JPH08328305A - Resin composition for toner and toner - Google Patents

Abstract

PURPOSE: To obtain a toner having a wide fixing temp. region and giving a stable image by incorporating at least two kinds of incompatible resins each having a specified glass transition temp. or above and constituting a mutual penetration structure and a specified compatibility imparting agent. CONSTITUTION: This resin compsn. contains at least two kinds of incompatible resins each having >=50 deg.C glass transition temp. and constituting a mutual penetration structure, a compatibility imparting agent made of a block or graft copolymer contg. the same component as at least one of the incompatible resins and a fixing aid. Each of the incompatible resins is a resin excellent in blocking resistance and having >=50 deg.C glass transition temp. The reason for the use of the block or graft copolymer is that the copolymer exists locally at the interface between phases, reduces free energy, makes the diameter of the continuous phase of the mutual penetration structure small and stable and therefore has an effect of considerably improving interaction at the continuous interface.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a toner used in electrophotography and a toner, more specifically, a resin for a toner used in a dry developing method among methods for developing an electrostatic image. Compositions and toners.

[0002]

2. Description of the Related Art In electrophotography and the like, a dry developing system is often used as a method for developing an electrostatic charge image. In the dry development method, a triboelectrically-chargeable toner obtained by mixing a carrier such as iron powder or glass beads with a fine powder containing a colorant such as carbon black and other additives in a toner resin serving as a binder ( Developer) is used.

In order to obtain a copy, an electrostatic latent image is usually formed on a photosensitive member, and triboelectrically-charged toner is electrically attached to the electrostatic latent image to develop the toner image. Is transferred onto a sheet such as a sheet of paper, and then fixed by a hot-pressing roller having releasability to toner to form a permanent visible image.

[0004] In this type of toner, mainly offset resistance (the toner adheres to the hot-press roller for fixing and does not stain the paper), low temperature fixability (the toner firmly adheres to the paper at low temperature). ), Blocking resistance (toner particles do not aggregate), and image stability (there is no change in the charge amount and the image density is uniform), and for toner production, A resin composition for toner having good pulverizability is also required.

In order to improve the low-temperature fixability, a fixing aid may be kneaded and dispersed in the toner to lower the softening point of the toner and lower the fixable temperature of the toner. However, in this case, the offset resistance becomes poor. Further, if the compositions of the matrix phase and the domain phase are largely changed from the same viewpoint, the offset resistance will be similarly deteriorated.

Further, from the viewpoint of offset resistance, the inorganic particles such as silica are kneaded and dispersed in the toner to reduce the adhesiveness of the toner, and thereby the offset resistance of the toner can be improved to some extent. It adversely affects the pulverizability, fixability and chargeability.

On the other hand, as a toner having improved various performances as described above, a resin composition for a toner formed of a matrix phase and a domain phase dispersed in the matrix phase, and a resin composition for the toner There are known toners using (for example, JP-B-57-6586 and JP-A-4-366176).

[0008]

The conventional toner composed of such a matrix phase and a domain phase has good low-temperature fixability, anti-offset property and anti-blocking property. When copying using a small-sized electronic copying machine, the above-mentioned performance is not always sufficiently satisfactory, and a toner having a wide fixing temperature range is particularly demanded.

The present invention is intended to solve the problems of the above-mentioned conventional toners, and its object is to provide excellent offset resistance, low-temperature fixing property, and blocking resistance.
In particular, it is to provide a resin composition for a toner and a toner that have a wide fixing temperature range and can obtain a sufficiently stable image even when copying is performed using a high-speed type or a small-sized electronic copying machine.

[0010]

The present invention has been made to achieve the above object and has a glass transition point of 50.
℃ or more, at least two types of incompatible resin constituting an interpenetrating structure, and the following specific compatibilizer,
Further, since the toner resin composition contains a fixing aid as required, at least the action of the compatibilizer further enhances the offset resistance and the low-temperature fixing property, and further obtains a stable image with a wide fixing temperature range. The feature is that it is possible.

That is, the inventions according to claims 1 to 5 are:
A glass transition point is 50 ° C. or higher, and at least two incompatible resins that form an interpenetrating structure, the following specific compatibilizing agent, and a fixing aid are included: In the invention described in 6, the glass transition point is 50 ° C. or higher,
A toner resin composition comprising at least two types of incompatible resins forming an interpenetrating structure and a specific compatibilizing agent described below.

In the invention according to claim 1, the compatibilizing agent is composed of a block copolymer or a graft copolymer containing at least one component which is the same as at least one of the incompatible resins.

In the invention according to claim 2, the compatibilizer is a solubility parameter value (δ value) sandwiched between the solubility parameter values (δ value) of the resin components of each phase forming the interpenetrating structure. ).

According to the third aspect of the present invention, the compatibilizing agent is composed of a polymer having a functional group capable of forming a hydrogen bond or an ionic bond, that is, a functional group having polarity.

In the invention according to claim 4, the compatibilizer is a solubility parameter value (δ value) of the resin component having the largest molecular weight among the resin components constituting the interpenetrating structure.
However, it is composed of a high molecular weight polymer having a solubility parameter value (δ value) that is within 2 but is less than the solubility parameter value (δ value).

In the invention according to claim 5, the compatibilizer has a solubility parameter value (δ) of the resin component having the smallest molecular weight among the resin components constituting the interpenetrating structure.
Value), but the solubility parameter value (δ value)
It is composed of a high molecular weight polymer having a solubility parameter value of which is less than or equal to 2.

In the invention according to claim 6, the incompatible resin and the compatibilizing agent are contained, and the fixing aid is not contained, but the compatibilizing agent is contained in any one of claims 1 to 5. It is composed of at least one of the compatibilizing agents used in the described invention.

The invention described in claim 7 is a toner characterized by using the resin composition for a toner according to the invention described in claims 1 to 6 as a main component. Less than,
The details of the present invention will be described.

Resin Component Constituting Interpenetrating Structure In the present invention, as the resin component constituting the interpenetrating structure, an appropriate resin capable of forming the interpenetrating structure is selected from resins usually used as binder resins. Are used, and are selected from vinyl resins, xylene resins, epoxy resins, coumarone-indene resins, styrene-butadiene-styrene (SBS) resins, butyral resins, and the like. In particular, vinyl resins are preferable because they are easy to manufacture (polymerize) and adjust physical properties. Among vinyl-based resins, styrene-based polymers, (meth) acrylic acid ester-based polymers, and styrene- (meth) acrylic acid ester-based copolymers are more preferable.

The resin forming the interpenetrating structure is
It is necessary that the glass transition point is 50 ° C. or higher. When a toner is produced using a resin forming an interpenetrating structure, each constituent resin is exposed on the surface of the toner particles. , Respectively, it is necessary to have sufficient blocking resistance. Therefore, as the resin forming the interpenetrating structure, as described above, each of the resins is excellent in blocking resistance and has a glass transition point of 50 ° C. or higher.

