JP3338378B2 - Toner binder - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a toner binder for a dry toner used in electrophotography, electrostatic recording, electrostatic printing, and the like.

[0002]

2. Description of the Related Art Conventionally, as a dry toner used in electrophotography and the like, a toner binder such as styrene acrylic resin or polyester is melt-kneaded together with a coloring agent and the like.
Finely pulverized ones are used. These dry toners are frictionally charged with a carrier such as ferrite powder or a charging member, and developed into an electrostatic latent image formed on a photoreceptor. Then, after transferring to paper or the like, fixing is performed by heating and melting using a hot roll.
In that case, it is necessary to have an appropriate charge amount in order to develop with sufficient image density. In addition, the difference in charge amount is small at any temperature and humidity (environmental stability)
Is required. Further, on the fixing surface, from the viewpoint of energy saving and downsizing of a copying machine or the like, the toner does not fuse to the hot roll even at a higher hot roll temperature than before (hot-offset resistance) and the hot roll temperature is low. However, it is required that the toner can be fixed (low-temperature fixability). In recent years, polyester toner binders have attracted attention because of their excellent low-temperature fixability and hot offset resistance. However, a toner using a polyester-based toner binder has a problem that the environmental stability of charging is insufficient. Further, the magnetic toner containing magnetic powder has a problem that the charge amount is low and a sufficient image density cannot be obtained. In particular, in a small developing device used for a printer or the like, the problem of the shortage of the charge amount is remarkable.

[0003]

In order to solve the problems of the charge amount and the environmental stability of the above-mentioned polyester-based toner binder, a method of compounding a styrene acrylic resin which is superior in charge characteristics with polyester (for example, Japanese Patent Application Laid-Open No. Sho 62-62). −
195682, JP-A-2-881 and JP-A-4-142301) have been proposed. However, although those disclosed in these documents have improved charge amount and environmental stability compared to conventional polyesters,
It has only intermediate properties between polyester and styrene acrylic resin, and is inferior in charging characteristics to styrene acrylic resin. Further, the characteristics of polyester are also reduced by half in terms of low-temperature fixability and hot offset resistance.

Although it is not intended to solve the problem of the charging characteristics of polyester, a toner in which polyester and styrene-butadiene resin are mixed (for example, Japanese Patent Application Laid-Open No. 58-119).
55, JP-A-58-190957, JP-A-60-262171 and the like. However, those disclosed therein are intended to improve the hot offset resistance by mixing a high molecular weight styrene-butadiene resin into a polyester having insufficient hot offset resistance. However, even if an incompatible polymer component is mixed, sufficient hot offset resistance cannot be obtained, and the low-temperature fixing property is worse than that of polyester, which is not practical.

[0005]

Means for Solving the Problems The present inventors have developed a toner binder which is excellent in both low-temperature fixability and hot-offset resistance, has a proper charge amount and is excellent in environmental stability, and provides a dry toner. As a result of intensive studies for development, the present invention has been reached. That is, the present invention relates to a toner binder comprising a polyester (A) and a styrene-based resin (B), wherein the (B) has a dielectric loss tangent (tan δ) at a measurement frequency of 100 kHz of 1.5 × 10 ⁻³ or less; Storage elastic modulus at a measurement frequency of 20 Hz is 1 × 10
^The temperature (T1) at which ⁵ dyne / cm ² is reached is 160 ° C. or higher,
And the viscosity at a measurement frequency of 20 Hz is 1 × 10 ⁴ poise
Is a styrene-based resin having a temperature of 90 to 140 ° C.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The dielectric loss tangent (tan δ) of the styrene-based resin (B) constituting the toner binder of the present invention is usually 1.5 × 10 ⁻³ or less at a measurement frequency of 100 kHz, and is preferably 0.010 ⁻³ or less.
1 × 10 ^{−3 to} 1.0 × 10 ⁻³ , more preferably 0.1
× 10 ^{−3 to} 0.8 × 10 ⁻³ . tan δ is 1.5 ×
If it exceeds 10 ^-3 , the charge amount will be insufficient and the environmental stability will deteriorate. The dielectric loss tangent can be measured, for example, by melting and kneading the resin using a Labo Plastomill at 130 ° C. and 70 rpm for 30 minutes, then pulverizing the resin to 20 μm or less, compression molding, and using a commercially available dielectric loss measuring device. .

As the storage elastic modulus (G ') of (B), a temperature (T1) at which the measurement frequency is 1 × 10 ⁵ dyne / cm ^{2 at} a measurement frequency of 20 Hz is usually 140 ° C. or higher, preferably 150 ° C.
As described above, the temperature is more preferably 170 to 230 ° C. 14
If the temperature is lower than 0 ° C., the hot offset resistance deteriorates. (B)
Is 1 at a measurement frequency of 20 Hz.
X10 ⁴ temperature (T2) is usually 90 to 140 ° C.
Preferably 100-130 ° C, more preferably 105
１２５125 ° C. If it exceeds 140 ° C., the low-temperature fixability deteriorates, and if it is less than 90 ° C., the heat-resistant storage stability becomes insufficient. T1
And T2 are determined by, for example, using a Labo Plastomill to melt and knead the resin at 130 ° C. and 70 rpm for 30 minutes, and then use a commercially available dynamic viscoelasticity measurement apparatus to change the storage elastic modulus (G ') And viscosity (η). The storage elastic modulus (G ′) of (A) is 6 × 10 ⁴ dyne / cm at a measurement frequency of 20 Hz.
² (T3) is usually 130 ° C. or higher, preferably 140 to 230 ° C., more preferably 150 to 220 ° C.
° C. The temperature is preferably 130 ° C. or higher from the viewpoint of hot offset resistance. As the viscosity (η) of (A), the temperature (T2) at which the measurement frequency is 1 × 10 ^{4 at} a measurement frequency of 20 Hz is usually 90 to 140 ° C., preferably 100 to 140 ° C.
130 ° C, more preferably 105 to 125 ° C.
The temperature is preferably 140 ° C. or lower from the viewpoint of low-temperature fixability, and is preferably 90 ° C. or higher from the viewpoint of heat resistance storage stability. T3 and T2 in (A) are determined by measuring in the same manner as in (B) above. The glass transition point (Tg) of (A) and (B) is usually from 35 to 85 ° C., preferably from 45 to 85 ° C.
To 75 ° C, more preferably 50 to 70 ° C. The temperature is preferably 35 ° C. or higher from the viewpoint of heat-resistant storage stability, and is preferably 85 ° C. or lower from the viewpoint of low-temperature fixability.

Examples of the styrene resin (B) include a styrene polymer (B1), a copolymer of styrene and a diene (B2), and a long-chain alkyl (meta) having a styrene and a C10 to C22 alkyl group. ) Acrylate copolymer (B3)
And combinations thereof. Preferred of these are (B1), (B2) and (B1) and (B2)
Is a combination of The styrenes constituting (B1) include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, and p-methylstyrene.
Examples include hydroxystyrene and p-acetoxystyrene. Of these, styrene and a combination of styrene and other styrenes are preferred, and styrene is particularly preferred.

