JPH02294658A - Color toner - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a color toner used in color electrophotography, which has particularly excellent light resistance, high chroma, and good charging stability. , relates to a magenta toner with improved offset properties.

[Prior Art] The qualities required of a coloring material for magenta toner for color electrophotography are: 1) excellent spectral reflection characteristics (color characteristics) and a clear magenta color; 2) good dispersibility in resin and high coloring. 3)
4) It must have excellent stability against light, that is, the light resistance of copies must be good; 4) It must match the functions required by the copying machine and have no significant side effects, such as charging characteristics and fixing, which affect development characteristics. Adhesion to the roller surface, stainability, etc.

Conventional magenta colorants for color electrophotography include quinacridone pigments, thioindigo 1184, xanthene dyes and pigments, anthraquinone dyes, and azo dyes and pigments.

For example, in Japanese Patent Publication No. 49-46951, 2.9-
The description of dimethyl quinacridone pigment was published in JP-A-55-28.
No. 574 describes thioindigo pigments, and JP-A-59-57256 describes xanthene dyes. Furthermore, Japanese Patent Publication No. 55-42383 describes anthraquinone dyes. Furthermore, in Japanese Patent Publication No. 53-47174, the applicant has proposed a magenta toner using a quinacridone or rhodamine colorant in combination with a suitable binder resin. However, none of these colorants satisfy all of the characteristics 1) to 4), and each has its own advantages and disadvantages. For example, a quinacridone organic pigment is a high-grade pigment with a slightly reddish color and excellent light resistance, but when added alone, it does not have sufficient performance as a magenta color. That is, in terms of hue, there is less reflection in the bluish portion than in the ideal magenta color, and the reflection is due to the reddish color. Furthermore, since it is a pigment, it has disadvantages such as insufficient dispersion in the binder resin, poor color saturation, and insufficient brightness. When used alone, the quality is insufficient in terms of color reproducibility.

However, when used as a toner, it has favorable characteristics in terms of less carrier contamination due to repeated copying.

Therefore, it is extremely difficult to formulate a single dye or pigment as a coloring agent for magenta, and in order to compensate for the shortcomings of each coloring agent, two
It is practical to use more than one type of colorant in combination.

For example, the present applicants have proposed a magenta toner using a 2 fffi oil-soluble dye, as disclosed in Japanese Patent Application Laid-open No. 57-130044 and Japanese Patent Application Laid-open No. 57-130046. This magenta toner has a vivid color tone and excellent saturation, but on the other hand, one of the dyes contains a component that contaminates the silicone rubber used in the heating roller fixing device, so it gradually deteriorates due to continuous copying. Finally, the toner fuses to the heating roller, causing a so-called offset phenomenon. Furthermore, the combination of these oil-soluble dyes is effective in reducing rather than increasing the charge of the toner. Therefore,
It is possible to sufficiently prevent charge-up under low temperature and low humidity conditions, and ensure a desirable image density. However, under high temperature and high humidity conditions, toner scatters due to insufficient charging, which contaminates the inside of the machine, and low-charging toner tends to cause fogging and image smudges. To summarize the above, it is as follows. When a pigment-based colorant is used, it has advantages such as light resistance and carrier stain resistance, but it has poor dispersion into the binder resin and is inferior in color tone and saturation. On the other hand, when a dye-based colorant is used, a toner with good dispersion and excellent color tone and saturation can be obtained, but it has disadvantages such as poor light resistance and poor staining of the fixing roller.

Therefore, attempts have been made to make use of the advantages while compensating for these drawbacks by using pigment-based colorants and dye-based colorants in combination.

For example, in JP-A-60-192957, the present applicant has disclosed a method for improving the dispersion of pigments in a binder resin by treating the pigments with an oil-soluble dye.

With this method, images with vivid hues and good quality can be obtained even under environments of high temperature, low temperature, and low humidity.

However, the fixing properties are still not satisfactory.

Although the purpose is different, JP-A-59-100453 uses an oil-soluble dye as a conductivity imparting agent in a toner containing an organic pigment using a polyester resin as a binder resin in order to prevent fogging and edge effects. A method is disclosed. In this method, due to the conductivity imparting effect of oil-soluble dye,
Fog and edge effects are suppressed, but when mixing two or more color toners to make toners of other colors, or when overlapping two or more color toners and fixing them on a fixing support, The dispersion of the dye is not sufficient, resulting in an image with poor chroma and light transmittance.

Further, Japanese Patent Application Laid-Open No. 60-66261 discloses a method for using a chromatic pigment and at least one chromatic dye soluble in an organic solvent for a functional color toner. However, since this method produces a toner with a high opacity, when used as a full-color toner, it has poor color mixing properties and light transmittance.

In addition, in the examples of JP-A-62-15555-7, the present applicant has proposed a combination system of a rhodamine-based basic dye and a pigment as a coloring agent, and has shown that no silicone rubber roller dyeing offset occurs at all. Indicated.

However, with this method, sufficient dispersion of the colorant cannot be obtained and the colorant tends to aggregate, and in particular, the toner adheres around the carrier during development and the carrier is developed together with the toner, so-called "carrier attraction". A phenomenon called "ki" is likely to occur. In addition, the present applicant has disclosed in Japanese Patent Application Laid-Open No. 54-5733,
A method of obtaining a color toner by treating a basic dye with a resin having an acid value of 5 to 120 was shown. In this method, the basic dye forms a type of resinate, resulting in a color toner with excellent spectral reflection characteristics and transparency, as well as stable sulfurability and triboelectric charging characteristics. However, even in this method, the light resistance is poor because only dye is used, and the image after fading becomes an image with almost no red tinge.

