JP6171687B2 - Energy-beam curable precursor for releasable information sheet, method for producing releasable information sheet, and apparatus for producing releasable information sheet - Google Patents

Description

  The present invention relates to an energy beam curable precursor for a releasable information sheet used when a releasable information sheet is produced from a sheet imaged using toner, and a method for producing a releasable information sheet using the same About.

In recent directs, a printing surface on which image information is formed is often pasted with a pressure sensitive adhesive to conceal the information, and a means that can be removed again when necessary is often used. As the pressure-sensitive adhesive, latex rubber, an ultraviolet curable pressure-sensitive composition, or the like is used, but an ultraviolet curable pressure-sensitive composition is mainly used as in surface processing.
Recently, information changes frequently, and the number of systems that can output variable information, such as changing information part by part, such as names, is increasing. The demand for on-demand printing has become very high.
As an apparatus used for on-demand printing, there are usually an electrophotographic system and an inkjet system, but an electrophotographic system using toner for output including an image is advantageous in terms of productivity and cost.
An image recorded by an electrophotographic method is reproduced by fixing a powder color material called toner to a recording medium with heat or pressure.

  Also, for UV curable pressure sensitive compositions, several commercially available UV curable compositions are commonly used in offset printing. However, when these commercially available UV curable compositions are used for images recorded by electrophotography, satisfactory results are hardly obtained due to incompatibility between the toner and the UV curable composition.

The varnish composition and the adjustment method disclosed in Patent Document 1 are more suitable for the printed matter to which the fixing oil is applied by using a water-based coating agent that does not contain ammonia and has a low static surface tension. Improved. Further, in the resin forming apparatus disclosed in Patent Document 2 and an image forming apparatus equipped with the apparatus, a silicon resin layer is formed on the printing surface to provide protection of the printing surface, waterproof treatment, glossing, and the like. In addition, the metal container printed on the surface disclosed in Patent Document 3 and the printing method of the metal container can efficiently perform multi-variety and small-volume printing by utilizing electrophotography, and an ultraviolet curable composition. Processing provides toner layer protection and gloss.
Further, a releasable UV-curable pressure-sensitive composition used for DM postcards and the like is disclosed in Patent Document 4. Patent Document 5 discloses an ultraviolet curable pressure-sensitive adhesive composition that matches liquid toner.

  However, even with these techniques, the combination of the dry toner and the UV curable composition is poor in matching with the UV curable composition with the toner image even though the UV curable composition can be applied. When an image laminated with the composition was to be peeled again, one image was partially peeled off.

By the way, in conventional electrophotographic images, silicon oil has been used as a fixing release agent, and when an image formed using silicon oil is used, the image peeling when re-peeling is somewhat reduced, but direct mail is used. The level used as was not reached.
In recent years, so-called oil-less toner in which a wax is contained in the toner has been generally used in order to prevent contamination of the office with silicone oil and deterioration of image quality due to running out of silicone oil. Furthermore, in order to save energy, so-called low-temperature fixing toner using a resin having a low toner softening temperature has been used.
When an image using these oil set toner and low-temperature fixing toner was bonded with an ultraviolet curable pressure-sensitive composition and re-peeled, the image peeled off severely and was not at a practical level.

  The present invention has been made in view of the above problems in the prior art, and an energy beam curable precursor for a releasable information sheet used for a releasable information sheet having excellent fixability and adhesion strength. The purpose is to provide.

  The energy beam curable precursor for a releasable information sheet according to the present invention for solving the above problems is applied to a recording medium image-formed using a toner to form an energy beam curable precursor layer, Next, after irradiating the energy beam to cure the energy beam curable precursor layer, the energy beam curing for the releasable information sheet in which the surfaces on which the energy beam curable precursor layer is cured is bonded and pressure-bonded. The energy ray curable precursor is characterized in that it contains a photopolymerization initiator and a thermal polymerization initiator.

  ADVANTAGE OF THE INVENTION According to this invention, the energy-beam curable precursor for releasable information sheets used for a releasable information sheet provided with the outstanding fixability and adhesion strength can be provided.

It is the schematic which shows an example of a structure of the image forming apparatus with which the manufacturing apparatus of the releasable information sheet which concerns on this invention is provided. It is the schematic which shows an example of the application | coating hardening means of the ultraviolet curable (pressure-sensitive) composition used for the manufacturing apparatus of the releasable information sheet which concerns on this invention. It is the schematic which shows an example of the heating-pressing apparatus used for the manufacturing apparatus of the releasable information sheet which concerns on this invention. It is the schematic which shows the other example of the heating-pressing apparatus used for the manufacturing apparatus of the releasable information sheet which concerns on this invention.

The present inventors investigated in detail how the image is peeled off why one image is peeled off when the sheet using toner is bonded with the ultraviolet curable pressure-sensitive composition and then peeled off again.
In order to improve the appearance of the paper used for direct mail, a paper layer with a coating layer coated with a white pigment such as calcium carbonate is formed and the whiteness is increased. It has been found that in most cases it will peel off the coat layer, not the image layer.
Therefore, it was found that when an ultraviolet curable pressure-sensitive composition was formed on a paper on which no image was formed, bonded, and peeled again, it was peeled off without any problem without being peeled off from the paper coating layer. As a result, it was found that when the toner image is present, the paper coat layer is weakened.

The inventors further investigated and obtained the following findings.
UV-curable pressure-sensitive composition is a liquid UV-curable pressure-sensitive composition precursor coated on a toner image and irradiated with ultraviolet rays to cause a radical reaction and cured as an ultraviolet-curable pressure-sensitive composition. However, the liquid UV curable pressure-sensitive composition precursor partially soaks into the toner image and slightly swells the toner image.
In general, the paper used for the re-peeling information sheet is coated paper in order to obtain a clean image, but since there is a gap in the toner image itself, the liquid UV-curable pressure-sensitive pressure reaches the coat layer under the toner. It was found that the composition precursor soaked.

A liquid UV-curable pressure-sensitive composition precursor can be converted into an UV-curable pressure-sensitive composition only when it is exposed to ultraviolet rays. However, ultraviolet rays reach the toner image layer where the toner image is present and the coat layer below it. However, since the ultraviolet curable pressure-sensitive composition precursor remained liquid, it was found that the coating layer was softened and the strength was lowered. In addition, the surface of the coat layer in contact with the toner image is strongly adhered by melting the toner image at the time of fixing, but the liquid UV-curable pressure-sensitive composition precursor is infiltrated into the toner image. It has been found that the strength of the coating layer is reduced by slightly swelling. In addition, it is more likely that the image is peeled off the next day than when it is peeled off immediately after bonding, but this also causes the liquid UV-curable pressure-sensitive composition precursor to form a coat layer or toner image. You can see that this is due to the fact that it is prevalent.
On the other hand, when an ultraviolet curable pressure sensitive composition precursor is applied to paper without a toner image and irradiated with ultraviolet rays, the ultraviolet curable pressure sensitive composition precursor penetrates into the coat layer, but the ultraviolet curable pressure sensitive composition. It turned out that the strength of the coating layer itself is increased and the re-peeling can be performed without any problem by curing the precursor.
For this reason, it was found that how to polymerize the uncured UV-curable pressure-sensitive composition precursor is important for the production of a releasable information sheet.

  The present inventors have intensively studied how to polymerize an uncured ultraviolet curable pressure-sensitive composition precursor. Since the conventional UV curable pressure sensitive composition precursor does not undergo a polymerization reaction unless it is exposed to UV rays, the uncured UV curable pressure sensitive composition precursor under the toner image cannot be cured. Therefore, the present inventors cannot cure the uncured UV-curable pressure-sensitive composition precursor under the toner image by using a method other than photopolymerization, specifically, thermal polymerization. I examined. Then, it is found that heat is generated in the entire image due to the photopolymerization reaction accompanying ultraviolet irradiation, and not only the photopolymerization initiator but also the thermal polymerization initiator can be mixed in the ultraviolet curable pressure-sensitive composition precursor. For example, it has been found that the uncured UV-curable pressure-sensitive composition precursor under the toner image can be cured. Furthermore, the present inventors have found that the uncured ultraviolet curable pressure-sensitive composition precursor under the toner image can be cured to a level at which no problem occurs if heated during or after the compression bonding.

Thus, the energy beam curable precursor for a releasable information sheet according to the present invention is applied onto a recording medium formed with an image by using a toner to form an energy beam curable precursor layer. In the energy beam curable precursor for a releasable information sheet, after irradiating and curing the energy beam curable precursor layer, the surface cured with the energy beam curable precursor layer is bonded and pressure bonded.
The energy ray curable precursor contains a photopolymerization initiator and a thermal polymerization initiator.

Next, the energy beam curable precursor for the releasable information sheet and the method for producing the releasable information sheet, the releasable information sheet manufacturing apparatus, and the releasable information sheet according to the present invention will be described in more detail. .
Although the embodiments described below are preferred embodiments of the present invention, various technically preferable limitations are attached thereto, but the scope of the present invention is intended to limit the present invention in the following description. Unless otherwise described, the present invention is not limited to these embodiments.

-Energy ray curable precursor and energy ray curable pressure sensitive composition-
The energy beam curable precursor of the present invention contains a thermal polymerization initiator and a photopolymerization initiator, and in addition, a polymerizable oligomer, a polymerizable unsaturated compound, a sensitizer, a polymerization inhibitor, a surfactant, and the like. Is contained as necessary.

-Thermal polymerization initiator-
The energy beam curable precursor for the releasable information sheet of the present invention contains not only a photopolymerization initiator described later but also a thermal polymerization initiator.
As thermal polymerization initiators, organic peroxides such as benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, azobisisovaleronitrile, etc., which are initiators having an appropriate use temperature range of about 40 to 100 ° C. The azo compounds are not limited to these.

Specific examples of the thermal polymerization initiator include organic peroxides such as isobutyl peroxide, lauroyl peroxide, benzoyl peroxide, m-toluoyl peroxide, 3,3,5-trimethylhexanoyl peroxide, t -Butylperoxy-2-ethylhexanoate, t-butylperoxybivalate, cumylperoxyneodecanoate, t-butylperoxyneodecanoate, diisopropylperoxydicarbonate, di- (2-ethoxy Ethyl) peroxydicarbonate, bis- (4-t-butylcyclohexyl) peroxydicarbonate, di- (2-ethylhexyl) peroxydicarbonate, di- (n-propyl) peroxydicarbonate, di- (methoxy) Isopropyl) peroxydicarbo And t-butyl peroxydicarbonate, di- (3-methyl-3-methoxybutyl) peroxydicarbonate, diallyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and the like. 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2, , 2'-azobis- (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, and the like, but are not limited thereto.
Among the peroxydicarbonate compounds, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and bis- (4-t-butylcyclohexyl) peroxydicarbonate are particularly preferable.
The thermal polymerization initiator is preferably contained in an amount of 0.005 to 5% by mass with respect to the polymerizable monomer and oligomer, so that further decomposition of the primary decomposition radical can be suppressed.

-Photopolymerization initiator-
There is no restriction | limiting in particular as a photoinitiator, According to the objective, it can select suitably, For example, benzophenone, benzoin ethyl ether, benzoin isopropyl ether, benzyl, 2-hydroxy-2-methyl-1-phenyl-propane- 1-one etc. are mentioned. A commercial item can be used as a photoinitiator. Examples of commercially available photopolymerization initiators include Irgacure 1300, Irgacure 369, Irgacure 907 manufactured by Ciba Specialty Chemicals, Inc., and Lucirin TPO manufactured by BASF.

