JP2578547B2 - Recording material and image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material for forming a toner image and an image forming method for forming a toner image on the recording material, and more particularly to an image for forming a color image or a full-color image by an electrophotographic system. It relates to a forming method.

[0002]

2. Description of the Related Art A conventional general full-color image forming method will be described.

The photosensitive drum of the photosensitive drum, which is an electrostatic latent image carrier, is uniformly charged by a primary charger, and is image-exposed by a laser beam modulated by a magenta image signal of a document. An electrostatic latent image is formed, and the electrostatic latent image is developed with magenta toner held in a magenta developing device to form a magenta toner image. Next, the developed magenta toner image is transferred to the photosensitive drum by a transfer charger on the conveyed recording material.

On the other hand, the photosensitive drum after transferring the toner image onto the recording material is neutralized by a neutralizing charger, further cleaned by cleaning means, and charged again by a primary charger. Forming a cyan toner image and transferring the cyan toner image to a recording material on which the magenta toner image has been transferred,
Further, the same process is performed for the yellow color and the black color in order, and the toner images of four colors of magenta, cyan, yellow, and black are transferred to the recording material. The recording material having the four color toner images is supplied to a fixing roller and fixed on the recording material by the action of heat and pressure to form a full-color image.

The toner used in the color image forming method needs to have good meltability and color mixing upon application of heat, and further has a low softening point, a low melt viscosity and a sharp melt property. High is preferred.

By using the toner having a high sharp-melt property, the color reproduction range of a copy can be widened and a color copy faithful to the original image can be obtained.

However, such a toner having a high sharp melt property has a high affinity with a fixing roller, and tends to be easily offset to the fixing roller during fixing.

Particularly, in the case of a fixing means in a full-color image forming method, since a plurality of toner layers of magenta, cyan, yellow and black are formed on a recording material, offset tends to occur particularly.

Therefore, conventionally, a releasing agent such as silicone oil has been applied to the fixing roller in order to improve the releasability of the toner from the fixing roller. However, such an image forming method has the following problems.

[0010] Since a releasing agent such as oil is applied to the fixing roller, the structure of the apparatus main body becomes complicated, and the application of oil promotes shortening of the life of the fixing roller.

In recent years, with various copying needs, for example, an overhead projector (OH
The formation of a fixed toner image using a resin-made laminated film such as a transparency film for P) has begun to be widely performed, but the toner image is recorded on a recording material by a fixing method using oil at the time of fixing as described above. When the toner is fixed on the recording material, the used oil adheres to the surface of the recording material, and the quality of the recording material for receiving the obtained toner image is greatly reduced.

Therefore, there has been great expectation for establishing a fixing system which solves the above-mentioned problem and does not require the application of oil at the time of fixing, and for developing a new toner for achieving the fixing system.

To solve the above-mentioned problems, a toner containing a release agent such as wax or a suspension polymerization method toner has been proposed (JP-B-36-10231). This suspension polymerization method uniformly dissolves or disperses a polymerizable monomer and a colorant (and, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives) to form a monomer composition. After the preparation, the monomer composition is dispersed in a continuous phase (for example, an aqueous phase) containing a dispersion stabilizer using a suitable stirrer, and at the same time, a polymerization reaction is carried out to obtain toner particles having a desired particle size. Is a way to get

In this suspension polymerization method, droplets of the monomer composition are formed in a dispersion medium having a large polarity such as water.
The component having a polar group contained in the monomer composition has a so-called pseudo-capsule structure in which the component having a polar group easily exists in the surface layer portion which is an interface with the aqueous phase, and the non-polar component hardly exists in the surface layer portion. By utilizing the characteristics of this production method, it is possible to incorporate a wax having a low melting point that cannot be used in the pulverization method, which is another method for producing toner.

The toner obtained by the polymerization method can achieve both the anti-blocking property and the contradictory performance of low-temperature fixing by incorporating the low melting point wax.
That is, since the low-melting wax is included, without lowering the blocking resistance, the thermal conductivity in the toner is improved by the wax that is melted at a low temperature,
As a result, low-temperature fixing becomes possible. More preferably, since the wax melted at the time of fixing also acts as a release agent, high-temperature offset can be prevented without applying a release agent such as oil to the fixing roller.

[0016] However, although the toner obtained by the polymerization method in which wax is included certainly exhibits advantageous performance at the time of fixing, when a recording film is used as a recording material, the transparency of the image after fixing is slightly increased. There is a new problem that the wax falls off and the wax encapsulated as a release agent oozes out at the time of fixing and flows onto the image.

That is, as shown in FIG. 8, the wax encapsulated in the toner is melted out by the action of pressure and heat at the time of fixing, and the recording material R having no wax absorption performance is formed on the resin laminate film. The direction of travel P of the film
The wax W flows toward the rear end of the fixed image I because it flows so as to be squeezed toward the rear side.
The image used for the OHP was inconvenient.

It is conceivable to reduce the amount of wax contained in the toner in order to prevent the flow of the wax. However, in this method, the releasability of the toner is reduced, and on the contrary, sufficient release is required. If a certain amount or more of wax is included in the toner so as to obtain a mold effect, the above-described phenomenon cannot be avoided.

This is because, in the case of a recording material such as paper, the wax absorbed by the paper is absorbed by the paper due to the absorption capacity of the paper itself.
In a recording material made of resin such as a film, the melted wax having no absorbing ability remains on the surface as it is and flows out to the non-image portion.

Further, when forming a toner image fixed on a recording material such as a resin laminate film, it is strongly required that the toner image on the recording material has high light transmittance. It is generally well-known that the fixing speed is made slower and the toner is sufficiently melted as compared with the case where such a recording material is used.

However, in this case, since the toner on the recording material tends to be remarkably easily offset to the fixing roller at the time of fixing, in order to obtain a sufficient releasing effect, the recording material such as paper is required. The amount of wax to be included in the toner must be set larger than when the toner image is fixed to the toner.

Further, in a method of forming a toner image using such a wax-containing toner,
It has been confirmed that the transparency of the transparency film is reduced due to the cloudiness accompanying the crystallization of the wax itself. This is because the wax contained in the toner layer on the recording material exudes from inside the toner when passing through the fixing roller, and the exuded wax covers the toner image surface or a part thereof, and the temperature drops after passing through the roller. It is considered that the crystallinity increased with this, and the light transmittance was extremely deteriorated.

Therefore, even if a sufficient amount of wax is included, some measures are taken so that the transparency is not impaired and that there is no trace of the flow of the wax at the time of fixing to a recording material such as a resin laminate film. It became urgent.

On the other hand, when a color toner image or a full-color toner image is formed on a transparent laminated film by using an electrophotographic method having a dry developing method, and is projected using an OHP device, the image on the film is In spite of this, the projected image shows a gray color tone as a whole, despite the fact that it shows sufficient color developability, and the phenomenon that the color tone reproduction range becomes very narrow occurs. This phenomenon is because the unfixed toner image formed on the smooth laminate film does not flow sufficiently due to heating during fixing and has granularity, so the incident light is scattered at the time of projection and a shadow is formed on the screen Because you do. In particular, in the intermediate tone portion where the image density is low, the absorption by the dye or pigment in the toner decreases due to the decrease in the number of toner particles, and this absorption level becomes equal to the black absorption level due to the scattering of the toner particles. The color tone becomes gray.

When a toner image on a recording material such as plain paper is visually observed, a reflected image of light applied to the fixed toner image is visually observed. Is less affected. However, when observing or projecting a toner image on a screen with transmitted light as in an OHP device, if the residual shape caused by the toner particles is clear, light scattering causes deterioration in light transmission. Therefore, the recording material used in the OHP apparatus is required to have the effects of reducing the granularity of the toner after fixing, improving the light transmission, and reducing the offset to the fixing roller during fixing.

[0026]

SUMMARY OF THE INVENTION An object of the present invention is to provide a recording material and an image forming method which solve the above-mentioned problems.

That is, an object of the present invention is to solve the above-mentioned problems and to provide a recording material and an image forming method capable of obtaining a full-color image excellent in quality by fixing without applying oil.

Another object of the present invention is to provide a recording material and an image forming method capable of obtaining a color or full-color transparency sheet having excellent transparency and good quality.

Further, the present invention provides a recording material and an image forming method capable of obtaining a high-quality image without causing a wax component contained in the toner to flow when a toner image is fixed on the recording material. Aim.

Further, the present invention is directed to a recording material capable of obtaining a color image or a full-color image having good color tone reproducibility without causing a projected image to be entirely grayish when used in an overhead projector (OHP). And an image forming apparatus.

