WO2006109451A1 - Support for image recording material, process for producing the same, and image recording material - Google Patents

Support for image recording material, process for producing the same, and image recording material Download PDF

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Publication number
WO2006109451A1
WO2006109451A1 PCT/JP2006/305593 JP2006305593W WO2006109451A1 WO 2006109451 A1 WO2006109451 A1 WO 2006109451A1 JP 2006305593 W JP2006305593 W JP 2006305593W WO 2006109451 A1 WO2006109451 A1 WO 2006109451A1
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WO
WIPO (PCT)
Prior art keywords
image recording
layer
support
recording material
base paper
Prior art date
Application number
PCT/JP2006/305593
Other languages
French (fr)
Japanese (ja)
Inventor
Yukio Hirashima
Shigekatsu Mochizuki
Shigehisa Tamagawa
Original Assignee
Fuji Photo Film Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co., Ltd. filed Critical Fuji Photo Film Co., Ltd.
Publication of WO2006109451A1 publication Critical patent/WO2006109451A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/06—Layered products comprising a layer of paper or cardboard specially treated, e.g. surfaced, parchmentised
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2429/00—Carriers for sound or information
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2559/00—Photographic equipment or accessories
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/08—Rearranging applied substances, e.g. metering, smoothing; Removing excess material
    • D21H25/12—Rearranging applied substances, e.g. metering, smoothing; Removing excess material with an essentially cylindrical body, e.g. roll or rod
    • D21H25/14—Rearranging applied substances, e.g. metering, smoothing; Removing excess material with an essentially cylindrical body, e.g. roll or rod the body being a casting drum, a heated roll or a calender

Definitions

  • the present invention relates to a support for an image recording material suitable for various image recording materials such as an electrophotographic material, a heat sensitive material, a sublimation transfer material, a thermal transfer material, a heat development material, a silver salt photographic material, and an ink jet recording material, and the like
  • the present invention relates to a method for efficiently producing a support for an image recording material, and an image recording material.
  • the industrial chrome plating has a high possibility of causing cracks when heated at a heating temperature of 150 ° C or higher. Therefore, it is necessary to suppress the coating thickness as much as possible.
  • the coating thickness is thin in this way, if the surface is scratched, the plating process must be performed again, leading to an increase in cost.
  • the industrial chrome plating cracks at a high temperature of 250 ° C or higher, and this crack forms the surface of the paper or the roll base material is worn out. However, there is a problem that it cannot be used.
  • a base paper having good smoothness can be obtained by calendering using a roll having an excellent antifungal effect in which cracks are not generated on the surface even at a high temperature, and a thermoplastic resin layer is provided on the base paper.
  • a method for efficiently and inexpensively producing a support for an image recording material excellent in smoothness with few small holes (micro-dents) after coating has not yet been provided.
  • Patent Document 1 Japanese Laid-Open Patent Application No. 41-1110939
  • Patent Document 2 Japanese Patent Laid-Open No. 6-282037
  • Patent Document 3 Japanese Patent Laid-Open No. 7-70973
  • the present invention provides a base paper having good smoothness by performing a calendering process using a roll having excellent wear resistance and antifungal effect in which cracks are not generated on the surface even at high temperatures. It is possible to coat the thermoplastic resin layer at a high speed on the surface of the base material for image recording materials and the base of the image recording material, where there are few small holes (small dents) after the thermoplastic resin layer is coated on the substrate. It is an object of the present invention to provide a method for producing a support for an image recording material at a low cost.
  • a support for an image recording material having a base paper and a thermoplastic resin layer on at least one surface of the base paper,
  • the base paper is calendered with a roll having a surface temperature of 200 ° C. or higher, and the roll has a surface layer containing at least one selected from cermet materials. Is the body.
  • ⁇ 4> The material according to any one of ⁇ 1> to ⁇ 3>, wherein the surface opposite to the surface on which the image recording layer is provided of the base paper is calendered so as to be in contact with a roll having a Shore D hardness of 60 to 95 °. This is a support for image recording material.
  • cermet material is a tungsten carbide cermet.
  • tungsten carbide cermet is any one of tungsten carbide-cobalt, tungsten carbide-cobalt chromium, and tungsten carbide-nickel chromium.
  • ⁇ 7> The support for an image recording material according to any one of ⁇ 1> to ⁇ 6>, wherein the surface layer has a thickness of 60 to 220111.
  • ⁇ 8> The support for an image recording material according to any one of ⁇ 1> to ⁇ 7>, wherein the surface roughness force of the roll is 0.5 S or less.
  • a roll having a surface layer containing at least one material selected from tungsten carbide-based cermet materials is in contact with the surface of the base paper on which the image recording layer is provided, so that the surface temperature of the roll is 200 °
  • a method for producing a support for image recording material comprising a step of calendering at C or higher.
  • ⁇ 13> The method for producing a support for an image recording material according to ⁇ 12>, further comprising a surface sizing process in which a liquid containing a water-soluble metal salt is applied to the surface of the base paper before calendering.
  • thermoplastic resin layer on at least one side of the calendered base paper
  • An image recording material comprising the image recording material support according to any one of ⁇ 1> to ⁇ 11> and an image recording layer on which at least an image is recorded.
  • image recording material is any one selected from electrophotographic materials, heat-sensitive materials, sublimation transfer materials, thermal transfer materials, silver salt photographic materials, and inkjet recording materials.
  • the support for image recording material of the present invention comprises a base paper and a thermoplastic resin layer on at least one surface of the base paper,
  • the base paper is calendered with a roll having a surface temperature of 200 ° C. or more, and the roll has a surface layer containing at least one selected from cermet materials.
  • the calender treatment using the roll is excellent in smoothness with few small holes (small dents), so that, for example, an electrophotographic material, Widely and suitably used for heat sensitive materials, sublimation transfer materials, thermal transfer materials, heat development materials, silver salt photographic materials, ink jet recording materials and the like.
  • the method for producing a support for an image recording material of the present invention comprises a roll having a surface layer containing at least one material selected from tungsten carbide cermet materials on the side of the base paper on which the image recording layer is provided. And a force-rendering process at a surface temperature of the roll of 200 ° C. or higher.
  • FIG. 1 is a schematic diagram of a belt fixing device in a printer used in an example.
  • the support for an image recording material of the present invention comprises a base paper and a thermoplastic resin layer on at least one surface of the base paper, and further comprises other layers as required.
  • the base paper is not particularly limited and can be appropriately selected according to the purpose. Specifically, it is a high-quality paper, for example, “Photographic Engineering Fundamental Silver Salt Photo Edition” edited by the Japan Photographic Society, Papers described on pages 223 to 224 of the company Corona (Showa 54) are preferred.
  • the base paper is not particularly limited as long as it is a known material used for a support, and can be appropriately selected from various materials according to the purpose.
  • natural paper such as conifers and hardwoods can be selected.
  • pulp a mixture of the natural pulp and synthetic pulp.
  • the pulp that can be used as the raw material of the base paper is preferably the hardwood pulp from the viewpoint of improving the flatness and dimensional stability of the base paper to a sufficiently balanced and sufficient level. Etc. can also be used.
  • Examples of the hardwood pulp include force S such as hardwood bleached kraft pulp (LBKP) and hardwood sulfite pulp (LBSP). Among these, hardwood bleached kraft panolep (LBKP) is preferable.
  • the content of the hardwood pulp with respect to the paper is not particularly limited and can be appropriately selected according to the purpose. For example, 50% by mass or more is preferred 60% by mass or more The force is preferred 75% by mass The above is more preferable.
  • softwood pulp examples include softwood bleached kraft panolep (NBKP).
  • the pulp it is preferable to mainly use hardwood pulp having a short fiber length.
  • the fiber length is not particularly limited and can be appropriately selected according to the purpose, and is preferably 0.5 to 0.8 mm.
  • a beater or a refiner can be used for beating the pulp.
  • Various additives may be further added to the pulp slurry obtained after beating the pulp (hereinafter, sometimes referred to as “pulp stock”) as necessary.
  • the additive include filler Materials, dry paper strength enhancers, sizing agents, wet paper strength enhancers, fixing agents, pH adjusters, and other chemicals.
  • Examples of the filler include calcium carbonate, clay, kaolin, clay, talc, titanium oxide, diatomaceous earth, barium sulfate, aluminum hydroxide, magnesium hydroxide, and the like.
  • dry paper strength enhancer examples include cationized starch, cationic polyacrylamide, anionized polyacrylamide, amphoteric polyacrylamide, and carboxy-modified polybutyl alcohol.
  • sizing agent examples include fatty acid salts, rosin derivatives such as rosin and maleated rosin, paraffin wax, alkyl ketene dimer, alkenyl succinic anhydride (ASA), compounds containing higher fatty acids such as epoxy fatty acid amide, Etc.
  • ASA alkenyl succinic anhydride
  • wet paper strength enhancer examples include polyamine polyamide epoxy hydrin, melamine resin, urea resin, epoxidized polyamide resin, and the like.
  • the fixing agent examples include polyvalent metal salts such as aluminum sulfate and aluminum chloride, and cationic polymers such as cationized starch.
  • Examples of the pH adjuster include caustic soda and sodium carbonate.
  • Examples of the other chemicals include antifoaming agents, dyes, slime control agents, fluorescent whitening agents, and the like.
  • a softening agent etc. can also be added as needed.
  • the softening agent for example, those described in New Handbook for Paper Processing (Edited by Paper Medicine Time), pages 554 to 555 (issued in 1980) can be used.
  • these various additives may be used alone or in combination of two or more. Further, the amount of these various additives and the like added to the pulp paper stock can be appropriately selected according to the purpose without particular limitation, and is usually preferably 0.1 to 1.0% by mass.
  • pulp paper containing the above-mentioned various additives, etc. is further added to a hand paper machine, a long paper machine, a round paper machine, a twin wire machine, and a combination machine. Paper is made using a paper machine such as, and then dried to produce a base paper. Further, if desired, surface sizing treatment can be performed either before or after the drying.
  • the surface sizing solution used for the surface sizing is, for example, a metal salt of at least one of an alkali metal salt and an alkaline earth metal salt, a water-soluble polymer compound, a fluorescent brightener, a water-resistant substance, and a pigment. , Dyes, and the like.
  • metal salt of at least one of the alkali metal salt and the alkaline earth metal salt those described above can be used.
  • the water-soluble polymer compound is not particularly limited and may be appropriately selected according to the purpose.
  • examples thereof include polybulualcohol, carboxy-modified polybulualcohol, canoleboxymethylenoresenorelose, hydroxyethino. Resenorelose, senorelose sanoleate, polyethylene oxide, gelatin, cationized starch, casein, sodium polyacrylate, sodium styrene-maleic anhydride copolymer, sodium polystyrene sulfonate, etc.
  • polyvinyl alcohol carboxy-modified polyvinylenoleconole, force noreoxymethinoresenorelose, hydroxyethinoresenorelose, cenoresulfate, polyethylene oxide, and gelatin are particularly preferred.
  • Lumpur (PVA) is more preferable.
  • the content of the water-soluble polymer compound is preferably 0.5 to 2 g / m 2 .
  • optical brightener examples include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazoline compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, diaminostilbene disulfones. Acid derivatives, imidazole derivatives, coumarin derivatives, triazole derivatives, force rubazole derivatives, pyridine derivatives, naphthalic acid derivatives, imidazolone derivatives, and the like. Among these, stilbene compounds are preferred.
  • the content of the fluorescent brightening agent is not particularly limited, 0.5 01-0. 5% by weight rather preferably, 0. 02-0. 2 mass 0/0 is more preferable.
  • water-resistant substance examples include latexes such as styrene-butadiene copolymer, ethylene-butyl acetate copolymer, polyethylene resin, vinylidene chloride copolymer; polyamide polyamine epichlorohydrin, etc. Is mentioned.
  • the base paper has a ratio (Ea / Eb) of the longitudinal Young's modulus (Ea) to the transverse Young's modulus (Eb) for the purpose of improving the rigidity and dimensional stability of the image recording material support. 1. 5 ⁇ 2.0 is preferred. When the Ea / Eb value is less than 1.5 or more than 2.0, the rigidity of the image recording material support and the dimensional stability are likely to deteriorate, which may hinder the running performance during transportation. May be.
  • the “strain” of paper differs based on the difference in the beating style, and the elastic force (rate) of the paper that is made after beating is an important factor that expresses the degree of “strain” of the paper. Can be used as a factor.
  • the rate can be obtained from the following mathematical formula.
  • E represents a dynamic elastic modulus.
  • p represents the density.
  • c represents the speed of sound in the paper.
  • n represents the Poisson's ratio.
  • n is about 0.2, even if it is calculated by the following formula, it can be calculated with a large difference.
  • the thickness of the base paper is not particularly limited and can be appropriately selected according to the purpose. Usually, it is 30 to 500 111 or more, 50 to 300/1 111 or more, 100 to 250 111 more preferable.
  • the basis weight of the base paper is not particularly limited and can be appropriately selected according to the purpose. For example, 50 to 250 g / m 2 force is preferable, and 70 to 200 g / m 2 force S is preferable.
  • the base paper is calendered with a roll having a surface temperature of 200 ° C or higher, and the roll has a surface layer containing at least one selected from cermet materials.
  • the roll is not particularly limited and can be appropriately selected according to the purpose.
  • the roll has a metal roll and a surface layer on the surface of the metal roll, and further, if necessary. It has other configurations.
  • the material of the metal roll is not particularly limited, and can be appropriately selected depending on the purpose. Examples thereof include chilled steel and forged steel.
  • the surface layer contains at least one selected from cermet materials, and further contains other components as necessary.
  • the cermet material is not particularly limited and can be appropriately selected according to the purpose.
  • tungsten carbide cermet is particularly preferable.
  • tungsten carbide cermet examples include tungsten carbide-cobalt, tungsten carbide-nickel chromium, tungsten carbide-cobalt chromium, tungsten carbide nickel, tungsten carbide cobalt-nickel platinum, tungsten carbide cobalt nickel-chromium aluminum, yttrium, carbonized. Examples include tungsten monochromate and cobalt nickel chrome. Of these, tungsten cobalt carbide, which is preferred to tungsten tungsten-cobalt, tungsten carbide cobalt-chromium, and tungsten-nickel carbide, can form a dense film after thermal spraying, and the surface roughness after polishing finish is reduced. It is particularly preferable because it is excellent in wear resistance and is suitable for calendar use.
  • the surface layer is not particularly limited and may be appropriately selected according to the purpose.
  • the cermet material is used, for example, high-speed flame spraying, plasma spraying, powder flame spraying, etc. Can be produced.
  • the thickness of the surface layer f is preferably 60 to 220 ⁇ m, more preferably 100 to 200 ⁇ m. If the thickness is less than 60 xm, the surface cannot be polished if the surface is scratched. Therefore, a treatment for providing a surface layer may be required again. If the thickness exceeds 220 zm, the thermal spray coating peels off and becomes concave. As a result, the surface of the base paper may be damaged.
  • the surface roughness (smoothness) of the roll is preferably 0.5S or less, and more preferably 0.3S or less.
  • the surface roughness of the roll can be measured by, for example, Surfcom 120A manufactured by Tokyo Seimitsu Co., Ltd. [0030] Calendar processing
  • the base paper is calendered with a roll having a surface layer containing at least one material selected from the tungsten carbide cermet materials and having a surface temperature of 200 ° C or higher. is there.
  • the surface temperature of the roll is 200 ° C or more, and 200 to 350.
  • C force S is preferable, and 230 to 280 ° C is more preferable. If the surface temperature is less than 200 ° C, the generation of small holes (fine dents) after coating with the thermoplastic resin may be worsened (increased), and if it exceeds 350 ° C, the surface of the base paper In some cases, yellowing and scorching may occur due to the chemicals being discolored by heat.
  • the surface of the base paper on which the image recording layer is provided has a surface layer containing at least one material selected from the carbonized tandusten cermet material, and the surface temperature is 200 °.
  • a so-called software is used in which a roll of C or higher is in contact, and the surface of the base paper on which the image recording layer is not provided is calendered so that a roll having a Shore D hardness of 60 to 95 ° (preferably a resin roll) is in contact. Calendar processing power This is preferable from the viewpoint of obtaining bulkiness and good smoothness.
  • the nip pressure at the time of the calendar treatment is not particularly limited, and can be appropriately selected according to the purpose.
  • a linear pressure of 50 kg / cm or more is preferable, and 80 to 350 kg / cm is more preferable.
  • the passing speed of the base paper when it passes through the two-part portion of the calendar is preferably 50-800 m / min, more preferably 70-600 m / min, more preferably 90-500 m / min. If the speed is less than 50 m / min, the production efficiency may be deteriorated. If the speed exceeds 800 m / min, the time for the base paper to pass through the two-pipe portion is shortened, so that the calendar processing effect may not be achieved. is there.
  • the base paper before the calendar treatment preferably contains an antistatic agent for the purpose of imparting an antistatic function.
  • the antistatic agent is a water-soluble metal salt, and the water-soluble metal salt is any one of calcium chloride, sodium chloride, and magnesium chloride.
  • the content of the antistatic agent in the base paper is preferably 1.0 to 5.0% by mass.
  • thermoplastic resin layer is provided on at least one side of the base paper, preferably on both sides. Note that at least one thermoplastic resin layer is provided, and two or more thermoplastic resin layers can be provided.
  • the polymer constituting the thermoplastic resin layer is particularly preferably a polyolefin resin, preferably a resin capable of forming a film.
  • polyethylene for example, polyethylene, polypropylene, a blend of polypropylene and polyethylene, high density polyethylene (HDPE), a blend of high density polyethylene and low density polyethylene (LDPE), and the like are suitable.
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • the thermoplastic resin layer may contain an inorganic pigment such as titanium dioxide, a bluing agent, a fluorescent brightening agent, an antioxidant and the like, and particularly preferably contains titanium dioxide. . Further, from the viewpoint of improving the adhesiveness of the thermoplastic resin layer to the base paper, a tackifier resin, an adhesive resin, or the like can be contained. Furthermore, if necessary, an antioxidant, a release agent, a hollow polymer and the like may be contained.
  • the thickness of the thermoplastic resin layer can be appropriately selected according to the purpose without any particular limitation, and is preferably 3 to 47 ⁇ .
  • the method for producing a support for an image recording material of the present invention comprises a calendering process, a surface sizing process, and a thermoplastic resin layer forming process, and further comprises other processes as necessary.
  • a roll having a surface layer containing at least one selected from the carbonized tansten cermet material is in contact with the surface of the base paper on which the image recording layer is provided, and the surface temperature of the roll is adjusted. Is the process of calendering above 200 ° C.
  • the material for the surface layer of the roll and the conditions for the calendar treatment are as described above.
  • the surface sizing process is carried out by applying a water-soluble metal salt on the surface of the base paper before calendering. It is the process of apply
  • the water-soluble metal salt as the antistatic agent can be appropriately selected according to the purpose for which there is no particular limitation, and examples thereof include calcium chloride, sodium chloride, magnesium chloride and the like.
  • the application method is not particularly limited and can be appropriately selected according to the purpose.
  • the coating method can be performed using a brush, a roll coater, a die coater, a curtain coater, or the like.
  • the thermoplastic resin layer forming step is a step of forming a thermoplastic resin layer on at least one surface of the base paper after the calendar process.
  • the method of forming the thermoplastic resin layer is not particularly limited and can be appropriately selected according to the purpose, such as a normal laminating method, a sequential laminating method, a foot block type, a multi-hold type, a multi-slot type, or the like. It is formed by coating the thermoplastic resin layer by either a single layer or multilayer extrusion die, a laminating method using a laminator or the like.
  • the shape of the single-layer or multi-layer extrusion die is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include a T die and a coat hanger die.
  • the coating speed of the thermoplastic resin layer is preferably 100 to 600 m / min.
  • the base paper is preferably subjected to activation treatment such as corona discharge treatment, flame treatment, glow discharge treatment, or plasma treatment.
  • the support for an image recording material of the present invention having excellent smoothness with few small holes (microscopic dents) is efficiently obtained. Moreover, it can be manufactured at a low cost.
  • the support for an image recording material of the present invention produced as described above includes an electrophotographic material, a heat sensitive material, a sublimation transfer material, a thermal transfer material, a heat developing material, a silver salt photographic material, and an ink jet recording material described below. It can use suitably for.
  • the image recording material of the present invention comprises at least an image recording layer on the support for image recording material, and further comprises other layers as necessary.
  • the image recording layer differs depending on the use and type of the image recording material.
  • a toner image receiving layer for electrophotographic materials for example, a thermochromic layer for heat sensitive materials, a heat diffusible dye for sublimation transfer materials, and a heat melting material for thermal transfer materials.
  • the image recording layer is not particularly limited and can be appropriately selected depending on the purpose, but a resin coating layer is preferably used. If necessary, other components may be added to the resin coating layer. It contains ingredients.
  • the polymer in the resin coating layer is not particularly limited as long as a coating liquid containing a resin composition can be prepared.
  • a thermoplastic resin that can be appropriately selected according to the purpose is suitable.
  • the thermoplastic resin includes (1) a polyolefin resin, (2) a polystyrene resin, (3) an acrylic resin, (4) polyvinyl acetate or a derivative thereof, (5) a polyamide resin, and (6) a polyester resin. (7) Polycarbonate resin, (8) Polyether resin (or acetal resin), (9) Other resins, and the like. These thermoplastic resins may be used alone or in combination of two or more.
  • Examples of the polyolefin resin (1) include polyolefin resins such as polyethylene and polypropylene, and copolymers of olefins such as ethylene and propylene with other vinyl monomers.
  • Examples of the copolymer resin of olefin and other vinyl monomers include an ethylene-butyl acetate copolymer and an ionomer resin which is a copolymer of acrylic acid and methacrylic acid.
  • Examples of the polyolefin resin derivative include chlorinated polyethylene and chlorosulfonated polyethylene.
  • Examples of the (2) polystyrene resin include polystyrene resin, styrene-isobutylene copolymer, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polystyrene— And maleic anhydride resin.
  • Examples of the acrylic resin (3) include polyacrylic acid or its esters, polymethacrylic acid or its esters, polyacrylonitrile, polyacrylamide and the like. The properties of the polyacrylates and polymethacrylates vary greatly depending on the type of ester group.
  • copolymer with other monomers (For example, acrylic acid, methacrylic acid, styrene, a butyl acetate etc.) is also mentioned.
  • the polyacrylonitrile is often used as a copolymer of the above AS resin and ABS resin rather than as a homopolymer.
  • polyacetic acid butyl or its derivative (4) examples include, for example, poly (vinyl acetate), poly (butyl alcohol) obtained by saponifying poly (vinyl acetate), and poly (butyl alcohol) aldehydes (for example, honolemanolaldehyde). , Acetoaldehyde, butyraldehyde, etc.) and the like.
  • the polyamide-based resin (5) is a polycondensate of diamine and dibasic acid, and 6-nylon
  • the polyester resin (6) is a polycondensate of alcohol and acid, and the characteristics differ greatly depending on the combination. Examples include general-purpose resin polyethylene terephthalate and polybutylene terephthalate composed of an aromatic dibasic acid and a dihydric alcohol.
  • the polycarbonate resin (7) is generally a polycarbonate obtained from bisphenol A and phosgene.
  • polyether resin (or acetal resin) of (8) examples include polyether resins such as polyethylene oxide and polypropylene oxide, and acetal resins such as polyoxymethylene as the ring-opening polymerization system.
  • Examples of the other resin (9) include polyaddition polyurethane resins.
  • the resin coating layer is preferably formed using an aqueous polymer such as a water-dispersible polymer or a water-soluble polymer for the following reasons. That is, the water-based polymer is excellent in environmental suitability and workability in which the organic solvent is not discharged in the coating drying process, and is used as a solvent for a release agent or the like to be blended in an image recording layer, particularly a toner image receiving layer described later.
  • the mold release agent can be easily released on the surface in the step of applying and drying the resin coating layer. As soon as the effect of the agent is obtained, the water dispersion form is more stable and more suitable for production.
  • the water-based polymer is more preferably a self-dispersing water-based polyester emulsion or a water-dispersed acrylic resin for the following reasons. That is, the self-dispersing water-based polyester emulsion or the water-dispersing acrylic resin is a self-dispersing type that does not use a surfactant, so that the resin has a low softness point decrease due to moisture that has low hygroscopicity even in a high humidity atmosphere. It is possible to suppress the occurrence of offset during fixing of the coating layer, exaggeration of adhesion between sheets during storage, etc.Furthermore, since it uses a polyester resin that has a high cohesive energy and a molecular structure, it is sufficient in a storage environment.
  • the water-based polymer is not intended to specify its composition, bond structure, molecular structure, molecular weight, molecular weight distribution, and morphology.
  • Examples of the water-based group of the water-based thermoplastic resin include a sulfonic acid group, a hydroxyl group, a carboxylic acid group, an amino group, an amide group, and an ether group.
  • Water-dispersible polymers include water-dispersed resins such as water-dispersed acrylic resins, water-dispersed polyester resins, water-dispersed polystyrene resins, and water-dispersed urethane resins; acrylic resin emulsion, polyvinyl acetate emulsion, SBR (Styrene 'Butadiene' rubber) Water dispersible emulsion such as emulsion; heat of resin having ester bond, polyurethane resin, polyamide resin, polysulfone resin, polyvinyl chloride resin, polyvinyl butyral, poly strength prolacton resin, polyolefin resin, etc.
  • the water-dispersible emulsion is not particularly limited and can be appropriately selected according to the purpose.
  • water-dispersible polyurethane emulsion water-dispersible polyester emulsion
  • water-dispersible polymers include, for example, Toyobo Co., Ltd. Bironal series, Takamatsu Yushi Co., Ltd. Pes Resin A series, Kao Corporation Tofton UE series, Nippon Gosei Co., Ltd. Polyester WR.
  • the water-soluble polymer is not particularly limited and may be appropriately selected according to the purpose.
  • examples thereof include polybulal alcohol, carboxy-modified polybulal alcohol, carboxymethylenosenorose, hydroxyethinoresenololose, Selellose sanoleate, polyethylene oxide, gelatin, cationized starch, casein, sodium polyacrylate, styrene-maleic anhydride copolymer sodium salt, sodium polystyrene sulfonate, etc.
  • Polyethylene oxide is preferred.
  • vinylpyrrolidone vinyl acetate copolymer styrene-vinyl vinylidone copolymer, styrene maleic anhydride copolymer, water-soluble polyester, water-soluble acrylic, water-soluble polyurethane, water-soluble nylon, water-soluble As the gelatin, so-called demineralized gelatin with reduced content of lime-processed gelatin, acid-processed gelatin, calcium, etc. can be selected according to various purposes. It ’s also good to use them together.
  • water-soluble polyester examples include, for example, various types of plastic coats manufactured by Tateo Chemical Industry Co., Ltd .; Finetex ES series manufactured by Dainippon Ink & Chemicals, Inc .; ; Finetex 6161, K-96 manufactured by Dainippon Ink & Chemicals, Inc .; High loss NL — 1189, BH-997L manufactured by Seiko Chemical Co., Ltd., and the like.
  • the content of the water-based polymer in the resin coating layer is not particularly limited. For example, based on the mass of the resin coating layer, 2
  • thermoplastic resin for the resin coating layer is disclosed in JP-A-5-127413, JP-A-8-194394, JP-A-8-334915, JP-A-8_334916,
  • a crosslinking agent As the other components contained in the resin coating layer, as long as the function of the resin coating layer is not impaired, a crosslinking agent, a UV curing agent, an EB curing agent 1J, a plasticizer, a slipping agent, Release agent, coloring agent
  • additives such as fillers, charge control agents, emulsifiers, and dispersants can be arbitrarily blended.
  • the electrophotographic material has at least a toner image-receiving layer as the image recording layer on the support, and other layers appropriately selected as necessary. Each of these layers may have a single layer structure or a laminated structure.
  • the toner image receiving layer is a layer for receiving color toner and black toner and forming an image.
  • the toner image-receiving layer receives toner that forms an image from a developing drum or an intermediate transfer body by (static) electricity, pressure, etc. in a transfer process in an image forming apparatus, and is fixed by heat, pressure, etc. in a fixing process.
  • the light transmittance of the toner image-receiving layer is preferably 78% or less, more preferably 73% or less, and even more preferably 72% or less, in terms of making the electrophotographic material feel like a photograph.
  • the light transmittance is obtained by separately forming a coating film having the same thickness on a polyethylene terephthalate film (100 xm), and using the direct reading haze meter (HGM-2DP, manufactured by Suga Test Instruments Co., Ltd.). Can be measured.
  • the 180 degree peel strength from the fixing member of the image forming apparatus at the fixing temperature of the toner image-receiving layer is preferably 0.1 lN / 25 mm or less, more preferably 0.041 N / 25 mm or less.
  • the 180 degree peel strength can be measured according to the method described in JIS K6887 using the surface material of the fixing member.
  • the toner image receiving layer preferably has high whiteness. The whiteness is preferably 85% or more as measured by the method defined in JIS P 8123.
  • the spectral reflectance is preferably 85% or more, and the difference between the maximum spectral reflectance and the minimum spectral reflectance in the same wavelength range is preferably within 5%. Furthermore, the spectral reflectance is preferably 85% or more in the wavelength range of 400 nm to 700 nm, and the difference between the maximum spectral reflectance and the minimum spectral reflectance in the same wavelength region is more preferably within 5%.
  • the L * value is preferably 80 or more, more preferably 85 or more, and more preferably 90 or more. Even better.
  • the white color is preferably as neutral as possible.
  • the value of (a *) 2 + (b *) 2 is preferably 50 or less, more preferably 18 or less, and even more preferably 5 or less.
  • the toner image-receiving layer preferably has high gloss after image formation.
  • glossiness in all areas from white without toner to black with the maximum density, 45 degree glossiness is preferably 60 or more and 110 or less, and 75 or more is more preferable than 90 or more. Is more preferable.
  • the glossiness exceeds 110, it becomes a metallic luster, which is not preferable for image quality.
  • the glossiness can be measured based on, for example, JIS Z 8741.
  • the toner image-receiving layer preferably has high smoothness after fixing.
  • the smoothness the arithmetic average roughness (Ra) is preferably 3 / im or less and more preferably 1 ⁇ or less in the entire region from white without toner to black having the maximum density. 5 / im or less is more preferable.
  • the arithmetic average roughness can be measured based on JIS B 0601, B 0651, B 0652.
  • the toner image-receiving layer has physical properties of all items more preferably having physical properties of a plurality of items, preferably having physical properties of one item in the following items. .
  • Tm (melting temperature) of the toner image-receiving layer is preferably 30 ° C or higher, and Tm + 20 ° C or lower is preferable.
  • the temperature at which the viscosity of the toner image-receiving layer becomes 1 X 10 5 cp is preferably 40 ° C or higher. Lower than that is preferable.
  • the loss tangent (G "ZG '), which is the ratio between the loss elastic modulus (G") at the fixing temperature of the toner image-receiving layer and the storage elastic modulus (G'), is preferably from 0.01 to 10:
  • the storage elastic modulus (G ′) at the fixing temperature of the toner image-receiving layer is preferably ⁇ 50 to +2500 with respect to the storage elastic modulus (G ′) at the fixing temperature of the toner.
  • the inclination angle of the molten toner on the toner image-receiving layer is preferably 50 ° or less, more preferably 40 ° or less.
  • the toner image-receiving layer satisfies the physical properties disclosed in Japanese Patent No. 2788358, Japanese Unexamined Patent Publication No. 7-248637, Japanese Unexamined Patent Publication No. 8-305067, Japanese Unexamined Patent Publication No. 10-239889, etc. preferable.
  • the toner image-receiving layer is preferably 1 10 6-1 10 15 0 / (: 111 preferably has a surface electric resistance of the second range (at 25 ° 65% RH conditions).
  • the toner image may have a low toner density when the toner is transferred to the toner image-receiving layer, and the resulting toner image density tends to be low.
  • the surface electrical resistance exceeds l X 10 15 Q / cm 2 , an excessive charge is generated during transfer, the toner is not sufficiently transferred, and the image receiving sheet for electrophotography with low image density is obtained. During handling, it becomes static and dust is likely to adhere. Misfeeds, double feeds, discharge marks, toner transfer missing, etc. may occur during copying.
  • the surface electrical resistance is based on, for example, JIS K 6911, the sample is conditioned at a temperature of 20 ° C. and a humidity of 65% for 8 hours or more, and in the same environment, R 8340 manufactured by Advantest Corporation. , And can be measured after 1 minute of energization under the condition of an applied voltage of 100V.
  • the toner image-receiving layer is preferably the resin coating layer.
  • the resin coating layer as the toner image-receiving layer contains at least a polymer for toner image-receiving layer and, if necessary, other components.
  • the polymer for the toner image-receiving layer satisfies the above-mentioned physical properties by using two or more kinds of the polymers in combination as long as the above-mentioned properties of the toner-image-receiving layer can be satisfied in the state where the toner image-receiving layer is formed.
  • a single polymer can satisfy the physical properties of the toner image-receiving layer described above.
  • the toner image-receiving layer polymer preferably has a molecular weight larger than that of the thermoplastic resin used in the toner.
  • the molecular weight is not always preferred depending on the relationship of the thermodynamic properties of the thermoplastic resin used in the toner and the toner image-receiving layer polymer. For example, when the softening temperature of the polymer for the toner image receiving layer is higher than that of the thermoplastic resin used for the toner, the molecular weight is the same or the resin used for the toner image receiving layer is the same. Smallness may be preferable.
  • the toner image-receiving layer polymer is preferably a mixture of resins having the same composition but different average molecular weights.
  • the relationship with the molecular weight of the thermoplastic resin used in the toner the relationship disclosed in JP-A-8-334915 is preferable.
  • the molecular weight distribution of the polymer for the toner image-receiving layer is preferably wider than the molecular weight distribution of the thermoplastic resin used in the toner.
  • Examples of the toner image-receiving layer polymer include JP-A-5-127413, JP-A-8-194394, JP-A-8-334915, JP-A-8-334916, and JP-A-9-171265. It is preferable to satisfy the physical properties disclosed in Japanese Patent Laid-Open No. 10-221877 and the like.
  • the toner image-receiving layer polymer has the following characteristics with respect to the later-described intermediate layer polymer.
  • the softening temperature (Ts) of the polymer for the toner image-receiving layer is 10 ° C. or higher, particularly preferably 20 ° C. or higher, than that of the polymer for the intermediate layer described later.
  • the glossiness can be controlled by adjusting the softening temperature in this way.
  • the softening temperature can be measured, for example, by the method specified in JIS K 7210.
  • the T1Z2 (1Z2 method soft spot) of the toner image-receiving polymer is 10 ° C. or more, particularly preferably 20 ° C. or more, higher than that of the intermediate layer polymer described later.
  • 1/2 method softening The gloss can be controlled by adjusting the points.
  • the Tfb (outflow start temperature) of the polymer for the toner image-receiving layer is 10 ° C or higher, particularly preferably 20 ° C or higher, than that of the polymer for the intermediate layer described later.
  • the viscosity at the fixing temperature of the toner image-receiving layer polymer is at least 3 times, particularly preferably at least 10 times higher than that of the intermediate layer polymer described later.
  • the glossiness can be controlled by adjusting the viscosity in this way.
  • the storage elastic modulus (G ′) at the fixing temperature of the toner image-receiving layer polymer is at least 3 times, particularly preferably at least 10 times higher than that of the intermediate layer polymer described later.
  • the glossiness can be controlled by adjusting the storage elastic modulus (G ′) in this way.
  • the loss elastic modulus (G ") at the fixing temperature of the toner image-receiving layer polymer is at least 3 times, particularly preferably at least 10 times higher than that of the intermediate layer polymer described below. Glossiness can be controlled by adjusting the loss modulus (G ").
  • the number average molecular weight of the toner image-receiving layer polymer is 1000 to 100000, more preferably 1000 to 10,000 / J, more preferable than that of the later-described intermediate layer polymer. By adjusting in this way, glossiness can be controlled.
  • the molecular weight distribution of the toner image-receiving layer polymer is preferably, for example, 0.2 to 5 narrower than that of the later-described intermediate layer polymer. By adjusting in this way, glossiness can be controlled.
  • the polymer for the toner image-receiving layer is not particularly limited as long as it can be deformed under temperature conditions such as fixing and can accept the toner, and can be appropriately selected according to the purpose.
  • a resin similar to the binder resin of the toner is preferable.
  • the polymer for the toner image-receiving layer since the toner uses a copolymer resin such as polyester resin, styrene, styrene monobutyl acrylate, for example, polyester resin, styrene monoacrylate copolymer, styrene Preferred examples thereof include thermoplastic resins such as monomethacrylate copolymers.
  • thermoplastic resin examples include the resin having an ester bond, the polyurethane resin, the polyamide resin, and the like exemplified as the resin coating layer for forming the image recording layer. , Polysulfone resin, polysalt vinyl resin, polyvinyl butyral, etc., polystrength plastic resin, polyolefin resin, etc.
  • the toner image-receiving layer polymer may be used singly or in combination of two or more, and in addition to these, a mixture thereof, a copolymer thereof, or the like may also be used. be able to
  • the toner image-receiving layer polymer (i) is excellent in environmental suitability and work suitability without discharge of an organic solvent in the coating and drying step.
  • Many release agents such as wax are difficult to dissolve in a solvent at room temperature, and are often dispersed in a solvent (water, organic solvent) in advance.
  • the water dispersion form is more stable and more suitable for the manufacturing process.
  • the water-based coating is more likely to have a release agent effect (offset resistance, adhesion resistance, etc.) that allows the wax to be easily bleached on the surface during coating and drying.
  • water-based resins such as water-dispersible polymers and water-soluble polymers are preferably used.
  • the water-based resin is not particularly limited in terms of its composition, bond structure, molecular structure, molecular weight, molecular weight distribution, morphology, etc., as long as it is either a water-dispersible polymer or a water-soluble polymer.
  • the polymer can be appropriately selected depending on the purpose, and examples of the water-based group of the polymer include a sulfonic acid group, a hydroxyl group, a carboxylic acid group, an amino group, an amide group, and an ether group.
  • Examples of the water-dispersible polymer include resins, emulsions, copolymers, mixtures, and cations of the polymers (1) to (9) in the resin-coated layer of the image recording layer dispersed in water. Two or more types can be combined by appropriately selecting from the modified products.
  • As the water-dispersible polymer an appropriately synthesized polymer or a commercially available product may be used.
  • Examples of the commercially available products include polyester-based water-dispersible polymers such as Toyobo Co., Ltd.'s Bironal series, Takamatsu Yushi Co., Ltd. Pesresin A series, Kao Corporation's Tufton UE series, Nippon Gosei Co., Ltd.
  • acrylic water-dispersible polymers include Hiros XE, KE, PE series manufactured by Seiko Chemical Industry Co., Ltd. and Jurimer ET series manufactured by Nippon Pure Chemical Co., Ltd.
  • the water-dispersible emulsion is particularly limited if the volume average particle diameter is 20 nm or more. It can be selected appropriately according to the purpose, for example, water-dispersible polyurethane emulsion, water-dispersible polyester emulsion, black-prene emulsion, styrene butadiene emulsion, nitrino butadiene emulsion, butadiene Emulsion, butyl chloride emulsion, butyl pyridine styrene butadiene emulsion, polybutene emulsion, polyethylene emulsion, vinyl acetate emulsion, ethylene-acetate emulsion emulsion, vinylidene chloride emulsion, methyl methacrylate
  • a water-dispersible polyester emulsion is particularly preferable.
  • the water-dispersible polyester emulsion is preferably a self-dispersing water-based polyester emulsion.
  • a carboxyl group-containing self-dispersing water-based polyester resin emulsion is particularly preferable.
  • the self-dispersing aqueous polyester emulsion means an aqueous emulsion containing a polyester resin that can be self-dispersed in an aqueous solvent without using an emulsifier or the like.
  • the carboxyl group-containing self-dispersing aqueous polyester resin emulsion means an aqueous emulsion containing a polyester resin that contains a carboxyl group as a hydrophilic group and can be self-dispersed in an aqueous solvent.
  • the self-dispersing water-dispersible polyester emulsion those satisfying the following characteristics (1) to (4) are preferable. Since this is a self-dispersion type that does not use a surfactant, it can suppress the occurrence of offset at the time of fixing and the occurrence of adhesive failure between sheets during storage, with less decrease in the softening point due to moisture having low hygroscopicity even in a high humidity atmosphere. In addition, it is environmentally friendly and workable because it is water based.
  • polyester resin that has a high molecular energy structure with high cohesive energy is used, it has a sufficient hardness in the storage environment, but it becomes a low elasticity (low viscosity) molten state in the fixing process of electrophotography, and the toner Is carried in the image receiving layer, and sufficient image quality can be achieved.
  • the molecular weight distribution (weight average molecular weight / number average molecular weight) is preferably 4 or less, more preferably 3 or less.
  • the glass transition temperature (Tg) is preferably 40 to 100 ° C, more preferably 50 to 80 ° C.
  • volume average particle diameter 20 to 200 nm force S, preferably 40 to 150 nm force S
  • the content of the water-dispersible emulsion in the toner image-receiving layer is 10 to 90 mass
  • the water-soluble polymer is not particularly limited as long as the weight average molecular weight (Mw) is 400,000 or less, and can be appropriately selected according to the purpose.
  • Mw weight average molecular weight
  • polyethylene oxide is preferable.
