JP3450634B2 - Toner for developing electrostatic images - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing toner used in electrophotography, electrostatic recording and magnetic recording.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, U.S. Pat. No. 2,297,691 and JP-B-42-23910 are known.
Although many methods are known as described in JP-B No. 43-24748 and Japanese Patent Publication No. 43-24748, generally, a photoconductive substance is used and an electric latent image is formed on a photoreceptor by various means. And then developing the latent image with toner,
After transferring the toner image to a transfer material such as paper, if necessary,
A copy is obtained by fixing with heat, pressure, heat and pressure, or solvent vapor.

Various methods and devices have been developed for the final step of fixing the toner image on a sheet such as paper, but the most general method at present is the pressure heating method using a heat roller.

In the pressure-bonding heating method using a heating roller, fixing is performed by allowing a toner image surface of a sheet to be fixed to pass through while contacting it with a heating roller having a surface formed of a material having releasability for toner. . In this method, since the surface of the heat roller and the toner image on the sheet to be fixed are brought into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image on the sheet to be fixed is extremely good, and quick fixing is possible. It is possible and very good in an electrophotographic copying machine. However, in the above method, since the surface of the heat roller and the toner image are in contact with each other in a molten state under pressure, a part of the toner image adheres to and transfers to the surface of the fixing roller, and this is retransferred to the next sheet to be fixed, so-called. An offset phenomenon may occur and the sheet to be fixed may be soiled. One of the essential conditions of the heat fixing system is to prevent the toner from adhering to the surface of the heat fixing roller.

Conventionally, for the purpose of preventing the toner from adhering to the surface of the fixing roller, for example, the roller surface is formed of a material having excellent releasability from the toner, such as silicone rubber or fluorine resin, and the surface is prevented from offsetting and In order to prevent fatigue of the roller surface, the roller surface is coated with a thin film of a liquid having a good releasing property such as silicone oil. However, this method is extremely effective in preventing toner offset, but has a problem that the fixing device becomes complicated because an apparatus for supplying the offset preventing liquid is required.

Therefore, it is not preferable to prevent the offset by supplying the offset preventing liquid, and it is the current situation that development of a toner having a wide fixing temperature range and high offset resistance is desired. Therefore, a method of adding a wax such as low-molecular weight polyethylene or low-molecular weight polypropylene, which is sufficiently melted when heated, is also used as a toner in order to increase releasability. However, while it is effective in preventing offset, the toner cohesiveness increases,
In addition, since the charging characteristics become unstable, the durability is likely to decrease. Therefore, as other methods, various attempts have been made to improve the binder resin.

For example, in order to prevent offset, a method is known in which the glass transition temperature (Tg) and the molecular weight of the binder resin in the toner are increased to improve the melt viscoelasticity of the toner. However, when the offset phenomenon is improved by such a method, the fixing property becomes insufficient, and there arises a problem that the fixing property at a low temperature required for a high-speed copying machine or energy saving, that is, the low temperature fixing property is deteriorated.

In order to improve the fixing property of the toner, it is necessary to lower the viscosity of the toner during melting and to increase the contact area with the fixing device. To this end, lower the Tg and the molecular weight of the binder resin used. Is required.

That is, since the low-temperature fixing property and the offset preventing property are contradictory to each other, it is very difficult to develop a toner satisfying these functions at the same time.

In order to solve this problem, for example, Japanese Patent Publication No. 51-23354 discloses a toner made of a vinyl polymer which is appropriately crosslinked by adding a crosslinking agent and a molecular weight modifier. In vinyl polymers, T
A large number of blend type toners have been proposed which combine g, molecular weight and gel content.

A toner containing such a crosslinked vinyl polymer or gel component in the toner is certainly improved in offset resistance.

However, when it is contained in the toner,
When this cross-linked vinyl polymer is used as a toner raw material, internal friction in the polymer becomes extremely large during melt kneading during toner production, and a large shearing force is applied to the polymer. For this reason, in many cases, molecular chain breakage occurs, which causes a decrease in melt viscosity and adversely affects offset resistance.

Therefore, in order to solve this, Japanese Patent Laid-Open No. 55-
90509, JP-A-57-178249,
JP-A-57-178250 and JP-A-60-49
According to Japanese Patent Laid-Open No. 46-46, a resin having a carboxylic acid and a metal compound are used as a toner raw material, and they are heated and reacted at the time of melt-kneading to form a crosslinked polymer, which is contained in the toner.

JP-A-63-214760, JP-A-63-217362 and JP-A-63-21736
In Japanese Patent Laid-Open No. 3, it is proposed that a vinyl type resin and a polyvalent metal compound, each of which has a vinyl ester and a specific half-ester compound as an essential constituent unit, are allowed to react with each other to perform crosslinking.

Further, it has been proposed to form a molecular weight distribution divided into two groups, a low molecular weight and a high molecular weight, and to react the carboxyl group of the unique half-ester compound contained on the low molecular weight side with the polyvalent metal ion. ing.

However, in these proposals, a carboxylic acid and a metal compound are used as raw materials for forming crosslinks. Many of these materials have strong or weak negative chargeability, and further, they have strong negative chargeability even in decomposition products that can be generated as a result of the crosslinking reaction. Therefore, it is effective for negatively chargeable toner, but when used for positively chargeable toner, there are many unfavorable points such as density decrease and fog.

As described above, in order to effectively contain the crosslinked polymer and gel content in the toner, a negatively chargeable material must be used, and a crosslinkable material suitable for the positively chargeable toner is desired. Is the current situation.

Further, the toners in these proposals are
The properties required for toner, particularly the offset resistance required for high-speed machines, have not been satisfied, and for example, high-speed machines with 80 or more sheets per minute cannot obtain sufficient fixability. Further, there is a problem that the recording material is soiled by the toner flowing out from the cleaning member that is brought into contact with the fixing roller.

That is, in a high-speed machine that exceeds 80 sheets per minute, even if the offset amount per sheet is extremely small, the number of sheets passed is enormous. Is a considerable amount and causes a failure of the fixing device. To remove this small amount of offset material,
A fixing cleaning member such as a silicone rubber cleaning roller or a web is attached in contact with the fixing roller. Conventional toner binder resins are designed mainly for low-temperature fixability and anti-offset properties, and are not designed to maintain a high melt viscosity up to a high temperature of over 200 ° C. Therefore, the toner substance attached to the fixing cleaning member is
If the temperature of the fixing roller exceeds the setting temperature of the fixing roller when the temperature of the copying machine is switched on and the fixing roller temperature overshoots because it exists for a long time at the setting temperature of the fixing roller, the temperature of the fixing roller exceeds 200 ° C. As a result, the melt viscosity of the adhered toner substance is remarkably lowered, and it is transferred to the fixing roller again, so that the recording material is stained.

[0020]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic charge image which solves the above problems.

The object of the present invention is to develop an electrostatic charge image which is excellent in low-temperature fixing property and anti-offset property, is free from ghost, is free from fog, and has a uniform sleeve coat without blotch, and can obtain a high density image. To provide a toner for use.

It is another object of the present invention to provide a toner for developing an electrostatic charge image, which has little influence on environmental changes and can obtain a good image even in a low humidity environment and a high humidity environment.

Another object of the present invention is to provide a toner for developing an electrostatic image which has no or very little toner flowing out from the cleaning means for the fixing device.

Another object of the present invention is to provide a toner for developing an electrostatic charge image, which can obtain stable and good images free of sticking even in a high-speed machine and which can be applied to any model.

[0025]

The electrostatic charge image developing toner of the present invention is an electrostatic charge image developing toner containing at least a binder resin and a colorant, and the binder resin has a molecular weight distribution measured by GPC. , Molecular weight 5 × 10 ^{3 to} 5 × 1
0 has at least one peak in the ^fourth region, Tetorahi
Dorofuran insoluble matter in the binder resin 5% by mass to 50% by mass
Contains, and has at least one peak in the molecular weight ¹⁰⁵ or more regions, the resin component constituting the molecular weight ¹⁰⁵ or more regions are present 5 to 50% by mass, and the acid value 0. The toner has an acid component of 5 to 100 mgKOH / g as a constituent component, and the toner further contains a imidazole compound
It is characterized by containing a soot body . Then, the toner can achieve the above object.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The acid component in the binder resin used in the present invention can be introduced into the binder resin by using a monomer having a carboxyl group and an acid anhydride group. The present inventors have reacted with this acid anhydride group and the amino group of the bis-form compound of the nitrogen-containing heterocyclic compound having a hydrogen atom on the nitrogen atom used in the present invention, which will be described later. It was found that the polymer chain can be effectively crosslinked by forming an imide bond having a high molecular weight.

