JP2006301656A - Fixing belt, fixing roller, method for manufacturing the same, heat fixing device, and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fixing belt, a fixing roller, a method for manufacturing the same, a heat fixing device, and an image forming method for achieving satisfactory glossiness of an image after being fixed, no peeling of a film of a fixing member during the heat fixing, and no offset. <P>SOLUTION: In the fixing belt performing the fixing in which a recording material is fed between a heating means a pressure means while the recording material and a surface having a releasing layer of a fixing belt having at least the releasing layer on a base material are facing each other, the releasing layer includes silicone resin prepared by a solvent addition type silicone. An adhesion improving layer is provided so as to be adjacent to each of the releasing layer and the base material. The adhesion improving layer includes a compound having at least one reactive group selected from a group consisting of a hydroxy group and so forth. The compound is at least one resin selected from a group consisting of a polyvinyl alcohol resin and so forth. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fixing belt, a fixing roller, a manufacturing method thereof, a heat fixing device, and an image forming method.

  Ink-jet recording is a method in which micro droplets of ink are ejected by various operating principles and adhered to a recording material to record images, characters, etc., but relatively high speed, low noise, and multi-coloring are easy. Has the advantage.

  In addition, due to recent technological advances, pigment inks using pigments with good light resistance as colorants are attracting attention as inks for applications that require images that are resistant to fading due to light.

  The pigment is insoluble in the solvent, and the dye molecule forms particles and contributes to the coloring in a state dispersed in the solvent. For example, even if the surface molecule is destroyed by a photochemical reaction or the like, a new one is formed below it. Due to the presence of the dye molecule layer, the apparent reduction in coloring power is small and the image storability is excellent.

  However, there is a problem that it is difficult to obtain a glossy image even after image fixing processing due to the influence of scattered light and reflected light caused by pigment particles.

  Japanese Patent Application Laid-Open No. 11-208097 discloses a technique for moving pigment particles into a thermoplastic resin layer after recording with a pigment ink containing no dispersant in a recording material whose outermost layer is a thermoplastic resin layer. After the pigment ink is attached to the surface of the recording material, the pigment particles are present on the surface of the thermoplastic resin layer, and the solvent component is absorbed by each layer constituting the recording material. Subsequently, by moving the pigment particles into the thermoplastic resin layer, the floating of the printed portion peculiar to the pigment ink with respect to the unprinted portion was eliminated, and the gloss improving effect due to the improvement in smoothness was confirmed.

  However, if the embedding of the pigment ink into the thermoplastic resin layer is halfway, image-like irregularities occur in the printed and unprinted areas, and gloss differences tend to occur. When it is sufficiently performed, the smoothness of the image surface is improved and the difference in gloss between the printed part and the unprinted part is eliminated, but there is a problem that sufficient characteristics cannot be obtained with respect to the glossiness.

  Japanese Patent Laid-Open No. 2000-103044 discloses a heating roller and a pressure roller disposed opposite to the heating roller as drying means for drying the ink ejected on the recording material. However, the rise of the ink is flat and the ink is glossy compared to the conventional image forming apparatus, but the gloss is not sufficient, and the peelability between the heating roller and the pigment ink is insufficient. There was a problem that there was.

  Japanese Patent Application Laid-Open No. 2000-1512 discloses an image forming unit that forms an image on a printing material using ink in order to output a high gloss image without using specific recording paper and ink, and this image. There is disclosed an image output apparatus including a pressurizing unit for pressurizing a printing material on which an image is formed by a forming unit.

  This image output device discloses a silicon rubber whose surface is fluorine coated as a fixing device, but the gloss of the formed image is not sufficient, and the peelability between the roller and the pigment ink is not sufficient. There was a problem that there was.

  In an image forming apparatus using an electrophotographic process, such as an electrophotographic copying machine or an electrophotographic printer, it is necessary to fix a toner image transferred from a photoreceptor surface to a transfer object such as a copy sheet to the transfer object. . As a method of fixing the toner image, a method of passing the copy paper between a heating roll and a pressure roll rotating in pressure contact with each other and thermally fusing and fixing the toner image on the copy paper is widely adopted. Yes.

