JP2754007B2 - Binder resin and toner for toner - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a binder resin for toner and a toner, and more particularly, to an excellent binder resin used for developing a latent image formed by an electrostatic printing method or the like. The present invention relates to a binder resin for a toner capable of providing a toner having a good balance of low-temperature fixability, non-offset property and blocking resistance, and a toner using the same.

[Summary of the Invention]

The toner of the present invention has a well-balanced low-temperature fixing property, non-offset property and anti-blocking property, which are extremely useful in the field of the electrostatic recording industry, by using a specific crosslinked polyester as a binder.

[Conventional technology]

Conventionally, in electrophotography, a latent image is usually formed on a latent image type roller made of a photoconductive photoreceptor by charging and exposing, developed with toner, and the obtained toner image is transferred to paper or the like. Then, the image is fixed on paper by heating and pressing to obtain an image.

It is desired that the image forming process through such a latent image is performed at a high speed, and therefore, a heat roller fixing system which has high thermal efficiency and can be operated at a high speed in a fixing process is widely used.

In recent years, there has been a strong demand for higher speeds, and for that purpose, high-speed constant deposition of toner images is a condition. In order to fix a toner image at a high speed in a heat roller system, it is required that the toner has good low-temperature fixability. To that end, the softening temperature of a binder, which is a main component of the toner, is lowered, and the adhesive property is lowered. Need to be improved.
On the other hand, when the softening temperature of the binder of the toner is lowered, a part of the toner is transferred to the heat roller during the fixing process, and the phenomenon (offset) that stains the next paper or the like is likely to occur.

Various proposals have been made as a result of various research and development efforts to solve such problems.

A first proposal is to obtain a linear polyester by reacting an etherified bisphenol A component and a dicarboxylic acid component, and then to give a trivalent or higher valent monomer component (for example,
The present invention relates to a toner having good non-offset properties, using, as a binder, a crosslinked polyester obtained by adding a trimellitic anhydride to form a crosslinked structure.

The second proposal relates to a method for improving the flowability of a toner by lowering the molecular weight of a binder in order to improve the low-temperature fixability.

A third proposal relates to a binder having a long-chain aliphatic hydrocarbon unit as a binder in order to improve low-temperature fixability.

[Problems to be solved by the invention]

However, the first proposal has a problem that the fixing performance is not always good, and when high-speed fixing is continuously performed at a fixing speed of 50 sheets / min or more, the toner is not sufficiently heated and the fixing strength tends to be insufficient. Atsuta.

In the second proposal, it has become clear that the method of reducing the molecular weight lowers the offset performance, making it impossible to produce a toner that can withstand practical use.

Further, the third proposal has a problem that the glass transition temperature of such a polyester is low and storage stability is poor.

What is the purpose of the present invention? An object of the present invention is to provide a toner which is excellent in low-temperature fixing property, non-offset property and blocking resistance in a well-balanced manner.

[Means for solving the problem]

The binder resin for a toner according to the present invention comprises a trihydric or higher polyhydric alcohol unit and / or a trihydric or higher polycarboxylic acid unit (a), and 1 mol% or more of 3 carbon atoms in all acid units.
At least one kind of a branched aliphatic monomer unit selected from the group consisting of aliphatic dicarboxylic acids and aliphatic diols of 1 to 12 and / or 1 mol% or more of 4 to 4 carbon atoms based on all acid units;
20 polyoxyalkylene glycol units (b), aromatic dicarboxylic acid units (c), 80 mol% based on all acid units
A non-linear polycondensate comprising the following aromatic diol unit (d) and 20 mol% or more of ethylene glycol units (e) based on all acid units, and having an acid value of 0.5 to 12 mgKOH /
g, a cross-linked polyester having a glass transition temperature of 20 to 68 ° C, a b value of 15 or less, and a softening temperature of 145 ° C or less.

Further, in the toner of the present invention, the binder resin comprises the following crosslinked polyester resin, and has an average particle size of 50 to 80.
It is characterized by containing 0.05 to 3% by weight of an inorganic powder of 00%.

