JP3347458B2 - Toner for developing electrostatic images - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to electrophotography, electrostatic recording,
The present invention relates to a toner for developing an electrostatic image in electrostatic printing or the like.

[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.
A number of methods are known as described in Japanese Patent Application Laid-Open Publication No. Sho 43-24748, and an electric latent image is generally formed on a photoreceptor by various means using a photoconductive substance. Then, the latent image is developed with toner, and a toner image is transferred to a transfer material such as paper as necessary, and then fixed by heating, pressure, heating and pressurizing, or solvent vapor to obtain a copy. The toner remaining on the photoreceptor without being transferred is removed by various methods, and the above-described steps are repeated.

[0003] In recent years, such a copying apparatus has been used as an information output device linked to another information processing machine by introducing digital technology, not as a mere business processing copy machine for copying an original, or as a multifunctional device. The processing and editing of image information has become easier due to the development of the original, and it has begun to be used as a copying machine for creating a new original document and as a personal copy for individuals.

[0004] Therefore, higher speed, higher image quality, smaller size and lighter weight have been pursued, and higher reliability has been strictly pursued. On the other hand, machines have been pursued at lower cost. It is becoming simpler in terms of elements. As a result, the performance required of the toner has become higher, and if the improvement of the performance of the toner cannot be achieved, a situation in which a more excellent electrophotographic apparatus cannot be realized is coming.

For example, various methods have been developed for fixing a toner image to a recording material such as transfer paper. The most common method at present is a compression heat method using a heat roller, and a so-called heat roll fixing method. It is.

In the hot roll fixing method, fixing is performed by allowing a toner image surface of a recording material to pass through the surface of a heat roller having a surface formed of a material having a releasing property with respect to toner while making contact with the toner image under pressure. It is. In this method, since the surface of the heat roller and the toner image of the recording material come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image onto the recording material is extremely good, and the fixing can be performed quickly. it can.

However, in the heat roll fixing, a wait time is required for the heat roller to reach a predetermined temperature, and the wait time can be shortened, and the recording material can be instantaneously fixed with an increase in the speed of the apparatus. In addition, a fixing failure due to a decrease in the temperature of the heating roller due to the passage of the recording material easily occurs.

On the other hand, since the surface of the heat roller and the toner image come into contact with each other under pressure in a molten state of the toner, a part of the toner image adheres and transfers to the surface of the fixing roller, and this is transferred to the next recording material. Re-transfer tends to cause a so-called offset phenomenon.

Therefore, in order to achieve a reduction in the wait time, a higher fixing speed, and a higher image quality while maintaining excellent fixability of the toner-visible image to the recording material without causing image stains due to the offset phenomenon, The characteristics of the toner largely depend on it, and the low-temperature fixing performance and the anti-offset performance of the toner are required.

In such a fixing method, in order to solve the problem of the offset phenomenon and enlarge the fixing area, a method of adding a releasing agent such as polyethylene or polypropylene having a low molecular weight to the toner is conventionally known.

However, it is usually difficult to uniformly disperse an amount sufficient to exert the releasing effect in the toner. As a general toner production method, after preliminarily mixing a release agent together with a binder resin, a colorant and other additives as necessary, heat-kneading, cooling and pulverizing and classifying, the desired particle size is obtained. Is obtained. However, because the compatibility between the binder resin and the release agent at the time of heating and melting is poor, it is difficult to sufficiently and uniformly disperse and mix the release agent in the obtained toner particles even after kneading, Since a large amount of the release agent is present alone as particles released between the toner particles,
The obtained toner tends to have a reduced releasing effect. Therefore, in order to exert a sufficient releasing effect on the toner, it is sufficient to add a large amount of the releasing agent. However, this causes a further increase in the releasing agent particles released between the toner particles, and the toner When applied to a copier / printer, adverse effects such as deterioration of fluidity in a developing device, contamination of the surface of a toner carrier such as a carrier or a sleeve, background fog at the time of development, and fusion to a photoreceptor occur. As a result, the image is degraded and poses a practical problem.

Therefore, in order to obtain a toner that satisfies the fixing property and the anti-offset property and has a wide fixing area, the properties of the binder resin largely depend on the properties. As a method of improving the fixing property by improving the binder resin, use of a binder resin containing an acid component has been proposed in JP-A-55-134861. As described in the publication, the toner using such a binder resin has some improvement in the chargeability of the toner, although the fixability is certainly improved. This is because the functional group in the acid component affects the chargeability of the toner. For example, when there is a carboxyl group in the polymer chain of the binder resin, it has a weak negative charge imparting ability, but as the amount of the carboxyl group increases, the hydrophilicity of the resin increases and the charge is released to moisture in the air. become. Therefore, it is easily affected by environmental fluctuations such as insufficient charging under high humidity or excessive charging under low humidity. In particular, in the case of a polyester resin having an acid value and a hydroxyl value in the binder resin, the humidity dependence of the charging characteristics is remarkable. Japanese Patent Application Laid-Open No. 61-284771 proposes that the amount of water in the toner be regulated to 5000 ppm or less to achieve both fixing performance and developing performance. The toner which has been demanded still has a problem.

[0013]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems.

That is, an object of the present invention is to provide a toner for developing an electrostatic image, which is excellent in low-temperature fixing performance, anti-offset performance and anti-blocking performance.

Another object of the present invention is to provide a toner for developing an electrostatic image which gives a good image even under low humidity and high humidity without being affected by environmental changes.

Another object of the present invention is to provide a toner for developing an electrostatic charge image which is excellent in durability, has a high image density even after long-term continuous use, and can obtain a copy image without background fog. is there.

[0017]

Means and Action for Solving the Problems The present inventors have
As a result of intensive studies to solve the above problems, the present inventors have found the present invention. That is, the present invention is obtained by a melt-kneading pulverization method containing at least a binder resin and a colorant .
The toner for developing an electrostatic charge image thus obtained, wherein the amount of water contained in the toner is 0.1 to 5% by weight and the binder resin has an acid value of 5 to 50 mgKOH / g; An electrostatic image wherein the glass transition temperature (Tg1) at the time of measurement of a closed system and the glass transition temperature (Tg2) at the time of measurement of an open system in DSC measurement of a toner for use with a differential scanning calorimeter satisfy the following relational expression. The present invention relates to a developing toner.