  • water-soluble polymer Commercially available products of the water-soluble polymer include water-soluble polyesters as various plus coats manufactured by Kairai Chemical Industry Co., Ltd., Finetex ES series manufactured by Dainippon Ink and Chemicals, and Nippon Pure Chemical Co., Ltd. as water-soluble acrylics. Jurimer AT series manufactured by Dainippon Ink & Chemicals, Inc. Finetex 6161, K-96; HIROS NL-1189, BH-997L manufactured by Seiko Chemical Industry Co., Ltd.
  • water-soluble polymer examples include Research 'Disclosure 17, 643, page 26, Research' Disclosure 18, 716, page 651, Research 'Disclosure 307, 105, pages 873-874, and JP-A 64-. Those described in the 13546 publication.
  • the content of the water-soluble polymer in the toner image-receiving layer can be appropriately selected according to the purpose without particular limitation, and is preferably 0.5 to 2 g / m2.
  • thermoplastic resin can also be used in combination with other polymer materials, but in that case, the thermoplastic resin is generally used so as to have a higher content than other polymer materials.
  • At least one of the water-dispersible emulsion and the water-soluble polymer may be used alone, or both may be used alone, or both may be used in combination.
  • the amount of water-soluble polymer (polyethylene oxide) dissolved in the liquid can be quantified by NMR, and the amount of polyethylene oxide adsorbed (mass%) can be determined from the amount of polyethylene oxide added.
  • the adsorption amount is 2 to 5% by mass, dry flocculation occurs, and when the adsorption amount is 30% by mass or more, it means that aggregation occurs due to adsorption or crosslinking. .
  • the mass ratio of the water-dispersible emulsion and the water-soluble polymer is as follows: -1 is preferred 1: 0. 1- :! is more preferred.
  • the content of the toner image-receiving layer polymer in the toner image-receiving layer is preferably 10% by mass or more, more preferably 30% by mass or more, and more preferably 50% by mass or more. Mass% is particularly preferred.
  • Examples of the other components contained in the toner image-receiving layer include release agents, plasticizers, colorants, fillers, cross-linking agents, charge control agents, and other additives.
  • the release agent is combined with the toner image receiving layer in order to prevent offset of the toner image receiving layer.
  • the release agent used in the present invention is heated and melted at the fixing temperature, is deposited on the surface of the toner image receiving layer, is unevenly distributed on the surface of the toner image receiving layer, and is further cooled and solidified to be cooled.
  • the type is not particularly limited and can be appropriately selected according to the purpose.
  • release agent examples include at least one selected from silicone compounds, fluorine compounds, waxes, and matting agents.
  • the mold release agent for example, compounds described in Sekishobo "Revised Wax Properties and Applications", published by Nikkan Kogyo Shimbun Co., Ltd., Silicone Knowbook can be used.
  • Shoko No. 59-38581 Japanese Patent Publication No. 4-32380, Japanese Patent No. 2838498, Japanese Patent No. 2949558, Japanese Unexamined Patent Publication No. 50-117433, Japanese Unexamined Patent Publication No. 52-52640, Japanese Unexamined Patent Publication No. 57-148755, Japanese Unexamined Patent Publication No. Sho 6
  • JP-A-6 119514, JP-A-6-59502, JP-A-6-161150, JP-A-6-175396, JP-A-6-219040, JP-A-6
  • JP-A-6-295093 JP-A-7-36210, JP-A-7-43940, JP-A-7-56387, JP-A-7-56390, JP-A-7-64335, JP-A-7- 19 9681, JP-A-7-223362, JP-A-7-287413, JP-A-8-184992, JP-A-8-227180, JP-A-8-248671, JP-A-8-248799, JP-A-8- 248801, JP-A-8-278663, JP-A-9-152739, JP-A-9-160278, JP-A-9-185181, JP-A-9-319139, JP-A-9-319143, JP-A-10
  • JP 10-48889 JP 10-198069, JP 10-20711 6, JP 112917, JP 11-449, JP 11-65156, JP
  • silicone compounds, fluorine compounds or waxes are also preferably used. S can. Further, a plurality of these compounds can be used in combination.
  • silicone compound examples include silicone oil, silicone rubber, silicone fine particles, silicone-modified resin, and reactive silicone compound.
  • silicone oil examples include non-modified silicone oil, amino-modified silicone oil, carboxy-modified silicone oil, carbinol-modified silicone oil, bur-modified silicone oil, epoxy-modified silicone oil, polyether-modified silicone oil, and silanol.
  • modified silicone oils methacrylic modified silicone oils, mercapto modified silicone oils, alcohol modified silicone oils, alkyl modified silicone oils, and fluorine modified silicone oils.
  • silicone-modified resin examples include olefin resin, polyester resin, vinyl resin, polyamide resin, cellulose resin, phenoxy resin, chloro-vinyl acetate copolymer resin, urethane resin, acrylic resin, styrene-acryl copolymer resin, Or this Examples thereof include resins obtained by modifying these copolymer resins with silicone.
  • the fluorine compound is not particularly limited and may be appropriately selected depending on the purpose.
  • fluorine oil for example, fluorine oil, fluorine rubber, fluorine-modified resin, fluorine sulfonic acid compound, fluorosulfonic acid, fluoric acid compound, or a compound thereof
  • fluorine oil for example, fluorine oil, fluorine rubber, fluorine-modified resin, fluorine sulfonic acid compound, fluorosulfonic acid, fluoric acid compound, or a compound thereof
  • examples thereof include salts and inorganic fluorides.
  • the wax can be roughly classified into a natural wax and a synthetic wax.
  • natural waxes plant waxes, animal waxes, mineral waxes and petroleum waxes are preferred.
  • plant-based nuts are particularly preferred.
  • the natural wax is particularly preferably a water-dispersed wax from the viewpoint of compatibility when a water-based resin is used as the toner image-receiving layer polymer.
  • the plant-based wax can be appropriately selected from known ones that are not particularly limited, and may be a commercially available product or an appropriately synthesized product.
  • Examples of the plant-based potato include carnauba wax, castor oil, rapeseed oil, soybean oil, wood wax, cotton wax, rice wax, sugarcane wax, candelilla wax, Japan wax, jojoba oil and the like.
  • Examples of the commercial products of the carnauba wax include EMUS TAR-0413 manufactured by Nippon Seiki Co., Ltd., Cellozol 524 manufactured by Chukyo Yushi Co., Ltd., and the like.
  • Examples of commercially available castor oil include refined castor oil manufactured by Ito Oil Co., Ltd.
  • the melting point is 70 in that it can provide an electrophotographic image-receiving sheet that is excellent in offset resistance, adhesion resistance, paper passing property, and glossiness, and can form a high-quality image that does not easily crack.
  • Carnauba wax of ⁇ 95 ° C is particularly preferred.
  • the animal wax can be appropriately selected from known ones that are not particularly limited, and examples include beeswax, lanolin, whale pod, stew (whale oil), and wool cocoon.
  • the mineral wax can be appropriately selected from known ones that are not particularly limited, and may be a commercially available product or an appropriately synthesized product.
  • examples include montan wax, montan ester wax, ozokerite, and ceresin.
  • the melting point is 70 in that it can provide an electrophotographic image-receiving sheet that is excellent in offset resistance, adhesion resistance, paper passing property, and glossiness, and can form a high-quality image that does not easily crack.
  • Particularly preferred is a montan wax of ⁇ 95 ° C.
  • the petroleum wax can be appropriately selected from known ones that are not particularly limited, and may be a commercially available product or an appropriately synthesized product. For example, paraffin wax, microcrystalline wax, petrolatum and the like can be mentioned.
  • the content of the natural wax in the toner image-receiving layer is preferably from 0.:! To 4 gZm 2 , and more preferably from 0.2 to 2 gZm 2 .
  • the melting point (° C) of the natural wax is 70 to 95 o C force S girl, especially 75 to 90 o C force S girl from the viewpoint of offset resistance and paper passage. Masle.
  • the synthetic waxes are classified into synthetic hydrocarbons, modified waxes, hydrogenated waxes, and other oil-based synthetic waxes. These waxes are preferably water-dispersed waxes in terms of compatibility when a water-based thermoplastic resin is used as the thermoplastic resin of the toner image-receiving layer.
  • Examples of the synthetic hydrocarbon include Fischer-Tropsch wax, polyethylene crumbs, and the like.
  • oil-based synthetic wax examples include acid amide compounds (for example, stearic acid amide) and acid imide compounds (for example, phthalic anhydride imide).
  • the modified wax is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include ammine-modified wax, acrylic acid-modified wax, fluorine-modified wax, olefin-modified wax, urethane-type wax, and alcohol-type wax. Etc.
  • the hydrogenated wax is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include hydrogenated castor oil, castor oil derivatives, stearic acid, lauric acid, myristic acid, panolemitic acid, and behenine. Acid, sebacic acid, undecylenic acid, heptylic acid, maleic acid, highly maleated oil, and the like.
  • Examples of the matting agent include various known ones. Solid particles used as a matting agent can be classified into inorganic particles and organic particles. Specific examples of the material for the inorganic matting agent include oxides (for example, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide). 2), alkaline earth metal salts (eg, barium sulfate, calcium carbonate, magnesium sulfate), silver halides (eg, silver chloride, silver bromide), and glass.
  • oxides for example, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide.
  • alkaline earth metal salts eg, barium sulfate, calcium carbonate, magnesium sulfate
  • silver halides eg, silver chloride, silver bromide
  • Examples of the inorganic matting agent include West German Patent No. 2529321, British Patent No. 760775, No. 1272, U.S. Patent Nos. 1201905, No. 2192241, No .; No. 3062649, No. 3257206, No. 3322555, No. 3353958, No. 3370951, No. 3411907, No. 3437484, No. 3523022, No. 3 615554, No. 3635714 No. 3769020, No. 4021245, No. 4029504, and the like.
  • Examples of the material for the organic matting agent include starch, cellulose ester (for example, senorelose acetate propionate), senorelose etherol (for example, ethinorescenole saccharide), and synthetic resin.
  • the synthetic resin is preferably water-insoluble or poorly water-soluble.
  • Examples of the water-insoluble or poorly water-soluble synthetic resin include, for example, poly (meth) acrylate (eg, polyalkyl (meth) acrylate, polyalkoxyalkyl (meth) acrylate, polyglycidyl (meth) acrylate).
  • hydrophilic repeating units may be contained.
  • monomers that form hydrophilic repeating units include acrylic acid, methacrylic acid, a, ⁇ -unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, and styrene sulfonate.
  • acrylic acid methacrylic acid, a, ⁇ -unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, and styrene sulfonate.
  • organic matting agents examples include British Patent No. 1055713, U.S. Patent No. 1939213, No. 2221873, No. 2268662, No. 2322037, No. 2376005, No. 2391181, No. 2701245, No. 2992101, No. 3079257, No. 3262 782, No. 3443946, No. 3516832, No. 3539344, No. 3591379, No. 3754924, No. 3767448 , Japanese Patent Laid-Open No. 49-106821, Examples thereof are those described in JP-A-57-14835.
  • the average particle size of the solid particles is:! -100 / im is preferred, 4-30 ⁇ ⁇ is more preferred.
  • the amount of solid particles, 0. 01 ⁇ 0. 5g / m 2 is preferred instrument 0. 02 ⁇ 0. 3g / m 2 is more preferable.
  • the melting point (° C) of the release agent is preferably from 70 to 95 ° C, more preferably from 75 to 90 ° C, particularly in terms of offset resistance and paper passing properties.
  • these derivatives, oxides, purified products, and mixtures can also be used. Further, these may have a reactive substituent.
  • the content of the releasing agent is preferably 0.1 to 10% by mass based on the mass of the toner image-receiving layer, and more preferably 0.3 to 8.0% by mass. More preferable is -5.0 mass%. When the content is less than 0.1% by mass, the offset resistance and the adhesion resistance may be insufficient. When the content exceeds 10% by mass, the amount of the release agent is excessively large. May reduce the image quality.
  • plasticizer known plasticizers for resins that are not particularly limited can be appropriately selected according to the purpose.
  • the plasticizer has a function of adjusting the flow or softening of the toner image-receiving layer by heat or pressure when fixing the toner.
  • plasticizers include “Chemical Handbook” (edited by the Chemical Society of Japan, Maruzen), “Plasticizers Theory and Application 1” (edited by Koichi Murai, Koshobo), “Research on plasticizers”, “Research on plasticizers” "(Polymer Chemical Society),” Handbook Rubber 'Plastic Compounded Chemicals "(Rubber Digest Co., Ltd.), etc.
  • plasticizer examples include those described as high-boiling organic solvents, thermal solvents, and the like.
  • esters e.g., phthalates, phosphates, fatty acid esters, abietic acid esters, adipic acid esters, sebacic acid esters, azelaic acid esters, benzoic acid esters, butyric acid esters, Epoxy fatty acid esters, glycolic acid esters, propionic acid esters, trimellitic acid esters, oxalic acid esters, sulfonic acid esters, carboxylic acid esters, succinic acid esters, maleic acid esters, Compounds such as fumaric acid esters, phthalic acid esters, stearic acid esters, etc.), amides (for example, fatty acid amides, sulfoamides, etc.), ethers, alcohols, latatones, polyethyleneoxys, etc. .
  • plasticizers can be used by mixing with a resin.
  • the plasticizer a polymer having a relatively low molecular weight can be used.
  • the molecular weight of the plasticizer is preferably lower than the molecular weight of the binder resin to be plasticized, and the molecular weight is preferably 15000 or less, more preferably 5000 or less.
  • the polymer is preferably the same type as the binder resin to be plasticized.
  • a low molecular weight polyester is preferable for plasticizing a polyester resin.
  • oligomers can also be used as plasticizers.
  • Ade force Sizer 1 PN-170, PN-1430 (Lesson, manufactured by Asahi Denka Kogyo Co., Ltd.), PARAPLEX-G-25, G-30, G — 40 (Lesson, also manufactured by CP Hall), Ester gum 8L—JA, Estenore R-95, Pentaline 4851, FK115, 4820, 830, Norizonore 28— JA, Hi.
  • Examples include COSLASTIC A75, Picotex LC, Crystallex 3085 (Lesson is also available from Rika Hercules).
  • the plasticizer contains stress and strain generated when toner particles are embedded in the toner image-receiving layer (physical strain such as elastic force and viscosity, strain due to mass balance of molecules, binder main chain, pendant portion, etc.) Etc.) can be optionally used to relax.
  • physical strain such as elastic force and viscosity, strain due to mass balance of molecules, binder main chain, pendant portion, etc.
  • Etc. can be optionally used to relax.
  • the plasticizer may be in a micro-dispersed state in the toner image-receiving layer, in a micro-phase-separated state in a sea-island shape, or in a sufficiently mixed and dissolved state with other components such as a binder. .
  • the content of the plasticizer in the toner image-receiving layer is preferably 0.001 to 90% by mass. 0.1 to 60% by mass is more preferable:! To 40% by mass is more preferable.
  • the plasticizer adjusts the smoothness (improves transportability due to reduced frictional force), improves the fixing unit offset (peeling off toner and layers from the fixing unit), adjusts the curl balance, and adjusts the charge (toner static). It may be used for the purpose of forming an image.
  • the colorant is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include a fluorescent brightener, a white pigment, a colored pigment, and a dye.
  • the optical brightener may be appropriately selected from known compounds that are not particularly limited as long as they are known compounds that absorb in the near ultraviolet region and emit fluorescence at 400 to 500 nm, for example, K. VeenRataraman. Preferable examples include compounds described in Ehe Chemistry of Synthetic Dyes V ⁇ 8.
  • the fluorescent whitening agent may be a commercially available product, or may be synthesized as appropriate. For example, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazoline compound, a naphthalimide. Compounds, pyrazoline compounds, carbostyryl compounds, and the like.
  • Examples of the commercially available products include white full fur PSN, PHR, HCS, PCS, B (all manufactured by Sumitomo Chemical Co., Ltd.), UVITEX-OB (manufactured by Ciba-Geigy), and the like.
  • the white pigment can be appropriately selected according to the purpose from known ones that are not particularly limited. Examples thereof include inorganic pigments such as titanium oxide and calcium carbonate.
  • the colored pigment can be appropriately selected according to the purpose from known ones that are not particularly limited.
  • the various pigments described in JP-A-63-44653, etc. Zo pigment, polycyclic pigment, condensed polycyclic pigment, lake pigment, carbon black and the like.
  • azo pigment examples include azo lake (for example, Carmine 6B, Red 2B, etc.), insoluble azo pigment (for example, monoazo yellow, disazo yellow, pyrazo mouth orange, balkan orange, etc.), condensed azo pigment (for example, chromophthalate). Yellow, chromophthaled red).
  • azo lake for example, Carmine 6B, Red 2B, etc.
  • insoluble azo pigment for example, monoazo yellow, disazo yellow, pyrazo mouth orange, balkan orange, etc.
  • condensed azo pigment for example, chromophthalate. Yellow, chromophthaled red).
  • polycyclic pigment examples include copper phthalocyanine pigments for phthalocyanine pigments. Roux, copper phthalocyanine green and the like.
  • condensed polycyclic pigment examples include dioxazine pigments (such as dioxazine violet), isoindolinone pigments (such as isoindolinone yellow), selenium pigments, perylene pigments, perinone pigments, thioindigo pigments, Etc.
  • dioxazine pigments such as dioxazine violet
  • isoindolinone pigments such as isoindolinone yellow
  • selenium pigments such as perylene pigments, perinone pigments, thioindigo pigments, Etc.
  • lake pigment examples include malachite green, rhodamine B, rhodamine G, and vitamin tria blue B.
  • the inorganic pigment examples include oxides (for example, titanium dioxide, bengara, etc.) sulfates (for example, precipitated barium sulfate), carbonates (for example, precipitated calcium carbonate), oxalates (for example, water-containing materials) Succinate, anhydrous succinate, etc.), metal powders (for example, aluminum powder, bronze powder, zinc dust, yellow lead, and bitumen). These may be used alone or in combination of two or more.
  • oxides for example, titanium dioxide, bengara, etc.
  • sulfates for example, precipitated barium sulfate
  • carbonates for example, precipitated calcium carbonate
  • oxalates for example, water-containing materials
  • Succinate for example, anhydrous succinate, etc.
  • metal powders for example, aluminum powder, bronze powder, zinc dust, yellow lead, and bitumen.
  • the dye can be appropriately selected from known ones without particular limitations according to the purpose, and examples thereof include anthraquinone compounds and azo compounds. These may be used alone or in combination of two or more.
  • water-insoluble dyes include vat dyes, disperse dyes, and oil-soluble dyes.
  • vat dyes include CI Vat Violet 1, CI Vat Violet 2, CI Vat Violet 9, CI Vat Violet 13, CI Vat Violet 21, CI Vat Blue 1, CI Vat Blue 3, CI Vat Blue 4, CI Vat Blue 6, CI Vat Blue 14, CI Vat Blue 20, CI Vat Blue 35 and the like.
  • disperse dye include C. I. Day Spurs Violet 1, C. I. Day Spurs Violet 4, C. I. Day Spurs Violet 10, C. I. Days Spurs Blue 3, C. I. Days Spurs Blue 7, C. I. Days Spurs Blue 58, and the like.
  • oil-soluble dyes examples include CI Solvent Violet 13, CI Solvent Violet ⁇ 14, CI Sonoren Vuai Age Rez 21, CI Sonoren Vu Eye Age Ret 27, CI Solvent Blue 11, CI Solvent Blue 12, CI Solvent Blue 25, CI Solvent Blue 55, etc.
  • a colored coupler used in silver salt photography can also be suitably used.
  • the content in the toner image-receiving layer 0.:! ⁇ 8g / m 2 is preferred instrument 0 5-5 g / m 2 is more preferred.
  • the content of the colorant is less than 0.1 lg / m 2 , the light transmittance in the toner image-receiving layer may be increased.
  • the content exceeds 8 g / m 2 , handling properties such as cracking and adhesion resistance are improved. May be inferior.
  • the amount of pigment added is preferably 40% by mass or less, more preferably 30% by mass or less, more preferably 20% by mass or less, based on the mass of the thermoplastic resin constituting the toner image-receiving layer. Is more preferable.
  • Examples of the filler include organic or inorganic fillers, and known reinforcing agents, fillers, and reinforcing materials for binder resins can be used.
  • known reinforcing agents, fillers, and reinforcing materials for binder resins can be used.
  • Refer to “Handbook Rubber 'Plastic Compounding Chemicals” (edited by Rubber Digest Co., Ltd.), “New Plastic Plastic Compounding Basics and Applications” (Taisei), “Fila I Handbook” (Taisei), etc. You can choose S.
  • an inorganic filler or an inorganic pigment can be used as the filler.
  • the inorganic filler or inorganic pigment include silica, alumina, titanium dioxide, zinc oxide, dinenoconium oxide, mica-like iron oxide, white lead, lead oxide, cobalt oxide, strontium chromate, molybdenum pigment, smectite, magnesium oxide. , Calcium oxide, calcium carbonate, mullite and the like. Of these, silica and alumina are particularly preferable. These may be used alone or in combination of two or more.
  • the filler one having a small particle size is preferable. If the particle size is large, the surface of the toner image-receiving layer tends to be roughened.
  • the silica includes spherical silica and amorphous silica.
  • the silica can be synthesized by a dry method, a wet method, or an air-mouth gel method.
  • the surface of the hydrophobic silica particles may be surface-treated with a trimethylsilanol group or silicone.
  • colloidal silica is preferable.
  • the silica is preferably porous.
  • the alumina includes anhydrous alumina and alumina hydrate.
  • alumina hydrate is preferable to anhydrous alumina.
  • monohydrate or trihydrate can be used as the alumina hydrate.
  • the monohydrate includes pseudo boehmite, boema And diaspore.
  • the trihydrate includes dibsite and bayerite.
  • the alumina is preferably porous.
  • the alumina hydrate can be synthesized by a sol-gel method in which ammonia is added to an aluminum salt solution for precipitation or a method in which an alkali aluminate is hydrolyzed.
  • the anhydrous alumina can be obtained by dehydrating alumina hydrate by heating.
  • the amount of the filler added is preferably 5 to 2000 parts by mass with respect to 100 parts by mass of the dry mass of the binder of the toner image-receiving layer.
  • the cross-linking agent can be blended in order to adjust the storage stability, thermoplasticity, and the like of the toner image-receiving layer.
  • the crosslinking agent a compound having two or more epoxy groups, isocyanate groups, aldehyde groups, active halogen groups, active methylene groups, acetylene groups and other known reactive groups in the molecule as reactive groups is used.
  • cross-linking agent a compound having two or more groups capable of forming a bond by a hydrogen bond, an ionic bond, a coordinate bond, or the like can be used.
  • crosslinking agent for example, known compounds can be used as coupling agents for resins, curing agents, polymerization agents, polymerization accelerators, coagulants, film-forming agents, film-forming aids, and the like.
  • the coupling agent include chlorosilanes, vinyl silanes, epoxy silanes, aminosilanes, alkoxyaluminum chelates, titanate coupling agents, etc., and “Handbook rubber 'plastic compounding chemicals' (Rubber Digest Co., Ltd.). Ed.) Can be used.
  • the toner image-receiving layer preferably contains a charge adjusting agent in order to adjust the transfer or adhesion of the toner or prevent the toner image-receiving layer from being charged and adhered.
  • charge control agent various conventionally known charge control agents without particular limitation can be appropriately used depending on the purpose.
  • the charge adjusting agent can be appropriately selected according to the purpose without particular limitation.
  • a surfactant such as a cationic surfactant, an anionic surfactant, an amphoteric surfactant, or a nonionic surfactant.
  • polymer electrolytes, conductive metal oxides, and the like can be used.
  • cationic antistatic agents such as quaternary ammonium salts, polyamine derivatives, cation-modified polymethyl metatalylate and cation-modified polystyrene, and anion-based materials such as alkyl phosphates and anionic polymers.
  • Nonionic antistatic agents such as antistatic agents, fatty acid esters, polyethylene oxide and the like can be mentioned.
  • the toner has a negative charge
  • cation nonionic is preferable as the charge adjusting agent blended in the toner image receiving layer.
  • Examples of the conductive metal oxide include ZnO, TiO
  • the conductive metal oxide may further contain (doping) a different element, for example, Al, In, etc. for ⁇ , Nb, Ta, etc. for TiO,
  • SnO can contain (doping) Sb, Nb, halogen elements, and the like.
  • the material that can be used for the toner image-receiving layer may contain various additives for improving the stability of the output image and improving the stability of the toner image-receiving layer itself.
  • the additive include various known antioxidants, anti-aging agents, deterioration inhibitors, ozone deterioration inhibitors, ultraviolet absorbers, metal complexes, light stabilizers, antiseptics, fungicides, and the like. It is done.
  • the antioxidant is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenol), hydroquinone derivatives, hindered amine derivatives, spiroindane. Compounds.
  • the antioxidant is described in JP-A 61-159644.
  • the anti-aging agent is not particularly limited and can be appropriately selected depending on the purpose.
  • “Handbook Rubber'Plastic Compounding Chemicals Revised 2nd Edition” (1993, Rubber Digest Corporation) p76-121 The thing of description is mentioned.
  • the ultraviolet absorber is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a benzotriazole compound (see US Pat. No. 3,533,794), 4_thiazolidone compound (US Pat. No. 3352681). Benzophenone compounds (see JP-A-46-2784) and UV-absorbing polymers (see JP-A-62-260152).
  • the metal complex is not particularly limited and can be appropriately selected according to the purpose.
  • UV absorbers and light stabilizers described in "Handbook Rubber 'Plastic Compounding Chemicals Revised 2nd Edition” (1993, Rubber Dyestone Co.) pl 22 ⁇ : 137 can also be suitably used.
  • a known photographic additive can be added to the material that can be used for the toner image-receiving layer as necessary.
  • the photographic additive include, for example, Research Disclosure Journal (hereinafter abbreviated as RD) ⁇ .17643 (December 1978), R DNo. 18716 (November 1979) and RDNo. 307105 (1989) (November), and the corresponding parts are summarized in the table below.
  • the toner image-receiving layer is provided by applying a coating liquid containing the toner image-receiving layer thermoplastic resin on the support with a wire coater or the like and drying it.
  • the film formation temperature (MFT) of the thermoplastic resin used in the present invention is preferably 100 ° C. or less for fixing toner particles, which is preferably room temperature or more for storage before printing. Les.
  • the toner image-receiving layer, the coating weight after drying, for example,:! Preferably is ⁇ 20 g / m 2 instrument 4 to 15 g / m 2 is more preferable.
  • the thickness of the toner image-receiving layer is not particularly limited and can be appropriately selected depending on the purpose.
  • the thickness of the toner used is preferably 1 to 3 times the thickness of the toner particles more than 1/2 of the particle size. More specifically, it is more preferable:! ⁇ 50 / im is preferable:! ⁇ 30 / im is more preferable 2 ⁇ 20 ⁇ m is more preferable, 5 ⁇ : 15 ⁇ m is particularly preferable Masle.
  • the other layer provided in the electrophotographic material can be appropriately selected according to the purpose without any particular limitation.
  • the surface protective layer, the back layer, the adhesion improving layer, the tacky layer, the intermediate layer, and the like examples include a layer, an undercoat layer, a charge control (prevention) layer, a reflection layer, a color adjustment layer, a storage stability improving layer, an adhesion prevention layer, an anti-curl layer, and a smoothing layer.
  • the surface protective layer is used for the purpose of protecting the surface of the electrophotographic material, improving storability, improving handleability, imparting writing properties, improving instrument passability, imparting anti-offset properties, etc. It can be provided on the surface of the layer.
  • the surface protective layer may be a single layer or may be composed of two or more layers.
  • Various thermoplastic resins, thermosetting resins, and the like can be used as the binder for the surface protective layer, and it is preferable to use the same type of resin as the toner image receiving layer.
  • the thermodynamic characteristics, electrostatic characteristics, etc. can be optimized without having to be the same as that of the toner image-receiving layer.
  • the surface protective layer preferably contains the particles as a matting agent contained in the toner image receiving layer.
  • various additives described above that can be used in the toner image-receiving layer can be blended.
  • the surface protective layer may contain other release agents and the like together with the particles as the matting agent.
  • the outermost surface layer in the electrophotographic material (for example, the surface protective layer when a surface protective layer is formed) preferably has good compatibility with the toner in terms of fixing properties. .
  • the contact angle with the melted toner is preferably 0 to 40 degrees, for example.
  • the back layer is provided on the opposite side of the toner image-receiving layer from the support for the purpose of imparting back surface output suitability, improving back surface output image quality, improving curl balance, improving device passability, and the like. Preferably it is provided.
  • the color of the back layer is not particularly limited.
  • the back layer is preferably white.
  • the whiteness and spectral reflectance are preferably 85% or more as in the case of the surface.
  • the back layer may have the same configuration as that of the toner image receiving layer for improving the duplex output suitability.
  • various additives described above can be used for the back layer.
  • the back layer may have a single layer structure or a laminated structure of two or more layers.
  • the back layer may have an oil absorption property.
  • the adhesion improving layer is preferably formed for the purpose of improving the adhesion between the support and the toner image receiving layer in the electrophotographic material.
  • the above-mentioned various additives can be blended in the adhesion improving layer, and it is particularly preferable to blend a crosslinking agent.
  • the electrophotographic material is preferably provided with a cushion layer between the adhesion improving layer and the toner image receiving layer in order to improve the acceptability of the toner.
  • the intermediate layer includes, for example, between the support and the adhesion improving layer, between the adhesion improving layer and the cushion layer, between the cushion layer and the toner image receiving layer, and between the toner image receiving layer and the toner receiving layer. It can be formed between the storage stability improving layers.
  • the intermediate layer can be present, for example, between the support and the toner image-receiving layer.
  • the intermediate layer is preferably the resin coating layer.
  • the resin coating layer as the intermediate layer contains at least an intermediate layer polymer, and various components as required.
  • the intermediate layer polymer can be appropriately selected without particular limitation as long as it is suitable for use as the coating solution.
  • the intermediate layer polymer may be the same as the toner image receiving layer polymer.
  • Such resins can be used, but among these, the water-soluble polymer, the water-dispersible polymer, etc. are preferred, and the self-dispersing water-based polyester emulsion and water-dispersed acrylic resin are more preferred.
  • the polymer for the intermediate layer include JP-B-5-127413, JP-A-8-194394, JP-A-8-334915, JP-A-8-334916, JP-A-9-171265, and JP-A-10-221877. Those satisfying the physical properties disclosed in the Gazette and the like are preferably used.
  • the content of the polymer for the intermediate layer in the intermediate layer is preferably 30 to 100% by mass, preferably 20% by mass or more based on the mass of the intermediate layer.
  • the various components described in the toner image-receiving layer can be arbitrarily blended as long as the function of the intermediate layer is not impaired.
  • the intermediate layer is prepared, for example, by preparing a coating solution for an intermediate layer and coating it.
  • the intermediate layer coating solution By using the intermediate layer coating solution, the intermediate layer can be prepared on the support relatively easily. Further, the polymer for the intermediate layer can be impregnated in the thickness direction of the support.
  • the heat-sensitive material has, for example, a structure in which at least a heat-sensitive recording layer is provided as an image recording layer on the support for image-recording material of the present invention, and heating by a heat-sensitive head and fixing by ultraviolet rays are repeated.
  • Examples thereof include heat-sensitive materials used in a thermoautochrome method (TA method) for forming an image.
  • TA method thermoautochrome method
  • the sublimation transfer material has, for example, a configuration in which an ink layer containing at least a heat diffusible dye (sublimation dye) is provided as an image recording layer on the image recording material support of the present invention
  • examples include a sublimation transfer method in which the ink layer force is transferred by a thermal head and the heat-diffusible dye is transferred onto the sublimation transfer sheet.
  • the thermal transfer material has, for example, a configuration in which at least a heat-meltable ink layer is provided as an image recording layer on the image recording material support of the present invention, and is heated and melted by a thermal head.
  • Ink layer strength includes methods such as melting and transferring ink onto a thermal transfer sheet. I can get lost.
  • the heat developing material has a structure in which a light and heat sensitive recording layer as described in, for example, JP-A-2002-40643 is provided as an image recording layer on the image recording material support of the present invention.
  • a visible image is formed by heating the heat-developable material that has been printed and exposed by a heating method using a heating roller, a heating belt, a plate heater, a thermal head, a laser, or a combination thereof. What can be used.
  • the image recording material support of the present invention has a structure in which a photothermographic layer as described in, for example, Japanese Patent Application Publication No. 2004-246026 is provided as an image recording layer, and printing exposure is performed.
  • an image recording layer an image recording that develops color at least yellow (Y), magenta (M), and cyan (C).
  • Y yellow
  • M magenta
  • C cyan
  • a silver halide photographic sheet having a constitution in which a layer is provided and subjected to baking exposure and passing through a plurality of processing baths while being dipped is subjected to color development, bleach-fixing, washing with water, and drying. Photographic system, etc.
  • the ink jet recording material examples include a liquid ink such as a water-based ink (using a dye or a pigment as a color material) and an oil-based ink as an image recording layer on the support for an image recording material of the present invention; Is a solid and has the color material receiving layer capable of receiving solid ink or the like which is melted and liquefied and used for printing.
  • a liquid ink such as a water-based ink (using a dye or a pigment as a color material) and an oil-based ink as an image recording layer on the support for an image recording material of the present invention
  • the image recording material support is also preferably used as printing paper.
  • printing paper When used as printing paper, it is preferable to have high mechanical strength from the viewpoint of applying ink or the like by a printing machine.
  • the printing paper is particularly suitable as offset printing paper, and can also be used as relief printing paper, gravure printing paper, and electrophotographic paper.
  • the present invention it is possible to solve the conventional problems, and a base paper having good smoothness by performing a calendering process using a roll having an excellent antifungal effect in which cracks are not generated on the surface even at high temperatures. It is possible to obtain a high-speed coating of the thermoplastic resin layer on the surface of the base paper and the support for image recording material with less generation of small holes (minute dents) after the base paper is coated with the thermoplastic resin layer. Thus, it is possible to provide a method for producing a support for an image recording material with efficiency and at low cost.
  • the prepared pulp slurry was paper-made with a long paper machine, and the felt surface of the web was pressed against a drum drier via a dryer canvas and dried.
  • polybulal alcohol Karl Fischer Co., Ltd., KL-118 5.0% by mass
  • calcium chloride as an antistatic agent
  • fluorescent whitening agent Sumitomo Chemical
  • Whitex BB liquid manufactured by Kogyo Co., Ltd.
  • a thermal spray material of tungsten carbide (WC) _ cobalt (Co) (O: 88 mass%, O0: 12 mass%) was sprayed onto the roll shell made of SNCM439 (forged steel) by high-speed flame melting.
  • the obtained roll was brought into contact with the base paper image recording layer side (front side) at a surface temperature of 350 ° C., while the base paper side not provided with the image recording layer side (back side). Then, soft calendering was performed in such a manner that a resin roll having a Shore D hardness of 90 ° was in contact. The dip linear pressure was 120 kg / cm. Thus, a base paper was prepared. Here, the surface roughness of the roll was measured with a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd., Surfcom 120A).
  • the tungsten carbide (WC) -cobalt-coated metal roll of Example 1 has a sufficient surface layer thickness of 150 zm. Therefore, even if the roll surface is damaged, it can be re-polished by polishing the roll surface again. Can be used (polishing possible).
  • the base paper after the soft calender treatment was adjusted to a density of 0.96 gZcm 3 with a machine calender, and the Oken type smoothness was measured, and it was 378 seconds.
  • both sides of the obtained base paper were subjected to corona discharge treatment, and then polyethylene was extruded using a laminator to coat both sides of the base paper by 28 ⁇ m in thickness.
  • a support having a glossy surface was prepared by using the surface of the laminator cooling roll forming the front polyethylene layer on the side of the base paper on which the image recording layer was provided as a mirror surface.
  • the number of dents called small holes with a diameter of 20 to 100 ⁇ m per unit area was measured with a universal projector (20 times). It should be noted, it was 100 pieces / cm 2 within a slip rating.
  • the electrical resistance of the obtained support was measured with a digital super insulation resistance meter manufactured by Takeda Riken Co., Ltd., and evaluated according to the following criteria.
  • Example 1 As shown in Table 2, a base paper was prepared in the same manner as in Example 1 except that the roll surface temperature was changed to 200 ° C. and soft calendering was performed, and polyethylene was formed on both sides of the base paper. A resin layer was formed to produce a support.
  • Example 1 a base paper was prepared in the same manner as in Example 1 except that the surface temperature of the roll was changed to 250 ° C. and soft calendering was performed as shown in Table 2. Polyethylene on both sides of the base paper was prepared. A resin layer was formed to produce a support.
  • Example 1 As shown in Table 2, tungsten carbide (WC) _cobalt (Co) ( ⁇ : 88 mass%, Co: 12 mass%) was coated to a thickness of 220 zm, and the roll surface A base paper was prepared in the same manner as in Example 1 except that the surface temperature was changed to 350 ° C., and a polyethylene resin layer was formed on both sides of the base paper. .
  • WC tungsten carbide
  • Co Co
  • Example 1 As shown in Table 2, tungsten carbide (WC) _cobalt (Co) (O: 88 mass%, Co: 12 mass%) was coated to a thickness of 50 zm, and the surface of the roll A base paper was prepared in the same manner as in Example 1 except that the temperature was changed to 350 ° C., and a polyethylene resin layer was formed on both sides of the base paper to prepare a support. , Occurrence of cracks on the roll surface, occurrence of cracks on the roll surface, discoloration of the surface of the base paper, whether or not polishing is possible, Oken-type smoothness, number of small holes, electrical resistance, wear resistance, and comprehensive evaluation. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.
  • Example 1 As shown in Table 2, a base paper was prepared in the same manner as in Example 1 except that the surface temperature of the roll was changed to 370 ° C. and soft calendering was performed, and polyethylene was formed on both sides of the base paper. A resin layer was formed to produce a support.
  • Example 1 As shown in Table 2, a base paper was prepared in the same manner as in Example 1 except that 3.8% by mass of alkyltrimethylammonium salt was added as an antistatic agent contained in the surface size liquid. Then, a polyethylene resin layer was formed on both sides of the base paper to prepare a support. Next, for the generation of cracks on the roll surface, the occurrence of cracks on the roll surface, discoloration of the base paper surface, whether or not polishing is possible, Oken smoothness, the number of small holes, electrical resistance, wear resistance, and comprehensive evaluation The evaluation was the same as in Example 1. The results are shown in Table 3. [Example 8]
  • Example 1 As shown in Table 2, tungsten carbide / cobalt was changed to tandene / cobalt chromium carbide to prepare a roll having a surface layer with a thickness of 150 ⁇ and a surface roughness of 0.3S.
  • a base paper was prepared in the same manner as in Example 1 except that it was soft calendered and a polyethylene resin layer was formed on both sides of the base paper to produce a support.
  • Example 1 As shown in Table 2, tungsten carbide-cobalt was changed to tandane carbide-cobalt nickel to prepare a tool having a surface layer with a thickness of 150 zm and a surface roughness of 0.3 S, and the roll A base paper was prepared in the same manner as in Example 1 except that a soft calender treatment was used, and a polyethylene resin layer was formed on both sides of the base paper to produce a support.
  • Example 1 a base paper was prepared in the same manner as in Example 1 except that the roll surface temperature was changed to 180 ° C. and soft calendering was performed as shown in Table 2. Polyethylene was formed on both sides of the base paper. A resin layer was formed to prepare a support.
  • Example 1 Preparation of base paper and support
  • Example 2 a roll shell was formed with an industrial chromium plating having a thickness of 150 / im and a surface roughness of 0.3S, and the roll surface temperature was changed to 200 ° C.
  • a base paper was prepared in the same manner as in Example 1 except that soft calendering was performed, and a polyethylene resin layer was formed on both sides of the base paper to prepare a support.
  • Example 1 As shown in Table 2, a roll shell is formed with a chrome plating for industrial use having a thickness of 150 zm and a surface roughness of 0.3 S, and the surface temperature of the roll is changed to 350 ° C. and softened.
  • a base paper was prepared in the same manner as in Example 1 except that the calendar treatment was performed, and a polyethylene resin layer was formed on both sides of the base paper to prepare a support.
  • Example 1 as shown in Table 2, the roll was not provided with a surface layer, and the surface temperature of the roll finished with SNCM439 (forged steel) with a surface roughness of 0 ⁇ 3S was changed to 200 ° C and soft calender treatment was performed. Except for the above, a base paper was prepared in the same manner as in Example 1, and a polyethylene resin layer was formed on both sides of the base paper to prepare a support.
  • SNCM439 forged steel
  • Example 1 WC spraying 150 350 300 Calcium chloride Cobalt
  • Example 2 WC spraying 150 200 300 Calcium chloride Cobalt
  • Example 3 WC spraying 150 250 300 Calcium chloride Cobalt
  • Example 4 WC spraying 220 350 300 Calcium chloride Cobalt
  • Example 5 WC spraying 50 350 300 Calcium chloride
  • Example 6 WC spraying 150 370 300 Calcium chloride
  • Example 8 WC spraying 150 350 300 Calcium chloride Cobalt chromium
  • Example 9 WC spraying 150 350 300
  • Example 1 o ⁇ 378 10 Yes Yes Yes 0 0.2y m Yes
  • Example 2 Yes Yes 217 90 Yes Yes Yes Yes 0 0.2 jU m Yes
  • Example 3 o Yes 284 64 Yes Yes Yes 0.2ym Yes
  • Example 4 ⁇ 0 376 12 Available ⁇ ⁇ 0. 2u ⁇
  • Example 5 ⁇ ⁇ 370 15 Impossible ⁇ ⁇ 0.