  In this method, since the contact width between the fixing roll and the copy paper is small due to the curvature of the roll, the copy paper is separated from the fixing roll in a short time, and the toner on the copy paper leaves the roll surface at a high temperature. The full-color toner has a low melting point, so it is easy to offset, and the toner surface is rough. Therefore, the toner image is not sufficiently mirror-finished, and it is difficult to obtain a glossy image. there were.

  In addition, conventionally, silicone oil is applied to the surface of the fixing roll to prevent offset, but there is a problem that the apparatus is complicated, for example, a device for applying silicone oil is required. is there. Further, it has been pointed out that when an original is copied to an OHP film, the film is contaminated with silicone oil.

  Japanese Patent Laid-Open No. 5-265337 discloses a fixing belt comprising at least a base material and a release layer formed on the surface thereof, wherein the release layer is made of a silicone resin. It is disclosed.

  Japanese Patent Application Laid-Open No. 2000-112271 discloses a fixing belt in which a surface layer containing a curable modified silicone resin is provided on the outermost surface (corresponding to a releasable layer) farthest from a base (base material) of a fixing member. It is disclosed.

  However, although the above fixing belt is effective in improving the glossiness of a full-color toner image, the effect of improving the glossiness of an inkjet recording image is insufficient, and the film of the release layer on the fixing belt There were problems such as easy peeling.

  An object of the present invention is to provide a fixing belt, a fixing roller, a manufacturing method thereof, a heat fixing apparatus, and an image forming method in which the gloss of an image after fixing is good and the film of the fixing member does not peel off at the time of heat fixing. is there.

  The above object of the present invention has been achieved by the following configurations 1 to 29.

  1. In a fixing belt for fixing by passing a recording material and a surface of a fixing belt having at least a releasing layer on a substrate while facing each other between a heating unit and a pressing unit. The release layer contains a silicone resin made of solvent-added silicone, and an adhesive improvement layer is provided so as to be adjacent to the release layer and the substrate, A compound in which the adhesion improving layer has at least one reactive group selected from the group consisting of a hydroxyl group, a carboxyl group, a group represented by the following general formula (a) and a group represented by the following general formula (b) These compounds include polyvinyl alcohol resins, butyral resins, ethylene-vinyl acetate copolymers, olefin resins such as vinylidene chloride and polybutadiene, urethane resins, and polyester resins. Fixing belt characterized in that at least one resin selected from the group consisting of acrylic resins, epoxy resins and polyethylenimine resins.

General formula (a)
-Si- (OH) _m
General formula (b)
-Ti- (OH) _n
[Wherein, m represents an integer of 1 to 3, and n represents an integer of 1 to 4. ]
2. 2. The fixing belt according to 1, wherein the releasable layer contains a silicone resin formed by dip-coating a curable silicone on a substrate and then heat-curing the curable silicone.

  3. 3. The fixing belt according to 1 or 2, wherein the base material is a seamless nickel belt.

  4). The fixing belt according to any one of 1 to 3, wherein the content of the compound having a reactive group in the adhesion improving layer is 20% by mass or less.

  5. The fixing belt according to any one of 1 to 4, wherein the adhesion improving layer contains at least one kind of resin, and the flow softening point of the resin is 130 ° C or higher.

  6). The fixing belt according to any one of 1 to 5, wherein the adhesion improving layer contains at least one compound selected from the group consisting of a silane coupling agent, a titanium coupling agent and an isocyanate.

  7). The fixing belt according to any one of 1 to 6, wherein the adhesion improving layer contains at least one thermosetting resin.

  8). 8. The fixing belt according to any one of 1 to 7, wherein the adhesive improvement layer has a thickness of 1 μm or more.

  9. A method for producing a fixing belt, wherein, in producing the fixing belt according to any one of 9.1 to 8, the adhesion improving layer and the release layer are each coated by dip coating.

  10. 10. The method for producing a fixing belt according to 9, further comprising a step of performing the following aging treatment A after the release layer coating and a step of performing the following aging treatment B.

  Aging treatment A: Represents treatment in which the temperature range is 25 ° C. to 100 ° C. and the relative humidity is 50% RH to 95% RH.

  Aging process B: represents a process of storing with aging at a temperature range of 40 ° C. to 200 ° C. and a relative humidity of less than 50% RH.

  A fixing belt manufactured using the manufacturing method according to 11.9 or 10.