  When the mixture of the polymerizable oligomer or the polymerizable unsaturated compound and the photopolymerization initiator is irradiated with ultraviolet rays, the photopolymerization initiator is represented by the following formulas (I) and (II): Generate radicals. The radical causes an addition reaction of the polymerizable oligomer or the polymerizable unsaturated compound to the polymerizable double bond. Further radicals are generated by the addition reaction, and by repeating the addition reaction to the polymerizable double bond of the other polymerizable oligomer or the polymerizable unsaturated compound, the polymerization reaction is performed as shown in the following formula (III). proceed.

(I) Hydrogen drawing type

(II) Photocleavage type

(III) Polymerization

  The photopolymerization initiator includes (i) high ultraviolet absorption efficiency, (ii) high solubility in the polymerizable oligomer or polymerizable unsaturated compound, (iii) odor, yellowing, and toxicity. Those having good characteristics such as low and (iv) no dark reaction are preferred.

  There is no restriction | limiting in particular as content of the said photoinitiator in the said energy-beam curable precursor, Although it can select suitably according to the objective, 1 mass%-10 mass% are preferable, and 2 mass%- 5 mass% is more preferable.

-Polymerizable oligomer-
There is no restriction | limiting in particular as said polymerizable oligomer, According to the objective, it can select suitably, For example, polyester acrylate, epoxy acrylate, urethane acrylate etc. are mentioned.
There is no restriction | limiting in particular as said polyester acrylate, According to the objective, it can select suitably, For example, the acrylic ester of the polyester polyol obtained from a polyhydric alcohol and a polybasic acid is mentioned. The polyester acrylate exhibits excellent reactivity.
There is no restriction | limiting in particular as said epoxy acrylate, According to the objective, it can select suitably, For example, the epoxy acrylate obtained by reaction of bisphenol-type epoxy, novolak-type epoxy, alicyclic epoxy, etc. and acrylic acid is mentioned. It is done. The epoxy acrylate is excellent in hardness, flexibility, and curability.
There is no restriction | limiting in particular as said urethane acrylate, According to the objective, it can select suitably, For example, the urethane acrylate obtained by reacting polyester polyol, polyether polyol, etc., acrylic acid ester with a diisocyanate and a hydroxyl group Is mentioned. When the urethane acrylate is used, a flexible and strong film can be obtained.
The said polymerizable oligomer may be used individually by 1 type, and may use 2 or more types together.

  There is no restriction | limiting in particular as content of the said polymerizable oligomer in an energy-beam curable precursor, Although it can select suitably according to the objective, 5 mass%-60 mass% are preferable, and 10 mass%-50 mass. % Is more preferable, and 20% by mass to 45% by mass is particularly preferable. When the content is less than 5% by mass, poor curing may occur, the viscosity may be too low, or the flexibility after curing may be impaired. When the content exceeds 60% by mass, the adhesion is deteriorated. Or the viscosity becomes too high. When the content is within the particularly preferable range, it is advantageous in terms of viscosity optimization, curability, flexibility of the coating layer after curing, and strength.

-Polymerizable unsaturated compound-
The polymerizable unsaturated compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a monofunctional polymerizable unsaturated compound, a bifunctional polymerizable unsaturated compound, and a trifunctional polymerizable compound. Examples thereof include unsaturated compounds and tetrafunctional or higher polymerizable unsaturated compounds.
Examples of the monofunctional polymerizable unsaturated compound include 2-ethylhexyl acrylate, 2-hydroxylethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, benzyl acrylate, phenyl glycol monoacrylate, and cyclohexyl acrylate. It is done.
Examples of the bifunctional polymerizable unsaturated compound include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, tripropylene glycol diacrylate, and tetraethylene glycol. Examples include diacrylate.
Examples of the trifunctional polymerizable unsaturated compound include trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, and the like.
Examples of the tetrafunctional or higher polymerizable unsaturated compound include pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hydroxypentaacrylate, and dipentaerythritol hexaacrylate.

Examples of the material having a high melting ability include 1,6-hexanediol diacrylate, ethyl carbitol acrylate, acryloylmorpholine, and the like. Since the melting ability varies depending on each material, the addition amount must be tuned individually. However, if the amount is too small, poor adhesion may occur, and if the amount is too large, image distortion may occur.
The said polymerizable unsaturated compound may be used individually by 1 type, and may use 2 or more types together.

  There is no restriction | limiting in particular as content of the said polymerizable unsaturated compound in the said energy-beam curable precursor, Although it can select suitably according to the objective, 35 mass%-90 mass% are preferable, and 40 mass% -85 mass% is more preferable, and 45 mass%-75 mass% is especially preferable. When the content is less than 35% by mass, the viscosity may be too high, and when it exceeds 90% by mass, the curing may be poor, the viscosity may be too low, or the flexibility after curing may be increased. It may be damaged. When the content is within the particularly preferable range, it is advantageous in terms of viscosity optimization, curability, and a coating layer after curing.

A polyfunctional one is faster than a monofunctional one and has a faster curing speed and is suitable for high-speed fixing, but has a large volume shrinkage. In the case of a polymerizable unsaturated compound that greatly shrinks due to a curing reaction, curling is likely to occur. Therefore, it is desirable to use a polymerizable unsaturated compound having a volumetric shrinkage as low as possible and its polymer.
The polymerizable unsaturated compound preferably has a volume shrinkage of 15% or less.

P. of the polymerizable unsaturated compound and the polymerizable oligomer. I. I. There is no restriction | limiting in particular as (skin irritation), Although it can select suitably according to the objective, 1.0 or less is preferable. P. I. I. If it is 5.0 or more, irritation to the skin is too strong, which may cause safety problems.
Further, the hue of the polymerizable unsaturated compound and the polymerizable oligomer is preferably as colorless and transparent as possible, and preferably 2 or less in the Gardner gray scale. When the Gardner gray scale exceeds 2, the color of the image portion may change, and the discoloration of the background portion may become conspicuous.

-Sensitizer-
In the case of using the hydrogen abstraction type benzophenone photopolymerization initiator of the formula (I), the reaction may be slowed only by the photopolymerization initiator. Therefore, the reaction can be achieved by using an amine sensitizer together. It is preferable to improve the property. By containing an amine-based sensitizer, there is an effect of supplying hydrogen to the photopolymerization initiator by a hydrogen abstraction action and an effect of preventing reaction inhibition due to oxygen in the air.
The amine-based sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include triethanolamine, triisopropanolamine, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid. , Ethyl 4-dimethylaminobenzoate, isoacyl 4-dimethylaminobenzoate and the like.

  There is no restriction | limiting in particular as content of the said sensitizer in the said energy-beam curable precursor, Although it can select suitably according to the objective, 1 mass%-15 mass% are preferable, and 3 mass%-8 The mass% is more preferable.

-Polymerization inhibitor-
The polymerization inhibitor is used to increase the storage stability of the energy beam curable precursor.
The polymerization inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 2,6-ditert-butyl-p-cresol (BHT), 2,3-dimethyl-6-tert. -Butylphenol (IA), anthraquinone, hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ) and the like.

  There is no restriction | limiting in particular as content of the said polymerization inhibitor in the said energy-beam curable precursor, Although it can select suitably according to the objective, 0.5-3 mass% is preferable.

-Surfactant-
By including the surfactant in the energy beam curable precursor, adsorptivity is imparted to the interface between the toner and the energy beam curable pressure sensitive composition, or the surface tension of the energy beam curable precursor is lowered. The wettability is improved.

There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, anionic surfactant, nonionic surfactant, silicon surfactant, fluorosurfactant etc. are mentioned.
Examples of the anionic surfactant include sulfosuccinate, disulfonate, phosphate ester, sulfate, sulfonate, and mixtures thereof.
Examples of the nonionic surfactant include polyvinyl alcohol, polyacrylic acid, isopropyl alcohol, acetylenic diol, ethoxylated octylphenol, ethoxylated branched secondary alcohol, bellfluorobutane sulfonate, alkoxylated alcohol, and the like. .
Examples of the silicon surfactant include polyether-modified polydimethyldimethylsiloxane.
Examples of the fluorosurfactant include ethoxylated nonylphenol.

  There is no restriction | limiting in particular as content of the said surfactant in the said energy-beam curable precursor, Although it can select suitably according to the objective, 0.1 mass%-5 mass% are preferable, 0.5 A mass% to 3 mass% is more preferable. When the content is less than 0.1% by mass, wettability may not be obtained, and when it exceeds 5% by mass, curability may be inhibited. When the content is within the more preferable range, it is advantageous in terms of improving wettability.

  The other components further include leveling agents, matting agents, waxes for adjusting film physical properties, tackifiers (adhesives that do not inhibit polymerization) to improve adhesion to recording media such as polyolefin and PET. Property-imparting agent).

-Viscosity of energy ray curable precursor-
There is no restriction | limiting in particular as a viscosity of the said energy-beam curable precursor, Although it can select suitably according to the objective, The viscosity in 25 degreeC is 10 mPa * s-800 mPa * s. If the viscosity is less than 10 mPa · s or exceeds 800 mPa · s, it may be difficult to control the coating thickness.
The viscosity can be measured by, for example, a B-type viscometer (manufactured by Toyo Seiki Seisakusho).

  The energy ray curable precursor can be made with an oil type using a solvent, but in the case of an ultraviolet curable type (photo curable type) using UV, ensuring safety, environmental protection, energy saving and high production. From the viewpoint of sex.

(Image forming apparatus and image forming method)
An image forming apparatus used for forming an image of a recording medium on which a toner image is recorded, which is used in the method for producing a releasable information sheet according to the present invention, includes an image carrier, an electrostatic latent image forming unit, and a developing unit. And at least a transfer means and a fixing means, preferably a cleaning means, and other means appropriately selected as necessary, for example, a static elimination means, a recycling means, a control means, etc. It has (FIG. 1). An image forming method used for forming an image on a recording medium on which a toner image is recorded, which is used in the method for producing a releasable information sheet according to the present invention, includes an electrostatic latent image forming step, a developing step, and a transferring step. And a fixing step, preferably a cleaning step, and other steps appropriately selected as necessary, for example, a static elimination step, a recycling step, a control step, and the like.

  The image forming method can be suitably performed by the image forming apparatus, the electrostatic latent image forming step can be performed by the electrostatic latent image forming unit, and the developing step is performed by the developing unit. The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

<Electrostatic latent image forming step and electrostatic latent image forming means>
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the image carrier.
-Image carrier-
The image carrier (sometimes referred to as “electrostatic latent image carrier” or “photoreceptor”) is not particularly limited in terms of material, shape, structure, size, etc., and is appropriately selected from known ones. The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine.
An image carrier (photoreceptor) used in the image forming apparatus includes a conductive support, and at least a photosensitive layer on the conductive support, and further includes other layers as necessary.

