JP2000147832A - toner - Google Patents

Abstract

(57) [abstract] (with correction) [Problem] Good low-temperature fixability, high-temperature offset resistance,
Provide a toner having excellent blocking resistance. SOLUTION: The binder resin contains at least two of a vinyl copolymer, a polyester resin, and a resin in which the vinyl copolymer and the polyester resin are chemically reacted, and a THF-soluble component of the toner. In GPC, Mw ≧ 10
Mw / Mn ≧ 20; contains 5% by weight or more of a high molecular weight component having a molecular weight of 100,000 or more; composition ratio H of the ratio of the vinyl copolymer component to the polyester resin component, and a molecular weight of less than 100,000 The ratio L of the ratio of the vinyl copolymer component and the ratio of the polyester resin component constituting the low molecular weight component satisfies 15 ≦ H ≦ 505 5 ≦ L ≦ 40 H> L, and further has 23 to 252 carbon atoms. A long-chain alkyl alcohol compound having a long-chain alkyl group and a long-chain alkyl carboxylic acid compound having a long-chain alkyl group having 22 to 251 carbon atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and a toner jet recording method.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Numerous methods are known as described in Japanese Patent Publication No. JP-B-43-24748 and Japanese Patent Publication No. 43-24748. In general, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is developed using toner, and if necessary, a toner image is formed on a transfer material such as paper. After the transfer, the toner image is fixed by heating, pressure, heating / pressing or solvent vapor to obtain a toner image.

As a method for fixing the toner image on a sheet such as paper, which is the last step, the most common fixing method at present is a pressure heating method using a heating roller.

In this method, fixing is performed by passing a toner image surface of a sheet to be fixed under pressure onto a surface of a heating roller having a surface formed of a material having a releasable property with respect to toner. is there.

According to this method, since the surface of the heating roller and the toner image of the sheet to be fixed come into contact with each other under pressure, the heat efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and Fixing can be performed.

However, in this method, since the surface of the heating roller and the toner image come into contact with each other under pressure in a molten state, a part of the toner image adheres and transfers to the surface of the fixing roller, and the toner image is re-transferred to the next sheet to be fixed. Transfer causes a so-called offset phenomenon, which causes a problem that the sheet to be fixed is soiled. Therefore, it is necessary to have excellent low-temperature fixability and high-temperature offset resistance.

Heretofore, vinyl resins such as polyester resins and styrene resins have been mainly used as toner resins. Polyester resins originally have excellent low-temperature fixability, but also have the drawback of easily causing an offset phenomenon at high temperatures. Attempts to increase the viscosity by increasing the molecular weight of the polyester resin to compensate for this drawback not only impair the low-temperature fixability, but also degrade the pulverizability during toner production, making it unsuitable for finer toner particles. It will be something.

[0008] Vinyl copolymers such as styrene resins are excellent in pulverizability at the time of toner production and high in high molecular weight, and thus are excellent in high-temperature offset resistance. If the molecular weight is too low, the blocking resistance and the developability deteriorate.

[0009] In order to make the best use of the advantages of these two types of resins and to compensate for the drawbacks, several methods of mixing and using these resins have been studied. For example, JP-A-54-1
Japanese Patent No. 14245 discloses a toner containing a resin obtained by mixing a polyester resin and a vinyl copolymer. However, since the compatibility between the polyester resin and the vinyl-based copolymer is essentially poor, the low-temperature fixing property, the high-temperature offset resistance, and the anti-blocking property are all satisfied unless the mixing ratio of these resins is appropriate. Difficult. In addition, the dispersibility of the coloring agent and wax added during the production of the toner becomes insufficient, so that the fixing member is liable to be stained due to deterioration of the releasability, and problems are likely to occur in the developing property. In particular, in recent years, this problem is remarkable in a toner in which fine particles are advanced.

JP-A-56-116043 and JP-A-58-159546 disclose a toner characterized by containing a polymer obtained by polymerizing a monomer in the presence of a polyester resin. It has been disclosed. JP 58
JP-A-102246 and JP-A-1-156759 disclose toners containing a polymer obtained by polymerizing a vinyl copolymer in the presence of an unsaturated polyester. JP-A-2-881 discloses that
A toner characterized by containing a polymer obtained by esterifying an acid value-containing styrenic resin and a polyester resin is disclosed. In these methods, although the compatibility between the polyester resin and the vinyl copolymer is improved, a toner having a wide fixing temperature range and excellent offset resistance still needs to be improved together with the image characteristics described below. Have left.

Further, in recent years, it has been desired to improve the quality of a copied image by digitizing a copying machine and making toner finer. However, even if the resolution and sharpness of an image can be improved by making the toner finer, various problems arise. First, the fixability of the halftone portion deteriorates due to the fine particles of the toner. This is because the toner transferred to the concave portion of the sheet to be fixed is not easily applied with a fixing pressure, and the amount of applied heat is reduced. Further, since the toner transferred to the projections has a small toner layer thickness, the shearing force applied to each toner particle is large and the offset phenomenon is likely to occur. Further, as the toner surface area increases, the charging characteristics of the toner become more susceptible to the environment. It is apparent that when the toner particle size is further reduced, the dispersion state of the magnetic substance, the colorant, and the release agent greatly affects the chargeability of the toner.

In recent digital copiers,
In a photographic image containing characters, it is required that the characters of the copy image be clear, and that the photographic image be provided with a density gradation faithful to the original. In general, when the line density is increased in order to make the characters clear in the copy of the image including the characters, not only the density gradation of the photographic image is impaired, but also the halftone portion becomes a very rough image. Furthermore, when the line density is increased, the amount of toner applied is large, so that the toner is pressed against the photoconductor at the time of transfer and adheres to the photoconductor, causing a so-called hollowing phenomenon in which the toner on the line is removed, resulting in low image quality. It becomes a copy image. Conversely, if an attempt is made to improve the density gradation of a photographic image, the density of the character lines will be reduced and the sharpness will be degraded. In recent years, the density gradation has been improved to some extent by reading the image density and performing digital conversion. However, it is still not enough.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to (1) excel in low-temperature fixability, high-temperature offset resistance and blocking resistance, and (2) reduce the particle size. The present invention also provides an excellent fixing property in a halftone portion, and (3) does not cause problems such as a dropout phenomenon at the time of transfer, fusion of a photoreceptor, and defective cleaning. .

