JPH01161258A - Electrostatic image developing toner - Google Patents

Abstract

PURPOSE:To enable stable image formation by incorporating a toner resin made of a block copolymer or a graft copolymer obtained by chemically combining a crystalline polyester with a specified amorphous vinyl polymer together with a specified alkylene-bis(fatty acid amide) wax. CONSTITUTION:The toner contains the toner resin made of the block copolymer or the graft copolymer obtained by chemically combining the crystalline polyester with the amorphous vinyl polymer having a weight average molecular weight Mw to number average molecular weight Mn ratio Mw/Mn of >=3.5, and one of the alkylene-bis(fatty acid amide) wax represented by formula I in which each of R1 and R2 is an optionally saturated and >=10C aliphatic hydrocarbon group, optionally same or different from each other, and each of R3 and R4 is H or -OCR5, optionally same or different from each other, thus permitting images to be stably formed.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to developing an electrostatic latent image formed on the surface of a latent image carrier in, for example, electrophotography, electrostatic printing, electrostatic recording, etc. This invention relates to toner for developing electrostatic images.

[Technology background]

For example, in electrophotography, an electrostatic latent image is usually formed on an electrostatic latent image carrier made of a photoconductive photoreceptor by charging and exposure, and then this electrostatic latent image is transferred using toner, which is a colored particle. After development, the resulting toner image is usually transferred to a recording material such as paper and then fixed to form a visible image.

Conventional methods for fixing toner images include a method in which the toner is heated and melted in a non-contact state using a heater;
Methods of fixing the toner by dissolving the toner with an organic solvent, methods of fixing the toner by pressurizing the toner, and so-called heated roller fixing methods of directly contacting the toner with a heating roller and melting and pressing the toner to fix it are known. A heated roller fixing method is preferred from the viewpoint of high thermal efficiency and high-speed fixing.

However, in recent years, efforts have been made to (a) suppress deterioration of copying machines due to overheating, and (b) shorten the warm-up time required for the heating roller to rise to a temperature capable of fixing after the heating roller fixing device is activated. (c) To reduce the temperature drop of the heating roller due to heat absorption by recording materials such as paper, making it possible to form stable images many times in a row; and (d) to improve copying machine performance. From the viewpoint of downsizing and improving safety, there is a strong demand for reducing power consumption of a heater incorporated in a fixing device to enable fixing processing at a lower temperature of a heating roller.

Therefore, toners are required to (1) be capable of achieving good fixing at lower temperatures, that is, have excellent low-temperature fixing properties, and basically meet the following conditions: is necessary.

(2) In the heating roller fixing method, which is preferable as a fixing method, there is an offset phenomenon, that is, a part of the toner forming the image is transferred to the surface of the heating roller during fixing, and this is transferred again to the recording material that is sent next. Since the phenomenon of smearing an image is likely to occur, toner should be provided with performance that prevents transfer to a heating roller, that is, hot offset resistance.

(3) When the fixing temperature is low, toner with poor fixing transfers to the surface of the heating roller, which tends to cause wrapping of the recording material (paper jam). To provide performance that prevents the occurrence of transfer, that is, under-offset resistance.

(4) It should be able to exist stably as a powder without agglomerating under the environmental conditions of use or storage, that is, it should have excellent storage stability.

(5) In order to obtain good developability, the powder should have excellent fluidity.

[Conventional technology]

Conventionally, however, the following techniques have been proposed.

■Technology to use a resin made by chemically bonding a crystalline part with a melting point Tm of 45 to 150°C and a non-quality part with a glass transition point Tg of 0°C or less as a resin for toner (Japanese Patent Laid-Open No.
(Refer to Publication No.-87032).

■As a toner resin, a crystalline portion with a melting point Tm of 45 to 90°C is chemically combined with a non-quality portion having a glass transition point Tg that is 10°C higher than the melting point Tm of the crystalline portion. Technology using resin (Unexamined Japanese Patent Publication No. 59-34
(See Publication No. 46).

■Technology using a graft polymer of a crystalline polymer obtained from ethylene, propylene, and vinyl acetate and a vinyl polymer as a resin for toner (Japanese Patent Laid-Open No. 56-154740)
(see publication).

(2) A technique using a graft polymer of a crystalline polymer obtained from ethylene, propylene, and vinyl acetate, an unsaturated polyester, and a vinyl polymer as a toner resin (see Japanese Patent Laid-Open No. 8549/1983).

■ As a toner resin, a block copolymer or graft copolymer of a hard component and a soft component, a non-grade resin with a glass transition point Tg of 50°C or higher and compatible with the hard component, and a melting point Tm Technology using a mixture of the hard component and an incompatible crystalline resin at 60°C or higher
(See Publication No. 32447).

■As a resin for toner, a kraft copolymer obtained by graft polymerizing a vinyl polymer to a crystalline polymer obtained from ethylene, propylene, and vinyl acetate, and a monomer common to the monomer of the kraft copolymer are used. A technique using a mixture of a crosslinked polymer obtained by copolymerizing a vinyl monomer containing a majority of divinyl monomers and a divinyl monomer (JP-A-60-2
(See Publication No. 63953).

■As a resin for toner, the surface tension rS of one of the polymers constituting the main chain and the polymer constituting the side chains is 3.
4 or more and the surface tension γ5 of the other polymer is less than 34 (Japanese Unexamined Patent Publication No. 59-135
(See Publication No. 478).

(2) A technique in which a styrene resin is used as a toner resin and an alkylene bis fatty acid amide wax is added thereto (see JP-A-49-107743).

[Problem that the invention seeks to solve]

However, in the above technologies (1) to (2), all aspects of (1) low temperature fixability, (2) hot offset resistance, (3) underoffset resistance, (4) storage stability, and (5) fluidity are It is still difficult to obtain a fully satisfactory toner.

In other words, the above technology (1) has poor storage stability even at room temperature due to the high tackiness of the toner resin, is prone to offset phenomenon during fixing, and has poor flowability and poor developability. As a result, the image quality becomes poor.

In the above technique (2), since the toner resin is soft, it has poor fluidity and developability, and hot offset phenomenon is likely to occur during fixing, resulting in poor image quality.