Still another object of the present invention is to provide a recording material and an image forming method having good offset resistance to a fixing means at the time of fixing.

[0032]

SUMMARY OF THE INVENTION The present invention relates to an image forming recording material for forming a toner image on the surface of a recording material with a toner containing at least a wax component and fixing the toner image to obtain a visible image. The recording material has a base layer and an absorption layer for absorbing the wax component, the absorption layer contains inorganic fine particles, and the average pore radius D of the absorption layer is 10 ° to 200 °. A recording material characterized by the following.

The present invention also provides a developing step of developing an electrostatic latent image on an electrostatic latent image carrier using a toner containing a wax component to form a toner image on the electrostatic latent image carrier.
An image forming method, comprising: a transfer step of transferring the toner image to a recording material; and a fixing step of fixing the toner image transferred to the recording material to the recording material by the action of heat and pressure. And an absorption layer that absorbs the wax component. The absorption layer contains inorganic fine particles, the average pore radius D of the absorption layer is 10 ° to 200 °, and the toner image is fixed on a recording material. The present invention relates to an image forming method, wherein the wax layer contained in the toner is absorbed by the absorbing layer.

A feature of the present invention is that the recording material has an absorbing layer for absorbing the wax component contained in the toner.

This absorbing layer can be formed by incorporating inorganic fine particles. The average pore radius (D) formed by the inorganic fine particles is involved in the absorbability of the wax component into the absorption layer.
Is preferably in the range of 10 ° to 200 °. When the average pore radius (D) is smaller than 10 ° or larger than 200 °, the absorbability of the wax component decreases.

The thickness of the absorbing layer is preferably 0.1 to 10
It is more preferably from 0.5 to 5 μm. When the thickness is less than 0.1 μm, the absorption capacity of the wax component is small, and when the thickness is more than 5 μm, cloudiness occurs and the light transmittance of the film is liable to decrease.

The recording material of the present invention preferably has a BET specific surface area of 0.1 to 30 m ² / g.
When the absorbing layer is formed so that the BET specific surface area of the recording material is smaller than 0.1 m ² / g, the absorption of the wax component is reduced, and when the absorbing layer is formed so as to exceed 30 m ² / g. In addition, the transparency of the recording material itself is reduced, and most of the wax component included in the toner as a release agent is absorbed by the transfer material, so that the intended release effect is hardly obtained.

In the present invention, the average pore radius of the inorganic fine particles and the specific surface area of the recording material were calculated by the Kelvin equation and the BET theory, respectively, using a constant volume method by nitrogen adsorption.

The measurement of the BET specific surface area of the recording material is 100
_(mm) × cut 60 a film of _(mm) to a size of 5 _(mm) × 5 _(mm), chopped 5 _(mm) × 5 _(mm) All films placed in the measuring apparatus as a sample of It was measured.

The gas adsorption amount measuring device used in the present invention is as follows.
Autosorb 1 (Yuasa Ionics Co., Ltd.).

The recording material according to the present invention will be described with reference to FIG.

In FIG. 1, A denotes a base film made of a transparent resin as a base material layer of a recording material. The base film A has a heat resistance that does not cause significant thermal deformation due to heating during heat fixing or heat and pressure fixing. Must have. 3. Base film A is described in ASTM D648.
Under a measurement condition of 6 kg / cm ² , a material having a heat deformation temperature of preferably 145 ° C. or more, more preferably 150 ° C. or more is good. Specifically, as the base film A,
Examples include polyethylene terephthalate (PET), polyester, polyamide or polyimide having a heat deformation temperature of 145 ° C. or more under the above measurement conditions and a heat resistance of 100 ° C. or more at a maximum use temperature. Among them, polyethylene terephthalate is particularly preferred in terms of heat resistance and transparency. The thickness of the base film A needs to be such that wrinkles do not occur even when the film is softened by heating during fixing. For example, in the case of polyethylene terephthalate, the thickness may be 50 μm or more. Even if it is a transparent film, the light transmittance decreases when the thickness increases, so that the thickness of the base film A is preferably 50 to 300 μm, more preferably 100 to 200 μm, and still more preferably 70 to 300 μm.
150 μm is good.

In FIG. 1, the absorption layer B may be contained or fixed on the base film A so that pores are formed using inorganic fine particles as described above.

Examples of the inorganic fine particles include activated alumina, aluminum hydroxide, alumina hydrate, silica, and titanium oxide, and one or more of these can be used.

The average particle size of the inorganic fine particles is preferably from 0.001 to 0.1 μm, more preferably from primary particles.
0.001 to 0.05 μm is good.

When the average particle size is less than 0.001, the cohesive force between the particles becomes strong, and it becomes difficult to form a uniform absorbing layer. When the average particle size exceeds 0.1 μm, the absorbing ability of the absorbing layer becomes poor. It tends to decrease.

As a method of forming the absorbing layer on the base material layer, as an example, the above-mentioned materials are dispersed or dissolved in an appropriate solvent to prepare a coating solution, and the coating solution is coated on the base material layer by a known coating method. And then drying quickly. However, the method is not limited thereto.

The above-mentioned suitable solvent is a solvent which slightly dissolves the surface of the heat-resistant resin which is the substrate layer, a solvent which dissolves the inorganic fine particles, and a binder layer for holding the inorganic fine particles on the surface of the substrate layer. It also includes a solvent in which the raw material for forming is dissolved.

Examples of the resin forming the binder layer include resins known as film-forming resins such as polyester resins, vinyl resins, butadiene resins, epoxy resins, polyamide resins and polyurethane resins.

The mixing ratio of the resin forming the binder layer and the inorganic fine particles is preferably 1: 1 to 1:50, more preferably 1: 3 to 1:20.

Other known CVD methods (chemical vapor deposition methods)
The inorganic fine particles can be coated on the surface of the base material layer by a treatment method such as PVD (physical vapor deposition method).

Further, a heat-resistant resin film as a base material layer;
For the purpose of improving the adhesion to the inorganic fine particles or the binder layer, it is preferable to perform a surface treatment such as a plasma treatment or a corona discharge treatment or to form an adhesive layer.

Examples of the resin that can be used as the adhesive layer include resins such as polyester resins, acrylate resins, methacrylate resins, styrene-acrylate copolymers, and styrene-methacrylate copolymers. No.

Hereinafter, the polymerized toner among the toners used in the present invention will be described in detail.

The polymerized toner is obtained by the following method.

Additives such as a release agent, a colorant and a charge control agent are added to the polymerizable monomer, and the mixture is heated until the release agent is dissolved or melted, and the mixture is heated with a homogenizer or an ultrasonic disperser. The monomer composition homogeneously dissolved or dispersed by the mixer is dispersed in the aqueous phase at substantially the same temperature as the monomer system containing the dispersion stabilizer using a conventional mixer or a mixer such as a homomixer or a homogenizer. Preferably, the stirring speed and the stirring time are adjusted so that the monomer droplets have a predetermined toner particle size, generally a particle size of 30 μm or less, and thereafter the particle state is maintained by the action of the dispersion stabilizer, and the particle size is maintained. The stirring may be performed to such an extent that sedimentation is prevented. The polymerization temperature is set at a temperature equal to or lower than the precipitation temperature of the release agent, and a polymerization initiator is added to carry out the polymerization. After the reaction, the generated toner particles are washed, collected by filtration, and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer composition.

The polymerizable monomers usable in the above-mentioned polymerized toner include styrene-based monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene and p-ethylstyrene. Body; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate,
Acrylates such as n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate; Methacrylic acid n
-Butyl, isobutyl methacrylate, n-methacrylate
Octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic esters such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and other monomers such as acrylonitrile, methacrylonitrile, and acrylamide. No.

These monomers can be used alone or in combination of two or more. Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or as a mixture with another monomer, from the viewpoint of the developing characteristics and durability of the toner.

The dispersion medium used for producing the above polymerized toner is, for example, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose,
Ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salts, starch, tricalcium phosphate, aluminum hydroxide, magnesium hydroxide, calcium metasilicate, barium sulfate and bentonite are dispersed in the aqueous phase. Can be used.
The stabilizer is used in an amount of 0.1 part based on 100 parts of the polymerizable monomer.
It is preferred to use 2 to 20 parts by weight.

In order to finely disperse these stabilizers, 0.001 to 0.1 parts by weight of a surfactant may be used. This surfactant is for promoting the intended action of the dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, and sodium oleate. Sodium laurate, potassium stearate and calcium oleate.