[0014]

According to the present invention, there is provided a toner containing at least a binder resin and a colorant, wherein the binder resin is a vinyl copolymer, a polyester resin, and a chemical mixture of the vinyl copolymer and the polyester resin. Gel permeation chromatography of a tetrahydrofuran (THF) soluble component of the toner containing two or more of the reactive resins, (a) Mw ≧ 100,000, Mw / Mn ≧
20 (b) containing 5% by weight or more of a high molecular weight component having a molecular weight of 100,000 or more, and (c) a ratio of a vinyl copolymer component constituting the high molecular weight component having a molecular weight of 100,000 or more (A _H : wt%) and the ratio (B _H : wt%) of the polyester resin component H (= 100 × A _H / (A _H +)
B _H)) and the proportion of the vinyl copolymer component constituting the low molecular weight component having a molecular weight of less than 100,000 (A _L: the ratio of the wt%) and polyester resin component (B _L: Ratio of wt%) L ( = 100 × _AL / ( _AL + _BL )) satisfies 15 ≦ H ≦ 50 (1) 5 ≦ L ≦ 40 (2) H> L (3) A long-chain alkyl alcohol compound containing a long-chain alkyl alcohol having a long-chain alkyl group having 23 to 252 carbon atoms as a main component;
And a long-chain alkyl carboxylic acid compound having a long-chain alkyl carboxylic acid having a long-chain alkyl group as a main component.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the toner of the present invention, the molecular weight and the molecular weight distribution of a vinyl copolymer and a polyester resin used as a binder resin are defined, and a low molecular weight component and a high molecular weight component are used to form a vinyl copolymer. By optimizing the composition ratio of the coalescing component and the polyester resin component as in the above formulas (1) to (3), it is possible to improve low-temperature fixing property, high-temperature offset resistance, and pulverization property.

Further, a long-chain alkyl alcohol compound mainly composed of a long-chain alkyl alcohol having a long-chain alkyl group having 23 to 252 carbon atoms, and a long-chain alkyl alcohol compound having 22 to 2 carbon atoms
By containing a long-chain alkyl compound selected from the group consisting of a long-chain alkyl carboxylic acid compound containing a long-chain alkyl carboxylic acid having a long-chain alkyl group as a main component, these components are added to the photoreceptor. Because of the excellent slipperiness, the hollowing phenomenon during transfer, the fusion of the photoconductor, and the poor cleaning are improved.

Further, since these long-chain alkylcarboxylic acid compounds exhibit good compatibility with both the vinyl copolymer component and the polyester resin component, the dispersibility in the toner is also improved. Even if the toner is finely divided, free components are not generated, and a toner having excellent releasability from the fixing member and stable developing properties over a long period of time can be achieved. Here, the "vinyl copolymer component"
It represents the sum of the vinyl copolymer and the vinyl copolymer chemically reacting with the polyester resin. Similarly, “polyester resin component” refers to a polyester resin,
It represents the sum of the polyester resins chemically reacting with the vinyl copolymer. In this method, the THF-soluble component in the toner is separated into a high molecular weight component having a molecular weight of 100,000 or more and a low molecular weight component having a molecular weight of less than 100,000 by preparative liquid chromatography, and these are separated by ¹ H-NMR (nuclear magnetic resonance) spectrum. Each component can be quantified.

In the above formula, when H (proportion of the vinyl copolymer component in the high molecular weight component) is less than 15%, the high-temperature offset resistance is deteriorated, and the effect of the polyester resin, which is originally poor in grindability, is reduced. Is notable, and it is difficult to make the toner into fine particles, and if it is attempted to make the particles fine, the production cost increases. When H is more than 50%, the high molecular weight vinyl copolymer impairs the low-temperature fixability. Therefore, H is preferably 15 to 50%, and more preferably 20 to 40%.

Here, the composition ratio of the high molecular weight component has been described. In order to obtain the above-mentioned effects, the GPC molecular weight of the THF-soluble component of the toner must include at least 5% by weight of a component having a molecular weight of 100,000 or more. is necessary.

When L (the ratio of the vinyl copolymer component in the low molecular weight component) is more than 40%, the low-temperature fixability deteriorates. When L is less than 5%, the compatibility with the high molecular weight component deteriorates, and when the toner is formed, poor dispersion of the colorant and the wax tends to occur. Becomes impossible. Therefore, L is 5 to 40%, preferably 5 to 30%.
Is good.

When L is larger than H, it is difficult to balance low-temperature fixability and high-temperature offset resistance, so that HL> 0, preferably HL ≧ 5 is preferred.

In the present invention, the TH of the binder resin in the toner is
Although the composition ratio of the F-soluble component is described, the binder resin in the toner may contain a THF-insoluble component to such an extent that the above effects are not impaired. Specifically, the THF-insoluble component in the entire binder resin in the toner is preferably 0 to 30% by weight.

The GP soluble in THF of the binder resin in the toner
In C, Mw needs to be 100,000 or more and Mw / Mn needs to be 20 or more. When Mw is smaller than 100,000, high-temperature offset resistance deteriorates. When Mw / Mn is smaller than 20, it becomes difficult to balance low-temperature fixability and high-temperature offset resistance.