By cross-linking a component having a molecular weight of 10 ⁵ or more, rubber elasticity can be imparted to the toner,
It was found that this rubber elasticity can improve the offset resistance and prevent the outflow of toner from the cleaning member of the fixing device.

In the present invention, the bis compound of the nitrogen-containing heterocyclic compound having a hydrogen atom on the nitrogen atom includes the following.

[0029]

[Chemical 1]

In the formula, R is hydrogen, an alkyl group, an amino group,
An alkylamino group, a dialkylamino group, a halogen, an unsubstituted phenyl group, a substituted phenyl group or an alkenyl group is shown, and the alkyl group in R has 1 carbon atom.
Preferably, the alkoxy group has 1 to 15 carbon atoms.
Preferably, the alkylamino group has 1 to 6 carbon atoms, the substituted phenyl group has 6 to 12 carbon atoms.

Some of these compounds also play a sufficient role as a positive charge control agent.
It is preferably used for positively chargeable toner. Particularly preferred is the bis form of the imidazole compound. Specific compound examples are shown below. However, the toner of the present invention is not limited at all.

[0032]

[Chemical 2]

As a typical example, the synthesis method of compound example (1) will be described below. Formaldehyde is added to 2-undecyl-5-methyl-1,3imidazole as an ethanol solvent, and potassium hydroxide is added as a catalyst, and the mixture is refluxed for several hours. The deposited material is filtered, washed with water, and then recrystallized with methanol to obtain Compound Example (1).

As a toner containing an amino-based crosslinking agent, for example, a certain alkylenediamine in JP-A-58-173752 and JP-A-58-17375.
No. 6, a kind of polyether amine is proposed. However, when the present inventors newly studied the alkylenediamines shown here, the toner containing them shows a preferable tendency with respect to the offset in the conventional toner. However, the dispersibility in the toner is not so good, and fog may occur depending on the toner manufacturing conditions. Further, as the number of copies increases, the developing device sleeve tends to be contaminated, so that the image density may decrease, which is particularly likely to occur in a high-speed machine. These are mainly due to the low melting points of the compounds proposed for them and many of them in the waxy form.

Further, the cross-linking agent disclosed in JP-A-5-173355 has a high melting point and is stable even at a temperature rise in the copying machine in the developing device or in the cleaning container, and it is extremely unlikely to cause fusion or contamination. Very few. Further, since the dispersibility in the toner is good, a clear image without fog can be obtained.

However, the cross-linking agent of the present invention can be contained in the toner as a charge control agent, and by cross-linking, the original performance as a charge control agent is hardly deteriorated, and the dispersibility in the toner, Excellent in fog prevention, less likely to cause sleeve contamination, and imparts good developing characteristics.

In the present invention, the amount is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin. 0.
If the amount is less than 01 parts by mass, crosslinking does not proceed easily and sufficient toner charging performance cannot be obtained. If the amount is more than 10 parts by mass, poor dispersion in the toner will occur.

As the acid component of the binder resin according to the present invention,
The acid value is required to be 0.5 to 100 mgKOH / g, and preferably 1 to 50 mgKOH / g.
When the acid value is less than 0.5 mgKOH / g, the compound having an amino group used in the present invention does not proceed with the reaction during the melt-kneading in the toner production process and the crosslinking tends to be insufficient, resulting in preferable offset resistance. In some cases, the toner may not be obtained, or the toner may not be prevented from flowing out by the cleaning member of the fixing device. Acid value is 50mgKOH / g
If it exceeds 100, it becomes difficult to control the charge, and 100
If it exceeds mgKOH / g, the chargeability of the toner may be hindered, or the crosslinking reaction may proceed excessively, which may adversely affect the fixability.

The tetrahydrofuran insoluble matter in the binder resin is
It is necessary to contain 5% by mass to 50% by mass. Preferably 5% by mass to 40% by mass, more preferably 10% by mass.
It is from 30% by mass to 30% by mass. During the kneading process of toner production, some of these insolubles break the polymer chains and affect the elasticity of the toner. If it is less than 5% by mass, the offset resistance will be poor, and if it is more than 50% by mass, the fixability will be adversely affected.

Since the bis compound of the nitrogen-containing heterocyclic compound having a hydrogen atom on the nitrogen atom in the present invention undergoes a cross-linking reaction with the acid anhydride, the acid anhydride present in the binder resin is The effect can be more significantly exhibited.

The amount of acid anhydride in the binder resin of the present invention is preferably adjusted in the range of 0 <total acid value (A) -JIS acid value (B) <50. More preferably, 0.5 <A-B <3
It is 0.

As A-B approaches 0, the cross-linking force weakens during melt-kneading in the toner manufacturing process, and the cross-linking reaction cannot be sufficiently performed, resulting in poor offset resistance. If it is 50 or more, there is a problem that the production of the binder resin itself becomes unstable.

The qualitative and quantitative determination of the functional group in the binder resin in the present invention is carried out by infrared absorption spectrum, JIS K-00.
A method of applying the acid value measurement of 70 and the hydrolysis acid value measurement (total acid value measurement) will be described.

For example, in infrared absorption, 1780 cm ^-1
Since an absorption peak derived from the carbonyl of the acid anhydride appears in the vicinity, the presence of the acid anhydride is confirmed. The carbonyl absorption of this acid anhydride appears at higher wavenumbers than with ester acid. The acid value derived from the acid anhydride is JIS K-0.
As an example, a method of applying an acid value measurement of 070, a hydrolysis acid value measurement (total acid value measurement), and the like can be mentioned.

For example, in the acid value measurement of JIS K-0070 (hereinafter referred to as JIS acid value), about 50% of the theoretical value (the acid anhydride has an acid value as a dicarboxylic acid) is measured. To be done.

On the other hand, in the measurement of total acid value, the measurement is carried out almost in theory. Therefore, the difference between the total acid value and the JIS acid value is about 50% of the theoretical value, and the acid anhydride is measured as a dibasic acid.
The total acid number derived from the acid anhydride per gram is determined. 1/2 of the total acid value of J is derived from acid anhydride in JIS acid value
IS acid value. That is, this corresponds to the difference between the total acid value and the JIS acid value.

To give a specific example, when monooctyl maleate is used as the acid component, a monooctyl maleate copolymer is first synthesized by solution polymerization. J of this copolymer
The total acid value (B) derived from the anhydride can be obtained by measuring the IS acid value and the total acid value (A). When this copolymer is further dissolved in a monomer and suspension polymerization is performed, a part of the ring is opened.
By measuring the JIS acid value and the total acid value (A) of the binder resin thus obtained, the total acid value (B) derived from the residual anhydride is obtained, and the total acid value of the entire binder resin is determined. The ratio of the total acid value (B) derived from the anhydride in (A) can be calculated.

In the present invention, the total acid value is determined as follows. 2 g of the sample resin was dissolved in 30 ml of dioxane, to which 10 ml of pyridine, 20 mg of dimethylaminopyridine, and 3.5 ml of water were added, and the mixture was mixed with stirring 4
Heat to reflux for hours. After cooling 1 / 10N KOH ・ THF
The acid value obtained by neutralization titration with phenolphthalein as an indicator in the solution is defined as the total acid value.

The 1/10 N KOH.THF solution is prepared as follows. Dissolve 1.5 g of KOH in about 3 ml of water, add 200 ml of THF and 30 ml of water, and stir. After standing, a small amount of methanol is added if the solution is separated, and a small amount of water is added if the solution is cloudy to make a uniform transparent solution, and the solution is standardized with a 1/10 N HCl standard solution.

Further, it is preferred that the binder resin contains a 5- or 6-membered carboxylic acid anhydride structure as a constituent. A 4-membered carboxylic acid anhydride has a problem in the production of the compound itself, and a 5- or 6-membered carboxylic acid anhydride is versatile, and is preferable in terms of production and cost.

The resin used in the present invention is not particularly limited as long as it has the acid value shown in the present invention. For example, styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, etc. And homopolymers of substitution products thereof; styrene-p-chlorostyrene copolymers,
Styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer Polymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer,
Styrene-based copolymers such as styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol resin, natural modified phenol resin, natural modified maleic acid resin, acrylic resin , Methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, rosin, modified rosin, terpene resin, coumarone indene resin, petroleum resin These may be a mixture of two or more kinds, a block copolymer, or a graft product.

