JP3320324B2 - Light-transmitting recording material for electrophotography and method for heat-fixing toner image using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-transmissive recording material for electrophotography for forming a toner image and a heat fixing method for forming a toner image on the recording material.

[0002]

2. Description of the Related Art Conventionally, in a general full-color image forming method, a photosensitive member of a photosensitive drum is uniformly charged, and image exposure is performed by a laser beam modulated by a magenta image signal of a document, and the image is statically placed on the photosensitive drum. An electrostatic latent image is formed, the electrostatic latent image is developed by a magenta developing device, a magenta toner image layer is formed on a photosensitive drum, and the developed magenta toner is conveyed by a transfer charger. The image is transferred onto a recording material to form a magenta image.

Next, the photosensitive drum after the above-mentioned development and transfer is neutralized by a neutralizing charger, cleaned, and then charged again by a primary charger. Formation of a cyan toner image, and transfer of the cyan toner image onto a recording material to which the magenta toner image has been transferred, and further, yellow,
In the same manner as for the black color, the four color toner images are transferred onto the recording material. Further, the recording material on which the four color toner images are formed is fixed by a fixing unit such as a fixing roller.
Fixes under the action of heat and pressure to form a full-color image.

[0004] In recent years, such image forming apparatuses have been used not only in office work copying machines for copying original documents, but also in printers as output devices of computers or personal copies for individuals. It is starting to be used. In addition to the field represented by such a laser beam printer, the development of plain paper fax using a basic engine is also rapidly developing.

Therefore, in the above-described image forming apparatus, smaller and lighter, higher speed, higher image quality, and higher reliability have been sought, and the machine is constituted by simpler elements in various points. It is becoming like. As a result, the performance required of the toner has become higher, and if the performance of the toner is not improved, a better machine cannot be realized.

In recent years, demands for color copying have rapidly increased in accordance with various needs for copying. In order to copy original color images more faithfully, higher image quality and higher resolution are desired. From these viewpoints, the toner used in the color image forming method needs to have good melting property and color mixing property when heat is applied, has a low softening point, and has a low melting temperature and a sharp melt property. A high toner is required. By using such a 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 color toner having a high sharp melt property generally has a high affinity with a fixing roller and tends to be easily offset to the fixing roller.
In particular, in the case of a fixing unit in a color image forming apparatus, since a magenta toner, a cyan toner, a yellow toner, and a black toner are formed on a recording material, a plurality of toner layers are formed. Tend to occur.

Conventionally, in order to improve the releasability of the toner from the fixing roller, for example, the surface of the fixing roller is formed of a material having excellent releasability from the toner (eg, silicone rubber or fluorine resin). Further, the surface is coated with a thin film of a liquid having a high releasability such as silicone oil or fluorine oil in order to prevent offset and prevent fatigue of the roller surface. Although this method is extremely effective in preventing offset of the toner, a device for supplying an anti-offset liquid is required, which complicates the fixing device, and the applied oil constitutes a fixing roller. This causes separation between the layers, which results in a problem of shortening the life of the fixing roller.

[0009] With the recent various needs for copying, various types of paper, coated paper, and plastic films are used as recording materials. Above all, attention has been paid to the necessity of a light-transmitting sheet (OHP sheet) for using an overhead projector (OHP) for presentation. In particular, the OHP sheet, unlike paper, has a low oil absorption capacity, so that the oil used in the fixing device adheres to the surface of the recording material, and as a result,
The OHP sheet after forming the image is inevitably sticky due to oil application, resulting in deterioration of image quality. Further, the releasable oil such as silicone oil may evaporate due to heat and contaminate the inside of the machine, and further, there may be a problem such as treatment of recovered oil.

Therefore, there is a great expectation for establishing a fixing system which does not require oil application at the time of fixing an image, which solves the above problems, and for developing a new toner for achieving the same.

To solve the above problem, a toner containing a release agent such as wax is disclosed in Japanese Patent Application Laid-Open No. 61-273554. In a toner containing a wax, the thermal conductivity in the toner is improved by the wax that is melted at a low temperature, and as a result, low-temperature fixing becomes possible. More preferably, high-temperature offset can be prevented without applying a releasing agent such as oil to the fixing roller because the wax melted at the time of fixing also functions as a releasing agent.

When a color toner image or a full-color toner image is formed on a light-transmitting sheet by using an electrophotographic method having a dry developing method, and these images are projected using an OHP device, the color toner image or the full-color toner image is projected on the light-transmitting sheet. Although the full-color image has a sufficient color developing property, the projected image shows a grayish color tone as a whole, resulting in a phenomenon that the color tone reproduction range becomes extremely narrow. This phenomenon is due to the fact that the unfixed toner image formed on the smooth light-transmitting sheet does not flow sufficiently due to heating during fixing and has granularity, so that the incident light is scattered during projection, and The result of shading is the result. Particularly, in an intermediate tone portion or a highlight portion where the image density is low, since the absorption by the dye or pigment in the toner decreases due to the decrease in the number of toner particles, the color tone to be reproduced becomes gray. .

On the other hand, when a toner image formed 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.
Even if some granularity remains on the toner surface, the effect on the image quality is small. 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 transmission deteriorates due to light scattering and the color tone becomes gray. It will be scrambled. Therefore, the recording material used in the OHP apparatus is required to have the effect of reducing the granularity of the toner after fixing the color image and improving the light transmission.

For this reason, conventionally, as a recording material for electrophotography, a light-transmitting recording material in which a surface layer made of a thermoplastic resin such as styrene-acrylic resin or polyester resin is provided on a transparent base sheet has been used. Various proposals have been made from the viewpoint of improving sharpness by improving the fixing property of the toner, and improving transportability and blocking resistance. For example, Japanese Patent Laid-Open No. 1-2
JP-A-63085, JP-A-6-19180, JP-A-6-19485, and JP-A-6-332221. Further, as a means for reducing the granularity of the toner after fixing and improving the light transmittance, as described in JP-A-2-263462 and JP-A-7-199515, A method of burying in a surface layer by heat and pressure during fixing is used. In these light-transmissive recording materials, the granularity of the toner after fixing is improved by the effect of the resin constituting the surface layer.
Light transmittance is improved, and excellent in projecting property with OHP device,
At this time, if a resin that is not sufficiently plasticized by heat and pressure at the time of fixing is used for the surface layer, penetration of the toner particles into the receiving layer is extremely reduced, and the projected image shows a gray color tone.

All of the above are used when fixing a toner image using a release agent such as oil on a fixing roller. That is, the above-mentioned OHP
The sheet does not consider an oil-less fixing process in which a wax is contained as a release agent in the toner, and there is no need to apply a release agent such as oil to the surface of the fixing roller. Therefore, using the toner as described above, the above-mentioned OHP sheet has an image area ratio of 5%.
When a toner image containing a small amount of toner is heat-fixed, although the offset resistance is good in the toner image portion due to the action of the wax contained in the toner as a release agent, the toner image can be spread over a wide range. In a portion where the wax is not formed, the action of the wax as a release agent is insufficient, and the phenomenon that the surface layer made of a thermoplastic resin is stuck to the fixing roller is likely to occur. Therefore, it is desired to improve a recording material suitable for an oilless fixing process using the toner.

Japanese Patent Application Laid-Open No. 5-181300 describes that a toner containing a wax component is heated and fixed on a transparent recording material by using an oilless fixing process in which a releasing agent such as oil is not applied to a fixing roller. However, there is no description about fixing a toner image with a small amount of toner having an image area ratio of 5% or less.

[0017]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light-transmitting recording material for electrophotography which solves the above-mentioned problems, and a heat fixing method using the same.

An object of the present invention is to provide a color image projected on an overhead projector (OHP), which is not grayed even in an intermediate tone portion having a low image density, and has good tone reproducibility. An object of the present invention is to provide a light-transmissive recording material for electrophotography which becomes a color image or a full-color image, and a method for heating and fixing a toner image using the same.

An object of the present invention is to provide a method for fixing a toner image to a toner image formed by a wax-containing toner, a method using an oil-free fixing means, and a method for fixing the toner image onto the surface of the fixing means. An object of the present invention is to provide a light-transmitting recording material for electrophotography having a surface layer without sticking, and a method for heating and fixing a toner image using the recording material.

An object of the present invention is to provide a light-transmitting recording material for electrophotography capable of obtaining a color or full-color transparency sheet having excellent transparency and high quality, and a method for heat-fixing a toner image using the same. It is in.

[0021]

The present invention achieves the above object by the following constitution.