  • Example 2 calendering was performed at a surface temperature of 200 ° C.
  • the Oken type smoothness was 217 seconds, and the number of small holes was 90 Zcm 2 , which was the lower specification limit. There was no problem.
  • Example 4 the thickness of the roll surface layer was set to 220 zm and calendered at 350 ° C, and there was no problem in practical use. .
  • Example 5 the roll surface layer had a thickness of 50 zm and calendered at 350 ° C., and no cracks or creases occurred. If the roll surface was scratched, it could not be polished and resprayed, but there was no problem in actual use.
  • Example 6 calendering was performed at a surface temperature of 370 ° C., and the Oken smoothness was 405 sec and the number of small holes was 6 / cm 2 . There was a slight yellow stain on the surface of the base paper, which was thought to be due to thermal discoloration of the internal chemicals, but there was no problem in practical use.
  • Example 7 since an alkyltrimethyl ammonium salt was used as an antistatic agent contained in the surface sizing solution, the electrical resistance increased and the antistatic property slightly decreased, but there was no problem in practical use.
  • Comparative Example 1 was calendered at a surface temperature of 180 ° C, so the Oken type smoothness was 195 sec and the number of small holes was 105 / cm 2, which was out of the standard.
  • the evaluation is X.
  • Comparative Example 2 an industrial chromium plating film with a thickness of 150 xm was formed and calendered at 200 ° C, and micro cracks were confirmed on the roll surface. .
  • Comparative Example 3 an industrial chrome plating film having a thickness of 150 xm was formed and calendered at 350 ° C, and a large number of cracks were confirmed on the roll surface. .
  • Example 10 As an image recording material of the present invention was produced by the following method.
  • Titanium dioxide (Typeter (registered trademark) A-220, manufactured by Ishihara Sangyo Co., Ltd.) 40.0 g, P VA102 (manufactured by Kuraray Co., Ltd.) 2. Og and ion-exchanged water 58.
  • a titanium dioxide dispersion (with a titanium dioxide pigment content of 40% by mass) was prepared by dispersing using NBK — 2 manufactured by NBK.
  • the resulting toner image-receiving layer coating solution has a viscosity of 40 mPa's and a surface tension of 34 mN / m.
  • Acrylic resin water dispersion solid content 30% by mass, Hi-Loss XBH-997L, manufactured by Seiko Chemical Co., Ltd.
  • Hydrin D337 manufactured by Chukyo Yushi Co., Ltd.
  • Anion Surfactant AOT 0.5 g
  • 80 ml of ion-exchanged water are mixed and stirred.
  • a layer coating solution was prepared.
  • the resulting back layer coating solution had a viscosity of 35 mPa's and a surface tension of 33 mN / m 2.
  • Coating of one back layer and toner image-receiving layer The back layer coating solution is applied to the back surface of the image recording material support of Example 1 (the surface on which the toner image-receiving layer is not provided) with a bar coater so that the dry mass is 9 g / m 2. Then, a back layer was formed. Further, the toner image-receiving layer coating solution was applied to the front surface of each of the image recording material supports with a bar coater so that the dry mass was 12 gZm 2 , thereby forming a toner image-receiving layer. The pigment content in the toner image-receiving layer was 5% by mass relative to the thermoplastic resin.
  • the back layer and the toner image-receiving layer were coated and then dried online with hot air.
  • the drying air volume and temperature were adjusted so that both the back layer and the toner image-receiving layer were dried within 2 minutes after coating.
  • the drying point was the point at which the coating surface temperature was the same as the wet bulb temperature of the drying air.
  • the calendering was performed under the condition of a nip pressure of 14.7 kNZm 2 using a daros calender and keeping the metal roller at 40 ° C.
  • the electrophotographic material obtained as described above was cut to produce an A4 size electrophotographic material.
  • Example 10 the electrophotographic material of Example 11 was produced in the same manner as in Example 10 except that the image recording material support of Example 2 was used.
  • Example 10 an electrophotographic material of Example 12 was produced in the same manner as Example 10 except that the image recording material support of Example 3 was used.
  • Example 10 the electrophotographic material of Example 13 was produced in the same manner as in Example 10 except that the image recording material support of Example 4 was used.
  • Example 10 an electrophotographic material of Example 14 was produced in the same manner as Example 10 except that the image recording material support of Example 5 was used.
  • Example 10 an electrophotographic material of Example 15 was produced in the same manner as in Example 10 except that the image recording material support of Example 6 was used.
  • Example 10 the electrophotographic material of Example 16 was produced in the same manner as in Example 10 except that the image recording material support of Example 7 was used.
  • Example 10 the electrophotographic material of Example 17 was produced in the same manner as in Example 10 except that the image recording material support of Example 8 was used.
  • Example 10 the electrophotographic material of Example 18 was produced in the same manner as in Example 10 except that the image recording material support of Example 9 was used.
  • Example 10 the electrophotographic material of Comparative Example 5 was produced in the same manner as Example 10 except that the image recording material support of Comparative Example 1 was used.
  • Example 10 an electrophotographic material of Comparative Example 6 was produced in the same manner as Example 10 except that the image recording material support of Comparative Example 2 was used.
  • Example 10 the electrophotographic material of Comparative Example 7 was produced in the same manner as Example 10 except that the image recording material support of Comparative Example 3 was used.
  • Example 10 an electrophotographic material of Comparative Example 8 was produced in the same manner as in Example 10 except that the image recording material support of Comparative Example 4 was used.
  • the printer used was a color laser printer (DocuColor 1250-PF) manufactured by Fuji Xerox Co., Ltd., in which the fixing unit was a belt fixing device 1 shown in FIG. That is, in the belt fixing device 1 shown in FIG. 1, the fixing belt 2 is suspended over the heating roller 3 and the tension roller 5, and the cleaning roller 6 is disposed above the tension roller 5 via the fixing belt 2. Further, a pressure roller 4 is provided below the heating roller 3 via a fixing belt 2. In FIG. 1, the electrophotographic material having the latent toner image is inserted between the heating roller 3 and the pressure roller 4 from the right side, fixed, and then moved on the fixing belt 2 and moved. In the process, it is cooled by the cooling device 7 and finally cleaned by the cleaning roller 6.
  • DocuColor 1250-PF DocuColor 1250-PF
  • the conveying speed of the fixing belt 2 is 30 mm / second
  • the nip pressure between the heating roller 3 and the pressure roller 4 is 0.2 MPa
  • the set temperature of the heating roller 3 Is 150 ° C., which corresponds to the fixing temperature.
  • the set temperature of the pressure roller 4 was set to 120 ° C.
  • the image quality of each electrophotographic print was visually observed, and based on the following criteria, the best image quality was ranked as A, then B, C, D, E and evaluated.
  • the method for producing an image recording support and the image recording material support of the present invention use a base paper obtained by calendering with a roll having a surface layer containing at least one selected from cermet materials. Excellent smoothness and few small holes (small dents).
  • cermet materials excellent smoothness and few small holes (small dents).
  • electrophotographic materials heat-sensitive materials, sublimation transfer materials, thermal transfer materials, thermal development materials, silver salt photographic materials, inkjet recording materials, etc.
  • thermal transfer materials thermal development materials
  • silver salt photographic materials inkjet recording materials

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  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
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Abstract

This invention provides a support for an image recording material, which, after covering a thermoplastic resin layer on a base paper, forms no significant pinholes (very small recesses), and a process for producing the same. The support comprises a base paper and a thermoplastic resin layer on at least one side of the base paper. The base paper has been calendered by a roll having a surface temperature of 200ºC or above, and the roll has a surface layer containing at least one material selected from cermet materials.

Description

明 細 書  Specification
画像記録材料用支持体及びその製造方法、並びに画像記録材料 技術分野  IMAGE RECORDING MATERIAL SUPPORT AND MANUFACTURING METHOD THEREOF
[0001] 本発明は、電子写真材料、感熱材料、昇華転写材料、熱転写材料、熱現像材料、 銀塩写真材料、インクジェット記録材料などの各種画像記録材料に好適な画像記録 材料用支持体及び該画像記録材料用支持体を効率良く製造する方法、並びに画像 記録材料に関する。  The present invention relates to a support for an image recording material suitable for various image recording materials such as an electrophotographic material, a heat sensitive material, a sublimation transfer material, a thermal transfer material, a heat development material, a silver salt photographic material, and an ink jet recording material, and the like The present invention relates to a method for efficiently producing a support for an image recording material, and an image recording material.
背景技術  Background art
[0002] 従来より、画像記録材料用支持体の製造に用いられる金属ロールは、鲭が発生し やすぐこの鯖が支持体に付着すると画像記録層形成時に乱れが生じ、外観故障を 引き起こす。このため、防鲭及びロール表面の傷付き防止の観点からロール表面に 工業用クロムメツキを施すことが一般に行われていた。  Conventionally, metal rolls used in the production of a support for an image recording material are wrinkled or immediately attached to the support, causing disturbance during the formation of the image recording layer and causing appearance troubles. For this reason, it has been common practice to apply industrial chrome plating to the roll surface from the viewpoint of flaw prevention and prevention of scratches on the roll surface.
また、画像記録材料用支持体では、良好な平滑性を得るため、原紙の画像記録面 にソフトカレンダー処理が行われている（例えば、特許文献 1、特許文献 2、及び特許 文献 3参照）。しかし、より嵩高で良好な平滑性を得るためには、 200〜350°Cの高い 加熱温度でカレンダー処理することが必要になる。  In addition, in the support for image recording material, soft calendar processing is performed on the image recording surface of the base paper in order to obtain good smoothness (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3). However, in order to obtain higher bulkiness and better smoothness, it is necessary to perform calendar treatment at a high heating temperature of 200 to 350 ° C.
[0003] 前記工業用クロムメツキは、 150°C以上の加熱温度では、昇温時にクラックを引き起 こす可能性が高ぐこのため、被覆厚みを極力抑える必要がある。また、カレンダ一口 ールは表面に傷が付くと、研磨を行って再使用するのが一般的である。しかし、この ように被覆厚みが薄いと、表面に傷が付いた場合には、再度メツキ処理をしなければ ならず、コストアップを招く原因となる。更に、前記工業用クロムメツキは、 250°C以上 の高温ではクラックが発生し、このクラックが紙の表面を型付したり、ロール母材が鲭 びてしまったりするため、 250°C以上の温度では使用することができないという問題が ある。  [0003] The industrial chrome plating has a high possibility of causing cracks when heated at a heating temperature of 150 ° C or higher. Therefore, it is necessary to suppress the coating thickness as much as possible. In addition, when the surface of a calendar bite is damaged, it is generally reused after polishing. However, if the coating thickness is thin in this way, if the surface is scratched, the plating process must be performed again, leading to an increase in cost. Furthermore, the industrial chrome plating cracks at a high temperature of 250 ° C or higher, and this crack forms the surface of the paper or the roll base material is worn out. However, there is a problem that it cannot be used.
[0004] このため、ロール表面に工業用クロムメツキを施さないでソフトカレンダー処理を行う と、特に、前工程で水溶性金属塩を含む液で表面サイズ処理を行った場合には、水 溶性金属塩と高温による酸化促進が原因でロールに鲭びが多量に発生し、外観故 障の原因となる。一方、水溶性金属塩を塗布しないと、画像記録材料用支持体に必 要な帯電防止機能を付与することができないため、金属ロールへの防鲭処理は必須 となる。 [0004] For this reason, when soft calendering is performed without applying industrial chrome plating to the roll surface, especially when surface sizing is performed with a liquid containing a water-soluble metal salt in the previous step, the water-soluble metal salt Due to the accelerated oxidation due to the high temperature Cause trouble. On the other hand, if the water-soluble metal salt is not applied, the antistatic function necessary for the image recording material support cannot be imparted, and thus the antifouling treatment to the metal roll is essential.
[0005] したがって、高温でも表面にクラックの発生がなぐ防鲭効果に優れたロールを用い てカレンダー処理を行うことで良好な平滑性を有する原紙が得られ、該原紙に熱可 塑性樹脂層を被覆した後の小孔 (微小な凹み）の発生が少なぐ平滑性に優れた画 像記録材料用支持体を効率良ぐ安価に製造する方法は、未だ提供されていないの が現状である。  [0005] Therefore, a base paper having good smoothness can be obtained by calendering using a roll having an excellent antifungal effect in which cracks are not generated on the surface even at a high temperature, and a thermoplastic resin layer is provided on the base paper. At present, there has not yet been provided a method for efficiently and inexpensively producing a support for an image recording material excellent in smoothness with few small holes (micro-dents) after coating.
[0006] 特許文献 1 :特開平 4一 110939号公報  [0006] Patent Document 1: Japanese Laid-Open Patent Application No. 41-1110939
特許文献 2：特開平 6 - 282037号公報  Patent Document 2: Japanese Patent Laid-Open No. 6-282037
特許文献 3：特開平 7— 70973号公報  Patent Document 3: Japanese Patent Laid-Open No. 7-70973
発明の開示  Disclosure of the invention
[0007] 本発明は、高温でも表面にクラックの発生がなぐ耐磨耗性及び防鲭効果に優れた ロールを用いてカレンダー処理を行うことで良好な平滑性を有する原紙が得られ、該 原紙に熱可塑性樹脂層を被覆した後の小孔 (微小な凹み）の発生が少ない画像記 録材料用支持体、及び原紙の表面に熱可塑性樹脂層を高速被覆することが可能と なり、効率よぐ安価に画像記録材料用支持体を製造する方法を提供することを目的 とする。  [0007] The present invention provides a base paper having good smoothness by performing a calendering process using a roll having excellent wear resistance and antifungal effect in which cracks are not generated on the surface even at high temperatures. It is possible to coat the thermoplastic resin layer at a high speed on the surface of the base material for image recording materials and the base of the image recording material, where there are few small holes (small dents) after the thermoplastic resin layer is coated on the substrate. It is an object of the present invention to provide a method for producing a support for an image recording material at a low cost.
[0008] 前記課題を解決するための手段としては、以下の通りである。即ち、  [0008] Means for solving the above-described problems are as follows. That is,
< 1 > 原紙と、該原紙の少なくとも一方の面に熱可塑性樹脂層を有する画像記録 材料用支持体であって、  <1> A support for an image recording material having a base paper and a thermoplastic resin layer on at least one surface of the base paper,
前記原紙は、表面温度が 200°C以上のロールでカレンダー処理されてなり、かつ 該ロールが、サーメット材料から選択される少なくとも 1種を含む表面層を有すること を特徴とする画像記録材料用支持体である。  The base paper is calendered with a roll having a surface temperature of 200 ° C. or higher, and the roll has a surface layer containing at least one selected from cermet materials. Is the body.
< 2 > ロールの表面温度が、 200〜350°Cである前記 < 1 >に記載の画像記録 材料用支持体である。  <2> The support for an image recording material according to <1>, wherein the roll has a surface temperature of 200 to 350 ° C.
< 3 > 原紙の画像記録層を設ける側の面が、サーメット材料から選択される少なく とも 1種を含む表面層を有するロールと接するようにカレンダー処理する前記 < 1 > 力ら < 2 >のレ、ずれかに記載の画像記録材料用支持体である。 <3> The above-mentioned <1> in which the surface of the base paper on which the image recording layer is provided is calendered so as to contact a roll having a surface layer containing at least one selected from cermet materials This is a support for an image recording material described in the item <2>.
<4> 原紙の画像記録層を設ける側の面の反対側の面が、ショァ一 D硬度 60〜 95° のロールと接するようにカレンダー処理する前記 <1>から < 3 >のいずれかに 記載の画像記録材料用支持体である。  <4> The material according to any one of <1> to <3>, wherein the surface opposite to the surface on which the image recording layer is provided of the base paper is calendered so as to be in contact with a roll having a Shore D hardness of 60 to 95 °. This is a support for image recording material.
<5> サーメット材料が、炭化タングステン系サーメットである前記 <1>からく 4 >のいずれかに記載の画像記録材料用支持体である。  <5> The support for an image recording material according to any one of <1> to <4>, wherein the cermet material is a tungsten carbide cermet.
<6> 炭化タングステン系サーメットが、炭化タングステン一コバルト、炭化タンダ ステン一コバルトクロム、及び炭化タングステン一ニッケルクロムのいずれかである前 記 < 5 >に記載の画像記録材料用支持体である。  <6> The support for an image recording material according to <5>, wherein the tungsten carbide cermet is any one of tungsten carbide-cobalt, tungsten carbide-cobalt chromium, and tungsten carbide-nickel chromium.
<7> 表面層の厚みが、 60〜220 111でぁる前記<1>から<6>のぃずれかに 記載の画像記録材料用支持体である。  <7> The support for an image recording material according to any one of <1> to <6>, wherein the surface layer has a thickness of 60 to 220111.
<8> ロールの表面粗度力 0.5S以下である前記 <1>から <7>のいずれか に記載の画像記録材料用支持体である。  <8> The support for an image recording material according to any one of <1> to <7>, wherein the surface roughness force of the roll is 0.5 S or less.
<9> カレンダー処理する前の原紙が、帯電防止剤を含有する前記 <1>から < 8 >のレ、ずれかに記載の画像記録材料用支持体である。  <9> The support for an image recording material according to <1> to <8>, wherein the base paper before the calendar treatment contains an antistatic agent.
<10> 帯電防止剤が水溶性金属塩であり、かつ該水溶性金属塩が、塩化カル シゥム、塩ィ匕ナトリウム、及び塩化マグネシウムのいずれかである前記く 9 >に記載 の画像記録材料用支持体である。  <10> The image recording material according to the above item 9>, wherein the antistatic agent is a water-soluble metal salt, and the water-soluble metal salt is any one of calcium chloride, sodium chloride salt, and magnesium chloride. It is a support.
<11> 熱可塑性樹脂層が、ポリオレフイン樹脂を含有する前記く 1 >からく 10 <11> The thermoplastic resin layer containing polyolefin resin 1>
>のいずれかに記載の画像記録材料用支持体である。 The support for image recording materials according to any one of the above.
<12> 原紙の画像記録層を設ける側の面に、炭化タングステン系サーメット材料 から選択される少なくとも 1種の材料を含む表面層を有するロールが接するようにして 、該ロールの表面温度が 200°C以上でカレンダー処理する工程を含むことを特徴と する画像記録材料用支持体の製造方法である。  <12> A roll having a surface layer containing at least one material selected from tungsten carbide-based cermet materials is in contact with the surface of the base paper on which the image recording layer is provided, so that the surface temperature of the roll is 200 ° A method for producing a support for image recording material, comprising a step of calendering at C or higher.
<13> カレンダー処理する前に、原紙表面に水溶性金属塩を含有する液を塗布 する表面サイズ処理工程を含む前記 < 12 >に記載の画像記録材料用支持体の製 造方法である。  <13> The method for producing a support for an image recording material according to <12>, further comprising a surface sizing process in which a liquid containing a water-soluble metal salt is applied to the surface of the base paper before calendering.
<14> カレンダー処理後の原紙の少なくとも一方の面に熱可塑性樹脂層を形成 する工程を含む前記 < 12 >から < 13 >のいずれかに記載の画像記録材料用支持 体の製造方法である。 <14> Form a thermoplastic resin layer on at least one side of the calendered base paper The method for producing a support for an image recording material according to any one of <12> to <13>, comprising the step of:
< 15 > 前記 < 1 >から < 11 >のいずれかに記載の画像記録材料用支持体と、 少なくとも画像が記録される画像記録層とを有することを特徴とする画像記録材料で ある。  <15> An image recording material comprising the image recording material support according to any one of <1> to <11> and an image recording layer on which at least an image is recorded.
ぐ 16 > 電子写真材料、感熱材料、昇華転写材料、熱転写材料、銀塩写真材料、 及びインクジェット記録材料から選択されるいずれかである前記 < 15 >に記載の画 像記録材料である。  <16> The image recording material according to <15>, wherein the image recording material is any one selected from electrophotographic materials, heat-sensitive materials, sublimation transfer materials, thermal transfer materials, silver salt photographic materials, and inkjet recording materials.
[0009] 本発明の画像記録材料用支持体は、原紙と、該原紙の少なくとも一方の面に熱可 塑性樹脂層を有してなり、  [0009] The support for image recording material of the present invention comprises a base paper and a thermoplastic resin layer on at least one surface of the base paper,
前記原紙は、表面温度が 200°C以上のロールでカレンダー処理されてなり、かつ 該ロールが、サーメット材料から選択される少なくとも 1種を含む表面層を有する。 本発明の画像記録材料用支持体においては、前記ロールを用いてカレンダー処 理することによって、小孔 (微小な凹み）の発生が少なぐ平滑性に優れているので、 例えば、電子写真材料、感熱材料、昇華転写材料、熱転写材料、熱現像材料、銀塩 写真材料、インクジェット記録材料などに幅広く好適に用いられる。  The base paper is calendered with a roll having a surface temperature of 200 ° C. or more, and the roll has a surface layer containing at least one selected from cermet materials. In the support for an image recording material of the present invention, the calender treatment using the roll is excellent in smoothness with few small holes (small dents), so that, for example, an electrophotographic material, Widely and suitably used for heat sensitive materials, sublimation transfer materials, thermal transfer materials, heat development materials, silver salt photographic materials, ink jet recording materials and the like.
[0010] 本発明の画像記録材料用支持体の製造方法は、原紙の画像記録層を設ける側の 面に、炭化タングステン系サーメット材料から選択される少なくとも 1種の材料を含む 表面層を有するロールが接するようにして、該ロールの表面温度が 200°C以上で力 レンダー処理する工程を含む。 [0010] The method for producing a support for an image recording material of the present invention comprises a roll having a surface layer containing at least one material selected from tungsten carbide cermet materials on the side of the base paper on which the image recording layer is provided. And a force-rendering process at a surface temperature of the roll of 200 ° C. or higher.
本発明の画像記録材料用支持体の製造方法においては、高温でも表面にクラック の発生がなぐ耐磨耗性及び防鲭効果に優れたロールを用いてカレンダー処理を行 うことで良好な平滑性を有する原紙が得られ、該原紙に熱可塑性樹脂層を被覆した 後の小孔 (微小な凹み）の発生が少ない画像記録材料用支持体を効率良ぐ製造す ること力 Sできる。  In the method for producing a support for an image recording material of the present invention, good smoothness is obtained by carrying out a calendering process using a roll having excellent wear resistance and antifungal effect that does not generate cracks on the surface even at high temperatures. Thus, it is possible to efficiently produce a support for an image recording material in which small holes (small dents) are not generated after the base paper is coated with a thermoplastic resin layer.
図面の簡単な説明  Brief Description of Drawings
[0011] [図 1]図 1は、実施例で使用したプリンターにおけるベルト定着装置の概略図である。  FIG. 1 is a schematic diagram of a belt fixing device in a printer used in an example.
発明を実施するための最良の形態 [0012] (画像記録材料用支持体） BEST MODE FOR CARRYING OUT THE INVENTION [0012] (Support for Image Recording Material)
本発明の画像記録材料用支持体は、原紙と、該原紙の少なくとも一方の面に熱可 塑性樹脂層を有してなり、更に必要に応じてその他の層を有してなる。  The support for an image recording material of the present invention comprises a base paper and a thermoplastic resin layer on at least one surface of the base paper, and further comprises other layers as required.
[0013] 一原紙一 [0013] One original paper
前記原紙としては、特に制限はなぐ 目的に応じて適宜選択することができるが、具 体的には、上質紙、例えば、 日本写真学会編「写真工学の基礎一銀塩写真編一」、 株式会社コロナ社刊（昭和 54年）（223)〜（224)頁記載の紙等が好適なものとして 挙げられる。  The base paper is not particularly limited and can be appropriately selected according to the purpose. Specifically, it is a high-quality paper, for example, “Photographic Engineering Fundamental Silver Salt Photo Edition” edited by the Japan Photographic Society, Papers described on pages 223 to 224 of the company Corona (Showa 54) are preferred.
[0014] 前記原紙としては、支持体に使用されるものとして公知の材料であれば特に制限な く、 目的に応じて各種の材料から適宜選択することができ、例えば、針葉樹、広葉樹 等の天然パルプ、該天然パルプと合成パルプの混合物等が挙げられる。  [0014] The base paper is not particularly limited as long as it is a known material used for a support, and can be appropriately selected from various materials according to the purpose. For example, natural paper such as conifers and hardwoods can be selected. Examples thereof include pulp, a mixture of the natural pulp and synthetic pulp.
[0015] 前記原紙の原料として使用できるパルプとしては、原紙の平面性及び寸法安定性 等を同時にバランス良ぐかつ十分なレベルにまで向上させる点から、前記広葉樹パ ルプが好ましいが、前記針葉樹パルプ等を使用することもできる。  [0015] The pulp that can be used as the raw material of the base paper is preferably the hardwood pulp from the viewpoint of improving the flatness and dimensional stability of the base paper to a sufficiently balanced and sufficient level. Etc. can also be used.
前記広葉樹パルプとしては、例えば、広葉樹晒クラフトパルプ (LBKP)、広葉樹サ ルファイトパルプ (LBSP)等が挙げられる力 S、これらの中でも広葉樹晒クラフトパノレプ (LBKP)が好ましい。  Examples of the hardwood pulp include force S such as hardwood bleached kraft pulp (LBKP) and hardwood sulfite pulp (LBSP). Among these, hardwood bleached kraft panolep (LBKP) is preferable.
前記紙に対する前記広葉樹パルプの含有量としては、特に制限はなぐ 目的に応 じて適宜選択することができる力 例えば、 50質量％以上が好ましぐ 60質量％以上 力はり好ましぐ 75質量％以上が更に好ましい。  The content of the hardwood pulp with respect to the paper is not particularly limited and can be appropriately selected according to the purpose. For example, 50% by mass or more is preferred 60% by mass or more The force is preferred 75% by mass The above is more preferable.
[0016] 前記針葉樹パルプとしては、例えば、針葉樹晒クラフトパノレプ (NBKP)等が挙げら れる。  [0016] Examples of the softwood pulp include softwood bleached kraft panolep (NBKP).
前記パルプとしては、繊維長のもともと短い広葉樹パルプを主体に使用することが 好ましい。該繊維長は、特に制限はなぐ 目的に応じて適宜選択することができ、 0. 5〜0. 8mmが好ましい。  As the pulp, it is preferable to mainly use hardwood pulp having a short fiber length. The fiber length is not particularly limited and can be appropriately selected according to the purpose, and is preferably 0.5 to 0.8 mm.
前記パルプの叩解には、ビータやリファイナ一等を使用できる。前記パルプを叩解 した後に得られるパルプスラリー（以下、「パルプ紙料」と称することがある）には、更に 必要に応じて、各種添加剤を添加することができる。該添加剤としては、例えば、填 料、乾燥紙力増強剤、サイズ剤、湿潤紙力増強剤、定着剤、 pH調整剤、その他の薬 剤、等が挙げられる。 A beater or a refiner can be used for beating the pulp. Various additives may be further added to the pulp slurry obtained after beating the pulp (hereinafter, sometimes referred to as “pulp stock”) as necessary. Examples of the additive include filler Materials, dry paper strength enhancers, sizing agents, wet paper strength enhancers, fixing agents, pH adjusters, and other chemicals.
[0017] 前記填料としては、例えば、炭酸カルシウム、クレイ、カオリン、白土、タルク、酸化 チタン、珪藻土、硫酸バリウム、水酸化アルミニウム、水酸化マグネシウム、等が挙げ られる。  [0017] Examples of the filler include calcium carbonate, clay, kaolin, clay, talc, titanium oxide, diatomaceous earth, barium sulfate, aluminum hydroxide, magnesium hydroxide, and the like.
前記乾燥紙力増強剤としては、例えば、カチオン化澱粉、カチオンィ匕ポリアクリルァ ミド、ァニオン化ポリアクリルアミド、両性ポリアクリルアミド、カルボキシ変性ポリビュル アルコール、等が挙げられる。  Examples of the dry paper strength enhancer include cationized starch, cationic polyacrylamide, anionized polyacrylamide, amphoteric polyacrylamide, and carboxy-modified polybutyl alcohol.
前記サイズ剤としては、例えば、脂肪酸塩、ロジン、マレイン化ロジン等のロジン誘 導体、パラフィンワックス、アルキルケテンダイマー、アルケニル無水琥珀酸（ASA)、 エポキシィ匕脂肪酸アミド等の高級脂肪酸を含有する化合物、などが挙げられる。 前記湿潤紙力増強剤としては、例えば、ポリアミンポリアミドェピクロロヒドリン、メラミ ン樹脂、尿素樹脂、エポキシ化ポリアミド樹脂、等が挙げられる。  Examples of the sizing agent include fatty acid salts, rosin derivatives such as rosin and maleated rosin, paraffin wax, alkyl ketene dimer, alkenyl succinic anhydride (ASA), compounds containing higher fatty acids such as epoxy fatty acid amide, Etc. Examples of the wet paper strength enhancer include polyamine polyamide epoxy hydrin, melamine resin, urea resin, epoxidized polyamide resin, and the like.
前記定着剤としては、例えば、硫酸アルミニウム、塩ィ匕アルミニウム等の多価金属塩 、カチオン化澱粉等のカチオン性ポリマー、等が挙げられる。  Examples of the fixing agent include polyvalent metal salts such as aluminum sulfate and aluminum chloride, and cationic polymers such as cationized starch.
前記 pH調整剤としては、例えば、苛性ソーダ、炭酸ソーダ、等が挙げられる。 前記その他の薬剤としては、例えば、消泡剤、染料、スライムコントロール剤、蛍光 増白剤、等が挙げられる。  Examples of the pH adjuster include caustic soda and sodium carbonate. Examples of the other chemicals include antifoaming agents, dyes, slime control agents, fluorescent whitening agents, and the like.
更に必要に応じて、柔軟化剤等を添加することもできる。前記柔軟化剤としては、 例えば、新'紙加工便覧 (紙薬タイム社編） 554〜555頁（1980年発行)等に記載の ものを用いることができる。  Furthermore, a softening agent etc. can also be added as needed. As the softening agent, for example, those described in New Handbook for Paper Processing (Edited by Paper Medicine Time), pages 554 to 555 (issued in 1980) can be used.
これら各種添加剤等は、 1種単独で使用してもよいし、 2種以上を併用してもよい。 また、これら各種添加剤等の前記パルプ紙料中への添加量は、特に制限はなぐ 目 的に応じて適宜選択することができ、通常 0. 1〜： 1. 0質量％が好ましい。  These various additives may be used alone or in combination of two or more. Further, the amount of these various additives and the like added to the pulp paper stock can be appropriately selected according to the purpose without particular limitation, and is usually preferably 0.1 to 1.0% by mass.
[0018] 前記パルプスラリーには、更に必要に応じて、前記各種添加剤等を含有させたパ ルプ紙料を手抄紙機、長網抄紙機、丸網抄紙機、ツインワイヤーマシン、コンビネー シヨンマシンなどの抄紙機を用いて抄紙し、その後乾燥して原紙を作製する。また、 所望により前記乾燥の前後のいずれかに表面サイズ処理を実施することができる。 前記表面サイズ処理に使用される表面サイズ処理液は、例えば、アルカリ金属塩及 びアルカリ土類金属塩の少なくともいずれかの金属塩、水溶性高分子化合物、蛍光 増白剤、耐水性物質、顔料、染料、などが含有されている。 [0018] To the pulp slurry, pulp paper containing the above-mentioned various additives, etc., if necessary, is further added to a hand paper machine, a long paper machine, a round paper machine, a twin wire machine, and a combination machine. Paper is made using a paper machine such as, and then dried to produce a base paper. Further, if desired, surface sizing treatment can be performed either before or after the drying. The surface sizing solution used for the surface sizing is, for example, a metal salt of at least one of an alkali metal salt and an alkaline earth metal salt, a water-soluble polymer compound, a fluorescent brightener, a water-resistant substance, and a pigment. , Dyes, and the like.
前記アルカリ金属塩及びアルカリ土類金属塩の少なくともいずれかの金属塩として は、上述した通りのものを使用することができる。  As the metal salt of at least one of the alkali metal salt and the alkaline earth metal salt, those described above can be used.
[0019] 前記水溶性高分子化合物としては、特に制限はなぐ 目的に応じて適宜選定する ことができ、例えば、ポリビュルアルコール、カルボキシ変性ポリビュルアルコール、 カノレボキシメチノレセノレロース、ヒドロキシェチノレセノレロース、セノレロースサノレフェート、 ポリエチレンオキサイド、ゼラチン、カチオン化澱粉、カゼイン、ポリアクリル酸ナトリウ ム、スチレン—無水マレイン酸共重合体ナトリウム塩、ポリスチレンスルホン酸ナトリウ ム、などが挙げられ、これらの中でも、ポリビュルアルコール、カルボキシ変性ポリビニ ノレアノレコーノレ、力ノレボキシメチノレセノレロース、ヒドロキシェチノレセノレロース、セノレロー スサルフェート、ポリエチレンオキサイド、ゼラチンが好ましぐ特にポリビニルアルコ ール（PVA)がより好ましい。  [0019] The water-soluble polymer compound is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include polybulualcohol, carboxy-modified polybulualcohol, canoleboxymethylenoresenorelose, hydroxyethino. Resenorelose, senorelose sanoleate, polyethylene oxide, gelatin, cationized starch, casein, sodium polyacrylate, sodium styrene-maleic anhydride copolymer, sodium polystyrene sulfonate, etc. Among these, polyvinyl alcohol, carboxy-modified polyvinylenoleconole, force noreoxymethinoresenorelose, hydroxyethinoresenorelose, cenoresulfate, polyethylene oxide, and gelatin are particularly preferred. Lumpur (PVA) is more preferable.
前記水溶性高分子化合物の含有量は、 0. 5〜2g/m2が好ましい。 The content of the water-soluble polymer compound is preferably 0.5 to 2 g / m 2 .
[0020] 前記蛍光増白剤としては、例えば、スチルベン系化合物、クマリン系化合物、ビフエ ニル系化合物、ベンゾォキサゾリン系化合物、ナフタルイミド系化合物、ピラゾリン系 化合物、カルボスチリル系化合物、ジアミノスチルベンジスルホン酸誘導体、イミダゾ ール誘導体、クマリン誘導体、トリァゾール誘導体、力ルバゾール誘導体、ピリジン誘 導体、ナフタル酸誘導体、イミダゾロン誘導体、等が挙げられ、これらの中でも、スチ ルベン系化合物が好ましレ、。 [0020] Examples of the optical brightener include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazoline compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, diaminostilbene disulfones. Acid derivatives, imidazole derivatives, coumarin derivatives, triazole derivatives, force rubazole derivatives, pyridine derivatives, naphthalic acid derivatives, imidazolone derivatives, and the like. Among these, stilbene compounds are preferred.
前記蛍光増白剤の含有量は、特に制限されないが、 0. 01-0. 5質量％が好まし く、 0. 02-0. 2質量0 /0がより好ましい。 The content of the fluorescent brightening agent is not particularly limited, 0.5 01-0. 5% by weight rather preferably, 0. 02-0. 2 mass 0/0 is more preferable.
前記耐水性物質としては、例えば、スチレン—ブタジエン共重合体、エチレン—酢 酸ビュル共重合体、ポリエチレン樹脂、塩化ビニリデン共重合体等のラテックス 'エマ ルジョン類；ポリアミドポリアミンェピクロノレヒドリン、などが挙げられる。  Examples of the water-resistant substance include latexes such as styrene-butadiene copolymer, ethylene-butyl acetate copolymer, polyethylene resin, vinylidene chloride copolymer; polyamide polyamine epichlorohydrin, etc. Is mentioned.
前記顔料としては、例えば、炭酸カルシウム、クレイ、カオリン、タルク、硫酸バリウム 、酸化チタン等が挙げられる。 [0021] 前記原紙は、画像記録材料用支持体の剛性及び寸法安定性の向上を図る目的か ら、縦方向ヤング率（Ea)と横方向ヤング率（Eb)の比（Ea/Eb)は 1. 5〜2. 0が好 ましレ、。前記 Ea/Eb値が、 1. 5未満、或いは 2. 0を超える範囲では、画像記録材料 用支持体の剛性や、寸法安定性が悪くなり易ぐ搬送時の走行性に支障をきたすこ とになることがある。 Examples of the pigment include calcium carbonate, clay, kaolin, talc, barium sulfate, and titanium oxide. [0021] The base paper has a ratio (Ea / Eb) of the longitudinal Young's modulus (Ea) to the transverse Young's modulus (Eb) for the purpose of improving the rigidity and dimensional stability of the image recording material support. 1. 5 ~ 2.0 is preferred. When the Ea / Eb value is less than 1.5 or more than 2.0, the rigidity of the image recording material support and the dimensional stability are likely to deteriorate, which may hinder the running performance during transportation. May be.
[0022] 一般に、紙の「こし」は、叩解の様式の相違に基づいて異なり、叩解後、抄紙してな る紙が持つ弾性力（率）を紙の「こし」の程度を表す重要な因子として用いることがで きる。特に、紙が持つ粘弾性体の物性を示す動的弾性率と密度との関係を利用し、 これに超音波振動素子を使って紙中を伝播する音速を測定することにより、紙の弾 性率は、下記数式から求めることができる。  [0022] In general, the “strain” of paper differs based on the difference in the beating style, and the elastic force (rate) of the paper that is made after beating is an important factor that expresses the degree of “strain” of the paper. Can be used as a factor. In particular, by utilizing the relationship between the dynamic elastic modulus and density, which indicates the physical properties of the viscoelastic body of paper, and measuring the speed of sound propagating through the paper using an ultrasonic vibration element, the elasticity of the paper is obtained. The rate can be obtained from the following mathematical formula.
E= p c ' ( l— n )  E = p c '(l— n)
前記数式において、 Eは、動的弾性率を表す。 pは、密度を表す。 cは、紙中の音 速を表す。 nは、ポアソン比を表す。  In the above formula, E represents a dynamic elastic modulus. p represents the density. c represents the speed of sound in the paper. n represents the Poisson's ratio.
[0023] また、通常の紙の場合、 n=0. 2程度であるため、下記数式で計算しても大差なぐ 算出することができる。 [0023] Further, in the case of normal paper, since n is about 0.2, even if it is calculated by the following formula, it can be calculated with a large difference.
匕 = p C  匕 = p C
従って、紙の密度、音速を測定することができれば、容易に弾性率を求めることが できる。前記数式において、音速を測定する場合には、例えば、ソニックテスター SS Τ— 110型 (野村商事株式会社製)等の公知の各種機器を用いることができる。  Therefore, if the density and sound speed of paper can be measured, the elastic modulus can be easily obtained. In the above equation, when measuring the speed of sound, for example, various known devices such as Sonic Tester SS IV-110 (manufactured by Nomura Corporation) can be used.
[0024] 前記原紙の厚みは、特に制限はなぐ 目的に応じて適宜選択することができるが、 通常、 30〜500 111カ 子ましく、 50〜300 /1 111カ り子ましく、 100〜250 111カ更 に好ましい。前記原紙の坪量は、特に制限はなぐ 目的に応じて適宜選択することが できるが、例えば、 50〜250g/m2力好ましく、 70〜200g/m2力 Sより好ましレヽ。 [0024] The thickness of the base paper is not particularly limited and can be appropriately selected according to the purpose. Usually, it is 30 to 500 111 or more, 50 to 300/1 111 or more, 100 to 250 111 more preferable. The basis weight of the base paper is not particularly limited and can be appropriately selected according to the purpose. For example, 50 to 250 g / m 2 force is preferable, and 70 to 200 g / m 2 force S is preferable.
[0025] 前記原紙は、表面温度が 200°C以上のロールでカレンダー処理されてなり、かつ 該ロールが、サーメット材料から選択される少なくとも 1種を含む表面層を有する。  [0025] The base paper is calendered with a roll having a surface temperature of 200 ° C or higher, and the roll has a surface layer containing at least one selected from cermet materials.
[0026] —ロール一  [0026] — roll one
前記ロールとしては、特に制限はなぐ 目的に応じて適宜選択することができるが、 例えば金属ロールと、該金属ロール表面に表面層とを有してなり、更に必要に応じて その他の構成を有してなる。 The roll is not particularly limited and can be appropriately selected according to the purpose. For example, the roll has a metal roll and a surface layer on the surface of the metal roll, and further, if necessary. It has other configurations.
[0027] 前記金属ロールの材料としては、特に制限はなぐ 目的に応じて適宜選択すること ができるが、例えば、チルド鋼、鍛鋼、などが挙げられる。  [0027] The material of the metal roll is not particularly limited, and can be appropriately selected depending on the purpose. Examples thereof include chilled steel and forged steel.
前記表面層は、サーメット材料から選択される少なくとも 1種を含み、更に必要に応 じてその他の成分を含有してなる。  The surface layer contains at least one selected from cermet materials, and further contains other components as necessary.
[0028] 前記サーメット材料としては、特に制限はなぐ 目的に応じて適宜選択することがで き、例えば、酸化アルミニウム一ニッケルクロム、ジルコニウム酸マグネシウム一ニッケ ルクロムアルミニウム、炭化タングステン系サーメット、炭化クロム一ニッケル、炭化クロ ム一ニッケルクロム、炭化クロム—ニッケルクロム—アルミニウム—イットリウムなどが挙 げられる。これらの中でも、炭化タングステン系サーメットが特に好ましい。  [0028] The cermet material is not particularly limited and can be appropriately selected according to the purpose. For example, aluminum cerium nickel oxide, magnesium zirconate mono nickel chromium aluminum, tungsten carbide cermet, chromium carbide mono Nickel, chromium carbide—nickel chromium, chromium carbide—nickel chromium—aluminum—yttrium, and the like. Among these, tungsten carbide cermet is particularly preferable.