Of these, vinyl copolymers or polyester resins are preferable, and vinyl copolymers are particularly preferable.

In order to obtain the vinyl copolymer preferred in the present invention, the following monomers having a carboxy group or monomers having an acid anhydride group which is a carboxy group derivative can be used as a monomer of the vinyl polymer. .

For example, succinic acid, maleic acid, citraconic acid, dimethylmaleic acid, itaconic acid, alkenylsuccinic acid, and their anhydrides, fumaric acid, metaconic acid,
Unsaturated dibasic acids such as dimethyl fumaric acid and monoesters of the above unsaturated dibasic acids; acrylic acid, methacrylic acid,
Crotonic acid, cinnamic acid and their anhydrides, α and β above
-Α, β-unsaturated acids such as anhydrides between unsaturated acids and anhydrides with lower fatty acids, their anhydride monomers; alkenylmalonic acid, alkenylglutanic acid, alkenylazibic acid, their anhydrides and , Monoesters.

Among these, maleic acid, fumaric acid,
Monoesters of α, β-unsaturated dibasic acid having a structure such as succinic acid are particularly preferably used as a monomer for obtaining the binder resin of the present invention.

Examples of such a monomer include monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate, monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, and fumarate. Acid monophenyl, n-butenyl monobutyl succinate, n
-Monomethyl octenyl succinate, monoethyl n-butenylmalonate, monomethyl n-dodecenyl glutarate,
Examples include monobutyl n-butenyl adipate, and the like.

Further, as the comonomer of the vinyl polymer,
Some examples are as follows.

For example, styrene, o-methylstyrene, m
-Methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
Styrene and its derivatives such as p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene and pn-dodecylstyrene; ethylene, Ethylenically unsaturated monoolefins such as propylene, butylene, isobutylene; Unsaturated polyenes such as butadiene;
Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid α-methylene aliphatic such as n-butyl, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate. Monocarboxylic acid esters; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethyl acrylate Hexyl, stearyl acrylate,
Acrylic esters such as 2-chloroethyl acrylate and phenyl acrylate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N -Vinylpyrrole, N-vinylcarbazole,
N such as N-vinylindole and N-vinylpyrrolidone
Vinyl compounds; vinylnaphthalene compounds; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; the above α, β-unsaturated acid esters and dibasic acid diesters; The monomers are used alone or in combination of two or more.

Among these, a combination of monomers that forms a styrene-based copolymer or a styrene-acrylic-based copolymer is preferable.

The binder resin used in the present invention may be a polymer which is mainly crosslinked with a crosslinkable monomer (crosslinking agent) having two or more polymerizable double bonds, if necessary.

Examples of the crosslinkable monomer include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; diacrylate compounds linked by an alkyl chain such as ethylene glycol diacrylate and 1,3-butylene glycol diester. Acrylate, 1,
4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol acrylate, neopentyl glycol diacrylate,
And those obtained by replacing the acrylate of the above compounds with methacrylate; diacrylate compounds linked by an alkyl chain containing an ether bond, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and any of the above compounds in which the acrylate is replaced with methacrylate; diacrylate compounds linked by a chain containing an aromatic group and an ether bond, for example, , Polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate,
Polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compounds with methacrylate; further, polyester type diacrylate compounds,
For example, the trade name MANDA (Nippon Kayaku) is listed.
As a polyfunctional crosslinking agent, pentaerythritol triacrylate, trimethylolethane triacrylate,
Trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylates, and compounds obtained by replacing the acrylates of the above compounds with methacrylates; triallyl cyanurate, triallyl trimellitate.

These crosslinking monomers can be used in an amount of about 0.01 to 5 parts by mass (more preferably about 0.03 to 3 parts by mass) with respect to 100 parts by mass of the other monomer components.

Among these crosslinkable monomers, those which are preferably used in the resin for toner from the viewpoints of fixing property and anti-offset property include an aromatic divinyl compound (particularly divinylbenzene), an aromatic group and an ether bond. Included are chain-linked diacrylate compounds.

The binder resin according to the present invention is a homopolymer, copolymer, polyester, polyurethane, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenolic resin, aliphatic resin or aforesaid vinyl monomer. An alicyclic hydrocarbon resin, an aromatic petroleum resin, a haloparaffin, and a paraffin wax can be mixed and used as necessary.

In the present invention, a polyester resin is also preferable. When a polyester resin is used, the composition of the polyester resin is as follows.

Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol and 1,5-pentanediol. 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-
Hexanediol, hydrogenated bisphenol A, bisphenol represented by the formula (A) and derivatives thereof;

[0067]

[Chemical 3]

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and
The average value of x + y is 0-10. )

Further, diols represented by the formula (B):

[0070]

[Chemical 4]

(In the formula, R ′ is —CH ₂ CH ₂ — or

[0072]

[Chemical 5] Where x ′ and y ′ are integers greater than or equal to 0, and x ′
The average value of + y 'is 0 to 10. ) Is mentioned.

As the divalent acid component, for example, phthalic acid,
Benzenedicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic anhydride, or their anhydrides, lower alkyl esters; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid or their anhydrides, lower alkyl esters; n- Alkenyl succinic acids such as dodecenyl succinic acid, n-dodecyl succinic acid or alkyl succinic acids, or their anhydrides, lower alkyl esters; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid or their anhydrides, lower Examples thereof include dicarboxylic acids such as alkyl ester; and derivatives thereof.

Further, it is preferable to use a trivalent or higher valent alcohol component which also functions as a crosslinking component and a trivalent or higher valent acid component in combination.

The trihydric or higher polyhydric alcohol component is
For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol,
1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,
3,5-trihydroxybenzene etc. are mentioned.

Examples of the trivalent or higher polycarboxylic acid component in the present invention include trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,
2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,
5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-
Octane tetracarboxylic acid, empol trimer acid, and their anhydrides, lower alkyl esters;

[0077]

[Chemical 6]

(Wherein, X is an alkylene group having 5 to 30 carbon atoms or an alkenylene group having at least one side chain having 3 or more carbon atoms), etc., and their anhydrides and lower alkyl esters. And polyvalent carboxylic acids and derivatives thereof.

The alcohol component used in the present invention is 35 to 65 mol%, preferably 40 to 60 mol.
%, 65-35 mol% as an acid component, preferably 6
It is preferably 0 to 40 mol%.

It is also preferable that the trivalent or higher polyvalent component accounts for 5 to 60 mol% of all components.

The preferred alcohol component of the polyester resin includes the bisphenol derivative represented by the general formula (A), and the preferred acid component is
Phthalic acid, terephthalic acid, isophthalic acid, or anhydride thereof; succinic acid, n-dodecenylsuccinic acid or anhydride thereof; dicarboxylic acids such as fumaric acid, maleic acid, maleic anhydride; tricarboxylic acid of trimellitic acid or its anhydride Is mentioned.

The polyester resins obtained with these acids and alcohols exhibit sharp melting characteristics, have good fixability as a heat roller fixing toner, and are excellent in offset resistance.

Further, the glass transition temperature of the polyester resin obtained here is 50 to 70 ° C., preferably 55 to 6 ° C.
5 ° C., number average molecular weight (Mn) of 1,500 to 10,0
00, preferably 2,000 to 7,000, weight average molecular weight (Mw) 6,000 to 200,000, preferably 1
It is good that it is 50,000 to 150,000.

In the synthesis of the binder resin of the present invention, a usual polymerization initiator used by the bulk polymerization method, the solution polymerization method, the suspension polymerization method and the emulsion polymerization method can be used.

Examples of the initiator include t-butylperoxy-2-ethylhexanoate, cumin perpivalate, t-butylperoxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, Di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,2′-azobis (2-isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2-2'-azobis (4-methoxy-2,4
-Dimethylvaleronitrile), 1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane,
1,1-bis (t-butylperoxy) cyclohexane, 1,4-bis (t-butylperoxycarbonyl)
Cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, 1,3 -Bis (t-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane,
2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di-t-butyldiperoxyisophthalate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, Di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutarate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, 2,5-dimethyl -2,5-di (t-butylperoxy) hexane, diethylene glycol-bis (t-butylperoxycarbonate), di-t-butylperoxytrimethyl adipate, tris (t-butylperoxy) triazine, vinyl tris (t -Butylperoxy) silane, which can be used alone or in combination. That.