45 ° C. ≦ Tg1 ≦ 60 ° C. (1) 50 ° C. ≦ Tg2 ≦ 65 ° C. (2) Tg2-Tg1 ≧ 3 ° C. (3)

Generally, the fixing property can be improved by lowering the glass transition temperature (Tg) represented by the above formula. However, an extreme decrease in Tg deteriorates the blocking resistance of the toner. The Tg of the toner is determined based on the balance between the toner and the blocking resistance. That is, ultimately, a toner that does not impair the blocking resistance even if the Tg is lowered is ideal.

The present inventors have conducted a detailed study focusing on this point, and as a result, by adding a certain amount of water to the toner using the binder resin having an acid group, the developability and the blocking resistance are improved. We found a way to improve fixability without loss.

That is, in the toner containing water, the glass transition temperature (Tg1) as measured in a closed system.
Was found to be involved in the fixability, and that the glass transition temperature (Tg2) as measured in an open system was involved in the blocking resistance. As described above, the binder resin having an acid group has a strong affinity for water. Therefore, it is possible to preferably retain water in the toner as compared with a binder resin having no acid group. Here, the state of water in the toner greatly differs depending on the temperature. At a high temperature near the fixing temperature, very fine water molecules uniformly enter the polymer chains or functional groups. Water in such a state loosens the entanglement between the polymer chains, that is, has a function as a plasticizer, so that the fixing property can be improved. Therefore, the glass transition temperature in this state determines the fixability. At a low temperature near normal temperature, water molecules associate with each other and are easily localized in the toner. Therefore, since it does not act as a plasticizer until the entanglement of the polymer chains is greatly loosened, the blocking resistance is not impaired. Therefore, the glass transition temperature in this state determines the blocking resistance.

Here, as a method for modifying the state of the toner containing water at high and low temperatures, DSC measurement in a closed system and an open system is effective. Specifically, the glass transition temperature (Tg
1) is Tg indicating the state of the water-containing toner at a high temperature, and is a glass transition temperature (Tg) determined by DSC measurement in an open system.
2g is Tg indicating the state of the water-containing toner at a low temperature. That is, in the Tg measurement (details will be described later) in the present invention, after the temperature is once increased to 200 ° C., the temperature is rapidly decreased. At this time, the toner becomes a kind of amorphous state, but when the temperature is raised in a closed system and then the temperature is lowered, the water molecules that became fine at high temperature remain fine in the toner due to rapid cooling. And exist uniformly. That is, this state is almost the same as the state when the temperature of the water-containing toner is high. Therefore, the glass transition temperature (Tg1) obtained by further raising the temperature from this state is Tg which is an index of the fixing property of the toner containing water.

On the other hand, in the case of the open system, since the water molecules are released to some extent when the temperature is raised, the state of the toner after the temperature is lowered is almost the same as that of the above-mentioned water-containing toner at a low temperature. Has no plasticizer-like action.
Accordingly, the glass transition temperature (Tg2) obtained by further raising the temperature from this state becomes Tg which is an index of the blocking resistance of the toner containing water.

Further, in the toner of the present invention, the functional groups of the binder resin are oriented in the toner before fixing, in order to retain moisture in the toner. Therefore, better developability can be obtained without being affected by environmental fluctuations than a normal acid group-containing toner. Only when this is fixed at the time of fixing under heat and pressure, the functional groups are oriented to the outside, so that the affinity with the transfer paper is enhanced, and the effect of improving the fixability by the conventional acid component, which improves the fixability, is also exerted.

The toner of the present invention has an acid value of 5 to 50 mg KO.
A binder resin of H / g, preferably 10 to 40 mgKOH / g is used, and the glass transition temperature (Tg1) by DSC measurement in a closed system is 45 ° C ≦ Tg1 ≦ 60 ° C, preferably 47 ° C ≦ Tg1 ≦ 57. ℃, glass transition temperature (Tg2) by DSC measurement in an open system, 50 ℃ ≤ Tg2 ≤ 65
C., preferably 53 ° C. ≦ Tg2 ≦ 63 ° C.
And Tg1 is desirably 3 ° C. or higher, preferably 5 ° C. or higher.

The water content for suitably obtaining the glass transition temperature of the present invention is 0.1% by weight to 5% by weight in the toner.
Preferably, the content is 0.5 to 4% by weight. Further, Tg2 and Tg, which are one of the constituent elements of the present invention,
Although the upper limit of the difference in g1 is not particularly limited, in view of fixability, anti-offset property, anti-blocking property, and developability, a more preferable form is preferably 10 ° C. or less.

When the acid value of the binder resin is less than 5, sufficient fixability cannot be obtained. When the acid value is more than 50, environmental fluctuations in the chargeability of the toner are too large, resulting in a decrease in density. If the water content of the toner is less than 0.1% by weight, good fixing performance and blocking resistance cannot be achieved at the same time. If it is more than 5% by weight, the preferred fixing, anti-offset and anti-blocking properties of the present invention are obtained. And the offset becomes worse, in particular. If the glass transition temperature (Tg1) at the time of measurement of the closed system in the DSC measurement is lower than 45 ° C., the offset resistance decreases, and if it is higher than 60 ° C., the fixability deteriorates. DS
Glass transition temperature (Tg) at the time of open system measurement in C measurement
If 2) is lower than 50 ° C., the blocking resistance deteriorates and 6
If the temperature is higher than 5 ° C., the fixing property is adversely affected. Furthermore, Tg
If the difference between 2 and Tg1 is smaller than 3 ° C., it is not possible to achieve both good fixability and blocking resistance.

The toner used in the present invention preferably has a weight average diameter of 4 to 9 μm from the viewpoint of high definition and high image quality. If the weight average diameter is larger than 9 μm, a high-definition image faithful to a latent image cannot be provided. On the other hand, if the thickness is smaller than 4 μm, the cleaning performance of the transfer residual toner on the latent image carrier is deteriorated, or the productivity of the toner becomes extremely poor, which leads to an increase in cost.