It is more preferable to polymerize the monomer composition by adding a polymer or copolymer having a polar group as an additive. Furthermore, in the present invention, a polymer having a polar group-containing polymer, copolymer or cyclized rubber is added to a monomer composition in an aqueous phase in which the polar polymer and a reverse charge dispersant are dispersed. It is preferred to suspend and polymerize. That is, the cationic polymer, copolymer or cyclized rubber or anionic polymer, copolymer, or cyclized rubber contained in the monomer composition is a reversely charged polymer dispersed in an aqueous phase. The anionic or cationic dispersant is electrostatically attracted to the particle surface of the toner that is undergoing polymerization, and the dispersant covers the particle surface to prevent coalescence of the particles and to stabilize the toner.
Since the polar polymer added at the time of polymerization collects on the surface layer of the particles serving as the toner, it forms a kind of shell, and the obtained particles have a pseudo capsule structure. Using a relatively high molecular weight polymer having a polar group, a copolymer or a cyclized rubber,
While imparting excellent properties of blocking properties and offset resistance to toner particles, the inside of the polymerization is performed at a relatively low molecular weight to contribute to the improvement of fixing properties, thereby contradicting demands for fixing properties and blocking properties. Satisfactory toner can be obtained. Examples of the polymer and copolymer having a polar group and the reverse charge dispersant which can be used in the present invention are shown below.

(1) Examples of the cationic polymer include a polymer of a nitrogen-containing monomer such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, or a mixture of the nitrogen-containing monomer and styrene or an unsaturated carboxylic acid ester. And copolymers thereof.

(2) Examples of the anionic polymer include nitrile monomers such as acrylonitrile, halogen-containing monomers such as vinyl chloride, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and other unsaturated dibasic compounds. Examples thereof include polymers such as acids, unsaturated dibasic acid anhydrides, and nitro monomers, and copolymers of these with styrene monomers.

A cyclized rubber may be used in place of these polar polymers.

(3) Examples of the anionic dispersant include silica fine powder, and particularly, the BET specific surface area is 200 m ^2.
/ G or more of colloidal silica is preferred.

(4) Examples of the cationic dispersant include fine powder of hydrophilic positively chargeable silica such as aminoalkyl-modified colloidal silica (preferably having a BET specific surface area of 200 m ² / g or more) or aluminum hydroxide. .

Such a dispersant may be used as the polymerizable monomer 100
It is preferably used in an amount of 0.2 to 20 parts by weight, more preferably 0.3 to 15 parts by weight, based on parts by weight.

In the present invention, a charge control agent is preferably added to the toner for the purpose of controlling the chargeability of the toner. As these charge control agents, among the known ones, those having little polymerization inhibitory property and almost no water phase transfer property can be used. Examples of positive charge control agents include nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts, amine compounds and polyamine compounds, and examples of negative charge control agents include metal-containing salicylic acid compounds and metal-containing compounds. Monoazo dye compound, styrene
An acrylic acid copolymer and a styrene-methacrylic acid copolymer are exemplified.

As the colorant contained in the toner used in the present invention, known colorants can be used, for example, carbon black; iron black; I. Direct Red 1, C.I.
I. Direct Red 4, C.I. I. Acid Red 1,
C. I. Basic Red 1, C.I. I. Modant Red 30, C.I. I. Solvent Red 49, C.I. I. Solvent Red 52, C.I. I. Direct Blue 1, C.I.
I. Direct Blue 2, C.I. I. Acid blue 9,
C. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6, C.I. I.
Basic Green 4, C.I. I. Basic Green 6
Dyes such as: graphite, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG,
Tartrazine Lake, Molybdenum Orange, Permanent Orange GTR, Benzidine Orange G, Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Brilliant Carmine 3B, Fast Violet B, Methyl Violet Lake, Navy Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, quinacridone, disazo yellow pigments, pigments such as phthalocyanine blue, fast sky blue, pigment green B, malachite green lake, and final yellow green G. In the case of obtaining a toner using a polymerization method in the present invention, it is necessary to pay attention to the polymerization inhibitory property and aqueous phase migration property of the colorant, preferably, surface modification, for example, by using a substance having no polymerization inhibition It is better to perform surface modification as in the case of hydrophobic treatment.

Examples of the wax as a release agent contained in the toner used in the present invention include paraffin wax, polyolefin wax and modified products thereof (for example, oxides and graft-treated products), higher aliphatic acids, Examples thereof include metal salts and amide waxes, but are not limited thereto.

The melting point of the wax contained in the toner used in the present invention is preferably from 30 to 150 ° C.
More preferably, the temperature is 40 to 140 ° C. Melting point is 30 ° C
When the temperature is lower, the blocking resistance and the shape retention of the toner are not sufficient. When the temperature is higher than 150 ° C., the effect of the releasability is not sufficient.

The melting point was calculated from the temperature of the maximum endothermic peak by DSC.

The heat of fusion ΔH of the wax contained in the toner used in the present invention is preferably 50 to 250 J / g.

Such a wax is used as the polymerizable monomer 100
It is preferably used in an amount of 0.1 to 50 parts by weight, more preferably 1 to 45 parts by weight, still more preferably 5 to 50 parts by weight.
~ 40 parts by weight is good. If the amount of the wax is less than 0.1 part by weight, the effect of the releasability is small.

As the polymerization initiator, for example, 2,2'-
Azobis- (2,4-dimethylvaleronitrile), 2,
2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2 '
Azo or diazo polymerization initiators such as azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4- Peroxide-based polymerization initiators such as dichlorobenzoyl peroxide and lauroyl peroxide are exemplified. Further, as the redox initiator, the above-mentioned peroxide, dimethylaniline, mercaptans, tertiary amines, iron (I
I) A salt and a reducing agent such as sodium hydrogen sulfite may be used in combination.

These polymerization initiators are suitably used for obtaining a desired molecular weight, but generally, an addition amount of 0.1 to 10% by weight of the polymerizable monomer is sufficient.

The release agent, polymerization initiator and polymerization temperature in the present invention will be described in more detail.

When a wax having a generally low melting point or softening point, such as paraffin wax, is used as the release agent, the temperature at which the release agent precipitates from the polymerizable monomer composition is low, and the polymerization temperature is also low. Lower. In such a case, a redox initiator or, for example, 2,2'-azobis-4
It is preferred to use a short half-life initiator such as -methoxy-2,4-dimethylvaleronitrile.

When a wax having a high melting point or softening point such as a polyolefin wax is used as a release agent, an autoclave is used to dissolve or melt the release agent in the polymerizable monomer composition. Further, since the precipitation temperature of the release agent is relatively higher than that of a wax having a high melting point or softening point, such as the above-mentioned paraffin wax, 2,2'-azobis (2,4-dimethylvaleronitrile) ) And a polymerizable initiator such as dimethyl 2,2'-azobisisobutyrate.

In the present invention, in addition to the polymerized toner, a toner obtained by kneading, pulverizing and classifying can be used. The polymer used in the binder resin of the toner is obtained by polymerizing an acid such as acrylic acid, methacrylic acid and maleic acid and esters thereof; polyester; polysulfonate; polyether; and a monomer such as polyurethane. Resins or resins obtained by copolymerizing two or more of these monomers can be used.

These resins and other toner constituent materials can be obtained by well kneading with a hot kneader such as a hot roll, kneader or extruder, followed by mechanical pulverization and classification.

Known additives may be added to the toner of the present invention for the purpose of imparting various properties. The additives are
From the viewpoint of durability when added to the toner, the particle diameter is preferably 1/10 or less of the volume average particle diameter of the toner particles. The particle size of the additive means an average particle size obtained by observing the surface of the toner particles with an electron microscope.
Examples of additives for imparting these properties include, for example,
The following are used.

1) Fluidity imparting agents: metal oxides (silicon oxide, aluminum oxide, titanium oxide), carbon black, and carbon fluoride. These are more preferably subjected to a hydrophobic treatment.

2) Abrasives: metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.),
Carbides (silicon carbide, etc.) and metal salts (calcium sulfate, barium sulfate, calcium carbonate, etc.).

3) Lubricants: fluororesin powder (vinylidene fluoride, polytetrafluoroethylene, etc.), metal salts of fatty acids (zinc stearate, calcium stearate, etc.).

4) Charge controllable particles: metal oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide, etc.) and carbon black.

These additives may be used in an amount of preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner particles. good. Even if these additives are used alone,
Also, a plurality of them may be used in combination.

In the present invention, a toner to be used for forming a color image on the surface of a heat-resistant resin film as a base material layer in order to obtain a recording material having good translucency and reproducibility of color tone of a projected image in an OHP apparatus. It is preferable to form a transparent resin layer formed of a transparent resin having compatibility with the resin constituting the particles (binder resin) and having a different heat melting property at the fixing temperature from the resin constituting the toner particles.