In addition, with the aim of improving the dispersion of pigments and obtaining toners with excellent color reproducibility and V j characteristics,
Japanese Patent No. 2110755 discloses a method in which a polyester resin is used as a binder resin, and a pigment treated with a polyester resin having a higher molecular weight than the binder resin is used. This method produces products with significantly improved pigment dispersion and other charging characteristics compared to conventional systems that use pigments alone, but as mentioned above, when dye-based colorants are used, In comparison, it is slightly inferior in terms of color tone and saturation.

Further, JP-A-62-30259 discloses a method of preparing a masterbatch containing a pigment dye, a charge control agent, and an anti-offset agent and diluting the masterbatch.

However, although this method also improves the dispersion of the colorant, it does not dramatically improve the fixing properties of the toner.

Furthermore, many improvements in binder resins have been reported for the purpose of improving fixing properties. For example, JP-A-59-226i358
．． No. 51-126562 discloses that the molecular weight measured by GPC 2 is 10' to 5 x 10' and
A color toner containing a vinyl-based jllLffi polymer or copolymer having at least one maximum in two regions of 106 to 106 has been proposed.

However, although containing about 70 wt% of a polymer having a maximum in the 10' to 10' region does improve high-temperature offset resistance, the increased viscosity of the toner makes it difficult to mix colors for full color applications. Unfortunately, the resulting image is dull and lacks saturation. Furthermore, in Japanese Patent Publication No. 53-23084, the applicant proposed using oligostyrene with a molecular i of 1000 or less and boristyrene with a molecular weight of tens of thousands or more as a binder resin. It is true that the fixing performance is improved compared to that of the previous version, but when used for full color toner, the fixing performance is still insufficient, especially when the three color toners are ffirt and there are many toner plates that produce black. I can't say that.

In other words, as a color toner, it has excellent light resistance and high saturation.
Currently, there is no magenta toner with good %F electric stability and excellent offset resistance.

[Problems to be Solved by the Invention] Therefore, an object of the present invention is to provide a magenta toner #1i! that solves the above-mentioned problems. It is about providing.

That is, an object of the present invention is to provide a magenta toner that provides vivid colors, high tinting power, and excellent light resistance.

Still another object is to provide a magenta toner that does not cause dyeing and deterioration of the fixing roller etc. during fixing and has a wide fixing area.

Another object of the present invention is to provide a magenta toner that can form a smooth fixing surface so that the fixed toner does not diffusely reflect light and interfere with color reproduction.

Still another object is to provide a magenta toner that has excellent environmental stability, does not cause changes in charging due to i5 dyeing, and can always be stably charged.

[Means and effects for solving the problem] The feature is that at least the binder resin is mainly styrene resin, phenol resin, quinac. A color toner containing a lydone pigment and an oil-soluble xanthene dye. Furthermore, the styrenic resin has at least one maximum below the molecule ffk toooo in the molecular weight distribution determined by GPC, and there is no maximum at a molecular weight of 10,000 or more,
Molecular weight distribution less than toooo, 10000-50000
, the proportions of areas A, B, and C in the range exceeding 50,000 are 55 to 80%, 5 to 25%, and 5 to 20%, respectively,
If T8 in each range is TgA, Tga*c, then 70℃
>TgA>50°C, 65°C>Tga. c>50℃
It is in the color toner that is.

This achieves the above-mentioned objective.

When considering full-color toner, the first important thing is color reproducibility. In particular, cyan toner, magenta toner, and yellow toner melt during fixing and mix colors to produce color, so the viscosity must be reduced in a short time during melting. However, the second important point is practicality.
In particular, problems related to fixing such as fixing temperature, offset, and wrapping must be satisfied at the same time as color mixing properties, which are generally contradictory.

However, as a result of intensive studies, the present inventors have been able to simultaneously satisfy these requirements to some extent by adjusting the molecular weight distribution and glass transition point of the binder resin, and by making the phenolic resin exist in the main binder resin. It has been discovered that full color toner can be obtained.

That is, in the molecular weight distribution determined by gel permeation (GPC), components with a molecular weight of less than 10,000 are related to color mixing properties and flatness of the fixing surface, which are most important for full-color toners, and components with a molecular weight of 10,000 to 50,000 are important for full-color toners. is particularly related to fusing temperature, and components exceeding 50,000 are
In particular, it is related to offset properties, mattability, colorant dispersibility, developability, durability, etc.

in ooo If the undropped component is less than 55%, color mixing and fixing surface flatness tend to be poor, and if it is more than 80%, offset property, colorant dispersibility, developability, etc. tend to be poor. . Also, 10,000~50,
If the proportion of the component 000 is less than 5%, the dispersibility of the colorant will be poor, and if it is more than 25%, problems such as fixing properties will occur. In addition, if the content of components exceeding 50,000 is less than 5%, problems such as offset property, oxidation property, colorant separation property, developability, durability, and halftone reproducibility may occur, especially image density, background stains, etc. tends to get worse. Furthermore, if it is more than 20%, fixing properties, color mixing properties,
Problems arise such as the flatness of the fixing surface.

Furthermore, if the Tg of the components in each range is lower than 50° C., blocking occurs, which becomes a problem. Also, TgA is 70℃
If Tgg-c is larger than 65°C, problems arise with fixing properties, color mixing properties, and flatness of the fixing surface.
Ru.