As the binder resin for toner used in the present invention, polyester resins and vinyl resins are preferable from the viewpoint of charging characteristics and fixing properties. Among them, a polyester resin having a hydroxyl group is more preferable because the hydroxyl group has a function of suitably taking in water similarly to the acid group. However, since the effect of the hydroxyl group on environmental changes is larger than that of the acid group, the smaller the hydroxyl value (OHv), the better, and 1 ≦ OHv.
≦ 40, preferably 5 ≦ OHv ≦ 35.

The polyester resin used in the present invention is obtained by polycondensation of an alcohol and a carboxylic acid.
Propylene glycol, tetramethylene glycol,
1,4-butylene diol, pentamethylene glycol, diethylene glycol, P-di (hydroxymethyl) benzene, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ) Ketone, bis (4
-Hydroxyphenyl) ether, bis (hydroxyphenyl) sulfone, 2,2-bis (2,3,5,6-tetrabromo-4-hydroxyphenyl) butane, etherified bisphenol, and a bisphenol derivative represented by the formula (a) ;

[0031]

Embedded image A diol represented by the formula (b);

[0032]

Embedded image Is mentioned.

Further, the dicarboxylic acids used in the present invention include fumaric acid, maleic acid, succinic acid, itaconic acid,
Acids such as phthalic acid, malonic acid and cyclohexanedicarboxylic acid, anhydrides, acid esters and acid chlorides of these acids are exemplified.

As the polyester resin used in the present invention, not only the above-mentioned polymer of diol and dicarboxylic acid but also a polymer containing polyol and / or polycarboxylic acid can be used. As polyols pentaerythritol, sorbitol, glycerol,
1,2,4-butanetriol, 1,2,5-pentanetriol, 2-methylpropanetriol, 1,3,3
5-trihydroxymethylbenzene, 1,2,3,6-
Hexane tetrol, 1,4-sorbitan, glucose, lactose, sucrose, polyoxyethylene (10)
Sorbitol, polyoxyethylene (4) 1,4-sorbitan, polyoxyethylene (30) pentaerythritol, polyoxypropylene (5) 1, 2, 3, 5, 6
-Hexane genthol.

Examples of the polycarboxylic acid include 1,2,5-hexanetricarboxylic acid, 1,2,4-butanetricarboxylic acid, tetra (methylenecarboxyl) methane,
2,7,8-octanetetracarboxylic acid, 1,2,4-
Examples include benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, and 1,2,4-naphthalenetricarboxylic acid.

In order to obtain the vinyl resin used in the present invention, the following monomers can be used as monomers of the vinyl copolymer.

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, pn-dodecylstyrene; ethylene; Ethylenically unsaturated monoolefins such as propylene, butylene and isobutylene; unsaturated polyenes such as butadiene;
Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl ester acids such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid α-methylene aliphatic monomers such as n-butyl, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Carboxylic esters;
Methyl acrylate, ethyl acrylate, acrylic acid n-
Butyl, isobutyl acrylate, propyl acrylate,
Acrylic esters such as n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 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-vinyl pyrrole, N-vinyl carbazole, N
N- such as vinylindole and N-vinylpyrrolidone
Vinyl compounds; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; esters of the above-mentioned α, β-unsaturated acids and diesters of dibasic acids.

Also, 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; Acid, methacrylic acid, crotonic acid, such as cinnamic acid alpha, beta-unsaturated acid; crotonic acid anhydride, such as alpha of cinnamic acid anhydride, beta-unsaturated acid anhydride, the alpha, beta
-Anhydrides of unsaturated acids and lower fatty acids; and monomers having a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides and monoesters thereof.

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

Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds 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 above Compounds in which the acrylate of the compound is replaced with methacrylate; 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 acrylates of the above compounds Include those obtained by changing the rate; for example, as an aromatic group and diacrylate compounds linked with a chain containing an ether bond, polyoxyethylene (2)
-2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and acrylates of the above compounds were replaced with methacrylates. And polyester-type diacrylate compounds, for example, trade name MANDA (Nippon Kayaku). Examples of polyfunctional crosslinking agents include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylol methanetetraacrylate,
Oligoester acrylates and those obtained by replacing the acrylates of the above compounds with methacrylates; triallyl cyanurate, triallyl trimellitate;

These cross-linking agents are used in combination with other monomer components 10
0.01 to 5% by weight (more preferably 0.03 to 3% by weight) can be used with respect to 0% 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), a chain containing an aromatic group and an ether bond. Diacrylate compounds tied together.

In the present invention, styrene-butadiene copolymer resin, polyurethane, epoxy resin, polyvinyl butyral, rosin,
Modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin and the like can be mixed and used as necessary.

When two or more resins are mixed and used as a binder resin, as a more preferred form, those having different molecular weights are preferably mixed at an appropriate ratio.

In the toner for developing an electrostatic image 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 a binder resin 100
0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight
It is preferred to use parts by weight.

[0046] Charge control agents known in the art today include the following.

To control the toner to be negatively charged,
For example, organic metal complexes and chelate compounds are effective. Examples thereof include a monoazo metal complex, an aromatic hydroxycarboxylic acid, a metal complex, and an aromatic dicarboxylic acid-based metal complex. Others include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters,
Phenol derivatives of bisphenol are mentioned.

In the case of preparing a positively chargeable toner, nigrosine, a triphenylmethane compound, a rhodamine dye, polyvinyl pyridine or the like may be used as a charge control agent having a positive charge. In the case of producing a color toner, an aminocarboxylic acid ester such as dimethylaminomethyl methacrylate having positive chargeability is used as a monomer in an amount of 0.1 to 40 mol%, preferably 1 to 40 mol%.
Use a binder resin containing 0 mol%, or
A colorless or light-colored positive charge control agent that does not affect the color tone of the toner may be used. Examples of the positive charge control agent include quaternary ammonium salts represented by the structural formulas (A) and (B).

[0049]

Embedded image

[0050]

Embedded image

Among the quaternary ammonium salts represented by the structural formulas (A) and (B), the positive charge control agents represented by the structural formulas (A) -1, -2 and (B) -1 are used. Is preferable because it shows good chargeability with little dependence on the environment.

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

In the case of using a positively chargeable toner containing an aminocarboxylic acid ester such as dimethylaminomethyl methacrylate, which exhibits positive charge characteristics, as a resin component of the binder resin, a positive charge control agent or a negative charge control agent is used. Use as needed.