The amount of the initiator used is preferably 0.05 parts by mass or more, and more preferably 0.1 to 15 parts by mass, based on 100 parts by mass of the monomer.

As a method for synthesizing the binder resin according to the present invention, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method and the like can be used. When a carboxylic acid monomer or an anhydride monomer is used, it is preferable to use the bulk polymerization method or the solution polymerization method due to the nature of the monomer.

In order to obtain a vinyl polymer in the present invention, the following method can be mentioned as an example. A vinyl copolymer can be obtained by a bulk polymerization method or a solution polymerization method using a monomer such as a dicarboxylic acid, a dicarboxylic acid anhydride, or a dicarboxylic acid monoester. In the solution polymerization method, the dicarboxylic acid and dicarboxylic acid monoester units can be partially dehydrated by devising the distillation conditions when the solvent is distilled off. Further, the vinyl-based copolymer obtained by the bulk polymerization method or the solution polymerization method is subjected to heat treatment to further dehydrate it. It is also possible to partially esterify the anhydride with alcohol.

On the contrary, the vinyl copolymer thus obtained can be hydrolyzed to ring-open the anhydride to form a part of the dicarboxylic acid.

On the other hand, using a dicarboxylic acid monoester monomer, a vinyl-based copolymer obtained by a suspension polymerization method or an emulsion polymerization method is subjected to heat treatment or hydrolysis treatment for dehydration or ring opening to give an anhydride or dicarboxylic acid. Obtainable. The bulk polymerization method obtained by the bulk polymerization method or the solution polymerization method is dissolved in a monomer, and the suspension polymerization method or the emulsion polymerization method is used to obtain a vinyl polymer.
A part of the anhydride can be opened to obtain the dicarboxylic acid. At this time, other resins may be mixed in the monomer,
The obtained resin can be subjected to heat treatment, weak alkaline water treatment or alcohol treatment for dehydration, ring opening or esterification.

Since the dicarboxylic acid and dicarboxylic acid anhydride monomers have strong alternating polymerizability, the following method should be used to obtain a vinyl-based copolymer in which functional groups such as anhydride and dicarboxylic acid are randomly dispersed. Is preferred. This is a method in which a vinyl-based copolymer is obtained by a solution polymerization method using a dicarboxylic acid monoester monomer, the vinyl-based copolymer is dissolved in the monomer, and a binder resin is obtained by a suspension polymerization method. According to this method, the carboxylic acid monoester moiety can be dealcoholized and ring-opened and dehydrated depending on the treatment conditions when the solvent is distilled off after the solution polymerization, and an acid anhydride can be obtained. Furthermore, during suspension polymerization, the acid anhydride undergoes ring opening by hydrolysis,
A dicarboxylic acid is obtained.

In the case of anhydride formation in the polymer, the infrared absorption of carbonyl shifts to a higher wave number side than that of the case of acid or ester, so that formation and disappearance can be confirmed.

In the binder resin thus obtained, the carboxyl group, the anhydride group and the dicarboxylic acid group are randomly and uniformly dispersed in the binder resin. Therefore, when the binder resin is crosslinked, it is uniformly dispersed in the toner. A crosslinked structure can be provided.

In the toner for developing an electrostatic charge image of the present invention, the toner particles have at least one peak in the region of 5 × 10 ^{3 to} 5 × 10 ⁴ in the molecular weight distribution measured by GPC and 10 ⁵ or more. When at least one peak or shoulder is included in the region of ⁵ and a resin component containing 5 to 50% by mass of the resin component constituting the region of 10 ⁵ or more is used and used in a high speed machine. Is particularly preferred.

In the present invention, the molecular weight distribution of the resin component in the toner particles measured by GPC is 5 × 1.
By having at least one peak in the region of 0 ^{3 to} 5 × 10 ⁴ , good fixability, blocking resistance and pulverizability can be obtained.

A component having a molecular weight of less than 5 × 10 ³ is likely to show the molecular weight dependence of Tg (glass transition point) of the toner measured for a long time, and the Tg of the toner measured for a long time tends to be low. Conceivable. Therefore, when the amount of the component having a molecular weight of less than 5 × 10 ³ is large in the resin component of the toner particles and the peak of the molecular weight measured by GPC is less than 5 × 10 ³ , the Tg is usually less than or equal to the measured Tg. And the performance expected from the Tg of the toner cannot be satisfied. For example, in a high-speed system, the frictional heat at the cleaner portion of the photoconductor is large, so that toner fusion to the photoconductor or filming by the toner on the photoconductor is likely to occur. Further, when the toner is continuously produced for a long time, the toner may be fused inside the crusher.

Further, the blocking resistance is poor under pressure (for example, in a large toner container having a capacity of 1 kg or more, the toner itself is allowed to stand under its own weight). Therefore, agglomeration easily occurs in the toner container during storage and transportation of the toner.

The component having a molecular weight of less than 5 × 10 ³ is a component for improving the pulverizability of the toner particles. However, in the resin component of the toner particles, the amount of the component having a molecular weight of less than 5 × 10 ³ is large, and it is determined by GPC. When the peak of the measured molecular weight distribution is less than 5 × 10 ³ , the toner particles are pulverized more than necessary, the generation of ultrafine powder is increased, and the productivity is lowered such as the deterioration of the classification efficiency. . When the toner contains a large amount of ultra-fine powder that cannot be classified, the content of the ultra-fine powder gradually increases as the toner is replenished, and the ultra-fine powder is electrostatically applied to the toner to impart a triboelectric charging member (toner). When the toner adheres to the carrier, it interferes with triboelectric charging of the toner and deteriorates the developability such as a decrease in image density or occurrence of fogging. Further, a component having a molecular weight of less than 5 × 10 ³ is a component that helps partially lower the viscosity of the toner particles and assists in improving the fixing property. However, in the resin component of the toner particles, the amount of the component having a molecular weight of less than 5 × 10 ³ When the peak of the molecular weight distribution measured by GPC is less than 5 × 10 ³ , it becomes impossible to prevent the toner from flowing out from the cleaning member of the fixing device, which will be described later. The toner adheres to the body) to contaminate the developing sleeve or cause the carrier to be spent, so that the triboelectrification imparting ability is lowered and the developability may be deteriorated.

A component having a molecular weight of 5 × 10 ⁴ or less is a component for improving fixability and pulverizability, and the amount of the resin component in the toner particles is 30 to 95% in the molecular weight distribution measured by GPC. Preferably, it is more preferably 40 to 90%. When the amount of the component is less than 30%, it is difficult to obtain sufficient fixability and the pulverizability tends to be poor. If the amount of the component exceeds 95%, it becomes difficult to obtain sufficient offset resistance.

In the toner for developing an electrostatic charge image of the present invention, when the toner component has at least one peak or shoulder in the region of 10 ⁵ or more in the molecular weight distribution measured by GPC of the resin component, it is preferable. It can have offset resistance.

The shoulder according to the present invention is a point where the differential value of the GPC chromatogram curve becomes an extreme value, that is, an inflection point.

A component having a molecular weight of 10 ⁵ or more is a component for improving the offset resistance, and the amount of the resin component in the toner particles is preferably 5 to 50% in the molecular weight distribution measured by GPC, more preferably Is 1
It is preferably 0 to 50%. When the amount of the component is less than 5%, it is difficult to obtain good offset resistance, and it tends to be difficult to prevent the toner from flowing out from the cleaning member of the fixing device described later. The amount of the component is 50%
If it exceeds, the fixability tends to be impaired.

Therefore, the toner for developing an electrostatic image of the present invention has at least one peak in the region of 5 × 10 ^{3 to} 5 × 10 ⁴ in the molecular weight distribution of the resin component in the toner particles measured by GPC. In addition, it is preferable to have at least one peak or shoulder in the region of 10 ⁵ or more.