  As the photosensitive layer, a single layer type in which a charge generation material and a charge transport material are mixed, a forward layer type in which a charge transport layer is provided on the charge generation layer, and a charge generation layer is provided on the charge transport layer. There is a reverse layer type. In order to improve the mechanical strength, abrasion resistance, gas resistance, cleaning property, etc. of the photoreceptor, an outermost surface layer can be provided on the photosensitive layer. An undercoat layer may be provided between the photosensitive layer and the conductive support. In addition, an appropriate amount of a plasticizer, an antioxidant, a leveling agent, etc. can be added to each layer as necessary.

The conductive support is not particularly limited as long as it has a volume resistance of 1.0 × 10 ¹⁰ Ω · cm or less, and can be appropriately selected according to the purpose. For example, aluminum, Metals such as nickel, chromium, nichrome, copper, gold, silver and platinum, metal oxides such as tin oxide and indium oxide, film or cylindrical plastic, paper coated or aluminum by vapor deposition or sputtering A plate made of aluminum alloy, nickel, stainless steel or the like, and a tube processed into a drum shape by a method such as extrusion or drawing, and then subjected to surface treatment such as cutting, superfinishing, or polishing can be used.
The drum-shaped support preferably has a diameter of 20 to 150 mm, more preferably 24 to 100 mm, and still more preferably 28 to 70 mm. When the diameter of the drum-shaped support is less than 20 mm, it may be physically difficult to arrange each step of charging, exposure, development, transfer, and cleaning around the drum. When the diameter exceeds 150 mm, The image forming apparatus may become large. In particular, when the image forming apparatus is a tandem type, since it is necessary to mount a plurality of photoconductors, the diameter is preferably 70 mm or less, and more preferably 60 mm or less.
Further, an endless nickel belt or an endless stainless steel belt as disclosed in JP-A-52-36016 can also be used as the conductive support.

The undercoat layer of the photoconductor may be composed of a single layer or a plurality of layers. For example, (1) the resin is the main component, and (2) the white pigment and the resin are the main components. And (3) a metal oxide film obtained by chemically or electrochemically oxidizing the surface of a conductive substrate. Among these, those containing a white pigment and a resin as main components are preferable.
Examples of the white pigment include metal oxides such as titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide. Among these, titanium oxide is particularly preferable because it is excellent in preventing injection of charges from the conductive support.
Examples of the resin include thermoplastic resins such as polyamide, polyvinyl alcohol, casein, and methyl cellulose; thermosetting resins such as acrylic, phenol, melamine, alkyd, unsaturated polyester, and epoxy. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular in the thickness of the said undercoat layer, According to the objective, it can select suitably, 0.1-10 micrometers is preferable and 1-5 micrometers is more preferable.

  Examples of the charge generation material in the photosensitive layer include monoazo pigments, bisazo pigments, trisazo pigments, tetrakisazo pigments and other azo pigments, triarylmethane dyes, thiazine dyes, oxazine dyes, xanthene dyes, Cyanine dyes, styryl dyes, pyrylium dyes, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, bisbenzimidazole pigments, indanthrone pigments, squarylium pigments, phthalocyanine pigments, etc. Organic pigments or dyes; selenium, selenium-arsenic, selenium-tellurium, cadmium sulfide, zinc oxide, titanium oxide, amorphous silicon, and other inorganic materials. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the charge transport material in the photosensitive layer include anthracene derivatives, pyrene derivatives, carbazole derivatives, tetrazole derivatives, metallocene derivatives, phenothiazine derivatives, pyrazoline compounds, hydrazone compounds, styryl compounds, styryl hydrazone compounds, enamine compounds, butadiene compounds, distyryl. Examples thereof include compounds, oxazole compounds, oxadiazole compounds, thiazole compounds, imidazole compounds, triphenylamine derivatives, phenylenediamine derivatives, aminostilbene derivatives, and triphenylmethane derivatives. These may be used individually by 1 type and may use 2 or more types together.

  As the binder resin used to form the photosensitive layer, it is electrically insulating and may be a known thermoplastic resin, thermosetting resin, photocurable resin, photoconductive resin, or the like. it can. Examples of the binder resin include polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, ethylene-vinyl acetate copolymer, polyvinyl butyral, Polyvinyl acetal, polyester, phenoxy resin, (meth) acrylic resin, polystyrene, polycarbonate, polyarylate, polysulfone, polyethersulfone, ABS resin and other thermoplastic resins, phenol resin, epoxy resin, urethane resin, melamine resin, isocyanate resin, Examples thereof include thermosetting resins such as alkyd resins, silicon resins, and thermosetting acrylic resins, polyvinyl carbazole, polyvinyl anthracene, and polyvinyl pyrene. These may be used individually by 1 type and may use 2 or more types together.

Examples of the antioxidant include phenolic compounds, paraphenylenediamines, hydroquinones, organic sulfur compounds, and organic phosphorus compounds.
Examples of the phenol compound include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-ethyl- 6-t-butylphenol), 4,4′-thiobis- (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), 1,1,3 -Tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxy Ben ) Benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis (4′-hydroxy-3 ′) -T-butylphenyl) butyric acid] cricol ester, tocopherols and the like.
Examples of the paraphenylenediamines include N-phenyl-N′-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl- Examples include p-phenylenediamine, N, N′-di-isopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine, and the like.
Examples of the hydroquinones include 2,5-di-t-octyl hydroquinone, 2,6-didodecyl hydroquinone, 2-dodecyl hydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methyl. Examples include hydroquinone and 2- (2-octadecenyl) -5-methylhydroquinone.
Examples of the organic sulfur compounds include dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like. .
Examples of the organic phosphorus compounds include triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine, and the like.
These compounds are known as antioxidants such as rubbers, plastics and fats and oils, and commercially available products can be easily obtained.
The addition amount of the antioxidant is preferably 0.01 to 10% by mass with respect to the total mass of the layer to be added.

As the plasticizer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is about 0 to 30 parts by mass with respect to 100 parts by mass of the binder resin. Is appropriate.
Further, a leveling agent may be added to the photosensitive layer. Examples of the leveling agent include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil; polymers having a perfluoroalkyl group in the chain or oligomers. The amount of the leveling agent used is preferably 0 to 1 part by mass with respect to 100 parts by mass of the binder resin.

  Next, the formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the image carrier and then performing imagewise exposure, and by the electrostatic latent image forming unit. Can do. The electrostatic latent image forming unit includes, for example, at least a charger that uniformly charges the surface of the image carrier and an exposure unit that exposes the surface of the image carrier imagewise.

The charging can be performed, for example, by applying a voltage to the surface of the image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotrons and corotrons.
The charger preferably has voltage applying means for applying a voltage having an AC component.

The exposure can be performed, for example, by exposing the surface of the image carrier imagewise using the exposure device.
The exposure device is not particularly limited as long as it can perform image-like exposure on the surface of the image carrier charged by the charger, and can be appropriately selected according to the purpose. Examples include various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
In the present invention, an optical back side system in which imagewise exposure is performed from the back side of the image carrier may be adopted.

<Development process and development means>
The developing step is a step of developing the electrostatic latent image using a toner or a developer to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer, and can be appropriately selected from known ones. For example, the toner or developer is accommodated. Preferred examples include those having at least a developing unit capable of bringing the toner or developer into contact or non-contact with the electrostatic latent image.

-Toner-
The toner in the present invention contains a binder resin and a colorant, and further contains a release agent (wax), a charge control agent, an external additive and the like as necessary.

  The toner preferably has an average circularity of 0.93 to 1.00, which is an average value of the circularity SR represented by the following formula 1, and more preferably 0.95 to 0.99. This average circularity is an index of the degree of unevenness of toner particles, and indicates 1.00 when the toner is a perfect sphere, and the average circularity becomes smaller as the surface shape becomes more complicated.

<Formula 1>
Circularity SR = (perimeter of circle having the same area as the projected area of toner particles) / (perimeter of projected image of toner particles)

  When the average circularity is in the range of 0.93 to 1.00, the surface of the toner particles is smooth, and the toner particles and the contact area between the toner particles and the photosensitive member are small, so that the transferability is excellent. Further, since the toner particles have no corners, the developer agitation torque in the developing device is small, and the agitation drive is stabilized, so that no abnormal image is generated. In addition, since there are no angular toner particles in the toner that forms the dots, the pressure is uniformly applied to the entire toner that forms the dots when pressed against the recording medium during transfer, and the transfer is not easily lost. Further, since the toner particles are not angular, the abrasive power of the toner particles themselves is small, and the surface of the image carrier is not damaged or worn.

The circularity SR can be measured using, for example, a flow type particle image analyzer (manufactured by Toa Medical Electronics Co., Ltd., FPIA-1000).
First, 0.1 to 0.5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance. Add ~ 0.5g. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the shape and particle size of the toner are measured by the above apparatus with the dispersion concentration being 3000 to 10000 / μl.

The toner has a mass average particle diameter (D4) of preferably 3 to 10 μm, and more preferably 4 to 8 μm. In this range, since the toner particles have a sufficiently small particle size with respect to the minute latent image dots, the dot reproducibility is excellent. When the mass average particle diameter (D4) is less than 3 μm, phenomena such as a decrease in transfer efficiency and a decrease in blade cleaning properties may occur, and when it exceeds 10 μm, it is difficult to suppress scattering of characters and lines. is there.
The toner has a mass average particle diameter (D4) to number average particle diameter (D1) ratio (D4 / D1) of preferably 1.00 to 1.40, and more preferably 1.00 to 1.30. The closer the ratio (D4 / D1) is to 1, the sharper the particle size distribution of the toner. In the range of (D4 / D1) from 1.00 to 1.40, selective development depending on the toner particle size. Since image quality does not occur, the image quality is excellent. In addition, since the toner particle size distribution is sharp, the triboelectric charge amount distribution is also sharp and the occurrence of fog is suppressed. Further, when the toner particle diameter is uniform, the latent image dots are developed so as to be arranged densely and orderly, so that the dot reproducibility is excellent.

  Here, the mass average particle diameter (D4) and the particle size distribution of the toner are measured by, for example, a Coulter counter method. Examples of the measuring device for the particle size distribution of toner particles by the Coulter counter method include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter).

  First, 0.1 to 5 ml of a surfactant (preferably alkyl benzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the mass average particle diameter (D4) and the number average particle diameter (D1) of the toner can be obtained.

  As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

  As the toner having such a substantially spherical shape, a toner composition containing a polyester prepolymer having a functional group containing a nitrogen atom, a polyester, a colorant, and a release agent is crosslinked in the presence of resin fine particles in an aqueous medium. It can be prepared by an extension reaction. In the toner produced by this reaction, the occurrence of hot offset can be reduced by curing the toner surface, and it is possible to prevent the fixing device from becoming dirty and appearing on the image.

Examples of the prepolymer made of the modified polyester resin include a polyester prepolymer (A) having an isocyanate group, and examples of the compound that extends or crosslinks with the prepolymer include amines (B).
Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen group, which is further reacted with a polyisocyanate (3). Is mentioned. Examples of active hydrogen groups possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are particularly preferable.

Examples of the polyol (1) include diol (1-1), trivalent or higher polyol (1-2), (1-1) alone or (1-1) and a small amount of (1-2). Mixtures are preferred.
Examples of the diol (1-1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (Diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); Bisphenols (bisphenol A) Bisphenol F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol Alkylene oxide of the bisphenols (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferable, and combined use of alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms is particularly preferable.