When a positively chargeable toner does not use an aminocarboxylic acid ester such as dimethylaminomethyl methacrylate exhibiting positive charge characteristics as a resin component, a positive charge control agent is added in an amount of 0 to 100 parts by weight of the binder resin. .1 to 1
It is desirable to use 5 parts by weight, preferably 0.5 to 10 parts by weight. When aminocarboxylic acid esters are used, a positive charge control agent and / or a negative charge control agent may be added to 100 parts by weight of the binder resin, if necessary, for the purpose of providing good chargeability with little environmental dependency. 0 to 10 parts by weight, preferably 0 to 8 parts by weight.

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, P
b, 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.

As a magnetic material, conventionally, triiron tetroxide (F
e ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe
₅ O ₁₂ ), cadmium iron oxide (CdFe ₂ O ₄ ), gadolinium iron oxide (Gd ₃ Fe ₅ -O ₁₂ ), copper iron oxide (CuF
e ₂ O _4), oxidation Tetsunamari (PbFe ₁₂ -O _19), iron oxide nickel (NiFe ₂ O _4), iron oxide, neodymium (NdFe ₂ O
₃ ), barium iron oxide (BaFe ₁₂ O ₁₉ ), magnesium iron oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnFe)
₂ O ₄ ), iron oxide lanthanum (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like are known, but according to the present invention, the above-mentioned magnetic materials are used alone or in combination of two or more. Particularly preferred magnetic materials for the purposes of the present invention are fine powders of iron tetroxide or γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
about 10 μm, the magnetic characteristics when a 10K Oersted is applied show a coercive force of 20 to 150 Oersted saturation magnetization of 50 to 200 e
mu / g (preferably 50 to 100 emu / g) and a residual magnetization of 2 to 20 emu / g are desirable.

The magnetic substance 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.

Further, when the toner of the present invention is used as a two-component developer, it is used by mixing with a carrier powder.
In this case, the mixing ratio of the toner and the carrier powder is 0.1 to 50% by weight as a toner concentration, preferably 0.5 to 1%.
0% by weight, more preferably 3 to 5% by weight.

As the carrier that can be used in the present invention, known carriers can be used. For example, powders having magnetism such as iron powder, ferrite powder, and nickel powder, and powders obtained by treating the surfaces thereof with a fluorine resin, a vinyl resin, a silicon resin, or the like can be given.

As the colorant irrespective of one component or two components, any pigment and / or dye other than carbon black and titanium white can be used. For example, when the toner of the present invention is used as a magnetic color toner, C.I. I. Direct Red 1, C.I.
I. Direct Red 4, C.I. I. Acid Red 1,
C. 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. 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: lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow N
CG, tartrazine lake, red-mouthed graphite, 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, Navy Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, Chrome Green, Chromium Oxide, 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 may be mentioned. Examples of the magenta coloring pigment include C.I. I. Pigment Red 1,2,3,4,5,6,7,8,9,1
0, 11, 12, 13, 14, 15, 16, 17, 1
8, 19, 21, 22, 23, 30, 31, 32, 3
7, 38, 39, 40, 41, 48, 49, 50, 5
1,52,53,54,55,57,58,60,6
3,64,68,81,83,87,88,89,9
0, 112, 114, 122, 123, 163, 20
2,206,207,209, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1,2,10,1
3, 15, 23, 29, 35 and the like.

Although such a pigment may be used alone, it is more preferable to use the dye and the pigment together to improve the sharpness from the viewpoint of the image quality of a full-color image. Examples of such magenta dyes include C.I. I. Solvent Red 1,
3, 8, 23, 24, 25, 27, 30, 49, 81,
82, 83, 84, 100, 109, 121, C.I. I.
Disperse Red 9, C.I. I. Solvent Violet 8, 13, 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, 3
6, 37, 38, 39, 40, C.I. I. Basic Violet 1,3,7,10,14,15,21,25
And basic dyes such as 26, 27 and 28.

Other color pigments include cyan color pigments such as 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 Chemical Formula 3.

[0067]

Embedded image

The coloring pigments 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 colorant used is 0.1 to 60 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the binder resin.
0 parts by weight.

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

The following are examples of the release agent used in the present invention. Aliphatic hydrocarbon-based waxes such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, microcrystalline wax, and paraffin wax; and aliphatic hydrocarbon-based waxes such as oxidized polyethylene wax, or block copolymers thereof; Examples of the wax include waxes mainly containing a fatty acid ester such as wax, sasol wax and montanic acid ester wax, and those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax.
Furthermore, saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid, unsaturated fatty acids such as brandinic acid, eleostearic acid, and vinaric acid, stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubivir alcohol, and seryl Alcohols, saturated alcohols such as merisyl alcohol, polyhydric alcohols such as sorbitol, fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide, methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebis Saturated fatty acid bisamides such as lauric acid amide, hexamethylene bisstearic acid amide, ethylene bisoleic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipamide, N, N ' Unsaturated fatty acid amides such as dioleyl sebacamide, aromatic bisamides such as m-xylene bisstearic acid amide, N, N'-distearyl isophthalic acid amide, calcium stearate, calcium laurate, zinc stearate; Fatty acid metal salts such as magnesium stearate (commonly referred to as metal soaps), waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid, and behenin Examples include partial esterified products of fatty acids such as acid monoglycerides and polyhydric alcohols, and methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and the like.

The amount of the release agent used in the present invention is desirably 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the binder resin.

These release agents are 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 mixing at the time of kneading. In the present invention, various additives can be contained in the toner to such an extent that the toner characteristics are not impaired.

Examples of the negatively chargeable fluidizing agent include fluororesin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder, fine powder silica such as wet-process silica and dry-process silica, and those silicas are silane-based. Coating agents, titanium coupling agents, silica treated with a surface treatment with silicon oil, and the like are available.

Preferred fluidizing agents are fine powders produced by the vapor phase oxidation of silicon halide compounds.
It is what is called dry silica or fumed silica, and is manufactured by a conventionally known technique. 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 ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl In this manufacturing process, another metal halide such as aluminum chloride or titanium chloride is used together with a silicon halide to obtain a composite fine powder of silica and another metal oxide. It is also possible to obtain bodies, including them. The particle size is 0.0 as an average primary particle size.
It is desirable to be within the range of 01 to 2 μm, and it is particularly preferable to use silica fine powder within the range of 0.002 to 0.2 μm.