前記炭化タングステン系サーメットとしては、炭化タングステン一コバルト、炭化タン グステン一ニッケルクロム、炭化タングステン一コバルトクロム、炭化タングステン一二 ッケル、炭化タングステン コバルトニッケル白金、炭化タングステン コバルトニッケ ル一クロムアルミニウム一イットリウム、炭化タングステン一炭化クロム一コバルトニッケ ルクロムなどが挙げられる。これらの中でも、炭化タングステン一コバルト、炭化タンダ ステン一コバルトクロム、炭化タングステン ニッケルクロムが好ましぐ炭化タンダス テン コバルトが、溶射後に緻密な被膜が形成でき、研磨仕上げ後の表面粗度が小 さくなり、耐摩耗性に優れ、カレンダー用途に適している点から特に好ましい。  Examples of the tungsten carbide cermet include tungsten carbide-cobalt, tungsten carbide-nickel chromium, tungsten carbide-cobalt chromium, tungsten carbide nickel, tungsten carbide cobalt-nickel platinum, tungsten carbide cobalt nickel-chromium aluminum, yttrium, carbonized. Examples include tungsten monochromate and cobalt nickel chrome. Of these, tungsten cobalt carbide, which is preferred to tungsten tungsten-cobalt, tungsten carbide cobalt-chromium, and tungsten-nickel carbide, can form a dense film after thermal spraying, and the surface roughness after polishing finish is reduced. It is particularly preferable because it is excellent in wear resistance and is suitable for calendar use.
[0029] 前記表面層は、特に制限はなぐ 目的に応じて適宜選択することができるが、前記 サーメット材料を用レ、、例えば高速フレーム溶射法、プラズマ溶射法、粉末式フレー ム溶射法、などにより作製することができる。 [0029] The surface layer is not particularly limited and may be appropriately selected according to the purpose. However, the cermet material is used, for example, high-speed flame spraying, plasma spraying, powder flame spraying, etc. Can be produced.
前記表面層の厚み fま、 60〜220 x mカ好ましく、 100〜200 μ mカより好ましレヽ。 前記厚みが 60 x m未満であると、表面に傷が付いた場合に研磨できないため、再度 、表面層を設ける処理が必要となることがあり、 220 z mを超えると、溶射被膜が剥離 して凹みとなり、原紙表面に傷を付けてしまうことがある。  The thickness of the surface layer f is preferably 60 to 220 × m, more preferably 100 to 200 μm. If the thickness is less than 60 xm, the surface cannot be polished if the surface is scratched. Therefore, a treatment for providing a surface layer may be required again. If the thickness exceeds 220 zm, the thermal spray coating peels off and becomes concave. As a result, the surface of the base paper may be damaged.
前記ロールの表面粗度（平滑度）は、 0. 5S以下が好ましぐ 0. 3S以下がより好ま しい。ここで、前記ロールの表面粗度は、例えば、東京精密社製のサーフコム 120A により測定することができる。 [0030] カレンダー処理 The surface roughness (smoothness) of the roll is preferably 0.5S or less, and more preferably 0.3S or less. Here, the surface roughness of the roll can be measured by, for example, Surfcom 120A manufactured by Tokyo Seimitsu Co., Ltd. [0030] Calendar processing
前記カレンダー処理としては、前記原紙を、前記炭化タングステン系サーメット材料 から選択される少なくとも 1種の材料を含む表面層を有し、かつ表面温度が 200°C以 上のロールでカレンダー処理するものである。  As the calendering, the base paper is calendered with a roll having a surface layer containing at least one material selected from the tungsten carbide cermet materials and having a surface temperature of 200 ° C or higher. is there.
[0031] 前記ロールの表面温度は 200°C以上であり、 200〜350。C力 S好ましく、 230〜280 °Cがより好ましい。前記表面温度が 200°C未満であると、熱可塑性樹脂を被覆した後 の小孔 (微細な凹み）の発生が悪化する（多くなる）ことがあり、 350°Cを超えると、原 紙表面に薬品が熱で変色したと思われる黄ばみ、焦げ付きが発生することがある。  [0031] The surface temperature of the roll is 200 ° C or more, and 200 to 350. C force S is preferable, and 230 to 280 ° C is more preferable. If the surface temperature is less than 200 ° C, the generation of small holes (fine dents) after coating with the thermoplastic resin may be worsened (increased), and if it exceeds 350 ° C, the surface of the base paper In some cases, yellowing and scorching may occur due to the chemicals being discolored by heat.
[0032] 前記カレンダー処理は、原紙の画像記録層を設ける側の面を、前記炭化タンダス テン系サーメット材料から選択される少なくとも 1種の材料を含む表面層を有し、かつ 表面温度が 200°C以上のロールが接するようにし、一方、原紙の画像記録層を設け ない側の面を、ショァ一 D硬度 60〜95° のロール（好ましくは樹脂ロール）が接する ようにカレンダー処理する、いわゆるソフトカレンダー処理力 嵩高で良好な平滑性を 得る点から好ましい。  [0032] In the calendering process, the surface of the base paper on which the image recording layer is provided has a surface layer containing at least one material selected from the carbonized tandusten cermet material, and the surface temperature is 200 °. A so-called software is used in which a roll of C or higher is in contact, and the surface of the base paper on which the image recording layer is not provided is calendered so that a roll having a Shore D hardness of 60 to 95 ° (preferably a resin roll) is in contact. Calendar processing power This is preferable from the viewpoint of obtaining bulkiness and good smoothness.
[0033] 前記カレンダー処理の際のニップ圧としては、特に制限はなぐ 目的に応じて適宜 選択することができる力 線圧 50kg/cm以上が好ましぐ 80〜350kg/cmがより 好ましい。  [0033] The nip pressure at the time of the calendar treatment is not particularly limited, and can be appropriately selected according to the purpose. A linear pressure of 50 kg / cm or more is preferable, and 80 to 350 kg / cm is more preferable.
前記原紙がカレンダーの二ップ部を通過する際の通過の速度としては、 50-800 m/分が好ましぐ 70〜600m/分がより好ましぐ 90〜500m/分が特に好ましい 。前記速度が 50m/分未満であると、生産効率が悪くなることがあり、 800m/分を 超えると、原紙が二ップ部を通過する時間が短くなるため、カレンダー処理効果が出 ないことがある。  The passing speed of the base paper when it passes through the two-part portion of the calendar is preferably 50-800 m / min, more preferably 70-600 m / min, more preferably 90-500 m / min. If the speed is less than 50 m / min, the production efficiency may be deteriorated. If the speed exceeds 800 m / min, the time for the base paper to pass through the two-pipe portion is shortened, so that the calendar processing effect may not be achieved. is there.
[0034] 前記カレンダー処理する前の原紙は、帯電防止機能を付与する目的から帯電防止 剤を含有することが好ましい。該帯電防止剤が水溶性金属塩であり、かつ該水溶性 金属塩が、塩化カルシウム、塩化ナトリウム、及び塩化マグネシウムのいずれかである ことが好適である。  [0034] The base paper before the calendar treatment preferably contains an antistatic agent for the purpose of imparting an antistatic function. It is preferable that the antistatic agent is a water-soluble metal salt, and the water-soluble metal salt is any one of calcium chloride, sodium chloride, and magnesium chloride.
前記帯電防止剤の前記原紙における含有量は、 1. 0〜5. 0質量％が好ましい。  The content of the antistatic agent in the base paper is preferably 1.0 to 5.0% by mass.
[0035] 一熱可塑性樹脂層一 前記熱可塑性樹脂層は、原紙の少なくとも一方の面に設けられ、好ましくは両面に 設ける。なお、該熱可塑性樹脂層は、少なくとも 1層設けられ、 2層以上設けることも できる。 [0035] One thermoplastic resin layer The thermoplastic resin layer is provided on at least one side of the base paper, preferably on both sides. Note that at least one thermoplastic resin layer is provided, and two or more thermoplastic resin layers can be provided.
前記熱可塑性樹脂層を構成するポリマーとしては、フィルム形成能のある樹脂が好 ましぐポリオレフイン樹脂が特に好ましい。  The polymer constituting the thermoplastic resin layer is particularly preferably a polyolefin resin, preferably a resin capable of forming a film.
前記ポリオレフイン樹脂としては、例えば、ポリエチレン、ポリプロピレン、ポリプロピ レンとポリエチレンとのブレンド、高密度ポリエチレン（HDPE)、高密度ポリエチレンと 低密度ポリエチレン (LDPE)とのブレンド等が好適である。  As the polyolefin resin, for example, polyethylene, polypropylene, a blend of polypropylene and polyethylene, high density polyethylene (HDPE), a blend of high density polyethylene and low density polyethylene (LDPE), and the like are suitable.
[0036] 前記熱可塑性樹脂層には、二酸化チタン等の無機顔料、ブルーイング剤、蛍光増 白剤、酸化防止剤等を含有させてもよぐ特に二酸化チタンを含有させるのが好まし レ、。また、前記熱可塑性樹脂層の原紙との接着性を良好にする観点から、粘着性付 与剤樹脂、接着性樹脂等を含有させることもできる。更に必要に応じて、適宜、酸化 防止剤、剥離剤、中空ポリマー等を含有させてもよい。 [0036] The thermoplastic resin layer may contain an inorganic pigment such as titanium dioxide, a bluing agent, a fluorescent brightening agent, an antioxidant and the like, and particularly preferably contains titanium dioxide. . Further, from the viewpoint of improving the adhesiveness of the thermoplastic resin layer to the base paper, a tackifier resin, an adhesive resin, or the like can be contained. Furthermore, if necessary, an antioxidant, a release agent, a hollow polymer and the like may be contained.
前記熱可塑性樹脂層の厚みは、特に制限はなぐ 目的に応じて適宜選択すること ができ、 3〜47 μ ΐηが好ましい。  The thickness of the thermoplastic resin layer can be appropriately selected according to the purpose without any particular limitation, and is preferably 3 to 47 μΐη.
[0037] (画像記録材料用支持体の製造方法） [0037] (Method for producing support for image recording material)
本発明の画像記録材料用支持体の製造方法は、カレンダー処理工程、表面サイ ズ工程、及び熱可塑性樹脂層形成工程を含んでなり、更に必要に応じてその他のェ 程を含んでなる。  The method for producing a support for an image recording material of the present invention comprises a calendering process, a surface sizing process, and a thermoplastic resin layer forming process, and further comprises other processes as necessary.
[0038] カレンダー処理工程 [0038] Calendar processing step
前記カレンダー処理工程は、原紙の画像記録層を設ける側の面に、前記炭化タン ダステン系サーメット材料から選択される少なくとも 1種を含む表面層を有するロール が接するようにして、該ロールの表面温度が 200°C以上でカレンダー処理する工程 である。  In the calendering step, a roll having a surface layer containing at least one selected from the carbonized tansten cermet material is in contact with the surface of the base paper on which the image recording layer is provided, and the surface temperature of the roll is adjusted. Is the process of calendering above 200 ° C.
なお、前記ロールの表面層の材料、カレンダー処理の条件などは、上述した通りで ある。  The material for the surface layer of the roll and the conditions for the calendar treatment are as described above.
[0039] —表面サイズ処理工程—  [0039] —Surface size treatment process—
前記表面サイズ処理工程は、カレンダー処理する前に、原紙表面に水溶性金属塩 を含有する液を塗布する工程である。これにより、画像記録材料用支持体に必要な 帯電防止機能を付与することができる。 The surface sizing process is carried out by applying a water-soluble metal salt on the surface of the base paper before calendering. It is the process of apply | coating the liquid containing this. Thereby, a necessary antistatic function can be imparted to the image recording material support.
前記帯電防止剤としての水溶性金属塩は、特に制限はなぐ 目的に応じて適宜選 択することができ、例えば、塩ィ匕カルシウム、塩化ナトリウム、塩化マグネシウム、など が挙げられる。 前記塗布方法としては、特に制限はなぐ 目的に応じて適宜選択することができ、 例えば、刷毛塗り、ロールコーター、ダイコーター、カーテンコーター、などを用いて 行うことができる。  The water-soluble metal salt as the antistatic agent can be appropriately selected according to the purpose for which there is no particular limitation, and examples thereof include calcium chloride, sodium chloride, magnesium chloride and the like. The application method is not particularly limited and can be appropriately selected according to the purpose. For example, the coating method can be performed using a brush, a roll coater, a die coater, a curtain coater, or the like.
[0040] 一熱可塑性樹脂層形成工程一  [0040] One thermoplastic resin layer forming step
前記熱可塑性樹脂層形成工程は、カレンダー処理後の原紙の少なくとも一方の面 に熱可塑性樹脂層を形成する工程である。  The thermoplastic resin layer forming step is a step of forming a thermoplastic resin layer on at least one surface of the base paper after the calendar process.
前記熱可塑性樹脂層の形成方法としては、特に制限はなぐ 目的に応じて適宜選 択することができ、通常ラミネート法、逐次ラミネート法、又はフィートブロックタイプ、 マルチマ二ホールドタイプ、マルチスロットタイプ等の単層若しくは多層押出ダイ、ラミ ネーター等によるラミネート法のいずれかの方法により熱可塑性樹脂層を被覆するこ とにより、形成される。  The method of forming the thermoplastic resin layer is not particularly limited and can be appropriately selected according to the purpose, such as a normal laminating method, a sequential laminating method, a foot block type, a multi-hold type, a multi-slot type, or the like. It is formed by coating the thermoplastic resin layer by either a single layer or multilayer extrusion die, a laminating method using a laminator or the like.
前記単層若しくは多層押出用ダイの形状としては、特に制限はなぐ 目的に応じて 適宜選択することができ、例えば、 Tダイ、コートハンガーダイ等が好適に挙げられる 。前記熱可塑性樹脂層の被覆速度は、 100〜600m/分が好ましい。  The shape of the single-layer or multi-layer extrusion die is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include a T die and a coat hanger die. The coating speed of the thermoplastic resin layer is preferably 100 to 600 m / min.
なお、前記熱可塑性樹脂層を形成する前に、前記原紙に、コロナ放電処理、火炎 処理、グロ一放電処理、又はプラズマ処理などの活性化処理を施すことが好ましい。  Before forming the thermoplastic resin layer, the base paper is preferably subjected to activation treatment such as corona discharge treatment, flame treatment, glow discharge treatment, or plasma treatment.
[0041] 本発明の画像記録材料用支持体の製造方法によれば、小孔 (微小な凹み）の発生 が少なぐ平滑性に優れた本発明の前記画像記録材料用支持体を効率良ぐしかも 低コストに製造することができる。 [0041] According to the method for producing a support for an image recording material of the present invention, the support for an image recording material of the present invention having excellent smoothness with few small holes (microscopic dents) is efficiently obtained. Moreover, it can be manufactured at a low cost.
以上のようにして製造された本発明の画像記録材料用支持体は、以下に説明する 電子写真材料、感熱材料、昇華転写材料、熱転写材料、熱現像材料、銀塩写真材 料、インクジェット記録材料などに好適に用いることができる。  The support for an image recording material of the present invention produced as described above includes an electrophotographic material, a heat sensitive material, a sublimation transfer material, a thermal transfer material, a heat developing material, a silver salt photographic material, and an ink jet recording material described below. It can use suitably for.
[0042] (画像記録材料） 本発明の画像記録材料は、前記画像記録材料用支持体上に、画像記録層を少な くとも有してなり、更に必要に応じてその他の層を有してなる。 [0042] (Image recording material) The image recording material of the present invention comprises at least an image recording layer on the support for image recording material, and further comprises other layers as necessary.
[0043] —画像記録層  [0043] —Image recording layer
前記画像記録層は、画像記録材料の用途、種類に応じてそれぞれ異なり、例えば 、電子写真材料ではトナー受像層、感熱材料では熱発色層、昇華転写材料では熱 拡散性色素、熱転写材料では熱溶融性インク、銀塩写真材料では少なくとも Y (イエ ロー）、 M (マゼンタ）、 C (シアン)等の各色素に発色する画像形成層、インクジェット 記録材料では水性又は油性インクを受容できる色材受容層、などが挙げられる。  The image recording layer differs depending on the use and type of the image recording material.For example, a toner image receiving layer for electrophotographic materials, a thermochromic layer for heat sensitive materials, a heat diffusible dye for sublimation transfer materials, and a heat melting material for thermal transfer materials. Ink-based inks, silver halide photographic materials, image forming layers that develop colors on at least Y (yellow), M (magenta), C (cyan), etc., and ink-jet recording materials that can accept water-based or oil-based inks , Etc.
[0044] 前記画像記録層としては、特に制限はなぐ 目的に応じて適宜選択することができ るが、樹脂塗工層が好適に挙げられ、必要に応じて、前記樹脂塗工層にその他の成 分を含有してなる。  [0044] The image recording layer is not particularly limited and can be appropriately selected depending on the purpose, but a resin coating layer is preferably used. If necessary, other components may be added to the resin coating layer. It contains ingredients.
[0045] 前記樹脂塗工層におけるポリマーとしては、樹脂組成物を含有した塗布液を調製 できるものであれば特に制限はなぐ 目的に応じて適宜選択することができる力 熱 可塑性樹脂が好適である。該熱可塑性樹脂としては、 （1)ポリオレフイン系樹脂、 （2) ポリスチレン系樹脂、（3)アクリル系樹脂、（4)ポリ酢酸ビニル又はその誘導体、（5) ポリアミド系樹脂、 （6)ポリエステル樹脂、（7)ポリカーボネート樹脂、 （8)ポリエーテル 樹脂（又はァセタール樹脂）、（9)その他の樹脂、などが挙げられる。これら熱可塑性 樹脂は、 1種単独で使用してもよいし、 2種以上を併用しても構わない。  [0045] The polymer in the resin coating layer is not particularly limited as long as a coating liquid containing a resin composition can be prepared. A thermoplastic resin that can be appropriately selected according to the purpose is suitable. . The thermoplastic resin includes (1) a polyolefin resin, (2) a polystyrene resin, (3) an acrylic resin, (4) polyvinyl acetate or a derivative thereof, (5) a polyamide resin, and (6) a polyester resin. (7) Polycarbonate resin, (8) Polyether resin (or acetal resin), (9) Other resins, and the like. These thermoplastic resins may be used alone or in combination of two or more.
[0046] 前記（1)のポリオレフイン系樹脂としては、例えば、ポリエチレン、ポリプロピレン等 のポリオレフイン樹脂、エチレン、プロピレン等のォレフィンと他のビニルモノマーとの 共重合樹脂、などが挙げられる。ォレフィンと他のビエルモノマーとの共重合樹脂とし ては、例えば、エチレン—酢酸ビュル共重合体、アクリル酸ゃメタクリル酸との共重合 体であるアイオノマー樹脂などが挙げられる。なお、ポリオレフイン樹脂の誘導体とし ては、塩素化ポリエチレン、クロルスルホン化ポリエチレンなどが挙げられる。  [0046] Examples of the polyolefin resin (1) include polyolefin resins such as polyethylene and polypropylene, and copolymers of olefins such as ethylene and propylene with other vinyl monomers. Examples of the copolymer resin of olefin and other vinyl monomers include an ethylene-butyl acetate copolymer and an ionomer resin which is a copolymer of acrylic acid and methacrylic acid. Examples of the polyolefin resin derivative include chlorinated polyethylene and chlorosulfonated polyethylene.
前記（2)のポリスチレン系樹脂としては、例えば、ポリスチレン樹脂、スチレン一イソ ブチレン共重合体、アクリロニトリル—スチレン共重合体 (AS樹脂）、アクリロニトリル —ブタジエン—スチレン共重合体 (ABS樹脂）、ポリスチレン—無水マレイン酸樹脂 などが挙げられる。 前記（3)のアクリル系樹脂としては、例えば、ポリアクリル酸又はそのエステル類、ポ リメタアクリル酸又はそのエステル類、ポリアクリロニトリル、ポリアクリルアミドなどが挙 げられる。前記ポリアクリル酸エステル類及びポリメタアクリル酸エステル類はエステ ル基の種類により特性が大きく異なる。また、他のモノマー（例えばアクリル酸、メタク リル酸、スチレン、酢酸ビュル等）との共重合体も挙げられる。前記ポリアクリロニトリル は単独重合物としてよりも上記 AS樹脂、 ABS樹脂の共重合体として用いることが多 レ、。 Examples of the (2) polystyrene resin include polystyrene resin, styrene-isobutylene copolymer, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polystyrene— And maleic anhydride resin. Examples of the acrylic resin (3) include polyacrylic acid or its esters, polymethacrylic acid or its esters, polyacrylonitrile, polyacrylamide and the like. The properties of the polyacrylates and polymethacrylates vary greatly depending on the type of ester group. Moreover, the copolymer with other monomers (For example, acrylic acid, methacrylic acid, styrene, a butyl acetate etc.) is also mentioned. The polyacrylonitrile is often used as a copolymer of the above AS resin and ABS resin rather than as a homopolymer.
前記 (4)のポリ酢酸ビュル又はその誘導体としては、例えば、ポリ酢酸ビュル、ポリ 酢酸ビュルをケン化することにより得られるポリビュルアルコール、ポリビュルアルコ ールをアルデヒド（例えば、ホノレムァノレデヒド、ァセトアルデヒド、ブチルアルデヒド等） と反応させて得られるポリビュルァセタール樹脂などが挙げられる。  Examples of the polyacetic acid butyl or its derivative (4) include, for example, poly (vinyl acetate), poly (butyl alcohol) obtained by saponifying poly (vinyl acetate), and poly (butyl alcohol) aldehydes (for example, honolemanolaldehyde). , Acetoaldehyde, butyraldehyde, etc.) and the like.
前記（5)のポリアミド系樹脂はジァミンと二塩基酸との重縮合体であり、 6—ナイロン The polyamide-based resin (5) is a polycondensate of diamine and dibasic acid, and 6-nylon
、 6,6—ナイロンなどが挙げられる。 6,6-Nylon and the like.
前記（6)のポリエステル樹脂は、アルコールと酸の重縮合体であり、各々の組み合 わせにより特性が大きく異なる。芳香族系二塩基酸と二価アルコールからなる汎用樹 脂ポリエチレンテレフタレート、ポリブチレンテレフタレートなどが挙げられる。  The polyester resin (6) is a polycondensate of alcohol and acid, and the characteristics differ greatly depending on the combination. Examples include general-purpose resin polyethylene terephthalate and polybutylene terephthalate composed of an aromatic dibasic acid and a dihydric alcohol.
前記（7)のポリカーボネート樹脂としては、ビスフエノール Aとホスゲンから得られる ポリ炭酸エステルが一般的である。  The polycarbonate resin (7) is generally a polycarbonate obtained from bisphenol A and phosgene.
前記（8)のポリエーテル樹脂（又はァセタール樹脂）としては、例えば、ポリエチレン オキサイド、ポリプロピレンオキサイド等のポリエーテル樹脂、開環重合系としてポリオ キシメチレン等のァセタール樹脂などが挙げられる。  Examples of the polyether resin (or acetal resin) of (8) include polyether resins such as polyethylene oxide and polypropylene oxide, and acetal resins such as polyoxymethylene as the ring-opening polymerization system.
前記（9)のその他樹脂として重付加系のポリウレタン樹脂などが挙げられる。  Examples of the other resin (9) include polyaddition polyurethane resins.
[水系ポリマー] [Water-based polymer]
前記樹脂塗工層としては、以下の理由により、水分散性ポリマー、水溶性ポリマー 等の水系ポリマーを用いて形成されることが好ましい。即ち、前記水系ポリマーは、塗 布乾燥工程での有機溶剤の排出がなぐ環境適性、作業性に優れ、また、後述する 画像記録層、特にトナー受像層に配合される離型剤等の溶媒として好適であり、また 、該離型剤が前記樹脂塗工層の塗布乾燥工程で表面にブリーデイングし易ぐ離型 剤の効果を得やすぐ更に、水分散形態の方が安定でかつ製造適性に優れる。 The resin coating layer is preferably formed using an aqueous polymer such as a water-dispersible polymer or a water-soluble polymer for the following reasons. That is, the water-based polymer is excellent in environmental suitability and workability in which the organic solvent is not discharged in the coating drying process, and is used as a solvent for a release agent or the like to be blended in an image recording layer, particularly a toner image receiving layer described later. In addition, the mold release agent can be easily released on the surface in the step of applying and drying the resin coating layer. As soon as the effect of the agent is obtained, the water dispersion form is more stable and more suitable for production.
[0048] 前記水系ポリマーとしては、以下の理由により、自己分散型水系ポリエステルエマ ノレジョン、又は水分散アクリル樹脂がより好ましい。即ち、前記自己分散型水系ポリェ ステルエマルジヨン、又は水分散アクリル樹脂は、界面活性剤を使用しない自己分散 型なので高湿雰囲気でも吸湿性が低ぐ水分による軟ィヒ点低下が少なぐ前記樹脂 塗工層の定着時のオフセット発生や、保存時のシート間接着誇張等の発生を抑制で き、更に、凝集エネルギーが高い分子構造をとりやすいポリエステル樹脂を用いてい るので、保存環境では十分な硬度を有しながら、前記画像記録層としてトナー受像 層を用いた電子写真の定着工程では低弾性 (低粘性)の溶融状態となり、トナーが受 像層に埋め込まれて十分な高画質が達成可能である。  [0048] The water-based polymer is more preferably a self-dispersing water-based polyester emulsion or a water-dispersed acrylic resin for the following reasons. That is, the self-dispersing water-based polyester emulsion or the water-dispersing acrylic resin is a self-dispersing type that does not use a surfactant, so that the resin has a low softness point decrease due to moisture that has low hygroscopicity even in a high humidity atmosphere. It is possible to suppress the occurrence of offset during fixing of the coating layer, exaggeration of adhesion between sheets during storage, etc.Furthermore, since it uses a polyester resin that has a high cohesive energy and a molecular structure, it is sufficient in a storage environment. In the electrophotographic fixing process using a toner image-receiving layer as the image recording layer, it has a low elasticity (low viscosity) in a molten state, and the toner is embedded in the image-receiving layer, so that sufficient image quality can be achieved. It is.
[0049] 前記水系ポリマーは、その組成、結合構造、分子構造、分子量、分子量分布、形態 を特定するものではなレ、。前記水系の熱可塑性樹脂の水系化基の例としては、スル ホン酸基、水酸基、カルボン酸基、アミノ基、アミド基、エーテル基などが挙げられる。  [0049] The water-based polymer is not intended to specify its composition, bond structure, molecular structure, molecular weight, molecular weight distribution, and morphology. Examples of the water-based group of the water-based thermoplastic resin include a sulfonic acid group, a hydroxyl group, a carboxylic acid group, an amino group, an amide group, and an ether group.
[0050] 水分散性ポリマーとしては、水分散アクリル樹脂、水分散ポリエステル樹脂、水分散 ポリスチレン系樹脂、水分散ウレタン樹脂等の水分散型樹脂；アクリル樹脂ェマルジ ヨン、ポリ酢酸ビニルェマルジヨン、 SBR (スチレン 'ブタジエン 'ゴム）ェマルジヨン等 の水分散性ェマルジヨン;エステル結合を有する樹脂、ポリウレタン樹脂、ポリアミド榭 脂、ポリスルホン樹脂、ポリ塩化ビニル樹脂、ポリビニルブチラール、ポリ力プロラクト ン樹脂、ポリオレフイン樹脂等の熱可塑性樹脂を水分散した樹脂ゃェマルジヨン;こ れらの共重合体、混合物、又はカチオン変性のものの中力 適宜選択し、 2種以上を 組み合わせることができる。  [0050] Water-dispersible polymers include water-dispersed resins such as water-dispersed acrylic resins, water-dispersed polyester resins, water-dispersed polystyrene resins, and water-dispersed urethane resins; acrylic resin emulsion, polyvinyl acetate emulsion, SBR (Styrene 'Butadiene' rubber) Water dispersible emulsion such as emulsion; heat of resin having ester bond, polyurethane resin, polyamide resin, polysulfone resin, polyvinyl chloride resin, polyvinyl butyral, poly strength prolacton resin, polyolefin resin, etc. A resin in which a plastic resin is dispersed in water; a copolymer, a mixture, or a cation-modified intermediate force is appropriately selected, and two or more kinds can be combined.
[0051] 前記水分散性ェマルジヨンとしては、特に制限はなぐ 目的に応じて適宜選択する ことができる力 例えば、水分散性ポリウレタンェマルジヨン、水分散性ポリエステルエ  [0051] The water-dispersible emulsion is not particularly limited and can be appropriately selected according to the purpose. For example, water-dispersible polyurethane emulsion, water-dispersible polyester emulsion
、ポリエチレン系ェマルジヨン、酢酸ビュル系ェマルジヨン、エチレン—酢酸ビュル系 ェマルジヨン、塩化ビニリデン系ェマルジヨン、メチルメタタリレート一ブタジエン系ェ マルジヨン、などが挙げられる。これらの中でも水分散性ポリエステルェマルジヨンが より好ましい。 , Polyethylene-based emulsion, acetate-based emulsion, ethylene-acetate-based emulsion, vinylidene chloride-based emulsion, methylmethacrylate-butadiene Marjiyon, etc. Among these, water dispersible polyester emulsion is more preferable.
前記水分散性ポリマーの市販品としては、例えば、ポリエステル系では東洋紡績株 式会社製バイロナールシリーズや、高松油脂社製ぺスレジン Aシリーズ、花王社製タ フトン UEシリーズ、 日本合成社ポリエスター WRシリーズ、ュニチカ製エリエールシリ ーズ、アクリル系では星光化学工業社製ハイロス XE、 KE、 PEシリーズ、 日本純薬社 製ジユリマー ETシリーズ等が挙げられる。  Commercially available water-dispersible polymers include, for example, Toyobo Co., Ltd. Bironal series, Takamatsu Yushi Co., Ltd. Pes Resin A series, Kao Corporation Tofton UE series, Nippon Gosei Co., Ltd. Polyester WR. For the series, uni-erica erière series, and acrylic-based high-loss XE, KE, PE series manufactured by Seiko Chemical Industry Co., Ltd., and Juririmer ET series manufactured by Nippon Seiyaku Co., Ltd. are listed.
[0052] 水溶性ポリマーとしては、特に制限はなぐ 目的に応じて適宜選択することができ、 例えば、ポリビュルアルコール、カルボキシ変性ポリビュルアルコール、カルボキシメ チノレセノレロース、ヒドロキシェチノレセノレロース、セノレロースサノレフェート、ポリエチレン オキサイド、ゼラチン、カチオン化澱粉、カゼイン、ポリアクリル酸ナトリウム、スチレン —無水マレイン酸共重合体ナトリウム塩、ポリスチレンスルホン酸ナトリウム、などが挙 げられる力 S、これらの中でも、ポリエチレンオキサイドが好ましい。 [0052] The water-soluble polymer is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include polybulal alcohol, carboxy-modified polybulal alcohol, carboxymethylenosenorose, hydroxyethinoresenololose, Selellose sanoleate, polyethylene oxide, gelatin, cationized starch, casein, sodium polyacrylate, styrene-maleic anhydride copolymer sodium salt, sodium polystyrene sulfonate, etc. Polyethylene oxide is preferred.
[0053] また、前記水溶性ポリマーとして、リサーチ 'ディスクロージャー 17, 643号の 26頁、 同 18, 716号の 651頁、同 307, 105号の 873〜874頁、特開昭 64— 13546号公 報の（71)頁〜（75)頁に記載されたものが挙げられる。 [0053] Further, as the water-soluble polymer, Research 'Disclosure 17, 643, page 26, 18, 716, page 651, 307, 105, pages 873 to 874, JP-A-64-13546 Those described in pages (71) to (75) of the report.
具体的には、例えば、ビニルピロリドン 酢酸ビニル共重合体、スチレンービニルビ 口リドン共重合体、スチレン 無水マレイン酸共重合体、水溶性ポリエステル、水溶 性アクリル、水溶性ポリウレタン、水溶性ナイロン、水溶性エポキシ樹脂を使用するこ とができ、また、ゼラチンとして、種々の目的に応じて石灰処理ゼラチン、酸処理ゼラ チン、カルシウム等の含有量を減らした所謂脱灰ゼラチン力 選択でき、それらを組 み合わせて用いることも好ましレ、。  Specifically, for example, vinylpyrrolidone vinyl acetate copolymer, styrene-vinyl vinylidone copolymer, styrene maleic anhydride copolymer, water-soluble polyester, water-soluble acrylic, water-soluble polyurethane, water-soluble nylon, water-soluble As the gelatin, so-called demineralized gelatin with reduced content of lime-processed gelatin, acid-processed gelatin, calcium, etc. can be selected according to various purposes. It ’s also good to use them together.
前記水溶性ポリエステルの市販品として、例えば、瓦応化学工業 (株)製の各種プ ラスコート；大日本インキ化学工業社製ファインテックス ESシリーズ;水溶性アクリルと して日本純薬社製ジユリマー ATシリーズ;大日本インキ化学工業社製ファインテック ス 6161、 K— 96 ;星光化学工業社製ハイロス NL_ 1189、 BH— 997L等が挙げら れる。  Commercially available products of the water-soluble polyester include, for example, various types of plastic coats manufactured by Tateo Chemical Industry Co., Ltd .; Finetex ES series manufactured by Dainippon Ink & Chemicals, Inc .; ; Finetex 6161, K-96 manufactured by Dainippon Ink & Chemicals, Inc .; High loss NL — 1189, BH-997L manufactured by Seiko Chemical Co., Ltd., and the like.
[0054] 前記樹脂塗工層における前記水系ポリマーの含有量としては、特に制限はなぐ 目 的に応じて適宜選択することができ、例えば、前記樹脂塗工層の質量に基づいて、 2[0054] The content of the water-based polymer in the resin coating layer is not particularly limited. For example, based on the mass of the resin coating layer, 2
0質量％以上が好ましぐ 30〜： 100質量％がより好ましい。 0% by mass or more is preferable 30-: 100% by mass is more preferable.
[0055] なお、前記樹脂塗工層用の前記熱可塑性樹脂としては、特開平 5— 127413号公 報、特開平 8— 194394号公報、同 8— 334915号公報、同 8_ 334916号公報、同[0055] The thermoplastic resin for the resin coating layer is disclosed in JP-A-5-127413, JP-A-8-194394, JP-A-8-334915, JP-A-8_334916,
9— 171265号公報、同 10— 221877号公報等に開示されている物性等を満足する ものが好ましく用いられる。 Those satisfying the physical properties disclosed in 9-171265, 10-221877 and the like are preferably used.
[0056] 前記樹脂塗工層に含有する前記その他の成分としては、前記樹脂塗工層の機能 を害さない限り、架橋剤、 UV硬化剤、 EB硬ィヒ斉 1J、可塑剤、滑り剤、離型剤、着色剤[0056] As the other components contained in the resin coating layer, as long as the function of the resin coating layer is not impaired, a crosslinking agent, a UV curing agent, an EB curing agent 1J, a plasticizer, a slipping agent, Release agent, coloring agent
、フィラー、帯電制御剤、乳化剤、分散剤等の添加剤などを任意に配合することがで きる。 In addition, additives such as fillers, charge control agents, emulsifiers, and dispersants can be arbitrarily blended.
[0057] 一電子写真材料一  [0057] One electrophotographic material
前記電子写真材料は、前記支持体上に、少なくとも、前記画像記録層としてのトナ 一受像層を有してなり、必要に応じて、適宜選択したその他の層を有する。また、こ れらの各層は単層構造であってもよいし、積層構造であってもよい。  The electrophotographic material has at least a toner image-receiving layer as the image recording layer on the support, and other layers appropriately selected as necessary. Each of these layers may have a single layer structure or a laminated structure.
[0058] [トナー受像層] [0058] [Toner image-receiving layer]
前記トナー受像層は、カラートナーや黒トナーを受容し、画像を形成するための層 である。該トナー受像層は、画像形成装置における転写工程において、（静)電気、 圧力等にて現像ドラム或いは中間転写体より画像を形成するトナーを受容し、定着 工程にて熱、圧力等にて固定化する機能を有する。  The toner image receiving layer is a layer for receiving color toner and black toner and forming an image. The toner image-receiving layer receives toner that forms an image from a developing drum or an intermediate transfer body by (static) electricity, pressure, etc. in a transfer process in an image forming apparatus, and is fixed by heat, pressure, etc. in a fixing process. Has the function of
[0059] 前記トナー受像層の光透過率としては、前記電子写真材料を写真に近い感触とす る点で、 78%以下が好ましぐ 73%以下がより好ましぐ 72%以下が更に好ましい。 ここで、前記光透過率は、別途ポリエチレンテレフタレートフィルム（100 x m)上に 厚みの同じ塗布膜を形成し、その塗布膜について、直読ヘイズメーター (スガ試験機 社製、 HGM— 2DP)を用いて測定することができる。 [0059] The light transmittance of the toner image-receiving layer is preferably 78% or less, more preferably 73% or less, and even more preferably 72% or less, in terms of making the electrophotographic material feel like a photograph. . Here, the light transmittance is obtained by separately forming a coating film having the same thickness on a polyethylene terephthalate film (100 xm), and using the direct reading haze meter (HGM-2DP, manufactured by Suga Test Instruments Co., Ltd.). Can be measured.
[0060] 前記トナー受像層の定着温度における画像形成装置の定着部材との 180度剥離 強さは、 0. lN/25mm以下が好ましぐ 0. 041N/25mm以下がより好ましレ、。こ こで、前記 180度剥離強さは、定着部材の表面素材を用い、 JIS K6887に記載の 方法に準拠して測定することができる。 前記トナー受像層は白色度が高いことが好ましい。該白色度としては、 JIS P 81 23に規定される方法で測定して、 85%以上が好ましい。また、 440nm〜640nmの 波長域で、分光反射率が 85%以上、かつ同波長域の最大分光反射率と最低分光 反射率の差は 5%以内が好ましい。更には、 400nm〜700nmの波長域で分光反射 率は 85%以上が好ましぐかつ同波長域の最大分光反射率と最低分光反射率の差 は 5%以内がより好ましい。 [0060] The 180 degree peel strength from the fixing member of the image forming apparatus at the fixing temperature of the toner image-receiving layer is preferably 0.1 lN / 25 mm or less, more preferably 0.041 N / 25 mm or less. Here, the 180 degree peel strength can be measured according to the method described in JIS K6887 using the surface material of the fixing member. The toner image receiving layer preferably has high whiteness. The whiteness is preferably 85% or more as measured by the method defined in JIS P 8123. Further, in the wavelength range of 440 nm to 640 nm, the spectral reflectance is preferably 85% or more, and the difference between the maximum spectral reflectance and the minimum spectral reflectance in the same wavelength range is preferably within 5%. Furthermore, the spectral reflectance is preferably 85% or more in the wavelength range of 400 nm to 700 nm, and the difference between the maximum spectral reflectance and the minimum spectral reflectance in the same wavelength region is more preferably within 5%.
前記トナー受像層の前記白色度としては、具体的には、 CIE 1976 (L*a*b*)色 空間において、 L*値は 80以上が好ましぐ 85以上がより好ましぐ 90以上が更に好 ましレ、。また、前記白色の色味はできるだけニュートラルであるのが好ましい。 白色色 味としては、 L*a*b*空間において、 (a*) 2+ (b*) 2の値は 50以下が好ましく、 18以 下がより好ましぐ 5以下が更に好ましい。 As the whiteness of the toner image-receiving layer, specifically, in the CIE 1976 (L * a * b *) color space, the L * value is preferably 80 or more, more preferably 85 or more, and more preferably 90 or more. Even better. The white color is preferably as neutral as possible. As the white color, in the L * a * b * space, the value of (a *) 2 + (b *) 2 is preferably 50 or less, more preferably 18 or less, and even more preferably 5 or less.
[0061] 前記トナー受像層は、画像形成後の光沢性が高いことが好ましい。該光沢度として は、トナーが無い白色から最大濃度の黒色までの全領域において、 45度光沢度は 6 0以上、 110以下が好ましぐ下限値については、 75以上がより好ましぐ 90以上が 更に好ましい。 [0061] The toner image-receiving layer preferably has high gloss after image formation. As for the glossiness, in all areas from white without toner to black with the maximum density, 45 degree glossiness is preferably 60 or more and 110 or less, and 75 or more is more preferable than 90 or more. Is more preferable.
[0062] 前記光沢度が 110を超えると金属光沢のようになり画質として好ましくない。ここで、 前記光沢度は、例えば JIS Z 8741に基づいて測定することができる。  [0062] When the glossiness exceeds 110, it becomes a metallic luster, which is not preferable for image quality. Here, the glossiness can be measured based on, for example, JIS Z 8741.
[0063] 前記トナー受像層は、定着後に平滑性が高いことが好ましい。該平滑度としては、ト ナ一が無い白色から最大濃度の黒色までの全領域において、算術平均粗さ（Ra)は 3 /i m以下が好ましぐ 1 μ ΐη以下がより好ましぐ 0. 5 /i m以下が更に好ましい。ここ で、前記算術平均粗さは、 JIS B 0601、 B 0651、 B 0652に基づいて測定する こと力 Sできる。  [0063] The toner image-receiving layer preferably has high smoothness after fixing. As the smoothness, the arithmetic average roughness (Ra) is preferably 3 / im or less and more preferably 1 μΐη or less in the entire region from white without toner to black having the maximum density. 5 / im or less is more preferable. Here, the arithmetic average roughness can be measured based on JIS B 0601, B 0651, B 0652.