The styrenes constituting (B2) include:
The same as the above (B1) are mentioned, and the preferable ones are also the same. Dienes include butadiene, isoprene, chloroprene, hexadiene and octadiene. Preferred among these are butadiene, isoprene and chloroprene, and particularly preferred are butadiene and isoprene. (B
In 2), a small amount of other monomers together with styrenes and dienes can be copolymerized. Other copolymerizable monomers include alkyl (meth) acrylates having a C1-C9 alkyl group [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, etc.], long-chain alkyl (meth) acrylate having an alkyl group of C10 to C22 [lauryl (meth) acrylate, stearyl (meth) acrylate, etc.], substituted alkyl (meth) acrylate [hydroxyethyl (meth)
Acrylate, dimethylaminoethyl (meth) acrylate, etc.], unsaturated carboxylic acids and their anhydrides [(meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and its anhydrides], unsaturated dicarboxylic acid alkyl esters [ Monomethyl maleate, monobutyl maleate, dibutyl maleate, monomethyl itaconate, etc.], unsaturated nitriles [(meth) acrylonitrile, etc.], vinyl esters [vinyl acetate, etc.], vinyl ethers [butyl vinyl ether, etc.], α-olefins [Hexene, octene, dodecene, etc.]. Among these, preferred are alkyl (meth) acrylates having a C1-C9 alkyl group, C10-C22
Long-chain alkyl (meth) acrylates having an alkyl group, unsaturated carboxylic acids and their anhydrides, unsaturated dicarboxylic acid alkyl esters, and unsaturated nitriles, and more preferably a long chain having a C10-C22 alkyl group. Chain alkyl (meth) acrylates, unsaturated carboxylic acids and their anhydrides, and unsaturated dicarboxylic acid alkyl esters. Unsaturated carboxylic acids and their anhydrides,
When carboxylic acid-containing monomers such as unsaturated dicarboxylic acid monoalkyl esters are copolymerized in large amounts, tanδ
However, a small amount of copolymerization is preferred in that the pigment dispersibility is improved. The copolymerization ratio of other monomers copolymerizable with styrenes and dienes is usually 60 to 9 for styrenes.
9% by weight, 1 to 40% by weight of dienes, and 0 to 10% by weight of other monomers.
0 to 95% by weight, 5 to 30% by weight of dienes, and 0 to 5% by weight of other monomers. The copolymerization ratio of dienes is 4
0% by weight or less is preferable from the viewpoint of heat-resistant storage stability. Also,
Other monomers, especially high polar monomers, have a large tan δ when copolymerized in a large amount. Therefore, a small amount is more preferable from the viewpoint of charging characteristics and environmental stability.

The styrenes constituting (B3) include:
The same as the above (B1) are mentioned, and the preferable ones are also the same. Examples of the long-chain alkyl (meth) acrylate having an alkyl group of C10 to C22 include decyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, and behenyl ( (Meth) acrylate and the like. Among these, preferred are long-chain alkyl (meth) acrylates having a C12 to C22 alkyl group, and particularly preferred are lauryl (meth) acrylate and stearyl (meth) acrylate. The larger the number of alkyl carbon atoms is, the smaller the tan δ is, which is preferable from the viewpoint of charging characteristics and environmental stability. In (B3), styrenes,
Other monomers can be copolymerized with the long-chain alkyl (meth) acrylate having a C10-C22 alkyl group. Examples of the other copolymerizable monomer include those similar to the above (B2) and dienes.
Among these, preferred are dienes, alkyl (meth) acrylates having a C1-C9 alkyl group, unsaturated carboxylic acids and anhydrides thereof, unsaturated dicarboxylic acid alkyl esters, and unsaturated nitriles, more preferably. Are dienes, unsaturated carboxylic acids and their anhydrides, and unsaturated dicarboxylic acid alkyl esters. Unsaturated carboxylic acids and their anhydrides, carboxylic acid-containing monomers such as unsaturated dicarboxylic acid monoalkyl esters, tan δ increases when copolymerized in large amounts,
A small amount of copolymerization is preferred in that the pigment dispersibility is improved.
The copolymerization ratio of styrenes and other monomers copolymerizable with the long-chain alkyl (meth) acrylate having an alkyl group of C10 to C22 is usually 70 to 99% by weight of styrenes, C10
1 to 30% by weight of a long-chain alkyl (meth) acrylate having a C22 to C22 alkyl group, and 0 to 10% of other monomers.
%, Preferably 80 to 95% by weight of styrenes, 5 to 20% by weight of a long-chain alkyl (meth) acrylate of C10 to C22, and 0 to 5% by weight of other monomers. The copolymerization ratio of the long-chain alkyl (meth) acrylate of C10 to C22 is preferably 30% by weight or less from the viewpoints of heat storage stability, charging characteristics and environmental stability. Further, other monomers, especially monomers having a high polarity, may be copolymerized in a large amount to obtain tanδ.
From the viewpoint of charging characteristics and environmental stability.

The molecular weight of the styrenic resin (B) is preferably wide in order to achieve both low-temperature fixability and hot offset resistance. That is, in gel permeation chromatography (GPC), the molecular weight has a maximum value of 1,000 to 15,000 and a molecular weight of 10
It is preferable to have another maximum value at 0000 or more or to contain a tetrahydrofuran (THF) -insoluble component (crosslinkable gel component). In order to obtain such a molecular weight distribution, a component (b1) having a maximum value of a molecular weight of 1,000 to 15,000 and having a molecular weight of less than 50,000 and a component having a molecular weight of 50,000 or more and / or tetrahydrofuran (THF)
It is preferably composed of an insoluble component (crosslinkable gel component) (b2). The maximum value of the molecular weight of (b1) is more preferably
2000 to 10000, particularly preferably 2500 to 80
00. When the THF-insoluble matter is not contained in (b2), the maximum value of the molecular weight of (b2) is usually 100,000.
Or more, preferably 200,000 or more, more preferably 300,000 or more. When the THF-insoluble component is contained in (b2), the maximum value of the molecular weight is not particularly limited. The ratio between (b1) and (b2) is usually (b1)
Is 30 to 90%, (b2) is 10 to 70%, preferably (b1) is 35 to 80%, and (b2) is 20 to 6
5%, more preferably (b1) is 40 to 75%,
(B2) is 25 to 60%. In the present invention, the ratio between (b1) and (b2) is such that when THF-insoluble components are not contained in (b2), the molecular weight in GPC is 5000.
Area less than 0 (α1) and area more than 50,000 (α2)
It is determined by the ratio of When the THF-insoluble component is contained in (b2), when the THF-insoluble component is β%, (100−
β) × (α1) and the ratio of [(100−β) × (α2) + β] are used as the ratio of (b1) and (b2).