The commercially available silica fine powder produced by the vapor phase oxidation of a silicon halide used in the present invention includes, for example, those commercially available under the following trade names.

AEROSIL (Aerosil Japan) 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, it is more preferable to use 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. It is particularly preferable that the treated silica fine powder be treated so that the degree of hydrophobicity measured by a methanol titration test shows a value of 30 or more.

The method for imparting hydrophobicity is provided by chemically treating an organic silicon compound or the like which reacts or physically adsorbs with the fine silica 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 such organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyl Dimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxy Silane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyl Disiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 per molecule
For example, dimethylpolysiloxane having a hydroxyl group bonded to Si and having one siloxane unit as a terminal unit may be used. These are used alone or as a mixture of two or more.

As the positively chargeable fluidizing agent used in the present invention, those obtained by treating the above-mentioned dry process silica with the following coupling agent having an amino group or silicone oil are used.

[0083]

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[0084]

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

[0086]

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(Where R ₁ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₂ represents an alkylene group or a phenylene group, and R ₃ and R ₄ represent a hydrogen, an alkyl group or an aryl group. However, the above alkyl group,
The aryl group, alkylene group and phenylene group may contain an amine, or may have a substituent such as halogen as long as the chargeability is not impaired. m and n are positive integers. )

The following are examples of such silicone oils having an amino group.

Viscosity at 25 ° C. Amine equivalent Equivalent Trade name (cPs) SF8417 (manufactured by Toray Silicone Co., Ltd.) 1200 3500 KF393 (manufactured by Shin-Etsu Chemical Co., Ltd.) 60 360 KF857 (manufactured by Shin-Etsu Chemical Co., Ltd.) 70 830 KF860 (manufactured by Shin-Etsu Chemical Co., Ltd.) 250 7600 KF861 (Shin-Etsu Chemical Co., Ltd.) 3500 2000 KF862 (Shin-Etsu Chemical Co., Ltd.) 750 1900 KF864 (Shin-Etsu Chemical Co., Ltd.) 1700 3800 KF865 (Shin-Etsu Chemical Co., Ltd.) 90 4400 KF369 (Shin-Etsu Chemical Co., Ltd.) 20 320 KF383 (Shin-Etsu Chemical Co., Ltd.) 20 320 X-22-3680 (Shin-Etsu Chemical Co., Ltd.) 90 8800 X-22-380D (Shin-Etsu Chemical Co., Ltd.) 2300 3800 X-22-3801C (Shin-Etsu Chemical Co., Ltd.) 3500 3800 X-22-3810B (Shin-Etsu Chemical Co., Ltd.) Shinetsu Gakusha, Ltd.) 1300 1700

The amine equivalent is a value obtained by dividing the molecular weight by the number of amines per molecule in terms of the equivalent per amine (g / equiv).

Good results are obtained when the fluidizing agent used in the present invention has a specific surface area of 30 m ² / g or more, preferably 50 m ² / g or more measured by nitrogen adsorption according to the BET method. Fluidizer 0.01 for 100 parts by weight of toner
To 8 parts by weight, preferably 0.1 to 4 parts by weight.

Other additives include lubricants such as Teflon and zinc stearate; abrasives such as cerium oxide, silicon carbide and strontium titanate; conductivity-imparting agents such as zinc oxide, antimony oxide and tin oxide; Developability improvers such as polar white fine particles and black fine particles are exemplified.

In the present invention, resin fine particles may be added internally or externally to the extent that the fixability is not impaired, if necessary.

The vinyl resin fine particles used in the present invention are produced by an emulsion polymerization method, a spray drying method or the like. Preferably, styrene, acrylic acid, 2-ethylhexyl acrylate, methyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N-methyl-N-phenylethyl methacrylate, diethylaminoethyl methacrylamide, dimethylaminoethyl methacrylamide, 4-vinylpyridine And vinyl monomers such as 2-vinylpyridine, or resin particles obtained by copolymerizing a mixture of these monomers by an emulsion polymerization method.

To prepare the toner for developing an electrostatic image 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. Then, using a hot kneader such as a kneader or extruder, melt, knead and knead to make the resins compatible with each other, and after cooling and solidifying the melt-kneaded material, pulverize the solidified material and classify the pulverized material. The toner of the present invention can be obtained. Another method is to obtain a toner by dispersing the constituent materials in a solution of the binder resin and then spray-drying, or an emulsion suspension in which a predetermined material is mixed with a monomer to constitute the binder resin. After that, there is a method for producing a toner by a polymerization method in which a toner is obtained by polymerization. The toner according to the present invention may be a microcapsule toner composed of a core material and a shell material.

Further, if necessary, an additive such as a fluidizing agent and the toner are sufficiently mixed by a mixer such as a Henschel mixer to obtain the toner for developing an electrostatic image of the present invention having the additive on the surface of the toner particles. Can be.

In the present invention, as a method for containing water in the toner, a method in which water is retained in a toner component itself (for example, adjustment of a resin drying step) and the toner is manufactured by the above-described toner manufacturing method, or For example, a method of forcibly adding water at the time of the above-described hot kneading may be used.

In the present invention, various measuring instruments
Physical properties are measured, and the toner is evaluated by various methods. The measuring method and the evaluation method are described below.

(1) Measurement of Acid Value of Resin A 2 to 10 g sample is weighed in a 200 to 300 ml Erlenmeyer flask, and about 50 ml of a mixed solvent of methanol: toluene = 30: 70 is added to dissolve the resin. If the solubility is poor, a small amount of acetone may be added. Using a mixed indicator of 0.1% bromthymol blue and phenol red, titrate with a pre-specified N / 10 potassium hydroxide-alcohol solution, and calculate the acid value from the consumption of the potassium alcohol solution by the following formula. Was.

Acid value = KOH (ml number) × N × 56.1 / sample weight (where N is a factor of N / 10 KOH)

(2) Moisture Measurement Using a trace moisture analyzer AQ-6 manufactured by Hiranuma Sangyo Co., Ltd. and an automatic moisture vaporizer SE-24, a nitrogen gas carrier of 0.2 liter / min. The sample was heated to 130 ° C. with ventilation, and the measurement was performed.