In the present invention, GP using THF as a solvent
The molecular weight distribution of the chromatogram by C (gel permeation chromatography) is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and THF was added as a solvent to the column at this temperature.
(Tetrahydrofuran) at a flow rate of 1 ml per minute,
About 100 μl of the THF sample solution 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 logarithmic value and the count number of the calibration curve prepared from several kinds of monodisperse polystyrene standard samples.
As a standard polyethylene sample for preparing a calibration curve, for example, a molecular weight of 10 manufactured by Tosoh or Showa Denko is used.
^It is suitable to use a standard polystyrene sample of at least about 10 points, using a sample of ² to 10 ⁷ . An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns, for example, Shodex GP manufactured by Showa Denko KK
C KF-801, KF-802, KF-803, KF
-804, KF-805, KF-806, KF-80
7 and KF-800P, or TSKge1G1000H (H _XL ), G2000H manufactured by Tosoh Corporation
(H _XL ), G3000H (H _XL ), G4000H
(H _XL ), G5000H (H _XL ), G6000H
(H _XL ), G7000H (H _XL ), and a combination of TSK guard columns.

The sample is manufactured as follows. Put the sample in THF, leave it for several hours, and shake it well for TH
Mix well with F (until sample coalescence disappears) and leave still for 12 hours or more. At this time, the leaving time in THF should be 24 hours or more. After that, a filter that passed through a sample processing filter (pore size 0.45 to 0.5 μm, for example, Maisho Redisk H-25-5 Tosoh Co., Ltd., Ekikurodisc 25CR Gelman Science Japan Co., Ltd. available) was used for GPC. Use as a sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

The resin component having a specific molecular weight distribution of the toner particles according to the present invention can be obtained by using, for example, the following method. Applying solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, block copolymerization, or grafting, the main peak in the region of molecular weight 5 × 10 ^{3 to} 5 × 10 ⁴ in the molecular weight distribution measured by GPC. It can be obtained by preparing the polymer (L) and the polymer (H) having a main peak in the region of 10 ⁵ or more and blending these components during melt-kneading.

As a particularly preferred method, the polymer (L) is used.
Alternatively, the polymer (H) is prepared by solution polymerization, and at the end of the polymerization, the other is blended in a solution, the other polymer is polymerized in the presence of one polymer, and the polymerization (H) is suspension polymerized. And a method of polymerizing the polymer (L) by solution polymerization in the presence of the polymer, a method of blending the polymer (H) in a solvent at the end of the solution polymerization, and the presence of the polymer (L). Then, a method of polymerizing the polymer (H) by suspension polymerization can be mentioned. By using these methods, a polymer in which a low molecular weight component and a high molecular weight component are uniformly mixed can be obtained.

In the bulk polymerization method, it is possible to obtain a low molecular weight polymer by polymerizing at a high temperature to accelerate the termination reaction rate, but it is difficult to control the reaction.
In the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in radical chain transfer depending on the solvent, or by adjusting the amount of the initiator and the reaction temperature. It is preferable for obtaining a low molecular weight polymer in the resin composition.

In the solution polymerization, solvents such as xylene, toluene, citric acid, cellosolve acetate, isopropyl alcohol and benzene are used. The solvent is appropriately selected depending on the polymer to be polymerized, but in the case of a styrene monomer mixture, xylene, toluene or citric acid is preferable.

The reaction temperature varies depending on the solvent used, the initiator and the polymer to be polymerized, but is preferably 70 ° C to 230 ° C.

The solution polymerization is preferably carried out with 30 to 400 parts by mass of the monomer per 100 parts by mass of the solvent.
Further, it is also preferable to mix another polymer in the solution at the end of the polymerization, and several polymers can be sufficiently mixed.

As a polymerization method for obtaining a high molecular weight component, an emulsion polymerization method or a suspension polymerization method is preferable.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is performed using a water-soluble polymerization initiator. . In this method, it is easy to control the heat of reaction, and the phase in which the polymerization takes place (oil phase consisting of polymer and monomer)
And the aqueous phase are different, the termination reaction rate is low, and as a result, the polymerization rate is high and the polymerization degree is high. Further, in the production of toner, due to the relatively simple polymerization process and the fine particles of the polymerization product,
Since it is a mixture with a colorant, a charge control agent and other additives, it is free as compared with other methods as a method for producing a binder resin for toner.

However, in the emulsion polymerization method, the produced polymer is apt to become impure due to the added emulsifier, and an operation such as salting out is required to take out the polymer. Therefore, it is not necessary to use these operations. It is further preferable to use turbid polymerization.

In the suspension polymerization, 100 parts by mass or less of the monomer (preferably 1 part by mass) is used with respect to 100 parts by mass of the aqueous solvent.
0 to 90 parts by mass) is preferable. Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, and calcium phosphate. These dispersants are used in an appropriate amount in view of the amount of the monomer in the aqueous solvent, and generally 0.05 to 1 part by mass is used with respect to 100 parts by mass of the aqueous solvent. Polymerization temperature is 50 ~
95 ° C is suitable, but it should be appropriately selected depending on the initiator used and the target polymer. As the initiator type, it is possible to use one that is insoluble or slightly soluble in water, but it is preferable to use a bifunctional or more polyfunctional initiator in order to obtain a high molecular weight component. .

The electrostatic charge developing toner of the present invention may contain two or more types of charge control agents, if necessary, in order to further stabilize the chargeability thereof.

Examples of charge control agents that can be used in the toner for developing an electrostatic charge image of the present invention include the following charge control agents known in the art.

For controlling the toner to be negatively charged, an organic metal complex or a chelate compound is effective, for example, a monoazo metal complex, an acetylaton metal complex, a metal complex of an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid. The metal complex of is mentioned. Others include aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids, aromatic polycarboxylic acids, and their metal salts, anhydrides, esters and phenol derivatives such as bisphenol.

To control the toner to be positively charged,
For example, modified products with 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 lake pigments thereof; triphenylmethane dyes and lake pigments thereof (as the laking agent, phosphotungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide and ferro cyanide) Etc.); metal salts of higher fatty acids, acetylacetone metal complexes; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyl Zuboreto, such diorgano tin borate dicyclohexyl tin borate and the like, can be used in combination thereof singly or two or more kinds. Among these, charge control agents such as nigrosine and quaternary ammonium salts are particularly preferably used.

In the toner for developing an electrostatic image of the present invention, it is preferable to add silica fine powder in order to improve charge stability, developability, fluidity and durability.

The fine silica powder used in the present invention is BE.
Specific surface area due to nitrogen adsorption measured by T method is 30 m ² / g
Those in the above range (particularly 50 to 400 m ² / g) give good results. The silica fine powder is preferably used in an amount of 0.01 to 8 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the toner.

The silica fine powder used in the present invention may contain a silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oil, a silane coupling agent, and a functional group for the purpose of hydrophobizing and controlling the charging property, if necessary. It is also preferable that the silane coupling agent is treated with a treating agent such as a silane coupling agent or other organic silicon compound, or these treating agents are used in combination.

Other additives can be added to the toner for developing an electrostatic image of the present invention for various purposes.

Other additives include, for example, lubricants such as Teflon, zinc stearate, and polyvinylidene fluoride (polyvinylidene fluoride is preferred); for example, abrasives such as cerium oxide, silicon carbide, and strontium titanate ( Of these, strontium titanate is preferred); fluidity-imparting agents such as titanium oxide and aluminum oxide (particularly hydrophobic ones are particularly preferred); anti-caking agents; conductivity such as carbon black, zinc oxide, antimony oxide, tin oxide. A property imparting agent; developability improving agents such as reverse polarity white fine particles and black fine particles, and these can be used as necessary.

A wax-like substance such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax is added to 100 parts by mass of the binder resin for the purpose of improving releasability at the time of heat roll fixing. On the other hand, it is preferable to add about 0.5 to 10 parts by mass to the toner particles.

Further, the electrostatic image developing toner of the present invention is
When used as a two-component developer, it is used as a mixture of toner particles and carrier particles. In this case, the mixing ratio of the toner particles and the carrier particles is 0.1 to 50% by mass, preferably 0.5 to 10% by mass, more preferably 3 to 10% by mass based on the two-component developer. It is preferable that the content is 5% by mass.

As the carrier particles which can be used as the two-component type developer for the toner for developing an electrostatic image of the present invention, all known carrier particles can be used, and magnetic particles such as iron powder, ferrite powder and nickel powder can be used. Examples thereof include powders, glass beads, and their surfaces, which are coated with a resin such as a fluorine resin, a vinyl resin, or a silicone resin.

Further, the toner for developing an electrostatic charge image of the present invention can be used as a magnetic toner by further containing a magnetic material in the toner particles. In this case, the magnetic material can also serve as a coloring agent. The magnetic material contained in the magnetic toner includes magnetite, maghemite,
Iron oxides such as ferrite; metals such as iron, cobalt and nickel, or these metals and aluminum and cobalt,
Mention may be made of alloys and mixtures with metals such as copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium.