At least one of the resin components constituting the above interpenetrating structure has a softening point of 80 to 1 in consideration of performance such as toner blocking resistance and low temperature fixing property.
It is preferably 50 ° C., especially 80 to 100 ° C. Further, the dispersity in the molecular weight distribution (weight average molecular weight / number average molecular weight) is preferably 5 or less.

Here, the softening point is a value measured by the following procedure using a Koka type flow tester. That is, 1.0 g of the sample was extruded from the pores of the die (1 mm diameter × 1 mm) under the conditions of a load of 20 kg / cm ² and a heating rate of 6 ° C./min, and a flow curve showing the relationship between the plunger descending distance and the temperature was obtained. create. In this flow curve, the temperature when the plunger descent distance is 50% of the total stroke is the softening point. The degree of dispersion in the above molecular weight distribution is determined by gel permeation chromatography (GP
It is a value obtained from the ratio of the weight average molecular weight and the number average molecular weight measured by C).

At least one resin component among the above resin components constituting the interpenetrating structure is composed of a low molecular weight vinyl resin component and has a weight average molecular weight of 40,000 or less, which is based on all resin components. It is preferable to occupy 60 to 95% by weight. Since such a low molecular weight vinyl resin component is hard and brittle, it improves the pulverizability of the toner.
Therefore, when the resin component is in the above range, the pulverizability of the toner is further improved.

Further, among the resin components constituting the interpenetrating structure, at least one other resin component is composed of a high molecular weight vinyl-based component and has a weight average molecular weight of 100,000 or more. It is preferable to occupy 5 to 40% by weight. Since such a high molecular weight vinyl resin component has a soft and tenacious property, it greatly affects the offset resistance, and when the resin component is in the above range, the offset resistance is further improved.

Further, at least two kinds of resin components constituting the interpenetrating structure are functionally capable of interacting with the compatibilizing agent and the fixing auxiliary in order to stably contain the compatibilizing agent and the fixing auxiliary. Those having a group, those having a sterically hindered side chain, and those having many branched structures are preferable, and they may have a crosslinked structure.

In the present specification, the weight average molecular weight of each resin component is a value measured by gel permeation chromatography (GPC), and the glass transition point of each resin component is a differential scanning calorimeter (DSC). It is the value measured in.

Compatibilizer in the invention of claim 1 The compatibilizer used in the invention of claim 1 contains the same components as at least two kinds of resins forming an interpenetrating structure, A block copolymer or a graft copolymer having components compatible with all or any of the phases forming the penetrating structure is used.

The reason for using the above block copolymer or graft copolymer is that they are localized at the interface between the phases to reduce the free energy and further stabilize the diameter of the continuous phase having an interpenetrating structure to be small. It has the effect of dramatically improving the interaction at the continuous phase interface.

For example, in the case of an interpenetrating structure composed of two kinds of incompatible resins, a diblock copolymer formed by two main components of the two kinds of incompatible resins is used as a compatibilizing agent. The respective homopolymer components are compatible with the continuous phase composed of each of the above two kinds of resins, and a strong interaction can be caused between the two phases. Therefore, since the interaction is imparted to the interface between the continuous phases, the viscosity of the whole resin is increased and the offset resistance is dramatically improved.

The degree of compatibilization of the compatibilizer into each continuous phase is
Those that do not break the interpenetrating structure and localize at the interface to cause a strong interaction between both continuous phases on both sides of the interface are preferable. Thus, as the composition of the resin which is easily compatible with each continuous phase, one containing at least one component of a resin capable of forming an interpenetrating structure is selected, and for example, a vinyl resin,
It is selected from xylene resin, epoxy resin, coumarone-indene resin, SBS resin and the like. Particularly preferably, a vinyl resin is used. Among vinyl-based resins, styrene-based copolymers, (meth) acrylic acid ester-based copolymers, and styrene- (meth) acrylic acid ester-based copolymers are more preferable.

Compatibilizer in the invention of claim 2 The compatibilizer used in the invention of claim 2 is a value sandwiched between the solubility parameter values (δ values) of the continuous phases, for example, two continuous phases. In this case, a high molecular polymer having a δ value sandwiched between the two continuous phases is used. The solubility parameter value (δ value) used in this specification is
It is calculated from the evaporation energy and the volume per 1 mol of the segment when the polymer chain is divided into segments of approximately the same volume as the solvent molecule, and is generally a value indicating the chemical affinity of the polymer.

The reason for using such high molecular weight polymers is that they localize at the interface and reduce the free energy,
Further, it has the effect of dramatically improving the interaction at the interface between the continuous phases by stabilizing the diameter of the continuous phases of the interpenetrating structure to be small and stable.

Since the above-mentioned high molecular weight polymer is partially compatible with each continuous phase and can cause a strong interaction between the continuous phases, slippage between the continuous phases can be prevented. As a result, the adhesive strength between the continuous phases is increased, and the offset resistance is dramatically improved.

The degree of compatibilization of the compatibilizing agent to each phase is preferably such that the interpenetrating structure is not destroyed and localized at the interface to cause a strong interaction between the continuous phases. Thus, the composition of the resin that is easily compatible with each continuous phase, for example,
It is selected from vinyl resin, xylene resin, epoxy resin, coumarone-indene resin, SBS resin, dienes and the like. Particularly preferably, a vinyl resin is used. Among vinyl-based resins, a styrene-based copolymer, a (meth) acrylic acid ester-based copolymer, and a styrene- (meth) acrylic acid copolymer are more preferable.

Compatibilizing agent in the invention of claim 3 As the compatibilizing agent used in the invention of claim 3, a polymer having a functional group capable of hydrogen bond or ionic bond in the molecular chain is used. The compatibilizer having such a functional group is dispersed in each continuous phase forming an interpenetrating structure, and the molecules exhibit strong pseudo-crosslinking behavior,
The interaction with each continuous phase can be strengthened. As a result, since each continuous phase can perform a cooperative movement, the offset resistance is improved.

The degree of compatibilization of the compatibilizing agent into each phase is preferably such that it does not break the interpenetrating structure and interacts with each continuous phase. Here, it is preferable that the above-mentioned functional group in the high molecular polymer contains a hydroxyl group, a ketone, an ester, an ether, a nitrile, a halogen, a sulfide, a thiol, an organic phosphorus, a nitric acid, a nitro compound and the like.

As the resin composition of the above-mentioned high molecular weight polymer which is easily compatible with each continuous phase, a resin capable of interacting with each continuous phase is selected, for example, vinyl resin, epoxy resin or the like. . Particularly preferably, styrene-based copolymers, sulfonated polystyrene, polyvinyl butyral, partially saponified vinyl acetate, polyethylene glycol, polyvinyl bromide, polyurethane and the like are used.