  12 In a fixing roller for fixing by passing a recording material and a surface of a fixing roller having at least a release layer on a substrate while facing each other between a heating unit and a pressurizing unit. The release layer contains a silicone resin made of solvent-added silicone, and an adhesive improvement layer is provided so as to be adjacent to the release layer and the substrate, A compound in which the adhesion improving layer has at least one reactive group selected from the group consisting of a hydroxyl group, a carboxyl group, a group represented by the following general formula (a) and a group represented by the following general formula (b) These compounds include polyvinyl alcohol resins, butyral resins, ethylene-vinyl acetate copolymers, olefin resins such as vinylidene chloride and polybutadiene, urethane resins, and polyester resins. Fixing roller, characterized in that at least one resin selected from the group consisting of acrylic resins, epoxy resins and polyethylenimine resins.

General formula (a)
-Si- (OH) _m
General formula (b)
-Ti- (OH) _n
[Wherein, m represents an integer of 1 to 3, and n represents an integer of 1 to 4. ]
13. 13. The fixing roller according to 12, wherein the releasable layer contains a silicone resin formed by dip-coating curable silicone on a substrate and then heat-curing the curable silicone.

  14 The fixing roller according to 12 or 13, wherein the substrate is a seamless nickel belt.

  15. The fixing roller according to any one of 12 to 14, wherein the content of the compound having a reactive group in the adhesion improving layer is 20% by mass or less.

  16. The fixing roller according to any one of 12 to 15, wherein the adhesion improving layer contains at least one kind of resin, and the flow softening point of the resin is 130 ° C or higher.

  17. The fixing roller according to any one of 12 to 16, wherein the adhesion improving layer contains at least one compound selected from the group consisting of a silane coupling agent, a titanium coupling agent and an isocyanate.

  18. The fixing roller according to any one of 12 to 17, wherein the adhesion improving layer contains at least one thermosetting resin.

  19. 19. The fixing roller according to any one of 12 to 18, wherein the film thickness of the adhesion improving layer is 1 μm or more.

  20. A method for manufacturing a fixing roller, wherein, when the fixing roller according to any one of 20.12 to 19 is manufactured, the adhesion improving layer and the release layer are each coated by dip coating.

  21. 21. The method for producing a fixing roller according to 20, wherein after the release layer is coated, the method includes a step of performing the following aging treatment A and then a step of performing the following aging treatment B.

  Aging treatment A: Represents treatment in which the temperature range is 25 ° C. to 100 ° C. and the relative humidity is 50% RH to 95% RH.

  Aging process B: represents a process of storing with aging at a temperature range of 40 ° C. to 200 ° C. and a relative humidity of less than 50% RH.

  A fixing roller manufactured using the manufacturing method according to 22.20 or 21.

  A heat fixing device for an ink jet recording material, comprising the fixing belt according to any one of 23.1 to 8 and 11, or the fixing roller according to any one of 12 to 19 and 22.

  24. A recording material on which printing has been performed by ejecting ink is subjected to a fixing process using the fixing belt according to any one of 1 to 8 and 11, or the fixing roller according to any one of 12 to 19 and 22. A heat fixing device for an ink jet recording material.

  25. 25. The heat fixing apparatus for ink jet recording material according to 24, wherein the ink is a pigment ink.

  26. 26. The heating for an ink jet recording material according to any one of 23 to 25, wherein the recording material has a surface layer containing thermoplastic resin particles and an ink absorbing layer containing inorganic fine particles adjacent to the surface layer. Fixing device.

  27. 27. An image forming method, wherein a recording material on which printing has been performed by ejecting ink is subjected to a fixing process using the heat fixing device for an inkjet recording material according to any one of 23 to 26.

  28. 28. The image forming method according to 27, wherein the ink is a pigment ink.

  29. 29. The image forming method according to 27 or 28, wherein the recording material has a surface layer containing thermoplastic resin particles and an ink absorbing layer containing inorganic fine particles adjacent to the surface layer.

  According to the present invention, it is possible to provide a fixing belt, a fixing roller, a manufacturing method thereof, a heat fixing apparatus, and an image forming method in which the gloss of the image after fixing is good and the film of the fixing member is not peeled off during heat fixing. .