A light-transmitting recording material for electrophotography having a light-transmitting substrate and a surface layer formed on the substrate, wherein the surface layer has a thermoplastic resin and a melting point in the range of 40 ° C. to 120 ° C. At least a release agent contained therein.
The agent is contained in the surface layer in an amount of from 0.01 μm to less than 1.00 μm
Exists in a dispersed state with an average dispersion diameter of
The recording material has a total light transmittance of 80% or more and a haze of 10 or less.
The present invention relates to a light-transmissive recording material for electrophotography, characterized in that

A heat fixing method for heating and fixing the toner image formed on the light transmitting recording material on the light transmitting recording material by a heat fixing means, wherein the light transmitting recording material comprises:
It has a light-transmitting substrate and a surface layer formed on the substrate, wherein the surface layer has a thermoplastic resin and a melting point of 40 ° C to 1 ° C.
Contact with at least contain a release agent in the range of 20 ° C.
The release agent has a thickness of 0.01 μm or more and 1.0 μm or more in the surface layer.
Exists in a dispersed state with an average dispersion diameter of less than 0 μm.
The recording material has a total light transmittance of 80% or more and a
The present invention relates to a method for fixing a toner image by heating, which has the following haze .

[0024]

DETAILED DESCRIPTION OF THE INVENTION The present inventors have conducted intensive studies in order to solve the above-mentioned problems of the prior art, and as a result, the surface layer (toner receiving layer) of a light-transmitting recording material is released from a thermoplastic resin. When a release agent having a specific value is used as the release agent, it is excellent in the discharge property from the heat fixing means and adversely affects the fixability of the toner image. It has been found that a light-transmitting recording material for electrophotography free from defects can be obtained, and the present invention has been accomplished. That is, the light-transmitting recording material for electrophotography of the present invention can be heated without the light-transmitting recording material sticking to the surface of the heating and fixing means even when a large amount of oil is not separately supplied to the fixing means. The recording material is satisfactorily discharged from the fixing means, and the resulting image is a high-quality image excellent in transparency without being grayed.

Next, an example of the light-transmitting recording material of the present invention having the above configuration will be described with reference to FIG.

In FIG. 1, A shows a light-transmitting resin base sheet as a base layer of a recording material, and B shows a light-transmitting surface layer (toner receiving layer). The base sheet is
It is necessary to have heat resistance enough to not cause significant thermal deformation due to heating during heat fixing or heat and pressure fixing. The base sheet used in the present invention has a heat distortion temperature of
4.6 kg / cm described in ASTM D684
^Under the measurement conditions of ^2, the temperature is preferably 145 ° C. or higher, more preferably 150 ° C. or higher. More specifically, the base sheet used in the present invention has a heat distortion temperature of 145 ° C. or more under the above-mentioned measurement conditions, and a resin having a maximum use temperature of 100 ° C. or more, such as polyethylene terephthalate. (PET), polyester,
Examples include polyamide or polyimide. Among these, polyethylene terephthalate is particularly preferred in terms of heat resistance and transparency.

The thickness of the base sheet made of the above-mentioned material must be such that wrinkles do not occur even when the sheet is softened by heating during image fixing. For example, in the case of polyethylene terephthalate, 50 μm
I just need more. Even if it is a light-transmitting sheet, since the transparency decreases as the thickness increases, the thickness of the base sheet is
Preferably 50 to 300 μm, more preferably 70 to 2
It is preferable to use one having a thickness of about 00 μm, more preferably about 100 to 150 μm.

In the light-transmitting recording material of the present invention, a surface layer B containing a thermoplastic resin and a release agent having a specific melting point is formed on the above-described base layer A. In the present invention, as a method of forming the surface layer, a coating solution containing at least a thermoplastic resin and a release agent dissolved or dispersed in an organic solvent or aqueous solution, a bar code method, a dip method, a spray method, and a spin method. A method of applying to the surface of a light-transmitting base sheet by a coating method such as a coating method, and drying at room temperature or by heating. Further, for the purpose of improving the adhesion between the heat-resistant resin sheet as the base layer and the surface layer, plasma treatment, performing a surface treatment such as a corona discharge treatment,
It is also preferable to form an adhesive layer between the heat-resistant resin film A and the surface.

In the present invention, examples of the resin that can be used as the adhesive layer include polyester resin, acrylate resin, methacrylate resin,
Styrene-acrylate copolymer and styrene-
An adhesive resin such as a methacrylic acid ester copolymer may be used.

The constituent material of the surface layer of the light transmitting recording material of the present invention will be described in detail. In the present invention, the thermoplastic resin used for the surface layer will be described.

The thermoplastic resin contained in the surface layer is not particularly limited. For example, polyester resins, polymethyl methacrylate resins, acrylic resins, styrene resins, styrene-acryl resins, rubbers -Based resins, epoxy resins, vinyl chloride resins, vinyl acetate resins, various thermoplastic resins such as polyurethane resins,
And those using a crosslinking agent therefor.

The number average molecular weight of the thermoplastic resin is preferably in the range of 3,000 to 500,000, more preferably 5,000 to 200,000. If the number average molecular weight is less than 3,000, sticking to the surface of the heating and fixing means is likely to occur, and
When it is larger than 000, the softening property of the surface layer at the time of heat fixing is insufficient, the effect of burying the toner particles in the surface layer to reduce the granularity of the toner is impaired, and the image quality is reduced, Furthermore, since the coating liquid used for forming the surface layer has a high viscosity, the coating property of the coating liquid is reduced and the workability is reduced.

In the present invention, the number average molecular weight of the thermoplastic resin was determined from the molecular weight distribution measured by GPC.

GPC was measured under the following conditions using GPC-150C (manufactured by Waters). The column was stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) was passed through the column at this temperature as a solvent at a flow rate of 1 ml per minute, and the sample concentration was 0.05 to
The THF sample solution of the resin prepared to 0.6% by weight is 50 to
Measure by injecting 200 μl. Then, the molecular weight distribution of the sample is determined from the relationship between the logarithmic value of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number, and the molecular weight is calculated. As a standard polystyrene sample for preparing a calibration curve, commercially available standard polystyrene manufactured by Tosoh Corporation was used, and the molecular weight was 6 × 10 ² , 2.1 × 10 ³ , and 4 × 1.
0 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 1
0 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.
48 × 10 ⁶ was used. The detector used was a RI (refractive index) detector, and the column was TSKgel manufactured by Tosoh.
A combination of G1000H, G2000H, G3000H was used.

The thermoplastic resin used in the present invention preferably has a glass transition temperature (Tg) measured by DSC in the range of -10 ° C to 80 ° C, more preferably in the range of 0 ° C to 70 ° C. Preferably, the temperature is in the range of 20 ° C to 70 ° C. When the glass transition temperature of the thermoplastic resin is lower than −10 ° C., sticking to the fixing roller or blocking is likely to occur, and the storage stability is reduced. In this case, the softening of the surface layer becomes insufficient, and the effect of reducing the granularity of the toner by burying the toner particles in the surface layer is reduced.

In the present invention, the glass transition temperature (T
The DSC measurement of g) was performed using an internal heating type input compensation type differential scanning calorimeter with high accuracy based on the measurement principle. As a measuring device, for example, DSC-7 manufactured by PerkinElmer can be used. The measuring method is ASTM D3418.
Performed according to -82. In the present invention, 5 to 20 m
g, preferably 10 mg, is precisely weighed, placed in an aluminum van, and an empty aluminum van is used as a reference at a heating rate of 10 ° C./min in a nitrogen atmosphere at −10 ° C.
The temperature was measured from 0 ° C to 200 ° C. In the present invention, in this heating process, each baseline before and after the shift of the baseline is extrapolated in the direction of each other, and the intersection of the line at the intermediate point and the differential heat curve is defined as Tg.

The transparent surface layer constituting the light-transmitting recording material of the present invention is formed mainly of the above-described thermoplastic resin and a release agent having a specific melting point. Hereinafter, the release agent will be described.

The release agent used in the present invention has a melting point preferably in the range of 40 ° C. to 120 ° C., more preferably in the range of 50 ° C. to 120 ° C. When the melting point of the release agent is lower than 40 ° C., the resulting light-transmissive recording material tends to block during storage, resulting in poor preservability. When the melting point exceeds 120 ° C., a fixing means for the recording material is used. Does not exhibit sufficient mold releasability,
It is not preferable because the fusion between the molten toner and the surface layer surface at the time of fixing the toner image becomes insufficient, and the image quality of the obtained light-transmissive recording material is deteriorated due to irregular reflection at the boundary surface.

In the present invention, the melting point of the release agent is determined by DSC
Was measured. Specifically, the measurement of DSC was performed using ASTM D-34 using Perkin Elmer's DSC-7.
It measured according to 18-82. In the present invention, the DSC curve at this time, after measuring the pre-history by raising the temperature once,
Using a DSC curve measured when the temperature was lowered and raised at a temperature rate of 10 ° C./min, as shown in FIG.
The maximum endothermic peak temperature in the DSC curve when the temperature was raised to 200 ° C. was defined as the melting point.

