JPS6336263A - Electrostatic image developing toner for heat roller fixing - Google Patents

Abstract

PURPOSE:To reduce temperature dependency of electrifiable quantity, and to prevent offset trouble and roller winding trouble by incorporating a specified polyester binder and a polyolefin wax in a toner. CONSTITUTION:The toner contains the optionally modified polyolefin wax and the binder made of the polyester obtained by polycondensation of an acid component and a polyol component represented by the formula shown on the right in which R is ethylene or propylene, and each of x and y is an integer and the average value of their sum is 2-7. Said acid component is a mixture of an aliphatic unsaturated dicarboxylic acid or its anhydride, and an aliphatic unsaturated >=3-carboxylic acid or its anhydride in a molar ratio of (100-5):5-(100-30):30. If the higher carboxylic acid component is <5, the offset resistance of the toner becomes deficient, and if >=30mol%, the electrifiable quantity is changed by humidity.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a toner for developing electrostatic latent images formed in electrophotography, electrostatic printing, electrostatic recording, etc. The present invention relates to toner used in a roller fixing method.

[Background of the invention]

For example, in electrophotography, an electrostatic latent image is usually formed on a latent image carrier made of a photoconductive photoreceptor by charging and exposure, and then this electrostatic latent image is developed with toner, and the resulting toner is After transferring the image to a support such as transfer paper, heating,
A visible image is formed by fixing the 1-ner by applying pressure or the like.

Formation of a visible image via such an electrostatic image is preferably achieved at high speed, and from this point of view, conventionally, a heat roller fixing method has been used in the fixing process, which has high thermal efficiency and is advantageous compared to other methods. Widely adopted.

However, in recent years, there has been a strong demand for even higher speeds, and in order to achieve this, it is essential to fix toner at high speeds.

However, in order to fix the toner at high speed in the hot roller fixing method, the toner used for development is required to have good low-temperature fixability. It is necessary to lower the softening point. However, if the softening point of the toner binder is lowered, part of the toner that makes up the image will transfer to the surface of the heat roller during fixing, and this will transfer again to the transfer paper that is sent next, staining the image. , the so-called offset phenomenon tends to occur more easily.

Conventionally, the following techniques have been disclosed as techniques for preventing the occurrence of such an offset phenomenon.

(1) A linear polyester obtained from a spray component containing a diol component made of a specific etherified bisphenol and an aromatic dicarboxylic acid is mixed with a trivalent or higher polycarboxylic acid (proportion in the acid component: 30 to 80 mol). %) as a toner binder (see Japanese Patent Application Laid-Open No. 57-373'53).

(2) A linear polyester obtained from a monomer component containing a specific etherified bisphenol (the proportion of propoxy groups is 50 mol% or more) and phthalic acids is Technique for using a crosslinked polyester resin (proportion: 40 mol% or less) as a toner binder (Japanese Patent Laid-Open No. 59-292
(See Publication No. 55).

[Problem that the invention seeks to solve]

However, in the technique (1) above, since the proportion of trivalent or higher polyhydric carboxylic acid used to form the crosslinked polyester is 30 mol% or more, many unreacted carboxyl groups remain, resulting in moisture loss. As a result, the amount of triboelectric charge in toner changes greatly depending on humidity, and there is a problem that the image density becomes highly dependent on the environment.

Furthermore, in both techniques (1) and (2) above, since the divalent carboxylic acid used to form the linear polyester 7 is an aromatic carboxylic acid, the glass transition point of the crosslinked polyester resin is Therefore, in the heat roller fixing method, if the pressure by the heat roller is large and the contact time with the heat roller is long, there will be no problem.
When the pressure applied by the heat roller is low and the contact time with the heat roller is short, such as when fixing is performed at high speed, there is a problem that the fixing performance is significantly deteriorated.

On the other hand, in high-speed fixing, when images are formed continuously, heat is absorbed by the image support such as transfer paper and the temperature of the heat roller tends to drop. There is a problem in that a so-called wrapping phenomenon, in which an image support such as paper adheres to the surface of a heated roller and wraps around it, tends to occur.

Therefore, in order to successfully achieve high-speed fixing, it is necessary to have excellent anti-offset properties as well as excellent anti-wrapping properties.