  An embodiment of the present invention will be described with reference to FIG. 1 for a fixing belt according to claims 1 to 8 and 11, and a fixing roller according to claims 12 to 19 and 22 will be described with reference to FIG. To do.

  FIG. 1 is a schematic configuration diagram showing an example of an ink jet recording apparatus used in the present invention. In FIG. 1, the recording material 1 sent out from the conveying roller pair 21 is subjected to ink jet recording by the recording head 3, is appropriately cut by the cutter 61, and has a deflection from the first roller pair to the second roller pair. Then, it is sent to the heating and fixing means 4 and passes along with the fixing belt 44 between the heating roller 41 having the heating element 43 inside and the pressure roller 42, whereby the heating and fixing process is performed.

  FIG. 2 is a schematic configuration diagram showing another example of the ink jet recording apparatus used in the present invention. In FIG. 2, the recording material 1 sent out from the conveying roller pair 21 is subjected to ink jet recording by the recording head 3 and is appropriately cut by the cutter 61, and has a deflection from the first roller pair to the second roller pair. Then, it is sent to the heat fixing means 4 and passes between a heating roller 41 having a heating element 43 inside and a pressure roller 42 to perform heat fixing processing.

  Although not shown, a surface of the heating roller described above is provided with a releasable layer, and the releasable layer contains the silicone resin according to the present invention.

  Although not shown in the figure, the surface of the fixing belt or the fixing roller described above contacting the recording material 1 is provided with a release layer, and the silicone resin according to the present invention is provided in the release layer. Contained.

  The effect described in the present invention, that is, the gloss of the image after the image formation is good, there is no film peeling of the release layer provided on the fixing belt or the fixing roller at the time of fixing, and an offset occurs at the time of fixing. In order to reduce the above, the fixing belt or fixing roller having a recording material and at least a releasable layer on the base material between the heating means and the pressing means as described in claim 1 or 13. In a fixing belt or a fixing roller for passing and fixing a surface having a releasable layer facing each other, the releasable layer contains a silicone resin, and the releasable layer and the base material It has been found that this can be achieved by providing an adhesion improving layer adjacent to each other.

<Release layer>
The releasable layer according to the present invention will be described.

  The releasable layer according to the present invention contains a silicone resin made of solvent-added silicone. As the silicone resin according to the present invention, a conventionally known silicone resin can be used. From the viewpoint that the effects described in the present invention can be preferably obtained, the release force of the releasable layer satisfies 30 g / 5 cm or more. Preferably used.

  As the silicone resin according to the present invention, for example, a silicone resin prepared using a curable silicone such as a solvent-added silicone or a condensation-curable silicone as shown below is preferable. Silicone resins prepared using these are preferred.

  The solvent addition type silicone described above is obtained by reacting linear methyl vinyl polysiloxane having a vinyl group and methyl hydrogen polysiloxane in both terminals, or both terminals and chains in the presence of a platinum-based catalyst. can get.

  Specific examples of the solvent addition type silicone include, for example, KS-887, KS-779H, KS-778, KS-835, X-62-2456, X-62-2494, and X-62-2461 manufactured by Shin-Etsu Silicone. , KS-3650, KS-3655, KS-3600, KS-847, KS-770, KS-770L, KS-776A, KS-856, KS-775, KS-830, KS-830E, KS-839, X -62-2404, X-62-2405, KS-3702, X-62-2232, KS-3503, KS-3502, KS-3703, KS-5508, and the like.

  As specific examples of the condensation curable silicone, silicones such as KS-881, KS-882, KS-883, X-62-9490, and X-62-9028 manufactured by Shin-Etsu Silicone are preferably used.

  The surface contact angle of the releasable layer according to the present invention is preferably 100 degrees to 120 degrees, and more preferably 105 degrees to 115 degrees. Here, the surface contact angle is a measurement of the contact angle with respect to pure water. For example, using an automatic contact angle meter DAC-VZ (manufactured by Kyowa Interface Science Co., Ltd.), a liquid suitable method (about 15 μl of pure water is gently applied to the measurement surface). Measure the contact angle 0.5 seconds after hanging and contacting).

  The surface roughness (the definition will be described later) of the releasable layer according to the present invention is preferably 0.2 μm or less, and more preferably 0.1 μm or less.