Compatibilizing agent in the invention of claim 4 As the compatibilizing agent used in the invention of claim 4, among the resin components constituting the interpenetrating structure, the resin component having the highest molecular weight (high molecular weight resin component) A polymer having a solubility parameter value (δ value) which is larger than the solubility parameter value (δ value) and has a difference of 2 or less with the solubility parameter value (δ value) of the resin component is used.
The melt viscosity of the compatibilizing agent used here is preferably smaller than the above-mentioned high molecular weight resin component.

The above-mentioned high molecular weight polymer is used because a mechanical shearing force is applied between the two phases in order to reduce the diameter of the continuous phase composed of the above high molecular weight resin component forming the interpenetrating structure. This is because the viscosity of the high molecular weight resin component at the time of melting is lowered so as to effectively work.

That is, by compatibilizing a high molecular weight polymer having a low melt viscosity capable of forming a single structure by being compatible with only the high molecular weight resin component,
The viscoelasticity of the high molecular weight resin component can be reduced. As a result, the high molecular weight resin component easily forms an interpenetrating structure with the resin component having a low molecular weight, and the interaction between the two is dramatically enhanced. Therefore, slippage between the high molecular weight resin component phase and the low molecular weight resin component phase can be prevented, and the offset resistance can be dramatically improved.

As the resin which is easily compatible with the high molecular weight resin component as described above, for example, vinyl resin is used.
Among vinyl resins, methyl acrylate, ethyl acrylate, vinyl acetate, polyvinyl butyral, partially saponified vinyl acetate and the like are used.

Compatibilizer in the invention of claim 5 The compatibilizer used in the invention of claim 5 has a solubility parameter value (δ value) of at least two resins forming an interpenetrating structure. A high molecular polymer having a value smaller than the solubility parameter value (δ value) of the resin component having the smallest molecular weight (low molecular weight resin component) and having a difference of 2 or less with the δ value of the low molecular weight resin component is used. .
Further, as the compatibilizing agent, one having a melt viscosity higher than that of the low molecular weight resin component is preferably used.

The use of the above-mentioned high molecular weight polymer as the compatibilizing agent is to increase the melt viscosity of the low molecular weight resin component among the at least two resin components constituting the interpenetrating structure to increase the molecular weight. This is because the diameter of the continuous phase of the high resin component is reduced and mechanical shearing force is effectively exerted between the continuous phases composed of the above-mentioned at least two resin components.

That is, the viscoelasticity of the low molecular weight resin component is increased by compatibilizing the high molecular weight polymer having a high melt viscosity which is completely compatible only with the low molecular weight resin component to form a single structure. . As a result, the low molecular weight resin component can easily form an interpenetrating structure with the high molecular weight component, and the interaction between the high molecular weight component and the low molecular weight resin component can be dramatically improved. for that reason,
Slip between the continuous phase composed of the low molecular weight resin component and the continuous phase composed of the high molecular weight resin component can be suppressed, and the offset resistance can be greatly improved.

As the resin which is easily compatible with the low molecular weight resin component, a vinyl resin, a diene resin or the like is used.
Among them, butadiene, isoprene, isobutylene,
Polyethylene or the like is used.

Compatibilizing agent in the invention of claim 6 As the compatibilizing agent in the invention of claim 6, at least one of the compatibilizing agents in the invention of claims 1 to 5 described above is used. Used. Therefore, the details of each compatibilizer will be omitted by referring to the description of the compatibilizer in the invention described in claims 1 to 5 described above.

Addition amount of compatibilizer The addition amount of the compatibilizer is generally 1 to 1 with respect to all resin components.
It is preferably in the range of 0% by weight. When the content of the compatibilizing agent is less than the above, the offset resistance of the resin is lowered, and when it is more than the above, the interpenetrating structure is destroyed and each phase is completely compatibilized, and good fixing property cannot be obtained.

Used in the invention described in claims 1 to 5.
The fixing aid used in the invention described in claims 1 to 5 has an effect of improving the low temperature fixability of the toner by lowering the softening point of the toner resin. Such fixing aids are, for example, at least selected from the group consisting of low molecular weight plasticizers, high molecular weight plasticizers, fatty acid esters, higher fatty acids, higher alcohols, fatty acid amides, paraffins, terpene resins and rosin resins. One kind of compound can be preferably used.

Usually, in order to lower the softening point of the resin, a plasticizer may be added, whereby the softening point of the resin can be easily lowered. However, in the resin for toner, the glass transition point of the resin is also lowered at the same time, so that the blocking resistance is deteriorated. Further, the resin is too plasticized, the melt viscosity at high temperature becomes too low, and the offset resistance often deteriorates. In addition, the plasticizer bleeds out from the toner resin, and although the fixing temperature can be lowered, there is a problem that the fixing strength is lowered. Such a phenomenon is often seen especially when a combination of compatible resins is used.

However, in the invention described in claims 1 to 5, the fixing aid is at least 2 having an interpenetrating structure.
It is added to some incompatible resin, and in this case, the degree of compatibility of the fixing aid with each continuous phase can be controlled by controlling the polarity of the incompatible resin. Also,
The fixing aid is preferably localized in a continuous phase composed of a high molecular weight resin among the incompatible resins. The reason for this is as follows.

When the fixing aid is localized in the continuous phase composed of the high molecular weight resin, the fixing aid is naturally distributed in a small amount in the continuous phase composed of the low molecular weight resin. Therefore, the decrease in the glass transition point of the low molecular weight resin is small, and the decrease in blocking resistance due to the low molecular weight resin component is not a problem.

On the other hand, when a large amount of the fixing aid is present in the continuous phase composed of the high molecular weight resin, the glass transition point of the high molecular weight resin is lowered to some extent, but the high molecular weight resin has a high melt viscosity of the resin, so The structure is quick and easy to freeze. Therefore, when melt-kneading or the like is performed, fixing aids include not only those which are compatibilized and mixed in the continuous phase of the high molecular weight resin but also those which exist as the fixing aid alone. Therefore, the decrease in blocking resistance of the high molecular weight resin component is not a problem. In addition, at the time of fixing, the softening temperature of the entire toner resin is lowered and the low-temperature fixability can be improved because the fixing aid, which is often present in the continuous phase composed of the high molecular weight resin, is dissolved.

The fixing aid preferably has a melting point of 50 ° C. or higher. In the case of a fixing aid having a melting point of less than 50 ° C., it easily becomes compatible with the resin components constituting the interpenetrating structure, and the softening point of the resin is lowered, and at the same time, the glass transition point is greatly lowered, and Blocking resistance often deteriorates. Further, the addition ratio of the fixing aid is 5 with respect to 100 parts by weight of the resin components constituting the interpenetrating structure.
The range of ˜30 parts by weight is preferred. If the amount is less than 5 parts by weight, the softening point of the resin for toner will not be sufficiently low,
When it is more than 0 parts by weight, the softening point is lowered and
The glass transition point may also be significantly lowered, the blocking resistance of the toner may be deteriorated, and the fixing aid may bleed out from the toner resin, resulting in a decrease in the offset resistance of the toner and a decrease in the fixing strength. .