Examples of the release agent having the above-mentioned melting point used in the present invention include plant waxes such as carnauba wax, candelilla wax, rice wax and wood wax and derivatives thereof; ceresin wax and montan wax. Mineral waxes and their derivatives (for example, derivatives of montan washes include acid waxes, ester waxes and partially saponified ester waxes); animal waxes such as beeswax, spermaceti and lanolin and their derivatives; paraffin Waxes such as waxes and microcrystalline waxes and their derivatives; synthetic waxes such as polyethylene wax and Fischer-Tropsch wax and their derivatives; In addition, higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid and behenic acid; higher alcohols such as stearyl alcohol and behenyl alcohol; esters such as fatty acid esters of sucrose and fatty acid esters of sorbitan; amides such as oleylamide It is also possible to use these in combination with the above waxes.

It is preferable that the release agent used in the present invention, in combination with a thermoplastic resin, maintain a dispersed fine particle state in the surface layer and does not impair the transparency of the recording material.

Therefore, the release agent used in the present invention preferably has an average dispersion diameter of the release agent present in the surface layer of less than 1 μm, more preferably 0.01 μm or more.
Within a range of less than 00 μm, more preferably 0.04 μm
It is preferably in the range of m to 0.5 μm.
If the average dispersion diameter of the release agent is 1 μm or more in the surface layer, the transparency of the surface layer is impaired. In the present invention, the release agent may be completely dissolved in the thermoplastic resin in the surface layer, and may be present in the surface layer in that state. In order to exhibit the property efficiently, 0.01 μm
It is preferable to use the release agent in a state having the above average dispersion diameter.

In the present invention, the release agent has an average dispersion diameter of 1
In order to allow the fine particles in a range smaller than μm to exist in the surface layer, the average dispersion diameter of the release agent is already 1.00 μm when preparing a coating solution used for forming the surface layer.
It is preferable to prepare a coating solution having a particle size of less than m, apply the coating solution on a light-transmitting substrate, and then form a film by drying to form a surface layer. Furthermore, in the present invention, it is preferable that the drying film forming and the temperature conditions at this time are a temperature not lower than the Tg of the thermoplastic resin and a temperature within a range of ± 40 ° C. with respect to the melting point of the release agent. .

The release agent used in the present invention is generally difficult to dissolve in an organic solvent and is difficult to use in a solvent system, especially at room temperature. Therefore, the release agent is prepared in advance as an aqueous dispersion, and the aqueous dispersion is prepared. It is preferable to mix the liquid and an aqueous dispersion of a thermoplastic resin to form a coating liquid, and to form a surface layer on the light-transmitting substrate using the coating liquid.

At this time, as a preferable method for obtaining an aqueous dispersion of the release agent, for example, (1) water heated near the melting point of the release agent is stirred at 5,000 rpm with a homomixer. A method in which a releasing agent melted therein is gradually added, and (2) a suspension polymerization method.

When the aqueous dispersion of the release agent thus obtained is mixed with the aqueous dispersion of the thermoplastic resin, the temperature, solid content, etc., are adjusted so that the viscosity of the aqueous dispersion of the thermoplastic resin becomes 200 cps or less. Is preferably adjusted. If the viscosity of the aqueous dispersion of the thermoplastic resin is greater than 200 cps,
It is not preferable because the particles of the release agent finely dispersed at the time of mixing with the aqueous dispersion of the release agent aggregate.

In the surface layer thus formed, the fine particles of the release agent are uniformly dispersed in the thermoplastic resin. For this reason, it is considered that the release agent is melted when passing through the heating and fixing means, moves to the surface of the surface layer, and the release effect is exhibited.

The amount of the release agent used to form the surface layer is
Although it varies somewhat depending on the thickness of the surface layer, it is preferably in the range of 0.01 to 30% by weight, more preferably 0.1 to 30% by weight, based on the total weight of the surface layer. . When the content of the release agent is less than 0.01% by weight, the release effect is insufficient. When the content is more than 30% by weight, the release agent is deposited and the transparency of the surface layer is reduced. It is not preferable because it is damaged.

In general, the material used for the above-mentioned release agent has crystallinity, and particularly, when the degree of crystallinity is high, the transparency tends to be remarkable. It has been found that if a material having a specific relationship between the Tg of the thermoplastic resin and the melting point of the release agent is selected and used, transparency is improved regardless of the type of material. That is, the melting point of the release agent is preferably higher than the glass transition temperature (Tg) of the thermoplastic resin by 10 ° C. or more, more preferably 20 ° C.
Higher is better. If the surface layer of the light-transmissive recording material is formed using such a combination of materials, the reason is not clear, but after the recording material has passed the heating and fixing roller, the release agent on the surface of the surface layer is cooled. When the melting point of the release agent is somewhat higher than the glass transition temperature (Tg) of the thermoplastic resin when microcrystals are formed, the release of the release agent is affected by the fluctuation due to the micro-Brownian motion of the thermoplastic resin. It is presumed that the transparency of the recording material is improved, partly because the crystallinity of the material is reduced.

When the melting point of the release agent is not higher than the glass transition temperature (Tg) of the thermoplastic resin by 10 ° C. or more, the effect of the lowered crystallinity is not so large, and the recording material becomes transparent. Hard to contribute.

In the present invention, the melting point of the release agent is preferably not higher than the glass transition temperature (Tg) of the thermoplastic resin by 120 ° C. When the melting point of the release agent is higher than 120 ° C. than the glass transition temperature (Tg) of the thermoplastic resin, sticking to the fixing roller and blocking are likely to occur at the fixing temperature of the toner, so that the toner is stored. The property is likely to decrease.

With the above-described structure, the thermoplastic resin used in the present invention has a softening temperature close to or lower than the fixing temperature of the toner. The toner is easily buried in the layer, and as described above, the granularity of the toner is improved, the smoothness of the image surface is improved, and the light transmittance of the obtained recording material is improved.

In the present invention, the optimum thickness of the surface layer varies depending on the particle diameter of the toner to be fixed.
Preferably 2 to 30 μm, more preferably 3 to 15 μm
Good to be. The optimum thickness of the surface layer is also limited by the light transmittance and image blur. However, since the surface layer has flexibility, there is no fear that the image will be cracked even if the surface layer becomes thick.

In the present invention, the surface layer made of the constituent materials as described above is a region having a surface resistivity suitable for toner transfer by mixing or applying an antistatic agent into the surface layer. It is preferable to adjust to 10 ⁷ to 10 ¹³ Ω / □.

In the present invention, the surface resistivity is measured by JI
It is measured according to SK6911. In the present invention, R8340A and R1270 manufactured by Advantest Corporation are used.
It measured at 20 degreeC, 60% RH, and voltage 100V using 2A.

As the antistatic agent used in the present invention, any of those conventionally known can be used.
Quaternary ammonium salt compounds, pyridinium salt compounds, phosphonium salt compounds, alkyl betaine compounds, alkyl imidazoline compounds, alkyl alanine compounds, polyoxyethylene type nonionic compounds, polyhydric alcohol type nonionic compounds, Examples thereof include conductive resins such as polyvinylbenzyl-type cations and polyacrylic acid-type cations, and ultrafine metal oxide particles such as SnO ₂ and SnO ₂ —Sb. These antistatic agents may be mixed and applied simultaneously with the coating liquid at the time of forming the surface layer, or after forming the surface layer, applying a solution in which the above antistatic agent is dissolved in a solvent such as alcohol, An antistatic layer can be formed.

The electrophotographic light-transmissive recording material of the present invention is required to be excellent in transparency, and the light transmittance is such that the total light transmittance as an OHP sheet is preferably 80% or more, more preferably 85%. The haze is preferably 10 or less, more preferably 7 or less, and still more preferably 3 or less. Measurement of transparency in the present invention,
The measurement was performed in accordance with JIS K-7105.

The heat fixing method of the present invention comprises a color copying machine,
The present invention is applicable to all electrophotographic systems using a toner, such as a color printer and a color fax. The heat fixing method of the present invention can be preferably applied to a heat fixing means in which a release agent such as oil is not applied to the heat fixing member, but using a toner prepared by a conventional pulverizing method, The present invention can also be applied to an electrophotographic system using a conventional heat fixing means for separately applying a mold agent to a heat fixing member.

The structure of the toner used in the heat fixing method of the present invention will be described. The toner used in the heat fixing method of the present invention preferably contains a wax component in order to be applied to an oilless fixing process or a fixing process with a small amount of applied oil.

The wax component as a release agent contained in the toner used in the present invention includes, for example, paraffin wax, polyolefin wax and modified products thereof (eg, oxides and grafted products), higher aliphatics,
And its metal salts and amide wax, but are not limited thereto.