In order to produce such a resin, it is preferable to synthesize it by the following production method. (1) Radical polymerization of a vinyl monomer in the presence of an unsaturated polyester resin. (2) A polyester resin is produced in the presence of a vinyl polymer having a functional group. (3) A vinyl monomer is mixed with a polyhydric alcohol and a polycarboxylic acid, and a radical polymerization and an esterification reaction are carried out simultaneously or stepwise to produce.

In the above (1) and (2), a low molecular weight polymer and a high molecular weight polymer are produced individually, or the other polymer is produced in the presence of either polymer. The mixing ratio of the polymer can be controlled by sequentially changing the composition of the monomer (vinyl monomer, acid, alcohol) to be used.

The long-chain alkyl alcohol used in the present invention is represented by the formula (1).

CH ₃ (CH ₂ ) _x CH ₂ OH (1) (x represents an average value, 21 to 250, preferably 21 to 250
100. )

For example, ethylene is polymerized using a Ziegler catalyst, and after polymerization is oxidized to produce an alkoxide of the catalyst metal and polyethylene. Thereafter, hydrolysis is performed to obtain a long-chain alkyl alcohol. The long-chain alkyl alcohol thus obtained has a small number of branches and a small molecular weight distribution, and is in accordance with the object of the present invention.

The long-chain alkyl carboxylic acid used in the present invention is represented by the formula (2).

CH ₃ (CH ₂ ) _y COOH (2) (y represents an average value, 21 to 250, preferably 21 to 250)
100. )

This long-chain alkyl carboxylic acid can be obtained by oxidizing a long-chain alkyl alcohol represented by the formula (1).

Content (% by weight) of each long-chain alkyl alcohol component in the long-chain alkyl alcohol compound
Can be analyzed by GC-MS analysis. For example, GC-MS manufactured by VG Organic
Using an analyzer (VG TRIO-1), column
Can be analyzed using DB-1 or DB-5 manufactured by J & W. In the analysis, it is preferable to perform a GC-MS analysis after the long-chain alkyl alcohol component is silylated with a silylating agent such as trimethylsilyl chloride. The content ratio of each long-chain alkylcarboxylic acid component in the long-chain alkylcarboxylic acid component can be analyzed by the same method.

In the formulas (1) and (2), x or y indicates an average value, and the average value x or y is 21.
~ 250, preferably 21-100. When x or y is less than 21, the ability to impart slipperiness to the photoreceptor is reduced, and problems such as a hollow phenomenon during transfer, fusion of the photoreceptor, and poor cleaning are likely to occur.
Further, the storage stability of the toner tends to decrease. When x or y is larger than 250, the melting point becomes high, so that the low-temperature fixability is impaired.

The long-chain alkyl alcohol having a long-chain alkyl group having 23 to 252 carbon atoms is preferably contained in a long-chain alkyl alcohol compound of 60% by weight or more (more preferably, 70% by weight or more). The long-chain alkyl carboxylic acid having a long-chain alkyl group having 22 to 251 carbon atoms is 60 wt% or more (preferably 70 w
(t% or more) It is preferable that the compound is contained in a long-chain alkylcarboxylic acid compound.

The long-chain alcohol preferably contains at least 50 wt% of a long-chain alkyl alcohol component having 37 or more carbon atoms in the total alkyl alcohol. The long-chain carboxylic acid preferably contains a long-chain alkylcarboxylic acid component having a carbon number of 38 or more in all alkylcarboxylic acids in an amount of 50% by weight or more. When the content of the long-chain alkyl alcohol component having 37 or more carbon atoms and the long-chain alkyl carboxylic acid component having 38 or more carbon atoms is less than 50% by weight, fusion of the toner to the photoreceptor occurs or the toner is stored. Stability tends to decrease.

The long-chain alkyl alcohol or long-chain alkyl carboxylic acid used in the present invention preferably has a melting point of 91 ° C. or higher. If the melting point of the long-chain alkyl alcohol or long-chain alkyl carboxylic acid is less than 91 ° C., it tends to dissolve and separate during kneading in the toner production process, and the dispersion in the toner particles tends to be poor. Therefore, such a toner is liable to cause fusion of the photoreceptor, and not only deteriorates storage stability, but also tends to cause a difference in fluidity of toner particles. It is easy to occur and the image quality is rough.

It is preferable to use 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight of the long-chain alkyl alcohol and / or long-chain alkyl carboxylic acid per 100 parts by weight of the binder resin component. When the amount is less than 0.1 part by weight, the above-mentioned effects are small, and when the amount is more than 30 parts by weight, the blocking resistance of the toner is reduced and the pulverizability at the time of toner production is reduced.

Examples of the polyester resin monomer used in the present invention include the following.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and a bisphenol derivative represented by the formula (a);

[0040]

Embedded image

Diols represented by the formula (b):

[0042]

Embedded image And the like.

The divalent carboxylic acid containing 50 mol% or more of the total acid component includes phthalic acid, terephthalic acid,
Benzenedicarboxylic acids such as isophthalic acid and phthalic anhydride or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; and further substituted with an alkyl group having 6 to 18 carbon atoms. Succinic acid or its anhydride; and unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, and anhydrides thereof.

Also, polyhydric alcohols such as glycerin, pentaerythritol, sorbit, sorbitan, and oxyalkylene ethers of novolak type phenol resin; trimellitic acid, pyromellitic acid,
Examples include polyvalent carboxylic acids such as benzophenonetetracarboxylic acid and its anhydride.

The particularly preferred alcohol component of the polyester resin in the practice of the present invention is a bisphenol derivative represented by the above formula (a), and the acidic component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, and amber. An acid, n-dodecenyl succinic acid, or an anhydride thereof,
Examples include dicarboxylic acids such as fumaric acid, maleic acid, and maleic anhydride. Further, the polyester resin of the present invention is preferably cross-linked by a trivalent or higher polyhydric carboxylic acid or polyhydric alcohol, and as a cross-linking component, trimellitic anhydride, benzophenonetetracarboxylic acid, pentaerythritol, a novolak type phenol resin. Oxyalkylene ethers are preferred.