[Purpose of the invention]

The present invention has been made based on the above circumstances, and its object is to provide an electrostatic image developing toner for heat roller fixing that satisfies all of the following conditions (1) to (4). It is in.

(1) Sufficient offset resistance can be obtained.

(2) Changes in the amount of charge due to humidity are small, and the dependence of image density on the environment is small.

(3) Excellent low-temperature fixing properties and high-speed fixing are possible.

(4) Sufficient winding resistance can be obtained.

[Means for solving problems]

The electrostatic image developing toner for heat roller fixing of the present invention is as follows (
It is characterized by containing a binder made of a polyester resin obtained by condensation polymerization of component a) and component (b) below, and a polyolefin wax.

(a) Component Diol component shown below - Noshiro (1).

- Noshiro (1) (wherein R is an ethylene group or a propylene group,
X and y are integers, and the average value of the sum of both is 2 to 7
It is. ) (b) Component A mixture of an aliphatic unsaturated dicarboxylic acid, its acid anhydride, or its derivative, and a trivalent or higher polyvalent carboxylic acid or its acid anhydride, which is a polyvalent carboxylic acid of 3 or more valent carboxylic acids or its acid anhydride. A mixed acid component in which the content of an acid or its acid anhydride is 5 mol% or more and less than 30 mol% of the acid component.

[Function and effect of the invention]

According to the electrostatic image developing toner for heat roller fixing of the present invention,
The following effects are achieved.

In the component (b) for forming the polyester resin contained in the toner as a binder, the content ratio of trivalent or higher polyhydric carboxylic acid or its acid anhydride is 5% of the acid component.
Since the amount is mol % or more and less than 30 mol %, the remaining unreacted carboxyl groups are reduced in the resulting polyester resin, and as a result, the stability of the charge amount against humidity is significantly improved in the toner. The environmental dependence of image density is reduced, and the presence of these (Ll) components makes the viscoelasticity of I'J at an appropriate level when the polyester resin is melted, ensuring sufficient anti-offset properties in the toner. be done.

In the component (b), since an aliphatic unsaturated dicarboxylic acid, its acid anhydride, or its derivative is used as the divalent carboxylic acid component, the glass transition point of the obtained polyester resin is appropriately high, and it can be used at high speed. Sufficient fixing can be achieved even when the pressure applied by the heat roller is small and the contact time with the heat roller is short, as in the case of fixing, and when images are formed many times in succession. In this case, a phenomenon occurs in which the temperature of the heat roller is taken away by the image support such as transfer paper and lowered, but even in such a case, sufficient low-temperature fixability can be obtained.

If an aliphatic saturated dicarboxylic acid, an acid anhydride, or a derivative thereof is used instead of an aliphatic unsaturated dicarboxylic acid, an acid anhydride, or a derivative thereof in component (b), the resulting polyester resin However, in the present invention, since the aliphatic unsaturated dicarboxylic acid or its acid anhydride or its derivative is used, the resulting polyester Since the glass transition point of the resin is set to an appropriate height, sufficient blocking resistance of the toner is ensured.

The toner of the present invention contains a polyolefin wax together with the above polyester resin, and since the polyolefin wax is incompatible with the above polyester resin, the mold release effect of the polyolefin wax is sufficient. As a result, even when the temperature of the heat roller decreases, excellent double-winding properties can be obtained.

Furthermore, since the toner of the present invention contains the above-mentioned specific polyester resin and polyolefin wax, the synergistic effect of the two results in excellent self-charging properties and triboelectric charging m having a large absolute value. There are also advantages.

[Specific structure of the invention]

The present invention will be explained in detail below.

In the present invention, basically the component (a) and (
Using a polyester resin obtained by condensation polymerization with component b) as a binder, containing a polyolefin wax in the binder, and containing a coloring agent or additives used as necessary, heat is applied to the powder using fine particles. It constitutes a toner for developing an electrostatic image for roller fixing. Alternatively, additives such as a fluidity improver may be added to and mixed with the fine particle powder to form a toner for electrostatic image development for heat roller fixation.

The component (a) is a diol component represented by the general formula (1) as described above, and is a component that constitutes the main body of the basic skeleton (main chain) of the polyester resin together with the aliphatic unsaturated dicarboxylic acid described in detail later. It is.