Preparation of Resin Composition for Toner The resin composition for toner according to claims 1 to 5 is, for example,
The compatibilizer and the fixing aid, the low molecular weight resin component, and the high molecular weight resin component can be produced by a method of melt mixing with an organic solvent. At this time, it is more economical to polymerize the low molecular weight resin component in the presence of the high molecular weight resin component, the compatibilizer and the fixing aid, and particularly, the low molecular weight resin component and the high molecular weight resin component are mixed. When it is difficult, it is effective to obtain a proper phase separation state. Further, it can also be produced by mixing the above-mentioned high-molecular weight resin component and low-molecular weight resin component with a predetermined amount of a compatibilizing agent and a fixing aid, and melt-kneading with a roll mill, a kneader, an extruder or the like. .

The resin composition for a toner according to the sixth aspect of the present invention is, for example, a method in which a compatibilizing agent, a low molecular weight resin component and a high molecular weight resin component are dissolved and mixed using an organic solvent. Can be manufactured by. Also in this case, it is more economical to polymerize the low molecular weight resin component in the presence of the high molecular weight resin component and the compatibilizer. In particular, when the low molecular weight resin component and the high molecular weight resin component are difficult to mix, it is effective because it becomes easy to obtain a proper phase separation state. Further, it can also be produced by mixing a predetermined amount of a compatibilizing agent with the above-mentioned high molecular weight resin component and low molecular weight resin component, and melt-kneading with a roll mill, a kneader, an extruder or the like.

In any of the above methods, the composition of the low molecular weight resin component and the high molecular weight resin component, the weight average molecular weight, the glass transition temperature, the type of the compatibilizer, the solution blending conditions, the melt kneading conditions, etc. are appropriately selected. By setting, a state in which the compatibilizing agent (in the case of the invention of claim 6) or the compatibilizing agent and the fixing aid (in the case of the inventions of claims 1 to 5) are selectively contained in the resin component It is possible to control the dispersion state of at least two kinds of resin components constituting the interpenetrating structure.

When the above-mentioned at least two resin components are uniformly compatibilized at the molecular level, a homogeneous compatible structure (single-phase structure) is obtained, and the characteristics of all resin components are averaged, which is sufficient as a toner. Fixing temperature, offset resistance, blocking resistance and fine crushing property cannot be obtained. On the other hand, when the at least two resin components are non-uniformly compatibilized at the molecular level, a heterogeneous microphase separation structure (multiphase structure) is formed. Specifically, such a microphase-separated structure includes
There are particles, cylinders, lamellas, and interpenetrating structures. These microphase-separated structures can be confirmed by, for example, observing an ultramicrotome section with a scanning electron microscope.

The resin composition for a toner according to the invention described in any one of claims 1 to 6 particularly has an interpenetrating structure among the microphase-separated structures, and has an interface between continuous phases or each continuous phase. A compatibilizing agent or a compatibilizing agent and a fixing aid are contained therein. Each of the plurality of continuous phases has a diameter of 0.1 to several μm, forms continuously expanded phases, and has a complicated structure in which they are randomly entangled with each other.

When the interaction between a plurality of continuous phases is small, each continuous phase behaves independently of each other, and the high molecular weight resin component exerting the effect of enhancing the offset resistance cannot affect the entire resin. . Therefore, the offset resistance of the toner is lowered. The diameter of the continuous phase is preferably 5 μm or less. When the diameter of the continuous phase is larger than 5 μm, when a toner is produced using the resin composition for toner, the ratio of each continuous phase contained in the toner particles varies, which may adversely affect various physical properties. is there.

[0060] Using the resin composition for toners Preparation invention toner, to produce a toner of the present invention, for example, the toner resin composition obtained by the above method, coloring agents, A method in which a charge control agent and other conventionally used toner additives are blended, melt-kneaded with a roll mill, a kneader, an extruder or the like, and then cooled and pulverized is employed. It should be noted that hydrophobic silica or the like may be added later to the pulverized toner in order to improve the fluidity of the toner particles.

As the colorant, carbon black,
Colorants commonly used for this type of toner such as chrome yellow and aniline blue are used. As the charge control agent, a dye such as nigrosine, spirone black (manufactured by Hodogaya Chemical Co., Ltd.), or other charge control agent composed of a phthalocyanine pigment is used. Further, polypropylene wax, low-molecular-weight polyethylene, or the like, which has a peeling action with respect to the hot pressing roller for fixing of the copying machine, may be blended.

[0062]

In the resin composition for a toner according to the present invention, the interpenetrating structure is formed by at least two incompatible resins having a glass transition point of 50 ° C. or higher.
The glass transition point of each resin component forming an interpenetrating structure is 50 ° C. or higher, and each resin component exhibits excellent blocking resistance, so even if each component is exposed on the surface, sufficient blocking resistance is obtained. Shows sex.

Further, an interpenetrating structure showing a structure in which two or more kinds of incompatible resins are entwined with each other in a three-dimensional manner is formed, and further, between the continuous phases formed by the respective incompatible resins, In the invention described in claim 5, a strong interaction is caused by the specific compatibilizing agent and the fixing aid, and in the invention described in claim 6, a strong interaction is generated by the specific compatibilizing agent.

Therefore, in the toner using the resin composition for a toner according to the first to sixth aspects of the invention (the invention according to the seventh aspect), the offset resistance is enhanced by the compatibilizing agent. Further, in the inventions described in claims 1 to 5, since the softening temperature of the toner resin composition as a whole is lowered due to the action of the fixing aid at the time of heat fixing, the fixing aid has different proportions in each continuous phase. Localization of the toner can improve the low temperature fixability of the toner while maintaining the blocking resistance of the toner.

[0065]

EXAMPLES The present invention will be clarified by giving non-limiting examples and comparative examples of the present invention.

(Example 1) Example of the invention of claim 1 Preparation of resin component A In a round reaction vessel having a volume of 5 liters, deionized water 200 was added.
0 parts by weight, 18 parts by weight of gum arabic and 18 parts by weight of ligninsulfonic acid were weighed and set in a water bath. Next, a stirring device equipped with plate-shaped blades, a Dimroth cooling pipe, a dropping device and a nitrogen introducing pipe were attached to the above-mentioned round reaction vessel, and while bubbling nitrogen, the temperature of the liquid in the reaction vessel was raised to 80 ° C. . After waiting for the inside of the system to be in a uniform state, nitrogen bubbling was stopped, the flow was switched to nitrogen, and 129 parts by weight of n-butyl acrylate monomer, 496 parts by weight of methyl methacrylate monomer and benzoyl peroxide were used.
A monomer mixed solution of 75 parts by weight was slowly added dropwise to carry out suspension polymerization. After reacting for 18 hours, the reaction product was taken out, washed with water and filtered repeatedly, and then air-dried.
-Butyl acrylate-methyl methacrylate copolymer (BA-MMA copolymer) was obtained. This resin is referred to as a resin component A. The weight average molecular weight of the obtained resin component A was 10
0,000, glass transition temperature 55 ℃, solubility parameter value δ
Was 9.22.