In the present invention, the content of the wax component contained in the toner is preferably 1 to 50 parts by weight, more preferably 5 to 45 parts by weight based on 100 parts by weight of the binder resin of the toner. .

When the content of the wax component contained in the toner is less than 1% by weight, it is difficult to sufficiently obtain the releasability of the toner when applied to an oilless fixing process or a fixing process with a small amount of applied oil. If the amount is more than 50 parts by weight, the blocking resistance and the storability of the toner deteriorate.

The toner containing the above wax component is
A polymerization toner manufacturing method for producing toner particles by polymerizing a monomer composition containing at least a polymerizable monomer, a wax component and a colorant, or a binder resin, a toner constituent material containing at least a wax and a colorant, The toner can be produced by any of the pulverized toner production methods of producing toner particles by melt-kneading, pulverization and classification.

In the present invention, the amount of the wax component to be contained in the toner is determined by the method for producing a polymerized toner, in particular, the method for producing toner particles by suspension polymerizing the above monomer composition in an aqueous medium. Is preferred because it is possible to increase the

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-zotyl 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, dimethylaminoethyl methacrylate, methacrylic esters such as diethylaminoethyl methacrylate, and other acrylonitriles and methacrylonitriles;
Examples include monomers such as acrylamide.

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.

In the case of producing a toner by the pulverized toner production method, the polymer used for the binder resin of the toner includes acids such as acrylic acid, methacrylic acid, and maleic acid and esters thereof; polyester; porsulfonate; A resin obtained by polymerizing a monomer such as polyurethane or a resin obtained by copolymerizing two or more of these monomers can be used.

As the colorant contained in the toner used in the present invention, known ones 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 pigment, 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.

The heat fixing method of the present invention will be described.

The heat fixing method of the present invention is characterized in that a toner image is fixed on the light transmitting recording material for electrophotography of the present invention having the above-mentioned structure by a heat fixing means. A fixing device suitable for applying the heat fixing method to the present invention will be described.

FIG. 2 is a schematic view showing an example of a heating roller type fixing device. As shown in FIG. 2, the apparatus of this embodiment includes a cylindrical heating roller 101 having a heating unit such as a heater 101a inside. The heating roller 101 rotates clockwise during fixing.

Reference numeral 102 denotes a pressure roller serving as a pressure rotating body having a cylindrical shape, and rotates counterclockwise while being pressed against the heating roller 101 for fixing. The recording material P as a heating material to which the unfixed toner T adheres as a toner image is conveyed from the right side of the drawing by a conveyance belt 103 and pressed and heated by the heating roller 101 and the pressure roller 102. Then, the unfixed toner T is fixed on the recording material P and is discharged to the left.

Reference numerals 104a and 104b shown in FIG. 2 denote separation claws used for separation in order to prevent the recording material P from being wound around the heating roller 101 or the pressure roller 102 and causing conveyance failure of the recording material P. It is. Also, 10
Reference numeral 6 denotes a felt-like oil pad impregnated with a release agent such as silicone oil having appropriate viscosity, and reference numeral 105 denotes a cleaning roller in which brush fibers are implanted in a cylindrical shape. The cleaning roller 105 rotates to remove the toner residue adhered to the peripheral surface of the heating roller 101, and to appropriately supply the release agent to the surface of the heating roller 101. The heat fixing means used in the present invention may be a heat fixing means for separately supplying oil as shown in FIG. 2, or may be an oilless heat fixing means which does not separately supply oil. In the case of this oilless type heat fixing means, the oil pad 106 is not necessary.

The heating device of the film heating system is a heating device such as a heat roller system, a hot plate system, a belt heating system, a flash heating system, an open heating system, or an image heating fixing device, which are known as other heating systems. In comparison, it has the following advantages and is effective. (1) In a film heating type heating device, a low heat capacity linear heating element having a low heat capacity can be used as a heating element, so that a low heat capacity can be used. Startability) is possible, and the temperature rise in the machine can be suppressed. (2) In a film heating type heating device, since the fixing point and the separation point can be set separately, offset can be effectively prevented. In addition, various disadvantages of other system devices can be solved.

FIG. 3 is a schematic diagram of a film heating type heat fixing means (image heat fixing apparatus) having the above-mentioned features.

In FIG. 3, reference numeral 203 denotes a heater (ceramic heater) fixedly supported by a support.
3, a heat-resistant film (fixing film) 201 is brought into close contact with a pressure roller 202 as a pressure rotating body and slid and conveyed. Then, the heating element 2 is sandwiched between the heat-resistant films 201.
A recording material P on which an image as a material to be heated is to be fixed between the heat-resistant film 201 and the pressure roller 202 in a pressure nip portion (fixing nip portion) N formed by the pressure roller 03 and the pressure roller 202. The heat is supplied to the surface of the recording material P via the heat-resistant film 201 by conveying the pressure-contact nip N with the heat-resistant film 201 while being sandwiched therebetween. The unfixed visible image (toner image) T is heated and fixed on the recording material P.
The recording material P that has passed through the pressure nip N is
1 and is transported to the left in the figure. Reference numeral 204 denotes a felt-shaped pad impregnated with oil as a release agent, which is in contact with the heat-resistant film 201. In the apparatus shown in FIG. Have been. The heat fixing means used in the present invention may be a heat fixing means for separately supplying oil as shown in FIG. 3, or may be an oilless heat fixing means which does not separately supply oil. In the case of this oilless type heat fixing means, the pad 204 is not impregnated with oil.

In the present invention, in the image fixing apparatus having the above configuration, it is preferable not to separately supply oil such as silicone oil from the viewpoint of preventing the recording material after fixing from becoming sticky. However, if the amount of oil is such that stickiness of the recording material after fixing is not a problem,
It is also possible to perform heat fixing while supplying oil to a fixing portion between the heat fixing means and the unfixed toner image on the recording material. Specifically, oil such as silicone oil is supplied to the oil pad indicated by 106 in the heat fixing device shown in FIG. 2 and to the pad indicated by 204 in the heat fixing device shown in FIG. This is done by impregnation. Regarding the amount of oil separately supplied to the fixing unit, the amount of oil applied on the recording material is preferably 0.04 mg / sheet (A4 size) or less, more preferably 0.02 mg / sheet (A4 size). A4 size)
It is preferable to make the following.

[0078]

The present invention will be described more specifically below with reference to examples and comparative examples.

Example 1 On a transparent substrate made of PET having a thickness of 100 μm, 90 parts of an aqueous polyester emulsion (number average molecular weight: 20,000, Tg: 40 ° C.) as a thermoplastic resin, and an aqueous microcrystalline wax as a release agent A solution obtained by mixing 10 parts of an emulsion (melting point: 90 ° C.) with a polyester emulsion having a viscosity of 80 cps was applied as a coating liquid by a bar code method, and then applied at 100 ° C. to 10 parts.
After drying for 5 minutes, a coating film having a dry thickness of 15 μm was obtained, and a surface layer was formed. Further, a coating solution comprising PQ-50B (manufactured by Soken Chemical Co., Ltd.) and isopropyl alcohol having a solid concentration of about 2% is applied to the surface thereon and dried, so that the surface resistance value becomes about 1.2 × 10 ¹⁰ Ω. / □ (20 ° C., 60% RH), light-transmitting OHP which is a light-transmitting recording material for electrophotography
Sheet 1 was obtained.

With respect to the obtained light-transmitting OHP sheet 1, two types of releasability were evaluated for the releasability with respect to the fixing roller by the following method. The result is
It is shown in Table 1.

(Production of Cyan Toner A) 100 parts by weight of styrene-butyl acrylate-divinylbenzene copolymer 5 parts by weight of polyolefin wax (melting point: 100 ° C.) I. Pigment Blue 15 4.5 parts by weight ・ Di-tert-butylsalicylate metal compound 3 parts by weight

After mixing the above materials, the mixture was melted and kneaded by a twin-screw kneading extruder, then cooled, and the cooled product was pulverized by an air-flow pulverizer. A blue powder toner having a diameter of about 8.5 μm was obtained. 0.8 part by weight of negatively chargeable colloidal silica was externally added to 100 parts by weight of this toner to obtain cyan toner A.

(Evaluation of Releasability) Evaluation of Releasability-1 for Fixing Roller 7 parts by weight of the cyan toner A obtained above were coated on a surface of Cu with a styrene-methyl methacrylate copolymer.
93 parts by weight of a Zn-Fe-based ferrite carrier were mixed to obtain a two-component cyan developer 1. Using this two-component cyan developer 1, a commercially available full-color copying machine (CLC-
500, made by Canon), temperature 23 ° C / temperature 6
The image was developed at a development contrast of 320 V in an environment of 5% RH and transferred to form an unfixed cyan toner image having an image area ratio of 5% on an A4-size light-transmitting OHP sheet 1. This unfixed cyan toner image was fixed at a fixing temperature of 170 ° C. and a fixing speed of 30 mm / sec by an external fixing machine (without an oil application function) having a fixing roller surface having a configuration shown in FIG. At that time, the releasability -1 to the fixing roller was evaluated by the following method and evaluation criteria. The results are shown in Table 1.