(3) Measurement of glass transition temperature Tg In the present invention, the measurement is carried out using a differential thermal analysis measuring device (DSC measuring device), DSC-7 (manufactured by PerkinElmer). The measuring method was performed according to ASTM D3418-82.

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely. This was put in an aluminum pan, an empty aluminum pan was used as a reference, and once the temperature was raised and lowered once at a temperature rise / fall rate of 10 ° C./min within a measurement temperature range of 30 to 200 ° C., and a pre-history was taken. Heating rate 10 ° C
The endothermic peak of the main peak is obtained in the temperature range of 40 to 100 ° C. when the temperature is raised at / min. The intersection between the line of the midpoint of the baseline before and after the endothermic peak appears and the differential heat curve is defined as the glass transition temperature Tg in the present invention.

Here, the glass transition temperature when using a closed aluminum pan is Tg1, and the glass transition temperature when using an open aluminum pan is Tg2.

(4) Measurement of Toner Particle Size The particle size can be measured by various methods. In the present invention, the measurement was performed using a multisizer of a Coulter counter.

That is, as a measuring apparatus, a Coulter counter Multisizer II (manufactured by Coulter) was used, and an interface (manufactured by Nikkaki) for outputting the number distribution and volume distribution and a CX-1 personal computer (manufactured by Canon) were connected. Then, a 1% NaCl aqueous solution is prepared using a special grade or primary grade sodium chloride as an electrolytic solution. As a measurement method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersing agent to 100 to 150 ml of the electrolytic aqueous solution, and the measurement sample is added to 2 to 100 ml.
Add ~ 20 mg. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the measurement was carried out using a 100 μm aperture as the aperture by the Coulter Counter Multisizer II.

(5) Evaluation of background fog The evaluation of the background fog was performed using REFLECTO manufactured by Tokyo Denshoku Co., Ltd.
Using METER MODEL TC-6DS, RE
It was calculated from the following equation using a green filter in the FLECTANCE mode. The smaller the value, the less background fog.

Background fog (reflectance)% = reflectance of standard paper (%) − reflectance of background portion of sample (%)

(6) Measurement of Fixing Start Temperature The fixing start temperature is determined by adjusting the temperature control of the fixing device, passing an unfixed image, rubbing it, and the temperature at which the density reduction rate is within 10%. I do.

[0110]

The present invention will be described below with reference to production examples and examples. However, this does not limit the present invention in any way.

(Resin Production Example 1) Polyoxypropylene (2,2) -2,2 150 parts by weight Bis (4-hydroxyphenyl) propane Polyoxyethylene (2,2) -2,2 100 parts by weight -Bis (4-hydroxyphenyl) propane ・ 50 parts by weight of terephthalic acid ・ 50 parts by weight of succinic acid ・ 50 parts by weight of 1,2,4-benzenetricarboxylic anhydride

These were charged into a four-necked flask, equipped with a reflux condenser, a water separator, a nitrogen gas inlet tube, a thermometer, and a stirrer.
The condensation polymerization reaction was carried out at about 5 ° C. for about 5 hours.
A polyester resin having KOH / g and Tg: 61 ° C. was obtained.
The polyester obtained here is referred to as resin A.

(Resin Production Example 2) A condensation polymerization reaction was carried out in the same manner as in Resin Production Example 1 except that the amount of succinic acid was changed to 30 parts by weight, acid value: 9 mgKOH / g, Tg:
A polyester resin B at 58 ° C. was obtained.

(Resin Production Example 3) Polyoxypropylene (2,2) -2,2 150 parts by weight Bis (4-hydroxyphenyl) propane Polyoxyethylene (2,2) -2,270 parts by weight -Bis (4-hydroxyphenyl) propane 50 parts by weight of isophthalic acid 30 parts by weight of n-dodecylsuccinic acid 30 parts by weight of terephthalic acid 50 parts by weight of 1,2,4 benzenetricarboxylic anhydride

The above raw materials were subjected to a condensation polymerization reaction in the same manner as in Resin Production Example 1 to obtain an acid value: 43 mgKOH / g, T
g: 58 ° C. polyester C was obtained.

(Resin Production Example 4) Polyoxypropylene (2,2) -2,2 110 parts by weight Bis (4-hydroxyphenyl) propane Polyoxyethylene (2,2) -2,2 110 parts by weight -Bis (4-hydroxyphenyl) propane 50 parts by weight of isophthalic acid 30 parts by weight of n-dodecylsuccinic acid 60 parts by weight of terephthalic acid 50 parts by weight of 1,2,4-benzenetricarboxylic anhydride

The above raw materials were subjected to a condensation polymerization reaction in the same manner as in Resin Production Example 1 to obtain an acid value: 52 mgKOH / g, T
g: Polyester D having a temperature of 58 ° C. was obtained.

(Resin Production Example 5) Polyoxypropylene (2,2) -2,2 180 parts by weight Bis (4-hydroxyphenyl) propane Polyoxyethylene (2,2) -2,270 parts by weight -Bis (4-hydroxyphenyl) propane-20 parts by weight of terephthalic acid-10 parts by weight of succinic acid-50 parts by weight of 1,2,4 benzenetricarboxylic anhydride

The above raw materials were subjected to a condensation polymerization reaction in the same manner as in Resin Production Example 1 to obtain an acid value: 4 mgKOH / g, T
g: Polyester E having a temperature of 57 ° C. was obtained.

(Resin Production Example 6) Polyoxypropylene (2,2) -2,2 150 parts by weight Bis (4-hydroxyphenyl) propane Polyoxyethylene (2,2) -2,2 100 parts by weight -Bis (4-hydroxyphenyl) propane 30 parts by weight of isophthalic acid 60 parts by weight of succinic acid 50 parts by weight of 1,2,4 benzenetricarboxylic anhydride

The above raw materials were subjected to a condensation polymerization reaction in the same manner as in Resin Production Example 1 to obtain an acid value of 33 mg KOH / g, T
g: 55 ° C. polyester F was obtained.