In the present invention, (b1) and (b2) are 1
Although both may be formed in one polymerization system, a polymer having a molecular weight corresponding to (b1) and (b2) may be polymerized in another polymerization system. Polymerization with another polymerization system is preferable in that the molecular weight distribution can be easily adjusted. When polymerizing in another polymerization system, the compositions of (b1) and (b2) do not necessarily have to be the same, and the copolymerization ratio can be varied between (b1) and (b2). (B1) compared to (b1)
It is preferable that the copolymerization amount of the monomer having a low Tg is larger in 2) because it is excellent in heat-resistant storage stability. For example (B)
When a styrene polymer (B1) and / or a copolymer of styrenes and dienes (B2) is used, the composition of (b1) is 80 to 100% by weight of styrenes and 0 to 100% of dienes. 20% by weight, other monomer is 0
5% by weight, 70-95% by weight of styrenes, 5-30% by weight of dienes and 0% of other monomers
A ratio of ５5% by weight is preferred. (B1) and (b)
2) is preferably compatible from the viewpoint of hot offset resistance. Therefore, it is preferable to use similar monomers for (b1) and (b2). For example, when a copolymer of styrenes and dienes is used as (b2),
As (b1), a polymer of styrenes or a copolymer of styrenes and dienes is more preferable than a copolymer of styrenes and lower alkyl (meth) acrylate.
Whether (b1) and (b2) are compatible or incompatible can be confirmed by visually observing the smudge. (B1) and (b2)
If (B) is compatible, the mixed (B) becomes transparent.

Examples of the polyester (A) include polycondensates of a polyol and a polycarboxylic acid. Examples of the polyol include a diol (1) and a trivalent or higher valent polyol (2), and examples of the polycarboxylic acid include a dicarboxylic acid (3) and a trivalent or higher polycarboxylic acid (4). In the present invention, the polyol (2) having a valency of 3 or more together with the diol (1) and the dicarboxylic acid (3) and / or
Alternatively, a non-linear polyester using a trivalent or higher polycarboxylic acid (4) is preferable, and (1), (2), (3),
The polyester composed of the four components (4) is particularly preferred.
The hot offset resistance is further improved by using both (2) and (4).

Examples of the diol (1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); Diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, Bisphenol F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Examples include alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of sphenols. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols, and alkylene glycols having 2 to 12 carbon atoms. Is a combination of Examples of the trihydric or higher polyol (2) include polyhydric aliphatic alcohols having 3 to 8 or more valences (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trisphenols (trisphenol PA, etc.) Novolak resins (phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trisphenols; alkylene oxide adducts of the above novolak resins. Among these, preferred are polyhydric aliphatic alcohols having 3 to 8 or more valences and alkylene oxide adducts of novolak resins, and particularly preferred are alkylene oxide adducts of novolak resins.

The dicarboxylic acids (3) include alkylenedicarboxylic acids (succinic acid, adipic acid, sebacic acid, dodecenyl succinic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid). Acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (4) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid) and vinyl polymers of unsaturated carboxylic acids (styrene / maleic acid copolymerization). Styrene / acrylic acid copolymer, α-olefin / maleic acid copolymer, styrene / fumaric acid copolymer, etc.). Of these, preferred are aromatic polycarboxylic acids having 9 to 20 carbon atoms, and particularly preferred is trimellitic acid. In addition, as the dicarboxylic acid (3) or the trivalent or higher polycarboxylic acid (4), the above-mentioned acid anhydride or lower alkyl ester (eg, methyl ester, ethyl ester, isopropyl ester) may be used.

The ratio of the polyol to the polycarboxylic acid is determined by the equivalent ratio [OH] of the hydroxyl group [OH] and the carboxyl group [COOH].
/ [COOH] is usually 2/1 to 1/2, preferably 1.5 / 1 to 1 / 1.5, and more preferably 1.3 / 1.
１ ／ 1 / 1.3. The ratio of the trivalent or higher polyol (2) and the trivalent or higher polycarboxylic acid (4) is such that the sum of the number of moles of (2) and (4) is based on the total number of moles of (1) to (4). Thus, it is usually 0 to 40 mol%, preferably 3 to 25 mol%, and more preferably 5 to 20 mol%. (2)
And the molar ratio of (3) is usually 0/100 to 100/0,
Preferably it is 80/20-20/80, More preferably, it is 70/30-30/70.

The molecular weight of (A) preferably has a maximum value in GPC of 1,000 to 20,000, more preferably 2,000 to 8,500.
Particularly preferably, the maximum value is 3000 to 8000. It is preferably 1,000 or more from the viewpoints of heat resistance storage stability and powder fluidity, and 20 from the viewpoint of productivity (pulverizability) of pulverization into toner.
000 or less is preferable. Further, the THF-insoluble content is 5-60.
%, More preferably 15 to 50%, particularly preferably 20 to 45%. It is preferably at least 5% from the viewpoint of hot offset resistance, and preferably at most 60% from the viewpoint of low-temperature fixability.

The hydroxyl value of (A) is usually 70 mgKOH / g or less, preferably 25 mgKOH / g or less, more preferably 2 mgKOH / g or less.
It is 0 mgKOH / g or less. The smaller the hydroxyl value is, the better from the viewpoints of charge amount and environmental stability. The acid value of (A) is usually 0 to 50 mgKOH / g, preferably 5 to 50 mgKOH / g, more preferably 8 to 30 mgKOH / g, and particularly preferably 8 to 2 mgKOH / g.
5 mgKOH / g. From the viewpoints of environmental stability and maintainability of charging, it is preferable that the acid value is small, but it is preferable that the acid value is appropriate since the rising of charging is improved.

The weight ratio of the polyester (A) to the styrene resin (B) is usually 10/90 to 95/5,
It is preferably from 25/75 to 90/10, and more preferably from 40/60 to 70/30. From the viewpoint of low-temperature fixability, it is preferable that the ratio of polyester is large, and from the viewpoint of environmental stability and charge amount, it is preferable that the ratio of styrene resin is large.

In the present invention, the polyester (A),
A compatibilizer can be used together with the styrene resin (B). The use of a compatibilizer is preferable in that the dispersibility of (A) and (B) is improved. As a compatibilizer,
A polymer (C) in which a polymer chain having an SP value difference of 0.5 or less from (A) and a polymer chain containing styrene as a main component is chemically bonded is exemplified. SP value difference from (A) is 0.5
Examples of the following polymer chains include a polyester chain obtained by polycondensing a monomer similar to (A), and a copolymer chain of a vinyl monomer having an SP value of 11 or less and a vinyl monomer having an SP value of 12 or more. . Note that the SP value is a known Fe value.
It can be calculated by the dors method. Examples of the monomer constituting the polyester chain include the same ones as in the case of the above (A), and preferred ones are also the same. Examples of the vinyl monomer having an SP value of 11 or less include styrene and methyl (meth) acrylate. Examples of the vinyl monomer having an SP value of 12 or more include (meth) acrylonitrile and (meth) acrylonitrile.
Acrylic acid, unsaturated dicarboxylic acid mono-lower alkyl ester (monomethyl maleate, monoethyl maleate,
Monobutyl maleate, monomethyl itaconate, and the like). The polymer chain containing styrene as a main component preferably has a composition similar to that of (B), and when (B2) is used as (B), a copolymer chain of styrene and a diene is preferable. When (B3) is used, a copolymer chain of styrene and a long-chain alkyl (meth) acrylate having a C10 to C22 alkyl group is preferable. Examples of the dienes and the long-chain alkyl (meth) acrylate having a C10 to C22 alkyl group include the same ones as in the above (B), and preferred ones are also the same. Also,
Other monomers similar to (B) can also be used in small amounts. Further, in the toner binder of the present invention, other resins can be contained together with (A), (B) and (C). Other resins include styrene acrylic resins (such as copolymers of styrene and lower alkyl (meth) acrylate), epoxy resins (such as addition condensation products of bisphenol A and epichlorohydrin), and urethane resins (polyaddition products of polyols and polyisocyanates) Etc.).