Such diol components include, for example, polyoxypropylene (2,2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (3,3)-2
, 2-bis(4-hydroxyphenyl)propane, polyoxyethylene(2,0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(2
, 0)-polyoxyethylene(2,0)-2,2-bis(4-hydroxyphenyl)propane, and others can be used.

The component (b) is an aliphatic unsaturated dicarboxylic acid, an acid anhydride thereof, or a derivative thereof, which is a component that constitutes the main body of the basic skeleton (main chain) of the polyester resin together with the diol component which is the component (a); It is a mixture with a trivalent or higher polyhydric carboxylic acid or its acid anhydride, which is a component for making a crosslinked polyester resin. In the present invention, it is necessary that the content of the trivalent or higher polyhydric carboxylic acid or its acid anhydride is 5 mol% or more and less than 30 mol% of the acid component.

If the content of the trivalent or higher polycarboxylic acid or its acid anhydride is less than 5 mol % of the acid component, the offset resistance of the toner will be insufficient and the resulting image will be unclear. On the other hand, if the content is 30 mol % or more of the acid component, the amount of charge of the toner changes greatly depending on the humidity, which increases the environmental dependence of image density and makes it difficult to form a stable image.

In addition, the component (b) contains an aliphatic unsaturated dicarboxylic acid, its acid anhydride, or its derivative as an essential component as a dicarboxylic acid component, thereby ensuring sufficient blocking resistance in the toner. On the other hand, if an aliphatic saturated dicarboxylic acid, its acid anhydride, or its derivative is used instead of the aliphatic unsaturated dicarboxylic acid, its acid anhydride, or its derivative, the resulting polyester resin glass The transition point is considerably lowered, resulting in poor blocking resistance of the toner.

Examples of the aliphatic unsaturated dicarboxylic acid or its acid anhydride or its derivative in component (b) include fumaric acid, maleic acid, citraconic acid, mesaconic acid, itaconic acid, glutaconic acid, acid anhydrides thereof, or acid halogens. compounds, lower alkyl esters of these acids, etc. can be used.

Examples of the trivalent or higher polycarboxylic acid or its acid anhydride in component (b) include 1,2.4-benzenetricarboxylic acid, 1,3.5-benzenetricarboxylic acid, and 1.2.4-cyclohexane. Tricarboxylic acid, 2.5
．． 7-naphthalenetricarboxylic acid, 1゜2.4-naphthalenetricarboxylic acid, 1,3.4-butanetricarboxylic acid, 1.2.5-hexanetricarboxylic acid, 1.3-dicarboxy-2-methyl-2-mer Carboxypropane, 1,3-dicarboxy-2-methyl-2-carboxymethylpropane, tetra(carboxymethyl)methane,
L2,7.8-octane tetracarboxylic acid, embol trimer acid, anhydrides of these acids, etc. can be used. Among these, 1,2,4-benzenetricarboxylic acid can be particularly preferably used.

In the present invention, a specific polyester resin as described above is used as a binder, but a mixture of the polyester resin and other resins can also be used as a binder.

The toner of the present invention contains polyolefin wax as an essential component.

Such a polyolefin wax may be either an unmodified polyolefin wax or a modified polyolefin wax in which a modified component is blocked or grafted to an olefin component.

The olefin component of unmodified polyolefin wax or modified polyolefin wax is either a homopolymer type obtained from a single olefin monomer or a copolymer type obtained by copolymerizing an olefin monomer with other monomers that can be copolymerized with it. There may be.

Examples of the olefin monomer include ethylene, propylene, butene-1, pentene-1, hexene-1,
Heptene-1, Octene-1, Nonene-1, Decene-]
, or these isomers with different positions of unsaturated bonds, as well as 3-methyl-1-butene, 3-methyl-2-
All other olefin monomers including those having a branched chain consisting of an alkyl group such as pentene and 3-propyl-5-methyl-2-hexene can be used.