(Resin Production Example 7) Polyoxypropylene (2,2) -2,2 150 parts by weight Bis (4-hydroxyphenyl) propane Polyoxyethylene (2,2) -2,2 100 parts by weight -Bis (4-hydroxyphenyl) propane ・ 60 parts by weight of terephthalic acid ・ 40 parts by weight of succinic acid ・ 50 parts by weight of 1,2,4 benzenetricarboxylic anhydride

The above raw materials were subjected to a condensation polymerization reaction in the same manner as in Resin Production Example 1 to obtain an acid value: 35 mgKOH / g, T
g: Polyester G at 65 ° C. was obtained.

(Resin Production Example 8) Polyoxypropylene (2,2) -2,2 130 parts by weight Bis (4-hydroxyphenyl) propane Polyoxyethylene (2,2) -2,2 120 parts by weight -Bis (4-hydroxyphenyl) propane 20 parts by weight of isophthalic acid 60 parts by weight of succinic acid 50 parts by weight of 1,2,4 benzenetricarboxylic anhydride

The above raw materials were subjected to a condensation polymerization reaction in the same manner as in Resin Production Example 1 to obtain an acid value of 18 mg KOH / g and a T
g: Polyester H at 52 ° C. was obtained.

(Resin Production Example 9) Polyoxypropylene (2,2) -2,2 150 parts by weight Bis (4-hydroxyphenyl) propane Polyoxyethylene (2,2) -2,2 100 parts by weight -Bis (4-hydroxyphenyl) propane 65 parts by weight of terephthalic acid 35 parts by weight of succinic acid 50 parts by weight of 1,2,4 benzenetricarboxylic anhydride

The above raw materials were subjected to a condensation polymerization reaction in the same manner as in Resin Production Example 1 to obtain an acid value: 34 mgKOH / g, T
g: Polyester I at 68 ° C. was obtained.

(Resin Production Example 10) Polyoxypropylene (2,2) -2,2 170 parts by weight Bis (4-hydroxyphenyl) propane Polyoxyethylene (2,2) -2,280 parts by weight -Bis (4-hydroxyphenyl) propane ・ 50 parts by weight of terephthalic acid ・ 35 parts by weight of succinic acid ・ 25 parts by weight of 1,2,4 benzenetricarboxylic anhydride

These were charged into a four-necked flask, equipped with a reflux condenser, a water separator, a nitrogen gas inlet tube, a thermometer, and a stirrer.
The condensation polymerization reaction was carried out for about 2.5 hours at
A polyester resin having a mgKOH / g and a Tg of 56 ° C. was obtained. The polyester obtained here is referred to as resin J.

(Resin Production Example 11) 70 parts by weight of styrene 25 parts by weight of n-butyl acrylate 10 parts by weight of monobutyl maleate 0.3 part by weight of divinylbenzene 1.2 parts by weight of benzoyl peroxide

To the above mixture was added 170 parts by weight of water in which 0.12 part by weight of a partially saponified polyvinyl alcohol was dissolved, and the mixture was vigorously stirred to obtain a suspension dispersion. The suspension dispersion was added to a reactor which was charged with 300 parts by weight of water and purged with nitrogen,
A suspension polymerization reaction was performed at a reaction temperature of 8 hours.

After completion of the reaction, the resultant was washed with water and dehydrated, and then washed with water.
Drying was performed at 24 ° C. for 24 hours to obtain a vinyl resin K. Vinyl resin K has an acid value of 33 mg KOH / g and a Tg of 5
7 ° C.

(Resin Production Example 12) A resin having an acid value of 31 mgKOH / g and a Tg of 56 ° C was obtained in the same manner as in Resin Production Example 11, except that the drying step was changed to 35 ° C for 4 hours. The styrene acrylic resin obtained here is used as a resin L
And

Example 1 100 parts by weight of polyester resin A 90 parts by weight of magnetic iron oxide 2 parts by weight of monoazo metal complex (negative charge control agent) 3 parts by weight of low molecular weight polypropylene

The above mixture was melt-kneaded with a twin-screw extruder heated to 95 ° C. At this time, a water application port was provided in the upper portion of the kneading shaft, which was located between the mixture input port and the discharge port of the kneading shaft, and 100 parts by weight of water was sprayed therefrom. After cooling the kneaded material obtained, coarsely pulverized with a hammer mill,
The coarsely pulverized product was finely pulverized by a jet mill, and the obtained finely pulverized powder was classified by a fixed wall type air classifier to produce a classified powder. Further, the obtained classified powder is strictly classified and removed simultaneously by a multi-segment classification device (Elbow Jet Classifier manufactured by Nippon Steel Mining Co., Ltd.) utilizing the Coanda effect to remove the classified fine powder and the classified coarse powder at the same time. A magnetic toner as a black fine powder was obtained.

100 parts by weight of this magnetic toner and 1.0 part by weight of hydrophobic dry silica (BET220 m ² / g) were mixed with a Henschel mixer to obtain a developing toner. Table 1 shows the physical properties of the developing toner.

This developing toner is referred to as NP6060
(Canon) and fixed at a speed of 380 mm / sec, and the fixing property and the offset resistance were evaluated.
Further, at room temperature and normal humidity (23.5 ° C./60% RH),
After image formation of 100,000 sheets, image formation of 50,000 sheets was performed under high temperature and high humidity, and the image characteristics were evaluated. Table 2 shows the evaluation results. The fixing start temperature was as good as 145 ° C., and both the high-temperature offset resistance and the blocking resistance were excellent. As for the image characteristics, the image density was high under normal temperature and normal humidity and under high temperature and high humidity, and the background fog was good.

Example 2 A toner was prepared and evaluated in the same manner as in Example 1 except that resin B was used instead of resin A. Table 1 shows the physical properties of the toner, and Table 2 shows the evaluation results. Although the fixing property was slightly inferior to 150 ° C. as compared with Example 1, it was not at a level that would cause a practical problem. Other characteristics were almost the same as in Example 1.

Example 3 A toner was prepared and evaluated in the same manner as in Example 1 except that the resin C was used instead of the resin A. Table 1 shows the physical properties of the toner, and Table 2 shows the evaluation results. Although the image characteristics under high temperature and high humidity were slightly inferior to those in Example 1, it was not at a level that would cause a practical problem. Other characteristics were almost the same as in Example 1.