In FIGS. 2 and 3, reference numeral 31 denotes a transparent resin base film as a base material layer of the recording material as described with reference to FIG.

In the recording material shown in FIGS. 2 and 3, 32
Denotes a transparent resin layer for improving the translucency of the color image after fixing. It is preferable that the transparent resin layer 32 be compatible with a resin (binder resin) constituting toner particles forming a color image at a temperature at the time of heat fixing. Being compatible with the binder resin of the toner means that the resin of the transparent resin layer 32 and the binder resin of the toner do not form a boundary in the image after fixing. As a guide for selection, the main resin used in the toner (based on the binder resin, 5
It is preferable that the value of the solubility parameter of the resin of the transparent resin layer 32 be within ± 1.5, more preferably ± 1.0 of the solubility parameter of the main resin which is contained in 0% by weight or more. good. Resin solubility parameters are described in publications such as the Polymer Handbook. For example, when a polyester resin is used as the binder resin for the toner, the value of the solubility parameter is about 11.0, so that the resin of the transparent resin layer 32 has a solubility parameter within the range of 11.0 ± 1.5. It is possible to use thermoplastic resins such as polyester resins, polymethyl methacrylate resins, epoxy resins, polyurethane resins, vinyl chloride resins, and vinyl chloride-vinyl acetate copolymers. In particular, it is more preferable to use the same resin as the main resin of the toner for the transparent resin layer 32.

The resin used for the transparent resin layer 32 preferably has a storage elastic modulus (G ') at a temperature of 160 ° C. and a frequency (w) of 100 rad / sec, preferably from 1 × 10 ³ to 1 × 10 ^3.
6 dyn / cm ² , more preferably 5 × 10 ^{3 to} 5 × 1
It is preferable to have 0 ⁵ dyn / cm ² . Temperature 160
° C., when the frequency (w) 100 rad / storage modulus sec (G ') was used 1 × 10 ³ dyn / cm ² less than the resin in the transparent resin layer 32 fixes the toner image by hot pressure roller At times, the offset phenomenon is likely to occur, and the transparent resin layer 32 is partly peeled off from the base film 31 to be easily broken. When a resin having a storage elastic modulus (G ') of more than 1 × 10 ⁶ dyn / cm ² at a temperature of 160 ° C. and a frequency (w) of 100 rad / sec is used for the transparent resin layer 32, the toner image is formed with a hot-press roller. Even when the toner image is fixed, the degree of penetration of the toner image into the transparent resin layer 32 is extremely small, so that the projected image shows a gray color tone as a whole.

The storage elastic modulus (G ') of the resin used for the transparent resin layer 32 is determined by Rheometrics (Rheome).
tricks Inc. ) Was measured using a mechanical spectrometer RMS-800. Conditions were such that the frequency was fixed at w = 100 rad / sec, and the distortion rate was automatic. In this state, the temperature was raised to measure the temperature dependency, and the storage elastic modulus G 'at 160 ° C. was measured from the result. Although the optimum thickness of the transparent resin layer 32 varies depending on the particle size of the toner to be fixed, it preferably has a thickness of 3 to 30 μm, preferably 8 to 15 μm.

In the recording material shown in FIGS. 2 and 3, B denotes an absorption layer that absorbs the wax component contained in the toner, similar to the recording material shown in FIG. 1 described above.

The formation of the absorbing layer B on the surface of the transparent resin layer 32 formed on the surface of the base film 31 is the same as that shown in FIG.
Can be performed by the same method as that described for the recording material shown in FIG.

The recording material shown in FIGS. 4 and 5 has the same structure as that of FIG. 1 except that it has a transparent resin layer 32B in which the above-mentioned inorganic fine particles for absorbing the wax according to the present invention are dispersed. It has the same configuration as the transparent resin layer 32 of the recording material shown. In this case, the surface of the transparent resin layer 32B has an average pore radius D of 10 ° due to the dispersed inorganic fine particles.
It is preferable that pores of up to 200 ° are formed.

As a method for forming the transparent resin layer 32 or the transparent resin layer 32B on the surface of the base film 31 of the recording material of the present invention, a volatile resin made of alcohol such as methanol or ethanol, or ketone such as methyl ethyl ketone or acetone is used. A resin for forming the transparent resin layer 32 or the transparent resin layer 32B is dissolved in an organic solvent, and the transparent resin layer 3
In the case of forming 2B, the above-mentioned inorganic fine particles according to the present invention are further dispersed, applied to the surface of the transparent base film 31 by a method such as a bar coating method, a dipping method, a spraying method, and a spin coating method, and dried. Method. In some cases, the adhesiveness between the transparent resin layer 32 or the transparent resin layer 32B and the base film 31 is increased, and the surface of the base film 31 is plasma-coated so that the fixed toner image does not peel off from the base film 31 during and after fixing. Surface treatment such as a treatment or corona discharge treatment, and an adhesive layer 33 that is compatible with the base film 31 and the transparent resin layer 32 or the transparent resin layer 32B and has high heat resistance and does not melt by heating during fixing. Can be provided as shown in FIG. 3 or FIG. Examples of the resin that can be used as the adhesive layer 33 include resins such as a polyester resin, an acrylate resin, a methacrylate resin, a styrene-acrylate copolymer, and a styrene-methacrylate copolymer.

The above-mentioned transparent resin layer 32 or transparent resin layer 32
The toner used in the image forming method using the recording material having B will be described below.

The toner used in the color electrophotographic apparatus needs to have good melting property and color mixing property when heat is applied, and has a low softening point, a low storage elastic modulus at a fixing temperature, and a sharp melt property. It is preferable to use a toner.

In relation to the above-mentioned recording material, it is preferable that the storage elastic modulus of the toner is clearly smaller than the storage elastic modulus (G ') of the resin forming the transparent resin layer 32 or the transparent resin layer 32B. . Specifically, the toner has a temperature of 16
A transparent resin having a storage elastic modulus of 1 × 10 ² to 1 × 10 ⁵ dyn / cm ² , preferably 5 × 10 ^{2 to} 5 × 10 ⁴ dyn / cm ² at 0 ° C. and a frequency (w) of 100 rad / sec. This is preferred in terms of compatibility with the layer 32 or the transparent resin layer 32B and color mixing between the toners.

In forming a color image or a full color image, by using a sharp melt toner,
The color reproduction range of a copy can be widened and a color copy faithful to a multicolor or full-color image of a document can be obtained favorably.

The toner used for the recording material shown in FIGS.
In consideration of the fixing property and the sharp melt property, those using a polyester resin as the binder resin are particularly preferable.
Examples of the sharp melt polyester resin include a polymer compound having an ester bond in the main chain of a molecule synthesized from a diol compound and a dicarboxylic acid.

In particular, the following equation

[0103]

[Outside 1] (Wherein R is an ethylene or propylene group, x, y
Is a positive integer of 1 or more, respectively, and the average value of x + y is 2 to 10. A) a bisphenol derivative or a substituted product thereof as a diol component, and a carboxylic acid component comprising a divalent or higher carboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof (eg, fumaric acid, maleic acid, maleic anhydride, phthalic acid) Acid, terephthalic acid, trimellitic acid, and pyromellitic acid) are more preferable because they have sharp melting properties.

The softening point of the polyester resin is preferably 7
The temperature is preferably 5 to 150C, more preferably 80 to 130C.
FIG. 6 shows the softening characteristics of a toner containing a polyester resin as a binder resin. The method for measuring the softening point used in the present invention will be described below.

Using a flow tester CFT-500A type (manufactured by Shimadzu Corporation), a die (nozzle) diameter of 0.2 m
m, a thickness of 1.0 mm, a 20 kg extrusion load, an initial set temperature of 70 ° C., a preheating time of 300 seconds, and a constant temperature rise at a rate of 6 ° C./min. A temperature curve (hereinafter referred to as a softening S-shaped curve) is obtained. The toner used as the sample is a fine powder obtained by precisely weighing 1 to 3 g, and the cross-sectional area of the plunger is 10 cm ² . The softening S-shaped curve is as shown in FIG. As the temperature rises at a constant speed, the toner is gradually heated and starts to flow (plunger descent A → B). Further, when the temperature rises, the toner in the molten state flows out greatly (B → C → D), the plunger descent stops, and the process ends (D → E).

The height H of the S-shaped curve indicates the total amount of outflow, and H /
The temperature T ₀ corresponding to the C point 2 indicates the softening point of the sample (for example, toner or resin).