(A) a trihydric or higher polyhydric alcohol unit and / or a trihydric or higher polyhydric carboxylic acid unit, and (b) 1 mol% or more of an aliphatic dicarboxylic acid and a fatty acid having 3 to 12 carbon atoms, based on all acid units. At least one kind of a branched aliphatic monomer unit selected from the group consisting of aliphatic diols and / or
Or a polyoxyalkylene glycol unit having 4 to 20 carbon atoms in an amount of 1 mol% or more based on all acid units, (c) an aromatic dicarboxylic acid unit, and (d) an aromatic diol having 80 mol% or less based on all acid units. And (e) a non-linear polycondensate comprising 20 mol% or more of ethylene glycol units based on all acid units, having an acid value of 0.5 to 12 mgKOH / g, a glass transition temperature of 20 to 68 ° C, b
A crosslinked polyester resin having a value of 15 or less and a softening temperature of 145 ° C or less.

In the present specification, the total acid unit means a total unit of a trivalent or higher polycarboxylic acid unit, an aliphatic dicarboxylic acid unit and an aromatic dicarboxylic acid unit in a branched aliphatic monomer having 3 to 12 carbon atoms. The dicarboxylic acid unit means a total unit of an aliphatic dicarboxylic acid unit and an aromatic dicarboxylic acid unit in a branched aliphatic monomer having 3 to 12 carbon atoms.

The acid value is measured by a neutralization titration method, the glass transition temperature is measured by a differential scanning calorimeter (DSC), the b value is measured by a colorimeter, and the softening temperature is measured by a flow tester (CFT-500, manufactured by Shimadzu Corporation). The value measured by the method of measuring the temperature at the time when 1/2 of the 1 g of the sample has flowed out when measured under a 1 mm φ × 100 mm nozzle, overload of 30 kg, and heating rate of 3 ° C./min. It is.

The trihydric or higher polyhydric alcohol unit constituting the crosslinked polyester used as the binder resin for a toner of the present invention is a unit in which a trihydric or higher polyhydric alcohol is generated in correspondence with a carboxylic acid, and is represented by the following formula. It is as follows.

(HO _m R ₁ O-) n (where m and n are integers satisfying m + n ≧ 3, m ≧ 0 and n ≧ 1, and R ₁ is a hydrocarbon residue.) As polyhydric alcohols,
For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5 -Pentanetriol, glycerol, 2-methylpropanetriol,
2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. can be introduced into a crosslinked polyester by reacting with a carboxylic acid component. It is. On the other hand, the trivalent or higher polyvalent carboxylic acid unit is a unit formed by reacting a trivalent or higher polyvalent carboxylic acid component with an alcohol, and is expressed as follows.

(R ₃ OCO _{m ′} R ₂ CO−) n ′ (where m ′ and n ′ are m ′ + n ′ ≧ 3, m ′ ≧ 0, n ′ ≧
1) is an integer, R ₂ is a hydrocarbon residue, R ₃
Is an alkyl group having 6 or less carbon atoms or a hydrogen atom. ) The polyvalent carboxylic acid constituting such a unit includes:
For example, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxylpropane, tetra (methylenecarboxyl) methane, 1,2,7 , 8
-Octanetetracarboxylic acid, or their acid anhydrides or their lower alkyl esters having 6 or less carbon atoms can be introduced into the crosslinked polyester by reacting with alcohol.

The units introduced by these trivalent or higher-valent monomers are not particularly limited, but the total amount thereof is the number of the acid units in the crosslinked polyester, that is, the units formed by the reaction of the carboxylic acid with the alcohol. It is preferably from 1 to 30 mol% based on the total amount.

If the content of these units exceeds 30 mol%, the low-temperature fixability of the toner tends to decrease, and if the content is less than 1 mol%, a sufficient crosslinked structure cannot be obtained and offset may easily occur.