  Examples of the trivalent or higher polyol (1-2) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); (Trisphenol PA, phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trivalent or higher polyphenols.

Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). Among these, (2-1) alone and (2-1) ) And a small amount of (2-2).
Examples of the dicarboxylic acid (2-1) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, Terephthalic acid, naphthalenedicarboxylic acid, etc.). Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are particularly preferable.
Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  As for the ratio of the polyol (1) and the polycarboxylic acid (2), the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH] is preferably 2/1 to 1/1. 5/1 to 1/1 is more preferable, and 1.3 / 1 to 1.02 / 1 is still more preferable.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; Those blocked with caprolactam, etc. These may be used individually by 1 type and may use 2 or more types together.

  As for the ratio of the polyisocyanate (3), the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group is preferably 5/1 to 1/1. 1 to 1.2 / 1 is more preferable, and 2.5 / 1 to 1.5 / 1 is still more preferable. If the [NCO] / [OH] exceeds 5, the low-temperature fixability may be deteriorated. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester becomes low, and hot offset resistance Sex worsens.

  The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass, and 2 to 20% by mass. Is more preferable. When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, low-temperature fixability is obtained. May get worse.

The average number of isocyanate groups contained per molecule in the prepolymer (A) having the isocyanate group is preferably 1 or more, more preferably 1.5 to 3 on average, and 1.8 to 2.5 on average. Further preferred. When the number is less than 1 per molecule, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance may be deteriorated.

  As the amines (B), the diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and amino groups of B1 to B5 were blocked. (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the B1-B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1-B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, if necessary, the molecular weight of the urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), or those obtained by blocking them (ketimine compounds).

  The ratio of the amines (B) is the equivalent ratio [NCO] / [NHx] of the isocyanate group [NCO] in the prepolymer (A) having an isocyanate group and the amino group [NHx] in the amine (B). Is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and still more preferably 1.2 / 1 to 1 / 1.2. When the [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low and the hot offset resistance deteriorates.

  In the present invention, the polyester (i) modified with a urea bond may contain a urethane bond together with a urea bond. The molar ratio between the urea bond content and the urethane bond content is preferably 100/0 to 10/90, more preferably 80/20 to 20/80, and still more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance may be deteriorated.

  By these reactions, the modified polyester used in the toner, especially the urea-modified polyester (i) can be produced. These urea-modified polyesters (i) are produced by a one-shot method or a prepolymer method. The mass average molecular weight of the urea-modified polyester (i) is preferably 10,000 or more, more preferably 20,000 to 10,000,000, and still more preferably 30,000 to 1,000,000. When the mass average molecular weight is less than 10,000, the hot offset resistance may be deteriorated.

  The number average molecular weight of the urea-modified polyester is not particularly limited when the unmodified polyester (ii) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the mass average molecular weight. (I) When used alone, the number average molecular weight is preferably 20,000 or less, more preferably 1,000 to 10,000, and still more preferably 2,000 to 8,000. When the number average molecular weight exceeds 20,000, low temperature fixability and glossiness when used in a full color image forming apparatus may be deteriorated.

  In the present invention, not only the polyester (i) modified with a urea bond but also the polyester (ii) not modified can be included as a binder resin component together with the (i). By using (ii) in combination, the low-temperature fixability and the gloss when used in a full-color apparatus are improved, so that it is preferable to use alone. Examples of (ii) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (i), and preferred ones are also the same as (i). Further, (ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, for example, may be modified with a urethane bond. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance.

  Therefore, the polyester component (i) and (ii) preferably have similar compositions. When (ii) is contained, the mass ratio of (i) and (ii) is preferably 5/95 to 80/20, more preferably 5/95 to 30/70, and further preferably 5/95 to 25/75. 7/93 to 20/80 is particularly preferable. When the mass ratio of (i) is less than 5% by mass, the hot offset resistance may be deteriorated, and it may be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of (ii) is preferably 1,000 to 30,000, more preferably 1,500 to 10,000, and still more preferably 2,000 to 8,000. When the peak molecular weight is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 10,000, the low temperature fixability may be deteriorated. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and still more preferably 20 to 80. If the hydroxyl value is less than 5, it may be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. 1-30 are preferable and, as for the acid value of said (ii), 5-20 are more preferable. By having an acid value, it tends to be negatively charged.

  The glass transition temperature (Tg) of the binder resin is preferably 50 to 70 ° C, and more preferably 55 to 65 ° C. When the glass transition temperature is less than 50 ° C., blocking of the toner during high-temperature storage may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the urea-modified polyester resin, the toner used in the present invention tends to have good heat storage stability even when the glass transition point is low, as compared with known polyester-based toners.

As the storage elastic modulus of the binder resin, the temperature (TG ′) at which the measurement frequency is 20 Hz is 10,000 dyne / cm ² is preferably 100 ° C. or more, and more preferably 110 to 200 ° C. When the temperature (TG ′) is less than 100 ° C., the hot offset resistance may be deteriorated.

  As the viscosity of the binder resin, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is preferably 180 ° C. or less, and more preferably 90 to 160 ° C. When the temperature (Tη) exceeds 180 ° C., the low-temperature fixability deteriorates. That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low-temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably greater than 0 ° C., more preferably 10 ° C. or more, and even more preferably 20 ° C. or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C, more preferably 10 to 90 ° C, and still more preferably 20 to 80 ° C.

The binder resin can be produced by the following method.
First, the polyol (1) and the polycarboxylic acid (2) are produced at 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and reduced pressure as necessary. Water is distilled off to obtain a polyester having a hydroxyl group. Subsequently, this is made to react with polyisocyanate (3) at 40-140 degreeC, and the prepolymer (A) which has an isocyanate group is obtained. Further, (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a polyester modified with a urea bond. When reacting (3) and reacting (A) and (B), a solvent may be used as necessary.
Usable solvents include, for example, aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.), Inactive to isocyanate (3) such as ethers (tetrahydrofuran, etc.).
When using polyester (ii) not modified with urea bond, (ii) is produced in the same manner as polyester having a hydroxyl group, and this is dissolved in the solution after completion of the reaction of (i). , Mix.

  The binder resin other than the polyester resin is not particularly limited and can be appropriately selected depending on the purpose. For example, styrene such as polystyrene, poly-p-styrene, polyvinyltoluene, or a homopolymer of a substitution product thereof, styrene -P-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-methacrylic acid copolymer , Styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer Styrene-vinyl methyl ether copolymer, styrene-vinyl methyl ketone Copolymer, styrene-butadiene copolymer, styrene-isopropyl copolymer, styrene copolymer such as styrene-maleic acid ester copolymer, polymethyl methacrylate resin, polybutyl methacrylate resin, polyvinyl chloride resin, Polyvinyl acetate resin, polyethylene resin, polyurethane resin, epoxy resin, polyvinyl butyral resin, polyacrylic acid resin, rosin resin, modified rosin resin, terpene resin, phenol resin, aliphatic or aromatic hydrocarbon resin, aromatic petroleum resin Etc. These may be used individually by 1 type and may use 2 or more types together. Among these, it is particularly preferable to use a polyester resin because of its affinity with the recording medium to be fixed.

Further, the toner used in the present invention can be produced by the following method, but is not limited thereto.
The toner may be formed by reacting a dispersion made of a prepolymer (A) having an isocyanate group in an aqueous medium with (B), or using a urea-modified polyester (i) produced in advance. Good. As a method for stably forming a dispersion comprising urea-modified polyester (i) or prepolymer (A) in an aqueous medium, a toner raw material comprising urea-modified polyester (i) or prepolymer (A) in an aqueous medium is used. And a method of dispersing by shearing force.
The prepolymer (A) and other toner compositions (hereinafter sometimes referred to as toner raw materials), colorants, colorant master batches, release agents, charge control agents, unmodified polyester resins, Mixing may be performed when the dispersion is formed in the medium, but it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner raw materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium. It may be added later. For example, after forming particles not containing a colorant, the colorant can be added by a known dyeing method.

  As the aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The amount of the aqueous medium used relative to 100 parts by mass of the toner composition containing the urea-modified polyester (i) and the prepolymer (A) is preferably 50 to 2000 parts by mass, and more preferably 100 to 1000 parts by mass. When the amount used is less than 50 parts by mass, the toner composition is not well dispersed, and toner particles having a predetermined particle size may not be obtained. When the amount used exceeds 2000 parts by mass, it is not economical.

Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.
The dispersion method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. . In order to make the particle diameter of the dispersion 2 to 20 μm, a high-speed shearing method is preferable. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. As temperature at the time of dispersion | distribution, 0-150 degreeC is preferable normally and 40-98 degreeC is more preferable. Higher temperatures are preferred in that the dispersion made of urea-modified polyester (i) or prepolymer (A) has a low viscosity and is easy to disperse.

  In the step of synthesizing the urea-modified polyester (i) from the prepolymer (A), the amine (B) may be added and reacted before the toner composition is dispersed in the aqueous medium, or may be dispersed in the aqueous medium. An amine (B) may be added later to cause a reaction from the particle interface. In this case, urea-modified polyester is preferentially produced on the surface of the manufactured toner, and a concentration gradient can be provided inside the particles.

In the reaction, it is preferable to use a dispersant as required.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a slightly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, and the like. Among these, those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC- 129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nippon Ink Chemical Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Neos) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M); F-824 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products);

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In the preparation of the dispersion, a dispersion stabilizer can be used as necessary. Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate salts.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.

  In the preparation of the dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

Furthermore, in order to lower the viscosity of the toner composition, a solvent in which the urea-modified polyester (i) or the prepolymer (A) is soluble can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. The solvent is preferably volatile from the viewpoint of easy removal.
Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Examples thereof include methyl ethyl ketone and methyl isobutyl ketone. These may be used individually by 1 type and may use 2 or more types together. Among these, aromatic solvents such as toluene and xylene; halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride are preferable, and aromatic solvents such as toluene and xylene are more preferable.
0-300 mass parts is preferable, as for the usage-amount of the solvent with respect to 100 mass parts of said prepolymers (A), 0-100 mass parts is more preferable, and 25-70 mass parts is still more preferable. When a solvent is used, it is removed by heating under normal pressure or reduced pressure after the elongation and / or crosslinking reaction.

  The elongation and / or crosslinking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually preferably 10 minutes to 40 hours, and preferably 2 to 24 hours. More preferred. The reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C. Furthermore, a known catalyst can be used as necessary. Specific examples include dibutyltin laurate and dioctyltin laurate.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. It is also possible to spray the emulsified dispersion in a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and also remove the aqueous dispersant by evaporating it. is there. As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short time treatment such as spray dryer, belt dryer, rotary kiln.

When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Although classification operation may be performed after obtaining as powder after drying, it is preferable in terms of efficiency to be performed in a liquid. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, unnecessary fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

  The resulting dried toner powder is mixed with dissimilar particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or mechanical impact force is applied to the mixed powder. As a result, it is possible to prevent the dissociation of the foreign particles from the surface of the composite particle obtained by immobilizing and fusing on the surface.

  As specific means, (1) a method of applying an impact force to the mixture by blades rotating at high speed, (2) the mixture is injected into a high-speed air stream, accelerated, and particles or composite particles are mixed with an appropriate collision plate. There is a method of making it collide. As equipment, Ong mill (manufactured by Hosokawa Micron Corporation), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.), with reduced pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron system ( Kawasaki Heavy Industries, Ltd.) and automatic mortar.