Preparation of compatibilizer Preparation of polymer initiator: A 200 ml round bottom flask was equipped with a thermometer, a stirrer and a calcium chloride tube, 50 ml of thionyl chloride was added and kept at 35-40 ° C.
18 g of 4'-azobis (4-cyanopentanoic acid) was added little by little, and the mixture was stirred at room temperature for 10 hours. Next, the solution was concentrated under reduced pressure and dried to dryness 4,4′-azobis (4-cyanopentanoic acid chloride) [hereinafter, abbreviated as ACPC. ] In a 100 ml round-bottomed flask, 1.9 g of 1,6-hexanediol, 20 g of chloroform and 3 g of triethylamine were placed and dissolved, then 5 g of the above ACPC was added dropwise, and the mixture was reacted with stirring at room temperature for 5 hours to give poly (hexamethylene-azo). Biscyanopentanate) [hereinafter, PHMACP
Abbreviated. ]

Preparation of PBA: A 300 ml round bottom flask was equipped with a thermometer, a stirrer and a reflux condenser, and the above PH was used.
0.36 g MACP, 58 g butyl acrylate and 85 g benzene were added. After replacing the inside of the flask with nitrogen gas, the mixture was reacted at 60 ° C. for 30 minutes and then dried with a vacuum dryer to obtain polybutyl acrylate (PBA).

Preparation of PBA-PSt block copolymer: A thermometer, a stirrer and a reflux condenser were attached to a 300 ml round bottom flask, 10 g of polybutyl acrylate (PBA) obtained above, 110 g of styrene and 17 of benzene.
0 g was added. After replacing the inside of the flask with nitrogen gas,
The temperature was raised to 60 ° C. in an oil bath and the reaction was carried out for 24 hours. After the reaction, the precipitate was reprecipitated with methanol and dried in a vacuum drier to obtain a polybutyl acrylate-styrene block copolymer X (PBA-PSt block copolymer, butyl acrylate: styrene = 1: 11) as a compatibilizer. It was

Preparation of Resin Component B and Resin Composition for Toner A round reactor having a capacity of 1 liter was charged with 20 parts of the above resin component A.
Parts by weight, 3 parts by weight of the above PBA-PSt block copolymer X as a compatibilizer, 10 parts by weight of behenyl alcohol (melting point: 70 ° C.) as a fixing aid, and 150 parts of toluene.
The weight part was weighed and set in an oil bath. In the reaction vessel, a stirrer, a reflux condenser, a nitrogen introducing pipe, a thermocouple for temperature measurement was attached, in a nitrogen stream, the temperature was raised to the reflux temperature,
The polymer dissolved. Next, 6 parts by weight of benzoyl peroxide was dissolved in 65 parts by weight of a styrene monomer and 5 parts by weight of an n-butyl acrylate monomer, and the resulting monomer solution was added dropwise to the reactor over 2 hours to obtain a polymer in the presence of a polymer. And a styrene-butyl acrylate copolymer (resin component B) was polymerized. After completion of the reaction, the solvent was removed from the polymer solution to obtain a resin composition for toner containing a fixing aid.

Only the above monomer solution was mixed with toluene 1
The polymer (resin component B) obtained when polymerized in 50 parts by weight has a weight average molecular weight of 85,000, a softening point of 100 ° C., a glass transition temperature of 55 ° C., and a solubility parameter value δ = 8. It was 0.88.

Preparation of Toner 100 parts by weight of the above resin composition for toner, 6 parts by weight of carbon black (MA-100: manufactured by Mitsubishi Chemical Co., Ltd.), and 1 part by weight of Spiron Black TRH (manufactured by Hodogaya Chemical Co., Ltd.),
3 parts by weight of polypropylene wax (Viscor 660P: manufactured by Sanyo Chemical Co., Ltd.) are melt-kneaded with a kneader and cooled,
After that, pulverize and classify with a jet mill, average particle size 10μ
m toner powder (toner resin composition) was obtained. The yield of the above toner powder was 80% by weight or more, and there was no problem in pulverization.

A part of the toner powder obtained as described above was embedded in an epoxy resin, exposed by an ultramicrotome, and dyed and observed with a scanning electron microscope. As a result, it was confirmed that the resin component A and the resin component B had an interpenetrating structure, and the size of each continuous phase was 1 μm or less in diameter. To the toner powder, 0.3 part by weight of hydrophobic silica powder (R-972: manufactured by Nippon Aerosil Co., Ltd.) was externally added to prepare a toner.

Agglomeration of Toner to be Evaluated : 10 g of the above toner was weighed into a 100 ml sample bottle and left in a constant temperature bath at 50 ° C. for 48 hours. After that, when the aggregation property of the toner was observed, no aggregation was observed in the toner.

Fixing temperature range and offset resistance: 4 parts by weight of the above toner and 96 parts by weight of iron powder carrier having a particle diameter of 50 to 80 μm were uniformly mixed to prepare a developer. Using this developer, the fixing temperature range was measured in the following manner.
As a result, the fixing temperature range where a stable copied image can be obtained is 120 to 250 ° C., and it was confirmed that the fixing property is good over the entire temperature range.

<Measurement of Fixing Temperature Range and Evaluation of Offset Resistance> Copying was carried out by changing the set temperature of the fixing heat-pressing roller of the electrophotographic copying machine stepwise, and no offset (double image) occurred. When the obtained copy image is rubbed with a sand eraser for a typewriter and the decrease in the density of the copy image is less than 10%, it is determined that the fixing property is good, and the temperature range in which the fixing property is good is determined. I asked. The electrophotographic copying machine used is U-IX 416 manufactured by Konica.
0AF, the temperature of the fixing hot pressing roller is 120 to 250
It was modified so that it could be changed to ℃. In addition,
Since the fixing temperature range is evaluated under the condition that no offset occurs, the offset resistance is also evaluated by the fixing temperature range.

(Example 2) -Example of the invention of claim 1 PBA-PSt containing butyl acrylate and styrene in a ratio different from that used in Example 1 as a compatibilizer.
Except for using the block copolymer Y (the content ratio of BA and St is BA: St = 1: 6 by weight ratio),
Same as Example 1.

A part of the toner powder obtained in Example 2 was embedded in an epoxy resin and exposed with an ultramicrotome,
When the dyed product was observed with a scanning electron microscope, it was confirmed that the resin component A and the resin component B had an interpenetrating structure. No aggregation was observed in the toner, the fixability was good over the entire temperature range of 120 to 250 ° C., and no offset phenomenon was observed.