Moreover, it is preferable that the polymer is composed of a small amount of monomers such as -C O OH groups and -OH groups. In other words, even a slight change in developability, especially due to durability or environmental changes, will appear in the full color image as a change in color, so it is preferable to have less -COOH and -OH groups, which are easily influenced by the environment. .

For the above reasons, the acid value of the polymer is preferably 90 or less.
is preferably 50 or less.

Furthermore, a styrene-acrylic copolymer whose polymer is mainly a styrene monomer can be easily and stably charged, either positively or negatively, by using a charge control agent. What is particularly important is that, since it is a polymer with low polarity, dyes and pigments for color toners are difficult to separate. However, it has been found that sufficient dispersibility can be obtained with the molecular weight distribution of the present invention. This relates in particular to the fact that the ratio of molecular weight distributions above 50,000 to below 10,000 is in the range 1:7.5 to 2:5.5. That is, so, ooo or higher, which is a component that requires shear during hot kneading, and io, which has good wettability. ooooo
Dispersibility is improved with the following appropriate ratios.

Further, in the present invention, the reason why a quinacridone pigment, a xanthene dye, and a phenol resin are used is as follows.

As mentioned above, if the colorant is only a dye, offset of dyeing onto the fixing roller is likely to occur. Since the dye and pigment combination systems have the same polarity, sufficient dispersion cannot be obtained in the styrene-acrylic binder resin generally used for toners.

In addition, using pigment alone has good light fastness, but results in images with poor color saturation and poor color tone. As a result of intensive studies, the inventors obtained the following knowledge.

This is because xanthene-based oil-soluble dyes have little affinity with nonpolar organic substances that have aromatic rings, and have strong dyeing power against oils, rubber, and metal oxides. It dissolves well in molecular esters. Therefore, rather than the toner binder containing non-polar aromatic rings (introducing aromatic rings can impart durability as an electrophotographic toner), developing materials made of iron oxide powder, magnetite, ferrite, magnetic alloys, etc. Silicone rubber used in the agent carrier or sleeve that carries the developer, the fixing device, and the silicone oil used as a bait agent at high temperatures can contaminate electrophotographic equipment and cause the rise of charging especially at high temperatures. This may cause toner to scatter,
If the fixing material is placed in contact with something containing a plasticizer, it may cause fogging or reversal phenomena, and xanthene-based oil-soluble dyes will be extracted and dyed, contaminating the surrounding area and changing the magenta color in the image. This causes the phenomenon of blurring or thinning.

Here, if a polar phenol resin coexists with a xanthene dye, the above-mentioned contamination phenomenon can be significantly prevented.

Although the xanthene dye does not completely dissolve into the phenol resin, it is thought that this is because the phenol resin has an effect of suppressing the movement of the dye into the main binder resin.

As a result, it has become possible to obtain images with good light fastness due to the pigment and high chroma due to the dye, and to prevent migration of the dye using the phenol resin.

The resin composition in the toner of the present invention is preferably one obtained by polymerizing one or more polymers selected from styrenes, acrylic acids, methacrylic acids, and conductors thereof, from the viewpoint of development characteristics and charging characteristics. Examples of usable polymers include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, and the like.

Acrylic acids, methacrylic acids, and their conductors include acrylic acid. Methyl acrylate, ethyl acrylate.
Probyl acrylate, butyl acrylate. octyl acrylate, 2-ethylhexyl acrylate, acrylic acid n
-Tetradecyl, n-hexadecyl acrylate. Lauryl acrylate. Examples include acrylic esters such as cyclohexyl acrylate, diethylaminoethyl acrylate, and dimethylaminoethyl acrylate; similarly, methacrylic acid, methyl methacrylate, ethyl methacrylate,
Provil methacrylate. Butyl methacrylate. Amyl methacrylate. Hexyl methacrylate, methacrylic acid 2-
Ethylhexyl. Octyl methacrylate. Decyl methacrylate. Dodecyl methacrylate, lauryl methacrylate. Cyclohexyl methacrylate. Phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-methacrylate
Examples include methacrylic acid esters such as -hydroxybutyvir, dimethylaminoethyl methacrylate, glycidyl methacrylate, and stearyl methacrylate. In addition to the monomers mentioned above, small amounts of other monomers may be used, such as acrylonitrile, 2-vinylpyridine, etc., to the extent that the objects of the invention are still achieved. 4-vinylpyridine, vinylcarbazole,
Vinyl methyl ether, butadiene. Isoprene, maleic anhydride, maleic acid monoesters. Maleic acid diesters, vinyl acetate, etc. may also be used.

In order to adjust the molecular weight distribution, the crosslinking agent used in the toner of the present invention includes divinylbenzene. Bis(4-acryloxypolyethoxyphenyl)
Bulobane, ethylene glycol diacrylate. 1.3
-Butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neobentyl glycol diacrylate. Diethylene glycol diacrylate. Triethylene glycol diacrylate. Tetraethylene glycol diacrylate polyethylene glycol #200, #400,
#600 each diacrylate. Dibrobylene glycol diacrylate 1 Dibrobylene glycol diacrylate, polyester type diacrylate (MAND^Nippon Kayaku), and those obtained by replacing the above acrylates with methacrylates are mentioned.

As polyfunctional crosslinking agents, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolbroban triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis(4-methacryloxy, polyethoxyphenyl) Propane, diallyl phthalate. Triallyl cyanurate, triallyl ancyanurate 5 Triallyl isocyanurate, triallyl trimellitate, diaryl cyanurate and the like can be mentioned.