[0064] 前記トナー受像層は、以下の項目における 1項目の物性を有するのが好ましぐ複 数の項目の物性を有するのがより好ましぐ全ての項目の物性を有するのが更に好ま しい。  [0064] It is further preferable that the toner image-receiving layer has physical properties of all items more preferably having physical properties of a plurality of items, preferably having physical properties of one item in the following items. .
(1)トナー受像層の Tm (溶融温度）は 30°C以上が好ましぐトナーの Tm+ 20°C以 下が好ましい。  (1) Tm (melting temperature) of the toner image-receiving layer is preferably 30 ° C or higher, and Tm + 20 ° C or lower is preferable.
(2)トナー受像層の粘度が 1 X 105cpになる温度は、 40°C以上が好ましぐトナーの それより低いことが好ましい。 (2) The temperature at which the viscosity of the toner image-receiving layer becomes 1 X 10 5 cp is preferably 40 ° C or higher. Lower than that is preferable.
(3)トナー受像層の定着温度における貯蔵弾性率 (G' )力 1 X 102〜1 X 105Pa、 損失弾性率（G")力 1 X 102〜1 X 105Paが好ましい。 (3) storage elastic modulus at a fixing temperature of the toner image layer (G ') force 1 X 10 2 ~1 X 10 5 Pa, the loss modulus (G ") forces 1 X 10 2 ~1 X 10 5 Pa is preferable.
(4)トナー受像層の定着温度における損失弾性率 (G")と、貯蔵弾性率 (G' )との比 である損失正接（G"ZG' )は、 0. 01〜： 10が好ましい。  (4) The loss tangent (G "ZG '), which is the ratio between the loss elastic modulus (G") at the fixing temperature of the toner image-receiving layer and the storage elastic modulus (G'), is preferably from 0.01 to 10:
(5)トナー受像層の定着温度における貯蔵弾性率 (G' )が、トナーの定着温度にお ける貯蔵弾性率（G' )に対して、― 50〜 + 2500が好ましレ、。  (5) The storage elastic modulus (G ′) at the fixing temperature of the toner image-receiving layer is preferably −50 to +2500 with respect to the storage elastic modulus (G ′) at the fixing temperature of the toner.
(6)溶融トナーのトナー受像層上の傾斜角が、 50度以下が好ましぐ 40度以下がよ り好ましい。  (6) The inclination angle of the molten toner on the toner image-receiving layer is preferably 50 ° or less, more preferably 40 ° or less.
また、トナー受像層としては、特許第 2788358号公報、特開平 7_ 248637号公 報、特開平 8— 305067号公報、特開平 10— 239889号公報等に開示されている 物性等を満足するものが好ましい。  The toner image-receiving layer satisfies the physical properties disclosed in Japanese Patent No. 2788358, Japanese Unexamined Patent Publication No. 7-248637, Japanese Unexamined Patent Publication No. 8-305067, Japanese Unexamined Patent Publication No. 10-239889, etc. preferable.
[0065] 前記トナー受像層としては、 1 106〜1 10150 /(：1112の範囲（25° 65%RHの 条件にて）の表面電気抵抗を有するのが好ましい。 [0065] As the toner image-receiving layer is preferably 1 10 6-1 10 15 0 / (: 111 preferably has a surface electric resistance of the second range (at 25 ° 65% RH conditions).
[0066] 前記表面抵抗が 1 X 106 Q /cm2未満であると、トナー受像層にトナーが転写され る際のトナー量が充分でなぐ得られるトナー画像の濃度が低くなり易いことがある。 一方、表面電気抵抗が、 l X 1015 Q /cm2を超えると、転写時に必要以上の電荷が 発生し、トナーが充分に転写されず、画像の濃度が低ぐ電子写真用受像シートの取 り扱い中に静電気を帯びて塵埃が付着し易くなる。また、複写時にミスフィード、重送 、放電マーク、トナー転写ヌケ等が発生することがある。 [0066] If the surface resistance is less than 1 X 10 6 Q / cm 2 , the toner image may have a low toner density when the toner is transferred to the toner image-receiving layer, and the resulting toner image density tends to be low. . On the other hand, if the surface electrical resistance exceeds l X 10 15 Q / cm 2 , an excessive charge is generated during transfer, the toner is not sufficiently transferred, and the image receiving sheet for electrophotography with low image density is obtained. During handling, it becomes static and dust is likely to adhere. Misfeeds, double feeds, discharge marks, toner transfer missing, etc. may occur during copying.
ここで、前記表面電気抵抗は、例えば JIS K 6911に準拠し、サンプルを温度 20 °C、湿度 65%の環境下に 8時間以上調湿し、同じ環境下で、アドバンテスト (株)製 R 8340を使用し、印加電圧 100Vの条件で、通電して 1分間経過した後に測定するこ とができる。  Here, the surface electrical resistance is based on, for example, JIS K 6911, the sample is conditioned at a temperature of 20 ° C. and a humidity of 65% for 8 hours or more, and in the same environment, R 8340 manufactured by Advantest Corporation. , And can be measured after 1 minute of energization under the condition of an applied voltage of 100V.
[0067] 前記トナー受像層は、前記樹脂塗工層であることが好ましい。前記トナー受像層と しての前記樹脂塗工層には、トナー受像層用ポリマーを少なくとも含有し、必要に応 じてその他の成分を含有する。  [0067] The toner image-receiving layer is preferably the resin coating layer. The resin coating layer as the toner image-receiving layer contains at least a polymer for toner image-receiving layer and, if necessary, other components.
[0068] <トナー受像層用ポリマー > 前記トナー受像層用ポリマーは、前記トナー受像層を形成した状態で前記トナー受 像層の上記各物性を満足できるものであれば、前記ポリマーを 2種以上併用して上 記各物性を満足するものでもよぐポリマー単独で前述のトナー受像層の物性を満足 できるあのでちょり。 <Polymer for toner image-receiving layer> The polymer for the toner image-receiving layer satisfies the above-mentioned physical properties by using two or more kinds of the polymers in combination as long as the above-mentioned properties of the toner-image-receiving layer can be satisfied in the state where the toner image-receiving layer is formed. A single polymer can satisfy the physical properties of the toner image-receiving layer described above.
[0069] また、前記トナー受像層用ポリマーは、トナーに用いられている熱可塑性樹脂に比 ベて分子量が大きいものが好ましい。ただし、該分子量はトナーに用いられている前 記熱可塑性樹脂と、前記トナー受像層用ポリマーとの熱力学的特性の関係によって は、必ずしも前述の分子量の関係が好ましいとは限らなレ、。例えば、トナーに用いら れている熱可塑性樹脂より、前記トナー受像層用ポリマーの軟化温度の方が高い場 合、分子量は同等か、前記トナー受像層に用レ、られている樹脂の方が小さいことが 好ましい場合がある。  [0069] The toner image-receiving layer polymer preferably has a molecular weight larger than that of the thermoplastic resin used in the toner. However, the molecular weight is not always preferred depending on the relationship of the thermodynamic properties of the thermoplastic resin used in the toner and the toner image-receiving layer polymer. For example, when the softening temperature of the polymer for the toner image receiving layer is higher than that of the thermoplastic resin used for the toner, the molecular weight is the same or the resin used for the toner image receiving layer is the same. Smallness may be preferable.
[0070] また、前記トナー受像層用ポリマーは、同一組成の樹脂であって互いに平均分子 量が異なるものを混合して用いることが好ましい。なお、トナーに用いられている熱可 塑性榭脂の分子量との関係としては、特開平 8— 334915号公報に開示されている 関係が好ましい。更に、前記トナー受像層用ポリマーの分子量分布は、前記トナーに 用いられている熱可塑性樹脂の分子量分布よりも広いものが好ましい。なお、前記ト ナー受像層用ポリマーとしては、特開平 5— 127413号公報、特開平 8— 194394号 公報、特開平 8- 334915号公報、特開平 8 - 334916号公報、特開平 9— 17126 5号公報、特開平 10— 221877号公報等に開示されている物性、などを満足するも のが好ましい。  [0070] The toner image-receiving layer polymer is preferably a mixture of resins having the same composition but different average molecular weights. As the relationship with the molecular weight of the thermoplastic resin used in the toner, the relationship disclosed in JP-A-8-334915 is preferable. Further, the molecular weight distribution of the polymer for the toner image-receiving layer is preferably wider than the molecular weight distribution of the thermoplastic resin used in the toner. Examples of the toner image-receiving layer polymer include JP-A-5-127413, JP-A-8-194394, JP-A-8-334915, JP-A-8-334916, and JP-A-9-171265. It is preferable to satisfy the physical properties disclosed in Japanese Patent Laid-Open No. 10-221877 and the like.
[0071] 前記トナー受像層用ポリマーは、後述する中間層用ポリマーに対して、以下の特性  [0071] The toner image-receiving layer polymer has the following characteristics with respect to the later-described intermediate layer polymer.
(1)〜（5)を有することが好ましレ、。  (1) to (5) preferred to have.
(1)トナー受像層用ポリマーの軟化温度 (Ts)が、後述する中間層用ポリマーのそれ よりも、 10°C以上、特に好ましくは、 20°C以上高い。このように軟ィ匕温度を調整するこ とにより、光沢性をコントロールすることができる。なお、軟化温度の測定は、例えば、 JIS K 7210に規定される方法によって行うことができる。  (1) The softening temperature (Ts) of the polymer for the toner image-receiving layer is 10 ° C. or higher, particularly preferably 20 ° C. or higher, than that of the polymer for the intermediate layer described later. The glossiness can be controlled by adjusting the softening temperature in this way. The softening temperature can be measured, for example, by the method specified in JIS K 7210.
(2)トナー受像層用ポリマーの T1Z2 (1Z2法軟ィ匕点）が、後述する中間層用ポリマ 一のそれよりも、 10°C以上、特に好ましくは、 20°C以上高い。このように 1/2法軟化 点を調整することにより、光沢性をコントロールすることができる。 (2) The T1Z2 (1Z2 method soft spot) of the toner image-receiving polymer is 10 ° C. or more, particularly preferably 20 ° C. or more, higher than that of the intermediate layer polymer described later. Thus 1/2 method softening The gloss can be controlled by adjusting the points.
(3)トナー受像層用ポリマーの Tfb (流出開始温度）が、後述する中間層用ポリマー のそれよりも、 10°C以上、特に好ましくは、 20°C以上高い。このように Tfbを調整する ことにより、光沢性をコントロールすることができる。  (3) The Tfb (outflow start temperature) of the polymer for the toner image-receiving layer is 10 ° C or higher, particularly preferably 20 ° C or higher, than that of the polymer for the intermediate layer described later. By adjusting Tfb in this way, glossiness can be controlled.
(4)トナー受像層用ポリマーの定着温度での粘度が、後述する中間層用ポリマーの それよりも、 3倍以上、特に好ましくは、 10倍以上高い。このように粘度を調整すること により、光沢性をコントロールすることができる。  (4) The viscosity at the fixing temperature of the toner image-receiving layer polymer is at least 3 times, particularly preferably at least 10 times higher than that of the intermediate layer polymer described later. The glossiness can be controlled by adjusting the viscosity in this way.
(5)トナー受像層用ポリマーの定着温度における貯蔵弾性率 (G' )が、後述する中間 層用ポリマーのそれよりも、 3倍以上、特に好ましくは、 10倍以上高レ、。このように貯 蔵弾性率 (G' )を調整することにより、光沢性をコントロールすることができる。  (5) The storage elastic modulus (G ′) at the fixing temperature of the toner image-receiving layer polymer is at least 3 times, particularly preferably at least 10 times higher than that of the intermediate layer polymer described later. The glossiness can be controlled by adjusting the storage elastic modulus (G ′) in this way.
(6)トナー受像層用ポリマーの定着温度における損失弾性率 (G")が、後述する中間 層用ポリマーのそれよりも、 3倍以上、特に好ましくは、 10倍以上高レ、。このように損 失弾性率 (G")を調整することにより、光沢性をコントロールすることができる。  (6) The loss elastic modulus (G ") at the fixing temperature of the toner image-receiving layer polymer is at least 3 times, particularly preferably at least 10 times higher than that of the intermediate layer polymer described below. Glossiness can be controlled by adjusting the loss modulus (G ").
更に、トナー受像層用ポリマーの数平均分子量は、後述する中間層用ポリマーの それよりも、 ί列えば、 1000〜： 100000、特に、 1000〜10000/Jヽさレヽこと力 s好ましレヽ。 このように調整することにより、光沢性をコントロールすることができる。  Further, the number average molecular weight of the toner image-receiving layer polymer is 1000 to 100000, more preferably 1000 to 10,000 / J, more preferable than that of the later-described intermediate layer polymer. By adjusting in this way, glossiness can be controlled.
また、トナー受像層用ポリマーの分子量分布は、後述する中間層用ポリマーのそれ よりも、例えば、 0. 2〜5狭いことが好ましい。このように調整することにより、光沢性を コントロールすることができる。  Further, the molecular weight distribution of the toner image-receiving layer polymer is preferably, for example, 0.2 to 5 narrower than that of the later-described intermediate layer polymer. By adjusting in this way, glossiness can be controlled.
[0072] 前記トナー受像層用ポリマーとしては、定着時等の温度条件下で変形可能であり、 トナーを受容し得るものであれば、特に制限はなぐ 目的に応じて適宜選択すること ができるが、トナーのバインダー樹脂と同系の樹脂が好ましい。前記トナー受像層用 ポリマーとしては、前記トナーがポリエステル樹脂、スチレン、スチレン一ブチルアタリ レートなどの共重合樹脂が用いられていることから、例えば、ポリエステル樹脂、スチ レン一アクリル酸エステル共重合体、スチレン一メタクリル酸エステル共重合体などの 熱可塑性樹脂が好適に挙げられる。  [0072] The polymer for the toner image-receiving layer is not particularly limited as long as it can be deformed under temperature conditions such as fixing and can accept the toner, and can be appropriately selected according to the purpose. A resin similar to the binder resin of the toner is preferable. As the polymer for the toner image-receiving layer, since the toner uses a copolymer resin such as polyester resin, styrene, styrene monobutyl acrylate, for example, polyester resin, styrene monoacrylate copolymer, styrene Preferred examples thereof include thermoplastic resins such as monomethacrylate copolymers.
[0073] 前記熱可塑性樹脂の具体例としては、前記画像記録層を形成する前記樹脂塗工 層として例示した、エステル結合を有する樹脂、ポリウレタン樹脂等、ポリアミド樹脂等 、ポリスルホン樹脂等、ポリ塩ィ匕ビニル樹脂等、ポリビニルブチラール等、ポリ力プロラ 外ン樹脂等、ポリオレフイン樹脂等、などが挙げられる。 [0073] Specific examples of the thermoplastic resin include the resin having an ester bond, the polyurethane resin, the polyamide resin, and the like exemplified as the resin coating layer for forming the image recording layer. , Polysulfone resin, polysalt vinyl resin, polyvinyl butyral, etc., polystrength plastic resin, polyolefin resin, etc.
[0074] 前記トナー受像層用ポリマーは、 1種単独で使用してもよいし、 2種以上を併用して もよぐこれらに加えて、これらの混合物、これらの共重合体等も使用することができる  [0074] The toner image-receiving layer polymer may be used singly or in combination of two or more, and in addition to these, a mixture thereof, a copolymer thereof, or the like may also be used. be able to
[0075] 前記トナー受像層用ポリマーとしては、（i)塗布乾燥工程での有機溶剤の排出がな ぐ環境適性、作業適性に優れている。 （ii)ワックス等の離型剤は、室温では溶剤に 溶解し難いものが多ぐ使用に際して予め溶媒 (水、有機溶剤）に分散することが多 レ、。また、水分散形態の方が安定で、かつ、製造工程適性に優れる。更に、水系塗 布の方が塗布乾燥の過程でワックスが表面にブリーデイングし易ぐ離型剤の効果（ 耐オフセット性、耐接着性等）が得やすい。という理由から、水分散性ポリマー及び水 溶性ポリマー等の水系の樹脂が好適に用いられる。 [0075] The toner image-receiving layer polymer (i) is excellent in environmental suitability and work suitability without discharge of an organic solvent in the coating and drying step. (Ii) Many release agents such as wax are difficult to dissolve in a solvent at room temperature, and are often dispersed in a solvent (water, organic solvent) in advance. In addition, the water dispersion form is more stable and more suitable for the manufacturing process. In addition, the water-based coating is more likely to have a release agent effect (offset resistance, adhesion resistance, etc.) that allows the wax to be easily bleached on the surface during coating and drying. For this reason, water-based resins such as water-dispersible polymers and water-soluble polymers are preferably used.
[0076] 前記水系の樹脂としては、水分散性ポリマー及び水溶性ポリマーのいずれかであ れば、その組成、結合構造、分子構造、分子量、分子量分布、形態などについて特 に制限するものではなぐ 目的に応じて適宜選択することができ、前記ポリマーの水 系化基としては、例えば、スルホン酸基、水酸基、カルボン酸基、アミノ基、アミド基、 エーテル基等が挙げられる。  [0076] The water-based resin is not particularly limited in terms of its composition, bond structure, molecular structure, molecular weight, molecular weight distribution, morphology, etc., as long as it is either a water-dispersible polymer or a water-soluble polymer. The polymer can be appropriately selected depending on the purpose, and examples of the water-based group of the polymer include a sulfonic acid group, a hydroxyl group, a carboxylic acid group, an amino group, an amide group, and an ether group.
[0077] 前記水分散性ポリマーとしては、例えば、前記画像記録層の樹脂塗工層における ポリマー（1)〜（9)を水分散した樹脂、ェマルジヨン、これらの共重合体、混合物、及 びカチオン変性物の中から適宜選択し、 2種以上を組み合わせることができる。 前記水分散性ポリマーは、適宜合成したものを使用してもよいし、市販品を使用し てもよレ、。該市販品としては、例えば、ポリエステル系の水分散性ポリマーとしては、 東洋紡績株式会社製のバイロナールシリーズ、高松油脂株式会社製のぺスレジン A シリーズ、花王株式会社製のタフトン UEシリーズ、 日本合成化学工業株式会社製の ポリエスター WRシリーズ、ュニチカ株式会社製のエリエールシリーズ等が挙げられる 。アクリル系の水分散性ポリマーとしては、星光化学工業株式会社製のハイロス XE、 KE、 PEシリーズ、 日本純薬株式会社製のジュリマー ETシリーズ等が挙げられる。  [0077] Examples of the water-dispersible polymer include resins, emulsions, copolymers, mixtures, and cations of the polymers (1) to (9) in the resin-coated layer of the image recording layer dispersed in water. Two or more types can be combined by appropriately selecting from the modified products. As the water-dispersible polymer, an appropriately synthesized polymer or a commercially available product may be used. Examples of the commercially available products include polyester-based water-dispersible polymers such as Toyobo Co., Ltd.'s Bironal series, Takamatsu Yushi Co., Ltd. Pesresin A series, Kao Corporation's Tufton UE series, Nippon Gosei Co., Ltd. Polyester WR series manufactured by Chemical Industry Co., Ltd. Examples of acrylic water-dispersible polymers include Hiros XE, KE, PE series manufactured by Seiko Chemical Industry Co., Ltd. and Jurimer ET series manufactured by Nippon Pure Chemical Co., Ltd.
[0078] 前記水分散性ェマルジヨンとしては、体積平均粒径が 20nm以上であれば特に制 限はなぐ 目的に応じて適宜選択することができ、例えば、水分散性ポリウレタンエマ ノレジョン、水分散性ポリエステルェマルジヨン、クロ口プレン系ェマルジヨン、スチレン ブタジエン系ェマルジヨン、二トリノレーブタジエン系ェマルジヨン、ブタジエン系ェ マルジヨン、塩化ビュル系ェマルジヨン、ビュルピリジン一スチレン一ブタジエン系ェ マルジヨン、ポリブテン系ェマルジヨン、ポリエチレン系ェマルジヨン、酢酸ビニル系ェ マルジヨン、エチレン—酢酸ビュル系ェマルジヨン、塩化ビニリデン系ェマルジヨン、メ チルメタタリレート一ブタジエン系ェマルジヨン等が挙げられる。これらの中でも、水分 散性ポリエステルェマルジヨンが特に好ましい。 [0078] The water-dispersible emulsion is particularly limited if the volume average particle diameter is 20 nm or more. It can be selected appropriately according to the purpose, for example, water-dispersible polyurethane emulsion, water-dispersible polyester emulsion, black-prene emulsion, styrene butadiene emulsion, nitrino butadiene emulsion, butadiene Emulsion, butyl chloride emulsion, butyl pyridine styrene butadiene emulsion, polybutene emulsion, polyethylene emulsion, vinyl acetate emulsion, ethylene-acetate emulsion emulsion, vinylidene chloride emulsion, methyl methacrylate One butadiene type emulsion is exemplified. Among these, a water-dispersible polyester emulsion is particularly preferable.
前記水分散性ポリエステルェマルジヨンとしては、自己分散型水系ポリエステルエ マルジヨンであることが好ましぐこれらの中でも、カルボキシル基含有自己分散型水 系ポリエステル樹脂ェマルジヨンが特に好ましい。ここで、前記自己分散型水系ポリ エステルェマルジヨンとは、乳化剤等を用いることなぐ水系溶媒中に自己分散し得 るポリエステル樹脂を含む水系ェマルジヨンを意味する。また、前記カルボキシル基 含有自己分散型水系ポリエステル樹脂ェマルジヨンとは、親水性基としてカルボキシ ル基を含有し、水系溶媒中に自己分散し得るポリエステル樹脂を含む水系ェマルジ ヨンを意味する。  The water-dispersible polyester emulsion is preferably a self-dispersing water-based polyester emulsion. Among these, a carboxyl group-containing self-dispersing water-based polyester resin emulsion is particularly preferable. Here, the self-dispersing aqueous polyester emulsion means an aqueous emulsion containing a polyester resin that can be self-dispersed in an aqueous solvent without using an emulsifier or the like. The carboxyl group-containing self-dispersing aqueous polyester resin emulsion means an aqueous emulsion containing a polyester resin that contains a carboxyl group as a hydrophilic group and can be self-dispersed in an aqueous solvent.
前記自己分散型の水分散性ポリエステルェマルジヨンとしては、下記（1)〜（4)の 特性を満たすものが好ましい。これは、界面活性剤を使用しない自己分散型なので、 高湿雰囲気でも吸湿性が低ぐ水分による軟化点低下が少なぐ定着時のオフセット 発生、保存時のシート間接着故障の発生を抑制できる。また、水系であるため環境 性、作業性に優れている。更に、凝集エネルギーが高い分子構造をとりやすぃポリエ ステル樹脂を用いているので、保存環境では十分な硬度を有しながら、電子写真の 定着工程では低弾性 (低粘性）の溶融状態となり、トナーが受像層に坦め込まれて十 分な高画質が達成可能となる。  As the self-dispersing water-dispersible polyester emulsion, those satisfying the following characteristics (1) to (4) are preferable. Since this is a self-dispersion type that does not use a surfactant, it can suppress the occurrence of offset at the time of fixing and the occurrence of adhesive failure between sheets during storage, with less decrease in the softening point due to moisture having low hygroscopicity even in a high humidity atmosphere. In addition, it is environmentally friendly and workable because it is water based. In addition, since a polyester resin that has a high molecular energy structure with high cohesive energy is used, it has a sufficient hardness in the storage environment, but it becomes a low elasticity (low viscosity) molten state in the fixing process of electrophotography, and the toner Is carried in the image receiving layer, and sufficient image quality can be achieved.
(1)数平均分子量（Mil) fま、 5000〜10000力 S好ましく、 5000〜7000力より好まし レ、。  (1) Number average molecular weight (Mil) f, 5000 to 10000 force S, preferably 5000 to 7000 force.
(2)分子量分布 (重量平均分子量/数平均分子量)は、 4以下が好ましぐ 3以下が より好ましい。 (3)ガラス転移温度 (Tg)は、 40〜： 100°Cが好ましぐ 50〜80°Cがより好ましい。 (2) The molecular weight distribution (weight average molecular weight / number average molecular weight) is preferably 4 or less, more preferably 3 or less. (3) The glass transition temperature (Tg) is preferably 40 to 100 ° C, more preferably 50 to 80 ° C.
(4)体積平均粒子径 ίま、 20〜200nm力 S好ましく、 40〜： 150nm力 Sより好ましレヽ。 前記水分散性ェマルジヨンの前記トナー受像層における含有量は、 10〜90質量 (4) Volume average particle diameter: 20 to 200 nm force S, preferably 40 to 150 nm force S The content of the water-dispersible emulsion in the toner image-receiving layer is 10 to 90 mass
%が好ましぐ 10〜70質量％がより好ましい。 10 to 70% by mass is more preferable.
[0080] 前記水溶性ポリマーとしては、重量平均分子量 (Mw)が 400,000以下であれば特 に制限はなぐ 目的に応じて適宜選択することができ、適宜合成したものを使用して もよレ、し、市販品を使用してもよぐ例えば、ポリビュルアルコール、カルボキシ変性ポ リビニノレアノレコーノレ、カノレボキシメチノレセノレロース、ヒドロキシェチノレセノレロース、セノレ ロースサルフェート、ポリエチレンオキサイド、ゼラチン、カチオン化澱粉、カゼイン、 ポリアクリル酸ナトリウム、スチレン一無水マレイン酸共重合体ナトリウム、ポリスチレン スルホン酸ナトリウム、等が挙げられる力 これらの中でも、ポリエチレンオキサイドが 好ましい。 [0080] The water-soluble polymer is not particularly limited as long as the weight average molecular weight (Mw) is 400,000 or less, and can be appropriately selected according to the purpose. However, it is also possible to use a commercially available product, for example, polybulu alcohol, carboxy-modified polyvinylinoreconole, canoleboxymethylenoresenorelose, hydroxyethinoresenorelose, senorelose sulfate, polyethylene oxide, gelatin, Forces including cationized starch, casein, sodium polyacrylate, sodium styrene / maleic anhydride copolymer, polystyrene sodium sulfonate, etc. Among these, polyethylene oxide is preferable.
前記水溶性ポリマーの市販品としては、水溶性ポリエステルとして瓦応化学工業株 式会社製の各種プラスコート、大日本インキ化学工業株式会社製のファインテックス ESシリーズ、水溶性アクリルとして日本純薬株式会社製のジュリマー ATシリーズ、大 日本インキ化学工業社製ファインテックス 6161、 K— 96；星光化学工業株式会社製 のハイロス NL— 1189、 BH— 997L等が挙げられる。  Commercially available products of the water-soluble polymer include water-soluble polyesters as various plus coats manufactured by Kairai Chemical Industry Co., Ltd., Finetex ES series manufactured by Dainippon Ink and Chemicals, and Nippon Pure Chemical Co., Ltd. as water-soluble acrylics. Jurimer AT series manufactured by Dainippon Ink & Chemicals, Inc. Finetex 6161, K-96; HIROS NL-1189, BH-997L manufactured by Seiko Chemical Industry Co., Ltd.
また、前記水溶性ポリマーとしては、リサーチ 'ディスクロージャー 17, 643号の 26 頁、リサーチ 'ディスクロージャー 18, 716号の 651頁、リサーチ 'ディスクロージャー 307, 105号の 873〜874頁、及び特開昭 64— 13546号公報に記載されたものが 挙げられる。  Examples of the water-soluble polymer include Research 'Disclosure 17, 643, page 26, Research' Disclosure 18, 716, page 651, Research 'Disclosure 307, 105, pages 873-874, and JP-A 64-. Those described in the 13546 publication.
[0081] 前記水溶性ポリマーの前記トナー受像層における含有量は、特に制限はなぐ 目 的に応じて適宜選択することができ、 0. 5〜2g/m2が好ましい。 [0081] The content of the water-soluble polymer in the toner image-receiving layer can be appropriately selected according to the purpose without particular limitation, and is preferably 0.5 to 2 g / m2.
[0082] 前記熱可塑性樹脂は、他のポリマー材料と併用することもできるが、その場合、他 のポリマー材料よりも、一般に含有量は多くなるように使用される。  [0082] The thermoplastic resin can also be used in combination with other polymer materials, but in that case, the thermoplastic resin is generally used so as to have a higher content than other polymer materials.
[0083] 前記トナー受像層は、前記水分散性ェマルジヨン及び前記水溶性ポリマーの少な くともレ、ずれか一方を単独で使用してもよく、両方を併用してもょレ、。  In the toner image-receiving layer, at least one of the water-dispersible emulsion and the water-soluble polymer may be used alone, or both may be used alone, or both may be used in combination.
[0084] 前記水分散性ェマルジヨン及び前記水溶性ポリマーを併用するトナー受像層用塗 布液における前記水溶性ポリマーの吸着量は 2質量％未満であることが好ましい。 前記水溶性ポリマーの吸着量が、 2質量％を超えると、前記水分散性ェマルジヨン と、前記水溶性ポリマーとを含有する受像層用塗布液に凝集が生じることがある。 前記水溶性ポリマーの吸着量は、前記水分散性ェマルジヨンと、前記水溶性ポリマ 一とを混合 (水分散性ェマルジヨン:水溶性ポリマー = 100 : 17 (質量比） )し、遠心分 離後の上澄み液中に溶解している水溶性ポリマー（ポリエチレンオキサイド）の量を N MRにより定量し、ポリエチレンオキサイドの添加量からポリエチレンオキサイドの吸着 量 (質量％)を求めることができる。なお、前記吸着量が 2〜5質量％の場合には、枯 渴凝集が生じており、前記吸着量が 30質量％以上の場合には吸着又は架橋による 凝集が生じてレヽることを意味する。 [0084] Toner image-receiving layer coating using the water-dispersible emulsion and the water-soluble polymer in combination The adsorption amount of the water-soluble polymer in the cloth liquid is preferably less than 2% by mass. When the adsorption amount of the water-soluble polymer exceeds 2% by mass, the image-receiving layer coating solution containing the water-dispersible emulsion and the water-soluble polymer may be aggregated. The amount of the water-soluble polymer adsorbed is determined by mixing the water-dispersible emulsion with the water-soluble polymer (water-dispersible emulsion: water-soluble polymer = 100: 17 (mass ratio)) and centrifuging the supernatant. The amount of water-soluble polymer (polyethylene oxide) dissolved in the liquid can be quantified by NMR, and the amount of polyethylene oxide adsorbed (mass%) can be determined from the amount of polyethylene oxide added. In addition, when the adsorption amount is 2 to 5% by mass, dry flocculation occurs, and when the adsorption amount is 30% by mass or more, it means that aggregation occurs due to adsorption or crosslinking. .
[0085] 前記水分散性ェマルジヨン及び前記水溶性ポリマーを併用する場合における前記 水分散性ェマルジヨンと前記水溶性ポリマーとの質量比（水分散性ェマルジヨン:水 溶性ポリマー）としては、 1 : 0. 01〜1が好ましぐ 1 : 0. 1〜：!がより好ましい。  [0085] When the water-dispersible emulsion and the water-soluble polymer are used in combination, the mass ratio of the water-dispersible emulsion and the water-soluble polymer (water-dispersible emulsion: water-soluble polymer) is as follows: -1 is preferred 1: 0. 1- :! is more preferred.
[0086] 前記トナー受像層用ポリマーの前記トナー受像層における含有量としては、 10質 量％以上が好ましぐ 30質量％以上がより好ましぐ 50質量％以上が更に好ましぐ 50〜90質量％が特に好ましい。  The content of the toner image-receiving layer polymer in the toner image-receiving layer is preferably 10% by mass or more, more preferably 30% by mass or more, and more preferably 50% by mass or more. Mass% is particularly preferred.
[0087] <その他の成分 >  [0087] <Other ingredients>
前記トナー受像層に含有する前記その他の成分としては、離型剤、可塑剤、着色 剤、フィラー、架橋剤、帯電制御剤、その他の添加剤などが上げられる。  Examples of the other components contained in the toner image-receiving layer include release agents, plasticizers, colorants, fillers, cross-linking agents, charge control agents, and other additives.
[0088] 前記離型剤は、前記トナー受像層のオフセットを防ぐため、前記トナー受像層に配 合される。本発明で使用される離型剤は、定着温度において加熱して融解し、前記ト ナー受像層表面に析出してトナー受像層表面に偏在し、更に、冷却され固化される ことによってトナー受像層表面に離型剤材料の層を形成するものであれば、その種 類は特に限定はなぐ 目的に応じて適宜選択することができる。  [0088] The release agent is combined with the toner image receiving layer in order to prevent offset of the toner image receiving layer. The release agent used in the present invention is heated and melted at the fixing temperature, is deposited on the surface of the toner image receiving layer, is unevenly distributed on the surface of the toner image receiving layer, and is further cooled and solidified to be cooled. As long as the layer of the release agent material is formed on the surface, the type is not particularly limited and can be appropriately selected according to the purpose.
前記離型剤としては、シリコーン化合物、フッ素化合物、ワックス及びマット剤から選 択される少なくとも 1種が挙げられる。  Examples of the release agent include at least one selected from silicone compounds, fluorine compounds, waxes, and matting agents.
[0089] 前記離型剤としては、例えば、幸書房「改訂 ワックスの性質と応用」、 日刊工業新 聞社発行のシリコーンノヽンドブック記載の化合物を用いることができる。また、特公昭 59— 38581号、特公平 4— 32380号、特許第 2838498号、特許第 2949558号、 特開昭 50— 117433号、特開昭 52— 52640号、特開昭 57— 148755号、特開昭 6[0089] As the mold release agent, for example, compounds described in Sekishobo "Revised Wax Properties and Applications", published by Nikkan Kogyo Shimbun Co., Ltd., Silicone Knowbook can be used. In addition, Shoko No. 59-38581, Japanese Patent Publication No. 4-32380, Japanese Patent No. 2838498, Japanese Patent No. 2949558, Japanese Unexamined Patent Publication No. 50-117433, Japanese Unexamined Patent Publication No. 52-52640, Japanese Unexamined Patent Publication No. 57-148755, Japanese Unexamined Patent Publication No. Sho 6
I— 62056号、特開昭 61— 62057号、特開昭 61— 118760号、特開平 2— 42451 号、特開平 3— 41465号、特開平 4— 212175号、特開平 4_ 214570号、特開平 4I-62056, JP 61-62057, JP 61-118760, JP 2-42451, JP 3-41465, JP 4-212175, JP 4-214570, JP Four
— 263267号、特開平 5— 34966号、特開平 5— 119514号、特開平 6— 59502号 、特開平 6— 161150号、特開平 6— 175396号、特開平 6— 219040号、特開平 6— 263267, JP-A-5-34966, JP-A-5-119514, JP-A-6-59502, JP-A-6-161150, JP-A-6-175396, JP-A-6-219040, JP-A-6
— 230600号、特開平 6— 295093号、特開平 7— 36210号、特開平 7— 43940号 、特開平 7— 56387号、特開平 7— 56390号、特開平 7— 64335号、特開平 7— 19 9681号、特開平 7— 223362号、特開平 7— 287413号、特開平 8— 184992号、 特開平 8— 227180号、特開平 8— 248671号、特開平 8— 248799号、特開平 8— 248801号、特開平 8— 278663号、特開平 9— 152739号、特開平 9— 160278号 、特開平 9— 185181号、特開平 9— 319139号、特開平 9— 319143号、特開平 10— 230600, JP-A-6-295093, JP-A-7-36210, JP-A-7-43940, JP-A-7-56387, JP-A-7-56390, JP-A-7-64335, JP-A-7- 19 9681, JP-A-7-223362, JP-A-7-287413, JP-A-8-184992, JP-A-8-227180, JP-A-8-248671, JP-A-8-248799, JP-A-8- 248801, JP-A-8-278663, JP-A-9-152739, JP-A-9-160278, JP-A-9-185181, JP-A-9-319139, JP-A-9-319143, JP-A-10
— 20549号、特開平 10— 48889号、特開平 10— 198069号、特開平 10— 20711 6号、特開平 11— 2917号、特開平 11— 449 号、特開平 11— 65156号、特開平— 20549, JP 10-48889, JP 10-198069, JP 10-20711 6, JP 112917, JP 11-449, JP 11-65156, JP
I I 73049号、特開平 11— 194542号の各公報に記載のトナーに用いられてレ、る シリコーン系化合物、フッ素化合物又はワックス（ただし、天然ワックスを除く）も好まし く用レ、ること力 Sできる。また、これら化合物を複数組み合わせて使用することもできる。 II Used in the toners described in JP-A-1173049 and JP-A-11-194542, silicone compounds, fluorine compounds or waxes (excluding natural waxes) are also preferably used. S can. Further, a plurality of these compounds can be used in combination.
[0090] 前記シリコーン系化合物としては、例えば、シリコーンオイル、シリコーンゴム、シリコ ーン微粒子、シリコーン変性樹脂、反応性シリコーン化合物などが挙げられる。  [0090] Examples of the silicone compound include silicone oil, silicone rubber, silicone fine particles, silicone-modified resin, and reactive silicone compound.
[0091] 前記シリコーンオイルとしては、例えば、無変性シリコーンオイル、ァミノ変性シリコ ーンオイル、カルボキシ変性シリコーンオイル、カルビノール変性シリコーンオイル、 ビュル変性シリコーンオイル、エポキシ変性シリコーンオイル、ポリエーテル変性シリ コーンオイル、シラノール変性シリコーンオイル、メタクリル変性シリコーンオイル、メル カプト変性シリコーンオイル、アルコール変性シリコーンオイル、アルキル変性シリコ 一ンオイル、フッ素変性シリコーンオイルなどが挙げられる。  [0091] Examples of the silicone oil include non-modified silicone oil, amino-modified silicone oil, carboxy-modified silicone oil, carbinol-modified silicone oil, bur-modified silicone oil, epoxy-modified silicone oil, polyether-modified silicone oil, and silanol. Examples include modified silicone oils, methacrylic modified silicone oils, mercapto modified silicone oils, alcohol modified silicone oils, alkyl modified silicone oils, and fluorine modified silicone oils.
前記シリコーン変性樹脂としては、例えば、ォレフィン樹脂、ポリエステル樹脂、ビニ ル樹脂、ポリアミド樹脂、セルロース樹脂、フエノキシ樹脂、塩化ビュル—酢酸ビニノレ 共重合樹脂、ウレタン樹脂、アクリル樹脂、スチレン—アクリル共重合樹脂、又はこれ らの共重合樹脂をシリコーン変性した樹脂等が挙げられる。 Examples of the silicone-modified resin include olefin resin, polyester resin, vinyl resin, polyamide resin, cellulose resin, phenoxy resin, chloro-vinyl acetate copolymer resin, urethane resin, acrylic resin, styrene-acryl copolymer resin, Or this Examples thereof include resins obtained by modifying these copolymer resins with silicone.
[0092] 前記フッ素化合物としては、特に制限はなぐ 目的に応じて適宜選択することができ 、例えば、フッ素オイル、フッ素ゴム、フッ素変性樹脂、フッ素スルホン酸化合物、フ ルォロスルホン酸、フッ素酸化合物又はその塩、無機フッ化物などが挙げられる。  [0092] The fluorine compound is not particularly limited and may be appropriately selected depending on the purpose. For example, fluorine oil, fluorine rubber, fluorine-modified resin, fluorine sulfonic acid compound, fluorosulfonic acid, fluoric acid compound, or a compound thereof Examples thereof include salts and inorganic fluorides.
[0093] 前記ワックスとしては、天然ワックスと合成ワックスに大別することができる。  [0093] The wax can be roughly classified into a natural wax and a synthetic wax.
前記天然ワックスとしては、植物系ワックス、動物系ワックス、鉱物系ワックス及び石 油ワックスから選択される少なくともいずれかが好ましぐこれらの中でも、植物系ヮッ タスが特に好ましい。前記天然ワックスとしては、特に、前記トナー受像層用ポリマー として水系樹脂を用いた場合の相溶性等の点で、水分散型ワックスが好ましい。  Among these natural waxes, plant waxes, animal waxes, mineral waxes and petroleum waxes are preferred. Among these, plant-based nuts are particularly preferred. The natural wax is particularly preferably a water-dispersed wax from the viewpoint of compatibility when a water-based resin is used as the toner image-receiving layer polymer.
[0094] 前記植物系ワックスとしては、特に制限はなぐ公知のものの中から適宜選択するこ とができ、市販品であってもよいし、適宜合成したものであってもよレ、。該植物系ヮッ タスとしては、例えば、カルナバワックス、ヒマシ油、ナタネ油、大豆油、木ろう、綿ろう 、ライスワックス、サトウキビワックス、キャンデリラワックス、ジャパンワックス、ホホバ油 等が挙げられる。  [0094] The plant-based wax can be appropriately selected from known ones that are not particularly limited, and may be a commercially available product or an appropriately synthesized product. Examples of the plant-based potato include carnauba wax, castor oil, rapeseed oil, soybean oil, wood wax, cotton wax, rice wax, sugarcane wax, candelilla wax, Japan wax, jojoba oil and the like.
前記カルナバワックスの市販品としては、例えば、 日本精鱲株式会社製の EMUS TAR— 0413、中京油脂株式会社製のセロゾール 524等が挙げられる。前記ヒマシ 油の市販品としては、伊藤製油株式会社製の精製ヒマシ油等が挙げられる。  Examples of the commercial products of the carnauba wax include EMUS TAR-0413 manufactured by Nippon Seiki Co., Ltd., Cellozol 524 manufactured by Chukyo Yushi Co., Ltd., and the like. Examples of commercially available castor oil include refined castor oil manufactured by Ito Oil Co., Ltd.