(Evaluation Criteria) A (very good): The sheet passed without sticking to the fixing roller. B (good): The first part of the sheet slightly adhered to the fixing roller, but passed without any problem by using a separation claw pressed against the roller with a pressure of about 10 gf. C (bad): The sheet stuck to the fixing roller even by using the separation claw pressed against the roller with a pressure of about 10 gf.

Evaluation of Releasability- 2 for Fixing Roller In the same manner as for the evaluation of releasability-1, the fixing roller surface is made of an external fixing machine made of a fluororesin (no oil coating function).
The fixing temperature is 170 ° C. and the fixing speed is 30 mm / s
Under the condition of ec, the light-transmitting OHP sheet 1 was evaluated based on the following evaluation criteria without forming a cyan toner image, and the results are shown in Table 1.

(Evaluation criteria) A (very good): The sheet passed without sticking to the fixing roller. B (good): The first part of the sheet slightly adhered to the fixing roller, but passed without any problem by using a separation claw pressed against the roller with a pressure of about 10 gf. C (bad): The sheet was stuck to the fixing roller by the action of the separation claw pressed against the roller with a pressure of about 10 gf.

Example 2 The release agent was a stearic acid amide emulsion (melting point: 10
Light transmissive OHP sheet 2 was obtained in the same manner as in Example 1 except that the temperature was changed to 0 ° C.). Light-transmitting OH used in Example 1
Instead of the P sheet 1, the obtained light transmissive OHP sheet 2
The peelability was evaluated in the same manner as in Example 1 except for using. Table 1 shows the evaluation results.

Example 3 A release agent was used as a behenyl ketene dimer emulsion (melting point:
Light transmissive OHP sheet 3 was obtained in the same manner as in Example 1 except that the temperature was changed to 66 ° C. Light-transmitting O used in Example 1
The releasability was evaluated in the same manner as in Example 1 except that the obtained light-transmitting OHP sheet 3 was used instead of the HP sheet 1. Table 1 shows the evaluation results.

Example 4 A release agent was a polyethylene wax emulsion (melting point: 1)
Light transmissive OHP sheet 4 was obtained in the same manner as in Example 1 except that the temperature was changed to 16 ° C.). Light-transmitting O used in Example 1
The releasability was evaluated in the same manner as in Example 1 except that the obtained light-transmitting OHP sheet 4 was used instead of the HP sheet 1. Table 1 shows the evaluation results.

Example 5 A light-transmitting OHP sheet 5 was obtained in the same manner as in Example 1 except that the thermoplastic resin was replaced with a polyester emulsion (number average molecular weight: 16,500, Tg: 16 ° C.). Except for using the obtained light transmissive OHP sheet 5 instead of the light transmissive OHP sheet 1 used in Example 1,
The peelability was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

Example 6 A thermoplastic resin was used as a styrene-2-ethylhexyl acrylate emulsion (number average molecular weight: 300,000, T
g: 20 ° C.), and a light transmissive OHP sheet 6 was obtained in the same manner as in Example 1. The peelability was evaluated in the same manner as in Example 1 except that the obtained light-transmitting OHP sheet 6 was used instead of the light-transmitting OHP sheet 1 used in Example 1. Table 1 shows the evaluation results.

Example 7 A polyester (number average molecular weight: 22,50) was used as a thermoplastic resin on a transparent substrate made of PET having a thickness of 100 μm.
0, Tg: 43 ° C.), 4 parts of lanolin wax (melting point: 64 ° C.) as a release agent, 61 parts of toluene, MEK
A mixed solution consisting of 15 parts was applied as a coating solution by a bar code method, and dried at 100 ° C. for 10 minutes to obtain a coated film having a dry thickness of 15 μm, thereby forming a toner receiving layer. Further, a coating solution comprising PQ-50B (manufactured by Soken Chemical Co., Ltd.) and isopropyl alcohol having a solid content of about 2% is applied to the surface thereon and dried, so that the surface resistance value becomes about 1.2 × 10 ¹⁰
Ω / □ (20 ° C, 60% RH)
HP sheet 7 was obtained. Light-transmitting OHP used in Example 1
The peelability was evaluated in the same manner as in Example 1 except that the obtained light-transmitting OHP sheet 7 was used instead of the sheet 1. Table 1 shows the evaluation results.

Example 8 The thermoplastic resin was a polyester (number average molecular weight: 22.5
(00, Tg: 72 ° C.), and a light transmissive OHP sheet 8 was obtained in the same manner as in Example 7. The peelability was evaluated in the same manner as in Example 1 except that the obtained light-transmitting OHP sheet 8 was used instead of the light-transmitting OHP sheet 1 used in Example 1. Table 1 shows the evaluation results.

Example 9 A light-transmitting OHP sheet 9 was obtained in the same manner as in Example 1 except that the thermoplastic resin was changed to urethane-modified polyester (number average molecular weight: 25,000, Tg: 73 ° C.).

Light-transmitting OHP sheet 1 used in Example 1
Was evaluated in the same manner as in Example 1 except that the obtained light-transmissive OHP sheet 9 was used instead. Table 1 shows the evaluation results.

Comparative Example 1 A release agent was a polyethylene wax emulsion (melting point: 1)
Light transmitting OHP sheet 10 was obtained in the same manner as in Example 1 except that the temperature was changed to 24 ° C.).

Light-transmitting OHP sheet 1 used in Example 1
Was evaluated in the same manner as in Example 1 except that the obtained light-transmitting OHP sheet 10 was used instead. Table 1 shows the evaluation results.

Comparative Example 2 The release agent was Garbet alcohol (manufactured by Condeavista, Inc.).
Light transmissive OHP sheet 11 was obtained in the same manner as in Example 7, except that ISOFOL36, melting point: 36 ° C) was used.

Light-transmitting OHP sheet 1 used in Example 1
Was evaluated in the same manner as in Example 1 except that the obtained light transmissive OHP sheet 11 was used instead of the above. Table 1 shows the evaluation results.

Comparative Example 3 A thermoplastic resin was converted to an acrylic emulsion (number average molecular weight:
A light-transmitting OHP sheet 12 was obtained in the same manner as in Example 1 except that the releasing agent was changed to a polyethylene wax emulsion (melting point: 124 ° C.).

Light-transmitting OHP sheet 1 used in Example 1
Was evaluated in the same manner as in Example 1 except that the obtained light transmissive OHP sheet 12 was used instead. Table 1 shows the evaluation results.

Comparative Example 4 A light-transmitting OHP sheet 13 was obtained in the same manner as in Example 1 except that no release agent was used.

Light-transmitting OHP sheet 1 used in Example 1
Was evaluated in the same manner as in Example 1 except that the obtained light transmissive OHP sheet 13 was used instead. Table 1 shows the evaluation results.

[0104]

[Table 1]

Example 10 96 parts by weight of an aqueous polyester emulsion (number average molecular weight: 20,000, Tg: 23 ° C.) as a thermoplastic resin and an aqueous carnauba wax as a releasing agent were placed on a transparent substrate made of 100 μm thick PET. Emulsion (melting point: 8
6 ° C., see FIG. 4) and a solution obtained by mixing 4 parts with a polyester emulsion having a viscosity of 100 cps was applied as a coating liquid by a bar coating method.
After drying for a minute, a coating film having a dry thickness of 8 μm was obtained, and a surface layer was formed. Further, a coating solution containing PQ-50B (manufactured by Soken Kagaku) and isopropyl alcohol having a solid concentration of about 2% is applied and dried on the surface layer to have a surface resistance of about 1.5%.
It was adjusted to × 10 ¹⁰ Ω / □ (20 ° C., 60% RH) to obtain a light transmissive OHP sheet 14 as a light transmissive recording material for electrophotography.

The measurement was carried out by a measuring method not more than the average dispersion diameter of the release agent present in the surface layer of the obtained light-transmitting OHP sheet 14. Table 2 shows the measurement results.

[0107] The cross-section of average dispersion diameter obtained surface layer of the light-transmitting OHP sheet 14 of the release agent present in the surface layer R
Prepared by uO ₄ -stained ultra-thin section method, transmission electron microscope H-
Acceleration voltage 100kV using 7100FA type (manufactured by Hitachi)
Observed in, measuring the major axis and minor axis of each release particles of the release agent at the maximum magnification at which 200 or more release agent dispersed particles can be confirmed,
(Long diameter + short diameter) / 2 was defined as the dispersion diameter of each dispersed particle, and the average value of 200 dispersion diameters was defined as the average dispersion diameter.