  The thickness of the release layer according to the present invention is preferably 1 μm to 50 μm, and more preferably 10 μm to 30 μm.

  In addition, the releasable layer according to the fixing belt of the present invention and the fixing roller of the present invention is preferably adjusted so that the peeling force is 30 g / 5 cm or more, more preferably from 30 g / 5 cm to 1000 g / 5 cm. In particular, it is preferably 50 g / 5 cm to 600 g / 5 cm.

  Here, the peel force of the release layer is measured by the method described below.

(Method for measuring peel force of releasable layer)
In the case of the fixing belt as shown in FIG. 1, the adhesive tape is applied to the release layer of the fixing belt. In the case of the fixing roller as shown in FIG. 2, the adhesive tape is applied to the release layer of the heating roller or the pressure roller. (Knit-polyester tape No. 31B (manufactured by Nitto Denko Corporation)) was bonded, and the pressure value of the pressure roller was set to 2 kg. The fixing belt or fixing roller was allowed to stand for 20 hours, and then the peel strength of the pressure-sensitive adhesive tape was measured using a commercially available tensile tester under an angle of 180 degrees and a speed of 0.3 m / min.

  However, when both the heating roller and the pressure roller of the fixing roller were provided with a release layer, the peeling force of the release layer on the side in contact with the recording material was measured.

<Adhesive improvement layer>
The adhesion improving layer according to the present invention will be described.

  In the fixing belt and the fixing roller of the present invention, from the viewpoint of effectively preventing film peeling of the fixing member at the time of heat fixing, an adhesion improving layer is provided so as to be adjacent to the base material and the release layer, respectively. It is essential.

  The adhesive improvement layer according to the present invention is a hydroxyl group, a carboxyl group, a group represented by the general formula (a) and the general formula (b) from the viewpoint of improving the adhesion between the substrate and the release layer. It is preferable to contain a compound having at least one reactive group selected from the group consisting of the groups represented.

(Compound having a reactive group)
The compound having a reactive group may be a low molecular compound or a high molecular compound, but in the present invention, a polyvinyl alcohol resin (for example, PVA-124, 224, 424 (both manufactured by Kuraray)), butyral resin ( For example, 3000K (manufactured by Denki Kagaku Kogyo Co., Ltd.), ethylene-vinyl acetate copolymer, olefin resin such as vinylidene chloride and polybutadiene, urethane resin, polyester resin, acrylic resin, epoxy resin, polyethyleneimine system Resins and the like are mentioned as preferable compounds. Of these, butyral resin is preferably used.

  The content of the compound having a reactive group in the adhesion improving layer is preferably 1% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass. In addition, when the adhesion improving layer according to the present invention is composed of a resin having a reactive group (one resin or a mixture of a plurality of resins), in all the repeating units constituting the resin, The content ratio of the repeating unit having a reactive group is preferably 20% or less, more preferably 1% to 20%.

(Coupling agent, isocyanate compound)
The adhesive improvement layer according to the present invention preferably contains at least one compound selected from the group consisting of a silane coupling agent, a titanium coupling agent and an isocyanate compound from the viewpoint of more preferably exhibiting an adhesive effect. However, it is more preferable to contain a titanium coupling agent or an isocyanate compound, and a titanium coupling agent is particularly preferably used.

  Examples of the titanium coupling agent include tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, and bis (dioctyl pyrophosphate) oxyacetate titanate.

  In addition, a monoalkoxy type having an isopropoxy group, a chelate type having an oxyacetic acid residue or an ethylene glycol residue, and a coordinated type in which a phosphite is added to a tetraalkyl titanate can be mentioned.

  Monoalkoxy types include isopropyl dimethacrylisostearoyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-aminoethylaminoethyl) titanate, isopropyl trioctanoyl titanate, isopropyl triisostearoyl titanate Isopropyltridecylbenzenesulfonyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, and the like.

  Further, titanium-i-propoxyoctylene glycolate (TOG: manufactured by Nippon Soda Co., Ltd.), tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium, tetrasteoxy titanium, di -I-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (triethanolaminato) titanium, dihydroxytitanium tri-i-stearate and the like.

  Examples of the chelate type include bis (dioctylpyrophosphate) oxyacetate titanate, dicumylphenyloxyacetate titanate, dicumylphenyloxyacetate titanate, diisostearoylethylene titanate, and the like.