In the above techniques (1), (2), and (2), the developability is poor due to poor fluidity, resulting in poor image quality.

Since the above-mentioned technique (1) uses toner for pressure fixing, there is a serious problem in that hot offset phenomenon t-1 occurs in the hot roller fixing method.

In the above technique (2), the mold releasability at low temperatures is poor, so-called under-offset resistance is poor, and it is difficult to obtain a stable image over a long period of time.

In the above technique (2), the hot offset resistance is good, but the low temperature fixing property is poor.

The present invention has been made based on the above circumstances, and includes (1) low temperature fixing properties, (2) hot offset resistance, (3) under-offset resistance, (4) storage stability, (5)
) It provides a toner that is fully satisfactory in all aspects of fluidity.

[Means for solving problems]

The electrostatic image developing toner of the present invention comprises a crystalline polyester and a ratio Mw of a weight average molecular weight Mw to a number average molecular weight Mn.
A toner resin comprising a block copolymer or a graft copolymer formed by chemically bonding an amorphous vinyl polymer having a /Mn value of 3.5 or more, and a toner resin represented by the following general formula (1). It is characterized by containing an alkylene bis fatty acid amide wax.

- and - General formula (1) [In the formula, R1 and R2 each represent a saturated or unsaturated aliphatic hydrocarbon group having 10 or more carbon atoms, which are the same or different from each other, and R3 and R4 are each the same or different from each other. Represents a different hydrogen atom or one CR5 group (wherein R5 represents a saturated or unsaturated aliphatic hydrocarbon group),
n represents a positive integer. [Operations and Effects of the Invention] According to the toner for electrostatic image development of the present invention, a block copolymer or a graft copolymer formed by chemically bonding a crystalline polyester and a specific amorphous vinyl polymer. Since it contains the alkylene bis fatty acid amide wax represented by the general formula [1] together with the toner resin, (1) low temperature fixing properties, (2) hot offset resistance,
(3) Under-offset resistance, (4) storage stability, (5)
Excellent effects are exhibited in all aspects of fluidity.

That is, under non-heating conditions, the value of the ratio Mw/Mn is 3.
．． The tough properties of the amorphous vinyl polymer with a polyester of 5 or more are exhibited, and the hard properties of the alkylene bis fatty acid amide wax are synergized, and the development of stickiness of the crystalline polyester is significantly suppressed, resulting in a long shelf life. It has the effect of improving properties and fluidity.

Under heating during heat fixing, the appropriate viscoelasticity of the specific amorphous vinyl polymer improves offset resistance, and the crystalline polyester has good low-temperature melting properties and recording properties such as paper. Excellent low-temperature fixing properties are exhibited due to good permeability into materials. In addition, the presence of alkylene bis fatty acid amide wax exhibits good mold releasability at high temperatures, suppressing toner transfer to heating rollers, etc., and as a result, exhibiting excellent hot offset resistance. Ru.

Because the toner exhibits excellent low-temperature fixing properties,
When applying the heat roller fixing method, the set temperature of the heat roller can be lowered than before, which not only improves the durability of the heat roller, but also enables rapid image formation by shortening warm-up time. It becomes possible.

Also, when forming images on both sides of the recording material, curling and
Images can be stably formed without causing wrinkles or the like.

[Specific structure of the invention]

In the present invention, a block copolymer is formed by chemically bonding a crystalline polyester and an amorphous vinyl polymer having a ratio Mw/Mn of a weight average molecule iMw to a number average molecular weight Mn of 3.5 or more. Alternatively, a toner for electrostatic image development is constituted by using an alkylene bis fatty acid amide wax represented by the general formula (1) as an essential component together with a toner resin made of a graft copolymer.

The toner of the present invention can be applied to either a one-component developer that does not contain a carrier or a two-component developer that contains a carrier.

The amorphous vinyl polymer needs to have a functional group to form a block copolymer or graft copolymer with the crystalline polyester. Such a functional group is
For example, preferred examples include carboxyl group, hydroxyl group, amino group, and epoxy group.

Examples of monomers having such functional groups include acrylic acid, β, β-dimethylacrylic acid, α-ethyl acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid, crotonic acid, hydroquine ethyl methacrylate, Examples include succinic acid monoacryloyloxyethyl ester, N-hydroxyethyl acrylamide, N-methylolacrylamide, p-aminostyrene, and glycidyl methacrylate. A monomer having such a functional group is used in a monomer composition for obtaining an amorphous vinyl polymer in a proportion of 0.1 to 20 mol%, preferably 0.5 to 10 mol%. It is preferable that

The amorphous vinyl polymer is particularly preferably an ionically crosslinked amorphous vinyl polymer having a structure crosslinked by ionic bonds. In other words, by having ionic cross-linking, even better low-temperature fixing properties, hot offset resistance,
Excellent storage stability and impact resistance. Examples of the vinyl polymer as a backbone for forming an ionic crosslinked structure include polystyrene, polymethyl methacrylate, polymethyl acrylate, polyvinyl chloride, polyvinyl acetate, polyacrylonitrile, and others. Among these, a vinyl polymer obtained using at least one selected from styrene monomers, acrylic acid monomers, and methacrylic acid monomers as an essential component is preferred. In particular, it is preferable that a polyvalent metal compound reacts with the carboxyl group of the vinyl polymer having a carboxyl group to form an ionic crosslink. In order to obtain such a vinyl polymer having a carboxyl group, polymerization may be carried out using, in addition to the above-mentioned monomers, a monomer selected from acrylic acid or methacrylic acid and derivatives thereof as an essential component.

For example, a half-ester compound having a structure obtained by an esterification reaction between an acrylic ester or methacrylic ester having a hydroxyl group, or a derivative thereof, and a dicarboxylic acid compound can be mentioned as a preferable compound. According to such a half-ester compound, a carboxyl group is introduced at a position that has little effect on the main chain structure, so
The steric hindrance of the chemical structure is reduced, and as a result, the reaction between the carboxyl group and the polyvalent metal compound proceeds efficiently to form ionic crosslinks, making it possible to obtain an ionic crosslinked amorphous vinyl polymer with a good crosslinked structure. can.