A known method is used to produce the resin. Polymerization methods include solution polymerization, suspension polymerization, and bulk polymerization, and the polymer of the present invention can be obtained by combining two or more resins. 2f! The mixing of one or more resins may be carried out in a thermal kneading process during toner production, but in advance, the resins may be mixed in a thermally molten state or melted and mixed using a solvent. However, when the first resin is solution polymerized and before the solvent is removed, two
f! A preferred method for obtaining the polymer of the present invention is a method in which an initiator and the like are dissolved in 1,100 mer of the 11th resin and polymerized. This is because the two types of resins can be dispersed at the molecular level. Furthermore, when producing a polymer using this method, either the low molecular weight component or the high molecular weight component may be produced first.

Furthermore, is this two-stage polymerization method called solution polymerization? Although not only the combination of θ liquid polymerization but also any combination of polymerization methods can be used, when considering the reaction treatment process, a combination of solution polymerization and suspension polymerization is preferable.

Examples of the phenolic resin used in the present invention include phenol, cresol, xylenol, catechol, naphthol, alkylphenol, paraphenylphenol, etc.
It is an addition condensation polymer between a phenolic hydroxyl group and an aldehyde or an aldehyde-generating substance such as formaldehyde, acetaldehyde, paraformaldehyde, hexamethylenetetramine, furfural, etc. Among them, it is called an oil-soluble phenol, at the rose position of the phenolic hydroxyl group. Those having an alkyl group, allyl group, or aralkyl group have high thermal stability and are therefore advantageous in toner production.

Typical examples of quinacridone pigments used in the present invention include the following structural formula: Among them, 5. C. I. Pigment R
ed 122 is bright and has high saturation, so it is used especially as a magenta colorant. In addition, the xanthene dye used in the present invention is often used as a basic dye, but basic dyes have a large drop in charging ability at high temperatures, so they can be used in the free base or acid state without converting them into salts. It is better to use dyes that are classified as oil-soluble dyes because they can better wet the resin and improve dispersibility.

As xanthene oil-soluble dyes, C.I. 145170
:I (C.I.Solvent Red 49),
C. 1.45185Cl. 45J9 (1:l (C.I.
．． Solvent Violet 10), C. 14
5195, C. 1.45350:1 (C.I.
Solvsnt Yellow 94). C. X.
I5365 (C.I.Solvenhi Orang
e32), C. 1.45366 (C.r.So
lvent Red 42), C. 1.453
7D:1 (C.ISolvent Red 7
2), C. l45371 (C.iSolvCn
tOrange 18). C. I. 45380:2
((:.I.Solvant Red43), C.1
．． 45385 (C.I. Solvent Red
44), C. r. 45381i (C.I.S.
olvent Red 45). C. T. 45385
．． C. I45396 (C.I. Solvent
Orange 16), C. I. 45410:
1 (C.I.Solvent Red 48), C.I.
i45415, C. I. 45425:1 (C.I.S.
over+t Red 73), C. 1.4543
0 (C.I.SolventI1ed 140),
C. I. 45435:l (C.I.Solvent
Red 47), C. I. 45440:1 (C.I.
Solvent Red 141). C. I. 454
58 (C.I.Solvent Orange 17)
．． C. 1.45457 (C.!.Solvent
Red 46). C. I. 45550 (C
．． I. Solvent Green 4), among others, C. I. Solv
ant Red 49, C. I. Solvent V
iolet 10 is suitable. The effects of the present invention are best achieved when the dye used in the present invention is treated with a phenol resin before being dispersed in the binder resin. In addition, for the purpose of improving the dispersibility of pigments,
It may be added to 1,000 nanomers when the main binder resin is polymerized, or it may be treated together when the dye is treated with phenol. The method of treating the xanthene dye with the phenol resin in the present invention includes (1) mixing the xanthene dye and the phenol resin with a Nikiguchi-Lumil, Banbury mixer,
A method of melt-kneading using a kneader, three-roll mill, etc.; (2) a method of dissolving phenol resin in a suitable solvent, dissolving or dispersing the xanthene dye therein, removing the solvent, and drying; (3) phenol ．． (4) Phenol. Examples include a method in which a xanthene dye is dissolved and dispersed in a mixture of formaldehyde to prepare a novolak resin under an acid catalyst, and then a crosslinking agent such as hexamethylenetetramine is added to the resin to cure it.

The content of the phenol resin, quinacridone pigment, and oil-soluble xanthene dye is preferably 0.01 to 20 parts per 100 fi parts of the styrene binder resin. 1 to 5 parts, 0.5 to 20 parts, preferably 1 to 10 parts,
(1.01 to 10 parts, preferably 0.1 to 5 parts).

This is due to the following reasons. The content of phenolic resin is 0.0! If the content is less than 20 parts, there will be little effect in preventing dye offset on the fixing roller, and since phenolic resin is easily colored by heat, light oxygen, etc., if the content exceeds 20 parts, the color of the copied image will be affected. This is because the transparency and transparency of the 01{P film will be inferior. If the amount of quinacridone pigment is less than 0.5 part, the light fastness will be poor, and if it exceeds 20 parts, the chroma of the copied image and the transparency of the OHP film will be poor.

If the amount of oil-soluble xanthene dye is less than 0.01 parts, the effect of increasing the color saturation by adding the dye will not be recognized, and if it exceeds 10 parts, light fastness will be poor and dyeing offset to the regular roller will occur. easy.

Further, when the ratio of the oil-soluble xanthene dye to the phenol resin is in the range of 1:10 to 1:0.1, the effect of preventing the offset of dyeing of the phenol resin onto the fixing roller is more fully exhibited.