Specific examples of the toner binder of the present invention include those obtained by mixing the following (A), (B) and (C). (A): Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct / ethylene oxide adduct of phenol novolak / terephthalic acid / dimethyl terephthalate / trimellitic anhydride polycondensate (B): styrene / Mixture of butadiene copolymer (b1) and styrene / butadiene copolymer (b2) (C): bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct / phenol novolak ethylene oxide adduct / terephthal Graft polymerized styrene / butadiene on acid / dimethyl terephthalate / maleic anhydride polycondensate (A): bisphenol A propylene oxide 2 mol adduct / bisphenol A propylene oxide 3 mol Product / ethylene oxide adduct of phenol novolak / terephthalic acid / dimethyl terephthalate / trimellitic anhydride polycondensate (B): mixture of styrene polymer (b1) and styrene / butadiene copolymer (b2) (C): Graft polymerization of styrene / butadiene on bisphenol A propylene oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct / ethylene oxide adduct of phenol novolak / terephthalic acid / dimethyl terephthalate / maleic anhydride polycondensate (A ): Bisphenol A propylene oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct / phenol novolak propylene oxide adduct / terephthalic acid / dimethyl terephthalate / trimellitic anhydride Compound (B): Mixture of styrene polymer (b1) and styrene / butadiene copolymer (b2) (C): Bisphenol A propylene oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct / terephthalic acid / anhydride Graft polymerization of maleic acid polycondensate with styrene / butadiene (A): bisphenol A propylene oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct / phenol novolak propylene oxide adduct / terephthalic acid polycondensate ( B): Styrene / butadiene copolymer (b1) and styrene / butadiene / monobutyl maleate copolymer (b)
Mixture of 2) (C): Bisphenol A propylene oxide 2 mol adduct / terephthalic acid / maleic anhydride polycondensate with styrene graft polymerized (A): Bisphenol A propylene oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct / propylene novolak propylene oxide adduct / terephthalic acid / dimethyl terephthalate / trimellitic anhydride polycondensate (B): styrene / stearyl methacrylate / butadiene copolymer (b1) and styrene / butadiene copolymer Mixture of (b2) (C): Bisphenol A propylene oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct / terephthalic acid / maleic anhydride polycondensate grafted with styrene (A): bis Enol A propylene oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct / propylene novolak propylene oxide adduct / terephthalic acid / dimethyl terephthalate / trimellitic anhydride polycondensate (B): styrene / isoprene copolymer Mixture of (b1) and styrene / isoprene copolymer (b2) (C): Grafting styrene onto bisphenol A propylene oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct / terephthalic acid / maleic anhydride polycondensate Polymerized product (A): bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct / terephthalic acid / trimellitic anhydride polycondensate (B): styrene polymer (b1) and styrene / butyl Mixtures of diene copolymer (b2) (C): polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct / terephthalic acid / fumaric acid and styrene / maleic anhydride copolymer

The method for producing the toner binder of the present invention will be exemplified. The polyester (A) is prepared by subjecting a polycarboxylic acid and a polyol to 150-150 in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide.
It is obtained by heating to 280 ° C. and performing dehydration condensation. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction. The styrene resin (B) is obtained by copolymerizing constituent monomers with a known radical initiator. Examples of the radical initiator include azo initiators (azobisisobutyronitrile, azobisvaleronitrile, etc.) and peroxide initiators (benzoyl peroxide, t-
Butyl perbenzoate, di-t-butyl peroxide, di-t-butyl peroxyhexahydroterephthalate, etc.). Known polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization can be used as the polymerization method. Solvents used in the solution polymerization include aromatic solvents (toluene, xylene, etc.); ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.); halogen solvents (dichloroethane, etc.); and amide solvents (dimethyl, etc.) Formamide) can be used. When a solvent is used, the solvent is distilled off under normal pressure and reduced pressure after polymerization.
When obtained by suspension polymerization, polymerization can be carried out in water using an inorganic dispersant such as calcium carbonate or calcium phosphate or an organic dispersant such as polyvinyl alcohol or methylated cellulose. The polymerization temperature is selected depending on the molecular weight of the radical initiator and the toner binder to be used, but is usually 5 to 200 ° C, preferably 50 to 200 ° C.
170 ° C. The polymerization time is generally 1 to 48 hours, preferably 2 to 24 hours. When (b1) and (b2) polymerized by different polymerization systems are used as (B), (b1)
And (b2) are separately polymerized and then mixed, or one of (b1) and (b2) is polymerized and then the other is polymerized in the presence thereof. As a method of mixing the separately polymerized (b1) and (b2),
A powder mixing method, a melt mixing method, and a solution mixing method can be used. Among them, the solution mixing method is the most uniform,
Particularly preferred. As the solvent used in the solution mixing method, the same solvents as those used in the solution polymerization can be used. For example, in the case of a polymer in which a polyester-based polymer chain and a styrene-based polymer chain are chemically bonded, the compatibilizer (C) can be produced by the following known method. A method in which a double bond is introduced into a polyester by using fumaric acid or the like, and the polyester and a monomer constituting a styrene-based polymer chain are copolymerized. A method of polycondensing a styrene polymer having a carboxyl group or a hydroxyl group (obtained by copolymerizing maleic anhydride, acrylic acid, or the like) with a monomer constituting a polyester polymer chain. The manufacturing conditions in the above method are the above-mentioned (A),
It is the same as the manufacturing condition of (B). As a method for mixing (A), (B) and (C), any method such as a polymerization method in the presence, a solution mixing method, a melt mixing method, and a powder mixing method can be used. The same method as the method used for mixing the above (b1) and (b2) can be applied to the polymerization method and the solution mixing method in the presence. In the melt mixing method, any of a batch type and a continuous type can be applied.
It is obtained by kneading at 0 to 230 ° C. In the case of a batch type, mixing is performed at 150 to 230 ° C. in a reaction tank or the like. In the powder mixing method, the powder is obtained by mixing powders of the respective components using a Nauta mixer, a Henschel mixer, or the like.

The toner binder of the present invention is used as a dry toner by mixing a colorant and, if necessary, various additives such as a release agent and a charge control agent. Known dyes, pigments, and magnetic powders can be used as the colorant. Specifically, carbon black, Sudan Black SM, Fast Yellow-G, Benzidine Yellow, Pigment Yellow, India First Orange, Irgasin Red, Baranitoaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B lake, Methyl Violet B lake, phthalocyanine blue, pigment blue, pliant green, phthalocyanine green, oil yellow GG, Kayaset YG, Orazol Brown B, oil pink OP, magnetite, iron black, and the like. The content of the colorant in the toner is usually 2 to 15% by weight when using a dye or a pigment, and usually 20 to 70% by weight when using a magnetic powder.
It is.

Known release agents can be used, for example, polyolefin waxes (such as polyethylene wax and polypropylene wax); long-chain hydrocarbons (such as paraffin wax and Sasol wax); Carnauba wax, montan wax, distearyl ketone, etc.). The content of the release agent in the toner is usually 0 to 10% by weight,
Preferably it is 1 to 7% by weight.