(Example 3) Example of the invention according to claim 1 As a fixing aid, stearyl acid and borate ester of glycerin (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Resist P)
A toner powder was prepared in the same manner as in Example 1 except that E139, melting point: 58 to 64 ° C.) was used, and evaluated in the same manner.

A part of the obtained toner powder was embedded in an epoxy resin, exposed by an ultramicrotome, and dyed and observed with a scanning electron microscope. As a result, it was confirmed that the resin component A and the resin component B had an interpenetrating structure. No aggregation was observed in the toner.
The fixability is good in the entire temperature range of 0 to 250 ° C.,
Moreover, the occurrence of the offset phenomenon was not observed.

(Example 4) -Example of the invention of claim 2 As a compatibilizer, styrene-obtained as follows:
An n-butyl acrylate-methyl methacrylate copolymer P was used.

Preparation of compatibilizer 400 parts by weight of deionized water, 3.6 parts by weight of gum arabic, and 3.6 parts by weight of ligninsulfonic acid were weighed out in a round reaction vessel having a capacity of 1 liter and set in a water bath. did. A stirring device, a Dimroth cooling pipe, a dropping device, and a nitrogen introduction pipe were attached to this while performing nitrogen bubbling.
The temperature was raised to ° C. Wait for the system to become uniform and switch the nitrogen bubbling to a nitrogen stream to remove styrene monomer 8
1.2 parts by weight, n-butyl acrylate monomer 18.
A monomer mixed solution of 8 parts by weight, 25 parts by weight of methyl methacrylate monomer and 0.6 parts by weight of benzoyl peroxide was slowly added dropwise to carry out suspension polymerization. After 18 hours, the reaction product was taken out, repeatedly washed with water and filtered,
Air-dried to obtain a styrene-n-butyl acrylate-methyl methacrylate copolymer (St-BA-MMA copolymer P). This St-BA-MMA copolymer P has a weight average molecular weight of 600,000 and a solubility parameter value δ of 8.95.
Met.

A toner resin component and a toner were prepared in the same manner as in Example 1 except that the above compatibilizer was used. In Example 4, the yield of the toner powder was 80% or more, and there was no problem in the pulverizability of the toner powder. Also,
When the toner powder was observed with a scanning electron microscope in the same manner as in Example 1, it was confirmed that the resin component A and the resin component B had an interpenetrating structure, and the size of the continuous phase was 1 μm or less. there were.

In the toner obtained in Example 4, no cohesiveness was observed. Further, the fixing temperature range was 120 to 250 ° C., the fixing property was good in the entire temperature range, and the offset phenomenon was not observed.

(Embodiment 5) -Embodiment of the invention of claim 2 St-BA in which the content ratios of styrene, n-butyl acrylate and methyl methacrylate are different as compatibilizers.
-MMA copolymer Q (62.5 parts by weight of styrene monomer, 37.5 parts by weight of n-butyl acrylate monomer,
The procedure of Example 4 was repeated, except that 25 parts by weight of a methyl methacrylate monomer, a weight average molecular weight of 600,000 and a solubility parameter value (δ = 8.97) were used.

A part of the toner powder obtained in Example 5 was embedded in an epoxy resin and exposed with an ultramicrotome,
When the dyed product was observed with a scanning electron microscope, it was confirmed that the resin component A and the resin component B had an interpenetrating structure.

No aggregation was observed in the toner, the fixing temperature range was 120 to 250 ° C., good fixing properties were exhibited over the entire temperature range, and no offset phenomenon was observed.

(Example 6) -Example of the invention of claim 2 As a fixing aid, stearyl acid and borate ester of glycerin (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Resist P)
E139, melting point 58-64 [deg.] C.) was carried out as in Example 4.

A part of the obtained toner powder was embedded in an epoxy resin, exposed by an ultramicrotome, and dyed, and observed with a scanning electron microscope. As a result, it was confirmed that the resin component A and the resin component B had an interpenetrating structure.

No aggregation was observed in the toner, the fixing temperature range was 120 to 250 ° C., good fixing property was exhibited over the entire temperature range, and the offset phenomenon was not observed.

(Example 7) Example of the invention of claim 3 As a compatibilizing agent, polyvinyl butyral (degree of polymerization: 170) was used.
0, the degree of acetalization 70 mol%)
A resin composition for toner and a toner were prepared and evaluated in the same manner as in Example 1.

The yield of toner powder was 80% or more, and there was no problem in pulverization. Further, when a part of the toner powder was embedded in an epoxy resin, exposed by an ultramicrotome, and dyed and observed with a scanning electron microscope, the resin component A and the resin component B had an interpenetrating structure. It was confirmed that the size of each continuous phase was 1 μm or less.

No toner aggregation was observed. In addition, the fixing temperature range was 120 to 250 ° C., the same good fixing property as in Example 1 was exhibited, and the offset phenomenon did not occur.

(Embodiment 8)-Embodiment of the invention according to claim 3 As a compatibilizing agent, a partially saponified product of vinyl acetate (degree of polymerization: 1) is used.
The same procedure as in Example 7 was repeated except that 700 and the residual vinyl acetate amount was 75% by weight).

A part of the obtained toner powder was embedded in an epoxy resin, surfaced with an ultramicrotome, and the dyed product was observed with a scanning electron microscope. As a result, resin component A and resin component B were found to have an interpenetrating structure. It was confirmed that it was taking.

No aggregation was observed in the obtained toner, the fixing temperature range was 120 to 250 ° C., good fixing property was exhibited over the entire temperature range, and the offset phenomenon was not observed.

(Embodiment 9) An embodiment of the invention of claim 3 As a fixing aid, stearyl acid and borate ester of glycerin (Daiichi Kogyo Seiyakusha, trade name: Resist P
E139, melting point 58 to 64 ° C.) were used, and the same procedure as in Example 7 was performed.

A part of the obtained toner powder was embedded in an epoxy resin, exposed by an ultramicrotome, and dyed and observed with a scanning electron microscope. As a result, it was confirmed that the resin component A and the resin component B had an interpenetrating structure.

No aggregation was observed in the toner, the fixing temperature range was 120 to 250 ° C., good fixing properties were exhibited over the entire temperature range, and no offset phenomenon was observed.

(Example 10) Example of the invention of claim 4 Example 1 was repeated except that vinyl acetate (polymerization degree 1000, solubility parameter value δ = 9.59) was used as a compatibilizing agent. A resin composition for toner and a toner were prepared and evaluated in the same manner as in. As described above, the solubility parameter values δ of the resin components A and B are 9.
22 and 8.88.

The yield of the obtained toner powder was 80% or more, and there was no problem in pulverization. A part of the toner powder was embedded in an epoxy resin, exposed to an ultramicrotome, and the dyed product was observed with a scanning electron microscope to find that the resin component A and the resin component B had an interpenetrating structure. The size of the continuous phase was confirmed to be 1 μm or less.