The color toner in the present invention has negative chargeability. Although it is not limited to positive chargeability, when producing a negatively chargeable color, it is preferable to add a charge control agent especially for the purpose of stabilizing the negative chargeability. In this case, it is preferable to use a colorless or light-colored negative charge control agent that does not affect the color tone of the toner. Examples of negative charge control agents include organometallic complexes such as metal complexes of alkyl-substituted salicylic acids (for example, chromium complexes or zinc complexes of tertiary butyl salicylic acid).

In addition, when producing a positively chargeable color toner, an aminocarboxylic acid ester containing a positively chargeable aminocarboxylic acid ester such as dimethylamine methyl methacrylate is used in a range of 0.1 to 4,000 nanomers.
A binder resin containing 0 tnol%, preferably 1 to 10 moiI% 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. As a positive charge control agent, for example, Yokozo type (I1)
Examples include quaternary ammonium salts represented by (Tl1).

Structural formula (I1) Rl, R2. R3, R4: an alkyl group having 1 to IO carbons or a phenyl group R' represented by 1R'=(); an alkyl group Rs having 1 to 5 carbons; -H, -0}1,- COOH, or an alkyl group having 1 to 5 carbon atoms Structural formula (III) R6. Alkyl group R7 having 1 to 5 C; -H, -0}1, -C:00}1, or C
Among the quaternary ammonium salts represented by structural formulas (II) and (III) in which the number of alkyl groups is 1 to 5, those represented by structural formulas (I1)-1, -2 and structural formula (II!)-1 are It is preferable to use a positive charge control agent because it exhibits good charging properties with less environmental dependence.

Structural formula (II)-1 In addition, when using an aminocarboxylic acid ester such as dimethylaminomethyl methacrylate, which exhibits positive charging characteristics, as a resin component of the binder resin in a positive charging toner, positive charging control is possible. A negative charge control agent is used as necessary.

In the case of a negatively chargeable color 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, per 10 parts by weight of the M binder resin.

Correct! When an aminocarboxylic acid ester containing an aminocarboxylic acid ester such as dimethylaminomethyl methacrylate, which exhibits positive charging characteristics, is not used as a resin component in an IF conductive color toner, the amount of positive charge control agent is 0% per 100 parts by weight of the binder resin. .1-15
It is desirable to use 1 part 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. It is desirable to use 0 to 8 parts by weight, preferably 0 to 8 parts by weight.

The color toner in the present invention comprises these binder resins, colorants, and a charge control agent and/or fluidity improver used as necessary.

The particle size distribution of the color toner in the present invention is such that the volume average diameter is 3 to 16μ, preferably 5 to 14μ, the number average distribution of 5μ or less is 40% or less, preferably 35% or less, and the volume average diameter is 20μ or less. .2μ or more is 8% or less, preferably 5% or less. This is because when the volume average diameter is 16 μm or more and/or the volume average distribution is 8% or more at 20.2 μm or more, there is an increased tendency for image roughness, character blurring, and so-called skipping. In addition, the distribution amount of 5 μ or less in the number average distribution, so-called fine powder amount, is closely related to the amount of scattering, and the fine powder amount of 40% or more is 30% of the more preferable mode a.
It has been found that the amount of scattered particles is more than twice the amount of fine powder. In other words, the scattering causes fogging in non-image areas, contamination of the charger wire, and the like, resulting in a significant deterioration in the quality of the fixed image.

Furthermore, a fluidity improver may be added to the color 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, polytetrafluoroethylene fine powder, etc.; or fatty acid metal salts, such as zinc stearate, calcium stearate, lead stearate, etc.; or metal oxides, such as zinc oxide powder, etc. or 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, 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, silicon tetrachloride gas acid? It utilizes a thermal decomposition oxidation reaction in a flame, and the basic reaction formula is as follows.

SiCj, + 2 II■+02→Si(h+ 4 H
CRAlso, 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. include.

The average primary particle size of the particles is preferably within the range of 0.001 to 2μ, particularly preferably 0.00μ.
It is best to use silica fine powder within the range of 2 to 0.2μ. Commercially available fine silica powder produced by vapor phase oxidation of a silicon halide compound used in the present invention includes, for example, those sold under the following trade names. ^ERQSIL 1:10
(Japan Aerosil Co.) 200 TT600 MOXl70 MOX 80 COK 84 Ca-0-SiL (CABOT Co.) 5 MS- 'I MS-75 HS- 5 El{- 5 Wacker HIIH N 20 (WACK
ER-CIIEMIE GMBI1) V15 N20E T3CI D-C Fine Silica (Dow Corning Co.) Fransol (Fransjl) Furthermore, the silica fine powder produced by vapor 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 powders, it is particularly preferable that the fine silica powder is treated so that the degree of hydrophobicity determined by methanol titration test is in the range of 30 to 8o.

Silica @. It is applied by chemically treating the powder with an organosilicon compound that reacts with it or 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 containing 2 to 12 siloxitin units per molecule, one each for the terminally located unit. Examples include dimethylpolysiloxane 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 1 μm.

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

For positively chargeable toner, positive IF chargeable silica fine particles may be used in order to not only improve the fluidity of the toner but also obtain good chargeability with little environmental dependence.