Examples of the styrenic monomer for obtaining the vinyl polymer include styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene,
p-ethylstyrene, 2゜3-dimethylstyrene, 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-phenyl styrene, p
-chlorstyrene, 3,4-dichlorostyrene, and the like. These monomers may be used alone or in combination.

Examples of the acrylic ester or methacrylic ester for obtaining the vinyl polymer include methyl acrylate, ethyl acrylate, ptinopacrylate, isobutyl acrylate, propyl acrylate, octyl acrylate, dodecyl acrylate, and acrylic acid. lauryl, 2-ethylhexyl acrylate, stearyl acrylate,
2-chloroethyl acrylate, phenyl acrylate,
Acrylic acid esters such as methyl α-chloroacrylate; for example, methyl methacrylate, etinope methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, octyl methacrylate, dodenyl methacrylate, lauryl methacrylate, -2 methacrylate - Methacrylic acid esters such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate; and the like.

Examples of the compound having a carboxyl group forming the half-ester compound include aliphatic dicarboxylic acid compounds such as malonic acid, succinic acid, and glutaric acid, and aromatic dicarboxylic acid compounds such as phthalic acid.

A half-ester compound can be obtained by subjecting these compounds to an esterification reaction with an acrylic ester or methacrylic ester having a hydroxyl group, or a derivative thereof. The dicarboxylic acid compound may have a hydrogen atom substituted with a halogen group element, a lower alkyl group, an alkoxy group, or the like, or may be an acid anhydride. The derivative of acrylic acid or methacrylic acid having a hydroxyl group may be one in which 1 or 2 moles or more of alkylene oxide such as ethylene oxide or propylene oxide is added to acrylic acid or methacrylic acid, or acrylic acid or methacrylic acid. It may also be a hydroxyl 16-alkyl ester obtained by subjecting a dihydric alcohol such as propylene glycol to an esterification reaction.

Preferred half-ester compounds include, for example, succinic acid monoacryloyloxyethyl ester, succinic acid monoacryloyloxypropyl ester, glutaric acid monoacryloyloxyethyl ester, phthalic acid monoacryloyloxyethyl ester, phthalic acid monoacryloyloxypropyl ester, Examples include succinic acid monomethacryloyloxyethyl ester, succinic acid monomethacryloyloxypropyl ester, glutaric acid monomethacryloyloxyethyl ester, phthalic acid monomethacryloyloxyethyl ester, phthalic acid monomethacryloyloxypropyl ester, etc. .

The metal element of the polyvalent metal compound to be reacted with the carboxyl group of the vinyl polymer having a carboxyl group is as follows:
For example, Cu, Ag, Be, Mg, Ca, Sr
.

Ba, Zn, Cd, AI, Ti, Ge, S
n, V, Cr, Mo, Mn.

Examples include Fe, Ni, Co, Zr, and Se.

Among these, alkaline earth metals (Be, Mg, C
a.

Sr, Ba) and zinc group elements (Zn, Cd) are preferred, with Mg and Zn being particularly preferred.

Examples of polyvalent metal compounds containing these metals include:
Fluorides, chlorides, chlorates, bromides, iodides, oxides, hydroxides, sulfides, sulfites, sulfates, selenides, tellurides, nitrides, nitrates, phosphides of the above metal elements, Examples include phosphinates, phosphates, carbonates, orthosilicates, acetates, phosphates, and lower alkyl metal compounds such as methyl compounds or ethyl compounds. Among these, acetates of the above metal elements and oxides of the above metal elements are particularly preferred.

The amount of the polyvalent metal compound added cannot be specified as it varies depending on the type and amount of monomers constituting the vinyl polymer having carboxyl groups, but for example, it is On the other hand, it is about 0.1 to 1 mol.

In order to react a polyvalent metal compound with the carboxyl group of a vinyl polymer having a carboxyl group, for example, the polyvalent metal is added to a solution containing a vinyl polymer having a carboxyl group obtained by polymerization by a solution polymerization method. The compound or the dispersion solution of the polyvalent metal compound is mixed, the temperature is raised, and the solvent is removed for about 1 to 3 hours, and the temperature in the reaction system is about 150 to 180°C, and this is carried out for more than 1 hour. It is best to maintain the temperature to complete the reaction. In some cases, a polyvalent metal compound may be present in the reaction system together with a solvent before starting the polymerization of the vinyl polymer having carboxyl groups, or the carboxyl groups obtained by the above-mentioned solvent removal treatment may be The vinyl polymer and the polyvalent metal compound may be melt-kneaded using a roll mill, kneader, extruder, etc. to react with each other.

The ionically crosslinked amorphous vinyl polymer obtained by reacting the sulvinyl polymer having carboxyl groups with the polyvalent metal compound in this way is produced by the reaction between the carboxyl groups of the vinyl polymer having carboxyl groups and the polyvalent metal atom. They are bonded by ionic bonds, and a kind of crosslinked structure is formed by these ionic bonds. This ionic bond is a much looser bond than a covalent bond.

Further, from the viewpoint of further improving low-temperature fixing properties and anti-offset properties, it is preferable that the amorphous vinyl polymer has at least two maximum values in its molecular weight distribution. Specifically, it has a molecular weight distribution that can be divided into at least two groups: a low molecular weight component with a small maximum molecular weight value and a high molecular weight component with a large maximum molecular weight value, and is measured by gel permeation chromatography (CPC). In the molecular weight distribution curve, at least one maximum value is 2
．． 000 to 20.0 (l [1), with at least one maximum value of 100.000 to 1.000.0
It is preferable to have at least two maximum values within a range of approximately 0.00. In addition, since the amorphous vinyl polymer can be made even stronger by the above-mentioned high molecular weight component, it has a great effect of suppressing toner particle destruction due to friction with the carrier or collision with the latent image carrier.
As a result, generation of fine powder that causes the filming phenomenon is suppressed. The proportion of the high molecular weight component is preferably at least 15=20% by weight of the amorphous vinyl polymer, particularly preferably from 15 to 50% by weight.