The branched aliphatic monomer unit having 3 to 12 carbon atoms constituting the crosslinked polyester used as the binder resin for a toner of the present invention is an aliphatic diol or an aliphatic dicarboxylic acid having 3 to 12 carbon atoms having a measured chain. The unit introduced by the reaction, as shown in the formula, is as follows.

[However, i, j, k, i ', j', k 'are j + k = 2,
j ≧ 0, k ≧ 1; j ′ + k ′ = 2, j ′ ≧ 0, and k ′ ≧ 1 are integers, and R ₅ and R ₇ are alkyl groups (provided that i,
When i ′ ≧ 2, different groups may be used), and R ₄ and R ₆
Is a hydrocarbon residue, and R ₆ is an alkyl group having 6 or less carbon atoms or a hydrogen atom. Examples of the branched aliphatic monomer having 3 to 12 carbon atoms constituting such a unit include, for example, 1,2-propylene glycol, 1,3-butanediol, 2,3-butanediol,
Methyl-1,3-propanediol, neopentyl glycol, 1,2-dimethyl-1,3-propanediol, 1,3-
Dimethyl-1,3-propanediol, 1,2,3-trimethyl-1,3-propanediol, 2,3-dimethyl-1,4-butanediol, 3,3-diethyl-1,5-pentadiol, etc. A branched aliphatic glycol, 1,2-propanedicarboxylic acid,
1,3-butanedicarboxylic acid, 2,3-butanedicarboxylic acid,
3-methylglutaric acid, 2,2-dimethyl-1,3-propanedicarboxylic acid, 1,2-dimethyl-1,3-propanedicarboxylic acid, 1,3-dimethyl-1,3-propanedicarboxylic acid,
2,3-trimethyl-1,3-propanedicarboxylic acid, 2,3-
Dimethyl-1,4-butanedicarboxylic acid, 3,3-diethyl-
Examples thereof include branched aliphatic carboxylic acids such as 1,5-pentanedicarboxylic acid and the like and lower alkyl esters thereof having 6 or less carbon atoms, the units of which can be introduced into a crosslinked polyester by reacting them with an acid or alcohol. .

On the other hand, the polyoxyalkylene glycol unit having 4 to 20 carbon atoms is a unit in which the polyoxyalkylene glycol is introduced as an acid component, and is represented by the following formula.

HO- (RO-) _i or -O- (RO-) _i (where i is an integer and R is an alkylene group) A polyoxyalkylene glycol having 4 to 20 carbon atoms constituting such a unit As, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight of less than 450, ditrimethylene ether glycol, tritrimethylene diether glycol, ethylene propylene ether glycol, ditetramethylene ether glycol,
Ethylene tetramethylene ether glycol, trimethylene tetramethylene ether glycol, polyoxytetramethylene glycol having a molecular weight of 350 or less,
The units can be introduced into the crosslinked polyester by reacting them with an acid component.

The presence of these units is effective not only for improving the glass transition temperature and lowering the softening temperature, but also for improving the solubility parameter (SP) value of the resin, and providing excellent blocking resistance and low-temperature fixability to the toner. Is to be granted. In particular, a crosslinked polyester containing a branched aliphatic monomer unit having 3 to 8 carbon atoms in an amount of 5 to 80 mol% based on all acid units is particularly preferable as a binder for a toner because it exhibits the above-mentioned effects. If the carbon number is too large, the glass transition temperature tends to decrease. Furthermore, if the proportion of the monomer unit is small, the effect is hardly obtained, while if too large, on the other hand, the reactivity decreases due to the steric structure of the monomer and the condensation polymerization reaction takes a long time. Cost.

The aromatic dicarboxylic acid unit constituting the crosslinked polyester used as the binder resin for the toner of the present invention,
The aromatic dicarboxylic acid component is a unit formed by reacting with an alcohol, and is represented by the following formula.