How to obtain positively charged silica particles like this? It is best to treat with a coupling agent or silicone oil containing an amino group. Examples of such a treatment agent include 11zNClhCLClhSj (OCH3) 3Ih
NCH2ClhCH2Si (OC2H5) sCH, HJClhClhCH2Si (OCL3) 2? }1
Co+1 2 N C I 2 C H 2 N H C
H2 C H 2 C H 2 S i (O C I
I 3) 2thN(:ONHClbCHzCH2Si
(OC2ms)! H 2 N C II ■ C tl
2 N H C It 2 C II■CIIzSi
(OCI+31 3IhNCH2CHzNHCHtC りI2NIC}I2CII, CH2Si (OCtl3)
sH3hOCOCthCH2NtlCH2CH2Cl
hSt (OC{13)3H5G20COC}12CI
12NIC82C}IJHCJC}12CthSi (
OCH3)s? 3C Q C O C H 2 C
H 2 N 11 C H 2 C H 2 N II
C H 2C H■CHz5f (■CI3)zHs
(There are aminosilane coupling agents such as 1:2.

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

II O C H 2 C I+ 2 (lf2GO) ssic112cH2fl:H2-N
}Ic}I2(thco) *SiClhClhCIh
-NHCfh(}15c20) ssicfhcToc
Hz\NH (+{SC2O}CoSiC}12ClhGHz112c
NHcH2c! 12CthSi (OCiH,)s11
2N (fjl2f:H2NH)2CH2CH2CHi
Si (QCH3) sHzC-N}lcONHcsH
asi (OCH3)s (where Rl represents hydrogen, an alkyl group, an aryl group, or an alkoxy group, R2 represents an alkylene group or a phenylene group, and R3. 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 they contain an amine. It may have a substituent such as halogen within a range that does not impair electrical properties.

m and n represent positive integers. ) Examples of such silicone oils having amino groups include the following.

SF8417 (manufactured by Toray Silicone) κF393 (manufactured by Shin-Etsu Chemical) KF857 (manufactured by Shin-Etsu Chemical) KF860 (manufactured by Shin-Etsu Chemical) KF851 (manufactured by Shin-Etsu Chemical) κF862 (manufactured by Shin-Etsu Chemical) 14Fδ64 (manufactured by Shin-Etsu Chemical) xFa6s (manufactured by Shin-Etsu Chemical) KF369 (manufactured by Shin-Etsu Chemical) κF383 (manufactured by Shin-Etsu Chemical) X-22-3680 (manufactured by Shin-Etsu Chemical) X-22-3
800 (manufactured by Shin-Etsu Chemical) X-22-380IC (
(manufactured by Shin-Etsu Chemical Co., Ltd.) X-22-3810B (manufactured by Shin-Etsu Chemical Co., Ltd.)
/eqiv) 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 cupsong agent or silicone oil containing these amino groups and further subjected to hydrophobization treatment with the above-mentioned organosilicon compound.

In order for the color toner in the present invention to fully exhibit its effects, the carrier used during development also plays an important role.

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, none of the conventionally known methods, such as a method in which a coating material such as a resin is melted or suspended in a solvent and applied and adhered to the carrier, or a method in which a powder is simply mixed, is not applicable.

Substances that adhere to the carrier surface vary depending on the toner material, but include, for example, polytetrafluoroethylene, monochrome trifluoroethylene, polyvinylidene fluoride, silicone resin, polyester resin, gold R complex of ditertiary butyl salicylic acid, and styrene resin. , acrylic resin, boriacid, polyvinyl butyral, nigrosine, aminoacrylate resin, basic dye and its lake, silicate fine powder, alumina fine powder, etc. are suitable to be used alone or in combination, but there are no restrictions on this. Not done.

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% of the carrier of the present invention! i amount% (preferably 0.5
~20% by weight) is desirable.

The average particle size of these carriers is preferably 10-100μ, preferably 20-70μ.

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: polytetra Fluorine-based ethylene and styrene-methyl methacrylate resin, fluorine-based copolymer and styrene-based copolymer:
etc. 90+10~20:80, preferably 70:30
A mixture with a ratio of ~3Q:70, 0.01~
Examples include coated ferrite carriers coated with 5mM%, 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 to 90:10), and examples of the styrene-based copolymer include styrene-2-ethylhexyl acrylate (20:80). ~80:20). Styrene-2-ethylhexyne acrylate-methyl methacrylate (20-60:5-30:10-50) is exemplified.

The above-mentioned C]-ferrite carrier has a sharp particle size distribution, provides favorable triboelectric charging properties for the color toner of the present invention, and has the effect of improving electrophotographic properties.

When a two-component developer is prepared by mixing with the color toner of the present invention, the mixing ratio is 2.0% by weight or more as a toner concentration in the developer! 5! ! amount%, preferably 4-fold view%
~13! Good results are usually obtained when the amount is i%. If the toner density is less than 2.0%, the image density will be too low to be practical! If it exceeds 5%, fog and in-flight scattering will increase.
Shortens the useful life of the developer.

Below, each measurement method in the present invention will be described. (1) Measurement of Molecular Weight In the present invention, the maximum value of the molecular weight in 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) is flowed at a flow rate of IIIN per minute, and 50 to 200 uJ of a THE sample solution of the resin adjusted to a sample concentration of 0.05 to 0.6% by weight is injected 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 monodispersed polystyrene standard samples. As a standard boristyrene 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 1
0', 2. Ix 10'. 4 x 103, 1.75
x 10', 5.1 x 10' 1.1x 10'
3.9x 10'8y6x 10', 2 x 1
It is appropriate to use a standard polystyrene sample of at least the 1O point. Further, an Rl (refractive index) detector is used as a detector.