Other monomers that can be copolymerized with the olefin monomer include, in addition to other olefin monomers, vinyl ethers such as vinyl methyl ether, vinyl-〇-butyl ether, and vinyl phenyl ether; Esters;
Examples Haloolefins such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, vinyl chloride, vinylidene chloride, and tetrachloroethylene; such as methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-
Butyl methacrylate, stearyl methacrylate, N
, N-dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, and other acrylic acid esters or methacrylic acid esters; e.g., acrylonitrile, N,N-dimethylacrylamide, and other acrylic acid derivatives; e.g., acrylic acid, methacrylic acid , maleic acid, fumaric acid, itaconic acid, and other organic acids; diethyl fumarate, β-pinene, and various other organic acids can be used.

When the olefin component is a copolymer type, an olefin copolymer type obtained by copolymerizing at least two or more of the above olefin monomers, such as an ethylene-propylene copolymer or an ethylene-butene copolymer. , copolymer types such as ethylene-pentene copolymer, propylene-butene copolymer, propylene-pentene copolymer, ethylene-3-methyl-1-butene copolymer, ethylene-propylene-butene copolymer, etc. Or an olefin copolymer type obtained by copolymerizing at least one of the above olefin monomers and at least one monomer other than the above olefin monomers, such as ethylene-vinyl acetate copolymer, ethylene-vinyl methyl Ether copolymer, ethylene-vinyl chloride copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-acrylic acid copolymer, propylene-vinyl acetate copolymer, propylene-vinylethyl ether Copolymer, propylene-ethyl acrylate copolymer, propylene-methacrylic acid copolymer, butene-vinyl methyl ether copolymer, butene-methyl methacrylate copolymer, pentene-vinyl acetate copolymer, hexene-vinyl butyrate copolymer, ethylene-propylene-vinyl acetate copolymer, ethylene-
It can be a copolymer type such as vinyl acetate-vinyl methyl ether copolymer.

When making a copolymer type using monomers other than olefin monomers, the ratio of olefin moieties due to olefin monomers in the polyolefin component is 5.
It is preferably 0 mol% or more. If the proportion of the olefin moiety is too small, sufficient mold releasability at low temperatures may not be obtained.

As the modification component in the modified polyolefin wax, aromatic vinyl monomers, α-methylene aliphatic monocarboxylic acid ester monomers, and the like can be preferably used.

Examples of the aromatic vinyl monomer include styrene,
O-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene,
2.4-dimethylstyrene, p-n-butylstyrene,
p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p- Styrene monomers such as phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene can be preferably used.

Examples of the α-methylene aliphatic monocarboxylic acid ester monomer include methyl acrylate, ethyl acrylate, n-methyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, and lauryl acrylate. , 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, methacrylic acid Diethylaminoethyl and the like can be preferably used.

When the above aromatic vinyl monomer is used as a modifying component,
The ratio of the modified component to the modified polyolefin is 0.
It is preferably 1 to 15% by weight, particularly preferably 1 to 10% by weight. In addition, when α-methylene aliphatic monocarboxylic acid ester monomer is used as a modifying component, the ratio of the modifying component to the modified polyolefin is preferably 0.1 to 50% by weight, particularly 1 to 4% by weight.
Preferably, it is 0%.

Further, such unmodified polyolefin wax or modified polyolefin wax itself preferably has a low softening point, for example, JIS K2
Those having a softening point of 80 to 180°C, particularly preferably 90 to 160°C, as measured by the ring and ball method specified in 531-1960.

Examples of commercially available polyolefin waxes include the following, and these can be preferably used.

[Viscol 660PJ (manufactured by Sanyo Chemical Industries, Ltd.)] [Viscol 550PJ (manufactured by Sanyo Chemical Industries, Ltd.) "Polyethylene 6A" (manufactured by Allied Chemical Company) "Hiwax 400PJ (manufactured by Mitsui Petrochemicals Co., Ltd.) [Hiwax 100PJ (manufactured by Mitsui Petrochemicals Co., Ltd.) (manufactured by) “High Wax 2
00PJ (manufactured by Mitsui Petrochemicals) [Hiwax 32
0PJ' (manufactured by Mitsui Petrochemicals) [Hiwax 220'
PJ (manufactured by Mitsui Petrochemicals) [Hiwax 2203
AJ (manufactured by Mitsui Petrochemicals) [Hiwax 420
2 El (manufactured by Mitsui Petrochemical Co., Ltd.) "Hoechstwasox PE520J (manufactured by Hoechst Japan)""Hoechstwasox PE 130J (manufactured by Hoechst Japan)""Hoechstwasox PE 190J (manufactured by Hoechst Japan) In addition to these commercial products, for example, methyl methacrylate Polyethylene waxes block copolymerized or graft copolymerized with butyl methacrylate, polyethylene waxes block copolymerized or graft copolymerized with styrene, etc. can also be used.