The vinyl monomers for producing the vinyl resin include the following.

Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p -Methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene,
styrene and its derivatives such as m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride; Vinyl halides such as vinyldene chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate , Isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Α-methylene aliphatic monocarboxylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate Acrylates such as stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone Vinyl ketones such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl compounds such as N-vinyl pyrrolidone; vinyl naphthalenes; acrylonitrile, methacrylonitrile And acrylic acid or methacrylic acid derivatives such as acrylamide.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride Unsaturated dibasic acid anhydrides such as those; methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, methyl itaconate Half esters of unsaturated dibasic acids such as half ester, methyl alkenyl succinate half ester, methyl fumarate half ester and methyl half mesaconic acid; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; Le acid, methacrylic acid, crotonic acid,
Α, β-unsaturated acids such as cinnamic acid; crotonic anhydride,
Α, β-unsaturated acid anhydrides such as cinnamic anhydride;
anhydrides of β-unsaturated acids and lower fatty acids; alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid,
Examples thereof include monomers having a carboxyl group such as acid anhydrides and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Monomers having a hydroxy group such as (hydroxy-1-methylhexyl) styrene are exemplified.

Further, if necessary, the polymer may be crosslinked with a crosslinking monomer as exemplified below.

Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene; examples of the diacrylate compound linked by an alkyl chain include:
Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate and the above compounds Examples of the acrylate include methacrylates; diacrylate compounds linked by an alkyl chain containing an ether bond include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate,
Tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and the above compounds in which the acrylate is replaced with methacrylate; including an aromatic group and an ether bond Examples of chain-linked diacrylate compounds include polyoxyethylene (2) -2,2
-Bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-
(Hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; polyester-type diacrylates include, for example, the trade name MANDA (Nippon Kayaku).

As the polyfunctional crosslinking agent, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and those obtained by replacing acrylate of the above compounds with methacrylate; Triallyl cyanurate and triallyl trimellitate;

These cross-linking agents may be used in combination with other monomer components 10
0.01 to 10 parts by weight (more preferably 0.03 to 5 parts by weight) can be used with respect to 0 parts by weight.

Among these crosslinkable monomers, those which are preferably used from the viewpoint of fixing property and offset resistance to the resin for toner include an aromatic divinyl compound (particularly divinylbenzene), an aromatic group and one ether bond. And diacrylate compounds linked by a chain.

In the present invention, the vinyl copolymer component and / or the polyester resin component preferably contain a monomer component capable of reacting with both resin components. Among the monomers constituting the polyester resin component, those that can react with the vinyl copolymer include, for example, phthalic acid, maleic acid,
Unsaturated dicarboxylic acids such as citraconic acid and itaconic acid and anhydrides thereof; Examples of the monomer constituting the vinyl copolymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite, and ferrite, and iron oxides containing other metal oxides; Fe, Co, Ni Or a metal such as Al, Co, Cu,
Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
Alloys with metals such as d, Ca, Mn, Se, Ti, W, and V, and mixtures thereof, and the like.

Specifically, examples of the magnetic material include iron trioxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), and yttrium iron oxide ( Y ₃ Fe ₅
O ₁₂ ), iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ —O ₁₂ ), iron oxide copper (CuFe)
₂ O ₄ ), lead iron oxide (PbFe ₁₂ —O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), and neodymium iron oxide (NdFe
₂ O ₃ ), barium iron oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnF
e ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni), etc., and the above-mentioned magnetic materials are used alone or in combination of two or more. Particularly preferred magnetic materials are fine powders of triiron tetroxide or gamma-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
μm (more preferably 0.1 to 0.5 μm) and 10K
The magnetic properties upon application of the Oersted are coercive force of 20 to 150 Oersted, saturation magnetization of 50 to 200 emu / g (preferably 50 to 100 emu / g), and residual magnetization of 2 to 20 em.
u / g is preferred.

The magnetic material 1 was added to 100 parts by weight of the binder resin.
It is preferable to use 0 to 200 parts by weight, preferably 20 to 150 parts by weight.

In addition to the magnetic material, carbon black, titanium white, and other pigments and / or dyes can be used as the colorant. For example, when using the toner of the present invention as a magnetic color toner, as the dye,
C. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I.
I. Acid Blue 9, C.I. I. Acid blue 15,
C. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I.
I. Basic Green 6 and the like. Pigments include mineral fast yellow, navel yellow, naphthol yellow S, Hanza yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange,
Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, First Sky Blue, Indanthrene Blue BC, Pigment Green B, Malachite Green Lake, Final Yellow Green G and the like.

When the toner of the present invention is used as a two-component full-color toner, the following colorants may be used. Examples of the magenta coloring pigment include C.I.
I. Pigment Red 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16,
17, 18, 19, 21, 22, 23, 30, 31, 3
2,37,38,39,40,41,48,49,5
0, 51, 52, 53, 54, 55, 57, 58, 6
0, 63, 64, 68, 81, 83, 87, 88, 8
9, 90, 112, 114, 122, 123, 163,
202, 206, 207, 209, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1,2,1
0, 13, 15, 23, 29, 35 and the like.

Although the above pigments may be used alone,
It is more preferable to improve the sharpness by using a dye and a pigment in combination from the viewpoint of the image quality of a full-color image. Magenta dyes include C.I. I. Solvent Red 1,3,8,2
3,24,25,27,30,49,81,82,8
3,84,100,109,121, C.I. I. Disperse Red 9, C.I. I. Solvent Violet 8,1
3, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1,
2, 9, 12, 13, 14, 15, 17, 18, 22,
23, 24, 27, 29, 32, 34, 35, 36, 3
7, 38, 39, 40, C.I. I. Basic violet 1,3,7,10,14,15,21,25,26,
And basic dyes such as 27 and 28.