No toner aggregation was observed. Further, the fixing temperature range was 120 to 250 ° C., the fixability was good over the entire temperature range, and the offset phenomenon was not observed.

(Embodiment 11) An embodiment of the invention of claim 4 As a compatibilizing agent, polyvinyl butyral (degree of polymerization: 170) is used.
The same procedure as in Example 10 was carried out except that 0, the solubility parameter value δ = 10.5) was used.

A part of the obtained toner powder was embedded in an epoxy resin, surface-exposed with an ultramicrotome, and the dyed product was observed with a scanning electron microscope. As a result, resin component A and resin component B were found to have an interpenetrating structure. It was confirmed that it was taking. No aggregation was observed in the toner, and the fixing temperature range was 1
The temperature was 20 to 250 ° C., the fixability was good over the entire temperature range, and the offset phenomenon was not observed.

(Example 12) Example of the invention of claim 4 As a fixing aid, stearyl acid and borate ester of glycerin (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Registered P)
E139, melting point 58 to 64 ° C.) were used, and the same procedure as in Example 10 was performed.

A part of the obtained toner powder was embedded in an epoxy resin, exposed by an ultramicrotome, and dyed and observed with a scanning electron microscope. As a result, it was confirmed that the resin component A and the resin component B had an interpenetrating structure.

No aggregation was observed in the toner, the fixing temperature range was 120 to 250 ° C., good fixing property was exhibited over the entire temperature range, and the offset phenomenon was not observed.

(Example 13) -Example of the invention of claim 5 As a compatibilizing agent, PBS rubber (manufactured by Asahi Kasei, trade name: Toughprene 125, solubility parameter value δ = 8.58)
A resin composition for toner and a toner were prepared in the same manner as in Example 1 except that was used. As described above, the solubility parameter values δ of the resin components A and B are 9.22 and 8.88, respectively.

The yield of the toner powder was 80% by weight or more, and there was no problem in pulverization. A part of this toner powder was embedded in an epoxy resin, exposed by an ultramicrotome, and dyed and observed with a scanning electron microscope. As a result, it was confirmed that the resin component A and the resin component B had an interpenetrating structure, and the size of the continuous phase was 1 μm or less.

No toner cohesiveness was observed. Further, the fixing temperature range is 120 to 250 ° C.,
Good fixability was exhibited over the entire temperature range, and no offset phenomenon was observed.

(Example 14) -Example of the invention of claim 5 As the compatibilizing agent, ethylene-acrylic resin (Sumitomo Chemical Co., Ltd., trade name: Acryft WH506, solubility parameter value δ = 8.51) was used. Example 1 except that
The same procedure as in 3 was performed.

A part of the obtained toner powder was embedded in an epoxy resin, exposed by an ultramicrotome, and dyed and observed with a scanning electron microscope. As a result, it was confirmed that the resin component A and the resin component B had an interpenetrating structure. No aggregation was observed in the toner. The fixing temperature range was 120 to 250 ° C., good fixing property was exhibited over the entire temperature range, and the offset phenomenon was not observed.

Example 15: Example of the invention of claim 5 As a fixing aid, stearyl acid and borate ester of glycerin (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Resist P)
E139, melting point 58 to 64 ° C.) were used, and the same procedure as in Example 13 was performed.

A part of the obtained toner powder was embedded in an epoxy resin, exposed by an ultramicrotome, and dyed and observed with a scanning electron microscope. As a result, it was confirmed that the resin component A and the resin component B had an interpenetrating structure.

No aggregation was observed in the toner, the fixing temperature range was 120 to 250 ° C., good fixing property was exhibited over the entire temperature range, and the offset phenomenon was not observed.

Example 16 Inventive Example of Claim 6 A toner resin composition and a toner were prepared and evaluated in the same manner as in Example 1 except that a fixing aid was not used. .

The yield of toner powder was 80% or more, and there was no problem in pulverization. A part of this toner powder was embedded in an epoxy resin, exposed by an ultramicrotome, and dyed and observed with a scanning electron microscope. As a result, it was confirmed that the resin component A and the resin component B had an interpenetrating structure, and the size of each continuous phase was 1 μm or less.

No aggregation was observed in the toner. Furthermore, the fixing temperature range was 140 to 250 ° C., good fixing properties were exhibited over the entire temperature range, and no offset phenomenon was observed.

(Example 17) Example of the invention of claim 6 St-BA-MM prepared in Example 4 as a compatibilizer
The procedure of Example 16 was repeated except that the A copolymer was used. The solubility parameter value δ of this compatibilizer is
It is 8.95. As described above, the resin components A and B
The solubility parameter values δ of are 9.22 and 8.88, respectively.

A part of the toner powder of Example 17 using the above compatibilizer was embedded in an epoxy resin, exposed with an ultramicrotome, and the dyed product was observed with a scanning electron microscope. It was confirmed that and the resin component B had an interpenetrating structure.

No cohesiveness was observed in the toner, the fixing temperature range was 140 to 250 ° C., the good fixing property was exhibited over the entire temperature range, and the offset phenomenon was not observed.

(Example 18) Example of the invention of claim 6 Example 16 except that polyvinyl butyral resin (polymerization degree 1700, acetalization degree 70 mol%) was used as the compatibilizing agent having polarity. I went in the same way.

A part of the obtained toner powder was embedded in an epoxy resin, exposed with an ultramicrotome, and the dyed product was observed with a scanning electron microscope. As a result, resin component A and resin component B were found to have an interpenetrating structure. It was confirmed that it was taking.

No aggregation was observed in the toner, the fixing temperature range was 140 to 250 ° C., good fixing properties were shown over the entire temperature range, and no offset phenomenon was observed.

(Example 19) Example of the invention of claim 6 Same as Example 16 except that vinyl acetate (polymerization degree 1000, solubility parameter value δ = 9.53) was used as a compatibilizing agent. And As described above, the solubility parameter values δ of the resin components A and B are 9.2, respectively.
2 and 8.88.

A part of the obtained toner powder was embedded in an epoxy resin, exposed with an ultramicrotome, and the dyed product was observed with a scanning electron microscope. As a result, the resin component A and the resin component B showed an interpenetrating structure. It was confirmed that it was taking.

No aggregation was observed in the toner, the fixing temperature range was 140 to 250 ° C., good fixing properties were shown over the entire temperature range, and no offset phenomenon was observed.

(Example 20) Example of the invention of claim 6 As the compatibilizing agent, ethylene-acrylic resin (Sumitomo Chemical Co., Ltd., trade name: Acryft WH506, solubility parameter value δ = 8.51) was used. Except for the above, the same procedure as in Example 16 was carried out. As described above, the resin component A,
The solubility parameter values δ for B are 9.22 and 8.88, respectively.