Further, as the colorant used in the toner, pigments and dyes that have been conventionally used as toner colorants can be used, and as colors, those exhibiting colors such as black, yellow, magenta, and cyan are used. be able to. Note that it is preferable to form a full-color image using at least four colors of black, yellow, magenta, and cyan.
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. Specifically, carbon black, lamp black, iron black, ultramarine, nigrosine dye, aniline blue, phthalocyanine Blue, phthalocyanine green, Hansa yellow G, rhodamine 6C lake, calco oil blue, chrome yellow, quinacridone red, benzidine yellow, rose bengal and the like can be used alone or in combination.
There is no restriction | limiting in particular as content of the said coloring agent, Although it can select suitably according to the objective, 1 mass part-15 mass parts are preferable with respect to 100 mass parts of said toners, and 3 mass parts-10 parts. Part by mass is more preferable.

Further, if necessary, in order to give the toner particles magnetic properties, for example, iron oxides such as ferrite, magnetite and maghemite; metals such as iron, cobalt and nickel, or alloys of these with other metals, etc. What is necessary is just to mix well-known things, such as a magnetic component, into a toner particle individually or in mixture. These components can also be used as a colorant component.
There is no restriction | limiting in particular as content of the said magnetic body, Although it can select suitably according to the objective, 10 mass parts-200 mass parts are preferable with respect to 100 mass parts of said binder resins, 20 mass parts -150 mass parts is more preferable.

  Further, the number average particle diameter of the colorant in the toner used in the present invention is preferably 0.5 μm or less, more preferably 0.4 μm or less, and further preferably 0.3 μm or less. When the number average particle diameter exceeds 0.5 μm, the dispersibility of the pigment does not reach a sufficient level, and preferable transparency may not be obtained. On the other hand, the colorant having a fine particle diameter of less than 0.1 μm is sufficiently smaller than a half wavelength of visible light, and thus is considered not to adversely affect the light reflection and absorption characteristics. Therefore, the colorant particles having a number average particle size of less than 0.1 μm contribute to good color reproducibility and transparency of the OHP sheet having a fixed image. On the other hand, when there are many colorants having a particle size larger than 0.5 μm, the transmission of incident light is hindered or scattered, and the brightness of the projected image of the OHP sheet is reduced. There is a tendency to decrease the color. Further, when a large amount of colorant having a particle size larger than 0.5 μm is present, the colorant is detached from the surface of the toner particles, which may cause various problems such as fogging, drum contamination, and poor cleaning. The colorant having a particle size larger than 0.7 μm is preferably 10% by number or less, more preferably 5% by number or less of the total colorant.

  In addition, by mixing the colorant together with a part or all of the binder resin in advance after adding a wetting liquid, the binder resin and the colorant are initially sufficiently attached, In the subsequent toner production process, the colorant is dispersed more effectively in the toner particles, the dispersed particle diameter of the colorant is reduced, and better transparency can be obtained.

  As the binder resin used for kneading in advance, the resins exemplified as the binder resin for toner can be used as they are, but are not limited thereto.

  As a specific method for kneading the mixture of the binder resin and the colorant with the wetting liquid in advance, for example, the binder resin, the colorant and the wetting liquid are obtained after mixing with a blender such as a Henschel mixer. The obtained mixture is kneaded at a temperature lower than the softening temperature of the binder resin using a kneader such as a two-roll or three-roll roll to obtain a sample.

Further, as the wetting liquid, a general one can be used in consideration of the solubility of the binder resin and the paintability with the colorant, but an organic solvent such as acetone, toluene, butanone, and water are used as the colorant. It is preferable from the viewpoint of dispersibility. Among these, the use of water is particularly preferable from the viewpoint of environmental considerations and maintaining the dispersion stability of the colorant in the subsequent toner production process.
According to this manufacturing method, not only the particle diameter of the colorant particles contained in the obtained toner is reduced, but also the uniformity of the dispersion state of the particles is increased, so that the color reproducibility of the projected image by OHP is further improved. Get better.

The toner contains a wax (release agent) in the toner in order to give release properties together with the binder resin and the colorant. The wax preferably has a melting point of 40 to 160 ° C, more preferably 50 to 120 ° C. If the melting point is less than 40 ° C., the heat resistant storage stability may be adversely affected, and if it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps at a temperature 20 ° C. higher than the melting point. When the melt viscosity exceeds 1000 cps, the effect of improving hot offset resistance and low-temperature fixability may be poor.
The content of the wax in the toner is preferably 0 to 40% by mass, and more preferably 3 to 30% by mass. When the wax content exceeds 40% by mass, the amount of wax deposited on the surface of the image after the fixing step becomes too large, and repels the ultraviolet curable composition and ultraviolet curable pressure sensitive composition described later, or the toner and ultraviolet In some cases, the adhesiveness at the interface between the curable composition and the ultraviolet curable pressure-sensitive composition may be impaired.

Examples of the wax include animal-derived waxes (such as beeswax, whale wax, shellac wax), plant-derived waxes (such as carnauba wax, wood wax, rice bran wax, and candelilla wax), and mineral-derived waxes (such as montan wax and ozokerite). Petroleum-derived waxes (paraffin wax, microcrystalline wax, etc.) can be exemplified, but petroleum-derived waxes are preferred because of their high mold release capability. Examples of the petroleum-derived wax include paraffin wax and microcrystalline wax, and two or more kinds of waxes may be mixed and used. In particular, when waxes having different melting points are mixed, the melting point of the wax as a whole is lowered.
Since microcrystalline wax contains components of isoparaffin and cycloparaffin, crystals are relatively small. For this reason, the wax on the oilless fixed image does not exist uniformly but tends to exist in a dispersed manner.

Further, in order to accelerate the toner charge amount and its rise, a charge control agent may be contained in the toner as necessary. Since a color change occurs when a colored material is used as the charge control agent, a colorless or nearly white material is preferable.
The charge control agent is not particularly limited and may be any one that imparts positive or negative chargeability, and can be appropriately selected from known ones according to the purpose. Phenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine based Examples include activators, metal salts of salicylic acid, and metal salts of salicylic acid derivatives.
As the charge control agent, a commercially available product can be used. Examples of the commercially available product include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, E-89 of a phenol-based condensate (both manufactured by Orient Chemical Industries); TP-302, TP-415 of a quaternary ammonium salt molybdenum complex (both manufactured by Hodogaya Chemical Co., Ltd.); Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (both manufactured by Hoechst); LRA-901, boron complex LR-147 (all manufactured by Nippon Carlit Co., Ltd.), quinacridone, azo face , Sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  The amount of the charge control agent added varies depending on the type of the binder resin, the presence or absence of the additive, the toner production method including the dispersion method, and the like, and cannot be uniquely defined. 0.1-10 mass parts is preferable with respect to it, and 0.2-5 mass parts is more preferable. When the addition amount exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction force with the developing roller is increased, the flowability of the developer is reduced, and the image The concentration may decrease. These charge control agents can be melted and kneaded together with a masterbatch and resin and then dissolved and dispersed, or they can be added directly when dissolved and dispersed in an organic solvent, or fixed after the toner particles are prepared on the toner surface. You may let them.

  Further, when the toner composition is dispersed in the aqueous medium during the toner production process, resin fine particles mainly for stabilizing the dispersion may be added.

The resin fine particles may be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resins, polyurethane resins, epoxy resins, polyester resins , Polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, or a combination thereof is preferable because an aqueous dispersion of fine spherical resin particles can be easily obtained.
As the vinyl resin, a polymer obtained by homopolymerization or copolymerization of a vinyl monomer is used. For example, a styrene- (meth) acrylate resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylate ester Examples thereof include a polymer, a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, and a styrene- (meth) acrylic acid copolymer.

As an external additive for assisting the fluidity, developability and chargeability of the toner particles, inorganic fine particles are suitable.
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, and diatomaceous earth. , Chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The specific surface area of the inorganic fine particles by BET method is preferably 20 to 500 m ² / g. The addition amount of the inorganic fine particles in the toner is preferably 0.01 to 5% by mass, and more preferably 0.01 to 2.0% by mass.

  Other polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, polycondensation system such as silicon, benzoguanamine and nylon, thermosetting resin And polymer particles.

  A fluidizing agent can also be added to the toner. The fluidizing agent performs surface treatment to increase hydrophobicity, and can prevent deterioration of flow characteristics and charging characteristics even under high humidity. Examples of the fluidizing agent include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. Can be mentioned.

  Examples of cleaning improvers for removing the developer after transfer remaining on the photosensitive member or intermediate transfer member include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid; polymethyl methacrylate fine particles, polystyrene Examples thereof include polymer fine particles produced by soap-free emulsion polymerization of fine particles and the like. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  By using such a toner, as described above, it is possible to form a high-quality toner image having excellent development stability.

  In addition, the image forming apparatus used in the present invention is not only used in combination with the above-described polymerization toner having a configuration suitable for obtaining a high-quality image, but also applied to an irregular shaped toner by a pulverization method. In this case as well, the life of the apparatus can be greatly extended. As a material constituting such a pulverized toner, those usually used as an electrophotographic toner can be applied without particular limitation.

  As the binder resin used in the pulverized toner, for example, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, or the like, or a substituted polymer thereof; styrene / p-chlorostyrene copolymer, styrene / propylene Copolymer, styrene / vinyl toluene copolymer, styrene / vinyl naphthalene copolymer, styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, styrene / acrylic Octyl acid copolymer, styrene / methyl methacrylate copolymer, styrene / ethyl methacrylate copolymer, styrene / butyl methacrylate copolymer, styrene / α-chloromethyl methacrylate copolymer, styrene / acrylonitrile copolymer Styrene / vinyl methyl ketone copolymer, Styrene copolymers such as tylene / butadiene copolymers, styrene / isoprene copolymers, styrene / maleic acid copolymers; polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate, etc. Acrylic ester-based homopolymers or copolymers thereof; polyvinyl derivatives such as polyvinyl chloride and polyvinyl acetate; polyester-based polymers, polyurethane-based polymers, polyamide-based polymers, polyimide-based polymers, polyol-based polymers, Examples thereof include epoxy polymers, terpene polymers, aliphatic or alicyclic hydrocarbon resins, and aromatic petroleum resins. These may be used individually by 1 type and may use 2 or more types together. Among these, a styrene-acrylic copolymer resin, a polyester resin, and a polyol resin are preferable from the viewpoint of electrical characteristics, cost, and the like, and further, polyester resins and polyol resins that have good fixing characteristics. Particularly preferred.

  In the pulverized toner, together with these resin components, the colorant component, wax component, charge control component, and the like as described above are premixed as necessary, and then kneaded at a temperature close to the softening temperature of the resin component, and then cooled. Thereafter, a toner may be prepared through a pulverizing and classifying step, and the external additive component may be appropriately added and mixed as necessary.

  In addition, the toner can be produced by a suspension polymerization method or an emulsion polymerization method.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the image carrier (photosensitive member), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is caused by the electric attractive force. It moves to the surface of the image carrier (photoreceptor). As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the image carrier (photoconductor).
The developer accommodated in the developing device is a developer containing the toner, but the developer may be a one-component developer or a two-component developer.