The average particle diameter of these magnetic materials is 2 μm or less, preferably 0.1 to 2 μm, more preferably 0.1 μm.
˜0.5 μm is preferable, and the amount contained in the toner particles is 100% of the resin component in the toner particles.
The amount is preferably about 20 to 200 parts by mass, more preferably 40 to 150 parts by mass with respect to 100 parts by mass of the resin component.

Further, these magnetic materials have magnetic properties of 20 to 300 oersted, more preferably 20 to 150 oersted, saturation magnetization of 50 to 200 emu / g, and residual magnetization of 2 to 20 emu when applied with 10 K oersted.
/ G is preferable.

As the colorant which can be used in the toner for developing an electrostatic image of the present invention, any suitable pigment or dye can be mentioned. Colorants for toner are well known, and examples of pigments include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, red iron oxide, phthalocyanine blue, and indanthrene blue. These are used in an amount necessary and sufficient for maintaining the optical density of the fixed image, and preferably 0.1 to 20 parts by mass, more preferably 2 to 10 parts by mass, based on 100 parts by mass of the resin component in the toner particles. The quantity is good. Further dyes can be used for the same purpose. Examples thereof include azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes, and the addition amount thereof is preferably 0.1 to 20 parts by mass, more preferably 0.1 part by mass with respect to 100 parts by mass of the resin component in the toner particles. 3 to 10 parts by mass is preferable.

To prepare the toner for developing an electrostatic charge image of the present invention, a vinyl resin, a metal salt or a metal complex, a pigment as a coloring agent, a dye, a magnetic substance, and if necessary, a charge control agent and other additives are added. The agent is thoroughly mixed with a mixer such as a Henschel mixer or a ball mill, and then melt-kneaded with a heat kneader such as a heating roll, a kneader, or an extruder to make the resins compatible with each other, a metal compound, The toner particles according to the present invention can be obtained by dispersing or dissolving a pigment, a dye, and a magnetic material, cooling and solidifying, and then pulverizing and classifying.

The toner particles may be used as they are as a toner for developing an electrostatic image, but the toner particles may be further mixed with a desired additive, if necessary, with a mixer such as a Henschel mixer. It is also possible to obtain a toner for developing a charge image.

Next, an image forming apparatus in which the toner of the present invention can be suitably used will be described with reference to FIGS. 1 and 2.

Numeral 12 is a charger as a charging means for charging the OPC photosensitive drum 11 as a static image bearing member. Reference numeral 25 is a power supply unit for applying a voltage to the charger 12, and supplies a predetermined voltage to the charger. A transfer charger 13 serves as a transfer unit. Transfer charger 13
A predetermined bias is applied from the constant voltage power supply 24 to the.
The bias conditions are preferably a current value of 0.1 to 50 μA and a voltage value (absolute value) of 500 to 4000V.

The surface of the OPC photosensitive member is charged, for example, to a negative polarity by the charger 12 having a power source section (voltage applying means) 25 as a charging means, and an exposed electrostatic latent image is formed by light image exposure as a latent image forming means. Form. The latent image is formed with the positively chargeable magnetic toner 20 of the present invention held in the developing device 19 provided with the iron magnetic blade 21 and the non-magnetic developing sleeve 14 as a toner carrier that contains the magnet 140. develop. The developing sleeve 14 is a stainless steel sleeve (SUS30) having a plurality of spherical dents with a diameter of 50 mm.
4) is used. In the developing section, the bias applying means 2 is provided between the conductive substrate of the photosensitive drum 11 and the developing sleeve 14.
Alternating bias, pulse bias and / or DC bias are applied from 2. The transfer paper P is conveyed,
At the transfer section, the transfer charging device 13 charges the transfer paper P from the back surface (the surface opposite to the photosensitive drum side) by the voltage applying means 24, so that the developed image on the surface of the photosensitive drum 11 is transferred onto the transfer paper P. Electrostatically transferred to. Photosensitive drum 11
The transfer paper P separated from is heated and pressed by the roller fixing device 17
Thus, the fixing process is performed to fix the developed image on the transfer paper P.

The positively chargeable magnetic toner 20 remaining on the photosensitive drum 11 after the transfer step is removed by the cleaning device 18 having a cleaning blade. After the cleaning process, the photosensitive drum 11 is gradually discharged by the erase exposure 16, and the process starting from the charging process by the charger 12 is repeated.

The photosensitive drum 11 has an OPC photosensitive layer and a conductive substrate, and moves in the arrow direction. The non-magnetic cylindrical developing sleeve 14, which is a developer bearing member, rotates so as to move in the same direction as the surface of the photosensitive drum 11 in the developing section. Inside the developing sleeve 14, a multi-pole permanent magnet 140 (magnet roll) which is a magnetic field generating means is arranged so as not to rotate. The multi-pole permanent magnet 140 has a magnetic pole N ₁ = 500-
900 Gauss, magnetic pole N ₂ = 600 to 1100 Gauss, magnetic pole S ₁ = 800 to 1500 Gauss, and magnetic pole S ₂ = 40
It is preferably set to 0 to 800 gauss. Developing device 19
The positively charged magnetic toner 20 in the inside is applied to the developing sleeve 14, and the surface of the developing sleeve 14 and the positively charged magnetic toner 20 are coated.
By the friction with the positively chargeable magnetic toner 20, a positive triboelectric charge is given. Further, a magnetic doctor blade 21 made of iron is placed close to the cylindrical surface of the developing sleeve 14 (interval 50 μm to 500 μm), and the multipolar permanent magnet 1
By disposing one magnetic pole position of 40 so as to face each other,
The toner layer 200 is thin (30 μm to 300 μm).
m) and uniformly regulate the photosensitive drum 1 in the developing unit.
1 and the developing sleeve 14 is thinner than the developer layer 200.
Are formed so as not to contact the photosensitive drum 11. The rotation speed of the developing sleeve 14 is adjusted so that the surface speed of the developing sleeve 14 becomes substantially the same as or close to the surface speed of the photosensitive drum 11. Instead of iron as the magnetic doctor blade 21, a permanent magnet may be used to form the opposing magnetic poles. In the developing section, an AC bias or a pulse bias may be applied between the developing sleeve 14 and the surface of the photosensitive drum 11 from a bias power source 32 as bias means. The bias condition is Vpp = 1500 to 23 as an AC bias.
It is preferable that 00V, f = 900 to 1600 (Hz), and DC bias is DC = −100 to −350V. When the toner 20 is transferred in the developing portion formed in the closest position between the developing sleeve (toner carrier) 14 and the photosensitive drum 11 and in the vicinity thereof, the photosensitive drum 11
The toner 20 is transferred to the photosensitive drum 11 side while reciprocating between the developing sleeve 14 and the photosensitive drum 11 by the electrostatic force of the electrostatic image carrying surface and the action of the AC bias or the pulse bias.

Instead of the magnetic doctor blade 21 as a toner layer regulating member, an elastic blade made of an elastic material such as silicone rubber is used, and the elastic blade is pressed against the surface of the photosensitive drum 11 to thereby develop the developer layer 2.
The toner layer having a predetermined layer thickness may be formed on the developing sleeve 14 by controlling the layer thickness of No. 00.

As the photosensitive drum 11, an insulating drum for electrostatic recording, a-Se, CdS, Z is used instead of the OPC photosensitive drum.
A photosensitive drum having a photoconductive insulating material layer such as nO ₂ and a-Si can be appropriately selected and used according to the developing conditions. Furthermore, the electrostatic image carrier is not limited to the drum shape,
It may have a belt shape.

An image forming apparatus is constituted by integrally combining a plurality of constituent elements such as the above-mentioned photosensitive drum (image carrier) developing means, charging means and cleaning means as an apparatus unit. May be detachably attached to the apparatus body. For example, at least one of the charging unit, the photosensitive drum, and the cleaning unit is integrally supported together with the developing unit to form a unit, and the unit is detachably attached to the apparatus body by using guide means such as rails of the apparatus body. You may make it the structure mounted freely. At this time, the above device unit may be provided with a charging unit, a cleaning unit and / or a photosensitive drum.

When an electrophotographic apparatus such as the image forming apparatus of the present invention is used as a printer of a facsimile, the optical image exposure 15 as a latent image forming means is a digital exposure with a laser beam for printing received data. is there. A specific example of this case is shown in the block diagram of FIG.