これらの中でも、耐オフセット性、耐接着性、通紙性、光沢感が優れ、ひび割れが 生じ難ぐ高画質の画像を形成可能な電子写真用受像シートを提供可能である点で 、融点が 70〜95°Cのカルナバワックスが特に好ましレ、。  Among these, the melting point is 70 in that it can provide an electrophotographic image-receiving sheet that is excellent in offset resistance, adhesion resistance, paper passing property, and glossiness, and can form a high-quality image that does not easily crack. Carnauba wax of ~ 95 ° C is particularly preferred.
[0095] 前記動物系ワックスとしては、特に制限はなぐ公知のものの中から適宜選択するこ とができ、例えば、蜜蠟、ラノリン、鯨蠟、ステ蠟 (鯨油）、羊毛蠟などが挙げられる。 [0095] The animal wax can be appropriately selected from known ones that are not particularly limited, and examples include beeswax, lanolin, whale pod, stew (whale oil), and wool cocoon.
[0096] 前記鉱物系ワックスとしては、特に制限はなぐ公知のものの中から適宜選択するこ とができ、市販品であってもよいし、適宜合成したものであってもよレ、。例えば、モンタ ンワックス、モンタン系エステルワックス、ォゾケライト、セレシン等が挙げられる。 これらの中でも、耐オフセット性、耐接着性、通紙性、光沢感が優れ、ひび割れが 生じ難ぐ高画質の画像を形成可能な電子写真用受像シートを提供可能である点で 、融点が 70〜95°Cのモンタンワックスが特に好ましい。 [0097] 前記石油ワックスとしては、特に制限はなぐ公知のものの中から適宜選択すること ができ、市販品であってもよいし、適宜合成したものであってもよい。例えば、パラフィ ンワックス、マイクロクリスタリンワックス、ペトロラタムなどが挙げられる。 [0096] The mineral wax can be appropriately selected from known ones that are not particularly limited, and may be a commercially available product or an appropriately synthesized product. Examples include montan wax, montan ester wax, ozokerite, and ceresin. Among these, the melting point is 70 in that it can provide an electrophotographic image-receiving sheet that is excellent in offset resistance, adhesion resistance, paper passing property, and glossiness, and can form a high-quality image that does not easily crack. Particularly preferred is a montan wax of ~ 95 ° C. [0097] The petroleum wax can be appropriately selected from known ones that are not particularly limited, and may be a commercially available product or an appropriately synthesized product. For example, paraffin wax, microcrystalline wax, petrolatum and the like can be mentioned.
[0098] 前記天然ワックスの前記トナー受像層における含有量は、 0. ：!〜 4gZm2が好まし く、 0. 2〜2gZm2がより好ましい。 [0098] The content of the natural wax in the toner image-receiving layer is preferably from 0.:! To 4 gZm 2 , and more preferably from 0.2 to 2 gZm 2 .
前記含有量が 0. lgZm2未満であると、耐オフセット性、耐接着性が特に不充分と なることがあり、 4g/m2を超えると、ワックス量が多過ぎ、形成される画像の画質が劣 ること力 sある。 When the content is less than 0.1 lgZm 2 , offset resistance and adhesion resistance may be particularly insufficient. When the content exceeds 4 g / m 2 , the amount of wax is excessive, and the image quality of the formed image is low. but there is inferior Rukoto force s.
[0099] 前記天然ワックスの融点（°C)としては、特に、耐オフセット性、及び、通紙性の点か ら 70〜95oC力 S女子ましく、 75〜90oC力 Sより女子ましレヽ。 [0099] The melting point (° C) of the natural wax is 70 to 95 o C force S girl, especially 75 to 90 o C force S girl from the viewpoint of offset resistance and paper passage. Masle.
[0100] 前記合成ワックスは、合成炭化水素、変性ワックス、水素化ワックス、その他の油脂 系合成ワックスに分類される。これらワックスは、前記トナー受像層の熱可塑性樹脂と して水系の熱可塑性樹脂を用いた場合の相溶性等の点で水分散型ワックスが好まし レ、。 [0100] The synthetic waxes are classified into synthetic hydrocarbons, modified waxes, hydrogenated waxes, and other oil-based synthetic waxes. These waxes are preferably water-dispersed waxes in terms of compatibility when a water-based thermoplastic resin is used as the thermoplastic resin of the toner image-receiving layer.
[0101] 前記合成炭化水素としては、例えば、フィッシャートロプシュワックス、ポリエチレンヮ ッタス、などが挙げられる。  [0101] Examples of the synthetic hydrocarbon include Fischer-Tropsch wax, polyethylene crumbs, and the like.
前記油脂系合成ワックスとしては、例えば、酸アミド化合物（例えばステアリン酸アミ ド等）、酸イミド化合物 (例えば無水フタル酸イミド等）、などが挙げられる。  Examples of the oil-based synthetic wax include acid amide compounds (for example, stearic acid amide) and acid imide compounds (for example, phthalic anhydride imide).
[0102] 前記変性ワックスとしては、特に制限はなぐ 目的に応じて適宜選択することができ 、例えば、ァミン変性ワックス、アクリル酸変性ワックス、フッ素変性ワックス、ォレフィン 変性ワックス、ウレタン型ワックス、アルコール型ワックスなどが挙げられる。  [0102] The modified wax is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include ammine-modified wax, acrylic acid-modified wax, fluorine-modified wax, olefin-modified wax, urethane-type wax, and alcohol-type wax. Etc.
[0103] 前記水素化ワックスとしては、特に制限はなぐ 目的に応じて適宜選択することがで き、例えば、硬化ひまし油、ヒマシ油誘導体、ステアリン酸、ラウリン酸、ミリスチン酸、 パノレミチン酸、ベへニン酸、セバシン酸、ゥンデシレン酸、ヘプチル酸、マレイン酸、 高度マレイン化油、などが挙げられる。  [0103] The hydrogenated wax is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include hydrogenated castor oil, castor oil derivatives, stearic acid, lauric acid, myristic acid, panolemitic acid, and behenine. Acid, sebacic acid, undecylenic acid, heptylic acid, maleic acid, highly maleated oil, and the like.
[0104] 前記マット剤としては、種々の公知のものが挙げられる。マット剤として用いられる固 体粒子は、無機粒子と有機粒子とに分類できる。無機マット剤の材料としては、具体 的には、酸化物（例えば、二酸化ケイ素、酸化チタン、酸化マグネシウム、酸化アルミ 二ゥム）、アルカリ土類金属塩 (例えば、硫酸バリウム、炭酸カルシウム、硫酸マグネシ ゥム）、ハロゲン化銀 (例えば、塩化銀、臭化銀）、ガラスなどが挙げられる。 [0104] Examples of the matting agent include various known ones. Solid particles used as a matting agent can be classified into inorganic particles and organic particles. Specific examples of the material for the inorganic matting agent include oxides (for example, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide). 2), alkaline earth metal salts (eg, barium sulfate, calcium carbonate, magnesium sulfate), silver halides (eg, silver chloride, silver bromide), and glass.
[0105] 前記無機マット剤としては、例えば、***特許第 2529321号、英国特許第 76077 5号、同第 12 72号、米国特許第 1201905号、同第 2192241号、同第; 30536 62号、同第 3062649号、同第; 3257206号、同第 3322555号、同第 3353958号、 同第 3370951号、同第 3411907号、同第 3437484号、同第 3523022号、同第 3 615554号、同第 3635714号、同第 3769020号、同第 4021245号、同第 40295 04号の各明細書に記載されたものが挙げられる。  [0105] Examples of the inorganic matting agent include West German Patent No. 2529321, British Patent No. 760775, No. 1272, U.S. Patent Nos. 1201905, No. 2192241, No .; No. 3062649, No. 3257206, No. 3322555, No. 3353958, No. 3370951, No. 3411907, No. 3437484, No. 3523022, No. 3 615554, No. 3635714 No. 3769020, No. 4021245, No. 4029504, and the like.
[0106] 前記有機マット剤の材料としては、例えば、デンプン、セルロースエステル（例えば 、セノレロースアセテートプロピオネート）、セノレロースエーテノレ（例えば、ェチノレセノレ口 ース)及び合成樹脂が含まれる。合成樹脂は、水不溶性又は水難溶性であることが 好ましレ、。前記水不溶性又は水難溶性の合成樹脂としては、例えば、ポリ（メタ）アタリ ル酸エステル（例えば、ポリアルキル (メタ）アタリレート、ポリアルコキシアルキル (メタ） アタリレート、ポリグリシジル (メタ）アタリレート）、ポリ（メタ）アクリルアミド、ポリビエルェ ステル（例えば、ポリ酢酸ビニル）、ポリアクリロニトリル、ポリオレフイン（例えば、ポリエ チレン）、ポリスチレン、ベンゾグアナミン樹脂、ホルムアルデヒド縮合ポリマー、ェポキ シ榭脂、ポリアミド、ポリカーボネート、フエノール樹脂、ポリビニルカルバゾール、ポリ 塩化ビニリデンなどが挙げられる。なお、以上のポリマーに使用されるモノマーを組 み合わせたコポリマーを用いてもょレ、。  [0106] Examples of the material for the organic matting agent include starch, cellulose ester (for example, senorelose acetate propionate), senorelose etherol (for example, ethinorescenole saccharide), and synthetic resin. The synthetic resin is preferably water-insoluble or poorly water-soluble. Examples of the water-insoluble or poorly water-soluble synthetic resin include, for example, poly (meth) acrylate (eg, polyalkyl (meth) acrylate, polyalkoxyalkyl (meth) acrylate, polyglycidyl (meth) acrylate). , Poly (meth) acrylamide, polyvinyl ester (for example, polyvinyl acetate), polyacrylonitrile, polyolefin (for example, polyethylene), polystyrene, benzoguanamine resin, formaldehyde condensation polymer, epoxy resin, polyamide, polycarbonate, phenol resin, polyvinyl Examples thereof include carbazole and polyvinylidene chloride. Use a copolymer that combines the monomers used in the above polymers.
[0107] 前記コポリマーの場合、少量の親水性の繰り返し単位が含まれていてもよい。親水 性の繰り返し単位を形成するモノマーとしては、例えばアクリル酸、メタクリル酸、 a , β—不飽和ジカルボン酸、ヒドロキシアルキル（メタ）アタリレート、スルホアルキル（メ タ）アタリレート、スチレンスルホン酸などが挙げられる。 [0107] In the case of the copolymer, a small amount of hydrophilic repeating units may be contained. Examples of monomers that form hydrophilic repeating units include acrylic acid, methacrylic acid, a, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, and styrene sulfonate. Can be mentioned.
有機マット剤としては、例えば、英国特許第 1055713号、米国特許第 1939213号 、同第 2221873号、同第 2268662号、同第 2322037号、同第 2376005号、同第 2391181号、同第 2701245号、同第 2992101号、同第 3079257号、同第 3262 782号、同第 3443946号、同第 3516832号、同第 3539344号、同第 3591379号 、同第 3754924号、同第 3767448号の各明糸田書、特開昭 49一 106821号公報、 特開昭 57— 14835号公報に記載されたものが挙げられる。 Examples of organic matting agents include British Patent No. 1055713, U.S. Patent No. 1939213, No. 2221873, No. 2268662, No. 2322037, No. 2376005, No. 2391181, No. 2701245, No. 2992101, No. 3079257, No. 3262 782, No. 3443946, No. 3516832, No. 3539344, No. 3591379, No. 3754924, No. 3767448 , Japanese Patent Laid-Open No. 49-106821, Examples thereof are those described in JP-A-57-14835.
また、 2種類以上の固体粒子を併用してもよい。固体粒子の平均粒径は、：!〜 100 /i mが好ましぐ 4〜30 μ ΐηがより好ましレ、。前記固体粒子の使用量は、 0. 01〜0. 5g/m2が好ましぐ 0. 02〜0. 3g/m2がより好ましい。 Two or more kinds of solid particles may be used in combination. The average particle size of the solid particles is:! -100 / im is preferred, 4-30 μ μη is more preferred. The amount of solid particles, 0. 01~0. 5g / m 2 is preferred instrument 0. 02~0. 3g / m 2 is more preferable.
[0108] 前記離型剤の融点（°C)としては、特に耐オフセット性、及び、通紙性の点で、 70〜 95°Cが好ましぐ 75〜90°Cがより好ましい。 [0108] The melting point (° C) of the release agent is preferably from 70 to 95 ° C, more preferably from 75 to 90 ° C, particularly in terms of offset resistance and paper passing properties.
なお、本発明のトナー受像層に添加される離型剤としては、これらの誘導体、酸化 物、精製品、混合物を用いることもできる。また、これらは、反応性の置換基を有して いてもよい。  As the releasing agent added to the toner image-receiving layer of the present invention, these derivatives, oxides, purified products, and mixtures can also be used. Further, these may have a reactive substituent.
[0109] 前記離型剤の含有量は、前記トナー受像層の質量を基準として 0. 1〜： 10質量％ が好ましぐ 0. 3〜8. 0質量％がより好ましぐ 0. 5〜5. 0質量％が更に好ましい。 前記含有量が 0. 1質量％未満であると、耐オフセット性及び耐接着性が不十分と なることがあり、 10質量％を超えると、離型剤の量が多すぎて形成される画像の画質 が低下することがある。  [0109] The content of the releasing agent is preferably 0.1 to 10% by mass based on the mass of the toner image-receiving layer, and more preferably 0.3 to 8.0% by mass. More preferable is -5.0 mass%. When the content is less than 0.1% by mass, the offset resistance and the adhesion resistance may be insufficient. When the content exceeds 10% by mass, the amount of the release agent is excessively large. May reduce the image quality.
[0110] 可塑剤  [0110] Plasticizer
前記可塑剤としては、特に制限はなぐ公知の樹脂用の可塑剤を目的に応じて適 宜選択することができる。該可塑剤は、前記トナーを定着する時の熱又は圧力によつ て、前記トナー受像層が流動又は柔軟化するのを調整する機能を有する。  As the plasticizer, known plasticizers for resins that are not particularly limited can be appropriately selected according to the purpose. The plasticizer has a function of adjusting the flow or softening of the toner image-receiving layer by heat or pressure when fixing the toner.
前記可塑剤としては、「化学便覧」（日本化学会編、丸善)、「可塑剤 その理論と 応用一」（村井孝一編著、幸書房)、「可塑剤の研究 上」「可塑剤の研究 下」（高分 子化学協会編）、「便覧 ゴム'プラスチック配合薬品」（ラバーダイジェスト社編)等を 参考にして選択することができる。  The plasticizers include “Chemical Handbook” (edited by the Chemical Society of Japan, Maruzen), “Plasticizers Theory and Application 1” (edited by Koichi Murai, Koshobo), “Research on plasticizers”, “Research on plasticizers” "(Polymer Chemical Society)," Handbook Rubber 'Plastic Compounded Chemicals "(Rubber Digest Co., Ltd.), etc.
[0111] 前記可塑剤としては、高沸点有機溶剤や熱溶剤等として記載されているものもある 、例えば、特開昭 59— 83154号、特開昭 59— 178451号、特開昭 59— 178453 号、特開昭 59— 178454号、特開昭 59— 178455号、特開昭 59— 178457号、特 開昭 62— 174754号、特開昭 62— 245253号、特開昭 61— 209444号、特開昭 6 1— 200538号、特開昭 62— 8145号、特開昭 62— 9348号、特開昭 62— 30247 号、特開昭 62— 136646号、特開平 2— 235694号等の各公報に記載されているよ うなエステル類（例えば、フタル酸エステル類、リン酸エステル類、脂肪酸エステル類 、ァビエチン酸エステル類、アジピン酸エステル類、セバシン酸エステル類、ァゼライ ン酸エステル類、安息香酸エステル類、酪酸エステル類、エポキシィヒ脂肪酸エステ ル類、グリコール酸エステル類、プロピオン酸エステル類、トリメリット酸エステル類、ク ェン酸エステル類、スルホン酸エステル類、カルボン酸エステル類、コハク酸エステ ル類、マレイン酸エステル類、フマル酸エステル類、フタル酸エステル類、ステアリン 酸エステル類等）、アミド類 (例えば、脂肪酸アミド類、スルホアミド類等）、エーテル類 、アルコール類、ラタトン類、ポリエチレンォキシ類等の化合物が挙げられる。これら 可塑剤は、樹脂に混合して使用することができる。 [0111] Examples of the plasticizer include those described as high-boiling organic solvents, thermal solvents, and the like. For example, JP-A-59-83154, JP-A-59-178451, JP-A-59-178453 JP, 59-178454, JP 59-178455, JP 59-178457, JP 62-174754, JP 62-245253, JP 61-209444, JP-A 61-200538, JP-A 62-8145, JP-A 62-9348, JP-A 62-30247, JP-A 62-136646, JP-A 2-235694, etc. It is mentioned in the gazette Such esters (e.g., phthalates, phosphates, fatty acid esters, abietic acid esters, adipic acid esters, sebacic acid esters, azelaic acid esters, benzoic acid esters, butyric acid esters, Epoxy fatty acid esters, glycolic acid esters, propionic acid esters, trimellitic acid esters, oxalic acid esters, sulfonic acid esters, carboxylic acid esters, succinic acid esters, maleic acid esters, Compounds such as fumaric acid esters, phthalic acid esters, stearic acid esters, etc.), amides (for example, fatty acid amides, sulfoamides, etc.), ethers, alcohols, latatones, polyethyleneoxys, etc. . These plasticizers can be used by mixing with a resin.
[0112] 更に前記可塑剤としては、比較的低分子量のポリマーを用いることができる。該可 塑剤の分子量としては、可塑化されるべきバインダー樹脂の分子量より低いものが好 ましぐ分子量は 15000以下が好ましぐ 5000以下がより好ましレ、。また、ポリマー可 塑剤の場合、可塑化されるべきバインダー樹脂と同種のポリマーであるのが好ましい 。例えば、ポリエステル樹脂の可塑化には、低分子量のポリエステルが好ましい。更 にオリゴマーも可塑剤として用いることができる。 [0112] Further, as the plasticizer, a polymer having a relatively low molecular weight can be used. The molecular weight of the plasticizer is preferably lower than the molecular weight of the binder resin to be plasticized, and the molecular weight is preferably 15000 or less, more preferably 5000 or less. In the case of a polymer plasticizer, the polymer is preferably the same type as the binder resin to be plasticized. For example, a low molecular weight polyester is preferable for plasticizing a polyester resin. Furthermore, oligomers can also be used as plasticizers.
上記に挙げた化合物以外にも市販品としては、例えば、アデ力サイザ一 PN— 170 、 PN— 1430 (レ、ずれも旭電化工業株式会社製）、 PARAPLEX— G— 25、 G— 30 、 G— 40 (レ、ずれも C. P. HALL社製）、エステルガム 8L— JA、エステノレ R— 95、ぺ ンタリン 4851、 FK115、 4820、 830、 ノレィゾーノレ 28— JA、ヒ。コラスチック A75、ピコ テックス LC、クリスタレックス 3085 (レ、ずれも理化ハーキュレス社製）等が挙げられる  In addition to the compounds listed above, commercially available products include, for example, Ade force Sizer 1 PN-170, PN-1430 (Lesson, manufactured by Asahi Denka Kogyo Co., Ltd.), PARAPLEX-G-25, G-30, G — 40 (Lesson, also manufactured by CP Hall), Ester gum 8L—JA, Estenore R-95, Pentaline 4851, FK115, 4820, 830, Norizonore 28— JA, Hi. Examples include COSLASTIC A75, Picotex LC, Crystallex 3085 (Lesson is also available from Rika Hercules).
[0113] 前記可塑剤は、トナー粒子が前記トナー受像層に埋め込まれる際に生じる応力や 歪み（弾性力や粘性等の物理的な歪み、分子やバインダー主鎖やペンダント部分等 の物質収支による歪みなど）を緩和するために任意に使用することができる。 [0113] The plasticizer contains stress and strain generated when toner particles are embedded in the toner image-receiving layer (physical strain such as elastic force and viscosity, strain due to mass balance of molecules, binder main chain, pendant portion, etc.) Etc.) can be optionally used to relax.
前記可塑剤は、前記トナー受像層中において、ミクロに分散された状態でもよいし、 海島状にミクロに相分離した状態でもよいし、バインダー等の他の成分と充分に混合 溶解した状態でもよい。  The plasticizer may be in a micro-dispersed state in the toner image-receiving layer, in a micro-phase-separated state in a sea-island shape, or in a sufficiently mixed and dissolved state with other components such as a binder. .
前記可塑剤の、前記トナー受像層における含有量は、 0. 001〜90質量％が好ま しく、 0. 1〜60質量％がより好ましぐ：!〜 40質量％が更に好ましい。 The content of the plasticizer in the toner image-receiving layer is preferably 0.001 to 90% by mass. 0.1 to 60% by mass is more preferable:! To 40% by mass is more preferable.
前記可塑剤は、スベリ性 (摩擦力低下による搬送性向上）の調整や、定着部オフセ ット（定着部へのトナーや層の剥離)の改良、カールバランスの調整、帯電調整（トナ ー静電像の形成)等の目的で使用してもよい。  The plasticizer adjusts the smoothness (improves transportability due to reduced frictional force), improves the fixing unit offset (peeling off toner and layers from the fixing unit), adjusts the curl balance, and adjusts the charge (toner static). It may be used for the purpose of forming an image.
[0114] 一着色剤一 [0114] One colorant
前記着色剤としては、特に制限はなぐ 目的に応じて適宜選択することができ、蛍 光増白剤、白色顔料、有色顔料、染料等が挙げられる。  The colorant is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include a fluorescent brightener, a white pigment, a colored pigment, and a dye.
前記蛍光増白剤は、近紫外部に吸収を持ち、 400〜500nmに蛍光を発する公知 の化合物であれば特に制限はなぐ公知のものの中力も適宜選択することができ、例 ば、 K. VeenRataraman編 Ehe Chemistry of Synthetic Dyes V卷 8早 に記載されている化合物などが好適に挙げられる。前記蛍光増白剤としては、市販 品であってもよいし、適宜合成したものであってもよぐ例えば、スチルベン系化合物 、クマリン系化合物、ビフヱニル系化合物、ベンゾォキサゾリン系化合物、ナフタルイ ミド系化合物、ピラゾリン系化合物、カルボスチリル系化合物等が挙げられる。該巿販 品としては、例えばホワイトフルファー PSN、 PHR、 HCS、 PCS, B (いずれも住友化 学株式会社製）、 UVITEX-OB (Ciba— Geigy社製）等が挙げられる。  The optical brightener may be appropriately selected from known compounds that are not particularly limited as long as they are known compounds that absorb in the near ultraviolet region and emit fluorescence at 400 to 500 nm, for example, K. VeenRataraman. Preferable examples include compounds described in Ehe Chemistry of Synthetic Dyes V 卷 8. The fluorescent whitening agent may be a commercially available product, or may be synthesized as appropriate. For example, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazoline compound, a naphthalimide. Compounds, pyrazoline compounds, carbostyryl compounds, and the like. Examples of the commercially available products include white full fur PSN, PHR, HCS, PCS, B (all manufactured by Sumitomo Chemical Co., Ltd.), UVITEX-OB (manufactured by Ciba-Geigy), and the like.
[0115] 前記白色顔料としては、特に制限はなぐ公知のものの中から目的に応じて適宜選 択することができ力 例えば、酸化チタン、炭酸カルシウム等の無機顔料が挙げられ る。 [0115] The white pigment can be appropriately selected according to the purpose from known ones that are not particularly limited. Examples thereof include inorganic pigments such as titanium oxide and calcium carbonate.
[0116] 前記有色顔料としては、特に制限はなぐ公知のものの中から目的に応じて適宜選 択することができ、例えば、特開昭 63— 44653号公報等に記載されている各種顔料 、ァゾ顔料、多環式顔料、縮合多環式顔料、レーキ顔料、カーボンブラック等が挙げ られる。  [0116] The colored pigment can be appropriately selected according to the purpose from known ones that are not particularly limited. For example, the various pigments described in JP-A-63-44653, etc. Zo pigment, polycyclic pigment, condensed polycyclic pigment, lake pigment, carbon black and the like.
前記ァゾ顔料としては、例えば、ァゾレーキ（例えばカーミン 6B、レッド 2B等）、不 溶性ァゾ顔料（例えばモノァゾイェロー、ジスァゾイェロー、ピラゾ口オレンジ、バルカ ンオレンジ等）、縮合ァゾ系顔料（例えばクロモフタルイェロー、クロモフタルレッド）等 が挙げられる。  Examples of the azo pigment include azo lake (for example, Carmine 6B, Red 2B, etc.), insoluble azo pigment (for example, monoazo yellow, disazo yellow, pyrazo mouth orange, balkan orange, etc.), condensed azo pigment (for example, chromophthalate). Yellow, chromophthaled red).
前記多環式顔料としては、例えば、フタロシアニン系顔料では、銅フタロシアニンブ ルー、銅フタロシアニングリーン等が挙げられる。 Examples of the polycyclic pigment include copper phthalocyanine pigments for phthalocyanine pigments. Roux, copper phthalocyanine green and the like.
前記縮合多環式顔料としては、ジォキサジン系顔料 (ジォキサジンバイオレット等） 、イソインドリノン系顔料 (イソインドリノンイェロー等）、スレン系顔料、ペリレン系顔料 、ペリノン系顔料、チォインジゴ系顔料、等が挙げられる。  Examples of the condensed polycyclic pigment include dioxazine pigments (such as dioxazine violet), isoindolinone pigments (such as isoindolinone yellow), selenium pigments, perylene pigments, perinone pigments, thioindigo pigments, Etc.
前記レーキ顔料としては、例えば、マラカイトグリーン、ローダミン B、ローダミン G、ビ タトリアブルー B等が挙げられる。  Examples of the lake pigment include malachite green, rhodamine B, rhodamine G, and vitamin tria blue B.
前記無機顔料としては、例えば、酸化物（例えば、二酸化チタン、ベンガラ等)硫酸 塩 (例えば、沈降性硫酸バリウム等）、炭酸塩 (例えば、沈降性炭酸カルシウム等）、 硅酸塩 (例えば、含水硅酸塩、無水硅酸塩等）、金属粉 (例えば、アルミニウム粉、ブ ロンズ粉、亜鉛末、黄鉛、紺青）、などが挙げられる。これらは、 1種単独で使用しても よぐ 2種以上を併用してもよい。  Examples of the inorganic pigment include oxides (for example, titanium dioxide, bengara, etc.) sulfates (for example, precipitated barium sulfate), carbonates (for example, precipitated calcium carbonate), oxalates (for example, water-containing materials) Succinate, anhydrous succinate, etc.), metal powders (for example, aluminum powder, bronze powder, zinc dust, yellow lead, and bitumen). These may be used alone or in combination of two or more.
[0117] 前記染料としては、特に制限はなぐ公知のものの中から目的に応じて適宜選択す ること力 Sでき、例えば、アントラキノン系化合物、ァゾ系化合物等が挙げられる。これら は、 1種単独で使用してもよぐ 2種以上を併用してもよい。 [0117] The dye can be appropriately selected from known ones without particular limitations according to the purpose, and examples thereof include anthraquinone compounds and azo compounds. These may be used alone or in combination of two or more.
水不溶性染料としては、例えば、建染染料、分散染料、油溶性染料、などが挙げら れる。前記建染染料としては、例えば C. I. Vatヴァイオレット 1、 C. I. Vatヴアイォレ ット 2、 C. I. Vatヴァイオレット 9、 C. I. Vatヴァイオレット 13, C. I. Vatヴァイオレット 21、 C. I. Vatブルー 1、 C. I. Vatブルー 3、 C. I. Vatブルー 4、 C. I. Vatブルー 6 、 C. I. Vatブルー 14、 C. I. Vatブルー 20、 C. I. Vatブルー 35等が挙げられる。 前記分散染料としては、例えば C. I.デイスパーズヴァイオレット 1、 C. I.デイスパー ズヴァイオレット 4、 C. I.デイスパーズヴァイオレット 10、 C. I.デイスパーズブルー 3、 C. I.デイスパーズブルー 7、 C. I.デイスパーズブルー 58等が挙げられる。前記油 溶性染料としては、例えば C. I.ソルベントヴァイオレット 13、 C. I.ソルベントヴアイォ レツ卜 14、 C. I.ソノレべン卜ヴアイ才レツ卜 21、 C. I.ソノレべン卜ヴアイ才レツ卜 27、 C. I. ソルベントブルー 11、 C. I.ソルベントブルー 12、 C. I.ソルベントブルー 25、 C. I. ソルベントブルー 55などが挙げられる。  Examples of water-insoluble dyes include vat dyes, disperse dyes, and oil-soluble dyes. Examples of vat dyes include CI Vat Violet 1, CI Vat Violet 2, CI Vat Violet 9, CI Vat Violet 13, CI Vat Violet 21, CI Vat Blue 1, CI Vat Blue 3, CI Vat Blue 4, CI Vat Blue 6, CI Vat Blue 14, CI Vat Blue 20, CI Vat Blue 35 and the like. Examples of the disperse dye include C. I. Day Spurs Violet 1, C. I. Day Spurs Violet 4, C. I. Day Spurs Violet 10, C. I. Days Spurs Blue 3, C. I. Days Spurs Blue 7, C. I. Days Spurs Blue 58, and the like. Examples of the oil-soluble dyes include CI Solvent Violet 13, CI Solvent Violet 卜 14, CI Sonoren Vuai Age Rez 21, CI Sonoren Vu Eye Age Ret 27, CI Solvent Blue 11, CI Solvent Blue 12, CI Solvent Blue 25, CI Solvent Blue 55, etc.
なお、銀塩写真で用いられているカラードカプラーも好適に使用することができる。  In addition, a colored coupler used in silver salt photography can also be suitably used.
[0118] 前記着色剤の、前記トナー受像層における含有量は、 0. ：!〜 8g/m2が好ましぐ 0 . 5〜5g/m2がより好ましい。 [0118] of the colorant, the content in the toner image-receiving layer, 0.:! ~ 8g / m 2 is preferred instrument 0 5-5 g / m 2 is more preferred.
前記着色剤の含有量が 0. lg/m2未満であると、トナー受像層における光透過率 が高くなることがあり、 8g/m2を超えると、ヒビ割れ、耐接着等の取り扱い性に劣るこ とがある。 When the content of the colorant is less than 0.1 lg / m 2 , the light transmittance in the toner image-receiving layer may be increased. When the content exceeds 8 g / m 2 , handling properties such as cracking and adhesion resistance are improved. May be inferior.
また、前記着色剤の中でも、顔料の添加量は、前記トナー受像層を構成する熱可 塑性樹脂の質量に基づいて 40質量％以下が好ましぐ 30質量％以下がより好ましく 、 20質量％以下が更に好ましい。  Among the colorants, the amount of pigment added is preferably 40% by mass or less, more preferably 30% by mass or less, more preferably 20% by mass or less, based on the mass of the thermoplastic resin constituting the toner image-receiving layer. Is more preferable.
[0119] 前記フイラ一としては、有機又は無機のフィラーが挙げられ、バインダー樹脂用の 補強剤や、充填剤、強化材として公知のものが用いることができる。該フイラ一として は、「便覧 ゴム'プラスチック配合薬品」（ラバーダイジェスト社編）、「新版 プラスチ ック配合剤 基礎と応用」（大成社)、「フイラ一ハンドブック」（大成社)等を参考にして 選択すること力 Sできる。 [0119] Examples of the filler include organic or inorganic fillers, and known reinforcing agents, fillers, and reinforcing materials for binder resins can be used. Refer to “Handbook Rubber 'Plastic Compounding Chemicals” (edited by Rubber Digest Co., Ltd.), “New Plastic Plastic Compounding Basics and Applications” (Taisei), “Fila I Handbook” (Taisei), etc. You can choose S.
また、前記フイラ一としては、無機フィラー又は無機顔料を用いることができる。前記 無機フィラー又は無機顔料としては、例えば、シリカ、アルミナ、二酸化チタン、酸化 亜鉛、酸化ジノレコニゥム、雲母状酸化鉄、鉛白、酸化鉛、酸化コバルト、ストロンチウ ムクロメート、モリブデン系顔料、スメクタイト、酸化マグネシウム、酸化カルシウム、炭 酸カルシウム、ムライト等が挙げられる。これらの中でも、特に、シリカ、アルミナが好ま しい。これらは、 1種単独で使用してもよぐ 2種以上を併用してもよい。また前記フイラ 一としては、粒径の小さいものが好ましい。粒径が大きいと、トナー受像層の表面が 粗面化し易い。  Further, as the filler, an inorganic filler or an inorganic pigment can be used. Examples of the inorganic filler or inorganic pigment include silica, alumina, titanium dioxide, zinc oxide, dinenoconium oxide, mica-like iron oxide, white lead, lead oxide, cobalt oxide, strontium chromate, molybdenum pigment, smectite, magnesium oxide. , Calcium oxide, calcium carbonate, mullite and the like. Of these, silica and alumina are particularly preferable. These may be used alone or in combination of two or more. As the filler, one having a small particle size is preferable. If the particle size is large, the surface of the toner image-receiving layer tends to be roughened.
[0120] 前記シリカには、球状シリカと無定形シリカが含まれる。該シリカは、乾式法、湿式 法又はエア口ゲル法により合成できる。疎水性シリカ粒子の表面を、トリメチルシリノレ 基又はシリコーンで表面処理してもよい。前記シリカとしては、コロイド状シリカが好ま しい。なお、前記シリカは、多孔質であることが好ましい。  [0120] The silica includes spherical silica and amorphous silica. The silica can be synthesized by a dry method, a wet method, or an air-mouth gel method. The surface of the hydrophobic silica particles may be surface-treated with a trimethylsilanol group or silicone. As the silica, colloidal silica is preferable. The silica is preferably porous.
[0121] 前記アルミナには、無水アルミナ及びアルミナ水和物が含まれる。前記無水アルミ ナの結晶型としては、 α、 β、 Ύ、 δ、 Ζ、 η、 θ、 ρ又は％を用いることができ、 無水アルミナよりもアルミナ水和物の方が好ましい。前記アルミナ水和物としては、一 水和物又は三水和物を用いることできる。前記一水和物には、擬ベーマイト、ベーマ イト、ダイァスポアが含まれる。前記三水和物には、ジブサイト、バイャライトが含まれ る。前記アルミナは、多孔質のものが好ましい。 [0121] The alumina includes anhydrous alumina and alumina hydrate. As the crystal form of the anhydrous alumina, α, β, Ύ , δ, 又 は , η, θ, ρ, or% can be used, and alumina hydrate is preferable to anhydrous alumina. As the alumina hydrate, monohydrate or trihydrate can be used. The monohydrate includes pseudo boehmite, boema And diaspore. The trihydrate includes dibsite and bayerite. The alumina is preferably porous.
前記アルミナ水和物は、アルミニウム塩溶液にアンモニアを加えて沈澱させるゾル ゲル法又はアルミン酸アルカリを加水分解する方法により合成できる。前記無水アル ミナは、アルミナ水和物を加熱により脱水することで得ることができる。  The alumina hydrate can be synthesized by a sol-gel method in which ammonia is added to an aluminum salt solution for precipitation or a method in which an alkali aluminate is hydrolyzed. The anhydrous alumina can be obtained by dehydrating alumina hydrate by heating.
[0122] 前記フィラーの添加量は、前記トナー受像層のバインダーの乾燥質量 100質量部 に対し 5〜2000質量部が好ましい。 [0122] The amount of the filler added is preferably 5 to 2000 parts by mass with respect to 100 parts by mass of the dry mass of the binder of the toner image-receiving layer.
[0123] 前記架橋剤は、前記トナー受像層の保存安定性や熱可塑性等を調整するために 配合することができる。該架橋剤としては、反応基としてエポキシ基、イソシァネート基 、アルデヒド基、活性ハロゲン基、活性メチレン基、アセチレン基、その他公知の反応 基を 2個以上分子内に有する化合物が用いられる。 [0123] The cross-linking agent can be blended in order to adjust the storage stability, thermoplasticity, and the like of the toner image-receiving layer. As the crosslinking agent, a compound having two or more epoxy groups, isocyanate groups, aldehyde groups, active halogen groups, active methylene groups, acetylene groups and other known reactive groups in the molecule as reactive groups is used.
前記架橋剤としては、これとは別に、水素結合、イオン結合、配位結合等により結 合を形成することが可能な基を 2個以上有する化合物も用いることができる。  As the cross-linking agent, a compound having two or more groups capable of forming a bond by a hydrogen bond, an ionic bond, a coordinate bond, or the like can be used.
前記架橋剤としては、例えば、樹脂用のカップリング剤、硬化剤、重合剤、重合促 進剤、凝固剤、造膜剤、造膜助剤等として公知の化合物を用いることができる。前記 カップリング剤としては、例えば、クロロシラン類、ビニルシラン類、エポキシシラン類、 アミノシラン類、アルコキシアルミニウムキレート類、チタネートカップリング剤等が挙 げられる他、「便覧 ゴム'プラスチック配合薬品」（ラバーダイジェスト社編)等に挙げ られた公知のものを用いることができる。  As the crosslinking agent, for example, known compounds can be used as coupling agents for resins, curing agents, polymerization agents, polymerization accelerators, coagulants, film-forming agents, film-forming aids, and the like. Examples of the coupling agent include chlorosilanes, vinyl silanes, epoxy silanes, aminosilanes, alkoxyaluminum chelates, titanate coupling agents, etc., and “Handbook rubber 'plastic compounding chemicals' (Rubber Digest Co., Ltd.). Ed.) Can be used.
[0124] 前記トナー受像層には、トナーの転写や付着等を調整したり、トナー受像層の帯電 接着を防止するために、帯電調整剤を含有させることが好ましい。 [0124] The toner image-receiving layer preferably contains a charge adjusting agent in order to adjust the transfer or adhesion of the toner or prevent the toner image-receiving layer from being charged and adhered.
前記帯電調整剤としては、特に制限はなぐ従来から公知の各種帯電調整剤を目 的に応じて適宜使用することができる。該帯電調整剤としては、特に制限はなぐ 目 的に応じて適宜選択することができ、例えば、カチオン界面活性剤、ァニオン系界面 活性剤、両性界面活性剤、ノニオン系界面活性剤等の界面活性剤等の他、高分子 電解質、導電性金属酸化物等を使用できる。具体的には、第 4級アンモニゥム塩、ポ リアミン誘導体、カチオン変性ポリメチルメタタリレート、カチオン変性ポリスチレン等の カチオン系帯電防止剤、アルキルホスフェート、ァニオン系ポリマー等のァニオン系 帯電防止剤、脂肪酸エステル、ポリエチレンオキサイド等のノニオン系帯電防止剤が 挙げられる。 As the charge control agent, various conventionally known charge control agents without particular limitation can be appropriately used depending on the purpose. The charge adjusting agent can be appropriately selected according to the purpose without particular limitation. For example, a surfactant such as a cationic surfactant, an anionic surfactant, an amphoteric surfactant, or a nonionic surfactant. In addition to agents, polymer electrolytes, conductive metal oxides, and the like can be used. Specifically, cationic antistatic agents such as quaternary ammonium salts, polyamine derivatives, cation-modified polymethyl metatalylate and cation-modified polystyrene, and anion-based materials such as alkyl phosphates and anionic polymers. Nonionic antistatic agents such as antistatic agents, fatty acid esters, polyethylene oxide and the like can be mentioned.
なお、トナーが負電荷を有する場合には、トナー受像層に配合される帯電調整剤と しては、例えば、カチオンゃノニオンが好ましい。  In the case where the toner has a negative charge, for example, cation nonionic is preferable as the charge adjusting agent blended in the toner image receiving layer.
前記導電性金属酸化物としては、例えば、 Zn〇、 Ti〇  Examples of the conductive metal oxide include ZnO, TiO
2、 SnO  2, SnO
2、 Al〇  2, Al〇
2 3、 In O  2 3, In O
2 3、 Si 2 3, Si
〇、 Mg〇、 Ba〇、 MoOなどが挙げられる。これらは、 1種単独で使用しても良ぐ 2Yes, MgO, BaO, MoO, etc. These can be used alone. 2
2 3 twenty three
種以上を併用してもよい。また、前記導電性金属酸化物は、異種元素を更に含有（ド 一ビング）させてもよぐ例えば、 ΖηΟに対して、 Al、 In等、 Ti〇に対して Nb、 Ta等、  More than one species may be used in combination. Further, the conductive metal oxide may further contain (doping) a different element, for example, Al, In, etc. for ΟηΟ, Nb, Ta, etc. for TiO,
2  2
SnOに対しては、 Sb、 Nb、ハロゲン元素等を含有（ドーピング）させることができる。  SnO can contain (doping) Sb, Nb, halogen elements, and the like.
2  2
[0125] —その他の添加剤一  [0125] —Other additives
前記トナー受像層に使用され得る材料には、出力画像の安定性改良や前記トナー 受像層自身の安定性改良のため各種添加剤を含めることができる。前記添加剤とし ては、種々の公知の酸化防止剤、老化防止剤、劣化防止剤、オゾン劣化防止剤、紫 外線吸収剤、金属錯体、光安定剤、防腐剤、防かび剤、等が挙げられる。  The material that can be used for the toner image-receiving layer may contain various additives for improving the stability of the output image and improving the stability of the toner image-receiving layer itself. Examples of the additive include various known antioxidants, anti-aging agents, deterioration inhibitors, ozone deterioration inhibitors, ultraviolet absorbers, metal complexes, light stabilizers, antiseptics, fungicides, and the like. It is done.