<Transfer process and transfer means>
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the image carrier (photosensitive member) with the transfer charger using the visible image, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.
The image carrier is an intermediate transfer member used for image formation by a so-called intermediate transfer method in which a toner image formed on a photosensitive member is primarily transferred to perform color superposition and further transferred to a recording medium. It may be.

-Intermediate transfer member-
As the intermediate transfer member, a material exhibiting conductivity of a volume resistance of 1.0 × 10 ^{5 to} 1.0 × 10 ¹¹ Ω · cm is preferable. When the volume resistance is less than 1.0 × 10 ⁵ Ω · cm, so-called transfer dust is generated in which the toner image is disturbed due to discharge when the toner image is transferred from the photosensitive member to the intermediate transfer member. If the toner image exceeds 1.0 × 10 ¹¹ Ω · cm, the counter charge of the toner image is transferred onto the intermediate transfer member after the toner image is transferred from the intermediate transfer member to a recording medium such as paper. It may remain and appear as an afterimage on the next image.

As the intermediate transfer member, for example, a metal oxide such as tin oxide or indium oxide, a conductive particle such as carbon black, or a conductive polymer, alone or in combination, kneaded with a thermoplastic resin, and then an extrusion molded belt A cylindrical or cylindrical plastic can be used. In addition to this, the above-mentioned conductive particles and conductive polymer are added to a resin solution containing a thermally crosslinkable monomer or oligomer, if necessary, and subjected to centrifugal molding while heating to obtain an intermediate transfer member on an endless belt. You can also.
When the surface layer is provided on the intermediate transfer member, among the surface layer materials used for the surface layer of the photoreceptor described above, the composition excluding the charge transport material is appropriately adjusted in combination with a conductive substance, Can be used.

The transfer means (the primary transfer means and the secondary transfer means) includes at least a transfer device that peels and charges the visible image formed on the image carrier (photoconductor) to the recording medium side. It is preferable to have. There may be one transfer means or two or more transfer means. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper). However, in consideration of use as direct mail, the recording medium itself may be white. Preferably, the recording medium surface has a coating layer of a white pigment such as calcium carbonate, talc, or kaolin. The size of the white pigment is an average particle diameter of 0.1 μm or more, preferably 0.5 to 5 μm. When the average particle size of the white pigment is less than 0.1 μm, the strength of the white pigment layer (coat layer) is very weak, and the white pigment powder is crushed and the white pigment layer is severely cracked. Peeling easily occurs.
In order to maintain the appearance of the information sheet, the thickness of the white pigment layer (coat layer) is 1 μm or more, preferably 1.5 to 3 μm or more.

<Fixing process and fixing means>
The fixing step is a step of fixing the visible image transferred to the recording medium using the fixing unit, and may be performed each time the toner of each color is transferred to the recording medium, or may be applied to the toner of each color. On the other hand, it may be carried out simultaneously at the same time in a state of being laminated.
The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose. However, a known heating and pressing unit is preferable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
It is preferable that the toner particles be in the range of 10 ³ Pa · s or more and 10 ⁴ Pa · s or less by the heating and pressing in the heating and pressing means.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the image carrier. For example, a neutralization lamp or the like is preferable. It is done.

The cleaning step is a step of removing the electrophotographic toner remaining on the image carrier and can be suitably performed by a cleaning unit.
The cleaning unit is preferably provided downstream of the transfer unit and upstream of the charger.
The cleaning means is not particularly limited, and may be appropriately selected from known cleaners as long as the toner remaining on the image carrier can be removed. For example, a magnetic brush cleaner or an electrostatic brush A cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, a web cleaner and the like are preferable.

The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

(Removable information sheet manufacturing method and removable information sheet manufacturing apparatus)
<Energy beam curable precursor coating and curing step and energy beam curable precursor coating and curing means>
The energy ray curable precursor can be applied on a recording medium carrying a toner image at any appropriate time after the fixing step. For example, energy ray curable precursors can be applied off-line as soon as an image is formed or on different printing devices, such as in-line coating devices where printing and overcoating are performed on the same printing device. Like a device, it can be applied on a recording medium carrying a toner image after a short or long delay after printing. Furthermore, the energy beam curable precursor can be applied over the entire recording medium, the entire image, a portion of the recording medium, or a portion of the image. When performing the bending described later, it is preferable not to apply the energy ray curable precursor to the bent portion in order to reduce the burden on the bent portion.

  To apply the energy ray curable precursor, roll coater, flexo coater, rod coater, blade, wire bar, air knife, curtain coater, slide coater, doctor knife, screen coater, gravure coater (for example, offset gravure coater), Liquid film coating equipment can be used, including slot coaters, extrusion coaters, and ink jet coaters. Such devices can be used in well-known manners such as forward and reverse roll coating, offset gravure, curtain coating, lithographic coating, screen coating, gravure coating, and inkjet coating. There is no restriction | limiting in particular as application | coating thickness of the said energy-beam curable precursor, Although it can select suitably according to the objective, 1 micrometer-15 micrometers are preferable. When the coating thickness is less than 1 μm, repelling or gloss may be insufficient, and when it exceeds 15 μm, the texture of the image may be deteriorated.

After the above application, the applied energy ray curable precursor is cured.
The energy ray-curable precursor can be cured by irradiating energy rays such as ultraviolet rays, X-rays, and electron beams.

  FIG. 2 shows an example of the application means. The coating unit in FIG. 2 includes a coating roller 2, a metal roller 3, a pressure roller 5, a conveyor belt 6, a tray 7, a light source 8, and a scraper 9. The energy beam curable precursor 1 is stored between the application roller 2 and the metal roller 3.

The recording medium 4 on which the toner image is formed passes between the application roller 2 and the pressure roller 5 while being in contact with the rotating application roller 2 and the pressure roller 5. At that time, the energy beam curable precursor 1 on the surface of the coating roller 2 is transferred to the recording medium 4, whereby the energy beam curable precursor 1 is applied to the recording medium 4.
The recording medium 4 coated with the energy ray curable precursor 1 is conveyed by the conveying belt 6 and passes under the light source 8. At that time, the energy ray curable precursor 1 applied to the recording medium 4 is cured by ultraviolet rays from the light source 8. Thereafter, the recording medium 4 moves onto the tray 7.
Unnecessary energy beam curable precursor 1 adhering to the pressure roller 5 is removed by a scraper 9.
In order to reduce the load at the bent part in the folding process described later, when the releasable information sheet is peeled off when the energy ray curable precursor is not applied to the bent part, the bent part is torn. Etc. can be prevented.

<Folding process, crimping process and folding means, crimping means>
When using the energy ray curable pressure-sensitive composition, after the coating and curing step, it is cut into a desired size as necessary, for example, folded into two (V-fold), three-fold (Z-fold), etc. A process is put and the energy beam hardening type pressure sensitive composition processed surfaces are matched. An adhesive having removability can be obtained by laminating the surfaces of the energy ray curable pressure-sensitive composition by roller pressure bonding. The amount of pressure applied when crimping is generally in the range of 50 to 1000 N / cm ² .
In addition, it is preferable not to apply the energy ray curable pressure-sensitive composition to the bent portion because the bent portion is not damaged when it is peeled again.

<Heating and pressing step and heating and pressing means>
The heating and pressing step in the present invention is performed in the next step of the coating and curing step of the energy beam curable precursor. Accordingly, the heating and pressing step may be performed in the folding step and folding unit subsequent to the energy beam curable precursor curing unit, or in the subsequent step of the crimping step and pressing unit. In the folding process and the subsequent process of the folding means, the heat pressurizing process and the constituent parts of the means do not come into contact with the processed surface of the energy ray curable pressure-sensitive composition, so that the processed surface is not damaged or soiled. Further, when the processed surface of the energy ray curable pressure-sensitive composition has tackiness, there is a possibility that the conveyance performance may be lowered, but this can be prevented. In the pressure bonding step and the subsequent step of the pressure bonding means, the processed surface of the energy ray curable pressure-sensitive composition is in a bonded state, so that it can be conveyed in any direction of the recording medium, and the conveyance design is further facilitated.

For the heating and pressing step and the heating and pressing unit, the fixing step and the fixing unit may be used. For example, after the fixing step, the fixing step is repeated again in the form of substituting blank paper printing (however, since a new developing step is not performed, a phenomenon such as fixing the toner does not occur). Heating and pressing can be performed using the fixing means. Alternatively, the fixing step in the image forming process in which the address is written instead of blank paper printing may be replaced with this heating and pressing step.
Moreover, you may add the function of a heating pressurization means to the said crimping | compression-bonding process and crimping | compression-bonding means.
However, since the sheet is transported through the folding process rather than the fixing process and the fixing means, the heating temperature and the applied pressure must be set with a margin. In addition, when the function of the heating and pressurizing unit is added to the pressurizing step and the pressurizing unit, the amount of pressurization is generally considerably higher than that of the fixing step and the fixing unit.

When the heating and pressurizing step is simultaneously performed in the crimping step, the productivity is remarkably improved. However, since the pressure during the crimping step is very large, the volume expansion of the crimping roller of the crimping device during heating may be a problem. The maintenance of the equipment tends to be complicated.
When the heating and pressurizing step is performed after the crimping step, the pressure is lower than that in the crimping step, so the apparatus is small, low cost, and high in durability.

FIG. 3 shows an example of the configuration of a heating and pressing apparatus applicable to the present invention.
In FIG. 3, the heating and pressing apparatus is driven, for example, with a recording medium or a folded recording medium sandwiched between a pair of heating and pressing rolls driven at a constant speed.
Here, one or both of the heating and pressing rolls are heated to a temperature at which the toner melts, for example, by an apparatus including a heat source inside, and the two heating and pressing rolls are pressed against each other. ing. Preferably, one or both heat and pressure roll surfaces are provided with a silicon rubber or fluororubber layer, and the length of the region to be heated and pressurized is preferably in the range of about 1 to 8 mm. Moreover, as shown in FIG. 4, a separation claw may be provided, and the phenomenon accompanied by the heating and pressing roll can be suppressed.

In addition, it is preferable that the toner particles be in the range of 10 ³ Pa · s to 10 ⁶ Pa · s by heating and pressing.
When the viscosity is less than 10 ³ Pa · s, the toner particles are excessively melted, and the toner particles may move in the energy ray-curable composition to cause image disturbance. Further, if it exceeds 10 ⁶ Pa · s, the toner is not sufficiently melted, and the energy ray curable composition does not sufficiently come out from the toner, so that the adhesion between the toner and the paper may be insufficient. .
The viscosity can be measured using a rotating plate rheometer (Rheometric Co., Ltd .: RDAII) at an angular velocity of 1 rad / sec.
In the measuring instrument, the temperature and pressure are measured by softening and melting the toner under the setting of an actual machine. In the present invention, when the toner is completely melted, the toner moves in the energy ray curable composition and the image is disturbed. Therefore, the viscosity of the toner in the middle of melting is measured.
More specifically, it is preferable that the heating temperature is within a range where the toner is not completely melted. The heating temperature is preferably within a range where the toner does not spread because the toner spreads when the pressure is too high. The heating temperature is 80 to 230. The pressurization pressure is 5 to 200 N / cm ² .