The controller 111 controls the image reading section 110 and the printer 119. The entire controller 111 is controlled by the CPU 117. The read data from the image reading unit is transmitted to the partner station through the transmission circuit 113. The data received from the partner station is sent to the printer 119 through the receiving circuit 112. Predetermined image data is stored in the image memory. Printer control 1
18 controls the printer 119. 114 is a telephone.

The image received from the line 115 (image information from the remote terminal connected via the line) is demodulated by the receiving circuit 112, and then the image information is reproduced by the CPU 117, and the image memory 116 is sequentially processed. Stored in. When the image of at least one page is stored in the memory 116, the image of that page is recorded. CPU 117
Reads out one page of image information from the memory 116 and sends the decoded one page of image information to the printer controller 118. The printer controller 118 is
When the image information of one page is received from the CPU 117, the printer 119 is controlled to record the image information of the page.

The CPU 117 receives the next page during recording by the printer 119.

[0147]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention. All parts in the following formulations are parts by mass.

Synthesis Example 1 Styrene 69.0 parts n-Butyl acrylate 20.0 parts Monobutyl maleate 11.0 parts 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) 0.4 parts of propane The above raw materials were dropped into 200 parts of heated xylene over 4 hours. Further, the polymerization was completed under the reflux of xylene.

-Styrene 82.0 parts-n-butyl acrylate 18.0 parts-Di-tert-butyl peroxide 1.0 parts The above raw materials were added dropwise to 200 parts of heated xylene over 4 hours. Further, the polymerization was completed under reflux of xylene, and the solutions were mixed so that the mass ratio of the resin components was the former 3 and the latter 7, and then the solvent was distilled off while heating to 200 ° C. under reduced pressure. The resin thus obtained is called resin A.

Synthesis Example 2 Styrene 72.0 parts n-Butyl acrylate 20.0 parts Monobutyl maleate 8.0 parts 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) Propane 0.3 parts The above raw materials were added dropwise to 200 parts of heated xylene over 4 hours. Further, the polymerization was completed under the reflux of xylene.

-Styrene 77.0 parts-n-butyl acrylate 18.0 parts-Monobutyl maleate 5.0 parts-Di-tert-butyl peroxide 1.0 parts The above raw materials were added to 200 parts of heated xylene. It was added dropwise over 4 hours. Further, the polymerization was completed under reflux of xylene, and the solutions were mixed so that the mass ratio of the resin components was the former 4 and the latter 6, and then the solvent was distilled off while heating to 200 ° C. under reduced pressure. The resin thus obtained is called resin B.

Synthesis Example 3 Styrene 82.0 parts n-Butyl acrylate 18.0 parts Di-tert-butyl peroxide 1.0 part The above raw materials were added dropwise to 200 parts of heated xylene over 4 hours. . Further, the polymerization was completed under the reflux of xylene, and the solvent was distilled off while raising the temperature to 200 ° C. under reduced pressure to obtain a resin.

Styrene 76.0 parts n-Butyl acrylate 20.0 parts Monobutyl maleate 4.0 parts 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane) 0.2 part The above raw materials were dropped into 200 parts of heated xylene over 4 hours. Further, the polymerization was completed under reflux of xylene, and the resin component had a mass ratio of 4 and a polyester resin (bisphenol A, terephthalic acid, n-dodecenylsuccinic acid, trimellitic acid, diethylene glycol) in a molar ratio of 20:38. Polycondensation at a ratio of 10: 5: 27,
Mn = 5,000 Mw = 50,000 Tg = 59 ° C.
After sufficiently mixing in the solution so that the acid value = 11.0) was 3 and the resin was 3, the solvent was distilled off while raising the temperature to 200 ° C. under reduced pressure. The resin thus obtained is called resin C.

Synthesis Example 4 Styrene 68.0 parts-Butyl acrylate 22.0 parts-Monobutyl maleate 10.0 parts-Divinylbenzene 0.8 parts-Di-tert-butyl peroxide 0.8 parts Then, it was added dropwise to 200 parts by mass of heated xylene over 4 hours. Further, under xylene reflux (138-144)
Polymerization was completed at (° C), and xylene was removed while raising the temperature to 200 ° C under reduced pressure. The resin thus obtained is referred to as Resin D.

Synthesis Example 5 Styrene 82.0 parts n-Butyl acrylate 18.0 parts Divinylbenzene 0.2 parts Di-tert-butyl peroxide 0.8 parts In 200 parts of xylene heated above. Over 4 hours. Further, the polymerization was completed under reflux of xylene, and the solvent was distilled off while heating to 200 ° C. under reduced pressure. The resin thus obtained is called resin e.

Resin 30.0 parts Styrene 53.0 parts n-Butyl acrylate 13.0 parts Monobutylmalate 4.0 parts 2,2'-Azobis (2,4-dimethylvaleronitrile) 1.0 part Polyvinyl alcohol partially saponified 0.12
170 parts of water in which 1 part was dissolved was added and stirred vigorously to obtain a suspension dispersion. The above suspension dispersion was added to a reactor in which 50 parts of water was placed and the atmosphere was replaced with nitrogen, and a suspension polymerization reaction was carried out at a reaction temperature of 80 ° C. for 8 hours. After completion of the reaction, the suspension was washed with water, dehydrated and dried to obtain suspension-polymerized pearls. The resin thus obtained is called resin E.

Synthesis Example 6 Styrene 78.0 parts n-Butyl acrylate 20.0 parts Acrylic acid 2.0 parts 2,2'-Azobis (2,4-dimethylvaleronitrile) 0.2 parts The above raw materials Was added dropwise to 200 parts of heated xylene over 4 hours. Further, the polymerization was completed under reflux of xylene, and the solvent was distilled off while heating to 200 ° C. under reduced pressure. The resin thus obtained is called resin f.

Resin f 30.0 parts Styrene 57.4 parts n-Butyl acrylate 12.6 parts Di-tert-butyl peroxide 1.0 parts The above raw materials are placed in 200 parts of heated xylene for 4 hours. It dripped over. Further, the polymerization was completed under reflux of xylene, and the solvent was distilled off while heating to 200 ° C. under reduced pressure. The resin thus obtained is called resin F.

Comparative Synthesis Example 1 Styrene 80.0 parts n-butyl acrylate 20.0 parts 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane 0.3 parts The above raw materials were used. Then, it was added dropwise to 200 parts of heated xylene over 4 hours. Further, the polymerization was completed under the reflux of xylene.

-Styrene 83.0 parts-n-butyl acrylate 17.0 parts-Di-tert-butyl peroxide 1.0 part The above raw materials were added dropwise to 200 parts of heated xylene over 4 hours. Further, the polymerization was completed under reflux of xylene, and the solutions were mixed so that the mass ratio of the resin components was the former 3 and the latter 7, and then the solvent was distilled off while heating to 200 ° C. under reduced pressure. The resin thus obtained is referred to as Resin G.

Table 1 shows the physical properties of the above resins A to G.

[0162]

[Table 1]

[0163]   [Example 1]   ・ Binder resin A 100 parts   ・ Magnetic material 90 parts   ・ Polyethylene wax 4 parts   ・ Compound Example 1 2 parts

The above materials were well premixed by a Henschel mixer, and then melt-kneaded by a twin-screw kneading extruder set at 140 ° C. The obtained kneaded product was cooled, coarsely pulverized by a cutter mill, finely pulverized by a fine pulverizer using a jet stream, and the obtained fine pulverizer was classified by an air classifier. Finely divided powder (1) having a weight average particle size of 8.4 μm
Got

The resin component of this fine powder was subjected to Soxhlet extraction with tetrahydrofuran (THF) to obtain T in the resin.
The content of HF insoluble matter is measured to obtain the mass fraction of THF insoluble matter, and the THF soluble matter is measured by gel permeation chromatography to find the peak or shoulder position in the molecular weight distribution and the mass of 100,000 or more components. The fraction was calculated. The results are summarized in Table 2.

100 parts of the obtained classified fine powder (1) was added to silica fine powder (BET specific surface area 200
m ² / g) 100 parts of amino-modified silicone oil (amine equivalent 830, viscosity at 25 ° C. 70 cSt) 17
0.7 part of the hydrophobic silica (1) treated with 1 part of the mixture was added, mixed with a Henschel mixer, and sieved with a mesh having an opening of 150 μm to obtain a toner.