(R ₁₀ OCO _{j ″} R ₉ CO−) _{k ″} (where j ″ and k ″ are j ″ + k ″ = 2, j ″ ≧ 0, k ″
Is an integer satisfying ≧ 1, R ₉ is an aromatic hydrocarbon residue, and R ₁₀ is an alkyl group having 6 or less carbon atoms or a hydrogen atom. As the aromatic dicarboxylic acid constituting such a unit, for example, terephthalic acid, isophthalic acid, orthophthalic acid, cyclohexanedicarboxylic acid, 3,5-toluenedicarboxylic acid, 2,4-toluenedicarboxylic acid, 2,5- Examples thereof include dicarboxylic acids such as toluene dicarboxylic acid, acid anhydrides thereof, and lower alkyl esters having 6 or less carbon atoms, and the units thereof can be introduced into a crosslinked polyester by reacting them with an alcohol. And contributes to the improvement of the glass transition temperature. Among these, units introduced from terephthalic acid and isophthalic acid (respectively referred to as terephthalic acid units and isophthalic acid units) are preferable in order to significantly lower the softening temperature of the crosslinked polyester. The content ratio is preferably such that the terephthalic acid unit is at least 20 mol% with respect to all dicarboxylic acid units and the isophthalic acid unit is at most 80 mol% with respect to all dicarboxylic acid units in consideration of the effect on the glass transition temperature. . More preferably, the content of terephthalic acid units is 30 mol% or more, and the content of isophthalic acid units is 70 mol% or less. If the terephthalic acid unit is too small and the isophthalic acid unit is too large, the glass transition temperature decreases.

The aromatic diol unit constituting the crosslinked polyester used as the binder resin for a toner of the present invention refers to a unit generated by reacting an aromatic diol with a carboxylic acid,
The expression is as follows.

(HO _j R ₉ O−) _k (where j and k are j + k = 2, j ≧ 0, k
Is an integer satisfying ≧ 1, and R ₉ is an aromatic hydrocarbon residue. ) As the aromatic diol constituting such a unit,
For example, polyoxypropylene-2,2-bis (4'-hydroxyphenyl) propane, polyoxyethylene-2,
2-bis (4'-hydroxyphenyl) propane, etc., whose units can be introduced into a crosslinked polyester by reacting them with a carboxylic acid, which contributes to lowering of the softening temperature. Among these, polyoxypropylene-2,2-bis (4'-hydroxyphenyl) propane is preferred because it significantly improves the glass transition temperature and significantly lowers the softening temperature. If the diol is used in a proportion exceeding 80% based on the total acid units, the reactivity tends to decrease, so that the diol is introduced into the crosslinked polyester in a range of 80 mol% or less. It is preferable that the ratio be as small as possible. On the other hand, the ethylene glycol unit is a unit shown below.

-O-CH ₂ CH ₂ -O- or HO-CH ₂ CH ₂ -O- such units of ethylene glycol can be introduced into by connexion crosslinked polyester to be reacted with carboxylic acids.

The crosslinked polyester used as the binder resin for a toner of the present invention needs to have the following physical property values.

Excellent thermal stability and charging stability which is the object of the present invention,
The acid value of the crosslinked polyester as a binder that is less thermally colored and can be used as a toner for color printing is preferably 12 mgKOH / g or less. More preferably, the acid value is 10 mgKOH / g or less. However, in the case of polyester, in order to synthesize a polyester with an extremely low acid value, although technical methods such as lowering the reaction temperature have already been established, it is actually possible to obtain a polyester of 0.5 mg KOH / g or less. It is difficult. That is, the acid value of the crosslinked polyester used in the present invention is preferably in the range of 0.5 to 12 mgKOH / g, and when the acid value is out of this range, the thermal stability becomes extremely low as a general property of the polyester, and The charge stability, which is an important property of, is also reduced due to an increase in hygroscopicity and an increase in negative charge due to a carboxyl group.

Further, the glass transition temperature is an important index for storage stability. However, if the glass transition temperature is less than 20 ° C., practical storage stability cannot be achieved. On the other hand, when the temperature exceeds 68 ° C., the softening temperature becomes excessively high, which adversely affects the fixing performance. A lower softening temperature is preferable for improving the fixing property,
Actually, there is no problem if the temperature is 145 ° C. or less.