As the charge control agent, known ones, that is, nigrosine dye, quaternary ammonium salt compound, quaternary ammonium base-containing polymer, metal-containing azo dye, salicylic acid metal salt, sulfonic acid group-containing polymer, fluorinated polymer, Examples include a halogen-substituted aromatic ring-containing polymer. The content of the charge control agent in the toner is usually 0 to 5% by weight. In addition, fluidizing agents can be used. Known fluidizers such as colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder can be used.

As a method for producing a dry toner, there is a known kneading and pulverizing method. After the above-mentioned toner components are dry-blended, they are melt-kneaded, then finely pulverized using a jet mill or the like, and further subjected to air classification to have a particle size of usually 2 to 2.
Obtained as 0 μm particles.

The dry toner using the toner binder of the present invention may contain iron powder, glass beads, nickel powder,
It is used as a developer for an electric latent image by being mixed with carrier particles such as ferrite, magnetite, and ferrite whose surface is coated with a resin (such as an acrylic resin or a silicone resin). In addition, instead of the carrier particles, friction with a member such as a charging blade can be performed to form an electric latent image. Next, the recording material is fixed on a support (paper, polyester film, etc.) by a known heat roll fixing method or the like.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. Hereinafter, "part" indicates "part by weight".

【Example】

The methods for measuring the properties of the toner binders obtained in Examples and Comparative Examples are described below. 1. Acid value and hydroxyl value Method specified in JIS K0070. If the sample has solvent-insoluble components due to crosslinking,
A sample after melt-kneading was used as a sample by the following method. Kneading device: Labo Plast Mill manufactured by Toyo Seiki Co., Ltd.
MODEL30R150 Kneading conditions: 130 ° C, 70 rpm for 30 minutes 2. Glass transition point (Tg) The method (DSC) specified in ASTM D3418-82
Law). Apparatus: DSC20, SSC manufactured by Seiko Electronic Industry Co., Ltd.
/ 580 3. Molecular weight The soluble matter in THF was measured by gel permeation chromatography (GPC). The conditions for molecular weight measurement by GPC are as follows. Apparatus: HLC-802A manufactured by Toyo Soda Column: 2 TSK GEL GMH6 (manufactured by Toyo Soda) Measurement temperature: 25 ° C. Sample solution: 0.25 wt% tetrahydrofuran solution Solution injection amount: 200 μl Detector: Refractive index detector The molecular weight calibration curve was created using standard polystyrene. 4. Tetrahydrofuran (THF) insoluble matter 50 ml of THF is added to 0.5 g of a sample, and the mixture is refluxed with stirring for 3 hours. After cooling, the insoluble matter is filtered off with a glass filter and dried under reduced pressure at 80 ° C. for 3 hours. The insoluble content is calculated from the weight ratio of the resin on the glass filter to the weight of the sample. 5. Measurement of storage elastic modulus (G ′) and viscosity (η) Apparatus: RDS-7700II Dynamic Spectrometer Test Fixture, manufactured by Rheometrics Co., Ltd. Test Fixture: 25 mmφ cone plate Measurement Frequency: 20 Hz (125.6 rad / sec) Strain Rate: 5% Fixation The sample after melt kneading by the following method was used as a sample. 5. Kneading device: Labo Plastomill MODEL30R150 manufactured by Toyo Seiki Co., Ltd. Kneading conditions: 30 minutes at 130 ° C. and 70 rpm Dielectric loss tangent (tan δ) measurement device: Ando Electric Co., Ltd. TR-1100 dielectric loss measuring device Electrode: Ando Electric Co., Ltd. SE-43 type powder electrode After melting and kneading by the following method, 20 μm The following pulverized material was used as a sample. Kneading device: Labo Plastomill MODEL30R150 manufactured by Toyo Seiki Co., Ltd. Kneading conditions: 130 ° C., 70 rpm for 30 minutes

Example 1 (Synthesis of polyester) In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 95 parts of adduct of bisphenol A propylene oxide 2 mol, 329 parts of adduct of bisphenol A propylene oxide 3 mol, phenol 23 parts of a 5 mol ethylene oxide adduct of a novolak resin (number of nuclei: about 5), 166 parts of terephthalic acid, and 1.7 parts of dibutyltin oxide were added.
The reaction was continued for a further 5 hours at a reduced pressure of 10 to 15 mmHg. Then, 22 parts of dimethyl terephthalate and 25 parts of xylene were added thereto, and the mixture was heated at 220 ° C. under normal pressure to obtain 7 parts.
The reaction was continued for another hour, and the solvent was further removed under reduced pressure of 10 to 15 mmHg for 2 hours. Thereafter, 21 parts of trimellitic anhydride was added and reacted at a reduced pressure of 10 to 15 mmHg. When the melt index (180 ° C., 2160 g) reached 0.6 g / 10 min, the polyester was taken out of the polyester (A).
1) was obtained. The THF-insoluble content of (A1) was 38%, the peak molecular weight was 6,800, the acid value was 11 mgKOH / g, and the hydroxyl value was 11 mgKOH / g. The glass transition point is 62 ° C,
T3 was 184 ° C and T2 was 120 ° C. (Synthesis of styrenic resin) In an autoclave reactor equipped with a thermometer and a stirrer, 2,000 parts of water and 3 parts of polyvinyl alcohol were added and sufficiently dissolved, and then 850 parts of styrene, 150 parts of butadiene, and bisphenol A ethylene oxide were added. Diacrylate (Neomer BA
641 (manufactured by Sanyo Chemical Industries, Ltd.), 1.1 parts of a mixed monomer and 2 parts of di-t-butylperoxyhexahydroterephthalate were added, and after purging with nitrogen, suspended at 85 ° C. for 10 hours and then at 95 ° C. for 3 hours. Polymerized. After cooling, the reaction product was separated by filtration, washed with water, and dried at 50 ° C. to obtain a resin (b1-1). 500 parts of xylene was placed in an autoclave reaction vessel equipped with a thermometer and a stirrer.
000 parts, and di-t-butyl peroxide 30
And a mixed solution of 180 parts of xylene were added dropwise at 185 ° C. over 3 hours to carry out polymerization. Then, the solvent was removed to obtain a resin (b2-1). 420 parts of resin (b1-1) and resin (b2-1) 5
80 parts was added to 2000 parts of xylene, and dispersed and dissolved under reflux for 2 hours. Next, the resultant was dried at 170 ° C. under reduced pressure to obtain a styrene resin (B1). The THF-insoluble content of (B1) is 3
0%, the peak molecular weight is 3800, and the molecular weight is 5000
The ratio less than 0 was 61%. The glass transition point was 59 ° C., T1 was 205 ° C., T2 was 121 ° C., and tan δ was 0.12 × 10 ⁻³ . (Synthesis of compatibilizer) In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 456 parts of a 3 mol adduct of bisphenol A propylene oxide and 5 mol of ethylene oxide of a phenol novolak resin (about 5 nuclei). Addendum 3
One part, 166 parts of terephthalic acid and 1.9 parts of dibutyltin oxide were added, and reacted at 230 ° C. under normal pressure for 12 hours, and further reacted under reduced pressure of 10 to 15 mmHg for 5 hours. Next, 43 parts of dimethyl terephthalate and 25 parts of xylene were added thereto, reacted at 220 ° C. under normal pressure for 3 hours, and further desolvated under reduced pressure of 10 to 15 mmHg for 2 hours. Thereafter, the mixture was cooled to 185 ° C., and maleic anhydride was added.
After adding 2 parts and reacting under normal pressure for 2 hours, the resin (c1-
1) was obtained. 691 parts of the resin (c1-1) and 415 parts of xylene were placed in an autoclave reaction vessel equipped with a thermometer and a stirrer, and after purging with nitrogen, a mixed monomer of 833 parts of styrene and 167 parts of butadiene, and di-t-butyl peroxide A mixture of 30 parts and 269 parts of xylene was added to 1
It was added dropwise at 50 ° C. for 4 hours to polymerize. Subsequently, the solvent was removed to obtain a compatibilizer (C1). (Synthesis of Toner Binder) Polyester (A1) 58
0 parts, 370 parts of a styrene resin (B1) and 50 parts of a compatibilizer (C1) were mixed with a Henschel mixer FM10B (manufactured by Mitsui Miike Kakoki Co., Ltd.), and then a twin screw extruder PCM-3 was mixed.
0 (manufactured by Ikegai Co., Ltd.) at 180 ° C. to obtain the toner binder (1) of the present invention.