Examples of the coloring pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by the following formula.

[0064]

Embedded image

Examples of the coloring pigment for yellow include C.I. I. Pigment Yellow 1,2,3,4,5,6,7,10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5, 73, 83, C.I. I. Bat Yellow 1,3,20
And the like.

The amount of the nonmagnetic colorant used is 100
0.1 to 60 parts by weight, preferably 0.5 part by weight,
５０50 parts by weight.

In the present invention, if necessary, one or more release agents may be contained in the toner particles.

The following are examples of the release agent used in the present invention. Low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, aliphatic hydrocarbon-based wax such as paraffin wax, or an oxide of an aliphatic hydrocarbon-based wax such as oxidized polyethylene wax, or a block copolymer thereof; carnauba wax; Waxes mainly containing fatty acid esters such as sasol wax and montanic acid ester wax,
And a partially or entirely deoxidized fatty acid ester such as deoxidized carnauba wax. Furthermore, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; brandinic acid, eleostearic acid,
Unsaturated fatty acids such as vinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melisyl alcohol; polyhydric alcohols such as sorbitol; linoleic acid amide, oleic acid amide; Fatty acid amides such as lauric acid amide; saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide;
Unsaturated fatty acid amides such as ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N, N'dioleyladipamide, N, N'dioleylsebacic acid amide; m-xylenebisstearic acid amide; Aromatic bisamides such as N 'distearyl isophthalamide; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metallic soaps); aliphatic hydrocarbons Waxes obtained by grafting waxes with vinyl monomers such as styrene and acrylic acid; partial esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; having hydroxyl groups obtained by hydrogenation of vegetable oils and fats Methyl ester compound Etc., and the like.

As the wax particularly preferably used in the present invention, an aliphatic hydrocarbon wax is exemplified. For example, a low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or a Ziegler catalyst under low pressure; an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer; Preferred is a synthetic hydrocarbon wax obtained from a hydrocarbon distillation residue obtained by the method or by hydrogenating them. Further, those obtained by separating hydrocarbon wax by use of a press sweating method, a solvent method, vacuum distillation or a fractional crystallization method are more preferably used. The hydrocarbon as a base is synthesized by a reaction between carbon monoxide and hydrogen using a metal oxide-based catalyst (often a multi-component system) [for example, the Zintol method, the hydrochol method (using a fluidized catalyst bed). Compound); hydrocarbons having a carbon number of up to about several hundreds obtained by the Aggé method (using an identified catalyst bed) in which a large amount of waxy hydrocarbons can be obtained; alkylenes such as ethylene can be converted by a Ziegler catalyst. The polymerized hydrocarbon is preferable since it is a straight-chain hydrocarbon having a small number of branches, a small number of branches, and a long saturation. Particularly, a wax synthesized by a method not based on the polymerization of alkylene is preferable in view of its molecular weight distribution.

In the molecular weight distribution of the wax, a molecular weight of 400
It is preferable that the main peak exists in the region of ２2400, preferably 450-2000, particularly preferably 500-1600. By providing such a molecular weight distribution, it is possible to impart favorable thermal characteristics to the toner.

The releasing agent is used in an amount of 0.1 per 100 parts by weight of the binder resin.
It is good to use 1 to 20 parts by weight, preferably 0.5 to 10 parts by weight.

The release agent is usually contained in the binder resin by dissolving the resin in a solvent, increasing the temperature of the resin solution, and adding and mixing while stirring, or by mixing at the time of kneading.

In the toner of the present invention, a charge control agent can be used if necessary in order to further stabilize the chargeability. The charge control agent is used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the resin component. Examples of the charge control agent include the following.

To control the toner to be negatively charged,
For example, an organic metal complex and a chelate compound are effective, and examples thereof include a monoazo metal complex, an acetylacetone metal complex, a metal complex or a metal salt of an aromatic hydroxycarboxylic acid or an aromatic dicarboxylic acid. Other examples include aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

To control the toner to be positively charged,
Modified products such as nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and oniums such as phosphonium salts which are analogs thereof Salts and their lake pigments; triphenylmethane dyes and these lake pigments (as the lakening agent, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanic acid, Russian compounds, etc.); metal salts of higher fatty acids;
Dibutyltin oxide, dioctyltin oxide,
Diorganotin oxides such as dicyclohexyltin oxide; and diorganotin borates such as dibutyltin borate, dioctyltin borate, and dicyclohexyltin borate. These can be used alone or in combination of two or more. Of these, charge control agents such as nigrosine compounds and quaternary ammonium salts are particularly preferably used.

A fluidity improver may be added to the toner of the present invention. The fluidity improver can be added to the toner to increase the fluidity before and after the addition. For example, fluororesin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fine powder silica such as wet-process silica and dry-process silica, fine powder titanium oxide, fine powder alumina, a silane coupling agent thereof, There are treated silica, treated titanium oxide, and treated alumina that have been surface-treated with a titanium coupling agent and silicone oil.

Preferred fluidity improvers are fine powders produced by the vapor phase oxidation of silicon halides, and are so-called dry silica or fumed silica. 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.

SiCl ₂ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

In this production step, it is possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride or titanium chloride together with the silicon halide. They are also included. The particle size is preferably in the range of 0.001 to 2 μm as an average primary particle size, and particularly preferably, fine silica powder in the range of 0.002 to 0.2 μm is used. .

Commercially available silica fine powder produced by the vapor phase oxidation of a silicon halide compound includes, for example, those commercially available under the following trade names.