Since the polyester binder according to the present invention is particularly excellent in thermal properties, the b value is easily reduced to 15 or less. As a binder for a thin toner in color printing, the b value is 15 or less, preferably the b value is 10 or less, and more preferably the b value is 6 or less.

The crosslinked polyester used in the binder resin for a toner of the present invention is prepared by a usual polyester synthesis method, that is, after an acid component and an alcohol component are subjected to an esterification reaction or a transesterification reaction, and then a low-boiling diol is removed under vacuum or a nitrogen stream. It can be synthesized by removing it out of the system below.

The toner of the present invention has an average particle diameter of 0.005 to 3% by weight based on 100% by weight of the toner of the crosslinked polyester.
It is a particle powder containing an inorganic powder which is 100% and a coloring agent or an additive used as required.

Examples of the inorganic powder used in the present invention include titanium oxide, acid value tungsten, acid value molybdenum, alumina, amorphous silica, colloidal silica, zirconia, kaolin, and talc.

The inorganic powder is contained in the toner in an amount of 0.05 to 3% by weight. If it is less than 0.05% by weight, the blocking resistance decreases, which is not preferable. On the other hand, if it exceeds 3% by weight, the image quality deteriorates, which is not preferable. Furthermore, the particle size of the inorganic particles is 50 to 8000Å
When the temperature exceeds 8000 °, the blocking resistance is undesirably reduced. In addition, particles having a particle size of less than 50 ° are not preferable because they are difficult to produce.

Specific examples of the colorant used in the present invention include, for example, carbon black, methylene blue chloride (C.
I.No.52015), phthalocyanine blue (CINo.7416)
0), Malachite Green Oxalate (CINo.4200
0), lamp black (CINo.77266), rose bengal (CINo.45435), nigrosine dye (CINo.50415)
B), aniline blue (CINo. 50405), calco oil blue (CINo. Azoec Blue 3), chrome yellow (C.
I.No.14090), Ultramarine Blue (CINo.7710)
3), DuPont Oil Red (CINo. 26105), Quinoline Yellow (CINo. 47005), or a mixture thereof.

These colorants are preferably contained in a sufficient ratio to form a visible image having a sufficient concentration, and are usually about 1 to 20 parts by weight based on 100 parts by weight of the crosslinked polyester.

Other additives include, for example, an offset inhibitor, a fluidity improver, and a charge control agent.Examples of the offset inhibitor include polyolefin-based waxes, carnauba waxes, and alkylene bis fatty acid amide compounds. Examples of the fluidity improver include fine silica powder and the like, and examples of the charge control agent include an electron donating dye (nigrosine-based dye), an alkoxylated amine, and a quaternary ammonium salt (containing an active ingredient). Agents), simple substances and compounds of alkylamides, phosphorus and tungsten, molybdate chelate pigments, fluorine-based activators and positive charge control agents such as hydrophobic silica; electron-accepting dyes (metal complex salts of monoazo dyes); Organic complex, chlorinated polyolefin, chlorinated polyester,
Negative charge control agents such as polyesters having excess acid groups, sulfonylamine of copper phthalocyanine, oil black (CI ^* 26150), metal salts of naphthenic acid, metal salts of fatty acids, and resin acid soaps.

In the case of constituting a magnetic toner, a magnetic substance is added to the crosslinked polyester together with the colorant or alone.

As the magnetic material, ferromagnetic metals or alloys such as ferrite, magnetite, and nickel, or nickel, or a compound containing these elements, or a compound containing these elements, or a ferromagnetic material obtained by performing an appropriate heat treatment. Alloys such as manganese-copper-aluminum, manganese-copper-tin, etc., and alloys of the type called Heusler alloys containing manganese and copper, chromium dioxide, and the like.

These magnetic substances are in the form of fine particles having an average particle diameter of 0.1 to 1 μm, and the content thereof is preferably 20 to 70 parts by weight, more preferably 40 to 70 parts by weight, per 100 parts by weight of the toner.