(Fixing Property / Offset Resistance Test) A fixing device of a commercially available copying machine NP8000 (manufactured by Canon Inc.) was removed to the outside, and the fixing roller temperature was modified so that the fixing roller temperature could be set arbitrarily. The fixing property and offset resistance were evaluated by passing an unfixed image using a fixing device.

In the case of evaluating the fixing property, the fixing roller temperature was raised from 120 ° C. at every 10 ° C., and the density decrease rate was obtained by a rubbing test, and 20% or less was set as the fixing area.

When evaluating the anti-offset property, the fixing roller temperature was raised from 200 ° C. at every 10 ° C., and it was evaluated whether or not an offset image was generated in the unfixed image passing through the paper.

(Backside Staining Evaluation Test) Commercial Copy Machine NP80
00 (Canon Co., Ltd.) is modified so that a reverse image can be formed, and halftone images are continuously fed through A3 for 200 sheets,
After resting for 1 minute, copying was performed again every 30 seconds. At this time, the amount of toner stains on the back side of the paper passing image was evaluated.

(Image Evaluation Test) Commercial Copy Machine NP408
0 (manufactured by Canon Inc.), 10,000 at normal temperature and humidity
Copies, 5000 in low temperature / low humidity, high temperature / high humidity environments
An image evaluation test was performed after copying one sheet. The image density and fog in each environment were evaluated.

Table 3 shows the evaluation results of these fixing property / offset resistance test, back stain evaluation test and image evaluation test.

[0173]   [Example 2]   ・ Binder resin B 100 parts   ・ Magnetic material 90 parts   ・ Polyethylene wax 4 parts   ・ Compound Example 2 2 parts

Fine powder and toner were obtained in the same manner as in Example 1 except that the above materials were used.

Physical properties were measured and images were evaluated in the same manner as in Example 1. The measurement results of the physical properties of the toner are shown in Table 2, and the image characteristic evaluation of the toner is shown in Table 3.

[ Reference Example 1 ] -Binder resin C 100 parts-Magnetic material 90 parts-Polyethylene wax 4 parts-Compound example 3 2 parts

Fine powder and toner were obtained in the same manner as in Example 1 except that the above materials were used.

In the same manner as in Example 1, the physical properties were measured and the images were evaluated. The measurement results of the physical properties of the toner are shown in Table 2, and the image characteristic evaluation of the toner is shown in Table 3.

Example 3 Binder resin D 100 parts Magnetic material 90 parts Polyethylene wax 4 parts Compound example 4 2 parts

Fine powder and toner were obtained in the same manner as in Example 1 except that the above materials were used.

Physical properties were measured and images were evaluated in the same manner as in Example 1. The measurement results of the physical properties of the toner are shown in Table 2, and the image characteristic evaluation of the toner is shown in Table 3.

Reference Example 2 100 parts of binder resin E 90 parts of magnetic substance 4 parts of polyethylene wax 4 parts of compound 5

Fine powder and toner were obtained in the same manner as in Example 1 except that the above materials were used.

Physical properties were measured and images were evaluated in the same manner as in Example 1. The measurement results of the physical properties of the toner are shown in Table 2, and the image characteristic evaluation of the toner is shown in Table 3.

Reference Example 3 100 parts of binder resin F 90 parts of magnetic substance 4 parts of polyethylene wax 4 parts of compound 6

Fine powder and toner were obtained in the same manner as in Example 1 except that the above materials were used.

Physical properties were measured and images were evaluated in the same manner as in Example 1. The measurement results of the physical properties of the toner are shown in Table 2, and the image characteristic evaluation of the toner is shown in Table 3.

[0188]   [Comparative Example 1]   ・ Binder resin G 100 parts   ・ Magnetic material 90 parts   ・ Polyethylene wax 4 parts   ・ Compound Example 1 2 parts

Fine powder and toner were obtained in the same manner as in Example 1 except that the above materials were used.

Physical properties were measured and images were evaluated in the same manner as in Example 1. The measurement results of the physical properties of the toner are shown in Table 2, and the image characteristic evaluation of the toner is shown in Table 3.

[0191]   [Comparative Example 2]   ・ Binder resin A 100 parts   ・ Magnetic material 90 parts   ・ Polyethylene wax 4 parts   ・ Nigrosine dye 2 parts

Fine powder and toner were obtained in the same manner as in Example 1 except that the above materials were used.

In the same manner as in Example 1, physical properties were measured and images were evaluated. The measurement results of the physical properties of the toner are shown in Table 2, and the image characteristic evaluation of the toner is shown in Table 3.

Example 4 Binder Resin A 100 parts Red Pigment 4 parts Compound Example 1 2 parts

The above materials were well premixed by a Henschel mixer, and then melt-kneaded by a twin-screw kneading extruder set at 140 ° C. The obtained kneaded product was cooled, coarsely pulverized by a cutter mill, finely pulverized by a fine pulverizer using a jet stream, and the obtained fine pulverizer was classified by an air classifier. A classified fine powder (2) having a weight average particle diameter of 8.6 μm was obtained.

100 parts of the obtained classified fine powder (2) was added to silica fine powder (BET specific surface area of 200) produced by a dry method.
m ² / g) 0.8 part of hydrophobic silica (2) obtained by treating 100 parts of aminopropyltriethoxysilane and 10 parts of hexamethyldisilazane was added, and mixed with a Henschel mixer to obtain a mesh having a mesh size of 150 μm. After sieving, a toner was obtained.

This toner was used as a commercially available copying machine NP4080.
(Manufactured by Canon Inc.) and image evaluation was performed.

Normal temperature / humidity (23 ° C., 60% RH), low temperature / low humidity (15 ° C., 10% RH), high temperature / high humidity (30 ° C.,
An image evaluation test was performed by copying 2000 sheets under each environment of 80% RH. The image density and fog in each environment were evaluated.

The image density was at a usable level of 1.10 or more in any environment and at the initial stage and after the durability test, and there was no fog. In addition, in this evaluation, neither fixing failure nor offset occurred.

Next, a halftone image is continuously printed at A3 200 times.
After passing the sheets, the sheet was paused for 1 minute and copied again every 30 seconds.
At this time, the amount of toner stains on the back side of the paper passing image was evaluated. No toner stain on the back surface of the image occurred.

[0201]

[Table 2]

[0202]

[Table 3]

[0203]

As described above, the toner of the present invention containing the above-mentioned components has a stable image density from the initial stage, and has a high density and good image quality without fog from low temperature and low humidity to high temperature and high humidity. Can be provided.

Further, the toner of the present invention can provide a toner excellent in low temperature fixing property and offset resistance.

Further, the toner of the present invention has excellent elasticity because the toner attached to the cleaning member of the fixing roller has excellent elasticity.
An excellent copy image is provided without flowing out to stain the image or the back surface.

[Brief description of drawings]

FIG. 1 is a schematic view showing an image forming apparatus in which a toner of the present invention is preferably used.

FIG. 2 is a partially enlarged view of FIG. 1 showing a developing unit of the image forming apparatus.

FIG. 3 is a block diagram of a facsimile apparatus using the electrophotographic apparatus as a printer.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Tsutomu Onuma Tsutomu Onuma 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP-A-7-301955 (JP, A) JP-A-7 -56394 (JP, A) JP-A-6-194869 (JP, A) JP-A-5-173355 (JP, A) JP-A-3-177847 (JP, A) JP-A-3-72375 (JP, A) ) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 9/08

Claims (3)

(57) [Claims] 1. An electrostatic charge image developing toner containing at least a binder resin and a colorant, wherein the binder resin has a molecular weight distribution measured by GPC,
It has at least one peak in the molecular weight range of 5 × 10 ^{3 to} 5 × 10 ⁴ and contains tetrahydrofuran insoluble matter in the binder resin.
To contain 5 wt% to 50 wt%, and having at least one peak in the molecular weight ¹⁰⁵ or more regions, molecular weight ¹⁰⁵
The resin component constituting the above region is 5% by mass to 50% by mass.
Present and with an acid value of 0.5 to 100 mg KOH
/ G of an acid component as a constituent component, and the toner further contains a bis form of an imidazole compound . 2. The binder resin has an acid value A measured by a total acid value.
2. The electrostatic image developing toner according to claim 1, wherein the toner is a styrene acrylic resin in which an acid component is present as a constituent so that the JIS acid value B is A> B. Wherein the binder resin has an electrostatic charge image developing toner according to claim 1 or 2, characterized in that it contains carboxylic acid anhydride structure five- as a constituent.