In addition, as a column, in order to accurately measure the molecular weight region of 103 to 2 x 10', it is recommended to combine a plurality of commercially available polystyrene gel columns, such as Waters
μ-styragel 500, 103. 1
0', 10' combination, Showa Denko's sho
dex KF-80M, κF-801, 803,
804, 805 combination, K^-802.80:l,
A combination of 804 and 805, or T made by Toyo Soda
SKgel GIOOOH, G200QH, G25
00H, G300011G4000H, G500 old 1
, G60(IOH, GV(JOOH, GMH) is preferred.

(2) Measurement of glass transition temperature Tg In the present invention, measurement is performed using a differential thermal analysis measuring device (DSC measuring device), OSC-7 (manufactured by Birkin Elmer).

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./win within the 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.

At this time, the intersection of the midpoint line between the base lines before and after the endothermic peak appears and the differential thermal curve is defined as the glass rolling 8 temperature Tg in the present invention. [Example] The present invention will be explained in detail with reference to Examples below.

Resin Synthesis Example 200 parts by weight of cumene was placed in a reactor and heated to reflux temperature. Add to this styrene/butyl acrylate = 91/9
A mixture to which 8 parts by weight of di-tert-butyl peroxide was added was added with 4 parts by weight of monomer mixture C having m proportion of
It dripped over time. Roughly cumene under reflux (146℃~1
Solution polymerization was completed at 56°C) and cumene was removed. The obtained polymer is soluble in TI{F and Mw=580
0, Mw/Mn = 2.0, the molecular temperature at which the main beak of GPC was located was 4500, and Tg = 60°C.

The polymer is designated as a, and its GPC chart is shown in FIG.

Next, 70 parts by weight of Polymer A were dissolved in 200 parts by weight of cumene to form a monomer mixture with a ratio of styrene/butyl acrylate = 78/22! ! Solution polymerization was carried out in the same manner as above using 1 part by weight of di-tert-butyl peroxide, and cumene was removed to obtain Resin A.

Resin A is soluble in 7 11 F, M stomach = HOO
OMw/Mn = 4.4, Tg = 59℃, G
The molecular weight of the main peak of PC was 5000. The GPC chart is shown in Figure 732.

In addition, Fig. 3 shows resin A when polymer a is not added.
Showing the molecular weight distribution of, Mw=g 38000, Mw
/Mn=2.7, GPC peak molecular weight 27000
, Tg = 59°C.

Hereinafter, resins B to G were synthesized as appropriate by changing the styrene/acrylic ratio, the amount of initiator, the ratio of polymer mixing, etc.

In particular, Resin E uses a crosslinking agent and penzoyl peroxide as an initiator at about 1. Polymerization using Om parts,
It is a polymer containing a THF-insoluble gel component. This gel content was extracted using a Soxhlet extractor, and the resin content was 0.5 to 1.
It was determined from the dry weight of the insoluble matter after extraction at 0 g and an extraction time of 6 hours.

I went. Table 1 was melt-kneaded using a roll mill, cooled, and coarsely ground. @Crushed and further classified to a volume average of 80 μm. We obtained a classified product with 32% of particles less than 5 μm and 0% of particles larger than 20.2 μm. As a flow improver, 0.5 parts by weight of fine silica powder treated with hexamethyldisilazane was added to 1 part of the classified product, and 0.2 parts by weight of fine aluminum oxide powder was added to 1 part of the classified product.
t was added to obtain a magenta toner.

As a carrier, styrene-acrylic 2-ethylhexy-methyl methacrylate (copolymerization weight ratio 50.20.
30) coated with 0.5 m% of Cu-Z low-Fe type ferrite carrier (average particle size 47.2 μm,
A developer was prepared using a 250 mesh pass (400 mesh on, 87% by weight) so that the toner concentration was 5% by weight.

Using these developers and toners, an image reproduction test was conducted using a Canon full-color copying machine CLC-1. As a result, even after printing 1,000,000 sheets in magenta single-color 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.

0} Even when the IP film was used, the toner permeability was very favorable. Furthermore, the environment is low temperature and low humidity.
An image output test was carried out by changing the temperature to a higher temperature, and good results were obtained, with stable image density, no fogging, and almost no toner scattering.

In addition, the images obtained here were exposed to sunlight for 3 months,
None of the colors faded, and the image remained the same as when it was printed.

Example 1 was carried out in the same manner as in Example 1 except that 100 ii parts of Resin B of Resin Synthesis Example was used, and the volume average particle size was 8.21 μm and 5 μm.
Below 30.5%. 20. A classified product with 0% of 2 μm or more was obtained. Thereafter, the same procedure as in Example 1 was carried out to obtain a toner and a developer.

Using these developers and toners, we conducted an image reproduction test using a Canon full-color copy @ CLC-1.

As a result, even after printing 120,000 sheets in magenta single-color 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. In addition, the toner transportability within the copying machine was good and stable image density was obtained. 0} Even when the IP film was used, the toner permeability was very favorable. Furthermore, the environment is low temperature and low humidity.
An image output test was carried out by changing the temperature to a higher temperature, but good results were obtained, with stable image density, no fogging, and almost no toner scattering.

In addition, the images obtained here were exposed to sunlight for 3 months,
None of the colors faded, and the image remained the same as when it was printed. The procedure was carried out in the same manner as in Example 1 except that the volume average particle size was 7.
．． 98 μm, 5 μaa or less 31.0%, 20
．． A classified product with 0% of 2 μi or more was obtained. Thereafter, the same procedure as in Example 1 was carried out to obtain a toner and a developer.