Further, the obtained light transmissive OHP sheet 14
Was measured by the following measurement method, and evaluated based on the following evaluation criteria. Table 2 shows the evaluation results.

Transparency-1 The transparency of the electro- transparent recording material for electrophotography was determined by measuring the total light transmittance and haze of the OHP sheet by using MODEL 10
JISK-71 using 01DP (manufactured by Nippon Denshoku Industries Co., Ltd.)
05.

(Evaluation Criteria) A (very good): When the total light transmittance is 87% or more and the haze is 3% or less. B (good): Total light transmittance of 84% or more and haze 1
Less than 0%. C (normal): Total light transmittance of 80% or more and haze 1
Less than 0%. D (bad): Total light transmittance of less than 80%, or haze 10
%that's all.

Further, the obtained light transmissive OHP sheet 14
Was evaluated in the same manner as in Example 1.
Table 2 shows the evaluation results.

Example 11 A light-transmitting OHP sheet 15 was obtained in the same manner as in Example 10 except that the thermoplastic resin was replaced with a polyester emulsion (number average molecular weight: 10,000, Tg: 62 ° C.).

Using the obtained light-transmitting OHP sheet 15, the average dispersion diameter of the release agent present in the surface layer was measured in the same manner as in Example 10, and the transmittance and peelability of the sheet were evaluated. Was done. Table 2 shows the measurement results and the evaluation results.

Example 12 A light-transmitting OHP sheet 16 was obtained in the same manner as in Example 10 except that the thermoplastic resin was changed to a polyester emulsion (number average molecular weight: 20,000, Tg: -10 ° C.).

Using the obtained light-transmitting OHP sheet 16, the average dispersion diameter of the release agent present in the surface layer was measured in the same manner as in Example 10, and the transmittance and peelability of the sheet were evaluated. Was done. Table 2 shows the measurement results and the evaluation results.

Example 13 A light-transmitting OHP sheet 17 was obtained in the same manner as in Example 10, except that the thermoplastic resin was replaced with a polyester emulsion (number average molecular weight: 20,000, Tg: -20 ° C.).

Using the obtained light-transmitting OHP sheet 17, the average dispersion diameter of the release agent present in the surface layer was measured in the same manner as in Example 10, and the transmittance and peelability of the sheet were evaluated. Was done. Table 2 shows the measurement results and the evaluation results.

Example 14 A release agent was a polyethylene wax emulsion (melting point: 1)
Light transmissive OHP sheet 18 was obtained in the same manner as in Example 10 except that the temperature was changed to 16 ° C.).

Using the obtained light-transmitting OHP sheet 18, the average dispersion diameter of the release agent present in the surface layer was measured in the same manner as in Example 10, and the transmittance and the peelability of the sheet were evaluated. Was done. Table 2 shows the measurement results and the evaluation results.

Example 15 A release agent was used as a stearic acid amide emulsion (melting point: 10
A light-transmitting OHP sheet 19 was obtained in the same manner as in Example 10 except that the temperature was changed to 0 ° C.).

Using the obtained light-transmitting OHP sheet 19, the average dispersion diameter of the release agent present in the surface layer was measured in the same manner as in Example 10, and the transmittance and the peelability of the sheet were evaluated. Was done. Table 2 shows the measurement results and the evaluation results.

Example 16 A styrene-2-ethylhexyl acrylate emulsion (number average molecular weight: 50,000, Tg:
33 ° C.) A light-transmitting OHP sheet 20 was prepared in the same manner as in Example 10 except that 85 parts by weight and the amount of the release agent were changed to 15 parts.
I got

Using the obtained light-transmitting OHP sheet 20, the average dispersion diameter of the release agent present in the surface layer was measured in the same manner as in Example 10, and the transmittance and peelability of the sheet were evaluated. Was done. Table 2 shows the measurement results and the evaluation results.

Example 17 Polyester (number average molecular weight: 15,50) was used as a thermoplastic resin on a transparent substrate made of PET having a thickness of 100 μm.
0, Tg: 47 ° C.), 20 parts of lanolin wax (melting point: 64 ° C.) as a release agent, 64 parts of toluene, MEK
The mixed solution consisting of 15 parts was applied as a coating solution by a bar coating method, and dried at 100 ° C. for 10 minutes to obtain a coating film having a dry thickness of 10 μm, thereby forming a surface layer. Further, a coating liquid containing PQ-50B (manufactured by Soken Chemical Co., Ltd.) and isopropyl alcohol having a solid concentration of about 2% is applied on the surface layer.
After drying, the surface resistance was set to about 1.2 × 10 ¹⁰ Ω / □ (20
C., 60% RH) and a light-transmitting OHP sheet 2
1 was obtained.

Using the obtained light-transmitting OHP sheet 21, the average dispersion diameter of the release agent present in the surface layer was measured in the same manner as in Example 10, and the transmittance and the peelability of the sheet were evaluated. Was done. Table 2 shows the measurement results and the evaluation results.

Example 18 The thermoplastic resin was converted to polyester (number average molecular weight: 22.5
(00, Tg: 72 ° C.), and a light transmissive OHP sheet 22 was obtained in the same manner as in Example 17.

Using the obtained light-transmitting OHP sheet 22, the average dispersion diameter of the release agent present in the surface layer was measured in the same manner as in Example 10, and the transmission and peelability of the sheet were evaluated. Was done. Table 2 shows the measurement results and the evaluation results.

Example 19 Polyester (number average molecular weight: 17,50) was used as a thermoplastic resin on a transparent substrate made of 100 μm thick PET.
0, Tg: 67 ° C.), 20 parts of lanolin wax (melting point: 64 ° C.) as a release agent, and P as a surface resistance adjuster
A coating liquid consisting of 5 parts of Q-50B, 37 parts of toluene and 37 parts of MEK is applied and dried to form a surface layer, and the surface resistance is about 2.3 × 10 ¹¹ Ω / □ (20 ° C., 60 ° C.). % RH)
Was obtained.

Using the obtained light-transmitting OHP sheet 23, the average dispersion diameter of the release agent present in the surface layer was measured in the same manner as in Example 10, and the transmittance and peelability of the sheet were evaluated. Was done. Table 2 shows the measurement results and the evaluation results.

REFERENCE EXAMPLE 1 A thermoplastic resin was used as a polyester (number average molecular weight: 15,0
(00, Tg: 67 ° C.), and a light transmissive OHP sheet 24 was obtained in the same manner as in Example 17.

Using the obtained light-transmitting OHP sheet 24, the average dispersion diameter of the release agent present in the surface layer was measured in the same manner as in Example 10, and the transmittance and peelability of the sheet were evaluated. Was done. Table 2 shows the measurement results and the evaluation results.

Reference Example 2 A light-transmitting OHP sheet 25 was obtained in the same manner as in Example 17 except that the thermoplastic resin was changed to urethane-modified polyester (number average molecular weight: 30,000, Tg: 23 ° C.).

Using the obtained light-transmitting OHP sheet 25, the average dispersion diameter of the release agent present in the surface layer was measured in the same manner as in Example 10, and the transmittance and peelability of the sheet were evaluated. Was done. Table 2 shows the measurement results and the evaluation results.

Reference Example 3 A light-transmitting OHP sheet 26 was obtained in the same manner as in Example 16 except that a coating solution was prepared under the condition that the viscosity of the styrene-2-ethylhexyl acrylate emulsion became 300 cps.

Using the obtained light transmissive OHP sheet 26, the average dispersion diameter of the release agent present in the surface layer was measured in the same manner as in Example 10, and the transmittance and peelability of the sheet were evaluated. Was done. Table 2 shows the measurement results and the evaluation results.

Comparative Example 5 A light-transmitting OHP sheet 27 was obtained in the same manner as in Example 10 except that the release agent was changed to an ethylene bisamide stearate emulsion (melting point: 141 ° C.).

Using the obtained light-transmitting OHP sheet 27, the average dispersion diameter of the release agent present in the surface layer was measured in the same manner as in Example 10, and the transmittance and peelability of the sheet were evaluated. Was done. Table 2 shows the measurement results and the evaluation results.

Comparative Example 6 A light-transmitting OHP sheet 28 was obtained in the same manner as in Example 17 except that the release agent was changed to garbet alcohol (melting point: 36 ° C.).

Using the obtained light-transmitting OHP sheet 28, the average dispersion diameter of the release agent present in the surface layer was measured in the same manner as in Example 10, and the transmittance and peelability of the sheet were evaluated. Was done. Table 2 shows the measurement results and the evaluation results.