When the amorphous vinyl polymer is an ionically crosslinked amorphous vinyl polymer and is composed of a high molecular weight component and a low molecular weight component as described above, the carboxyl group that reacts with the polyvalent metal compound has at least a low molecular weight component. Preferably, it is incorporated into the ingredients.

In other words, the destruction of toner particles caused by friction with the carrier or collision with the surface of the latent image carrier is mainly caused by low molecular weight and relatively brittle components in the toner particles. By cross-linking the toner particles with the polyvalent metal compound described below through so-called ionic bonds to make them strong, it is possible to effectively prevent the generation of fine powder that causes the filming phenomenon caused by the destruction of toner particles.

In addition, in the amorphous vinyl polymer, the weight average molecular weight M
The value of the ratio Mw /Mn of νJ and number average molecular weight Mn is 3.5
It is necessary that it is above, and 4 to 40 is particularly preferable. When the ratio Mw/Mn is too small, sufficient offset resistance and durability cannot be obtained. Means for making the value of the ratio Mw/Mn 3.5 or more include (1) means for having two or more maximum values in the molecular weight distribution;
) A possible method is to broaden the molecular weight distribution by adding a crosslinking agent or a molecular weight regulator, but the former method (1) is preferable from the viewpoint of improving the pulverizability in the toner pulverization step. Here, the values of the weight average molecular weight Mw and the number average molecular weight Mn can be determined by various methods, and there are slight differences depending on the measurement method, but in the present invention, the values determined by the following measurement method are used. It is.

The weight average molecular weight MIl+, number average molecular weight Mn, and peak molecular weight are measured by Sunawachi gel permeation chromatography (GPC) under the conditions described below. At a temperature of 40°C, the solvent (tetrahydrofuran) was flowed at a flow rate of 1.2+d per minute, and the concentration was 0.2 g.
/20m of tetrahydrofuran sample solution is injected with a sample weight of 3 mg and measured. When measuring the molecular weight of a sample, select measurement conditions in which the molecular weight of the sample falls within a range where the logarithm of the molecular weight and the count number of the calibration curve prepared using several types of monodispersed polystyrene standard samples are linear. . The reliability of the measurement results is based on the NB5706 polystyrene standard sample measured under the above measurement conditions (weight average molecular weight 1vh = '28.8X10', number average molecular weight Mn-13,7X10', Mw /Mn = 2.
11), the ratio Mw/Mn is 2.11±0.10 (more certain δ).

Moreover, any column may be used as the GPC column as long as it satisfies the above conditions. Specifically, for example, TSK-GEL, GMH (manufactured by Toyo Soda Co., Ltd.), etc. can be used. Note that the solvent and measurement temperature are not limited to the above conditions, and may be changed to appropriate conditions.

As the amorphous vinyl polymer, one having at least two maximum values in the molecular weight distribution curve can be preferably used as described above, but the method for obtaining such a vinyl polymer is not particularly limited. For example, a first stage polymerization is performed to obtain either a high molecular weight component with a large maximum molecular weight value or a low molecular weight component with a small maximum molecular weight value, and one component obtained thereby is used to obtain the other component. The second stage polymerization is performed by dissolving the other component in the monomer composition of
Polymers with two local maxima can be obtained. It is presumed that the polymer obtained by the two-stage polymerization is a mixture of a low molecular weight component and a high molecular weight component uniformly at the molecular level. This two-stage polymerization is, for example, a solution polymerization method,
This can be carried out by methods such as suspension polymerization and emulsion polymerization, but solution polymerization is particularly preferred.

Furthermore, a polymer having at least two maximum values in the molecular weight distribution curve can also be obtained by mixing a low molecular weight polymer component with a small maximum molecular weight value and a high molecular weight polymer component with a large maximum molecular weight value. However, since the polymer obtained by mixing may not be uniformly mixed at the molecular level, it is preferable to use the two-stage polymerization described above.

In addition, from the viewpoint of further improving low-temperature fixability, offset resistance, and durability, the glass transition point Tg of the amorphous vinyl polymer is preferably 50 to 100°C, particularly 50 to 85°C.
°C is preferred. Here, the glass transition point Tg is a value measured based on differential scanning calorimetry (DSC). When measured at 10° C./min, it refers to the temperature at the intersection of the extension line of the baseline below the glass transition point and the tangent line showing the maximum slope from the rising part of the peak to the top of the peak.

The crystalline polyester that forms a block copolymer or graft copolymer with the above amorphous vinyl polymer has a crystal structure in at least a part of the polyester, and at least one part of the polyester has a crystal structure in the homopolymer or copolymer. It includes those whose components are crystalline, that is, partially crystallized, and exhibits a sharp and clear melting point, and when in a solid state at a temperature below the melting point, it becomes cloudy due to the crystallized portion.

As such crystalline polyester, polyalkylene polyester is particularly preferred from the viewpoint of low-temperature fixability and fluidity. Specifically, for example, polyethylene sebacate, polyethylene adipate, polyethylene adipate, polyethylene succinate, polyethylene p-(carbophenoxy) undecaate, polyhexamethylene sebacate.
Polyhexamethylene sebacate, polyhexamethylene decanedioate, polyoctamethylene dodecanedioate, polynonamethylene azelate, polydecamethylene adipate, polydecamethylene azelate, polydecamethylene adipate, poly Decamethylene sebacate, polydecamethylene succinate, polydecamethylene dodecanedioate, polydecamethylene octadecanedioate, polytetramethylene sebacate, polytrimethylene dodecanedioate, polytrimethylene octadecanedioate, polydecamethylene azelate , polyhexamethylene-decamethylene-sebacate, polyoxydecamethylene-2-methyl-1,3-propane-dodecanedioate, and the like.

The melting point Tm of the crystalline polyester is preferably 50 to 120°C, particularly 50 to 100°C. When the melting point Tm is too low, storage stability tends to deteriorate, and when the melting point Tm is too high, low-temperature fixability tends to deteriorate. Note that the melting point Tm of this crystalline polyester was measured in a state where it was not bonded to an amorphous vinyl polymer. Here, the melting point T
m is the sample 10 according to differential scanning calorimetry (DSC).
It refers to the melting peak value when heating mg at a constant temperature increase rate (10° C./m1n).