Example 2 (Synthesis of Polyester) The polyester of Example 1 (A
In the same manner as in 1), 456 parts of an adduct of 3 mol of bisphenol A propylene oxide and an adduct of 5 mol of ethylene oxide of a phenol novolak resin (about 5 nuclei) 3
7 parts, 166 parts of terephthalic acid, 1.9 parts of dibutyltin oxide, 43 parts of dimethyl terephthalate and 28 parts of trimellitic anhydride were reacted to obtain a melt index (1).
(80 ° C., 2160 g) became 2.5 g / 10 min, and was taken out of the reaction vessel to obtain a polyester (A2).
(A2) has a THF insoluble content of 41% and a peak molecular weight of 59.
The acid value was 19 mgKOH / g and the hydroxyl value was 11 mgKOH / g. The glass transition point is 57 ° C. and T3 is 175.
° C and T2 were 115 ° C. (Synthesis of Styrene Resin) Polymerization was carried out in the same manner as in (b1-1) of Example 1, except that diacrylate of bisphenol A ethylene oxide adduct was not used and the monomer was changed to 780 parts of styrene and 220 parts of butadiene. b1-
2) was obtained. 350 parts of xylene is placed in an autoclave reaction vessel equipped with a thermometer and a stirrer, and after replacing with nitrogen, a mixed monomer of 909 parts of styrene and 91 parts of butadiene, 30 parts of di-t-butyl peroxide, and a chain transfer agent NOFMER MSD ( Nippon Yushi Co., Ltd.) 50 parts, xylene 2
00 parts of the mixed solution was added dropwise at 150 ° C. over 4 hours to carry out polymerization. Then, the solvent was removed to obtain a resin (b2-2). 300 parts of the resin (b1-2) and 700 parts of the resin (b2-2) were added to 2000 parts of xylene, and dispersed and dissolved under reflux for 2 hours. Next, the resultant was dried under reduced pressure at 170 ° C. to obtain a styrene resin (B2). (B2) had a THF-insoluble content of 16%, a peak molecular weight of 7,100, and a ratio of a molecular weight of less than 50,000 to 73%. The glass transition point is 62 ° C,
T1 is 178 ° C., T2 is 116 ° C., tan δ is 0.10
× 10 ^-3 . (Synthesis of Toner Binder) Polyester (A2) 68
0 parts, 270 parts of styrene resin (B2) and 50 parts of compatibilizer (C1) were mixed in the same manner as in Example 1 to obtain toner binder (2) of the present invention.

Example 3 (Synthesis of styrene resin) 270 parts of resin (b1-1)
270 parts of the resin (b1-2) and 460 parts of the resin (b2-1) were added to 2000 parts of xylene, and dispersed and dissolved under reflux for 2 hours. Next, the resultant was dried under reduced pressure at 170 ° C. to obtain a styrene resin (B3). The THF-insoluble content of (B3) is 32%,
The peak molecular weight was 3700, and the ratio of molecular weights lower than 50,000 was 50%. The glass transition point is 57
C., T1 was 220 ° C. or higher, T2 was 125 ° C., and tan δ was 0.16 × 10 ⁻³ . (Synthesis of Toner Binder) Polyester (A1) 58
0 parts, 370 parts of styrene resin (B3) and 50 parts of compatibilizer (C1) were mixed in the same manner as in Example 1 to obtain toner binder (3) of the present invention.

Example 4 (Synthesis of styrene resin) In a reaction vessel equipped with a thermometer, a nitrogen inlet tube and a stirrer, 2000 parts of water and 3 parts of polyvinyl alcohol were sufficiently dissolved, and then styrene 8 was added.
50 parts, 150 parts of stearyl methacrylate, 1.8 parts of a diacrylate of bisphenol A ethylene oxide adduct (Neomer BA641 manufactured by Sanyo Chemical Industries, Ltd.) and 2 parts of di-t-butylperoxyhexahydroterephthalate were added. After the replacement with nitrogen, suspension polymerization was carried out at 85 ° C. for 10 hours and then at 95 ° C. for 3 hours. After cooling, the reaction product was separated by filtration, washed with water, and dried at 50 ° C. to obtain a resin (b).
1-3) was obtained. 350 parts of xylene was placed in an autoclave reaction vessel equipped with a thermometer and a stirrer, and after replacing with nitrogen, 909 parts of styrene and 60 parts of stearyl methacrylate were added.
Parts, butadiene 31 parts mixed monomer, and di-t-
Butyl peroxide 30 parts, chain transfer agent NOFMER MS
A mixture of 50 parts of D (manufactured by NOF Corporation) and 200 parts of xylene was added dropwise at 150 ° C. for 4 hours to polymerize. Then, the solvent was removed to obtain a resin (b2-3). Resin (b1-3) 42
0 parts and 580 parts of the resin (b2-3) were added to 2000 parts of xylene, and dispersed and dissolved under reflux for 2 hours. Then 170
Drying under reduced pressure at ℃ gave a styrene resin (B4).
(B4) has a THF insoluble content of 32% and a peak molecular weight of 78.
00, and the ratio with a molecular weight of less than 50,000 was 60%. The glass transition point is 60 ° C., T1 is 196 ° C.,
T2 was 119 ° C. and tan δ was 0.56 × 10 ⁻³ . (Synthesis of compatibilizer) In the same manner as in compatibilizer (C1) of Example 1, in the presence of 691 parts of resin (c1-1), a mixed monomer of 850 parts of styrene and 150 parts of butyl acrylate, and di-t A mixture of 30 parts of -butyl peroxide and 269 parts of xylene was added dropwise at 150 ° C. for 4 hours to polymerize. Subsequently, the solvent was removed to obtain a compatibilizer (C2). (Synthesis of Toner Binder) Polyester (A2) 38
0 parts, 570 parts of styrene resin (B4) and 50 parts of compatibilizer (C2) were mixed in the same manner as in Example 1 to obtain toner binder (4) of the present invention.