The content of the polyolefin wax is preferably 1 to 20% by weight based on the binder.

By setting the ratio within such a preferable range, the function of the polyolefin wax as a mold release agent can be fully exhibited without deteriorating the toner properties.

Further, the toner of the present invention may contain various additives such as a charge control agent, a fluidity improver, and a lubricant, as necessary, in addition to a colorant such as carbon black.

Examples of colorants include carbon black, nigrosine dye (C, TJkt50415B), aniline blue (C, r, 1th50405), calco oil blue (C, 1Naazoic B1ue3), chrome yellow (c, r, 14090), ultra Marine Blue (C, T, l1h77103), DuPont Oil Red (C, 1, 1126105),
Quinoline yellow (C, 1, 47005), methylene blue chloride (c, t, m 52015), phthalocyanine blue (c, t, m 74160), malachite green offsalate (C, 1).

l1h42000), lamp black (C,1,Th
77266), Rose Bengal (C, LI&t4543)
5), mixtures thereof, etc. can be used.

Examples of negatively chargeable charge control agents include JP-A-57-141452 and JP-A-58-76.1.
5, JP 58-111.049, JP 58-185653, JP 57-167033
2:1 type metal-containing azo dyes disclosed in Japanese Patent Publication No. 44-6397, etc.; for example, JP-A-57-104
940, JP 57-111541, JP 57-124357, JP 53-1.277
Metal complexes of aromatic oxycarboxylic acids and aromatic dicarboxylic acids disclosed in Publication No. 26, etc.; for example, JP-A-52
Sulfonylamine derivatives of copper phthalocyanine dyes or sulfonamide derivative dyes of copper phthalocyanine, dyes of sulfonamide and sulfonic acid or sulfonate derivatives of copper phthalocyanine disclosed in Japanese Patent No. 45931, etc. Examples of chargeable compounds include quaternary ammonium compounds disclosed in JP-A-49-51951 and JP-A-52-10141; for example, JP-A-56-11461 and JP-A-Sho No. 54-1.58932, U.S. Patent No. 42
Alkylpyridinium compounds and alkylpicolinium compounds disclosed in No. 54205, etc.; Nigrosine dyes such as Nigrosine SO1 Nigrosine EX;
For example, the I' polycondensate disclosed in Japanese Patent Publication No. 49-80320 can be mentioned.

As the fluidity improver, fine particles of silica, alumina, titania, etc. can be used, and those treated with hydrophobization are particularly preferred. Specifically, those having a hydrophobization rate of 30% or more are preferable, and those having a hydrophobicity of 50% or more are particularly preferable. "Hydrophobization" here refers to crushing the hydroxyl groups bonded to silica, etc., and hydrophobization treatment is performed by adding dialkyldihalogenated silane, trialkylhalogenated silane, alkylhalogenated silane, hexane, etc. to silica, etc. This can be carried out by reacting an alkyldisilazane or the like at high temperature. The average particle size of the fluidity improver is preferably 1 μm or less, particularly preferably 0.5 μm or less.

In addition, it is preferable that the fluidity-promoting agent is used in a state where it is adhered to or implanted on the surface of the toner sheet.
The amount added is preferably 0.01 to 10% by weight, particularly preferably 0.05 to 5% by weight, based on the total amount of l.

As the lubricant, for example, zinc stearate, lithium stearate, sodium stearate, stearic acid, hydrogenated castor oil, etc. can be used. The amount of the lubricant added is preferably 0.01 to 2% by weight based on the total toner.