In addition, the crystalline polyester has a weight average molecular weight Mw of 5.000 to 50.000, a number average molecular weight Mn
is preferably 2.000 to 20.000.

The proportion of crystalline polyester in the block copolymer or graft copolymer is 3250% by weight.
, particularly preferably 5 to 40% by weight. When the proportion of crystalline polyester is too small, low-temperature fixing properties tend to deteriorate, while when it is too large, anti-offset properties tend to deteriorate.

It is preferable that the crystalline polyester and the amorphous vinyl polymer are substantially incompatible. Note that “substantially incompatible” means
It refers to the fact that the crystalline polyester and the amorphous vinyl polymer are not sufficiently dispersed, and specifically, for example, S, P, values (R, F, Fedors, P) by the Fedors method.
o1y+y+, Eng, Sci,, 14. (
2>147 (1974)] is greater than 0.5.

In order to obtain a block copolymer or a graft copolymer formed by chemically bonding a crystalline polyester and an amorphous vinyl polymer, for example, a head-to-tail coupling reaction between terminal functional groups is performed. They can be bonded directly to each other or via a terminal functional group and a bifunctional coupling agent. For example, a urethane bond formed by a reaction between a polymer whose terminal group is a hydroxyl group and a diisocyanate, a reaction between a polymer whose terminal group is a hydroxyl group and a dicarboxylic acid, or a reaction between a polymer whose terminal group is a carboxyl group and a glycol. The bond can be formed by an ester bond formed by ester bond, or another bond formed by reaction of a polymer whose terminal group is a hydroxyl group with phosgene or dichlorodimethylsilane.

Such camping agents include, for example, difunctional isocyanates such as hexamethylene diisocyanate, diphenylmethane diisocyanate, toridine diisocyanate, toridine diisocyanate, naphthylene diisocyanate, inphorone diisocyanate, xylylene diisocyanate; for example, ethylenediamine, hexamethylenediamine, phenylenediamine, etc. difunctional amine;
For example, sulfuric acid, succinic acid, adipic acid, sebacic acid,
Difunctional carboxylic acids such as terephthalic acid and isophthalic acid;
For example, ethylene glycol, propylene glycol, butanediol, bentanediol, hexanediol,
Difunctional alcohols such as cyclohexane dimanope p-xylylene glycol; difunctional acid chlorides such as terefucuric acid chloride, isophthalic acid chloride, adipic acid chloride, sebacic acid chloride; e.g. diisothiocyanate, bisketene, Other bifunctional coupling agents such as biscarbodiimide can be mentioned.

The amount of the camping agent is 1 to 10% by weight, especially 2 to 7% by weight, based on the total amount of crystalline polyester and amorphous vinyl polymer.
Preferably, it is used in proportions of % by weight. When the proportion of the coupling agent is too large, the softening point of the resulting block copolymer or graft copolymer becomes too high, resulting in poor low-temperature fixing properties, and on the other hand, when the proportion is too small, anti-offset properties tend to deteriorate.

In the present invention, the above-mentioned specific block copolymers or graft copolymers are used as toner resins, but other resins may be used in combination as necessary. However, it is preferable that the proportion of the block copolymer or graft copolymer in the toner is 30% by weight or more.

In the present invention, an alkylene bis fatty acid amide wax represented by the general formula (1) is used together with the above toner resin.

Representative examples of the alkylene bis fatty acid amide wax represented by the general formula (1) include those represented by the following structural formula.

1, C, oH2, C0-NH-(CL)S-NH-
OCC, oH2゜2, C,, H23CO-NH-(
CH2)4-NH-OCC,, N233, C13H
27[:ONH(CH2)2 NHOCC+3L74
, C,oH2,CD-NH-(CII2)3-NH
-OCC,,H2゜5, C,5H3,CD-N11
-(CH2)2-NH-OCC, NH3゜6, C1
7H35CONHC)12 NH0CCISH317
,C1J3sCONH(CH2)2NH0CCIS
H318, C23H<tcONHC)12NH0C
CI5831113UU
0CCH312, C2, H4, CD-N11-CL-
NL-OCC, H2゜14, C11H3SCO-N
H-(C)12)2-NH-OCC,,H,,15,C
17H35CO\N CR2NHOCC+J3s/C,,)135CO Examples of commercially available alkylene bis fatty acid amide waxes represented by the general formula (1) include the following.

"Bisamide" (manufactured by Nippon Hydrogen Industry Co., Ltd.) "Plastflow" (manufactured by Nitto Kagaku Co., Ltd.) "Diamid 200 Bis"
(manufactured by Nippon Hydrogen Industries Co., Ltd.) "Luburon El (manufactured by Nippon Hydrogen Industries Co., Ltd.)""Alflo H3O5J (manufactured by Nippon Oil & Fats Corporation)"
[Alflow V-60J (manufactured by NOF Corporation)-, jL
! , - "Amide-6L" (manufactured by Yoken Fine Chemical Co., Ltd.) "
Amide-78” (manufactured by Yoken Fine Chemical Co., Ltd.) “Amide-6H” (manufactured by Yoken Fine Chemical Co., Ltd.) “Armor Wax EBSJ (manufactured by Lion Armor Co., Ltd.) “Hoechst Wax Cl (manufactured by Hoechst Japan Co., Ltd.)
“Nobukowax-22DSJ (manufactured by Nobuko Chemical Co., Ltd.) [Adubawax-280J (manufactured by Advance Co., Ltd.) [
Kaohwax-EBJ (manufactured by Kao Soap Co., Ltd.) [Harin-285J (manufactured by Heker Star Oil Co., Ltd.) The above-mentioned alkylene bis fatty acid amide wax generally has a melting point that increases as the number of carbon atoms in the aliphatic hydrocarbon group and the length of the alkylene chain increase. Although the melting point is high, from the viewpoint of reducing the heating temperature or fixing temperature during toner production, the melting point is 100 to 180°C, preferably 130 to 160°C.
Those having a melting point of °C are desirable. For this reason, the alkylene chain preferably has a length such that the number of carbon atoms is 5 or less. Further, from the viewpoint of preventing agglomeration in the toner and further lowering the fixing temperature, it is preferable that the melting point is within the range of 100 to 160°C.