In relation between the toner and the recording material, the temperature of the toner or the binder resin is 160 ° C., the frequency is 100 rad /
The storage elastic modulus (G ′) in sec.
Or, the temperature 16 of the resin used for the transparent resin layer 32B.
It is preferably smaller than the storage elastic modulus (G ') at 0 ° C. and a frequency of 100 rad / sec. It is preferable that the transparent resin layer 32 or the transparent resin layer 32B exhibit higher elasticity than the toner or the binder resin at a fixing temperature (for example, 130 to 170 ° C.). When the storage elastic modulus (G ') of the resin forming the transparent resin layer 32 or the resin forming the transparent resin layer 32B at the fixing temperature is close to that of the binder resin of the toner, the toner of two or more colors is obtained as a full-color image. When the overlapping portion and the single-color toner portion are fixed under a condition that sufficient transparency as a light-transmitting image can be obtained by one heat fixing, the transparent resin layer 32 or the transparent resin layer 32B is also sufficiently heated. As a result, the viscoelasticity decreases, so that separation of the transparent resin layer 32 or the transparent resin layer 32B easily occurs at the interface between the transparent resin layer 32 or the transparent resin layer 32B and the base film 31, and the image is heated for fixing. This may cause a hot offset phenomenon that is partially stripped off the roll.

When the storage elastic modulus (G ′) of the transparent resin of the transparent resin layer 32 or the transparent resin layer 32B is lower than the storage elastic modulus (G ′) of the binder resin of the toner, the transparent resin layer 32 or the transparent resin layer 32B Although it is possible to fix a single color toner image on the top, if the color toner images having different color tones are overlaid and fixed, the melt viscosity of the transparent resin layer 32 or the transparent resin layer 32B becomes lower than the viscosity of the binder resin of the toner. Therefore, it is difficult to develop good color mixture.

In the relationship between the toner and the recording material, the storage elastic modulus (G ′) of the transparent resin layer 32 or the transparent resin layer 32B at the fixing temperature (for example, 160 ° C.) is 1000 times the storage elastic modulus (G ′) of the toner. In the case where the ratio is more than twice, practically possible translucency is obtained in a thin layer image of a single toner, but in a multi-color or full-color image or a high-density image, the transparent resin layer 32 or the transparent resin layer 32B is sufficient at the time of fixing. Since no significant deformation occurs, unevenness due to uneven thickness of the multilayer toner remains on the image. Therefore, the light transmittance tends to decrease. Further, the transparent resin layer 32 or the transparent resin layer 32
Since the adhesion between B and the toner is poor, separation in the toner layer occurs, which may cause offset.

The thickness of the transparent resin layer 32 or the transparent resin layer 32B varies depending on the toner particle size to be used. The thickness must be 0.5 times or more the average value of the toner particle diameter. When the thickness is three times or more the toner particle size, the amount of the molten resin increases, which causes not only blurring and distortion of the image but also cracking of the image due to bending. Preferably, the average value of the volume particle diameter of the toner is 0.5 to
It is twice.

Specifically, when a toner having a volume average particle diameter of 6 μm is used, the transparent resin layer 3 having a thickness of 3 to 12 μm is used.
It is preferable to use a recording material having a transparent resin layer 32 or a transparent resin layer 32B. When a toner having a volume average particle diameter of 15 μm is used, a recording material having a transparent resin layer 32 or a transparent resin layer having a thickness of 7.5 to 30 μm is used. Preferably, a material is used.

In the present invention, the average particle size of the toner was measured according to the following method.

As a measuring device, Coulter Counter T
Using an A-II type (manufactured by Coulter), connected to an interface (manufactured by Nikkaki) that outputs the number distribution, volume distribution, number average and volume average, and a CX-1 personal computer (manufactured by Canon), the electrolyte is first class A 1% NaCl aqueous solution is prepared using sodium chloride. As a measuring method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzenesulfonate, is added as a dispersing agent to 100 to 150 ml of the electrolytic aqueous solution, and the sample to be measured is 0.5 to 50 m
g, preferably 2-20 mg. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes by an ultrasonic disperser, and the particle size of particles having a particle size of 2 to 40 μ is measured by the Coulter Counter TA-II using a 100 μ aperture as an aperture. The distribution is measured to determine the volume average particle size.

The color image forming method according to the present invention will be described.

FIG. 7 is a schematic sectional view of an electrophotographic apparatus capable of forming a full-color image according to the present invention. In the drawing, a recording material transport system I provided from the right side of the apparatus main body 100 (right side in FIG. 7) to a substantially central portion of the apparatus main body 100, and the recording material transport system I And a developing unit (that is, a rotary developing device III) provided in close proximity to the latent image forming unit II. It is roughly divided. The recording material transport system I described above is
The recording material supply trays 101 and 102 are detachable from the opening formed on the right side of FIG. 7 (the right side in FIG. 7), and the paper feed rollers 103 and 104, paper feed guides 4A and 4B provided near the paper feed rollers 103 and 104 and provided with a paper feed roller 106, provided near the paper feed guide 4B, and rotated near the outer peripheral surface. A roller 7 for contact, a gripper 6, a charger 12 for separating recording material, and a separation claw 14 are provided from upstream to downstream in the direction, and a transfer charger 9 and a transfer material separating A charger 13 is provided. A transfer drum 8 rotatable in the direction of an arrow in FIG. 7 and a transport belt means 1 provided in proximity to the separation claw 14.
5 and an apparatus main body 1 which is disposed close to the conveying direction end end of the conveying belt means 15 and extends outside the apparatus main body 100.
The fixing device 16 includes a discharge tray 17 that is detachable from the fixing device 00 and a fixing device 16 that is close to the tray.

The latent image forming section II has an outer peripheral surface provided in contact with the outer peripheral surface of the transfer drum 8 and is rotatable in the direction of the arrow in FIG. 2) and a charge eliminator 10, a cleaning unit 11, a primary charger 3, which are disposed near the outer peripheral surface of the photosensitive drum 2 from the upstream side to the downstream side in the rotation direction of the photosensitive drum 2. An image exposure means such as a laser beam scanner for forming an electrostatic latent image on the outer peripheral surface of the photosensitive drum 2 and an image exposure reflection means such as a polygon mirror are provided. The rotary developing device III includes a rotatable housing (hereinafter, referred to as a “rotating body”) 18 and the rotating body 18.
Each of the yellow toners is mounted inside the photosensitive drum 2 so as to visualize (ie, develop) an electrostatic latent image formed on the outer circumferential surface of the photosensitive drum 2 at a position facing the outer circumferential surface of the photosensitive drum 2. It has a developing unit 18Y, a magenta developing unit 18M, a cyan developing unit 18C, and a black developing unit 18Bk.

The sequence of the entire image forming apparatus having the above configuration will be described by taking a full color mode as an example. When the aforementioned photosensitive drum 2 rotates in the direction of the arrow in FIG. 7, the photosensitive member on the photosensitive drum 2 is uniformly charged by the primary charger 3. When the photosensitive member is uniformly charged by the primary charger 3, a document (not shown)
The image exposure is performed by the laser light E modulated by the yellow image signal, a latent electrostatic image is formed on the photosensitive drum 2, and the yellow developing unit 18 </ b> Y previously set at the developing position by the rotation of the rotating body 18. Thus, the electrostatic latent image is developed.

On the other hand, the paper feed guide 4A and the paper feed roller 10
6. The recording material conveyed via the paper feed guide 4B is held by the gripper 6 at a predetermined timing,
The transfer roller 8 is electrostatically wound around the contact roller 7 and an electrode facing the contact roller 7. The transfer drum 8 rotates in the direction of the arrow in FIG. 7 in synchronization with the photosensitive drum 2, and the developed image developed by the yellow developing device 18 </ b> Y is formed on the outer peripheral surface of the photosensitive drum 2 and the outer peripheral surface of the transfer drum 8. The image is transferred by the transfer charger 9 at a portion where the surface contacts. The transfer drum 8 continues to rotate as it is to prepare for transfer of the next color (magenta in FIG. 7).

The photosensitive drum 2 is provided with the charge removing charger 10.
, And after being cleaned by the cleaning means 11, charged again by the primary charger 3,
The image is exposed as described above by the next magenta image signal. The rotary developing device rotates while an electrostatic latent image based on a magenta image signal is formed on the photosensitive drum 2 by the image exposure, and fixes the magenta developing device 18M at the above-described predetermined developing position. A predetermined magenta development is performed. Subsequently, the above-described process is performed for the cyan and black colors, respectively. When the transfer of the four colors is completed, the multicolored visual image formed on the recording material is charged by the chargers 12 and 13. The electricity is removed, the gripping of the recording material by the gripper 6 is released, and the recording material is separated from the separation claw 14.
Is transferred from the transfer drum 8 to the fixing device 16 by the conveyor belt 15, and is fixed by heat and pressure, thereby completing a series of full-color print sequences, thereby forming a required full-color print image.