AEROSIL (Aerosil Nippon) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N20 V15 WAK -CHEMIE GMBH) N20E T30 T40 DC Fine Silica (Dow Corning Co.) Fransol (Fransil)

Further, a treated silica fine powder obtained by subjecting a silica fine powder produced by vapor-phase oxidation of the silicon halide compound to a hydrophobic treatment is more preferable. It is particularly preferable that the treated silica fine powder is obtained by treating the silica fine powder such that the degree of hydrophobicity measured by a methanol titration test shows a value in the range of 30 to 80.

The hydrophobizing method is applied by chemically treating with an organic silicon compound or the like which reacts or physically adsorbs with the silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of the organosilicon compound include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, Bromomethyldimethylchlorosilane,
α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule, each having one to each of the terminal units. Examples include dimethylpolysiloxane containing a hydroxyl group bonded to Si. Further, a silicone oil such as dimethyl silicone oil may be used. These are used alone or as a mixture of two or more.

The fluidity improver has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, preferably 5 m ² / g or more.
Those with 0 m ² / g or more give good results. Toner 1
0.01 to 8 parts by weight of the fluidity improver based on 00 parts by weight,
Preferably, 0.1 to 4 parts by weight is used.

To prepare the toner of the present invention, a binder resin,
A colorant and / or a magnetic substance, a charge control agent or other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and are melted, kneaded and kneaded using a hot kneader such as a kneader or an extruder. Then, the resins are mutually dissolved, and the melt-kneaded product is cooled and solidified, and then the solidified product is pulverized, and the pulverized product is classified to obtain the toner of the present invention.

Further, the fluidity improver and the toner are sufficiently mixed by a mixer such as a Henschel mixer to obtain a toner having a fluidity improver on the surface of toner particles.

The molecular weight of the THF-soluble component, the ratio of the THF-insoluble component and the ¹ H-NMR measurement method of the toner according to the present invention are as follows. The embodiments described below are also based on this method.

(1) Measurement of Molecular Weight The molecular weight of a chromatogram by GPC (gel permeation chromatography) is measured under the following conditions.

That is, the column is stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) as a solvent is flown through the column at this temperature at a flow rate of 1 ml per minute. After the developer was dissolved in THF and allowed to stand overnight,
Filter through a 2 μm filter and use the filtrate as a sample. The measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6% by weight. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. Standard polystyrene samples for preparing a calibration curve include, for example, Pressure Chemical C
o. Or Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 1
0 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ ,
5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8,
It is suitable to use 6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

It is preferable to use a plurality of commercially available polystyrene gel columns in order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ^6.
ers, μ-styragel 500, 10 ³ ,
Combinations of 10 ⁴ and 10 ⁵ and Showa Denko's Shod
ex KA-801, 802, 803, 804, 80
A combination of 5, 806 and 807 is preferred.

(2) Measurement of THF Insoluble Content 1 g of the toner is weighed, placed in a cylindrical filter paper (for example, No. 86R size 28 × 100 mm manufactured by Toyo Roshi Kaisha, Ltd.) and subjected to a Soxhlet extractor. THF 200ml as solvent
For about 6 hours. At this time, extraction is performed at a reflux rate such that the THF extraction cycle is about once every 4 to 5 minutes. After the completion of the extraction, the cylindrical filter paper is taken out and weighed to obtain an insoluble portion of the resin in the toner.

When the toner contains a THF-insoluble component such as a magnetic substance or a pigment other than the resin component, the weight of the toner put in the cylindrical filter paper is defined as W ₁ g, and the weight of the extracted THF-soluble resin component is defined as W ₁ g. and W ₂ g, when the weight of the THF-insoluble components other than the resin component contained in the toner and W ₃ g, T
The content of the HF-insoluble component is obtained from the following equation.

[0094]

(Equation 1)

FIG. 1 shows an example of a Soxhlet extraction apparatus.

The THF 2 contained in the container 1 is a heater 8
Is heated and vaporized, and the vaporized THF is led to the cooler 5 through the pipe 7. The cooler 5 is constantly cooled by the cooling water 6. The THF cooled and liquefied by the cooler 5 accumulates in the storage section having the cylindrical filter paper 3, and when the liquid level of THF becomes higher than the middle pipe 4, the THF is discharged from the storage section into the container 1. The toner contained in the cylindrical filter paper is extracted by the circulating THF.

(3) ¹ H-N of THF-soluble component in toner
Measurement of MR (nuclear magnetic resonance) spectrum Measurement device: FT NMR device JNM-EX400
(Manufactured by JEOL Ltd.) Measurement frequency: 400 MHz Pulse condition: 5.0 μs Data point: 32768 Delay time: 25 sec Frequency range: 10500 Hz Number of integrations: 16 Measurement temperature: 40 ° C. Sample: 200 mg of a measurement sample is placed in a φ5 mm sample tube. And CDCl ₃ (TMS0.0
5%) and dissolved in a 40 ° C. thermostat to prepare.

(4) Measurement of Melting Point of Long-Chain Alkyl Compound The melting point of the wax is defined as the melting point of the wax, which is the maximum temperature of the endothermic peak of the wax measured by DSC.

In the DSC measurement of a wax with a differential scanning calorimeter, it is preferable to measure the wax with a high-precision internal heating input compensation type differential scanning calorimeter. For example, DSC-7 manufactured by PerkinElmer can be used. Measurement method is ASTM D3
Performed according to 418-82. DSC used in the present invention
The curve is a DS measured when the temperature is raised at a rate of 10 ° C./min after the temperature has been raised and lowered once to obtain a pre-history.
Use the C curve.

[0100]

EXAMPLES The present invention will be described below with reference to resin production examples and examples, but the present invention is not limited to these examples.