The content of the alkylene bis fatty acid amide wax represented by the general formula (1) is preferably 1 to 20 parts by weight based on 100 parts by weight of the toner resin.When the proportion of the wax is too small, the hot offset resistance and storage In addition, when the amount is too large, poor dispersion of carbon black and the like occurs, leading to a decrease in the degree of blackening of the toner and a decrease in the amount of charge.

The toner of the present invention may contain various additives as necessary. Examples of such additives include colorants, charge control agents, and the like.

Examples of colorants include carbon black, nigrosine dye, aniline blue, calco oil blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene flu chloride, fucrocyanine blue, malachite green offsalate,
Mention may be made of lamp black, rose bengal, mixtures thereof, and others.

Examples of the charge control agent include metal complex dyes, nigrosine dyes, and ammonium compounds.

Further, the toner of the present invention may further contain inorganic fine particles as a fluidity improver or abrasive. The average diameter of secondary particles (particles separated into individual unit particles) of such inorganic fine particles is preferably 5 Mμ to 2 μm, particularly preferably 5 mμ to 500 mμ. Also, BET
The specific surface area determined by the method is preferably 20 to 500 m2/g.

The addition ratio of inorganic fine particles to the toner is 0.01 to 5.
It is preferably 0.01 to 2.0% by weight, particularly preferably 0.01 to 2.0% by weight.

Specific examples of inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, and oxide. Examples include chromium, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Particularly preferred is silica fine powder.

This fine silica powder is a fine powder having a 5i-0-3i bond, and includes those produced by a dry method or a wet method. In addition to anhydrous silicon dioxide, aluminum silicate, sodium silicate, potassium silicate, magnesium silicate, zinc silicate, etc. may be used, but those containing 5iO7 in an amount of 85% by weight or more are preferable. As specific examples of fine silica powder, those having a hydrophobic group on the surface are preferable, such as "Aerosil R-972", "Aerosil R-972", "Aerosil R-972", "Aerosil R
-974", "Aerosil R-805J, "Aerosil R-812J (El top, manufactured by Nippon Aerosil Co., Ltd.),"
Commercially available products such as Talanox 500J (manufactured by Talco) can be preferably used. In addition to these, it is also possible to use fine silica powder whose surface has been treated with a silane coupling agent, a titanium coupling agent, silicone oil, a silicone oil having an amine in its side chain, or the like.

Further, a cleaning property improving agent may be further added to the toner of the present invention. Examples of such cleaning property improvers include zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, and polymer particles such as methyl methacrylate particles and styrene particles.

Further, when obtaining a magnetic toner, fine particles of a magnetic substance are contained in the toner particles. Such magnetic materials include iron,
Metals or alloys that exhibit ferromagnetism, such as iron, nickel, and cobalt, including ferrite and magnetite, or compounds that contain these elements, and compounds that do not contain ferromagnetic elements but become ferromagnetic through appropriate heat treatment. Mention may be made of alloys of the type called Heusler alloys containing manganese and copper, such as evamanganese-copper-aluminum, manganese-copper-tin, chromium dioxide, and the like. The magnetic material is preferably contained in the form of a fine powder having an average particle size of 0.1 to 1 μm and uniformly dispersed. The content of the magnetic material is preferably 10 to 70% by weight, particularly preferably 20 to 50% by weight of the toner.

The toner according to the present invention can be manufactured, for example, as follows. That is, the toner resin described above, the alkylene bis fatty acid amide wax represented by the general formula (1), or other additives added as necessary are melt-kneaded using, for example, an extruder, and then cooled. After that, it is finely pulverized using a jet mill or the like, and then classified to produce a toner having a predetermined particle size. Alternatively, a toner having a predetermined particle size is produced by melting and kneading the toner using an extruder and then spraying it in a molten state using a spray dryer or dispersing it in a liquid.

In the case of using a two-component developer, the developer is basically formed by mixing the toner according to the present invention and a carrier. Such a carrier is not particularly limited, and conventionally known carriers can be used. Specifically, there are uncoated carriers made of only magnetic particles, resin-coated carriers in which the surfaces of magnetic particles are coated with resin, and magnetic material-dispersed carriers in which magnetic particles are dispersed in resin particles. A carrier etc. can be used. The average particle size of the carrier is preferably 20 to 200 μm, particularly 30 to 200 μm.
150 μm is preferred. Here, the average particle size of the carrier (
Weight) is a value measured using "Microtrack" (manufactured by Nikkiso Co., Ltd.).

According to the toner of the present invention, an image can be formed, for example, in the following manner. That is, in electrophotography, an electrostatic latent image formed on a latent image carrier is developed with an electrostatic image developer, and the resulting unfixed toner image is transferred to a recording material such as paper using an electrostatic charge. The transferred toner is then fixed by a heated roller fixing method to form a fixed toner image.

A heating roller fixing device used in the heating roller fixing method is usually composed of a heating roller, a pressure roller disposed in opposition to the heating roller, and a heat source. Further, a cleaning roller is arranged opposite to the heating roller as necessary. Heated by a heating source -39 ~ While maintaining the temperature of the roller within a certain range, the recording material with the toner transferred is passed between the heating roller and the pressure roller, so that the toner is brought into direct contact with the heating roller. The toner is then thermally fixed onto the recording material. Note that the material for the surface of the heating roller is preferably a fluorine-based substance or a silicone-based substance, and the synergistic effect with the toner of the present invention can significantly improve the durability of the heating roller fixing device.

〔Example〕

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

<Manufacture of crystalline polyester> (1) Crystalline polyester 1, sebacic acid 1500g, hexamethylene glycol 9
64 g of nitrogen were placed in a 5β round bottom flask equipped with a thermometer, a stainless steel stirrer, a glass nitrogen inlet tube and a down-flow condenser, then the flask was placed on a heating mantle and 4 U of glass nitrogen was added. Nitrogen gas was introduced from the inlet tube to raise the temperature while maintaining an inert atmosphere inside the reactor.