Further, when forming a magnetic toner, a magnetic substance is contained in the binder together with or in place of the colorant. Such magnetic materials include ferrite, magnetite, iron, cobalt, nickel, and other ferromagnetic metals or alloys, or compounds containing these elements, or materials that do not contain ferromagnetic elements but are subjected to appropriate heat treatment. It is possible to use alloys which exhibit ferromagnetism due to ferromagnetism, such as a type of alloy called a Heusler alloy containing manganese and copper, such as manganese-copper-aluminum, manganese-copper-tin, or chromium dioxide, among others. It is preferable that these magnetic substances are uniformly dispersed in the binder in the form of fine particles having an average particle size of 0.1 to 1 μm. The content of the magnetic material is preferably 20 to 70 parts by weight, particularly preferably 30 to 60 parts by weight, per 100 parts by weight of toner.

Further, the electrostatic image developing agent of the present invention may contain a property improving agent for imparting various properties. As such a property improver, for example, a resin which is an uncrosslinked polymer and does not contain chloroform-insoluble matter can be preferably used. Specifically, for example, styrenes, vinyl esters, methylene aliphatic carboxylic acid esters,
Acrylics, vinyl ethers, vinyl ketone tfi,
Homopolymers or copolymers obtained by polymerizing monomers such as N-vinyl compounds, or mixtures of these homopolymers and copolymers, or rosin-modified phenol-pormarine resins, oil-modified epoxy resins,
Non-vinyl resins such as polyurethane resins, cellulose resins, and polyether resins, or mixtures of these and double vinyl resins can be used. These resins may be contained in a proportion of, for example, 90% by weight or less of the binder, as long as the effects of the present invention are not impaired.

According to the electrostatic image developing toner of the present invention, images can be formed by applying various developing methods. Specifically, for example, a magnetic brush of (a)-component or two-component developer is supported on a developer transporting carrier in a state where the layer thickness is larger than the gap in the developing area, and this magnetic brush is carried into the developing area. (b) -component or two-component development; (b) -component or two-component development; For example, a magnetic brush of the agent is supported on a developer transporting carrier in a state where the layer thickness is smaller than the gap between the developing areas, and this magnetic brush is carried into the developing area, and at the same time, an oscillating electric field or the like is applied to the developing area. Applying a developing method such as the jumping magnetic brush method, (c) cascade method, etc., in which toner particles or particle groups in a magnetic brush are caused to fly and the toner particles or particle groups are attached to the electrostatic latent image for development. Can be done.

[Specific examples]

Specific examples of the present invention will be described below, but the present invention is not limited to these examples.

Manufacture of binder shield (1) Resin A (for the present invention) 0 polyoxypropylene (2,2)-2,2-bis(4
-hydroxyphenyl) propane 490g (1,42 mol)
0 polyoxyethylene (2,0)-2,2-bis(4-
Hydroxyphenyl)propane 193g (0.61 mol)
0 Fumaric acid 202 g (1,74 mol) 0 Diisopropyl orthotitanate (esterification catalyst) 0.8 g The above substances were mixed with a thermometer, a stainless steel stirrer,
Place it in a round bottom flask with a capacity IIl equipped with a glass nitrogen gas inlet tube and a flow-down condenser, set this flask on a mantle heater, and introduce nitrogen gas through the nitrogen gas inlet tube to create an inert atmosphere inside the flask. The temperature was raised to 230° C. while the temperature was maintained at 230° C., and the reaction was carried out under stirring. When the water produced by the reaction stopped flowing out, the acid value was measured and found to be 1.5.

Furthermore, L2,4-benzenetricarboxylic acid anhydride 3
7 g (0.19 mol) was added and reacted for about 8 hours, and the reaction was terminated when the acid value reached 19.

The obtained resin is referred to as "Resin A". This resin A was a pale yellow solid, and the softening point of the resin A was measured with a flow tester CFT-500J (manufactured by Shimadzu Corporation) and was 130°C.

(2) Resin B (for the present invention) 0 polyoxypropylene (2,2) -2,2-bis(
4-hydroxyphenyl) propane 490g (1,42 mol)0
Polyoxyethylene (2,0) -2,2-bis(4-
Hydroxyphenyl)propane 193g (0.61 mol)
0 Mesaconic acid 191 g (1,47 mol) 0 Diisopropyl orthotitanate (esterification catalyst) 0.8 g The above substances were reacted in the same manner as in the production of resin A, and further, 1,2,4-benzenetricarboxylic acid Anhydride 71
g (0.37 mol) was added and reacted, and the reaction was terminated when the acid value reached 20.