Further, the toner of the present invention has a modifier for improving the pulverizability, an additive for improving the triboelectric charging property of the toner, or a toner substance attached to the surface of the carrier particles or the surface of the latent image carrier to perform these functions. A property improving agent such as an additive for preventing the occurrence of a so-called toner filming phenomenon, which lowers the property, may be added.

As such a property improving agent, for example, a fat which is an uncrosslinked polymer and does not contain chloroform-insoluble matter can be preferably used. Examples of such a resin include styrene, parachlorostyrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, and n-acrylate.
Octyl, 2-chloroethyl acrylate, phenyl acrylate, α-methyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide,
Vinyl methyl ether, vinyl isobutyl ether, vinyl ethyl ether, vinyl methyl ketone, vinyl hexyl ketone, N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone,
Vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate,
Examples include homopolymers obtained by polymerizing vinyl monomers such as vinyl propionate, vinyl benzoate, and vinyl acetate, copolymers thereof, and mixtures of the polymers. Such a modifier can be used in a range that does not impair the properties of the crosslinked polyester, and can be used in a range that does not impair the properties of the crosslinked polyester, and is usually in an amount equal to or less than that of the crosslinked polyester. It may be used.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the examples, “parts” and “%” are all on a molar basis.

〔Example〕

Examples 1 to 8 Trivalent or higher carboxylic acids, branched aliphatic dicarboxylic acids, branched aliphatic diols, polyoxyalkylene glycols,
A monomer selected from an aromatic dicarboxylic acid, an aromatic diol and ethylene glycol is charged into an autoclave having a distillation bath and subjected to an esterification reaction. Then, 500 ppm of antimony trioxide is added to the acid component, and the mixture is placed under a vacuum of 3 torr. The polycondensation was carried out while removing the glycol from the system to obtain a crosslinked polyester as shown in Table 1.

Next, carbon black was added to the obtained cross-linked polyester, and kneaded, cooled, pulverized, and classified, and the average particle size was 10 to 13.
μm particles were obtained, and 0.2% by weight of amorphous silica (Nippon Aerosil, R972) was added to obtain particles of the present invention.

The composition, glass transition temperature, softening temperature, acid value and b value of each unit in the crosslinked polyester, the minimum fixing temperature of toner, offset generation temperature, and blocking resistance were examined.

The composition of each unit was determined by a liquid chromatograph and a gas chromatograph of a crosslinked polyester decomposed in accordance with a conventional method.

 Glass transition temperature was determined by DSC.

 The softening temperature was measured by a flow tester.

 The acid value was determined by a titration method.

 The b value was measured by a colorimeter.

The minimum fixing temperature consisted of a Teflon roller (heat roller) and a rubber roller. Using a device whose temperature could be set freely, the peripheral speed of the Teflon roller was set at 20 cm / sec and the toner image was transferred between both rollers. It was measured by a method of examining the toner fixing rate of a fixed image obtained by passing through paper. Here, the fixing rate of the toner was measured by using a reflection densitometer (manufactured by Macbeth) to measure the density of the toner before and after the cellotape (Nichiban No. 405) was applied and peeled off. The fixing temperature was the temperature at which the fixing rate reached 95%.

In the measurement of the temperature at which the offset occurs, the toner image is transferred according to the measurement of the minimum fixing temperature, the fixing process is performed by the above-described fixing device, and then the blank transfer paper is sent to the fixing device under the same conditions, and The operation of observing whether or not toner contamination occurs is performed by repeating the operation in a state in which the temperature of the heat roller of the fixing unit is configured in accordance with the temperature of the heat roller. Generated temperature.

Blocking resistance is as follows: 55 ° C, 50 ° C
%, The presence or absence of the temperature when left for 48 hours, and the degree thereof were evaluated. ◎ indicates very good, 良好 indicates good, 良好 indicates slightly poor, and × indicates bad.

Examples 9 to 17 Crosslinked polyesters as shown in Table 2 were obtained in the same manner as in Example 1 except that dibutyltin oxide was used as the condensation polymerization catalyst. The physical properties of the binder and the toner of the present invention produced by the same method as in Example 1 were measured. Second result
It is shown in the table.