Then, 132 g of p-)luenesulfonic acid was added to react at a temperature of 150°C. When the amount of distilled water reached 250 ml, the reaction was stopped and the reaction system was cooled to room temperature to produce crystalline polyester 1 made of polyhexamethylene sepacate having a hydroxyl group at the end of the molecule.

This crystalline polyester 1 has a melting point Tm of 64°C and a weight average molecular weight Mv+ of 14.000.

(2) Crystalline polyester 2 Same as crystalline polyester 1, melting point Tm is 77°C
A crystalline polyester 2 made of polydecamethylene adipate having a weight average molecular weight Mw of 8.370 was produced.

<Production of amorphous vinyl polymer> (1) Amorphous vinyl polymer 1 100 parts by weight of toluene was placed in a separable flask with a capacity of 1β, and 75 parts by weight of styrene and 75 parts by weight of styrene were added therein as monomers for high molecular weight components. , 25 parts by weight of n-butyl acrylate and 0.2 parts by weight of benzoyl peroxide were added and dispersed, and the gas phase in the flask was replaced with nitrogen gas.
The temperature was raised to 80° C. and maintained at that temperature for 15 hours to carry out the first stage polymerization. In addition, the weight average molecular weight Mw of the homopolymer of the monomer for the high molecular weight component is 461.000.
, the glass transition point Tg is 61°C.

Thereafter, the inside of the flask was cooled to a temperature of 40°C, and 85 parts by weight of styrene, 10 parts by weight of n-butyl methacrylate, 5 parts by weight of acrylic acid, and peroxide were added as monomers for low molecular weight components. After adding 4 parts by weight of benzoyl and continuing stirring at a temperature of 40°C for 2 hours, the temperature was increased to 80°C.
The temperature was raised again to 100 mL and maintained at that temperature for 8 hours to carry out the second stage polymerization. In addition, the weight average molecular weight Mw of the homopolymer of the monomer for the low molecular weight component is 8.200, and the glass transition point Tg is 64°C.

Next, add 0 zinc oxide, which is a polyvalent metal compound, to the flask.
．． 5 g was added, and the reaction was carried out for 2 hours while maintaining the temperature at reflux and stirring.

After that, the reaction system is cooled to separate the solid matter, and after repeated dehydration and washing, it is dried to produce amorphous vinyl, which is produced by reacting zinc oxide with the carboxyl groups of the vinyl polymer to form ionic crosslinks. Polymer 1 was produced. Note that this amorphous vinyl polymer 1 has a carboxyl group as a functional group for bonding with the crystalline polyester.

This amorphous vinyl polymer 1 has two peaks in its molecular weight distribution by GPC, the peak molecular weight on the high molecular weight side is 363.000, and the peak molecular weight on the low molecular weight side is 7.000.
It is 590. In addition, the weight average molecular weight Mw is 165.0
00, the value of the ratio Mw/Mn is 25.9, the glass transition point Tg
is 62°C, and the softening point Tsp is 130°C.

(2) Amorphous vinyl polymer 2 Amorphous vinyl polymer 2 was produced in the same manner as in the production of amorphous vinyl polymer 1 above, except that zinc oxide was not added. This amorphous vinyl polymer 2 has a carboxyl group as a functional group for bonding with the crystalline polyester.

This amorphous vinyl polymer 2 has two peaks in its molecular weight distribution by GPC, the peak molecular weight on the high molecular weight side is 355.000, and the peak molecular weight on the low molecular weight side is 6.000.
It is 840. In addition, the weight average molecular weight Mw is 142.0
00, the value of the ratio Mw/Mn is 24.5, the glass transition point Tg
is 60°C, and the softening point Tsp is 128.5°C.

(1) Toner resin A: 15 parts by weight of crystalline polyester 1, 1085 parts by weight of amorphous vinyl polymer, and 0.0 parts by weight of p-)luenesulfonic acid.
5 parts by weight and 100 parts by weight of xylene were placed in a separable flask with a capacity of 31 and refluxed at a temperature of 150°C for 1 hour, and then the xylene was distilled off using an aspirator and a vacuum pump to form a crystalline polyester. Toner resin A consisting of a graft copolymer with an amorphous vinyl polymer was produced.

(2) Toner resin B-D In the production of the above toner resin A, the crystalline polyester and amorphous vinyl polymer were produced in the same manner except that the combinations of the crystalline polyester and the amorphous vinyl polymer were changed to those shown in Table 1 below. Each toner resin BD consisting of a graft copolymer with a polymer was produced.

Example 1 Resin A for toner 100 parts by weight Carbon blank "Mogulshi" 10 parts by weight (manufactured by Kabonoto Co., Ltd.) Alkylene bis fatty acid amide wax represented by general formula (1) "Hoechst Wax C" (manufactured by Hoechst Co., Ltd.) 5 parts by weight The above substances were mixed, melted and kneaded with heated rolls, cooled, coarsely pulverized, finely pulverized with a supersonic jet mill, and classified with an air classifier to obtain powder with an average particle size of 11.0 μm. . To 100 parts by weight of this powder, add hydrophobic phosphoric acid fine powder "Aerosil R-972J (manufactured by Nippon Aerosil Co., Ltd.)" to 100 parts by weight of this powder.
Toner 1 according to the present invention was manufactured by mixing 0.8 parts by weight using a V-type mixer.

Example 2 Toner 2 according to the present invention was produced in the same manner as in Example 1 except that the amount of "Hextowanox C" added was changed to 15 parts by weight.

Example 3 Toner 3 according to the present invention was produced in the same manner as in Example 1, except that the amount of "Hoechstwanx C" added was changed to 2 parts by weight.

Example 4 The same procedure as in Example 1 was carried out except that 5 parts by weight of the alkylene bis fatty acid amide wax "Bisamide" (manufactured by Nitto Kagaku Co., Ltd.) represented by the general formula (1) was used instead of "Hoechst wax C". Toner 4 according to the present invention was manufactured.