[Resin Production Example] Terephthalic acid 32.0 mol% Dodecenyl succinic acid 8.2 mol% Trimellitic anhydride 0.8 mol% Bisphenol derivative represented by the formula (A) (R: x + y = 2 in propylene group) .2) 38.8 mol% (R: x + y = 2.2 in ethylene group) 20.2 mol% The above raw materials were charged into a 5-liter autoclave together with an esterification catalyst, and a reflux condenser, a water separator, a N ₂ gas introduction pipe, A thermometer and a stirrer were attached, and a polycondensation reaction was performed at 230 ° C. while introducing N ₂ gas into the flask to obtain a polyester resin having a low degree of crosslinking.

After completely dissolving 90 parts by weight of the obtained polyester resin in 100 parts by weight of xylene, 7.5 parts by weight of styrene and 2.5 parts by weight of 2-ethylhexyl acrylate were used.
Parts by weight and 0.1 parts by weight of azobisisobutyronitrile dissolved as a polymerization initiator were dissolved in a nitrogen atmosphere at about 1 part by weight.
At a temperature of 35 ° C., it was added dropwise over about 1 hour. By aging at the same temperature and removing the solvent, a resin A containing a polyester resin, a vinyl copolymer and a resin in which these were chemically reacted was obtained.

Next, 24.0 mol% of terephthalic acid, 14.6 mol% of dodecenylsuccinic acid, 7.0 mol% of trimellitic anhydride, bisphenol derivative represented by the formula (A) (R: x + y = 2.2 in propylene group) 35 mol% (R: x + y = 2.2 in ethylene group) 19.4 mol% was subjected to a condensation polymerization reaction in the same manner as described above, and 75 parts by weight of the obtained polyester resin was dissolved in 100 parts by weight of xylene.
A solution prepared by dissolving 19 parts by weight of styrene, 6 parts by weight of 2-ethylhexyl acrylate and 0.04 part by weight of the above polymerization initiator was added dropwise at about 125 ° C. for about 3 hours in a nitrogen atmosphere. By aging at the same temperature and removing the solvent, a resin B containing a polyester resin, a vinyl copolymer and a resin in which these were chemically reacted was obtained.

In the resins A and B of the present invention, the fact that the vinyl copolymer and the polyester resin composition are chemically reacted can be verified by ¹³ C-NMR.

In general, the signal measured by ¹³ C-NMR of the ester group of the acrylate copolymerized with styrene is higher than that of the homopolymer of the acrylate toward the high magnetic field due to the influence of the benzene ring of styrene. Several pp
The phenomenon of m shift is known. This phenomenon is the same when the polyester resin composition is present as an ester group. Here, we focused on the carbon of the carboxyl group of trimellitic acid.

The low-crosslinking polyester resin composition of ¹³ C-
FIG. 2 shows the NMR measurement results, FIG. 3 shows the measurement results of styrene and 2-ethylhexyl acrylate having the same composition as those reacted with the low crosslinking polyester resin composition, and FIG. 3 shows the ¹³ C-NMR measurement results of the resin A of the present invention. As shown in FIG.

Table 1 shows the measurement results of the respective resin compositions.

[0108]

[Table 1]

Each of the resins A and B obtained above was
By melt-blending 0 parts by weight and 30 parts by weight, a binder resin (A) containing 23% by weight of a THF-insoluble content was obtained. The proportion of the vinyl copolymer in the THF-soluble matter of this resin was 20% by weight.

In the same manner, binder resins (a) to (co) as shown in Table 2 were obtained by changing the monomers.

Example 1 Binder resin (A) 100 parts by weight Azo-based iron complex compound 3 parts by weight Magnetic iron oxide 80 parts by weight Long-chain alkyl alcohol represented by formula (1) (x = 48) 5 parts by weight The above mixture is melt-kneaded with a twin-screw extruder heated to 130 ° C., the cooled mixture is roughly pulverized by a hammer mill, and the coarsely pulverized product is finely pulverized by a jet mill, and the obtained finely pulverized The product was classified with an air classifier to obtain a magnetic toner having a weight average diameter of 7.5 μm. GPC of the THF soluble portion of this toner
And a low-molecular-weight component having a molecular weight of less than 100,000 by preparative liquid chromatography.
As a result of being divided into high molecular weight components of not less than 100,000, the content of the high molecular weight component was 12% by weight, the ratio L of the vinyl copolymer in the low molecular weight component was 18, and the vinyl copolymer in the high molecular weight component was 18 Was 30. Further, 10% of a THF-insoluble content of the binder resin in the toner was contained.

To 100 parts by weight of the magnetic toner, 1.0 part by weight of hydrophobic dry silica (BET 200 m ² / g) was externally added using a Henschel mixer to prepare a developer.

By using this developer, a copier N
Unfixed images having image densities of 1.3 and 0.5 were obtained at P-6750, and a fixing test was performed by changing the temperature with a fixing device having the same structure as NP-6750. As a result, the fixable area was 150 to 240 ° C. for the image density of 1.4 and 160 to 240 ° C. for the image density of 0.5.

Further, using this developer, a copy test of 50,000 sheets was carried out with a Canon copier NP-6750. At this time, a cleaning test was performed by removing the cleaning web of the fixing roller. As a result, there was little fogging in the white background, there was no omission during transfer, and the image quality was high with little change from the initial image. Further, no fusion of the toner to the photoreceptor and defective cleaning did not occur at all. In addition, no stain was generated on the fixing member. See Table 4 for details.
Shown in

Examples 2 to 6 In Example 1, the binder resin was changed to (a) to (f), and the long-chain alkyl compound was
As a result of preparing a developer in place of the alkyl alcohol shown in Table 3, a developer as shown in Table 3 was obtained. When a test similar to that of Example 1 was performed using these developers,
As shown in FIG.

Example 7 A developer was prepared in the same manner as in Example 1 except that the long-chain alkyl compound was changed to the alkyl carboxylic acid shown in Table 3, and a developer as shown in Table 3 was obtained. When a test similar to that of Example 1 was performed using these developers, good results as shown in Table 4 were obtained.