Comparative Example 1 A toner was prepared and evaluated in the same manner as in Example 1, except that resin A (acid value: 52) was used instead of resin A (acid value: 36). Table 1 shows the physical properties of the toner, and Table 2 shows the evaluation results. Compared with Example 1, the image characteristics under high temperature and high humidity were Dmax: 1.17, background fog: 3.9%
It was remarkably inferior and was not usable.

Comparative Example 2 A toner was prepared and evaluated in the same manner as in Example 1, except that the resin A (acid value: 4) was used instead of the resin A (acid value: 36). Table 1 shows the physical properties of the toner, and Table 2 shows the evaluation results. 160 ° C. low-temperature fixability as compared with Example 1
Was inferior.

Example 4 A toner was prepared and evaluated in the same manner as in Example 1 except that the amount of water added during kneading was changed to 10 parts by weight. Table 1 shows the physical properties of the toner, and Table 2 shows the evaluation results. Although the low-temperature fixability was slightly inferior to that of Example 1,
It was not at a level that would cause a problem in practical use. Other characteristics were almost the same as in Example 1.

Example 5 A toner was prepared and evaluated in the same manner as in Example 1 except that the amount of water added during kneading was changed to 130 parts by weight. Table 1 shows the physical properties of the toner, and Table 2 shows the evaluation results.
Although the low-temperature fixability was better than that of Example 1, the high-temperature offset resistance was slightly inferior. However, it was not at a level that would pose a practical problem. Other characteristics were almost the same as in Example 1.

Comparative Example 3 A toner was prepared and evaluated in the same manner as in Example 1 except that the amount of water added during kneading was changed to 2 parts by weight. Table 1 shows the physical properties of the toner, and Table 2 shows the evaluation results. Above all, the toner had a very low water content of 0.07% by weight. In the evaluation results, the low-temperature fixability was lower by 20 ° C. than that of Example 1.

Comparative Example 4 A toner was prepared and evaluated in the same manner as in Example 1 except that the amount of water added during kneading was changed to 170 parts by weight. Table 1 shows the physical properties of the toner, and Table 2 shows the evaluation results.
Above all, the toner had a high water content of 5.3% by weight. Regarding the evaluation results, a high-temperature offset was generated, and was not usable.

Example 6 A toner was prepared and evaluated in the same manner as in Example 1, except that resin A was used instead of resin A. Table 1 shows the physical properties of the toner, and Table 2 shows the evaluation results. Although the low-temperature fixability was superior to that of Example 1, the high-temperature offset resistance was slightly inferior. However, it was not at a level that would pose a practical problem. For other characteristics, see Example 1.
Was almost equivalent to

Example 7 A toner was prepared and evaluated in the same manner as in Example 1 except that the amount of water added during kneading was changed to 60 parts by weight, except that the resin A was changed to the resin A and the resin G was used. Table 1 shows the physical properties of the toner.
Table 2 shows the evaluation results. Although the low-temperature fixability was slightly inferior to that of Example 1, it was not at a level that would cause a practical problem. Other characteristics were almost the same as in Example 1.

Example 8 A toner was prepared and evaluated in the same manner as in Example 1 except that the amount of water added at the time of kneading was 35 parts by weight, except that the resin A was changed to the resin A and the resin H was used. Table 1 shows the physical properties of the toner.
Table 2 shows the evaluation results. Although the blocking resistance was slightly inferior to that of Example 1, it was not at a level that would pose a practical problem. Other characteristics were almost the same as in Example 1.

Example 9 A toner was prepared and evaluated in the same manner as in Example 1, except that resin A was used instead of resin A. Table 1 shows the physical properties of the toner, and Table 2 shows the evaluation results. Although the low-temperature fixability was slightly inferior to that of Example 1, it was not at a level that would cause a practical problem. Other characteristics were almost the same as in Example 1.

Comparative Example 5 A toner was prepared and evaluated in the same manner as in Example 7, except that the amount of water added during kneading was changed to 20 parts by weight. Table 1 shows the physical properties of the toner, and Table 2 shows the evaluation results. Physically, Tg1 was as high as 61 ° C. In addition, the evaluation results show that the low-temperature fixability was lower than that of Example 1 by 20%.
° C was inferior.

Comparative Example 6 A toner was prepared and evaluated in the same manner as in Example 8, except that the amount of water added during kneading was changed to 90 parts by weight. Table 1 shows the physical properties of the toner, and Table 2 shows the evaluation results. Physically, Tg1 was as low as 43 ° C. and Tg2 was as low as 48 ° C. As to the evaluation results, neither the high-temperature offset resistance nor the blocking resistance was acceptable for use as compared with Example 1.

Comparative Example 7 A toner was prepared and evaluated in the same manner as in Example 9 except that the amount of water added during kneading was changed to 40 parts by weight. Table 1 shows the physical properties of the toner, and Table 2 shows the evaluation results. Physically, Tg1 was as high as 59 ° C. and Tg2 was as high as 67 ° C. As for the evaluation result, the low-temperature fixability was 170 ° C., which was considerably inferior to that of Example 1.

[0153]

[0154]

[0155]

[0156]

[Table 1]

[0157]

[Table 2]

[0158]

According to the present invention, the fixing property, the anti-offset property and the anti-blocking property are improved in a well-balanced manner, and the durability is excellent. Image can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03G 9/087

Claims (2)

(57) [Claims] 1. A toner for developing an electrostatic charge image obtained by a melt-kneading pulverization method comprising at least a binder resin and a colorant , wherein the toner contains 0.1 to 5% by weight of water. ,
The binder resin has an acid value of 5 to 50 mgKOH / g, and the toner for developing an electrostatic image is measured by a differential scanning calorimeter (DS).
Glass transition temperature (Tg) when measuring closed system in C measurement
(1) A toner for developing an electrostatic image, wherein the glass transition temperature (Tg2) at the time of measurement of the open system satisfies the following relational expression. 45 ° C ≦ Tg1 ≦ 60 ° C (1) 50 ° C ≦ Tg2 ≦ 65 ° C (2) Tg2-Tg1 ≧ 3 ° C (3) 2. A binder resin comprising at least polyester.
The electrostatic charge image according to claim 1, further comprising:
Development toner.