Comparative Example 1 (Synthesis of Polyester) In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 700 parts of a 2-mol adduct of bisphenol A propylene oxide, 130 parts of fumaric acid, 53 parts of dodecenylsuccinic anhydride, 53 parts of hydroquinone 0.1 part and 1.8 parts of dibutyltin oxide were added, and reacted at 230 ° C. under normal pressure for 12 hours.
The reaction was carried out under reduced pressure for 3 hours. Next, 64 parts of trimellitic anhydride was added and reacted at a reduced pressure of 10 to 15 mmHg. When the acid value reached 20, the product was taken out of the reaction vessel to obtain a polyester (A3). (A3) has a THF insoluble content of 28%, a peak molecular weight of 6200, and an acid value of 19 mg KO.
H / g and hydroxyl value were 41 mgKOH / g. The glass transition point was 63 ° C, T3 was 139 ° C, and T2 was 110 ° C. Polyester (A3) is used as comparative toner binder (1).

Comparative Example 2 (Synthesis of styrenic resin) Styrene 720
Part, 280 parts of butyl acrylate, diacrylate of bisphenol A ethylene oxide adduct (Neomer B
A641 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) The polymerization was carried out in the same manner as in the resin (b1-3) of Example 4 except that the amount was changed to 1.8 parts.
1-4) was obtained. 450 parts of xylene was placed in an autoclave reaction vessel equipped with a thermometer and a stirrer, and after purging with nitrogen, a mixed monomer of 870 parts of styrene, 130 parts of butyl acrylate, and di-t-butyl peroxide 1
A mixture of 5 parts and 120 parts of xylene was added dropwise at 170 ° C. over 3 hours to carry out polymerization. Then, the solvent is removed and the resin (b2-4) is removed.
I got 380 parts of resin (b1-4) and resin (b2-4)
620 parts were added to 2000 parts of xylene, and dispersed and dissolved under reflux for 2 hours. Next, drying under reduced pressure was performed at 170 ° C. to obtain a styrene resin (B5). (B5) had a THF insoluble content of 27%, a peak molecular weight of 7,200, and a molecular weight of 500.
The ratio of less than 00 was 65%. The glass transition point is 61 ° C., T1 is 194 ° C., T2 is 120 ° C., tan δ
Was 1.8 × 10 ⁻³ . (Synthesis of Toner Binder) Polyester (A1) 58
0 parts, 370 parts of styrene resin (B5) and 50 parts of compatibilizer (C2) were mixed in the same manner as in Example 1 to obtain comparative toner binder (2).

Comparative Example 3 (Synthesis of styrene resin) In an autoclave reactor equipped with a thermometer and a stirrer, 1800 parts of water, 22 parts of a fatty acid potassium salt, 22 parts of disproportionated potassium rosinate, and 4 parts of potassium phosphate After sufficient dissolution, 900 parts of styrene, 100 parts of butadiene, and 1.
6 parts of the mixed monomer, 0.05 parts of ferrous sulfate, 0.2 parts of paramenthane hydroperoxide, and 5 parts of t-dodecylmercaptan were added, and the mixture was replaced with nitrogen and emulsion-polymerized at 5 ° C. Calcium chloride was added to the obtained latex to aggregate the polymer, followed by centrifugation and drying at 50 ° C. to obtain a resin (B6). The THF-insoluble content of (B6) is 18
%, The ratio of which is less than 50,000 is 49%, but the molecular weight distribution was broad and no clear peak could be identified. The glass transition point is 65 ° C., T1 is 178 ° C.,
T2 was 157 ° C. and tan δ was 0.98 × 10 ⁻³ . (Synthesis of Toner Binder) Polyester (A3) 40
0 parts and 600 parts of a styrene resin (B6) were mixed in the same manner as in Example 1 to obtain a comparative toner binder (3).

Evaluation Examples 1a to 4a and Comparative Evaluation Examples 1a to
3a 8 parts of carbon black (MA100 manufactured by Mitsubishi Kasei Co., Ltd.) and low molecular weight polypropylene (Sanyo Chemical Co., Ltd.) are used for 100 parts of the toner binders (1) to (4) and the comparative toner binders (1) to (3) of the present invention. Industrial Co., Ltd. Viscole 550P) 4 parts, charge control agent TRH (Hodogaya Chemical)
(Manufactured)) 1 part was formed into a toner by the following method. First, after premixing using a Henschel mixer (FM10B manufactured by Mitsui Miike Kakoki Co., Ltd.), a twin-screw kneader (PCM manufactured by Ikegai Co., Ltd.)
-30). Then, after crushing finely using a supersonic jet crusher Labjet (manufactured by Nippon Pneumatic Industries, Ltd.), an airflow classifier (Nippon Pneumatics, Inc.)
MDS-I), and the particle size d50 is 5 to 20 μm.
Was obtained. Next, 0.5 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) was mixed with 100 parts of the toner particles using a sample mill, and the toner (1) was mixed.
a) to (4a) Comparative toners (1a) to (3a) were obtained.
Table 1 shows the evaluation results.

[0038]

Table 1------------------------------------------------------------------------------------------------------------------------------- Amount (H / H) MFT HOT -------------------------------------------------------------------------- Toner (1a) -16 1.2-13.7 135 ° C 230 ° C or higher Toner (2a) -15.1 -12.1 130 ° C 230 ° C or higher Toner (3a) -16.5 -14.0 135 ° C 230 ° C or higher Toner (4a) − 18.5 -13.9 135 ° C 220 ° C Comparative toner (1a) -13.4 -8.0 130 ° C 170 ° C Comparative toner (2a) -15.9 -10.3 135 ° C 220 ° C Comparative toner (3a) -20.8 -13.9 150 ° C 180 ° C ---------------------------------------------------------- [----] Value Method] Charge Amount 1 g of toner and 24 g of a ferrite carrier for electrophotography (FL961-150, manufactured by Powder Tech Co., Ltd.) are mixed for 20 minutes using a turbuler shaker mixer, and the charge amount is measured by a blow-off charge amount measuring device (Toshiba Chemical Co.). Room temperature and humidity for friction mixing and charge measurement
(23 ° C., 50% RH), the charge amount (N / N),
Charge measured at high temperature and high humidity (35 ° C, 85% RH)
(H / H). Minimum fixing temperature (MFT) An unfixed image developed using a commercially available black-and-white copying machine (AR5030; manufactured by Sharp) is converted into a commercially available copying machine (SF8400A;
A fixing unit (made by Sharp Corporation) was modified and evaluated using a fixing machine with a variable fixing temperature. The minimum fixing temperature was the fixing roll temperature at which the residual ratio of the image density after rubbing the fixed image with a pad was 70% or more. Hot offset occurrence temperature (HOT) The fixing was evaluated in the same manner as in the above MFT, and the presence or absence of hot offset to the fixed image was visually evaluated. The temperature of the fixing roll at which the hot offset occurred was defined as the hot offset occurrence temperature.