Using these developers and toners, an image reproduction test was conducted using a full color copying machine CLC-1 manufactured by Canon.

As a result, even after printing 11,000 sheets in magenta single-color mode, there was no offset to the fixing roll, and a full-color image faithfully reproducing the original color chart 1 without fog was obtained. Furthermore, the toner transportability within the copying machine was good and stable image density was obtained.

Even when the 041P film was used, the l property of the toner was very favorable. Furthermore, we conducted an image reproduction test in which the environment was changed to low temperature and low humidity, high temperature and high temperature, and good results were obtained, with stable image density, no fogging, and almost no toner scattering6. The resulting image was exposed to sunlight for 3 months, but none of the colors faded, and the image remained the same as when it was printed. The same procedure as in Example 1 was carried out except that 100 parts by weight of Resin D in Resin Synthesis Example was used, and the volume average particle diameter was 12.5 μm. 5 μm
A classified product with a size of 8% or less and a size of 1.2% of 20.2 μm or more was obtained. Thereafter, a toner and a developer having a toner concentration of 8% were obtained in the same manner as in Example 1 except that aluminum oxide was not used as a flow improver.

Using these developers and toners, an image reproduction test was conducted using a full color copying machine CLC-1 manufactured by Canon.

As a result, even after printing 130,000 sheets in magenta single-color 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 the 011P film was used, the toner permeability was very favorable. Furthermore, the environment is low temperature and low humidity.
An image output test was carried out by changing the temperature to a higher temperature, and good results were obtained, with stable image density, no fogging, and almost no toner scattering.

In addition, the images obtained here were exposed to sunlight for 3 months,
None of the colors faded, and the image remained the same as when it was printed.

Example 5 The same procedure as Example 1 was carried out except that 3.0 parts by weight of the positive charge control agent represented by the above-mentioned structural formula (II)-1 was used, and the volume average particle diameter was 1.8 μta and 5 μm or less 7.5 %, 2
A product classified as 0.2 μm or more and 0.5% was obtained. After this, a silicone oil having an amino group (
A magenta toner was prepared by externally adding 0.5 parts by weight of silica treated with KF-857). Thereafter, a developer having a toner concentration of 8% was obtained in the same manner as in Example 4.

Using these developers and toners, Canon Copy Al
An image output test was conducted using NP-4835.

As a result, even after printing 10,000 sheets in magenta single-color 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 the 0 11 P film was used, the toner permeability was very favorable. Furthermore, low temperature environment? ``An image output test was performed by changing the temperature to A2 high temperature, and good results were obtained with stable image density, no fogging, and almost no toner scattering.

In addition, the images obtained here were exposed to sunlight for 3 months,
None of the colors faded, and the image remained the same as when it was printed.

Comparative Example 1 The same procedure as Example 1 was carried out except that 100 parts by weight of Resin E of Resin Synthesis Example was used, and the volume average particle diameters were 8.31 μm and 5 μm.
A classified product with a size of 29.0% or less and a size of 20.2 μm or more and 0% was obtained. Thereafter, the same procedure as in Example 1 was carried out to obtain toner and developer. Using these developers and toners, we conducted an image reproduction test on a Canon full-color copier CL (;-1). Although there was no offset, the flatness of the copy image fixing surface was poor, resulting in a dull colored image with poor color mixing properties.

Using 100 parts by weight of Resin F in the Example of Resin Synthesis, C.I. I. The same procedure as in Example 3 was carried out except that the solvent violet 1O was not treated with phenolytic resin, and the volume average particle size was 8.
38 μm, 5 μm or less 28.0%, 20.2 μm
A classified product of m or more O% was obtained. After this, further Example 3
A toner and a developer were obtained in the same manner as above.

Using these developers and toners, an image reproduction test was conducted using a full color copying machine CLC-1 manufactured by Canon.

As a result, in magenta single-color mode, an offset to the checking roller occurred after printing on 30,000 sheets.

Example 1 was repeated except that 100 parts by weight of Resin G of Resin Synthesis Example was used, and the volume average particle diameter was 2.2 μm. 5μI
7.2% or less, 20.2 μm or more L. A classified product of S% was obtained. Thereafter, the same procedure as in Example 4 was carried out to obtain toner and developer. Using these developers and toners, an image reproduction test was conducted using a Canon full-color copying machine CLC-1. As a result, after printing 200 sheets in magenta single-color mode, toner that had been offset at a low temperature on the fixing roller began to appear on the copied image, and after 300 sheets, full-scale offset occurred. [Effects of the Invention] According to the toner of the present invention, there is no dyeing deterioration of the fixing roller, it has excellent offset resistance, and it is also possible to form a smooth fixing surface and obtain a very clear color image. It's coming out.

[Brief explanation of the drawing]

Claims (2)

[Claims] (1) A color toner characterized by containing at least a styrene resin as a binder resin, a phenol resin, a quinacridone pigment, and an oil-soluble xanthene dye. (2) In the molecular weight distribution determined by GPC, the styrene resin has at least one maximum at a molecular weight of less than 10,000, has no maximum at a molecular weight of 10,000 or more, and has a molecular weight distribution of less than 10,000, 10,000 to 50,000, 500,
The ratio of areas A, B, and C in the range exceeding 00 is 5 each.
5 to 80%, 5 to 25%, and 5 to 20%, and if the Tg of each range is Tg_A and Tg_B_+_C, then 70°C>
T_g_A>50℃, 65℃>Tg_B_+_C>50
2. The color toner according to claim 1, wherein the temperature is .degree.