A part of the obtained toner powder was embedded in an epoxy resin, exposed by an ultramicrotome, and the dyed product was observed with a scanning electron microscope. As a result, resin component A and resin component B were found to have an interpenetrating structure. It was confirmed that it was taking.

No aggregation was observed in the toner, the fixing temperature range was 140 to 250 ° C., good fixing properties were exhibited over the entire temperature range, and no offset phenomenon was observed.

Comparative Example 1 The procedure of Example 1 was repeated except that the compatibilizer was not used. In this case, when the toner powder was embedded in an epoxy resin and observed with a scanning electron microscope in the same manner as in Example 1, it was confirmed that an interpenetrating structure was formed, and no aggregation was observed in the toner. The fixing temperature range was 120 to 200 ° C., and the low temperature fixability was good, but at a temperature higher than 200 ° C., the offset phenomenon was observed and the offset resistance was poor.

(Comparative Example 2) In Example 1, instead of the resin component B, a methyl methacrylate-n-butyl acrylate copolymer (80 parts by weight of methyl methacrylate,
The same procedure as in Example 1 was carried out except that 20 parts by weight of n-butyl acrylate, a molecular weight when polymerized alone, and a glass transition point = 63 ° C. were used.

It was confirmed that the obtained toner resin had a compatible structure. The fixing temperature range is 120 to 250.
C., and good fixing property was exhibited over the entire temperature range, but toner agglomeration was observed at 50.degree.

(Comparative Example 3) The same procedure as in Example 16 was carried out except that the compatibilizer was not used in Example 16. It was confirmed that the obtained resin for toner had an interpenetrating structure, and there was no problem in toner cohesiveness. However, although the fixing temperature range is 140 to 200 ° C. and the low temperature fixing property is good, when the temperature exceeds 200 ° C., an offset phenomenon is observed and the offset resistance is poor.

COMPARATIVE EXAMPLE 4 Except that n-butyl acrylate / methyl methacrylate copolymer (weight average molecular weight 1,000,000, glass transition point = 40 ° C.) was used in place of the resin component A in Example 16. Example 16
Same as.

It was found that the obtained toner powder had an interpenetrating structure. Fixing temperature range is 140 ~ 200
However, the low temperature fixability was not sufficient, and an offset phenomenon was observed at a temperature exceeding 200 ° C., and the offset resistance was lowered. Further, aggregation of the toner was recognized.

(Comparative Example 5) In Example 16, as the resin component B, a methyl methacrylate-n-butyl acrylate copolymer (80 parts by weight of methyl methacrylate, n
-Butyl acrylate 20 parts by weight: The same as in Example 16 except that a polymer having a molecular weight of 8,000 when polymerized alone and a glass transition point of 63 ° C) were used.

In this case, the toner resin had a compatible structure. No aggregation was observed in the toner. The fixing temperature range is 140 ° C to 200 ° C, and the fixing property is good in this temperature range. However, the low temperature fixing property is not sufficient, and an offset phenomenon is observed at a temperature of more than 200 ° C. It was inferior.

Examples 1 to 20 and Comparative Examples 1 to 5 described above
The configurations and evaluation results of are shown in Tables 1 to 3 below.

[0140]

[Table 1]

[0141]

[Table 2]

[0142]

[Table 3]

[0143]

The toner resin composition of the present invention has at least two kinds of incompatible resins having a glass transition point of 50 ° C. or higher, and these incompatible resins form an interpenetrating structure. In the invention described in claims 1 to 5, the specific compatibilizing agent and the fixing aid are contained, and in the invention described in claim 6, the specific compatibilizing agent is contained.

Therefore, by using the resin composition for a toner of the present invention, a book having excellent offset resistance, low-temperature fixing property and blocking resistance, good pulverizability, and a wide fixing temperature range can be obtained. The toner according to the invention can be provided. Therefore, according to the present invention, it is possible to reliably obtain a sufficiently stable image even when it is used for copying using a high-speed electronic copying machine or a small electronic copying machine.

Claims (7)

[Claims] 1. A block containing at least two incompatible resins having a glass transition point of 50 ° C. or higher and forming an interpenetrating structure, and at least one component which is the same as at least one of the incompatible resins. A resin composition for a toner, comprising a compatibilizing agent comprising a copolymer or a graft copolymer, and a fixing aid. 2. At least two incompatible resins having a glass transition point of 50 ° C. or higher and forming an interpenetrating structure, and a resin of each phase composed of the at least two incompatible resins. A resin composition for toner, comprising a compatibilizing agent composed of a high-molecular polymer having a solubility parameter value (δ value) sandwiched between the solubility parameter values (δ value) of the components, and a fixing aid. . 3. A high molecular polymer having a glass transition point of 50 ° C. or higher and at least two incompatible resins forming an interpenetrating structure, and a functional group capable of forming a hydrogen bond or an ionic bond. A resin composition for a toner, comprising a compatibilizing agent consisting of (1) and a fixing aid. 4. The largest molecular weight of at least two incompatible resins having a glass transition point of 50 ° C. or more and constituting an interpenetrating structure and a resin component constituting the interpenetrating structure. A compatibilizing agent composed of a high-molecular polymer having a solubility parameter value (δ value) which is larger than the solubility parameter value (δ value) of the resin component but has a difference from the solubility parameter value (δ value) of 2 or less. And a fixing aid, the resin composition for toner. 5. The smallest molecular weight of at least two incompatible resins having a glass transition point of 50 ° C. or more and forming an interpenetrating structure and a resin component forming the interpenetrating structure. A compatibilizer composed of a polymer having a solubility parameter value (δ value) which is smaller than the solubility parameter value (δ value) of the resin component, but has a difference from the solubility parameter value (δ value) of 2 or less. And a fixing aid, the resin composition for toner. 6. At least two incompatible resins having a glass transition point of 50 ° C. or higher and forming an interpenetrating structure, and (a) the incompatible resin forming an interpenetrating structure. A block copolymer or a graft copolymer containing at least one of the same components as at least one, (b) a solubility parameter value sandwiched between the solubility parameter values (δ values) of the phases forming the interpenetrating structure. A high molecular weight polymer having (δ value), (c) a high molecular weight polymer having a functional group capable of forming a hydrogen bond or an ionic bond, (d) a molecular weight of the resin component constituting the above interpenetrating structure. It is larger than the solubility parameter value (δ value) of the largest resin component, but the solubility parameter value (δ
Value) and the solubility parameter value (δ
Value), and (e) the solubility parameter value (δ) of the resin component having the smallest molecular weight among the resin components constituting the interpenetrating structure.
Value), but the solubility parameter value (δ value)
And a compatibilizing agent comprising at least one compound selected from the group consisting of (a) to (e) above. A resin composition for a toner, comprising: 7. A toner comprising the resin composition for a toner according to claim 1 as a main component.