  Moreover, you may perform a thermocompression-bonding means with the said press-fit means. By doing so, the productivity of the re-peeling information sheet is significantly improved. However, since the volume of the pressure-bonding roller is changed by heating, the structure of the pressure-bonding device becomes large and it is necessary to pay close attention to maintenance.

Next, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
The parts and percentages used in the following examples and comparative examples are all based on weight, and the weight average molecular weight is measured by GPC (Gel Permeation Chromatography) based on the following measurement conditions.

<Method for measuring weight average molecular weight>
A THF solution was prepared so that each sample had a solid content of 10 mg / ml, and each sample was measured with an injection volume of 100 μl.
Measurement conditions GPC measuring apparatus: SHODEX SYSTEM 11 manufactured by Showa Denko KK Column: Four series moving layers of SHODEX KF-800P, KF-805, KF-803 and KF-801: THF Flow rate: 1 ml / min Column temperature: 45 ° C. Detection Apparatus: RI conversion: polystyrene In addition, in an Example, the mass% of the isoparaffin of the wax concerning the Example shown below, and an average molecular weight are in FD (Field Deposition) method using JMS-T100GC "AccuTOF GC". It was measured.

<Resin solution A>
Monomer consisting of (10 parts 2-ethylhexyl acrylate, 30 parts 2-hydroxyl acrylate, 50 parts butyl methacrylate, 10 parts acrylic acid) in a 500 ml reaction vessel equipped with a stirrer, nitrogen gas inlet, thermometer and reflux condenser. 100 parts of isopropyl alcohol as a polymerization solvent and 1 part of azobisisobutyronitrile as a polymerization initiator were added and polymerized at 82 ° C. under reflux of isopropyl alcohol for 6 hours in a stream of nitrogen gas. A resin solution A containing 50% by weight of a resin component having consistency ((meth) acrylic copolymer used in the present invention) was obtained.
The obtained resin had a weight average molecular weight of 50,000. The glass transition temperature was -0.1 ° C.

<Resin solution B>
In a 500 ml reaction vessel equipped with a stirrer, nitrogen gas inlet, thermometer, and reflux condenser, a total of 100 parts of monomer composed of (50 parts of butyl methacrylate, 40 parts of butyl methacrylate, 10 parts of acrylic acid), and isopropyl as a polymerization solvent 100 parts of alcohol and 1 part of azobisisobutyronitrile as a polymerization initiator were added and polymerized at 82 ° C. under reflux of isopropyl alcohol in a nitrogen gas stream for 6 hours to obtain a transparent and viscous resin component (this invention Resin solution 3A containing 50% by weight of (meth) acrylic copolymer used in the above was obtained.
The obtained resin had a weight average molecular weight of 45,000. The glass transition temperature was -5.5 ° C.

<Intermediate precursor A>
39 parts of lipoxy SP-1509 (epoxy acrylate oligomer manufactured by Showa Polymer Co., Ltd.), 41 parts of tetraethylene glycol diacrylate, 20 parts of Aronix M-400 (dipentaerythritol hexaacrylate manufactured by Toagosei Co., Ltd.), 2 5 parts of -hydroxy-2-methyl-1-phenyl-propan-1-one (photopolymerization initiator: manufactured by BASF) and 0.1 part of methoquinone were stirred and mixed to obtain an intermediate precursor A.

<Intermediate precursor B>
KAYARAD UX-2031 (Nippon Kayaku Co., Ltd. urethane acrylate oligomer) 10 parts, Aronix M-309 (Toagosei Co., Ltd. trimethylolpropane triacrylate) 38 parts, tetraethylene glycol diacrylate 52 parts, 2- 5 parts of hydroxy-2-methyl-1-phenyl-propan-1-one (photopolymerization initiator: manufactured by BASF) and 0.1 part of methoquinone were stirred and mixed to obtain an intermediate precursor B.

<Energy beam curable precursor 1>
The resin solution A is blended with 60 parts of the intermediate precursor A 105.1 parts and 0.7 parts of diisobutyl peroxide (thermal polymerization initiator: manufactured by NOF Corporation) to form an energy ray-curable precursor in a transparent solution state. Body 1 was obtained.

<Energy beam curable precursor 2>
The resin solution A is blended with 60 parts of the intermediate precursor B 105.1 parts and 0.5 parts of azobisisobutyronitrile (thermal polymerization initiator: manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a transparent solution state energy. A linear curable precursor 2 was obtained.

<Energy beam curable precursor 3>
The resin solution B is blended with 60 parts of the intermediate precursor A 105.1 parts and 0.7 parts of dimethyl (2,2′-azobis (isobutyrate)) (thermal polymerization initiator: manufactured by Wako Pure Chemical Industries, Ltd.) A transparent solution state energy ray curable precursor 3 was obtained.

<Energy ray curable precursor 4>
The resin solution B is blended with 60 parts of the intermediate precursor B 105.1 parts and 0.5 parts of azobisisobutyronitrile (thermal polymerization initiator: manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a transparent solution state energy. A linear curable precursor 4 was obtained.

<Energy beam curable precursor 5>
60 parts of resin solution A was blended with respect to 105.1 parts of intermediate precursor A to obtain energy ray-curable precursor 5 in a transparent solution state.

<Energy beam curable precursor 6>
60 parts of the resin solution B was blended with respect to 105.1 parts of the intermediate precursor B to obtain an energy ray-curable precursor 6 in a transparent solution state.

<Embodiment 1>
-Developer-
(Toner 1)
A specific example of toner production will be described. The toner used in the present invention is not limited to these examples.

Polyester resin 89 parts by mass (weight average molecular weight: 68200, glass transition temperature (Tg): 65.5 ° C.)
Petroleum wax 5 parts by mass Carbon black (Mitsubishi Kasei: # 44) 5 parts by mass Charge control agent (Spiron Black TR-H: Hodogaya Chemical) 1 part by mass

After kneading at 120 ° C. using a biaxial extruder with the above formulation, pulverizing and classifying with an airflow pulverizer to obtain a mass average particle diameter of 11.0 μm, using a Henschel mixer, silica (R-972: Nippon Aerosil) The toner was obtained by mixing 2.2% by mass.
The obtained toner had a toner circularity of 0.90 and a volume average particle size of 8 μm.
As a carrier, magnetite particles having an average particle diameter of 50 μm coated with a silicon resin (film thickness 0.5 μm) were mixed with the toner at a toner 1 concentration of 5.0% by mass to obtain a developer 41 of the present invention.

-Heating and pressurizing device 1-
A halogen lamp was provided as a heat source on the image surface side of the pair of heating and pressing rolls of the heating and pressing apparatus of FIG. The surface pressure of the pair of heating and pressing rolls was set to 40 N / cm ² , and the roll surface of the heating and pressing apparatus 1 was set to 100 mm / sec. The temperature of the surface of the heating and pressing roll was adjusted so that the viscosity of the toner particles immediately after the exit of the roll was in the range of 10 ³ Pa · s to 10 ⁶ Pa · s. In this experiment, it was 160 ° C.

Example 1
The developer 1 is mounted on Ricoh Co. MFPimagio Neo 750, OK Top to A4 size coated 110kg paper, the developer 1 with imagio MP C7500 manufactured by Ricoh Co., Ltd. of the solid portion coating weight 0.4 mg / cm ² using In accordance with the conditions, ISO / IEC 15775: 1999 compliant test chart No. 4 was output to obtain a printed matter.
The energy ray-curable precursor 1 was coated and cured on one side with a film thickness of 5 to 6 g / cm ² using a UV varnish coater (SAC-18E) manufactured by Hirose Tekko on the printed matter.
Next, a sample cut into a width of 150 mm and a length of 150 mm is prepared. The surfaces of the two samples subjected to the surface treatment with the energy ray curable precursor 1 were put together, pressed by applying a load of Yuri roll tabletop super calender, gauge pressure 100 N / cm ² , and then passed through the thermocompression bonding apparatus 1. .
The adhesion and peelability after standing at room temperature for 12 hours were evaluated.

(Example 2)
In Example 1, adhesiveness and peelability were evaluated in the same manner as in Example 1 except that the energy ray curable precursor 2 was used instead of the energy ray curable precursor 1.

(Example 3)
In Example 1, adhesiveness and peelability were evaluated in the same manner as in Example 1 except that the energy beam curable precursor 3 was used instead of the energy beam curable precursor 1.

Example 4
In Example 1, adhesiveness and peelability were evaluated in the same manner as in Example 1 except that the energy ray curable precursor 4 was used instead of the energy ray curable precursor 1.

(Comparative Example 1)
The developer 1 is mounted on Ricoh Co. MFPimagio Neo 750, OK Top to A4 size coated 110kg paper, the developer 1 with imagio MP C7500 manufactured by Ricoh Co., Ltd. of the solid portion coating weight 0.4 mg / cm ² using In accordance with the conditions, ISO / IEC 15775: 1999 compliant test chart No. 4 was output to obtain a printed matter.
The energy ray-curable precursor 5 was coated and cured on one side with a film thickness of 5 to 6 g / cm ² using a UV varnish coater (SAC-18E) manufactured by Hirose Tekko on the printed matter.
Next, a sample cut into a width of 150 mm and a length of 150 mm is prepared. The surfaces of these two samples that were surface-treated with a ghee curable precursor were joined together, and pressure-bonded by applying a Yuri roll tabletop super calender and a gauge pressure of 100 N / cm ² .
The adhesion and peelability after standing at room temperature for 12 hours were evaluated.

(Comparative Example 2)
The developer 1 is mounted on Ricoh Co. MFPimagio Neo 750, OK Top to A4 size coated 110kg paper, the developer 1 with imagio MP C7500 manufactured by Ricoh Co., Ltd. of the solid portion coating weight 0.4 mg / cm ² using In accordance with the conditions, ISO / IEC 15775: 1999 compliant test chart No. 4 was output to obtain a printed matter.
The energy ray-curable precursor 6 was coated and cured on one side with a film thickness of 5 to 6 g / cm ² using a UV varnish coater (SAC-18E) manufactured by Hirose Tekko on the printed matter.
Next, a sample cut into a width of 150 mm and a length of 150 mm is prepared. The surfaces of these two samples that were surface-treated with a ghee curable precursor were joined together, and pressure-bonded by applying a Yuri roll tabletop super calender and a gauge pressure of 100 N / cm ² .
The adhesion and peelability after standing at room temperature for 12 hours were evaluated.

  The evaluation results of Examples 1 to 4 and Comparative Examples 1 and 2 are shown in Table 1 below.

<Embodiment 2>
-Developer-
(Toner 2)
A specific example of toner production will be described. The toner used in the present invention is not limited to these examples.

[Dissolution of toner material or preparation of dispersion]
~ Synthesis of unmodified polyester (low molecular weight polyester) ~
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 84 parts by mass of bisphenol A propion oxide 3 mol adduct, 274 parts by mass of terephthalic acid, and dibutyltin oxide 2 parts by mass were added and reacted at 230 ° C. under normal pressure for 8 hours.
Next, the reaction solution was reacted under reduced pressure of 10 to 15 mmHg for 5 hours to synthesize an unmodified polyester.
The obtained unmodified polyester had a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 5,600, and a glass transition temperature (Tg) of 55 ° C.