Example 5 Toner 5 according to the present invention was produced in the same manner as in Example 1 except that 100 parts by weight of toner resin B was used instead of toner resin A.

Example 6 Toner 6 according to the present invention was produced in the same manner as in Example 1 except that 100 parts by weight of toner resin 0 was used instead of toner resin A.

Comparative Example 1 Comparative Toner 1 was produced in the same manner as in Example 1, except that 100 parts by weight of Amorphous Vinyl Polymer 2 was used instead of Toner Resin A.

Comparative Example 2 Comparative toner 2 was produced in the same manner as in Example 1 except that "Hextowanox C" was not used.

<Preparation of Developer> A carrier for an electrophotographic copying machine rU-Bix1550MRJ (manufactured by Konica ■) and each of the above toners were mixed to prepare each two-component developer having a toner concentration of 5% by weight.

<Evaluation> (1) Evaluation of low-temperature fixing performance An electrophotographic copying machine equipped with a selenium latent image carrier, a developing device for two-component developer, and a heating roller fixing device, and modified so that the set temperature of the heating roller can be variably adjusted. rU-Bix1550
Using a modified machine manufactured by MR (manufactured by R Nika), the linear speed of the heating roller was set to 139 mm/sec, and the temperature of the heating roller was set to 100 mm while keeping the temperature of the pressure roller lower than the set temperature of the heating roller. A photocopying test was conducted in which a fixed toner image was formed using each of the above developers while changing the temperature stepwise within the range of ~240°C, and a constant load was applied to the edge of the obtained fixed toner image using a rubbing tester. After rubbing, the residual rate of the image at the edge was measured using a microdensitometer, and the lowest set temperature (minimum fixing temperature) that provided a sufficient residual rate was determined.

The heating roller fixing device includes a heating roller with a diameter of 30 mm whose surface layer is made of PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), and a silicone rubber rKE-1 whose surface layer is coated with PFA.
300RTVJ (manufactured by Shin-Etsu Chemical Co., Ltd.), and the linear pressure is 0.8 kg/cm.
The nip width was 4.3 mm, and no mechanism for applying a release agent such as silicone oil was provided.

(2) Evaluation of under-offset resistance A live copying test was conducted in the same way as in the evaluation of low-temperature fixing properties above, using a so-called black-black original while sequentially lowering the temperature setting of the heating roller, and it was found that the recording material became wrapped. The highest temperature (temperature at which coiling occurs) was determined.

(3) Evaluation of hot offset resistance A fixed toner image was formed in the same manner as in the evaluation of low temperature fixability above, except that the pressure roller was kept at a temperature close to the set temperature of the heating roller, and immediately after that, a fixed toner image was formed on a blank sheet of paper. The recording material was sent to the heating roller fuser under similar conditions and visually observed to see if toner stains were formed on it, at each heating roller temperature setting, and the lowest temperature when toner stains occurred was performed. The set temperature (offset generation temperature) was determined.

(4) Evaluation of fluidity Taking advantage of the fact that powder and granules with high fluidity have a low degree of compression, each of the above toners was loosely filled from above into a container with a diameter of 28 mm and a volume of 100 mm, and its weight was measured. Then, the static bulk density of the toner was determined. The evaluation is that the static bulk density is 0.38 g
/- or more was rated as "○J", and less than 0.38 g/d was rated as "x".

(5) Evaluation of storage stability 2g of each toner was taken into a sample tube and tapped 500 times with a xopdenser, then the temperature was 55°C and the relative humidity was 2.
The mixture was left in a 6% atmosphere for 2 hours, and then separated using a 48-mesh sieve, and the proportion of aggregates remaining on the sieve was measured.

(6) Evaluation of durability The electrophotographic copying machine "U-Bix 1550MR" (Konica side Using a modified machine, the linear speed of the heating roller was set to 139 mm for 7 seconds, the set temperature of the heating roller was set to the lowest fixing temperature of each toner, and the temperature was set at normal temperature and humidity (temperature 20°C, relative humidity 60%).
30,000 live-photography tests were conducted, and durability was evaluated by visually observing the resulting images.

The above results are shown in Table 1.

As can be understood from the results in Table 1, toners 1 to 6 according to the present invention have (1) low temperature fixing properties, (2) hot offset resistance, (3) under offset resistance, ( 4
) Excellent performance is exhibited in all aspects of storage stability and (5) fluidity.

On the other hand, in Comparative Toner 1, the toner resin is composed only of an amorphous vinyl polymer, and therefore, the low-temperature fixability and under-offset resistance are poor.

Comparative Toner 2 does not contain the alkylene bis fatty acid amide wax represented by the general formula (1), and therefore has poor low-temperature fixability and storage stability.

Claims (1)

[Scope of Claims] 1) A block formed by chemically bonding a crystalline polyester and an amorphous vinyl polymer having a ratio Mw/Mn of weight average molecular weight Mw to number average molecular weight Mn of 3.5 or more. A toner for electrostatic image development, comprising a toner resin made of a copolymer or a graft copolymer, and an alkylene bis fatty acid amide wax represented by the following general formula (1). General formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. R_4 is the same or different hydrogen atom or -OCR_5 group (however, R
_5 represents a saturated or unsaturated aliphatic hydrocarbon group. ), and n represents a positive integer. ] 2) The functional groups that chemically bond with the crystalline polyester in the amorphous vinyl polymer are carboxyl groups, hydroxyl groups,
The toner for electrostatic image development according to claim 1, characterized in that the toner has an amino group or an epoxy group. 3) The toner for electrostatic image development according to claim 1 or 2, wherein the amorphous vinyl polymer has at least two maximum values in its molecular weight distribution. 4) The amorphous vinyl polymer is formed by reacting a polyvalent metal compound with the carboxyl group of a vinyl polymer having a carboxyl group to form an ionic crosslink. The toner for electrostatic image development according to any one of items 3 to 3. 5) Claims 1 to 4, characterized in that the content of the alkylene bis fatty acid amide wax represented by the general formula (1) is 1 to 20 parts by weight based on 100 parts by weight of the toner resin. The toner for electrostatic image development according to any one of the preceding items.