[0126] 前記酸化防止剤としては、特に制限はなぐ 目的に応じて適宜選択することができ 、例えば、クロマン化合物、クマラン化合物、フエノール化合物（例、ヒンダードフヱノ ール）、ハイドロキノン誘導体、ヒンダードァミン誘導体、スピロインダン化合物が挙げ られる。なお、前記酸化防止剤については、特開昭 61— 159644号公報等に記載さ れている。  [0126] The antioxidant is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenol), hydroquinone derivatives, hindered amine derivatives, spiroindane. Compounds. The antioxidant is described in JP-A 61-159644.
[0127] 前記老化防止剤としては、特に制限はなぐ 目的に応じて適宜選択することができ 、例えば、「便覧 ゴム'プラスチック配合薬品 改訂第 2版」（1993年、ラバーダイジ エスト社） p76〜121に記載のものが挙げられる。  [0127] The anti-aging agent is not particularly limited and can be appropriately selected depending on the purpose. For example, "Handbook Rubber'Plastic Compounding Chemicals Revised 2nd Edition" (1993, Rubber Digest Corporation) p76-121 The thing of description is mentioned.
[0128] 前記紫外線吸収剤としては、特に制限はなぐ 目的に応じて適宜選択することがで き、例えば、ベンゾトリアゾール化合物（米国特許第 3533794号明細書参照）、 4_ チアゾリドン化合物（米国特許第 3352681号明細書参照）、ベンゾフエノン化合物（ 特開昭 46— 2784号公報参照）、紫外線吸収ポリマー（特開昭 62— 260152号公報 参照）が挙げられる。  [0128] The ultraviolet absorber is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a benzotriazole compound (see US Pat. No. 3,533,794), 4_thiazolidone compound (US Pat. No. 3352681). Benzophenone compounds (see JP-A-46-2784) and UV-absorbing polymers (see JP-A-62-260152).
[0129] 前記金属錯体としては、特に制限はなぐ 目的に応じて適宜選択することができ、 例えば、米国特許第 4241155号、米国特許第 4245018号、米国特許第 4254195 号の各明細書、特開昭 61— 88256号、特開昭 62— 174741号、特開昭 63— 199 248号、特開平 1 75568号、特開平 1— 74272号の各公報に記載されているもの が適当である。 [0129] The metal complex is not particularly limited and can be appropriately selected according to the purpose. For example, U.S. Pat.No. 4,241,155, U.S. Pat.No. 4245018, U.S. Pat.No. 4,254,195, JP-A 61-88256, JP-A 62-174741, JP-A 63-199 248, Those described in the publications of Kaihei 1 75568 and JP-A-1-74272 are suitable.
また、「便覧 ゴム'プラスチック配合薬品 改訂第 2版」（1993年、ラバーダイジヱス ト社) pl 22〜： 137に記載の紫外線吸収剤、光安定剤も好適に使用することができる  In addition, UV absorbers and light stabilizers described in "Handbook Rubber 'Plastic Compounding Chemicals Revised 2nd Edition" (1993, Rubber Dyestone Co.) pl 22 ~: 137 can also be suitably used.
[0130] なお、前記トナー受像層に使用され得る材料には、上述したように公知の写真用添 加剤を必要に応じて添加することができる。前記写真用添加剤としては、例えば、リ サーチ.ディスクロージャー誌（以下、 RDと略記する） Νο.17643 (1978年 12月）、 R DNo. 18716 (1979年 11月）及び RDNo. 307105 (1989年 11月）に記載されて おり、その該当箇所を下記表にまとめて示す。 [0130] As described above, a known photographic additive can be added to the material that can be used for the toner image-receiving layer as necessary. Examples of the photographic additive include, for example, Research Disclosure Journal (hereinafter abbreviated as RD) Νο.17643 (December 1978), R DNo. 18716 (November 1979) and RDNo. 307105 (1989) (November), and the corresponding parts are summarized in the table below.
[0131] [表 1]  [0131] [Table 1]
Figure imgf000039_0001
Figure imgf000039_0001
[0132] 前記トナー受像層は、前記支持体上に、前記トナー受像層用熱可塑性樹脂を含有 する塗工液をワイヤーコーター等で塗布し、乾燥することによって設けられる。本発 明において使用される前記熱可塑性樹脂の成膜温度（MFT)は、プリント前の保存 に対しては、室温以上が好ましぐトナー粒子の定着に対しては 100°C以下が好まし レ、。  [0132] The toner image-receiving layer is provided by applying a coating liquid containing the toner image-receiving layer thermoplastic resin on the support with a wire coater or the like and drying it. The film formation temperature (MFT) of the thermoplastic resin used in the present invention is preferably 100 ° C. or less for fixing toner particles, which is preferably room temperature or more for storage before printing. Les.
[0133] 前記トナー受像層は、乾燥後の塗布質量は、例えば、：!〜 20g/m2が好ましぐ 4 〜15g/m2がより好ましい。 前記トナー受像層の厚みとしては、特に制限はなぐ 目的に応じて適宜選択するこ とができ、例えば、使用されるトナーの粒子径の 1/2以上が好ましぐ 1倍〜 3倍の厚 みがより好ましぐ具体的には、：!〜 50 /i mが好ましぐ：!〜 30 /i mがより好ましぐ 2 〜20 μ mが更に好ましく、 5〜： 15 μ mが特に好ましレヽ。 [0133] The toner image-receiving layer, the coating weight after drying, for example,:! Preferably is ~ 20 g / m 2 instrument 4 to 15 g / m 2 is more preferable. The thickness of the toner image-receiving layer is not particularly limited and can be appropriately selected depending on the purpose. For example, the thickness of the toner used is preferably 1 to 3 times the thickness of the toner particles more than 1/2 of the particle size. More specifically, it is more preferable:! ~ 50 / im is preferable:! ~ 30 / im is more preferable 2 ~ 20 μm is more preferable, 5 ~: 15 μm is particularly preferable Masle.
[0134] 前記電子写真材料に設けられる前記その他の層としては、特に制限はなぐ 目的 に応じて適宜選択することができ、例えば、表面保護層、バック層、密着改良層、タツ シヨン層、中間層、下塗り層、帯電調節（防止)層、反射層、色味調整層、保存性改 良層、接着防止層、アンチカール層、平滑化層などが挙げられる。  [0134] The other layer provided in the electrophotographic material can be appropriately selected according to the purpose without any particular limitation. For example, the surface protective layer, the back layer, the adhesion improving layer, the tacky layer, the intermediate layer, and the like. Examples include a layer, an undercoat layer, a charge control (prevention) layer, a reflection layer, a color adjustment layer, a storage stability improving layer, an adhesion prevention layer, an anti-curl layer, and a smoothing layer.
[0135] <表面保護層 >  [0135] <Surface protective layer>
前記表面保護層は、前記電子写真材料における表面の保護、保存性の改良、取り 扱い性の改良、筆記性の付与、機器通過性の改良、アンチオフセット性の付与等の 目的で、前記トナー受像層の表面に設けることができる。前記表面保護層は、 1層で あってもよいし、 2層以上の層からなっていてもよい。前記表面保護層には、バインダ 一として各種の熱可塑性樹脂、熱硬化性樹脂等を用いることができ、前記トナー受像 層と同種の樹脂を用いるのが好ましい。ただし、熱力学的特性、静電特性等は、前記 トナー受像層と同じである必要はなぐ各々最適化することができる。  The surface protective layer is used for the purpose of protecting the surface of the electrophotographic material, improving storability, improving handleability, imparting writing properties, improving instrument passability, imparting anti-offset properties, etc. It can be provided on the surface of the layer. The surface protective layer may be a single layer or may be composed of two or more layers. Various thermoplastic resins, thermosetting resins, and the like can be used as the binder for the surface protective layer, and it is preferable to use the same type of resin as the toner image receiving layer. However, the thermodynamic characteristics, electrostatic characteristics, etc. can be optimized without having to be the same as that of the toner image-receiving layer.
[0136] 前記表面保護層には、前記トナー受像層に含有するマット剤としての前記粒子を 配合することが好ましい。また、前記トナー受像層に使用可能な、前述の各種の添加 剤を配合することができる。特に、前記表面保護層には、前記マット剤としての前記 粒子と共に、その他の離型剤等を配合することができる。  [0136] The surface protective layer preferably contains the particles as a matting agent contained in the toner image receiving layer. In addition, various additives described above that can be used in the toner image-receiving layer can be blended. In particular, the surface protective layer may contain other release agents and the like together with the particles as the matting agent.
前記電子写真材料における最表面層（例えば、表面保護層が形成されている場合 には、表面保護層等）としては、定着性の点で、トナーとの相溶性が良いのが好まし レ、。具体的には、溶融したトナーとの接触角が、例えば 0〜40度であることが好まし レ、。  The outermost surface layer in the electrophotographic material (for example, the surface protective layer when a surface protective layer is formed) preferably has good compatibility with the toner in terms of fixing properties. . Specifically, the contact angle with the melted toner is preferably 0 to 40 degrees, for example.
[0137] ぐバック層 >  [0137] Gu back layer>
前記バック層は、前記電子写真材料において、裏面出力適性付与、裏面出力画質 改良、カールバランス改良、機器通過性改良等の目的で、前記支持体に対して、前 記トナー受像層の反対側に設けられるのが好ましい。 前記バック層の色としては、特に制限はなレ、が、前記電子写真材料が、裏面にも画 像を形成する両面出力型受像材料の場合、バック層も白色であることが好ましい。 白 色度及び分光反射率は、表面と同様に 85%以上が好ましい。 In the electrophotographic material, the back layer is provided on the opposite side of the toner image-receiving layer from the support for the purpose of imparting back surface output suitability, improving back surface output image quality, improving curl balance, improving device passability, and the like. Preferably it is provided. The color of the back layer is not particularly limited. However, when the electrophotographic material is a double-sided output type image receiving material that forms an image on the back surface, the back layer is preferably white. The whiteness and spectral reflectance are preferably 85% or more as in the case of the surface.
また、両面出力適性改良のため、前記バック層の構成が前記トナー受像層側と同 様であってもよい。前記バック層には、前記トナー受像層に含有するマット剤としての 前記粒子の他、上記で説明した各種の添加剤を用いることができる。このような添カロ 剤として、特に、帯電調整剤等を配合することが適当である。前記バック層は、単層 構成であってもよぐ 2層以上の積層構成であってもよい。  In addition, the back layer may have the same configuration as that of the toner image receiving layer for improving the duplex output suitability. In addition to the particles as the matting agent contained in the toner image-receiving layer, various additives described above can be used for the back layer. In particular, it is appropriate to add a charge adjusting agent or the like as such an additive. The back layer may have a single layer structure or a laminated structure of two or more layers.
また、定着時のオフセット防止のため、定着ローラ等に離型性オイルを用いている 場合、バック層は、オイル吸収性としてもよい。  In order to prevent offset at the time of fixing, when a releasable oil is used for a fixing roller or the like, the back layer may have an oil absorption property.
[0138] <密着改良層 > [0138] <Adhesion improving layer>
前記密着改良層は、前記電子写真材料において、前記支持体及び前記トナー受 像層の密着性を改良する目的で形成するのが好ましい。前記密着改良層には、前 述の各種の添加剤を配合することができ、特に架橋剤を配合するのが好ましい。  The adhesion improving layer is preferably formed for the purpose of improving the adhesion between the support and the toner image receiving layer in the electrophotographic material. The above-mentioned various additives can be blended in the adhesion improving layer, and it is particularly preferable to blend a crosslinking agent.
[0139] ぐクッション層 > [0139] Gush cushion layer>
また、前記電子写真材料には、トナーの受容性を改良するため、前記密着改良層 と前記トナー受像層との間に、クッション層を設けるのが好ましい。  The electrophotographic material is preferably provided with a cushion layer between the adhesion improving layer and the toner image receiving layer in order to improve the acceptability of the toner.
[0140] <中間層 > [0140] <Middle layer>
前記中間層は、例えば、前記支持体と前記密着改良層との間、前記密着改良層と 前記クッション層との間、前記クッション層と前記トナー受像層との間、前記トナー受 像層と前記保存性改良層との間、などに形成することができる。前記支持体、前記ト ナー受像層、及び、前記中間層力 なる電子写真材料の場合には、前記中間層は、 例えば、前記支持体と前記トナー受像層との間に存在させることができる。  The intermediate layer includes, for example, between the support and the adhesion improving layer, between the adhesion improving layer and the cushion layer, between the cushion layer and the toner image receiving layer, and between the toner image receiving layer and the toner receiving layer. It can be formed between the storage stability improving layers. In the case of the electrophotographic material having the support, the toner image-receiving layer, and the intermediate layer force, the intermediate layer can be present, for example, between the support and the toner image-receiving layer.
[0141] 前記中間層は、前記樹脂塗工層であることが好ましい。前記中間層としての前記樹 脂塗工層は、少なくとも中間層用ポリマーを含有し、必要に応じて、各種の成分を含 有してなる。 [0141] The intermediate layer is preferably the resin coating layer. The resin coating layer as the intermediate layer contains at least an intermediate layer polymer, and various components as required.
前記中間層用ポリマーは、前記塗布液として使用するのに適したものであれば、特 に制限はなぐ適宜選択することができ、例えば、上記トナー受像層用ポリマーと同 様の樹脂を用いることができるが、これらの中でも、前記水溶性ポリマー、前記水分 散性ポリマー等が好ましぐ前記自己分散型水系ポリエステルェマルジヨン、水分散 アクリル樹脂がさらに好ましい。前記中間層用ポリマーとしては、特公平 5— 127413 号公報、特開平 8— 194394号公報、同 8— 334915号公報、同 8— 334916号公 報、同 9— 171265号公報、同 10— 221877号公報等に開示されている物性等を満 足するものが好ましく用いられる。前記中間層用ポリマーの前記中間層における含有 量としては、前記中間層の質量に基づいて、 20質量％以上が好ましぐ 30〜： 100質 量％がより好ましい。 The intermediate layer polymer can be appropriately selected without particular limitation as long as it is suitable for use as the coating solution. For example, the intermediate layer polymer may be the same as the toner image receiving layer polymer. Such resins can be used, but among these, the water-soluble polymer, the water-dispersible polymer, etc. are preferred, and the self-dispersing water-based polyester emulsion and water-dispersed acrylic resin are more preferred. Examples of the polymer for the intermediate layer include JP-B-5-127413, JP-A-8-194394, JP-A-8-334915, JP-A-8-334916, JP-A-9-171265, and JP-A-10-221877. Those satisfying the physical properties disclosed in the Gazette and the like are preferably used. The content of the polymer for the intermediate layer in the intermediate layer is preferably 30 to 100% by mass, preferably 20% by mass or more based on the mass of the intermediate layer.
[0142] 前記中間層用ポリマーには、中間層の機能を害さない限り、上記トナー受像層で言 及されるような前記各種の成分を任意に配合することができる。  [0142] In the polymer for the intermediate layer, the various components described in the toner image-receiving layer can be arbitrarily blended as long as the function of the intermediate layer is not impaired.
[0143] 前記中間層は、例えば、中間層用塗布液を調製し、それを塗工することによって調 製される。前記中間層用塗布液の使用によって、比較的簡易に前記中間層を前記 支持体上に調製することができる。また、前記支持体の厚み方向での前記中間層用 ポリマーのしみ込みを行わせることが可能となる。  [0143] The intermediate layer is prepared, for example, by preparing a coating solution for an intermediate layer and coating it. By using the intermediate layer coating solution, the intermediate layer can be prepared on the support relatively easily. Further, the polymer for the intermediate layer can be impregnated in the thickness direction of the support.
[0144] —感熱材料  [0144] —Thermal material
前記感熱材料としては、例えば、本発明の前記画像記録材料用支持体上に、画像 記録層として、少なくとも感熱記録層を設けた構成を有し、感熱ヘッドによる加熱と紫 外線による定着の繰り返しにより画像を形成するサーモオートクローム方式 (TA方式 )において用いられる感熱材料等が挙げられる。  The heat-sensitive material has, for example, a structure in which at least a heat-sensitive recording layer is provided as an image recording layer on the support for image-recording material of the present invention, and heating by a heat-sensitive head and fixing by ultraviolet rays are repeated. Examples thereof include heat-sensitive materials used in a thermoautochrome method (TA method) for forming an image.
[0145] 一昇華転写材料 [0145] One sublimation transfer material
前記昇華転写材料としては、例えば、本発明の前記画像記録材料用支持体上に、 画像記録層として、少なくとも熱拡散性色素 (昇華性色素）を含有するインク層を設け た構成を有し、感熱ヘッドにより加熱してインク層力 熱拡散性色素を昇華転写シー ト上に転写する昇華転写方式などが挙げられる。  The sublimation transfer material has, for example, a configuration in which an ink layer containing at least a heat diffusible dye (sublimation dye) is provided as an image recording layer on the image recording material support of the present invention, Examples include a sublimation transfer method in which the ink layer force is transferred by a thermal head and the heat-diffusible dye is transferred onto the sublimation transfer sheet.
[0146] 一熱転写材料一 [0146] One heat transfer material
前記熱転写材料としては、例えば、本発明の前記画像記録材料用支持体上に、画 像記録層として、少なくとも熱溶融性インク層を設けた構成を有し、感熱ヘッドにより 加熱して熱溶融性インク層力もインクを熱転写シート上に溶融転写する方式などが挙 げられる。 The thermal transfer material has, for example, a configuration in which at least a heat-meltable ink layer is provided as an image recording layer on the image recording material support of the present invention, and is heated and melted by a thermal head. Ink layer strength includes methods such as melting and transferring ink onto a thermal transfer sheet. I can get lost.
[0147] 熱現像材料  [0147] Thermal development material
前記熱現像材料としては、本発明の前記画像記録材料用支持体上に、画像記録 層として、例えば、特開 2002— 40643号公報に記載されているような感光感熱記録 層を設けた構成を有し、焼付露光された熱現像材料を、加熱ローラ、加熱ベルト、プ レートヒーター、サーマルヘッド、レーザー、又はこれらの組み合わせのいずれかを 用いた加熱方式で加熱することにより可視画像を形成することができるものが挙げら れる。  The heat developing material has a structure in which a light and heat sensitive recording layer as described in, for example, JP-A-2002-40643 is provided as an image recording layer on the image recording material support of the present invention. A visible image is formed by heating the heat-developable material that has been printed and exposed by a heating method using a heating roller, a heating belt, a plate heater, a thermal head, a laser, or a combination thereof. What can be used.
また、本発明の前記画像記録材料用支持体上に、画像記録層として、例えば、特 開 2004— 246026号公報に記載されているような熱現像感光層を設けた構成を有 し、焼付露光された熱現像材料を、加熱ローラ、加熱ベルト、プレートヒーター、サー マルヘッド、レーザー、又はこれらの組み合わせのいずれかを用いた加熱方式で加 熱することにより可視画像を形成することができるものが挙げられる。  Further, the image recording material support of the present invention has a structure in which a photothermographic layer as described in, for example, Japanese Patent Application Publication No. 2004-246026 is provided as an image recording layer, and printing exposure is performed. A material capable of forming a visible image by heating the heat-developable material by a heating method using any one of a heating roller, a heating belt, a plate heater, a thermal head, a laser, or a combination thereof. It is done.
[0148] 銀塩写真材料 [0148] Silver salt photographic materials
前記銀塩写真材料としては、例えば、本発明の前記画像記録材料用支持体上に、 画像記録層として、少なくともイェロー (Y)、マゼンタ（M)、及びシアン (C)に発色す る画像記録層を設けた構成を有し、焼付露光されたハロゲン化銀写真用シートを複 数の処理槽内を浸漬しながら通過することにより、発色現像、漂白定着、水洗を行い 、乾燥するハロゲン化銀写真方式、等が挙げられる。  As the silver salt photographic material, for example, on the support for image recording material of the present invention, as an image recording layer, an image recording that develops color at least yellow (Y), magenta (M), and cyan (C). A silver halide photographic sheet having a constitution in which a layer is provided and subjected to baking exposure and passing through a plurality of processing baths while being dipped is subjected to color development, bleach-fixing, washing with water, and drying. Photographic system, etc.
[0149] インクジェット記録材料 [0149] Inkjet recording material
前記インクジェット記録材料としては、例えば、本発明の画像記録材料用支持体上 に、画像記録層として、水性インク（色材として染料又は顔料を用いたもの）及び油性 インク等の液状インクや、常温では固体であり、溶融液状化させて印画に供する固体 状インク等を受容できる前記色材受容層を有する。  Examples of the ink jet recording material include a liquid ink such as a water-based ink (using a dye or a pigment as a color material) and an oil-based ink as an image recording layer on the support for an image recording material of the present invention; Is a solid and has the color material receiving layer capable of receiving solid ink or the like which is melted and liquefied and used for printing.
[0150] 一印刷用紙一 [0150] One printing paper
前記画像記録材料用支持体は、印刷用紙として用いることも好ましい。印刷用紙と して用いる場合には、印刷機械によりインク等を塗布する点から、機械強度が高いも のが好ましい。 前記印刷用紙は、オフセット印刷用紙として特に好適であり、その他にも凸版印刷 用紙、グラビア印刷用紙、電子写真用紙として使用することが可能である。 The image recording material support is also preferably used as printing paper. When used as printing paper, it is preferable to have high mechanical strength from the viewpoint of applying ink or the like by a printing machine. The printing paper is particularly suitable as offset printing paper, and can also be used as relief printing paper, gravure printing paper, and electrophotographic paper.
[0151] 本発明によると、従来における問題を解決することができ、高温でも表面にクラック の発生がなぐ防鲭効果に優れたロールを用いたカレンダー処理を行うことで良好な 平滑性を有する原紙が得られ、該原紙に熱可塑性樹脂層を被覆した後の小孔 (微小 な凹み）の発生が少ない画像記録材料用支持体、及び原紙の表面に熱可塑性樹脂 層を高速被覆することが可能となり、効率よぐ安価に画像記録材料用支持体を製造 する方法を提供することができる。  [0151] According to the present invention, it is possible to solve the conventional problems, and a base paper having good smoothness by performing a calendering process using a roll having an excellent antifungal effect in which cracks are not generated on the surface even at high temperatures. It is possible to obtain a high-speed coating of the thermoplastic resin layer on the surface of the base paper and the support for image recording material with less generation of small holes (minute dents) after the base paper is coated with the thermoplastic resin layer. Thus, it is possible to provide a method for producing a support for an image recording material with efficiency and at low cost.
[0152] 以下、本発明の実施例について説明するが、本発明は下記実施例に何ら限定され るものではない。  [0152] Hereinafter, examples of the present invention will be described. However, the present invention is not limited to the following examples.
[0153] (実施例 1)  [0153] (Example 1)
アカシアからなる LBKPを 50質量部と、アスペンからなる LBKPを 50質量部とをそ れぞれディスクリファイナ一によりカナディアンフリーネス 300mlに叩解し、パルプスラ リーを調製した。  50 parts by mass of LBKP made of acacia and 50 parts by mass of LBKP made of aspen were each beaten to 300 ml of Canadian freeness with a disc refiner to prepare a pulp slurry.
次いで、得られたパルプスラリーに対パルプ当たり、カチオン性デンプン（日本 NS C社製、 CATO304D 1. 3質量0 /0、ァニオン性ポリアクリルアミド（星光化学社製、ポ リアクロン ST— 13) 0· 15質量％、アルキルケテンダイマー（荒川化学社製、サイズ パイン K) 0. 29質量％、エポキシ化べヘン酸アミド 0. 29質量％、及びポリアミドポリ アミンェピクマ一（荒川化学社製、ァラフィックス 100) 0· 32質量0 /0を添加した後、消 泡剤（BASFジャパン社製、アフラニール MG) 0. 12質量0 /0を添カ卩した。 Then, per pulp to the obtained pulp slurry, cationic starch (Nippon NS C Co., CATO304D 1. 3 mass 0/0, Anion polyacrylamide (stars photochemical Co., Po Riakuron ST- 13) 0 · 15 % By weight, alkyl ketene dimer (Arakawa Chemical Co., size pine K) 0.29% by weight, epoxidized behenamide 0.29% by weight, and polyamide polyamine epoxy bear (Arakawa Chemical Co., Ltd., Arafix 100) 0 · after addition of 32 mass 0/0, defoamers (BASF Japan Ltd., Afuraniru MG) a 0.12 mass 0/0 was添Ka卩.
[0154] 次に、調製したパルプスラリーを長網抄紙機で抄紙し、ウエッブのフェルト面をドラム ドライヤーにドライヤーカンバスを介して押し当てて乾燥した。これに、ポリビュルアル コール (株式会社クラレ製、 KL- 118) 5. 0質量％、帯電防止剤としての塩化カルシ ゥム (株式会社トクャマ製) 3. 8質量％、及び蛍光増白剤 (住友化学工業株式会社製 , Whitex BB liquid) 0. 8質量％を水に溶解した溶液をサイズプレスにて両面に 塗布し、乾燥させた。 [0154] Next, the prepared pulp slurry was paper-made with a long paper machine, and the felt surface of the web was pressed against a drum drier via a dryer canvas and dried. In addition, polybulal alcohol (Kuraray Co., Ltd., KL-118) 5.0% by mass, calcium chloride as an antistatic agent (Tokuyama Co., Ltd.) 3.8% by mass, and fluorescent whitening agent (Sumitomo Chemical) Whitex BB liquid (manufactured by Kogyo Co., Ltd.) A solution obtained by dissolving 0.8% by mass in water was applied to both sides with a size press and dried.
[0155] 次に、 SNCM439 (鍛鋼）で作製したロールシェル上にタングステンカーバイト（W C) _コバルト（Co) ( 〇：88質量％、〇0 : 12質量％)の溶射材料を高速フレーム溶 射し、厚み 150 / m、表面粗度 0· 3Sの表面層を有するロールを作製した。 [0155] Next, a thermal spray material of tungsten carbide (WC) _ cobalt (Co) (O: 88 mass%, O0: 12 mass%) was sprayed onto the roll shell made of SNCM439 (forged steel) by high-speed flame melting. A roll having a surface layer with a thickness of 150 / m and a surface roughness of 0 · 3S was produced.
得られたロールを表面温度 350°Cで原紙の画像記録層を設ける側（おもて面）に接 するようにし、一方、原紙の画像記録層を設けない側の面（うら面）には、ショァ一 D硬 度 90° の樹脂製ロールを接するようにして、ソフトカレンダー処理を行った。なお、二 ップ線圧は 120kg/cmであった。以上により、原紙を作製した。ここで、前記ロール の表面粗度は、表面粗さ計 (東京精密社製、サーフコム 120A)で測定した。  The obtained roll was brought into contact with the base paper image recording layer side (front side) at a surface temperature of 350 ° C., while the base paper side not provided with the image recording layer side (back side). Then, soft calendering was performed in such a manner that a resin roll having a Shore D hardness of 90 ° was in contact. The dip linear pressure was 120 kg / cm. Thus, a base paper was prepared. Here, the surface roughness of the roll was measured with a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd., Surfcom 120A).
この実施例 1のタングステンカーバイト（WC)—コバルト被覆金属ロールは、表面層 の厚みが 150 z mと充分であるため、ロール表面に傷が付いた場合でも再度ロール 表面を研磨することでそのまま再使用することができる (研磨可能)。  The tungsten carbide (WC) -cobalt-coated metal roll of Example 1 has a sufficient surface layer thickness of 150 zm. Therefore, even if the roll surface is damaged, it can be re-polished by polishing the roll surface again. Can be used (polishing possible).
[0156] 次に、以下のようにして、ロール表面のクラックの発生、鲭びの発生、原紙表面の変 色、及び耐磨耗性について評価した。結果を表 3に示す。 [0156] Next, the occurrence of cracks on the roll surface, the occurrence of cracks, discoloration of the base paper surface, and abrasion resistance were evaluated as follows. The results are shown in Table 3.
[0157] くロール表面のクラック、剥がれの発生 > [0157] Cracks on the roll surface and occurrence of peeling>
1二ップのソフトカレンダーで 7日間使用後のロール表面のクラック、剥がれの発生 状況を目視観察し、下記基準で評価した。  The occurrence of cracks and peeling on the roll surface after 7 days of use was visually observed with a 1-cup soft calender and evaluated according to the following criteria.
〔評価基準〕  〔Evaluation criteria〕
〇：クラック、剥がれの発生なし  ○: No cracking or peeling
△:クラック、剥がれの発生があるが、実使用上問題にならないレベル X：クラック、剥がれの発生があり、実使用上問題になるレベル  △: Level where cracks and peeling occur but does not cause problems in actual use X: Level where cracks and peeling occur and causes problems in actual use
X X：クラック、剥がれが多発し、実使用不能なレベル  X X: Level where cracks and peeling occur frequently and cannot be used
[0158] <ロール表面の鲭びの発生 > [0158] <Occurrence of rust on roll surface>
1二ップのソフトカレンダーで 7日間使用後のロール表面の鲭びの発生状況を目視 観察し、下記基準で評価した。  Using a 1-cup soft calendar, the occurrence of cracks on the roll surface after 7 days of use was visually observed and evaluated according to the following criteria.
〔評価基準〕  〔Evaluation criteria〕
〇：鲭びの発生なし  ○: No occurrence of pleasure
△：鲭びの発生がある力 実使用上問題にならなレ、レベル  △: Power that generates joy
X：鲭びの発生があり、実使用上問題になるレベル  X: Level of occurrence of joy and a problem in actual use
X X：鲭びが多発し、実使用不能なレベル  X X: Level of joy and frequent use
[0159] <原紙表面の変色 > 得られた原紙表面の変色の有無を目視観察し、下記基準で評価した。 [0159] <Discoloration of base paper surface> The obtained base paper surface was visually observed for discoloration and evaluated according to the following criteria.
〇：変色なし  ○: No discoloration
△：やや変色あり（実使用可能なレベル）  Δ: Slightly discolored (Available level)
X：変色あり（実使用不可能なレベル）  X: Discoloration (level that cannot be used)
[0160] 次に、ソフトカレンダー処理後の原紙を、マシンカレンダーで密度 0. 96gZcm3に 調整して、王研式平滑度を測定したところ、 378秒であった。 Next, the base paper after the soft calender treatment was adjusted to a density of 0.96 gZcm 3 with a machine calender, and the Oken type smoothness was measured, and it was 378 seconds.
[0161] 次に、得られた原紙の両面をコロナ放電処理した後、ラミネーターを用いてポリェチ レンを押し出しコーティングにより、原紙の両面にそれぞれ厚み 28 μ mずつ被覆した 。その際、原紙の画像記録層を設ける側のおもて面ポリエチレン層を形成するラミネ 一ターのクーリングロール表面を鏡面として、おもて面が光沢面である支持体を作製 した。  [0161] Next, both sides of the obtained base paper were subjected to corona discharge treatment, and then polyethylene was extruded using a laminator to coat both sides of the base paper by 28 µm in thickness. At that time, a support having a glossy surface was prepared by using the surface of the laminator cooling roll forming the front polyethylene layer on the side of the base paper on which the image recording layer was provided as a mirror surface.
[0162] 次に、得られた支持体について、以下のようにして、小孔の個数及び電気抵抗を測 定し、総合評価を行った。結果を表 3に示す。  [0162] Next, the obtained support was subjected to comprehensive evaluation by measuring the number of small holes and the electrical resistance as follows. The results are shown in Table 3.
[0163] <小孔の個数の測定 > [0163] <Measurement of the number of small holes>
得られた支持体の光沢面における直径 20〜： 100 μ mの小孔と呼ばれる凹みの単 位面積当たりの個数を万能投影機で測定した（20倍)。なお、 100個 /cm2以内を合 格とした。 On the glossy surface of the obtained support, the number of dents called small holes with a diameter of 20 to 100 μm per unit area was measured with a universal projector (20 times). It should be noted, it was 100 pieces / cm 2 within a slip rating.
[0164] <電気抵抗の測定 > [0164] <Measurement of electrical resistance>
得られた支持体の電気抵抗をタケダ理研社製デジタル超絶縁抵抗計により測定し 、下記基準で評価した。  The electrical resistance of the obtained support was measured with a digital super insulation resistance meter manufactured by Takeda Riken Co., Ltd., and evaluated according to the following criteria.
〇：良好  Y: Good
△:普通（実使用可能レベル）  △: Normal (Available level)
X：不良（実使用不可能レベル）  X: Defect (actually unusable level)
[0165] <耐磨耗性試験 > [0165] <Abrasion resistance test>
ロールスピード lOOmZminで幅 5mmの鉄製ブレードをロール表面に当てて 2kg /cmの荷重をかけて 10時間後の傷の深さを表面粗さ計 (東京精密社製、サーフコ ム 120A)で測定した断面曲線から計測した。  Cross section measured with a surface roughness meter (Tokyo Seimitsu Co., Ltd., Surfcom 120A) with a roll speed of lOOmZmin and a steel blade with a width of 5mm placed on the roll surface and a load of 2kg / cm. Measured from the curve.
[0166] <総合評価 > 以上のすべての評価結果を総合して、下記基準により評価した。 [0166] <Comprehensive evaluation> All the above evaluation results were synthesized and evaluated according to the following criteria.
〇：良好  Y: Good
△:普通 (実使用可能）  △: Normal (Available)
X：不良 (実使用不可能）  X: Defect (cannot be used)
[0167] (実施例 2) [Example 2]
一原紙及び支持体の作製一  Preparation of base paper and support
実施例 1において、表 2に示すようにロールの表面温度を 200°Cに変えてソフトカレ ンダー処理を行った以外は、実施例 1と同様にして、原紙を調製し、該原紙の両面に ポリエチレン樹脂層を形成して、支持体を作製した。  In Example 1, as shown in Table 2, a base paper was prepared in the same manner as in Example 1 except that the roll surface temperature was changed to 200 ° C. and soft calendering was performed, and polyethylene was formed on both sides of the base paper. A resin layer was formed to produce a support.
次に、ロール表面のクラックの発生、ロール表面の鲭びの発生、原紙表面の変色、 研磨の可否、王研式平滑度、小孔の個数、電気抵抗、耐磨耗性、及び総合評価に ついて、実施例 1と同様に評価した。結果を表 3に示す。  Next, for the generation of cracks on the roll surface, the occurrence of cracks on the roll surface, discoloration of the base paper surface, whether or not polishing is possible, Oken smoothness, the number of small holes, electrical resistance, wear resistance, and comprehensive evaluation The evaluation was the same as in Example 1. The results are shown in Table 3.
[0168] (実施例 3) [Example 3]
一原紙及び支持体の作製  Production of base paper and support
実施例 1において、表 2に示すようにロールの表面温度を 250°Cに変えてソフトカレ ンダー処理を行った以外は、実施例 1と同様にして、原紙を調製し、該原紙の両面に ポリエチレン樹脂層を形成して、支持体を作製した。  In Example 1, a base paper was prepared in the same manner as in Example 1 except that the surface temperature of the roll was changed to 250 ° C. and soft calendering was performed as shown in Table 2. Polyethylene on both sides of the base paper was prepared. A resin layer was formed to produce a support.
次に、ロール表面のクラックの発生、ロール表面の鲭びの発生、原紙表面の変色、 研磨の可否、王研式平滑度、小孔の個数、電気抵抗、耐磨耗性、及び総合評価に ついて、実施例 1と同様に評価した。結果を表 3に示す。  Next, for the generation of cracks on the roll surface, the occurrence of cracks on the roll surface, discoloration of the base paper surface, whether or not polishing is possible, Oken smoothness, the number of small holes, electrical resistance, wear resistance, and comprehensive evaluation The evaluation was the same as in Example 1. The results are shown in Table 3.
[0169] (実施例 4) [Example 4]
一原紙及び支持体の作製一  Preparation of base paper and support
実施例 1において、表 2に示すようにタングステンカーバイト (WC) _コバルト（Co) ( 〇：88質量％、 Co : 12質量％)を厚みが 220 z mとなるように被覆し、ロールの表 面温度を 350°Cに変えてソフトカレンダー処理を行った以外は、実施例 1と同様にし て、原紙を調製し、該原紙の両面にポリエチレン樹脂層を形成して、支持体を作製し た。  In Example 1, as shown in Table 2, tungsten carbide (WC) _cobalt (Co) (◯: 88 mass%, Co: 12 mass%) was coated to a thickness of 220 zm, and the roll surface A base paper was prepared in the same manner as in Example 1 except that the surface temperature was changed to 350 ° C., and a polyethylene resin layer was formed on both sides of the base paper. .
次に、ロール表面のクラックの発生、ロール表面の鲭びの発生、原紙表面の変色、 研磨の可否、王研式平滑度、小孔の個数、電気抵抗、耐磨耗性、及び総合評価に ついて、実施例 1と同様に評価した。結果を表 3に示す。 Next, occurrence of cracks on the roll surface, occurrence of cracks on the roll surface, discoloration of the base paper surface, Evaluation was made in the same manner as in Example 1 with respect to whether polishing was possible, the Oken smoothness, the number of small holes, electrical resistance, wear resistance, and comprehensive evaluation. The results are shown in Table 3.
[0170] (実施例 5) [0170] (Example 5)
一原紙及び支持体の作製一  Preparation of base paper and support
実施例 1において、表 2に示すようにタングステンカーバイト (WC) _コバルト（Co) ( 〇：88質量％、 Co : 12質量％)を厚みが 50 z mとなるように被覆し、ロールの表面 温度を 350°Cに変えてソフトカレンダー処理を行った以外は、実施例 1と同様にして 、原紙を調製し、該原紙の両面にポリエチレン樹脂層を形成して、支持体を作製した 次に、ロール表面のクラックの発生、ロール表面の鲭びの発生、原紙表面の変色、 研磨の可否、王研式平滑度、小孔の個数、電気抵抗、耐磨耗性、及び総合評価に ついて、実施例 1と同様に評価した。結果を表 3に示す。  In Example 1, as shown in Table 2, tungsten carbide (WC) _cobalt (Co) (O: 88 mass%, Co: 12 mass%) was coated to a thickness of 50 zm, and the surface of the roll A base paper was prepared in the same manner as in Example 1 except that the temperature was changed to 350 ° C., and a polyethylene resin layer was formed on both sides of the base paper to prepare a support. , Occurrence of cracks on the roll surface, occurrence of cracks on the roll surface, discoloration of the surface of the base paper, whether or not polishing is possible, Oken-type smoothness, number of small holes, electrical resistance, wear resistance, and comprehensive evaluation. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.
[0171] (実施例 6) [Example 6]
一原紙及び支持体の作製  Production of base paper and support
実施例 1において、表 2に示すようにロールの表面温度を 370°Cに変えてソフトカレ ンダー処理を行った以外は、実施例 1と同様にして、原紙を調製し、該原紙の両面に ポリエチレン樹脂層を形成して、支持体を作製した。  In Example 1, as shown in Table 2, a base paper was prepared in the same manner as in Example 1 except that the surface temperature of the roll was changed to 370 ° C. and soft calendering was performed, and polyethylene was formed on both sides of the base paper. A resin layer was formed to produce a support.
次に、ロール表面のクラックの発生、ロール表面の鲭びの発生、原紙表面の変色、 研磨の可否、王研式平滑度、小孔の個数、電気抵抗、耐磨耗性、及び総合評価に ついて、実施例 1と同様に評価した。結果を表 3に示す。  Next, for the generation of cracks on the roll surface, the occurrence of cracks on the roll surface, discoloration of the base paper surface, whether or not polishing is possible, Oken smoothness, the number of small holes, electrical resistance, wear resistance, and comprehensive evaluation The evaluation was the same as in Example 1. The results are shown in Table 3.
[0172] (実施例 7) [Example 7]
一原紙及び支持体の作製一  Preparation of base paper and support
実施例 1において、表 2に示すように表面サイズ液に含まれる帯電防止剤としてァ ルキルトリメチルアンモニゥム塩を 3. 8質量％添加した以外は、実施例 1と同様にして 、原紙を調製し、該原紙の両面にポリエチレン樹脂層を形成し、支持体を作製した。 次に、ロール表面のクラックの発生、ロール表面の鲭びの発生、原紙表面の変色、 研磨の可否、王研式平滑度、小孔の個数、電気抵抗、耐磨耗性、及び総合評価に ついて、実施例 1と同様に評価した。結果を表 3に示す。 [0173] (実施例 8) In Example 1, as shown in Table 2, a base paper was prepared in the same manner as in Example 1 except that 3.8% by mass of alkyltrimethylammonium salt was added as an antistatic agent contained in the surface size liquid. Then, a polyethylene resin layer was formed on both sides of the base paper to prepare a support. Next, for the generation of cracks on the roll surface, the occurrence of cracks on the roll surface, discoloration of the base paper surface, whether or not polishing is possible, Oken smoothness, the number of small holes, electrical resistance, wear resistance, and comprehensive evaluation The evaluation was the same as in Example 1. The results are shown in Table 3. [Example 8]
実施例 1において、表 2に示すように炭化タングステン コバルトを炭化タンダステ ン一コバルトクロムに変え、厚み 150 μ πι、表面粗度 0. 3Sの表面層を形成したロー ルを作製し、該ロールを用いてソフトカレンダー処理した以外は、実施例 1と同様にし て、原紙を調製し、該原紙の両面にポリエチレン樹脂層を形成して、支持体を作製し た。  In Example 1, as shown in Table 2, tungsten carbide / cobalt was changed to tandene / cobalt chromium carbide to prepare a roll having a surface layer with a thickness of 150 μπι and a surface roughness of 0.3S. A base paper was prepared in the same manner as in Example 1 except that it was soft calendered and a polyethylene resin layer was formed on both sides of the base paper to produce a support.
