met.

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

As a result, even after printing 12,000 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, the toner was left in a hot air dryer at 45° C. for 3 days and the blocking state of the toner was observed, but no change was observed and it had good fluidity.

Example 2.3 and Comparative Example 1 The same procedure as Example 1 was carried out except that the resins were changed to B, C, F, and G, and the results shown in the following table were obtained.

(Left below) 1d A was melt-kneaded using a roll mill, cooled, and coarsely ground. The product was finely pulverized and classified, and 0.6 parts of positively charged hydrophobized dry silica was externally added as a flow improver to 100 parts of the classified product to obtain a one-component magnetic toner.

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 205°C. Furthermore, an image reproduction test was conducted using this toner and a copying machine. As a result, even after printing 10,000 sheets, there was no offset to the fixing roll, and a good image without fogging or scattering was obtained.

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

Example 5 and Comparative Example 3 The resin was treated with E. The same procedure as in Example 4 was carried out except that H was used, and the results shown in the following table were obtained.

[Effects of the Invention] According to the present invention, a specific ABA type block polymer is used as the binder resin, and the high temperature offset resistance of the A segment and the low temperature fixing property of the B segment can be compatible, and it is possible to use a heat fixing method. This is a suitable toner.

Furthermore, since it is copolymerized with a vinyl-based monomer containing a carboxyl group, its affinity for paper is improved and fixing properties can be further improved.

Claims (1)

[Claims] 1) (ABA) n-type block copolymer (n = 1 to 20
) or a toner containing a binder resin containing a mixture of the block copolymer and a polymer synthesized from a vinyl monomer, wherein A constituting the block copolymer is synthesized from a styrene monomer and a methacrylic monomer. A copolymer in which B constituting the block copolymer is synthesized from styrene and acrylic monomers, and at least one of A and B is copolymerized with a vinyl monomer containing a carboxyl group. A heat fixing toner characterized by: 2) (ABA) n-type block copolymer at 25-95°C
The toner for heat fixing according to claim 1, having a glass transition point of at least two points between 1 and 2.