Comparative Example 7 A light-transmitting OHP sheet 29 was obtained in the same manner as in Example 10 except that no release agent was used.

Using the obtained light-transmitting OHP sheet 29, the average dispersion diameter of the release agent present in the surface layer was measured in the same manner as in Example 10, and the transmittance and the peelability of the sheet were evaluated. Was done. Table 2 shows the measurement results and the evaluation results.

Example 23 Using a fixing device having the same roller configuration as the external fixing device used in the evaluation of Example 1, a 0.04 mg / sheet (A4 size) was applied by an oil applicator. The light-transmitting OHP sheet 14 obtained in Example 10 was evaluated by the same method and evaluation criteria as in Example 1 while separately applying oil at a fixing temperature of 170 ° C. and a fixing speed of 30 mm / sec. did. Table 2 shows the evaluation results.

[0143]

[Table 2]

Example 24 (Production of Cyan Toner B) 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.
After heating to 60 ° C., the mixture was stirred at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 67.7 parts by weight of a 1.0 M CaCl ₂ aqueous solution was gradually added to obtain a dispersion medium containing Ca ₃ (PO ₄ ) ₂ . 170 parts by weight of styrene 30 parts by weight of 2-ethylhexyl acrylate 50 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 battle 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 mixture was filtered, washed with water and dried to obtain cyan toner particles.

When the particle size of the obtained cyan toner particles was measured by a Coulter counter, the weight average particle size was 8.2 μm.
m and had a sharp particle size distribution. To 100 parts by weight of the obtained toner particles, 0.7 part by weight of hydrophobic silica having a specific surface area of 200 m ² / g by the BET method was externally added to obtain a cyan toner B.

(Production of magenta toner C) C.I. I. Pigment Blue 15 and C.I. I. Magenta toner C was obtained in the same manner as in the production of cyan toner B, except that 9 parts by weight of CI Pigment Red 122 was used.

(Production of Yellow Toner D) C.I. I. Pigment Blue 15 and C.I. I. A yellow toner D was obtained in the same manner as in the production of the cyan toner B, except that 8 parts by weight of CI Pigment Yellow 17 was used.

(Production of Black Toner E) C.I. I. A black toner E was obtained in the same manner as in the production of the cyan toner B, except that 12 parts by weight of a commercially available carbon black was used instead of Pigment Blue 15.

A Cu-Zn-Fe-based ferrite carrier 93 surface-coated with a styrene-methyl methacrylate copolymer was added to 7 parts by weight of each of the obtained cyan toner B, magenta toner C, yellow toner D and black toner E. The two parts by weight were mixed to prepare a two-component cyan developer 2, a two-component magenta developer 3, a two-component yellow developer 4, and a two-component black developer 5, respectively.

Using the four-color two-component developer, a commercially available full-color copying machine (CLC-500, manufactured by Canon) was remodeled and developed with a developing contrast of 320 V in an environment of a temperature of 23 ° C. and a humidity of 65% RH. Then, the image was transferred to form an unfixed full-color toner image having an image area ratio of 5% on the A4-size light transmissive OHP sheet 14 used in Example 10. The unfixed full-color toner image was fixed on the surface of a fixing roller having a configuration shown in FIG. 2 using a fluorine-based resin external fixing machine (no oil coating function) at a fixing temperature of 170 ° C. and a fixing speed of 30 mm / sec.

As a result, the light transmitting OHP
When the sheet on which the obtained full-color image is formed is projected onto an OHP, the intermediate image density portion and the highlight image density portion are not grayed out. A perfect full-color projection image was obtained.

Example 25 A water-based polyester emulsion (number average molecular weight: 20,000, Tg: 40 ° C., solid content: 30%, softening point: 160 ° C.) as a thermoplastic resin on a transparent substrate made of PET having a thickness of 100 μm. 320 parts by weight of an aqueous carnauba wax emulsion as a release agent (melting point: 86 ° C., solid content:
(45%) was applied as a coating liquid by a bar coating method, and dried at 100 ° C. for 10 minutes to obtain a coating film having a dry thickness of 12 μm, thereby forming a surface layer. Further, a coating solution composed of PQ-50B (manufactured by Soken Chemical Co., Ltd.) and isopropyl alcohol having a solid concentration of about 2% is applied and dried on the surface layer to have a surface resistance of about 10 ¹¹ Ω / □ (20
C., 60% RH) and the light transmissive OHP sheet 3
0 was obtained.

With respect to the obtained light-transmitting OHP sheet 30, evaluation of the image quality of the image obtained by heating and fixing the toner image by the following method, and the light-transmitting OHP sheet for fixing the toner image were carried out. The following method was used to evaluate the releasability-3 and transparency-2 from the fixing roller. Table 4 shows the results. As a result, the O
All the HP sheets were discharged without sticking to the fixing roller, and a good transparent image was obtained. When the obtained sheet on which a color image was formed was projected by an OHP device, transparency was not impaired, and a clear projected image was obtained without graying the intermediate image density portion and the highlight image portion.

(Production of Yellow Toner F) 100 parts of styrene-butyl acrylate-divinylbenzene copolymer 5 parts of polyolefin wax (melting point 100 ° C.) I. Pigment Yellow 17 4.5 parts ・ Di-tert-butylsalicylic acid metal oxide 3 parts

After mixing the above materials, 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 weight average particle size of about 8.5 μm.
m yellow powder toner was obtained. 0.8 part of negatively chargeable colloidal silica was externally added to 100 parts of the toner to obtain a yellow toner F.

(Image generation) The obtained yellow toner F was converted to a commercially available full-color copying machine (CLC-500, manufactured by Canon Inc.).
Developed at a development contrast of 320 V in an environment of a temperature of 23 ° C. and a humidity of 65% RH, transferred, and formed an unfixed yellow toner image on the light transmissive OHP sheet 30 as follows. The image was fixed by external fixing means. For fixing, a yellow image was heated and fixed at a fixing temperature of 170 ° C. and a fixing speed of 30 mm / sec by using an external fixing machine (with no oil application function) in which the surface of a fixing roller having the configuration shown in FIG.

Evaluation of Image Properties Light transmitting OH having the obtained yellow color image
Using the P sheet 30 as an OHP, a yellow color image was projected on a screen, and the color tone reproducibility of the intermediate image density portion and the highlight image portion was evaluated by visual sensory evaluation based on the following evaluation criteria.

Here, the intermediate image density portion and the highlight image portion are portions where the obtained yellow toner image has a yellow density of 0.2 to 1.5 measured by a Macbeth reflection densitometer RD-1255. Show.

(Evaluation Criteria) A (very good): The intermediate image density portion and the highlight image portion are not grayed and have good color tone reproducibility. B (good): The intermediate image density portion and the highlight image portion are slightly grayish, and the color tone is slightly orange. C (poor): The intermediate image density portion and the highlight image portion are grayish.

Evaluation of Releasability -3 A 7% by weight of the yellow toner F obtained above was coated with a styrene-methyl methacrylate copolymer.
93 parts by weight of a u-Zn-Fe-based ferrite carrier were mixed to obtain a two-component yellow developer 6. Using this two-component yellow developer 6, a commercially available full-color copying machine (CL
C-500, manufactured by Canon Inc.), developed at a development contrast of 320 V in an environment of a temperature of 23 ° C. and a humidity of 65% RH, transferred, and transferred an unfixed yellow toner image having an image area ratio of 5% to A4 size. The light transmitting OHP sheet 30 was formed. The unfixed yellow toner image was fixed at a fixing temperature of 170 ° C. and a fixing speed of 30 mm / sec by an external fixing machine (without an oil application function) of a fluorine-based resin having a fixing roller surface having a configuration shown in FIG. The releasability -3 from the fixing roller at that time was evaluated by the following method and evaluation criteria. Table 4 shows the evaluation results.

(Evaluation Criteria) A (very good): The sheet passed without sticking to the fixing roller. B (good): The first part of the sheet slightly adhered to the fixing roller, but passed without any problem by using a separation claw pressed against the roller with a pressure of about 10 gf. C (bad): The sheet was stuck to the fixing roller even by using the separation claw pressed against the roller with a pressure of about 10 gf.

Evaluation of Transparency-2 The transparency of the light-transmitting OHP sheet 30 was measured by measuring the total light transmittance and haze using MODEL 1001DP (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K-7105. Then, evaluation was performed based on the following evaluation criteria. Table 4 shows the evaluation results.

(Evaluation Criteria) A (very good): Total light transmittance of 84% or more B (Good): Total light transmittance of 80% or more and less than 84% C (Bad): Total light transmittance of less than 80%

Examples 26 to 32 The same procedure as in Example 25 was carried out except that the coating liquid used in Example 25 was changed to the one shown in Table 3, and the light-transmitting O.D.
HP sheets 31 to 37 were obtained.