The obtained resin is referred to as "Resin B". This resin B was a pale yellow solid, and the softening point of the resin B was measured in the same manner as the resin-containing sample, and was found to be 130°C.

(3) Resin C (for the present invention) 0 polyoxypropylene (2,2)-2,2-bis(4
-hydroxyphenyl) propane 698g (2.03 mol)0
Fumaric acid 176g (1.52 mol)
0 diisopropyl orthotitanate (esterification catalyst) 0.8 g The above substances were reacted in the same manner as in the production of resin A, and further 1.2.4-benzenetricarboxylic acid anhydride 65
g (0.34 mol) and reacted, the acid value was 21
The reaction was terminated when the

The obtained resin is referred to as "Resin C". This resin C was a pale yellow solid, and the softening point of the resin C was measured in the same manner as resin A, and was found to be 134°C.

(4) Resin D (for comparison) 0 polyoxypropylene (2,2)-2,2-bis(4
-Hydroxyphenyl) propane 490g (1,42 mol)0
Polyoxyethylene(2,0)i,2-bis(4-hydroxyphenyl)propane 193g (0.61 mol)
0 Terephthalic acid 103 g (0.62 mol) 0 Diisopropyl orthotitanate (esterification catalyst) 0.8 g The above substances were reacted in the same manner as in the production of resin A, and further 1,2,4-benzenetricarboxylic acid Anhydride of 1.
80 g (0.94 mol) was added and reacted, and the reaction was terminated when the acid value reached 34.

The obtained resin is referred to as "Resin D". This resin was a pale yellow solid, and the softening point of the resin was measured in the same manner as Resin A and found to be 135°C.

Example 1 Resin A (for the present invention) 100 parts by weight Polyolefin wax [Viscol 660PJ (manufactured by Sanyo Chemical Industries, Ltd.) 3 parts by weight Carbon black 10 parts by weight Example 2 Resin A (for the present invention) 100 parts by weight Polyolefin wax "Viscol" 660 PJ(
Sanyo Chemical Industries, Ltd.) 10 parts by weight Carbon black 10 parts by weight Example 3 Resin B (for the present invention) 100 parts by weight Polyolefin wax [Hiwax 400 P J
(manufactured by Mikata Petrochemical Co., Ltd.) 3 parts by weight Carbon blank 10 parts by weight Example 4 Resin C (for the present invention) 100 parts by weight Polyolefin wax [Hiwax 1105AJ (
(manufactured by Mikata Petrochemical Co., Ltd.) 5 parts by weight Carbon blank 10 parts by weight Comparative Example 1 Resin D (for comparison) 100 parts by weight Polyolefin wax "Viscol 660 P j (
Sanyo Chemical Industries, Ltd.) 3 parts by weight Carbon blank 10 parts by weight Comparative Example 2 Resin D (for comparison) 100 parts by weight [Hoechst Wax El (manufactured by Hoechst) 3 parts by weight Carbon black 10 parts by weight Comparative Example 3 Resin A (for comparison) 100 parts by weight of Hoechstwasox Cl (manufactured by Hoechst) 3 parts by weight Carbon blank 10 parts by weight In each of the examples and comparative examples, materials of the indicated formulation were melted, kneaded, cooled, crushed, A toner consisting of particles with an average particle size of 10 μm was obtained by a normal toner manufacturing method involving classification.The toners obtained in Examples 1 to 4 were referred to as "Toner 1" to "Toner 4", respectively, and Comparative Example 1 The toners obtained in steps 3 to 3 are referred to as "comparative toner 1" to "comparative toner 3," respectively.

For each of these toners, the minimum fixing temperature, offset occurrence temperature, winding occurrence temperature, humidity dependence of charge amount,
Initial image density and blocking resistance under low humidity were examined by the following method.