Examples 18 to 26 Crosslinked polyesters as shown in Table 3 were obtained in the same manner as in Examples 9 to 17, except that the inorganic powder was changed to 0.3% by weight of OSCAP (catalyst chemical industry). The crosslinked polyester and Example 1
The physical properties of the toner manufactured in the same manner as in the above were measured. The results are shown in Table 3.

Examples 27 to 30 Crosslinked polyesters as shown in Table 4 were obtained in the same manner as in Example 1. When producing a toner using the crosslinked polyester, Aerosil R-972 (manufactured by Nippon Aerosil Co., Ltd.) was used.
Example 1 except that 1.0 weight percent (based on toner) was added.
A toner was produced in the same manner as in Example 1. Table 4 shows the physical properties of the crosslinked polyester and the toner.

Comparative Examples 1 to 5 Polyester binders for comparison as shown in Table 5 were obtained in the same manner as in Examples 1 to 8. The properties of the binder and the toners manufactured in the same manner as in Examples 1 to 8 were measured. The results are shown in Table 5.

[Effects of the Invention] As described in detail above, the toner of the present invention has a low softening point and good adhesion to a substrate, so that it has excellent low-temperature fixability and also has excellent non-offset properties. In addition, the lowering of the glass transition temperature was suppressed by the introduction of a branched monomer unit, etc., and the addition of inorganic powders resulted in excellent blocking resistance, which eliminated storage problems. .

Therefore, high-speed development of a toner image can be stably performed, and high-speed copying and printing can be achieved, and its industrial value is extremely large.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Shinji Kubo 4-1-1-60 Sunadabashi, Higashi-ku, Nagoya-shi, Aichi Examiner, Mitsubishi Rayon Co., Ltd. Yaichi Inoue (56) References A) JP-A-63-68853 (JP, A) JP-A-60-176054 (JP, A) JP-A-61-6656 (JP, A)

Claims (2)

(57) [Claims] 1. An aliphatic dicarboxylic acid having 3 to 12 carbon atoms and / or a polyhydric alcohol unit (a) having a valence of 3 or more and / or a carboxylic acid unit (a) having a valence of 3 or more, based on all acid units. At least one kind of a branched aliphatic monomer unit selected from the group consisting of an acid and an aliphatic diol and / or a polyoxyalkylene glycol unit having 4 to 20 carbon atoms (b) in an amount of 1 mol% or more based on all acid units; An aromatic dicarboxylic acid unit (c), 80 mol% or less of an aromatic diol unit (d) based on the total acid units, and 20 mol% or more of an ethylene glycol unit (e) based on the total acid units. Non-linear polycondensate, acid value 0.5 ~ 12mgKOH / g, glass transition temperature
A binder resin for a toner comprising a crosslinked polyester resin having a b value of 15 or less and a softening temperature of 145 ° C. or less at 20 to 68 ° C. 2. A toner characterized in that the binder resin comprises the following crosslinked polyester resin and contains 0.05 to 3% by weight of an inorganic powder having an average particle size of 50 to 8000 °. (A) a trihydric or higher polyhydric alcohol unit and / or a trihydric or higher polyhydric carboxylic acid unit, and (b) 1 mol% or more of 3 to 12 carbon atoms in all acid units.
At least one kind of branched aliphatic monomer unit selected from the group consisting of aliphatic dicarboxylic acids and aliphatic diols and / or 1 mol% or more of a polyoxyalkylene glycol having 4 to 20 carbon atoms based on all acid units (C) an aromatic dicarboxylic acid unit, (d) an aromatic diol unit of 80 mol% or less based on all acid units, and (e) an ethylene glycol unit of 20 mol% or more based on all acid units. A non-linear polycondensate having an acid value of 0.5 to 12 mg KOH / g, a glass transition temperature of 20 to 68 ° C, and b
A crosslinked polyester resin having a value of 15 or less and a softening temperature of 145 ° C or less.