-Preparation of master batch (MB)
1000 parts by mass of water, carbon black “Printex35”; manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9.5), 540 parts by mass, and 1200 parts by mass of the unmodified polyester were combined with a Henschel mixer (Mitsui Mining Co., Ltd.). And mixed).
The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

~ Synthesis of prepolymer ~
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride 22 parts by mass of acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure.
Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined.
The obtained intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,600, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.
Next, 411 parts by mass of the intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are charged in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Thus, a prepolymer (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained prepolymer was 1.60% by mass, and the solid content concentration of the prepolymer (after standing at 150 ° C. for 45 minutes) was 50% by mass.

-Synthesis of ketimine (the active hydrogen group-containing compound)-
In a reaction vessel equipped with a stir bar and a thermometer, 30 parts by mass of isophoronediamine and 70 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).
The amine value of the obtained ketimine compound (the active hydrogen machine-containing compound) was 423.

~ Synthesis of styrene-acrylic copolymer resin ~
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 300 parts by mass of ethyl acetate was charged, and a styrene-acrylic monomer mixture (styrene / 2-ethylhexyl acrylate / acrylic acid / hydroxylethyl acrylate = 75/15 / 5/5) 300 parts by mass and 10 g of azobisisobutyronitrile were added and reacted at 60 ° C. for 15 hours under a normal pressure nitrogen atmosphere.
Next, 200 parts by mass of methanol was added to the reaction solution, and after stirring for 1 hour, the supernatant was removed and dried under reduced pressure to synthesize the styrene-acrylic copolymer resin.
In a beaker, 10 parts by mass of the prepolymer, 60 parts by mass of the unmodified polyester, 130 parts by mass of ethyl acetate, and 30 parts by mass of a styrene-acrylic copolymer were stirred and dissolved.
Next, 10 parts by mass of petroleum-based wax (cycloparaffin 15% mass, average molecular weight = 650) and 10 parts by mass of the master batch were charged, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Corporation), the liquid feeding speed A raw material solution is prepared by three passes under conditions of 1 kg / hr, disk peripheral speed 6 m / s, and 80% by volume of 0.5 mm zirconia beads, and 2.7 parts by mass of the ketimine is added and dissolved. A material dissolution or dispersion was prepared.

[Preparation of aqueous medium phase]
An aqueous medium phase was prepared by mixing and stirring 306 parts by mass of ion-exchanged water, 265 parts by mass of a 10% by mass tricalcium phosphate suspension, and 0.2 parts by mass of sodium dodecylbenzenesulfonate, and dissolving them uniformly.

[Preparation of emulsion or dispersion]
150 parts by mass of the aqueous medium phase is placed in a container, and stirred at a rotational speed of 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), and 100 parts by mass of the solution or dispersion of the toner material is added thereto. The mixture was added and mixed for 10 minutes to prepare an emulsified dispersion (emulsified slurry).

[Removal of organic solvent]
100 parts by mass of the emulsified slurry was charged into a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min.

[Washing and drying]
After 100 parts by mass of the dispersion slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at a rotational speed of 12,000 rpm), and then filtered.
To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice.
To the obtained filter cake, 20 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added, mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered.
To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice.
Furthermore, 20 mass parts of 10 mass% hydrochloric acid was added to the obtained filter cake, mixed with a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes) and then filtered.
To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at a rotation speed of 12,000 rpm), and then filtered twice to obtain a final filter cake.
The obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with an opening of 75 μm mesh to obtain toner base particles.

[External processing]
Further, with respect to 100 parts by weight of the toner base particles, 0.6 part by weight of hydrophobic silica having an average particle diameter of 100 nm, 1.0 part by weight of titanium oxide having an average particle diameter of 20 nm, and hydrophobic silica having an average particle diameter of 15 nm 0.8 parts of the fine powder was mixed with a Henschel mixer to obtain a toner.
The weight average particle diameter was 5.7 μm and the average circularity was 0.940.

<Career>
Next, a specific example of manufacturing the carrier used for evaluation will be described.
The carrier used in the present invention is not limited to these examples.

-Fabrication of carrier-
・ Acrylic resin solution (solid content 50 wt%) 21.0 parts ・ Guanamine solution (solid content 70 wt%) 6.4 parts ・ Alumina particles [0.3 μm, specific resistance 10 ¹⁴ (Ω · cm)] 7.6 parts ・Silicone resin solution 65.0 parts [solid content 23 wt% (SR2410: manufactured by Toray Dow Corning Silicone)]
Aminosilane 1.0 part [solid content 100 wt% (SH6020: manufactured by Toray Dow Corning Silicone)]
-Toluene 60 parts-Butyl cellosolve 60 parts The above-mentioned raw materials were dispersed with a homomixer for 10 minutes to obtain a blend coating film forming solution of acrylic resin and silicon resin containing alumina particles.

Using the sintered ferrite powder [(MgO) _1.8 (MnO) _49.5 (Fe ₂ O ₃ ) _48.0 : average particle size; 35 μm] as the core material, the coating film forming solution has a thickness of 0.15 μm on the surface of the core material. Thus, it was applied and dried with a Spira coater (Okada Seiko Co., Ltd.)
The obtained carrier was baked by standing in an electric furnace at 150 ° C. for 1 hour.
After cooling, the ferrite powder bulk was pulverized using a sieve having an aperture of 106 μm to obtain a carrier having a weight average particle diameter of 35 μm.
A developer was prepared by uniformly mixing and charging 32 and 7 parts by weight of toner with respect to 100 parts by weight of a carrier using a type of tumbler mixer in which the container rolls and stirs.

-Energy ray curable precursor-
The energy ray curable precursor 1 was used as it was.

-Heating and pressurizing device-
The heating and pressing apparatus 1 was used as it was.

(Example 5)
The developer 2 was mounted on a Ricoh color MFP RICOH Pro C751, and a full color image having an image area ratio of 20% was printed on an A4 plate of OK top coat 110 kg paper.
The energy ray-curable precursor 3 was coated and cured on one side with a film thickness of 5 to 6 g / cm ² using a UV varnish coater (SAC-18E) manufactured by Hirose Tekko on the printed matter.
Next, a sample cut into a width of 150 mm and a length of 150 mm is prepared. The surfaces of the two samples that were surface-treated with an energy ray curable precursor were combined and bonded together by applying a load of Yuri Roll desktop super calender and gauge pressure of 100 N / cm ² , and then passed through the thermocompression bonding apparatus 1. .
After leaving in a constant temperature bath at 40 ° C. for 10 hours, the adhesiveness and peelability were evaluated.

(Example 6)
In Example 5, adhesiveness and peelability were evaluated in the same manner as in Example 5 except that the energy beam curable precursor 4 was used instead of the energy beam curable precursor 3.

(Comparative Example 3)
The developer 2 was mounted on a Ricoh color MFP RICOH Pro C751, and a full color image having an image area ratio of 20% was printed on an A4 plate of OK top coat 110 kg paper.
The energy ray-curable precursor 5 was coated and cured on one side with a film thickness of 5 to 6 g / cm ² using a UV varnish coater (SAC-18E) manufactured by Hirose Tekko on the printed matter.
Next, a sample cut into a width of 150 mm and a length of 150 mm is prepared. The surfaces of the two samples subjected to surface processing with an energy ray curable precursor were combined, and bonded by applying a Yuri roll desktop super calender and a load of 100 N / cm ² gauge pressure.
After leaving in a constant temperature bath at 40 ° C. for 10 hours, the adhesiveness and peelability were evaluated.

The evaluation results of Examples 5 to 6 and Comparative Example 3 are shown in Table 2 below.

  As described above, according to the present invention, it is possible to provide an apparatus for producing a releasable information sheet having excellent fixability and adhesion strength.

DESCRIPTION OF SYMBOLS 1 Energy-beam curable (pressure-sensitive) composition 2 Application | coating roller 3 Metal roller 4 Recording medium 5 Pressure roller 6 Conveyor belt 7 Tray 8 Light source 9 Scraper 10 Photosensitive drum 10K Black photoconductor 10Y Yellow photoconductor 10M Magenta photoconductor Body 10C Cyan photoreceptor 14, 15, 16 Support roller 17 Cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Inversion Device 30 Exposure light 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 42K, 42Y, 42M, 42C Developer container 43K, 43Y, 43M, 43C Developer supply roller 44K, 44Y, 44M, 44C Development low 45K Black developer 45Y Yellow developer 45M Magenta developer 45C Cyan developer 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Corona charger 53 Manual feed path 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Separation Roller 60 Cleaning device 61 Developing device 62 Transfer roller 63 Cleaning device 64 Static elimination lamp 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Recording medium 100A, 100B Image forming device 120 Tandem type development device 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feeding cassette 145 Separating roller 146 Paper feeding path 147 Conveying roller 148 Paper feeding path 150 Copier main body 151 Manual feed tray 200 Paper feeding table 300 Scanner 400 Automatic document feeder L Exposure light

JP 2007-277547 A Japanese Patent No. 3708853 Japanese Patent No. 2522333 Japanese Patent No. 3827124 Japanese Patent No. 4471334

Claims (9)

An energy beam curable precursor layer is formed by coating on a recording medium imaged using a toner, and then the energy beam curable precursor layer is cured by irradiating the energy beam. In the energy beam curable precursor for the releasable information sheet in which the cured surface of the curable precursor layer is bonded and pressure-bonded,
The energy ray curable precursor for a releasable information sheet, wherein the energy ray curable precursor contains a photopolymerization initiator and a thermal polymerization initiator. An energy beam curable precursor layer for a releasable information sheet according to claim 1 is applied onto a recording medium imaged using a toner to form an energy beam curable precursor layer, and then irradiated with an energy beam. And a coating curing step for curing the energy ray curable precursor layer,
A method for producing a releasable information sheet, comprising: a pressure-bonding step in which a surface of the recording medium image-formed using the toner is bonded to the surface of the energy ray-curable precursor layer, which is bonded to the surface. .   The method for producing a releasable information sheet according to claim 2, further comprising a heating and pressing step of heating and pressurizing the recording medium on which the energy beam curable precursor is coated and cured. The method for producing a releasable information sheet according to claim 3, wherein the pressure-bonding step is performed by applying pressure while applying a temperature equal to or higher than a softening point of the toner, and also serving as the heating and pressing step. 4. The method for producing a releasable information sheet according to claim 3, wherein the heating and pressurizing step is a step after the pressure-bonding step, and the pressure-bonding is performed while applying a temperature equal to or higher than a softening point of the toner.   6. The method for producing a releasable information sheet according to claim 2, wherein a coating layer having a thickness of 1 [mu] m or more is laminated on the surface of the recording medium.   The method for producing a releasable information sheet according to any one of claims 2 to 6, wherein in the pressing step, a single recording medium is bent and bonded to be pressed.   The method for producing a releasable information sheet according to claim 7, wherein a layer obtained by curing the energy beam curable precursor does not exist in the bent portion of the recording medium. An energy beam curable precursor layer for a releasable information sheet according to claim 1 is applied onto a recording medium imaged using a toner to form an energy beam curable precursor layer, and then irradiated with an energy beam. And a coating curing means for curing the energy beam curable precursor layer,
An apparatus for producing a releasable information sheet, comprising: a pressure-bonding means for bonding and pressure-bonding a surface of the recording medium on which an image is formed using the toner, the energy ray-curable precursor layer being cured. .