Obtained Light-Transmissive OHP Sheets 31-37
Were evaluated in the same manner as in Example 25, except that the image quality, the releasability-3, and the transparency were used. Table 4 shows the evaluation results.

Comparative Example 8 The same procedure as in Example 25 was carried out except that the coating liquid used in Example 25 was changed to the one shown in Table 3, and the light-transmitting O
An HP sheet 38 was obtained.

Evaluation was carried out on image quality, releasability-3 and transparency in the same manner as in Example 25 except that the obtained light-transmitting OHP sheet 38 was used. Table 4 shows the evaluation results.

[0171]

[Table 3]

[0172]

[Table 4]

Example 33 A two-component two-component cyan developer 2, a two-component magenta developer 3, a two-component yellow developer 4, and a two-component black developer 5 used in Example 24 were used. Using a developer, a commercial full-color copying machine (CLC-500, manufactured by Canon) was remodeled and developed at a development contrast of 320 V in an environment of a temperature of 23 ° C. and a humidity of 65% RH. A toner image was formed on the A4 size light transmissive OHP sheet 30 used in Example 25. The unfixed color toner image is applied to the fixing roller surface of the configuration shown in FIG. 2 using an external fixing machine made of a fluorine resin and separately applying oil at 0.04 mg / sheet (A4 size) by an oil applicator. The fixing was performed on the light transmitting OHP sheet 30 under the conditions of a fixing temperature of 170 ° C. and a fixing speed of 30 mm / sec.

As a result, the light transmitting OHP
Good fixation could be performed without the sheet 30 sticking, and a good transparent image without stickiness due to oil adhesion was obtained. When the obtained sheet on which a full-color image was formed was projected by an OHP device, a clear projected image was obtained without impairing transparency and without graying the intermediate image density portion and the highlight image portion.

Example 34 Instead of the external fixing device used in Example 33, a film heating fixing device (having no oil coating function) having the structure shown in FIG. 3 was used, and the fixing temperature was 170 ° C. and the fixing speed was 30 mm / sec.
c, except that the unfixed full-color toner image was transferred to the light-transmitting OHP sheet 3.
As a result, as in Example 33, the light-transmitting OHP sheet 30 was not adhered to the fixing film, and satisfactory fixing could be performed. When the obtained sheet on which a full-color image was formed was projected by an OHP apparatus, a transparent projected image was obtained without impairing the transparency and without graying the intermediate image density portion and the highlight image portion.

[0176]

According to the present invention, at the time of fixing a toner image, an oilless type heat-fixing means which does not use oil is used, or a heat-fixing means which uses a small amount of oil is used. Even in this case, the recording material does not stick to the surface of the heat fixing means during fixing, and the obtained image is transferred to an overhead projector (O
HP), a color image or a full-color image having good color tone reproducibility can be obtained without graying even in a projected image, especially in an intermediate color tone portion having a low image density.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a configuration of a transparent recording material for electrophotography according to the present invention.

FIG. 2 is an explanatory diagram of a heat fixing unit that can be used in the heat fixing method of the present invention.

FIG. 3 is an explanatory view of a heat fixing unit having another configuration usable in the heat fixing method of the present invention.

FIG. 4 is a view showing a DSC curve of a release agent used in Example 10.

[Explanation of symbols]

 Reference Signs List A light transmitting substrate B surface layer P recording material T toner 101 heating roller 102 pressure roller 201 heat-resistant film 202 pressure roller 203 heating element 204 oil pad

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI B32B 27/18 B32B 27/18 D G03G 9/08 365 G03G 9/08 365 15/20 101 15/20 101 (72) Inventor Naoki Kushida Canon Inc. 3- 30-2 Shimomaruko, Ota-ku, Tokyo (56) References JP-A-5-104868 (JP, A) JP-A-60-43666 (JP, A) JP-A-63- 33749 (JP, A) JP-A-7-301937 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 7/00

Claims (22)

(57) [Claims] 1. A light-transmitting recording material for electrophotography having a light-transmitting substrate and a surface layer formed on the substrate, wherein the surface layer has a thermoplastic resin and a melting point of 40 ° C. to 120 ° C.
The release agent is in the range of which contains at least, release agent is, 0.01 [mu] m or more on the surface layer 1.00μ
m, wherein the recording material has a total light transmittance of 80% or more and a haze of 10 or less. Transmissive recording material. 2. The thermoplastic resin according to claim 1, wherein said thermoplastic resin is 3,000 to 500.
The light-transmissive recording material for electrophotography according to claim 1, having a number average molecular weight of 00. 3. The light-transmissive recording material for electrophotography according to claim 1, wherein the thermoplastic resin has a glass transition temperature (Tg) of −10 to 80 ° C. 4. The light-transmissive recording material for electrophotography according to claim 1, wherein the release agent has a melting point of 50 to 120 ° C. 5. The release agent is any of claims 1 to 4, characterized in that 0.01% to 30% by weight, based on the weight of the surface layer is contained in the surface layer A light-transmitting recording material for electrophotography according to the above item. The melting point of 6. The releasing agent is electrophotographic light according to any one of claims 1 to 5, characterized in that high 10 ° C. or higher than the glass transition temperature of the thermoplastic resin (Tg) Transmissive recording material. The melting point of 7. A releasing agent is electrophotographic light according to any one of claims 1 to 5, characterized in that high 20 ° C. or higher than the glass transition temperature of the thermoplastic resin (Tg) Transmissive recording material. The method according to claim 8 said surface layer, the electrophotographic light-transmitting recording material according to any one of claims 1 to 7, characterized in that the layer containing the antistatic agent is formed. 9. surface layer, the electrophotographic light-transmitting recording material according to any one of claims 1 to 7, characterized by containing an antistatic agent further. 10. A heat-fixing method for heat-fixing onto light transmissive recording material by a heating fixing means the toner image formed on the light-transmitting recording material on, the light-transmitting recording material, has a light transmissive substrate and a surface layer formed on said substrate, said surface layer is a thermoplastic resin and a melting point of 40 ° C. to 120 ° C.
Release agent which contains at least the releasing agent is in the range of, 0.01 [mu] m or more on the surface layer 1.00μ
m, and the recording material has a total light transmittance of 80% or more and 10 or less.
A method for heat-fixing a toner image, characterized by having the following haze . 11. The method according to claim 1, wherein when the toner image is heat-fixed to the temporary recording material, heat fixing is performed without supplying oil to a fixing surface of the heat fixing unit that is in contact with the toner image. The method for heat-fixing a toner image according to claim 10 . 12. An oil of 0.04 mg / sheet (A4 size) or less is applied to a fixing surface of the heat fixing unit in contact with the toner image when the toner image is heat-fixed to the temporary recording material. 11. The heat fixing method for a toner image according to claim 10 , wherein the heat fixing is performed by supplying an amount of oil applied to the light transmitting recording material. 13. The thermoplastic resin according to claim 13, wherein said thermoplastic resin is 3,000 to 50.
Heat fixing a toner image according to any one of claims 10 to 12, characterized in that it has a number average molecular weight of 000. 14. The thermoplastic resin has a temperature of -10 to 80 ° C.
Heat fixing a toner image according to any one of claims 10 to 12, characterized in that it has a glass transition temperature of (Tg). 15. The release agent is heat fixing a toner image according to any one of claims 10 to 14, characterized in that it has a melting point of 50 to 120 ° C.. 16. releasing agent is any of claims 10 to 15, characterized in that 0.01% to 30% by weight, based on the weight of the surface layer is contained in the surface layer A method for heat-fixing a toner image according to any one of the above. The melting point of 17. releasing agent is heated toner image according to any one of claims 10 to 16, wherein the high 10 ° C. or higher than the glass transition temperature of the thermoplastic resin (Tg) Fixing method. The melting point of 18. releasing agent is heated toner image according to any one of claims 10 to 16, wherein the high 20 ° C. or higher than the glass transition temperature of the thermoplastic resin (Tg) Fixing method. 19. The method according to claim 10, wherein a layer containing an antistatic agent is formed on the surface layer.
19. The method for heat-fixing a toner image according to any one of 18 . 20. The surface layer is heat-fixing a toner image according to any one of claims 10 to 18, characterized by containing an antistatic agent further. 21. A toner for forming the toner image contains at least a binder resin, a wax component, and a colorant, and the wax component is added in an amount of 1 to 100 parts by weight of the binder resin. heat fixing a toner image according to any one of claims 10 to 20, characterized in that it is contained in 50 parts by weight the toner. 22. The toner for forming the toner image contains at least a binder resin, a wax component and a colorant, and the wax component is contained in an amount of 5 to 50 parts by weight based on 100 parts by weight of the binder resin. 22. The method according to claim 10, wherein 50 parts by weight of the toner image is contained in the toner.