次に、ロール表面のクラックの発生、ロール表面の鲭びの発生、原紙表面の変色、 研磨の可否、王研式平滑度、小孔の個数、電気抵抗、耐磨耗性、及び総合評価に ついて、実施例 1と同様に評価した。結果を表 3に示す。  Next, for the generation of cracks on the roll surface, the occurrence of cracks on the roll surface, discoloration of the base paper surface, whether or not polishing is possible, Oken smoothness, the number of small holes, electrical resistance, wear resistance, and comprehensive evaluation The evaluation was the same as in Example 1. The results are shown in Table 3.
[0174] (実施例 9) [Example 9]
実施例 1において、表 2に示すように炭化タングステン—コバルトを炭化タンダステ ン—コバルトニッケルに変え、厚み 150 z m、表面粗度 0. 3Sの表面層を形成した口 ールを作製し、該ロールを用いてソフトカレンダー処理した以外は、実施例 1と同様 にして、原紙を調製し、該原紙の両面にポリエチレン樹脂層を形成して、支持体を作 製した。  In Example 1, as shown in Table 2, tungsten carbide-cobalt was changed to tandane carbide-cobalt nickel to prepare a tool having a surface layer with a thickness of 150 zm and a surface roughness of 0.3 S, and the roll A base paper was prepared in the same manner as in Example 1 except that a soft calender treatment was used, and a polyethylene resin layer was formed on both sides of the base paper to produce a support.
次に、ロール表面のクラックの発生、ロール表面の鲭びの発生、原紙表面の変色、 研磨の可否、王研式平滑度、小孔の個数、電気抵抗、耐磨耗性、及び総合評価に ついて、実施例 1と同様に評価した。結果を表 3に示す。  Next, for the generation of cracks on the roll surface, the occurrence of cracks on the roll surface, discoloration of the base paper surface, whether or not polishing is possible, Oken smoothness, the number of small holes, electrical resistance, wear resistance, and comprehensive evaluation The evaluation was the same as in Example 1. The results are shown in Table 3.
[0175] (比較例 1) [0175] (Comparative Example 1)
一原紙及び支持体の作製  Production of base paper and support
実施例 1において、表 2に示すようにロールの表面温度を 180°Cに変えてソフトカレ ンダー処理を行った以外は、実施例 1と同様にして、原紙を調製し、該原紙の両面に ポリエチレン樹脂層を形成し、支持体を作製した。  In Example 1, a base paper was prepared in the same manner as in Example 1 except that the roll surface temperature was changed to 180 ° C. and soft calendering was performed as shown in Table 2. Polyethylene was formed on both sides of the base paper. A resin layer was formed to prepare a support.
次に、ロール表面のクラックの発生、ロール表面の鲭びの発生、原紙表面の変色、 研磨の可否、王研式平滑度、小孔の個数、電気抵抗、耐磨耗性、及び総合評価に ついて、実施例 1と同様に評価した。結果を表 3に示す。  Next, for the generation of cracks on the roll surface, the occurrence of cracks on the roll surface, discoloration of the base paper surface, whether or not polishing is possible, Oken smoothness, the number of small holes, electrical resistance, wear resistance, and comprehensive evaluation The evaluation was the same as in Example 1. The results are shown in Table 3.
[0176] (比較例 2) [0176] (Comparative Example 2)
一原紙及び支持体の作製一 実施例 1において、表 2に示すようにロールシェルに工業用クロムメツキを厚み 150 /i m、表面粗度 0. 3Sとなるようにローノレを形成し、該ロールの表面温度を 200°Cに 変えてソフトカレンダー処理を行った以外は、実施例 1と同様にして、原紙を調製し、 該原紙の両面にポリエチレン樹脂層を形成し、支持体を作製した。 Preparation of base paper and support In Example 1, as shown in Table 2, a roll shell was formed with an industrial chromium plating having a thickness of 150 / im and a surface roughness of 0.3S, and the roll surface temperature was changed to 200 ° C. A base paper was prepared in the same manner as in Example 1 except that soft calendering was performed, and a polyethylene resin layer was formed on both sides of the base paper to prepare a support.
次に、ロール表面のクラックの発生、ロール表面の鲭びの発生、原紙表面の変色、 研磨の可否、王研式平滑度、小孔の個数、電気抵抗、耐磨耗性、及び総合評価に ついて、実施例 1と同様に評価した。結果を表 3に示す。  Next, for the generation of cracks on the roll surface, the occurrence of cracks on the roll surface, discoloration of the base paper surface, whether or not polishing is possible, Oken smoothness, the number of small holes, electrical resistance, wear resistance, and comprehensive evaluation The evaluation was the same as in Example 1. The results are shown in Table 3.
[0177] (比較例 3) [0177] (Comparative Example 3)
一原紙及び支持体の作製一  Preparation of base paper and support
実施例 1において、表 2に示すようにロールシェルに工業用クロムメツキを厚み 150 z m、表面粗度 0. 3Sとなるようにローノレを形成し、該ロールの表面温度を 350°Cに 変えてソフトカレンダー処理を行った以外は、実施例 1と同様にして、原紙を調製し、 該原紙の両面にポリエチレン樹脂層を形成し、支持体を作製した。  In Example 1, as shown in Table 2, a roll shell is formed with a chrome plating for industrial use having a thickness of 150 zm and a surface roughness of 0.3 S, and the surface temperature of the roll is changed to 350 ° C. and softened. A base paper was prepared in the same manner as in Example 1 except that the calendar treatment was performed, and a polyethylene resin layer was formed on both sides of the base paper to prepare a support.
次に、ロール表面のクラックの発生、ロール表面の鲭びの発生、原紙表面の変色、 研磨の可否、王研式平滑度、小孔の個数、電気抵抗、耐磨耗性、及び総合評価に ついて、実施例 1と同様に評価した。結果を表 3に示す。  Next, for the generation of cracks on the roll surface, the occurrence of cracks on the roll surface, discoloration of the base paper surface, whether or not polishing is possible, Oken smoothness, the number of small holes, electrical resistance, wear resistance, and comprehensive evaluation The evaluation was the same as in Example 1. The results are shown in Table 3.
[0178] (比較例 4) [0178] (Comparative Example 4)
一原紙及び支持体の作製  Production of base paper and support
実施例 1において、表 2に示すようにロールに表面層を設けず、 SNCM439 (鍛鋼 )を表面粗度 0· 3Sに仕上げたロールの表面温度を 200°Cに変えてソフトカレンダー 処理を行った以外は、実施例 1と同様にして、原紙を調製し、該原紙の両面にポリエ チレン樹脂層を形成し、支持体を作製した。  In Example 1, as shown in Table 2, the roll was not provided with a surface layer, and the surface temperature of the roll finished with SNCM439 (forged steel) with a surface roughness of 0 · 3S was changed to 200 ° C and soft calender treatment was performed. Except for the above, a base paper was prepared in the same manner as in Example 1, and a polyethylene resin layer was formed on both sides of the base paper to prepare a support.
次に、ロール表面のクラックの発生、ロール表面の鲭びの発生、原紙表面の変色、 研磨の可否、王研式平滑度、小孔の個数、電気抵抗、耐磨耗性、及び総合評価に ついて、実施例 1と同様に評価した。結果を表 3に示す。  Next, for the generation of cracks on the roll surface, the occurrence of cracks on the roll surface, discoloration of the base paper surface, whether or not polishing is possible, Oken smoothness, the number of small holes, electrical resistance, wear resistance, and comprehensive evaluation The evaluation was the same as in Example 1. The results are shown in Table 3.
[0179] [表 2] 表面層の厚み ロール温度 スピード [0179] [Table 2] Surface layer thickness Roll temperature Speed
ロール表面処理 带電防止剤  Roll surface treatment Antistatic agent
(^m) (¾) (m/ mm)  (^ m) (¾) (m / mm)
炭化タングステン一  Tungsten carbide
実施例 1 WC溶射 150 350 300 塩化カルシウム コバルト  Example 1 WC spraying 150 350 300 Calcium chloride Cobalt
炭化タングステン一  Tungsten carbide
実施例 2 WC溶射 150 200 300 塩化カルシウム コバルト  Example 2 WC spraying 150 200 300 Calcium chloride Cobalt
炭化タングステン一  Tungsten carbide
実施例 3 WC溶射 150 250 300 塩化カルシウム コバルト  Example 3 WC spraying 150 250 300 Calcium chloride Cobalt
炭化タングステン一  Tungsten carbide
実施例 4 WC溶射 220 350 300 塩化カルシウム コバルト  Example 4 WC spraying 220 350 300 Calcium chloride Cobalt
炭化タングステン一  Tungsten carbide
実施例 5 WC溶射 50 350 300 塩化カルシウム  Example 5 WC spraying 50 350 300 Calcium chloride
コノくルト  Cono Kurt
炭化タングステン一  Tungsten carbide
実施例 6 WC溶射 150 370 300 塩化カルシウム  Example 6 WC spraying 150 370 300 Calcium chloride
コノくルト  Cono Kurt
炭化タングステン一 アルキルトリメチル 実施例 7 WC溶射 150 350 300  Tungsten carbide monoalkyltrimethyl Example 7 WC spraying 150 350 300
コノくルト アンモニゥム塩 炭化タングステン一  Conoult Ammonium salt Tungsten carbide
実施例 8 WC溶射 150 350 300 塩化カルシウム コバルトクロム  Example 8 WC spraying 150 350 300 Calcium chloride Cobalt chromium
炭化タングステン一  Tungsten carbide
実施例 9 WC溶射 150 350 300  Example 9 WC spraying 150 350 300
コバルトニッケル 塩化カルシウム 炭化タングステン一  Cobalt nickel Calcium chloride Tungsten carbide
比較例 1 WC溶射 150 180 300 塩化カルシウム コバルト  Comparative Example 1 WC sprayed 150 180 300 Calcium chloride Cobalt
比較例 2 工業用クロムメツキ 150 200 300 塩化カルシウム 比較例 3 工業用クロムメツキ 150 350 300 塩化カルシウム 比較例 4 無し - 200 300 塩化カルシウム  Comparative example 2 Industrial chromium plating 150 200 300 Calcium chloride Comparative example 3 Industrial chromium plating 150 350 300 Calcium chloride Comparative example 4 None-200 300 Calcium chloride
* WC溶射：タングステンカーバイト溶射 * WC spraying: tungsten carbide spraying
*スピード：原紙のカレンダー処理の速度  * Speed: The speed of calendar processing of the base paper
[表 3] クラ、ジク、 平滑度 小孔  [Table 3] Class, Jig, Smoothness Small hole
鯖ぴ 研磨の可否 表面の変色 電気抵抗 耐磨耗性 総合判定 剥離 (sec (個 cm2〕 鯖 PI Polishing possible Surface discoloration Electrical resistance Abrasion resistance Comprehensive judgment Peeling (sec (piece cm 2 )
実施例 1 o 〇 378 10 可 〇 〇 0. 2y m 〇 実施例 2 〇 〇 217 90 可 〇 〇 0. 2jU m 〇 実施例 3 o 〇 284 64 可 〇 〇 0.2y m 〇 実施例 4 Δ 0 376 12 可 〇 〇 0. 2u Δ 実施例 5 〇 〇 370 15 不可 〇 〇 0. 2jU m Δ 実施例 6 〇 〇 405 6 可 Δ 〇 0. 2u 厶 実施例 7 〇 〇 380 15 可 〇 Δ 0. 2jU m Δ 実施例 8 o 〇 377 11 可 〇 〇 0. 25jU m 厶 実施例 9 〇 〇 380 10 可 〇 〇 0. 25jL/ m Δ 比較例 1 〇 〇 195 105 可 〇 〇 0. 2jU m X 比較例 2 X 0 212 88 可 〇 〇 0. 4jW m X 比較例 3 X X 〇 375 15 可 〇 〇 0. 4jU m X 比較例 4 - 216 90 可 〇 〇 0. X [0181] 以上の結果から、実施例:!〜 9は、比較例:!〜 4に比べて、総合的にみて良好な性 能を有することが分かった。 Example 1 o ○ 378 10 Yes Yes Yes 0 0.2y m Yes Example 2 Yes Yes 217 90 Yes Yes Yes 0 0.2 jU m Yes Example 3 o Yes 284 64 Yes Yes Yes 0.2ym Yes Example 4 Δ 0 376 12 Available ○ ○ 0. 2u Δ Example 5 ○ ○ 370 15 Impossible ○ ○ 0. 2jU m Δ Example 6 ○ ○ 405 6 Possible Δ ○ 0.2u 実 施 Example 7 ○ ○ 380 15 Possible ○ Δ 0.2 0.2jU m Δ Example 8 o ○ 377 11 Possible ○ ○ 0.25jU m 厶 Example 9 ○ ○ 380 10 Possible ○ ○ 0.25jL / m Δ Comparative example 1 ○ ○ 195 105 Possible ○ ○ 0.2jU m X Comparative example 2 X 0 212 88 Yes Yes Yes 0.4jW m X Comparative Example 3 XX Yes 375 15 Yes Yes Yes Yes 0.4jU m X Comparative Example 4-216 90 Yes Yes Yes 0.X [0181] From the above results, it was found that Examples:! To 9 had better overall performance than Comparative Examples:! To 4.
また、実施例 2は、表面温度 200°Cでカレンダー処理を行ったものであり、王研式 平滑度が 217secで、小孔の個数 90個 Zcm2と規格下限となったが、実使用上問題 は無かった。 In Example 2, calendering was performed at a surface temperature of 200 ° C. The Oken type smoothness was 217 seconds, and the number of small holes was 90 Zcm 2 , which was the lower specification limit. There was no problem.
また、実施例 4は、ロール表面層の厚みを 220 z mとし、 350°Cでカレンダー処理し たものであり、使用後にロール表面層の剥がれが一部確認された力 実使用上問題 は無かった。  In Example 4, the thickness of the roll surface layer was set to 220 zm and calendered at 350 ° C, and there was no problem in practical use. .
また、実施例 5は、ロール表面層の厚みを 50 z mとし、 350°Cでカレンダー処理し たものであり、クラック、鲭びの発生はなかった。ロール表面に傷が付いた場合には、 研磨ができず再溶射が必要になるが、実使用上問題は無かった。  In Example 5, the roll surface layer had a thickness of 50 zm and calendered at 350 ° C., and no cracks or creases occurred. If the roll surface was scratched, it could not be polished and resprayed, but there was no problem in actual use.
また、実施例 6は、表面温度 370°Cでカレンダー処理を行ったものであり、王研式 平滑度 405sec、小孔の個数が 6個/ cm2と良好であった。原紙表面に部分的に内 添薬品が熱変色したと思われる黄色の汚れが僅かに見られたが、実使用上問題は なかった。 In Example 6, calendering was performed at a surface temperature of 370 ° C., and the Oken smoothness was 405 sec and the number of small holes was 6 / cm 2 . There was a slight yellow stain on the surface of the base paper, which was thought to be due to thermal discoloration of the internal chemicals, but there was no problem in practical use.
また、実施例 7は、表面サイズ液に含まれる帯電防止剤としてアルキルトリメチルァ ンモニゥム塩を使用したので、電気抵抗が増加し、帯電防止性がやや低下したが、 実使用上問題はなかった。  In Example 7, since an alkyltrimethyl ammonium salt was used as an antistatic agent contained in the surface sizing solution, the electrical resistance increased and the antistatic property slightly decreased, but there was no problem in practical use.
[0182] これに対し、比較例 1は、表面温度 180°Cでカレンダー処理を行ったので、王研式 平滑度が 195secで、小孔の個数が 105個/ cm2と規格外となり、総合評価を Xとし た。 [0182] On the other hand, Comparative Example 1 was calendered at a surface temperature of 180 ° C, so the Oken type smoothness was 195 sec and the number of small holes was 105 / cm 2, which was out of the standard. The evaluation is X.
また、比較例 2は、工業用クロムメツキ被膜を厚み 150 x mで形成し、 200°Cでカレ ンダー処理したものであり、ロール表面に微小なクラックが確認できたので、総合評 価を Xとした。  In Comparative Example 2, an industrial chromium plating film with a thickness of 150 xm was formed and calendered at 200 ° C, and micro cracks were confirmed on the roll surface. .
また、比較例 3は、工業用クロムメツキ被膜を厚み 150 x mで形成し、 350°Cでカレ ンダー処理したものであり、ロール表面に多数のクラックが確認できたので、総合評 価を Xとした。  In Comparative Example 3, an industrial chrome plating film having a thickness of 150 xm was formed and calendered at 350 ° C, and a large number of cracks were confirmed on the roll surface. .
また、比較例 4は、ロール表面層を設けなかったものであり、カレンダー処理後、口 ール表面に多数の鲭びが確認できたので、総合評価を Xとした。 In Comparative Example 4, the roll surface layer was not provided. Since a large number of joys were confirmed on the surface of the tool, the overall evaluation was X.
[0183] (実施例 10) [0183] (Example 10)
<電子写真材料の作製 >  <Production of electrophotographic materials>
前記実施例 1の画像記録材料用支持体を用いて、下記方法により本発明の画像記 録材料としての実施例 10の電子写真材料を作製した。  Using the image recording material support of Example 1, the electrophotographic material of Example 10 as an image recording material of the present invention was produced by the following method.
[0184] 一二酸化チタン分散液の調製一 [0184] Preparation of titanium dioxide dispersion
二酸化チタン (タイペータ（登録商標) A— 220、石原産業株式会社製) 40. 0g、 P VA102 (株式会社クラレ製） 2. Og、及びイオン交換水 58. Ogを混合し、 日本精機製 作所製 NBK_ 2を用いて分散させて、二酸化チタン分散液 (二酸化チタン顔料含有 量が 40質量％)を調製した。  Titanium dioxide (Typeter (registered trademark) A-220, manufactured by Ishihara Sangyo Co., Ltd.) 40.0 g, P VA102 (manufactured by Kuraray Co., Ltd.) 2. Og and ion-exchanged water 58. A titanium dioxide dispersion (with a titanium dioxide pigment content of 40% by mass) was prepared by dispersing using NBK — 2 manufactured by NBK.
[0185] 一トナー受像層用塗布液の調製一 [0185] Preparation of one toner image-receiving layer coating solution
前記二酸化チタン分散液 15. 5g、カルナバワックス分散液（セロゾール 524、中京 油脂株式会社製） 15. 0g、ポリエステル樹脂水分散物（固形分 30質量％、 KZA- 7 049、ュニチカ株式会社製） 100· 0g、増粘剤 (アルコックス E30、明成化学株式会 社製) 2· 0g、ァニオン界面活性剤（ΑΟΤ) 0· 5g、及びイオン交換水 80mlを混合し、 攪拌してトナー受像層用塗布液を調製した。  Said titanium dioxide dispersion 15.5 g, carnauba wax dispersion (Cerosol 524, manufactured by Chukyo Yushi Co., Ltd.) 15.0 g, polyester resin aqueous dispersion (solid content 30% by mass, KZA-7 049, manufactured by Unitika Ltd.) 100 · Mix 0g, thickener (Alcox E30, Meisei Chemical Co., Ltd.) 2.0g, anionic surfactant (ΑΟΤ) 0.5g, and 80ml of ion-exchanged water, stir and apply for toner image-receiving layer A liquid was prepared.
得られたトナー受像層用塗布液の粘度は、 40mPa' sであり、表面張力は 34mN/ mであつに。  The resulting toner image-receiving layer coating solution has a viscosity of 40 mPa's and a surface tension of 34 mN / m.
[0186] バック層用塗布液の調製 [0186] Preparation of coating solution for back layer
下記の成分を混合し、攪拌して、バック層用塗布液を調製した。  The following components were mixed and stirred to prepare a back layer coating solution.
アクリル樹脂水分散物（固形分 30質量％、ハイロス XBH— 997L、星光化学株式 会社製) 100. 0g、マット剤 (テクポマー MBX_ 12、積水化成品工業 (株)製） 5. 0g、 離型剤 (ハイドリン D337、中京油脂株式会社製) 10. 0g、増粘剤（CMC) 2. 0g、ァ 二オン界面活性剤 (AOT) 0. 5g、及びイオン交換水 80mlを混合し、撹拌してバック 層用塗布液を調製した。  Acrylic resin water dispersion (solid content 30% by mass, Hi-Loss XBH-997L, manufactured by Seiko Chemical Co., Ltd.) (Hydrin D337, manufactured by Chukyo Yushi Co., Ltd.) 10.0 g, Thickener (CMC) 2.0 g, Anion Surfactant (AOT) 0.5 g, and 80 ml of ion-exchanged water are mixed and stirred. A layer coating solution was prepared.
得られたバック層用塗布液の粘度は、 35mPa' sであり、表面張力は、 33mN/m であった。  The resulting back layer coating solution had a viscosity of 35 mPa's and a surface tension of 33 mN / m 2.
[0187] 一バック層及びトナー受像層の塗工一 前記実施例 1の画像記録材料用支持体におけるうら面（トナー受像層を設けない側 の表面）に、前記バック層用塗布液をバーコ一ターで乾燥質量が 9g/m2となるよう に塗布し、バック層を形成した。また、前記各画像記録材料用支持体のおもて面に、 前記トナー受像層塗布液を、バーコ一ターにて乾燥質量が 12gZm2となるように塗 布し、トナー受像層を形成した。なお、トナー受像層中の顔料の含有量は、熱可塑性 樹脂に対して 5質量％であった。 [0187] Coating of one back layer and toner image-receiving layer The back layer coating solution is applied to the back surface of the image recording material support of Example 1 (the surface on which the toner image-receiving layer is not provided) with a bar coater so that the dry mass is 9 g / m 2. Then, a back layer was formed. Further, the toner image-receiving layer coating solution was applied to the front surface of each of the image recording material supports with a bar coater so that the dry mass was 12 gZm 2 , thereby forming a toner image-receiving layer. The pigment content in the toner image-receiving layer was 5% by mass relative to the thermoplastic resin.
[0188] 前記バック層及び前記トナー受像層は、塗布した後、オンラインで熱風により乾燥 した。前記乾燥は、バック層及びトナー受像層ともに塗布後 2分間以内に乾燥するよ うに、乾燥風量及び温度を調整した。なお、乾燥点は、塗布表面温度が乾燥風の湿 球温度と同じ温度となる点とした。 [0188] The back layer and the toner image-receiving layer were coated and then dried online with hot air. In the drying, the drying air volume and temperature were adjusted so that both the back layer and the toner image-receiving layer were dried within 2 minutes after coating. The drying point was the point at which the coating surface temperature was the same as the wet bulb temperature of the drying air.
次いで、乾燥後、カレンダー処理を行った。前記カレンダー処理は、ダロスカレンダ 一を用い、金属ローラを 40°Cに保温した状態で、二ップ圧 14. 7kNZm2の条件で 行った。 Next, after drying, a calendar process was performed. The calendering was performed under the condition of a nip pressure of 14.7 kNZm 2 using a daros calender and keeping the metal roller at 40 ° C.
以上のようにして得られた電子写真材料を裁断して、 A4サイズの電子写真材料を 作製した。  The electrophotographic material obtained as described above was cut to produce an A4 size electrophotographic material.
[0189] (実施例 11) [0189] (Example 11)
電子写真材料の作製  Production of electrophotographic materials
実施例 10において、前記実施例 2の画像記録材料用支持体を用いた以外は、実 施例 10と同様にして、実施例 11の電子写真材料を作製した。  In Example 10, the electrophotographic material of Example 11 was produced in the same manner as in Example 10 except that the image recording material support of Example 2 was used.
[0190] (実施例 12) [0190] (Example 12)
電子写真材料の作製  Production of electrophotographic materials
実施例 10において、前記実施例 3の画像記録材料用支持体を用いた以外は、実 施例 10と同様にして、実施例 12の電子写真材料を作製した。  In Example 10, an electrophotographic material of Example 12 was produced in the same manner as Example 10 except that the image recording material support of Example 3 was used.
[0191] (実施例 13) [0191] (Example 13)
一電子写真材料の作製一  Production of electrophotographic materials
実施例 10において、前記実施例 4の画像記録材料用支持体を用いた以外は、実 施例 10と同様にして、実施例 13の電子写真材料を作製した。  In Example 10, the electrophotographic material of Example 13 was produced in the same manner as in Example 10 except that the image recording material support of Example 4 was used.
[0192] (実施例 14) 電子写真材料の作製 [Example 14] Production of electrophotographic materials
実施例 10において、前記実施例 5の画像記録材料用支持体を用いた以外は、実 施例 10と同様にして、実施例 14の電子写真材料を作製した。  In Example 10, an electrophotographic material of Example 14 was produced in the same manner as Example 10 except that the image recording material support of Example 5 was used.
[0193] (実施例 15) [Example 15]
一電子写真材料の作製一  Production of electrophotographic materials
実施例 10において、前記実施例 6の画像記録材料用支持体を用いた以外は、実 施例 10と同様にして、実施例 15の電子写真材料を作製した。  In Example 10, an electrophotographic material of Example 15 was produced in the same manner as in Example 10 except that the image recording material support of Example 6 was used.
[0194] (実施例 16) [Example 16]
一電子写真材料の作製一  Production of electrophotographic materials
実施例 10において、前記実施例 7の画像記録材料用支持体を用いた以外は、実 施例 10と同様にして、実施例 16の電子写真材料を作製した。  In Example 10, the electrophotographic material of Example 16 was produced in the same manner as in Example 10 except that the image recording material support of Example 7 was used.
[0195] (実施例 17) [0195] (Example 17)
電子写真材料の作製  Production of electrophotographic materials
実施例 10において、前記実施例 8の画像記録材料用支持体を用いた以外は、実 施例 10と同様にして、実施例 17の電子写真材料を作製した。  In Example 10, the electrophotographic material of Example 17 was produced in the same manner as in Example 10 except that the image recording material support of Example 8 was used.
[0196] (実施例 18) [0196] (Example 18)
電子写真材料の作製  Production of electrophotographic materials
実施例 10において、前記実施例 9の画像記録材料用支持体を用いた以外は、実 施例 10と同様にして、実施例 18の電子写真材料を作製した。  In Example 10, the electrophotographic material of Example 18 was produced in the same manner as in Example 10 except that the image recording material support of Example 9 was used.
[0197] (比較例 5) [0197] (Comparative Example 5)
電子写真材料の作製  Production of electrophotographic materials
実施例 10において、前記比較例 1の画像記録材料用支持体を用いた以外は、実 施例 10と同様にして、比較例 5の電子写真材料を作製した。  In Example 10, the electrophotographic material of Comparative Example 5 was produced in the same manner as Example 10 except that the image recording material support of Comparative Example 1 was used.
[0198] (比較例 6) [0198] (Comparative Example 6)
一電子写真材料の作製一  Production of electrophotographic materials
実施例 10において、前記比較例 2の画像記録材料用支持体を用いた以外は、実 施例 10と同様にして、比較例 6の電子写真材料を作製した。  In Example 10, an electrophotographic material of Comparative Example 6 was produced in the same manner as Example 10 except that the image recording material support of Comparative Example 2 was used.
[0199] (比較例 7) 電子写真材料の作製 [0199] (Comparative Example 7) Production of electrophotographic materials
実施例 10において、前記比較例 3の画像記録材料用支持体を用いた以外は、実 施例 10と同様にして、比較例 7の電子写真材料を作製した。  In Example 10, the electrophotographic material of Comparative Example 7 was produced in the same manner as Example 10 except that the image recording material support of Comparative Example 3 was used.
[0200] (比較例 8) [0200] (Comparative Example 8)
一電子写真材料の作製一  Production of electrophotographic materials
実施例 10において、前記比較例 4の画像記録材料用支持体を用いた以外は、実 施例 10と同様にして、比較例 8の電子写真材料を作製した。  In Example 10, an electrophotographic material of Comparative Example 8 was produced in the same manner as in Example 10 except that the image recording material support of Comparative Example 4 was used.
[0201] 次に、画像を実施例 10〜： 18及び比較例 5〜8の各電子写真材料について、電子 写真用プリンターを用い、それぞれプリントし、各電子写真プリントを作成した。 [0201] Next, images were printed on each of the electrophotographic materials of Examples 10 to 18 and Comparative Examples 5 to 8 using an electrophotographic printer, and each electrophotographic print was created.
使用したプリンタ一は、定着部を図 1に示すベルト定着装置 1とした富士ゼロックス 株式会社製のカラーレーザープリンター（DocuColor 1250— PF)を用レ、た。即ち 、図 1に示すベルト定着装置 1では、加熱ローラ 3と、テンションローラ 5とにわたって 定着ベルト 2が懸架され、テンションローラ 5には、その上方で、定着ベルト 2を介して 、クリーニングローラ 6が設けられ、更に、加熱ローラ 3の下方には、定着ベルト 2を介 して、加圧ローラ 4が設けられている。トナー潜像を有する電子写真材料は、図 1にお いて、右側から、加熱ローラ 3と、加圧ローラ 4との間に挿入され、定着され、次いで、 定着ベルト 2に載って移動し、その過程で、冷却装置 7によって冷却され、最後に、ク リーユングローラ 6で清浄化される。  The printer used was a color laser printer (DocuColor 1250-PF) manufactured by Fuji Xerox Co., Ltd., in which the fixing unit was a belt fixing device 1 shown in FIG. That is, in the belt fixing device 1 shown in FIG. 1, the fixing belt 2 is suspended over the heating roller 3 and the tension roller 5, and the cleaning roller 6 is disposed above the tension roller 5 via the fixing belt 2. Further, a pressure roller 4 is provided below the heating roller 3 via a fixing belt 2. In FIG. 1, the electrophotographic material having the latent toner image is inserted between the heating roller 3 and the pressure roller 4 from the right side, fixed, and then moved on the fixing belt 2 and moved. In the process, it is cooled by the cooling device 7 and finally cleaned by the cleaning roller 6.
前記ベルト定着装置 1においては、定着ベルト 2の搬送速度は、 30mm/秒であり 、加熱ローラ 3と加圧ローラ 4との間のニップ圧力は、 0. 2MPaであり、加熱ローラ 3の 設定温度は、 150°Cであり、これが定着温度に相当する。なお、加圧ローラ 4の設定 温度は、 120°Cに設定した。  In the belt fixing device 1, the conveying speed of the fixing belt 2 is 30 mm / second, the nip pressure between the heating roller 3 and the pressure roller 4 is 0.2 MPa, and the set temperature of the heating roller 3 Is 150 ° C., which corresponds to the fixing temperature. The set temperature of the pressure roller 4 was set to 120 ° C.
[0202] 次に、得られた各電子写真プリントについて、以下のようにして、画質及び光沢感 の評価を行った。結果を表 4に示す。 [0202] Next, the obtained electrophotographic prints were evaluated for image quality and glossiness as follows. The results are shown in Table 4.
[0203] <画質の評価 > [0203] <Evaluation of image quality>
各電子写真プリントの画質を目視で観察し、下記基準に基づいて、画質の最も良 好なものを Aとして、次いで、 B、 C、 D、 Eとランク付けし、評価した。  The image quality of each electrophotographic print was visually observed, and based on the following criteria, the best image quality was ranked as A, then B, C, D, E and evaluated.
〔評価基準〕 A:非常に優れている（高画質記録材料として有効） 〔Evaluation criteria〕 A: Excellent (effective as a high-quality recording material)
B：優れてレ、る（高画質記録材料として有効）  B: Excellent, effective (effective as a high-quality recording material)
C:中間  C: Intermediate
D：劣る（高画質記録材料として不可）  D: Inferior (not possible as a high-quality recording material)
E：非常に劣る（高画質記録材料として不可）  E: Very inferior (not possible as a high-quality recording material)
[0204] <光沢感> [0204] <Glossy>
各電子写真プリントの光沢感を目視で観察し、下記基準に基づいて、光沢の最も 良好なものを Aとして、次いで、 B、 C、 D、 Eとランク付けし、評価した。  The glossiness of each electrophotographic print was visually observed, and the best glossiness was ranked as A and then evaluated as B, C, D, E based on the following criteria.
〔評価基準〕  〔Evaluation criteria〕
A:非常に優れている（高画質記録材料として有効）  A: Excellent (effective as a high-quality recording material)
B：優れてレ、る（高画質記録材料として有効）  B: Excellent, effective (effective as a high-quality recording material)
C:中間  C: Intermediate
D：劣る（高画質記録材料として不可）  D: Inferior (not possible as a high-quality recording material)
E：非常に劣る (高画質記録材料として不可）  E: Very inferior (not possible as a high-quality recording material)
[0205] [表 4] 支持体 画質 光沢感 実施例 10 実施例 1 A A 実施例 11 実施例 2 A C 実施例 12 実施例 3 A B 実施例 13 実施例 4 A A 実施例 14 実施例 5 A A 実施例 15 実施例 6 A A 実施例 16 実施例 7 A A 実施例 17 実施例 8 A A 実施例 18 実施例 9 A A 比較例 5 比較例 1 A C 比較例 6 比較例 2 A C 比較例 7 比較例 3 A A 比較例 8 比較例 4 A C 表 4の結果から、実施例：!〜 9の画像記録材料用支持体を用レ、た実施例 10〜： 18の 各電子写真材料は、比較例：!〜 4の画像記録材料用支持体を用いた比較例 5〜8の 各電子写真材料と比較して、同レベルの優れた画質を有し、更に光沢感が向上して レ、ることが認められる。 [0205] [Table 4] Support Image Quality Glossy Example 10 Example 1 AA Example 11 Example 2 AC Example 12 Example 3 AB Example 13 Example 4 AA Example 14 Example 5 AA Example 15 Example 6 AA Example 16 Example 7 AA Example 17 Example 8 AA Example 18 Example 9 AA Comparative Example 5 Comparative Example 1 AC Comparative Example 6 Comparative Example 2 AC Comparative Example 7 Comparative Example 3 AA Comparative Example 8 Comparative Example 4 AC From the results shown in Table 4, each of the electrophotographic materials in Examples 10 to 18 was used as a support for an image recording material in Comparative Examples:! Compared to each of the electrophotographic materials of Comparative Examples 5 to 8 using the above, it is recognized that the image quality is at the same level and the glossiness is further improved.
産業上の利用可能性 Industrial applicability
本発明の画像記録用支持体の製造方法及び画像記録材料用支持体は、サーメッ ト材料から選択される少なくとも 1種を含む表面層を有するロールでカレンダー処理さ れて得られる原紙を用いており、平滑性に優れ、小孔 (微小な凹み）の発生が少ない ので、例えば、電子写真材料、感熱材料、昇華転写材料、熱転写材料、熱現像材料 、銀塩写真材料、インクジェット記録材料などに幅広く好適に用いられる。  The method for producing an image recording support and the image recording material support of the present invention use a base paper obtained by calendering with a roll having a surface layer containing at least one selected from cermet materials. Excellent smoothness and few small holes (small dents). For example, it is widely used for electrophotographic materials, heat-sensitive materials, sublimation transfer materials, thermal transfer materials, thermal development materials, silver salt photographic materials, inkjet recording materials, etc. Preferably used.

Claims

請求の範囲 The scope of the claims
[1] 原紙と、該原紙の少なくとも一方の面に熱可塑性樹脂層を有する画像記録材料用 支持体であって、  [1] A support for an image recording material having a base paper and a thermoplastic resin layer on at least one surface of the base paper,
前記原紙は、表面温度が 200°C以上のロールでカレンダー処理されてなり、かつ 該ロールが、サーメット材料から選択される少なくとも 1種を含む表面層を有すること を特徴とする画像記録材料用支持体。  The base paper is calendered with a roll having a surface temperature of 200 ° C. or higher, and the roll has a surface layer containing at least one selected from cermet materials. body.
[2] ロールの表面温度が、 200〜350°Cである請求の範囲第 1項に記載の画像記録材 料用支持体。 [2] The support for an image recording material according to claim 1, wherein the roll has a surface temperature of 200 to 350 ° C.
[3] 原紙の画像記録層を設ける側の面が、サーメット材料から選択される少なくとも 1種 を含む表面層を有するロールと接するようにカレンダー処理する請求の範囲第 1項か ら第 2項のいずれかに記載の画像記録材料用支持体。  [3] The method according to any one of claims 1 to 2, wherein the surface of the base paper on which the image recording layer is provided is calendered so as to contact a roll having a surface layer containing at least one selected from cermet materials. The support for image recording materials according to any one of the above.
[4] 原紙の画像記録層を設ける側の面の反対側の面力 ショァ一 D硬度 60〜95° の ロールと接するようにカレンダー処理する請求の範囲第 1項から第 3項のいずれかに 記載の画像記録材料用支持体。 [4] The surface force on the side opposite to the side on which the image recording layer is provided of the base paper Shore 1 D calendering so as to contact a roll having a D hardness of 60 to 95 °, according to any one of claims 1 to 3 The support for image recording materials described in the above.
[5] サーメット材料が、炭化タングステン系サーメットである請求の範囲第 1項から第 4項 のいずれかに記載の画像記録材料用支持体。 5. The support for an image recording material according to any one of claims 1 to 4, wherein the cermet material is a tungsten carbide cermet.
[6] 炭化タングステン系サーメットが、炭化タングステン一コバルト、炭化タングステン一 コバノレトクロム、及び炭化タングステン一ニッケルクロムのいずれかである請求の範囲 第 5項に記載の画像記録材料用支持体。 6. The support for an image recording material according to claim 5, wherein the tungsten carbide-based cermet is any one of tungsten carbide-cobalt, tungsten carbide-cobalent chromium, and tungsten carbide-nickel chromium.
[7] 表面層の厚みが、 60〜220 111でぁる請求の範囲第1項から第6項のぃずれかに 記載の画像記録材料用支持体。 [7] The support for an image recording material according to any one of [1] to [6], wherein the surface layer has a thickness of 60 to 220 111.
[8] ロールの表面粗度力 0. 5S以下である請求の範囲第 1項から第 7項のいずれかに 記載の画像記録材料用支持体。 [8] The image recording material support according to any one of [1] to [7], wherein the surface roughness force of the roll is 0.5S or less.
[9] カレンダー処理する前の原紙が、帯電防止剤を含有する請求の範囲第 1項から第[9] The base paper before calendering contains the antistatic agent in claims 1 to
8項のいずれかに記載の画像記録材料用支持体。 9. The support for an image recording material according to any one of items 8.
[10] 帯電防止剤が水溶性金属塩であり、かつ該水溶性金属塩力 塩ィ匕カルシウム、塩 化ナトリウム、及び塩ィ匕マグネシウムのいずれかである請求の範囲第 9項に記載の画 像記録材料用支持体。 [10] The image according to claim 9, wherein the antistatic agent is a water-soluble metal salt, and is one of the water-soluble metal salt strength salt calcium salt, sodium chloride, and salt salt magnesium. Support for image recording material.
[11] 熱可塑性樹脂層が、ポリオレフイン樹脂を含有する請求の範囲第 1項力も第 10項 のレ、ずれかに記載の画像記録材料用支持体。 [11] The image recording material support according to [10], wherein the thermoplastic resin layer contains a polyolefin resin.
[12] 原紙の画像記録層を設ける側の面に、炭化タングステン系サーメット材料から選択 される少なくとも 1種の材料を含む表面層を有するロールが接するようにして、該ロー ルの表面温度が 200°C以上でカレンダー処理する工程を含むことを特徴とする画像 記録材料用支持体の製造方法。  [12] A roll having a surface layer containing at least one material selected from tungsten carbide cermet materials is in contact with the surface of the base paper on which the image recording layer is provided so that the surface temperature of the roll is 200. A method for producing a support for image recording materials, comprising a step of calendering at a temperature of ° C or higher.
[13] カレンダー処理する前に、原紙表面に水溶性金属塩を含有する液を塗布する表面 サイズ処理工程を含む請求の範囲第 12項に記載の画像記録材料用支持体の製造 方法。  13. The method for producing a support for an image recording material according to claim 12, further comprising a surface sizing process in which a liquid containing a water-soluble metal salt is applied to the surface of the base paper before calendering.
[14] カレンダー処理後の原紙の少なくとも一方の面に熱可塑性樹脂層を形成する工程 を含む請求の範囲第 12項から第 13項のいずれかに記載の画像記録材料用支持体 の製造方法。  14. The method for producing a support for an image recording material according to any one of claims 12 to 13, further comprising a step of forming a thermoplastic resin layer on at least one surface of the base paper after the calendar process.
[15] 請求の範囲第 1項から第 11項のいずれかに記載の画像記録材料用支持体と、少 なくとも画像が記録される画像記録層とを有することを特徴とする画像記録材料。  [15] An image recording material comprising the support for image recording material according to any one of claims 1 to 11 and an image recording layer on which at least an image is recorded.
[16] 電子写真材料、感熱材料、昇華転写材料、熱転写材料、銀塩写真材料、及びイン クジェット記録材料から選択されるいずれかである請求の範囲第 15項に記載の画像 記録材料。 16. The image recording material according to claim 15, wherein the image recording material is any one selected from electrophotographic materials, heat-sensitive materials, sublimation transfer materials, thermal transfer materials, silver salt photographic materials, and ink jet recording materials.
PCT/JP2006/305593 2005-03-30 2006-03-20 Support for image recording material, process for producing the same, and image recording material WO2006109451A1 (en)

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JP2011168045A (en) * 2010-01-11 2011-09-01 Rohm & Haas Co Recording material
EP2678167B1 (en) * 2011-04-20 2015-05-20 Rohm and Haas Company Recording material

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