Evaluation Examples 1b to 4b and Comparative Evaluation Examples 1b to
3b 100 parts of magnetic powder (EPT-1000 manufactured by Toda Kogyo KK) and 100 parts of low molecular weight polypropylene (100 parts) are based on 100 parts of toner binders (1) to (4) of the present invention and comparative toner binders (1) to (3). 4 parts of Viscol 550P manufactured by Sanyo Chemical Industries, Ltd., charge control agent T-77 (Hodogaya Chemical)
(Manufactured)), and the mixture was converted into a toner by the following method. First, a Henschel mixer (FM1 manufactured by Mitsui Miike Kakoki Co., Ltd.)
OB), and kneaded with a twin-screw kneader (PCM-30, manufactured by Ikegai Co., Ltd.). Then supersonic jet crusher Lab Jet (manufactured by Nippon Pneumatic Industries, Ltd.)
After finely pulverizing by using an airflow classifier (MDS-I manufactured by Nippon Pneumatic Industries, Ltd.), the particle size d50 is 8
μm toner particles were obtained. Then, 1 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) was mixed with 100 parts of the toner particles using a sample mill, and the toner (1
b) to (4b) Comparative toners (1b) to (3b) were obtained.
Table 2 shows the evaluation results.

[0040]

Table 2 ---------------------------------------------------------------------------- Toner No. Image density (N / N) image.------------------------------------------------------------------------------ Concentration (H / H) MFT HOT----------------------------Toner (1b) 54 1.18 125 ° C 220 ° C Toner (2b) 1.48 1.08 120 ° C 210 ° C Toner (3b) 1.52 1.17 125 ° C 230 ° C Toner (4b) 1.42 1.09 130 ° C 200 ° C Comparative toner (1b) 0.75 0.55 115 ° C 160 ° C Comparative toner (2b) 0.95 0.76 125 ° C 200 ° C Comparative toner (3b) 1.38 0.98 135 ° C 170 ° C −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− [Evaluation method] Image density Commercial laser Linters; printing the black solid image using (LBP-210 manufactured by Canon) and the image density was measured using a Macbeth densitometer. Develop at room temperature and humidity (23
C., 50% RH) is referred to as image density (N / N), and that performed at high temperature and high humidity (35.degree. C., 85% RH) is referred to as image density (H / H). Minimum fixing temperature (MFT) An unfixed image developed using a commercially available laser printer (LBP-210; manufactured by Canon) is converted to a commercially available copier (SF
(8400A; manufactured by Sharp) was modified and evaluated using a fixing machine having a paper feeding speed of 160 mm / sec and a variable fixing temperature. The minimum fixing temperature was the fixing roll temperature at which the residual ratio of the image density after rubbing the fixed image with a pad was 70% or more. Hot offset occurrence temperature (HOT) The fixing was evaluated in the same manner as in the above MFT, and the presence or absence of hot offset to the fixed image was visually evaluated. The temperature of the fixing roll at which the hot offset occurred was defined as the hot offset occurrence temperature.

[0041]

The toner binder of the present invention has the following effects. 1. When a dry toner is used, the charge amount is appropriate and the environment stability is excellent. In particular, the magnetic toner has a high charge amount and a high image density. 2. Excellent in both low-temperature fixability and hot offset resistance. 3. Excellent durability and little deterioration of image after long-term copying.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Takashi Ono 11-11, Hitotsubashi Nohonmachi, Higashiyama-ku, Kyoto Sanyo Kasei Kogyo Co., Ltd. (56) References JP-A-7-230186 (JP, A) JP-A Heisei 7-191496 (JP, A) JP-A-6-118700 (JP, A) JP-A-3-213879 (JP, A) JP-A-3-274576 (JP, A) JP-A-6-194870 (JP, A) A) JP-A-6-59504 (JP, A) JP-A-1-219977 (JP, A) JP-A-3-116055 (JP, A) JP-A-5-188636 (JP, A) JP-A-58 JP-A-11955 (JP, A) JP-A-9-251217 (JP, A) JP-A-5-27478 (JP, A) JP-A-4-274254 (JP, A) JP-A-9-179343 (JP, A) (58) Fields surveyed (Int. Cl. ⁷ , DB name) G03G 9/08

Claims (11)

(57) [Claims] 1. A toner binder comprising a polyester (A) and a styrene-based resin (B).
Is the dielectric loss tangent (tan) at a measurement frequency of 100 kHz.
δ) is 1.5 × 10 ⁻³ or less, and the measurement frequency is 20 Hz.
(T1) at which the storage elastic modulus is 1 × 10 ⁵ dyne / cm ² at 140 ° C. or higher, and the measurement frequency is 20H
A toner binder, which is a styrene-based resin having a temperature (T2) at which the viscosity at z becomes 1 × 10 ⁴ poise is 90 to 140 ° C. 2. A temperature (T3) at which (A) has a storage elastic modulus of 6 × 10 ⁴ dyne / cm ^{2 at} a measurement frequency of 20 Hz.
Is 130 ° C. or higher and the temperature (T2) at which the viscosity at a measurement frequency of 20 Hz becomes 1 × 10 ⁴ poise is 90 to 1
The toner binder according to claim 1, which is a polyester having a temperature of 40 ° C. 3. The method according to claim 1, wherein (B) is a styrene polymer (B
1) a polymer 1 selected from the group consisting of a copolymer of styrenes and dienes (B2), and a copolymer of styrenes and long-chain alkyl (meth) acrylates having C10 to C22 alkyl groups (B3) 3. The toner binder according to claim 1, which is at least one kind. 4. The method according to claim 1, wherein said (B) has a molecular weight of 1,000 to 1 in gel permeation chromatography (GPC).
The component (b1) having a maximum value of 5,000 and having a molecular weight of less than 50,000 is 30 to 90%, and the component having a molecular weight of 50,000 or more and / or a tetrahydrofuran-insoluble component (b
The toner binder according to any one of claims 1 to 3, which contains 10 to 70% of 2). 5. The method according to claim 1, wherein (B) is (B1) and / or (B)
2) and (b1) is a copolymer of 80 to 100% by weight of styrene, 0 to 20% by weight of butadiene and / or isoprene, and 0 to 5% by weight of other monomers;
5. The toner binder according to claim 4, wherein (b2) is a copolymer of 70 to 95% by weight of styrene, 5 to 30% by weight of butadiene and / or isoprene, and 0 to 5% by weight of other monomers. 6. The (A) contains 5 to 60% by weight of a tetrahydrofuran-insoluble content, and has a molecular weight of 100 by GPC.
The toner binder according to any one of claims 1 to 5, which is a polyester having a maximum value of 0 to 10,000. 7. The hydroxyl value of (A) is 25 or less,
The toner binder according to any one of claims 1 to 6, wherein the acid value is 5 to 50. 8. The (A) is a polycondensate comprising a diol (1), a trivalent or higher valent polyol (2), a dicarboxylic acid (3), and a trivalent or higher polycarboxylic acid (4). 1
8. The toner binder according to any one of items 7 to 7. 9. The toner binder according to claim 8, wherein the trivalent or higher polyol (2) is an alkylene oxide adduct of a novolak resin. 10. The weight ratio of (A) to (B) is 30 /
The toner binder according to any one of claims 1 to 9, wherein the ratio is 70 to 90/10. 11. A combination of (A) and (B) together with (A)
The toner according to any one of claims 1 to 10, further comprising, as a compatibilizer, a polymer (C) in which a polymer chain having a SP value difference of 0.5 or less and a polymer chain mainly composed of styrene is chemically bonded. binder.