The fixing device 16 includes a heat fixing roller 161 and a pressure roller 162. Heating roller 161
Preferably has a surface layer having excellent release properties such as silicone rubber and fluorine-based resin. Pressure roller 162
Is preferably formed of a fluorine-based resin.

Hereinafter, the present invention will be described in detail with reference to examples.

[0122]

EXAMPLE 1 To 709 parts by weight of ion-exchanged water, 451 parts by weight of a 0.1 M Na ₃ PO ₄ aqueous solution were added, and after heating to 60 ° C., TK
12,000 using a homo homomixer (manufactured by Tokushu Kika Kogyo)
The mixture was stirred at 0 rpm. 67.7 parts by weight of a 1.0 M CaCl ₂ aqueous solution was gradually added thereto, and Ca ₃ (PO ₄ )
A dispersion medium containing ₂ was obtained. 170 parts by weight of styrene 30 parts by weight of 2-ethylhexyl acrylate 60 parts by weight of paraffin wax (mp 75 ° C.) I. Pigment Blue 15 10 parts by weight ・ Styrene-methacrylic acid-methyl methacrylate copolymer 5 parts by weight ・ Di-tert-butylsalicylate metal compound 3 parts by weight

Among the above formulations, C.I. I. Pigment Blue 15, metal di-tert-butylsalicylate and styrene alone were premixed using an Ebara Milder (manufactured by Ebara Corporation). Next, all of the above formulations were heated to 60 ° C. and dissolved and dispersed to obtain a monomer mixture. Further 60
While maintaining the temperature at 10 ° C., 10 parts by weight of an initiator dimethyl 2,2′-azobisisobutyrate was added and dissolved to prepare a monomer composition.

The above monomer composition was charged into a dispersion medium prepared in a 2 l flask of the homomixer. 60 ° C
And using a TK homomixer in a nitrogen atmosphere for 100
The mixture was stirred at 00 rpm for 20 minutes to granulate the monomer composition. Thereafter, the mixture was reacted at 60 ° C. for 3 hours while stirring with a paddle stirring blade, and then polymerized at 80 ° C. for 10 hours.

After the completion of the polymerization reaction, the reaction product was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , and the polymer was filtered, washed with water and dried to obtain a polymerized toner.

When the particle size of the obtained toner was measured by a Coulter counter, it was found to have a weight average particle size of 8.2 μm and a sharp particle size distribution. Furthermore, when the cross section of the particles was observed with a transmission electron microscope using a stained ultrathin section method,
It was divided into a surface layer mainly composed of styrene-acrylic resin and a central part mainly composed of wax, and the capsule structure was confirmed.

With respect to 100 parts by weight of the obtained toner, B
0.7 parts by weight of a hydrophobic silica having a specific surface area of 200 m ² / g by the ET method was externally added. To 7 parts by weight of this toner, 93 parts by weight of a Cu-Zn-Fe-based ferrite carrier surface-coated with a styrene-methyl methacrylate copolymer were mixed to prepare a developer.

Using this developer, an image was formed using a commercially available full-color copying machine (manufactured by CLC-500 Canon).
The development was performed at a development contrast of 320 V in an environment of a temperature of 23 ° C. and a humidity of 65% RM.

As a recording material, a recording material A obtained by forming a thin film of inorganic fine particles containing aluminum as a main element as a wax component absorbing layer by a known CVD method (chemical vapor deposition method) on a PET layer having a thickness of about 100 μm was used. Using. The obtained recording material A had an average pore radius of 32 ° and a BET specific surface area of 7 m ² / g.

The unfixed toner image on the recording material which had just been developed and transferred by the modified CLC-500 was fixed by an external fixing machine (with the same roller configuration as the commercially available CLC-500 and without an oil application function). Fixing speed is 20mm /
sec.

The obtained fixed toner image was a clear image having no offset and no trace of the exudation of the wax component. When actually projected by an overhead projector, a very clear cyan projected image was obtained, and the effect of the recording material of the present invention was confirmed.

Example 2 A laminated film B was prepared in which a silica-based inorganic fine particle was used in place of the inorganic fine particle containing aluminum as a main element in Example 1, and a similar absorption layer of a wax component was provided. The average pore radius of the absorption layer of the wax component of the obtained recording material B was 55 °, and the BET specific surface area was 11 m ² /
g.

When an image was formed and fixed in the same manner as in Example 1, a good fixed image was obtained without traces of wax component oozing. When taken with an OHP device, a clear projected image was obtained without impairing the transparency.

Example 3 In the toner used in Example 1, C.I. Pigment Blue 15 instead of C.I. Pigment Red 122, 9 parts by weight of magenta toner, C.I. A yellow toner was obtained by using 8 parts by weight of I Pigment Yellow 17, and a black toner was obtained by using 12 parts by weight of commercially available carbon black.

A developer was prepared from the obtained three-color toner in substantially the same manner as in Example 1, and a CLC-500 toner was prepared using the four-color developer including the blue developer used in Example 1. The full-color unfixed toner image just developed and transferred by the remodeling machine is oil-coated with an external fixing machine (using a fluorine-based resin-coated soft roller for the fixing roller and a silicone-based rubber roller for the pressure roller). It settled without.

As the recording material, recording material A having a wax component absorbing layer used in Example 1 was used. The obtained fixed toner image was excellent in quality without offset and showing no trace of exudation of the wax component.

When projected with an overhead projector in the same manner as in Example 1, a very clear full-color projected image was obtained. Further, this transparent film was obtained by fixing a full-color toner image without applying oil, and was excellent in storage stability without stickiness.

Example 4 Instead of the recording material A used in Example 1, a PET of about 100 μm was used.
A coating solution prepared by mixing 90 parts by weight of alumina hydrate and 10 parts by weight of polyvinyl alcohol in 1000 parts by weight of water was coated on a base material layer having a thickness of m by a bar coating method.
After drying in a drying oven at 50 ° C. for 10 minutes, the thickness after drying is 8
A recording material C having a wax component absorption layer formed to a thickness of μm was used. The average pore radius of the wax component absorption layer of the recording material C was 50 °, and the BET specific surface area was 1 °.
It was 0 m ² / g. An image was formed and fixed in the same manner as in Example 1 except that the recording material C was used. As a result, a good fixed toner image having no trace of exudation of the wax component was obtained. When I projected it with an OHP device,
A clear projected image was obtained without impairing the transparency.

Comparative Example 1 A commercially available overhead projector film (transparency OHP film for NP series, sold by Canon Sales Co., Ltd.), which is a polyethylene terephthalate film subjected to static elimination, instead of the recording material A used in Example 1. When development, transfer and fixing were carried out in the same manner as in Example 1 except that the toner was used, no offset was caused by the effect of the wax component included in the toner, but the exudation trace of the wax component on the rear end of the image portion. And an image with low transparency was obtained as a whole.

Example 5 In the recording material A used in Example 1, when the amount of the inorganic fine particles used was reduced to form a thin film, the specific surface area of the obtained recording material D was 0.08 m ² / g. .

When development, transfer and fixation were carried out in the same manner as in Example 1 except that the above-mentioned recording material D was used, no offset was observed, but a slight trace of wax component exudation was observed at the rear end of the image area. However, it was just enough for use.

Example 6 100 parts by weight of styrene-butyl acrylate copolymer 7 parts by weight of low molecular weight polyolefin wax 4.5 parts by weight of phthalocyanine pigment 3 parts by weight of metal di-tert-butylsalicylate

After mixing the above pigment, the mixture is melt-kneaded by a twin-screw kneading extruder, cooled, pulverized by an air-flow type pulverizer, and classified by an air classifier to obtain a blue powder toner having a weight average diameter of about 8.5 μm. Was. 0.8 part by weight of negatively chargeable colloidal silica was externally added to 100 parts by weight of this toner to obtain a cyan toner. These toners and ferrite particles coated with a fluoroacrylic resin were mixed at a ratio of 1: 9 to obtain a blue developer.

In Example 1, an inorganic fine particle containing aluminum as a main element was formed into a thin film by a conventionally known CVD method (chemical vapor deposition method) on a base material layer having a thickness of PET of about 100 μm as a recording material and as a wax component absorbing layer. The recording material A was used.

A commercially available full-color copying machine (CLC-500, manufactured by Canon Inc.) was modified using the blue developer, and an image was formed on a recording material A to obtain an unfixed toner image.

As the fixing device, an external fixing device having a fluorine-based resin coated roller as an upper roller and a silicon rubber roller as a lower roller and having no oil application function was used.