Comparative Examples 1 to 4 In Example 1, the binder resin was changed to (G) to (K), and
As a result of preparing a developer in place of the alkyl alcohol shown in Table 3, a developer as shown in Table 3 was obtained. When a test similar to that of Example 1 was performed using these developers,
The result as shown in FIG.

Comparative Example 5 A developer was prepared in the same manner as in Example 3 except that the long-chain alkyl compound was changed to polypropylene (melting point: 138 ° C.). As a result, a developer as shown in Table 3 was obtained. When a test similar to that of Example 1 was performed using these developers, the results shown in Table 4 were obtained.

Comparative Example 6 A developer was prepared in the same manner as in Example 1 except that the binder resin was changed to a polyester resin (S). As a result, a developer as shown in Table 3 was obtained. When a test similar to that of Example 1 was performed using these developers,
The result as shown in FIG.

[0120]

[Table 2]

[0121]

[Table 3]

[0122]

[Table 4]

[Evaluation of Image] The image density is Macbeth.
It was measured by RD918 (manufactured by Macbeth).

The fog was evaluated as follows.

The fog density (%) was calculated from the difference between the whiteness of the white background portion of the printout image and the whiteness of the transfer paper measured by a “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.). Was evaluated.

Evaluation criteria: less than 1.2% △: 1.2 to less than 1.8% ・ ・ ・: 1.8 to less than 2.5% ×: 2.5 to Less than 4.0% × ... 4.0% or more

Missing portions during transfer, fusion, and poor cleaning were evaluated according to the following criteria. A: not generated B: slightly generated but not affecting the image C: generated and affected the image.

The stain on the fixing member was evaluated according to the following criteria. A: There is no stain on the fixing member. B: There is a little stain on the fixing member. C: The fixing member is stained but there is no effect on the image. D: The fixing member is stained and the image is offset.

[0129]

The toner of the present invention has good low-temperature fixability, and is excellent in high-temperature offset resistance, blocking resistance, multi-sheet durability and the like by the above-described improvement and optimization of the binder resin. It is.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a specific example of a Soxhlet extraction device used for Soxhlet extraction.

FIG. 2 shows an NMR spectrum of the polyester resin composition having a low crosslinking degree.

FIG. 3 shows an NMR spectrum of a styrene / 2-ethylhexyl acrylate copolymer.

FIG. 4 shows an NMR spectrum of Resin A of the present invention.

Continuation of the front page (72) Inventor Yuichi Mizoo 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Iwaichi Endo 3- 30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F term (reference) 2H005 AA01 AA02 AA06 CA04 CA08 CA17 CA18 CA30 EA06 EA07 FA06

Claims (11)

[Claims] 1. A toner containing at least a binder resin and a colorant, wherein the binder resin is a vinyl copolymer, a polyester resin, or a resin in which the vinyl copolymer and the polyester resin are chemically reacted. Including two or more of them,
According to gel permeation chromatography (GPC) of a tetrahydrofuran (THF) soluble component of the toner, (a) Mw ≧ 100,000 and Mw / Mn ≧ 20;
(B) containing 5% by weight or more of a high molecular weight component having a molecular weight of 100,000 or more, and (c) ratio of a vinyl copolymer component constituting the high molecular weight component having a molecular weight of 100,000 or more (A _H :
wt%) and the ratio of the polyester resin component (B _H : wt
Composition ratio of%) H (= 100 × A H / (A H + B H)) and the proportion of the vinyl copolymer component constituting the low molecular weight component having a molecular weight of less than 100,000 (A _L: wt%) and polyester Composition ratio L (= 100) of the ratio of resin components (B _L : wt%)
× A _L / (A _L + B _L )) satisfies 15 ≦ H ≦ 505 5 ≦ L ≦ 40 H> L, and further comprises a long-chain alkyl alcohol having a long-chain alkyl group having 23 to 252 carbon atoms. A long-chain alkyl alcohol compound having 22 to 251 carbon atoms
And a long-chain alkyl carboxylic acid compound having a long-chain alkyl carboxylic acid having a long-chain alkyl group as a main component. 2. The toner according to claim 1, wherein the composition ratio H and the composition ratio L satisfy the following relationship: 20 ≦ H ≦ 405 ≦ L ≦ 30 H ≧ L + 5. 3. The toner according to claim 1, wherein the vinyl copolymer component and / or the polyester resin component in the binder resin contains a monomer component capable of reacting with both components. 4. The toner according to claim 1, wherein the binder resin contains a resin in which at least a vinyl copolymer and a polyester resin are chemically reacted. 5. The toner according to claim 1, wherein the proportion of the THF-insoluble component in the total binder resin in the toner is from 0 to 30% by weight. 6. The toner according to claim 1, wherein the polyester resin in the toner is cross-linked by a trivalent or higher polyhydric carboxylic acid or polyhydric alcohol. 7. The long-chain alkyl alcohol is represented by the following formula: CH ₃ (CH ₂ ) _x CH ₂ OH, wherein x is an average value and is 21 to 250. And a compound represented by the formula:
The toner according to any one of the above. 8. The long-chain alkyl alcohol is represented by the following formula: CH ₃ (CH ₂ ) _x CH ₂ OH, wherein x is an average value and is 21 to 100. And a compound represented by the formula:
The toner according to any one of the above. 9. The long-chain alkyl carboxylic acid is represented by the following formula: CH ₃ (CH ₂ ) _y COOH wherein y represents an average value and is 21 to 250. And a compound represented by the formula:
The toner according to any one of the above. 10. A long-chain alkyl carboxylic acid is represented by the following formula: CH ₃ (CH ₂ ) _y COOH wherein y represents an average value and is 21 to 100. And a compound represented by the formula:
The toner according to any one of the above. 11. The toner according to claim 1, wherein the colorant is a magnetic powder.