A heated roller whose surface layer is made of Teflon (polytetrafluoroethylene manufactured by DuPont) and a silicone rubber rKE-
1300RTVj (manufactured by Shin-Etsu Chemical Co., Ltd.), an electrophotographic copying machine ``U
- Using the old X5000J (manufactured by Konishiroku Photo Industry Co., Ltd.), the linear velocity of the heat roller was set to 200 mm/sec, and the temperature of the heat roller was initially set to 240°C, and the temperature was 64 g/%.
The toner transferred to the transfer paper was continuously fixed in an environment of 10°C and 20% relative humidity until the temperature of the heat roller dropped to 140°C, and the toner was thoroughly rubbed with Kimwipe. The lowest temperature of the heat roller at which a fixed image exhibiting abrasion resistance was obtained was defined as the lowest fixing temperature. Note that the fixing device used here does not have a silicone oil supply mechanism.

However, a cleaning roller is arranged opposite to the heat roller.

Offset The toner is transferred according to the measurement of the warm temperature minimum fixing temperature, and the fixing process is performed by the above-mentioned fixing device, and then a blank transfer paper is sent to the fixing device under the same conditions to check whether toner stains occur on it. The observation operation was repeated while the temperature of the heat roller of the fixing device was successively lowered, and the lowest temperature of the heat roller when toner staining occurred was taken as the offset generation temperature.

The operation of fixing the surface with toner adhered to it was repeated while the set temperature of the heat roller of the fixing device was successively lowered according to the above measurement of the offset occurrence temperature, and the wrapping phenomenon of the transfer paper occurred. The highest starting temperature was taken as the coiling occurrence temperature.

The amount of charge in a low humidity atmosphere (temperature 10℃, relative humidity 20%) and high humidity atmosphere (temperature 33℃, relative humidity 80%)
%) of the toner was measured by a known blow-off method, and quality was evaluated based on the absolute value of the difference between the two.

The smaller the value, the less humidity dependence, and it can be said that the toner is better.

Incidentally, the frictional charging was performed by leaving the toner in each atmosphere for 3 hours, and then mixing and stirring the toner with the carrier.

Using a modified electrophotographic copying machine r U Bix 5000J (manufactured by Konishiroku Photo Industry Co., Ltd.) at a low temperature, 3.
With a two-component developer prepared by mixing 5 parts by weight of carrier and 96.5 parts by weight of carrier, a solid part with an original density of 1.30 can be developed under low humidity (temperature 10°C, relative 4°C 20%). Ten copy images were formed, and the average value of these image densities was taken as the initial image density.

In this test, a developer was prepared by selecting a carrier such that each toner had the same amount of charge at room temperature and humidity.

A violet-based toner is left for 48 hours under an environmental condition of a temperature of 55°C and a relative humidity of 40%, and a judgment is made based on whether or not agglomerates form in the toner, and if no agglomerates are observed. "○"
The case where some agglomerates were observed was rated as "Δ", and the case where significant agglomerates were observed was rated as "x".

The above results are shown in Table 1.

As understood from the results in Table 1, toners 1 to 4 according to the present invention all have low-temperature fixing properties, offset resistance,
It is excellent in terms of both winding properties, blocking resistance, and environmental dependence of the amount of charge, and can stably form good images at high speed regardless of environmental conditions.

On the other hand, in comparison toners 1 and 2, aromatic dicarboxylic acid was used as the dicarboxylic acid component in forming the resin, and the proportion of trivalent carboxylic acid was excessive, so the minimum fixing temperature was considerably high. Moreover, there is a problem in that the amount of charge is highly dependent on the environment. Furthermore, in Comparative Toner 2, since the wax is not a polyolefin wax, there is a problem in that the temperature at which wrapping occurs is high.

Furthermore, in Comparative Toner 3, since the wax is not a polyolefin wax, there is a problem in that the temperature at which wrapping occurs is high.

Claims (1)

[Claims] 1) A hot roller fixing device characterized by containing a binder made of a polyester resin obtained by condensation polymerization of the following component (a) and the following component (b), and a polyolefin wax. Toner for electrostatic image development. (a) Component A diol component represented by the following general formula (1). General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is an ethylene group or a propylene group,
x and y are integers, and the average value of the sum of both is 2 to 7
It is. ) (b) Component A mixture of an aliphatic unsaturated dicarboxylic acid, its acid anhydride, or its derivative, and a trivalent or higher-valent polyvalent carboxylic acid or its acid anhydride, the said trivalent or higher-valent polyvalent carboxylic acid or the content of the acid anhydride is 5 mol% of the acid component
The mixed acid component is at least 30 mol%.