When a fixing test was carried out using the above fixing device without applying oil, no offset phenomenon occurred and a fixed toner image could be obtained. Further, the image did not lose transparency and had no trace of exudation of the wax component.

Example 7 As a recording material, a thin film of silica was formed on a substrate layer having a thickness of about 100 μm of PET by a CVD method (chemical vapor deposition method) to have an average pore radius of 26 ° and a BET specific surface area of 12 m ² / g
An image was formed and fixed in the same manner as in Example 6 except that the recording material E was used, and a fixed toner image was obtained without causing an offset phenomenon.
Further, the image did not lose transparency and had no trace of exudation of the wax component.

Example 8 100 parts by weight of polyester 9 parts by weight of paraffin wax 4.5 parts by weight of phthalocyanine pigment 3 parts by weight of metal compound di-tert-butylsalicylate

The above raw materials were kneaded, crushed, and kneaded in the same manner as in Example 6.
Classification, external addition, and mixing with a carrier gave a blue developer.

An unfixed toner image was formed on the recording material A in the same manner as in Example 6, and a fixing test was performed.

As a result, it was possible to obtain a fixed toner image having excellent transparency without any trace of exudation of the wax component.

Example 9 An image was formed and fixed in the same manner as in Example 6, except that the recording material C used in Example 4 was used instead of the recording material A used in Example 6. As a result, an offset phenomenon did not occur, and a fixed toner image could be obtained. Further, the image did not lose transparency and had no trace of exudation of the wax component.

Comparative Example 2 The same procedure as in Example 6 was carried out except that the blue developer used in Example 6 was replaced with a blue developer having a toner obtained by removing the wax component of the toner in the blue developer. Then, when an image was formed on the recording material A and fixed in the same manner, an offset phenomenon occurred, and a good fixed toner image could not be obtained.

Example 10 A recording material F having a BET specific surface area of 0.09 m ² / g was obtained by changing the film forming conditions of the wax component absorbing layer of the recording material A used in Example 6.

An image was formed and fixed in the same manner as in Example 6 except that the recording material F used in place of the recording material A used in Example 6 was fixed in the same manner. Although the properties were slightly reduced, they were just enough to withstand practical use.

Example 11 A biaxially stretched 100 μm thick polyethylene terephthalate (PET) film having a heat distortion temperature of 152 ° C. and a maximum operating temperature of 150 ° C.
A solution prepared by dissolving a polyester resin (solubility parameter: about 11) having a storage elastic modulus (G ′) of 8 × 10 ⁴ dyn / cm ² at a frequency (w) of 100 rad / sec and a softening point of 116 ° C. in acetone was used as a bar. After coating by a coating method and forming a transparent resin layer so that the thickness after drying was 16 μm, an absorption layer of a wax component was formed in the same manner as in Example 3 to obtain a recording material G.

Temperature 160 ° C., frequency (w) 100 rad
/ Sec storage elastic modulus (G ′) is 4 × 10 ³ dy
a n / cm ^2, the polyester resin P ₂ (solubility parameter of about 11) having ℃ softening point 105 to 100 parts by weight,
A yellow powder toner was prepared using 9 parts by weight of paraffin wax, 3.5 parts by weight of a yellow colorant, and 4 parts by weight of a chromium-containing organic complex. The volume average particle diameter of the yellow powder toner is 12 μm, the temperature is 160 ° C., and the frequency (w) is 1
The storage elastic modulus (G ') at 00 rad / sec is 8 ×
10 ³ a dyn / cm ^2, a softening point of 107 ° C..

To 100 parts by weight of the obtained yellow powder toner, 0.4 parts by weight of hydrophobic colloidal silica was externally added to obtain a yellow toner. These toners and ferrite particles coated with a fluoroacrylic resin were mixed at a ratio of 5: 100 to obtain a yellow developer.

The above-mentioned yellow developer is used in the image forming apparatus shown in FIG. 7 (the surface layer of the heat fixing roller 161 is formed of silicone rubber, and the surface layer of the pressure roller 162 is formed of a fluorine resin). An image was formed so that the fixed image density became 1.5 (Macbeth reflection densitometer), a yellow toner image was formed uniformly, and the image was transferred to the recording material G obtained above. The yellow unfixed toner image is heated with a fixing roller temperature of 160 ° C., an average heating time of 25 msec, and a pressing force of 3K.
The image was fixed by heat and pressure with a heat and pressure fixing device under the condition of g / cm ² to form a fixed yellow toner image on the recording material G.

The obtained fixed toner image was a clear fixed toner image with no offset and no trace of exudation of the wax component. When actually projected by an overhead projector, very clear yellow transmitted light was obtained, and a clear yellow projected image was obtained, thereby confirming the effect of the recording material of the present invention.

Example 12 Except for using 1.9 parts by weight of a magenta colorant,
In the same manner as in Example 13, a magenta powder toner having a volume average particle size of 12 μm was prepared. The magenta powder toner had a storage elastic modulus (G ′) of 6 × 10 ³ dyn / cm ² at a temperature of 160 ° C. and a frequency (w) of 100 rad / sec.

Using the obtained magenta powder toner, a red developer was prepared in the same manner as in Example 11, and an image was formed on a recording material G in the same manner as in Example 11 except that the red developer was used. When the toner was discharged and fixed in the same manner, the obtained fixed image was a clear fixed toner image without offset and without traces of the exudation of the wax component. When actually projected by an overhead projector, very clear red transmitted light was obtained, and a clear red projected image was obtained. The effect of the recording material of the present invention was confirmed.

Example 13 A cyan powder toner having a volume average particle diameter of 12 μm was prepared in the same manner as in Example 11, except that 5.0 parts by weight of a cyan coloring agent was used. Cyan powder toner has a temperature of 160
The storage elastic modulus (G ′) at 100 ° C. and a frequency (w) of 100 rad / sec was 1 × 10 ⁴ dyn / cm ² , and the softening point was 108 ° C.

Using the obtained cyan powder toner, a blue developer was prepared in the same manner as in Example 11, and a recording material G was prepared in the same manner as in Example 11 except that the blue developer was used. When the image was formed and fixed in the same manner, the obtained fixed toner image was a clear fixed toner image without offset and no trace of exudation of the wax component. When actually projected by an overhead projector, very clear blue transmitted light was obtained, and a clear blue projected image was obtained, thereby confirming the effect of the recording material of the present invention.

Example 14 A wax component absorbing layer of the recording material G used in Example 11 was formed in the same manner as in Example 4, and a 16 μm-thick polyester resin coating layer was formed on a PET layer having a thickness of about 100 μm. (Transparent resin layer), and a recording material H in which alumina fine particles having a thickness of 8 μm and a polyvinyl alcohol coat layer (absorption layer of a wax component) were further laminated thereon was formed. Recording material H
The image was formed and fixed in the same manner as in Example 11 except for using, and the obtained fixed toner image was not offset, and the trace of exudation of the wax component was also clear. It was a fixed toner image.
When actually projected by an overhead projector, very clear yellow transmitted light was obtained, and a clear yellow projected image was obtained, thereby confirming the effect of the recording material of the present invention.

Example 15 The value of the solubility parameter in the transparent resin layer was 10.5,
An epoxy resin having a weight average molecular weight of 20,000, a storage elastic modulus (G ′) of 5 × 10 ⁴ dyn / cm ² at a temperature of 160 ° C. and a frequency (w) of 100 rad / sec, and a softening point of 114 ° C. is converted to methyl ethyl ketone. The melted solution was applied, a transparent resin layer having a thickness of 15 μm after drying was applied on the same PET film base layer as in Example 11, and a wax component absorbing layer was further formed in the same manner as in Example 1. The recording material I was formed.

An image was formed and fixed in the same manner as in Example 11 except that the fixed image density was adjusted to 0.5 using the obtained recording material I. The toner image was a clear fixed image with no offset and no trace of exudation of the wax component. When actually projected by an overhead projector, very clear yellow transmitted light was obtained, and a clear yellow projected image was obtained, thereby confirming the effect of the recording material of the present invention.

Example 16 The same procedure as in Example 15 was repeated except that the magenta toner prepared in Example 12 was used, and a fixed toner image using a magenta color toner was formed on the recording material I so that the fixed image density became 0.5. Formed on top.

The obtained fixed toner image was a clear fixed image with no offset and no trace of exudation of the wax component. When actually projected by an overhead projector, very clear red transmitted light was obtained, and a clear red image was obtained. The effect of the recording material of the present invention was confirmed.

Example 17 The same procedure as in Example 15 was carried out except that the cyan toner prepared in Example 13 was used, so that the fixed toner image of the cyan color toner was changed to the recording material I so that the fixed image density became 0.5. Formed on top.

The obtained fixed toner image was a clear fixed image with no offset and no trace of exudation of the wax component. When actually projected by an overhead projector, a very clear blue transmitted light was obtained and a clear blue image was obtained, and the effect of the recording material of the present invention was confirmed.

Examples 18 to 20 Except that the recording material G having the polyester resin coat layer (transparent resin layer) used in Example 11 was used,
In the same manner as in Examples 15 to 17, a fixed toner image using a yellow toner, a fixed toner image using a magenta toner, and a fixed toner image using a cyan toner having an image density of 0.5 were formed. Since the recording material G uses a polyester resin similar to the binder resin of the toner for the transparent resin layer, the transmittance was further excellent as compared with Examples 15 to 17.

Example 21 Example 21 was repeated except that the recording material H having the polyester resin coat layer (transparent resin layer), the fine alumina particles and the polyvinyl alcohol coat layer (wax absorbing layer) used in Example 14 was used. In the same manner as in Example 15, a fixed toner image was formed using a yellow toner having an image density of 0.5. As the recording material H, a polyester resin similar to the binder resin of the toner was used for the transparent resin layer, so that the transmittance was further superior to that of Example 14.

Example 22 A sharp-melting polyester resin obtained by condensation polymerization of propoxylated bisphenol and fumaric acid was used as a binder resin for a toner. Table 1 shows the physical properties of the polyester resin.

[0176]

[Table 1]

Each color powder toner was prepared using 100 parts by weight of the polyester resin and the materials shown in Table 2 below.

[0178]

[Table 2]

Table 3 below shows the physical properties of each color powder toner.

[0180]

[Table 3]

To 100 parts by weight of the obtained powdery toner of each color, 0.5 parts by weight of hydrophobic colloidal silica was externally added, and each color toner prepared by external addition and a resin-coated ferrite carrier were mixed at a ratio of 5: 100. Thus, each color developer was obtained. A multicolor full-color fixed toner image was formed on the recording material G used in Example 11 by using the obtained color developers and the image forming apparatus shown in FIG. The recording material G having a full-color fixed toner image is OH
As a result of projection using the P apparatus, a high-definition full-color projected image was projected on the screen, and no trace of wax exudation was observed.

Example 23 An image was formed and fixed in the same manner as in Example 22 except that the recording material H used in Example 14 was used instead of the recording material G, and the image was fixed in the same manner as described above. A toner image was formed. When the recording material H was projected using an OHP device,
A high-definition full-color projected image was projected on the screen, and no trace of exudation of the wax component was seen.

Example 24 Recording material I (transparent resin layer) having a transparent resin layer formed by replacing the polyester resin layer (transparent resin layer) of recording material G described above with the polyester resin used as the binder resin in Example 16 Was formed, and the recording material I was used as an OHP film.

In the same manner as in Example 16, the yellow toner
A full-color fixed toner image was formed on the recording material I by forming a multicolor toner image formed of magenta toner, cyan toner and black toner, and fixing and mixing under the fixing conditions shown in Table 4 below. No water was generated and no trace of exudation of wax was observed.

[0185]

[Table 4]

[0186]

According to the recording material and the image forming method of the present invention, the recording material has an absorption layer for absorbing the wax component contained in the toner, and the absorption layer contains inorganic fine particles. And the average pore radius D of the absorbing layer is 10 ° to 200 °.
Å has the following effects. (1) Even if a toner image formed by a toner containing a wax component is fixed, the wax component does not exude. (2) Since it is not necessary to use a release agent such as oil at the time of fixing, an image of good quality can be obtained without sticking due to oil. (3) When a recording material having a fixed image is projected on an OHP device, a color or full-color projected image having good color tone reproducibility can be obtained without causing the projected image to be entirely grayish.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a specific example of a recording material of the present invention.

FIG. 2 is a sectional view showing another specific example of the recording material of the present invention.

FIG. 3 is a cross-sectional view showing another specific example of the recording material of the present invention.

FIG. 4 is a sectional view showing another specific example of the recording material of the present invention.

FIG. 5 is a sectional view showing another specific example of the recording material of the present invention.

FIG. 6 is a diagram illustrating the melting characteristics of the toner according to the present invention.

FIG. 7 is an explanatory diagram for explaining the image forming method of the present invention in which the recording material of the present invention can be used.

FIG. 8 is an explanatory diagram for describing a problem that occurs when an image is formed using a conventional recording material.

[Explanation of symbols]

 2 electrostatic image carrier 8 transfer drum 16 fixing device 18Y, 18M, 18C, 18Bk developing device 31 base material 32 transparent resin layer 32B transparent resin layer 33 adhesive layer A base material B transparent resin layer I image P Recording material traveling direction R recording material W wax

Continuing on the front page (72) Inventor Tatehiko Chiba 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Tatsuya Nakamura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Koji Inaba, Canon, Inc. 3- 30-2 Shimomaruko, Ota-ku, Tokyo (72) Inventor Takayuki Nagatsuka Canon, Inc. 3- 30-2, Shimomaruko, Ota-ku, Tokyo (56) References JP-A-2-127447 (JP, A) JP-A-58-7673 (JP, A)

Claims (14)

(57) [Claims] 1. A recording material for forming an image, wherein a toner image is formed on a surface of the recording material with a toner containing at least a wax component, and the toner image is fixed to obtain a visible image. and possess an absorption layer for absorbing a wax component, the absorbent layer contains the inorganic fine particles, the
A recording material, wherein the average pore radius D of the absorbing layer is from 10 ° to 200 ° . 2. The recording material according to claim 1, wherein said absorbing layer is an absorbing layer that absorbs a wax component contained in a polymerized toner obtained by a suspension polymerization method. 3. The absorption layer according to claim 1, wherein the absorption layer absorbs a wax component contained in the toner obtained by kneading, pulverizing and classifying the raw materials of the toner.
The recording material described. 4. The recording material according to claim 1, wherein said absorbing layer is laminated on a base material layer. 5. The recording material according to claim 1, wherein the absorbing layer is laminated on the base material layer via a transparent resin layer formed of a transparent resin. 6. The absorption layer has a solubility parameter of 9.5 to 12.5, a temperature of 160 ° C. and a frequency (w) of 100 r.
1 × 10 ³ to 1 × 10 ⁶ dyn / ad / sec
The recording material of claim 5, wherein the storage modulus cm ² (G ') and through the transparent resin layer formed of a transparent resin having been laminated on the base layer. 7. The absorption layer is formed via a transparent resin layer formed of a transparent resin having a storage elastic modulus (G ′) larger than that of the toner at a temperature of 160 ° C. and a frequency (w) of 100 rad / cm ² . 6. The recording material according to claim 5, wherein the recording material is laminated on the material layer. 8. The recording material having the absorbing layer has a thickness of 0.1 to 3
8. The recording material according to claim 1, which has a specific surface area of 0 m ² / g. 9. A developing step of developing an electrostatic latent image on a latent electrostatic image bearing member using a toner containing a wax component to form a toner image on the latent electrostatic image bearing member; An image forming method comprising: a transfer step of transferring an image; and a fixing step of fixing a toner image transferred to the recording material to the recording material by the action of heat and pressure, wherein the recording material comprises a base material layer and the wax component. Has an absorption layer that absorbs inorganic particles , and the absorption layer contains inorganic fine particles.
And the average pore radius D of the absorbing layer is 10 ° to 200 °.
An image forming method, wherein a wax component contained in a toner is absorbed by the absorbing layer when the toner image is fixed on a recording material. 10. The image forming method according to claim 9 , wherein said absorbing layer is laminated on a base material layer. 11. The image forming method according to claim 9 , wherein the absorbing layer is laminated on the base material layer via a transparent resin layer formed of a transparent resin. 12. The absorption layer has a solubility parameter of 9.5 to 12.5, a temperature of 160 ° C. and a frequency (w) of 100.
1 × 10 ³ to 1 × 10 ⁶ dyn at rad / sec
The image forming apparatus according to claim 11, wherein the image forming apparatus is laminated on a base material layer via a transparent resin layer formed of a transparent resin having a storage elastic modulus (G ') of / cm ^2. Method. 13. The absorption layer is formed via a transparent resin layer formed of a transparent resin having a storage elastic modulus (G ′) at a temperature of 160 ° C. and a frequency (w) of 100 rad / cm ² larger than that of the toner. The image forming method according to claim 11 , wherein the image forming method is laminated on a material layer. 14. The recording material having the absorbing layer has a thickness of 0.1 to 0.1.
30m ^Two  / G specific surface area
Item 14. The image forming method according to any one of Items 9 to 13.