  Examples of coordinated types include tetraisopropyl bis (ditridecyl phosphite) titanate and tetraoctyl bis (ditridecyl phosphite) titanate.

  Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β-. (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxysilane hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltri Examples include methoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, KBM503 (manufactured by Shin-Etsu Chemical Co., Ltd.), p-methylphenyltrimethoxysilane, and the like.

  As an isocyanate compound, the compound represented by the following general formula is mentioned, for example.

General formula O = C = N-L- (N = C = O) v
In the formula, v is 0, 1 or 2, and L represents a divalent linking group having an alkylene group, alkenylene group, arylene group or aralkyl group as a partial structure.

  These groups may further have a substituent, and examples of preferable substituents include halogen (for example, Br and Cl), hydroxyl group, amino group, carboxyl group, alkyl group, alkoxyl group and the like.

  Although the example of the specific isocyanate compound which can be obtained from a manufacturer is shown below, this invention is not limited to these.

IC-1 Desmodur N100, Mobay, aliphatic isocyanate IC-2 Desmodur N3300, Mobay, aliphatic isocyanate IC-3 Mondur TD-80, Mobay, aromatic isocyanate IC-4 Mondeau M, Mobay, aromatic isocyanate IC-5 Mondew MRS, Mobay, polymer isocyanate IC-6 Desmodu W, Mobay, aliphatic isocyanate IC-7 Papi27, Dow, polymer isocyanate IC-8 Isocyanate T1890, Huls (Huels), aliphatic isocyanate IC-9 octadecyl isocyanate, Aldrich, aliphatic isocyanate Further, coronate 2030, coronate 2255, coronate 513, Coronate 2507, Coronate L, Coronate HL, Coronate HK, Coronate HX, Coronate 341, Coronate MX, Coronate 2067, or more Made by Nippon Polyurethanes, Takenate D103H, Takenate D204EA, Takenate D-172N, Takenate D-170N, or more Takeda The product made from a medicine, Sumijoule 3200, Sumijoule 44V-20, Sumijoule IL, the above make by Sumitomo Bayer Urethane Co., Ltd., etc. are mentioned.

  In the present invention, an aluminum coupling agent such as acetoalkoxyaluminum diisopropylate can also be used.

  As content in adhesive improvement layers, such as the above-mentioned coupling agent and an isocyanate compound, 1 mass%-99 mass% are preferable, More preferably, it is 1 mass%-50 mass%.

(Thickness of the adhesive improvement layer)
The film thickness of the adhesion improving layer according to the present invention is preferably adjusted to 1 μm to 300 μm, more preferably 1 μm to 100 μm, and particularly preferably 1 μm to 50 μm.

(Thermoplastic resin)
Examples of the thermoplastic resin according to the present invention include polycarbonate, polyacrylonitrile, polystyrene, polystyrene-acrylic copolymer, polyacrylic ester copolymer, polyvinyl alcohol, polymethacrylic acid, polyvinyl chloride-vinyl acetate copolymer. Polymer, polyethylene, polyethylene-vinyl acetate copolymer, vinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyester, polyamide, polyether, silicon, polybutadiene, styrene-butadiene copolymer, ABS rubber, acrylonitrile-butadiene copolymer , Polyurethane, silicon-acrylic copolymer, acrylic-modified fluororesin, and the like.

  Also included are random copolymers, block copolymers, graft copolymers and the like obtained by copolymerizing these polymer compounds.

  Among them, a styrene-acrylic resin in which a monomer having a vinyl group is polymerized is preferable. Preferred monomers used in this styrene-acrylic resin include styrene and acrylates (acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, methacrylic acid, methyl methacrylate. , Butyl methacrylate) and acrylonitrile, and thermoplastic resins containing these monomers as main components are preferred. For this thermoplastic resin, in addition to styrene-acrylic, vinyl acetate is copolymerized and a part or all of vinyl acetate is led to vinyl alcohol. After polymerization, urethane-modified, silicone-modified, polyvinyl alcohol Those subjected to modification treatment such as modification are also preferably used.

  As the thermoplastic resin according to the present invention, a resin having a specific weight average molecular weight and a specific molecular weight distribution is used. The molecular weight and molecular weight distribution of the thermoplastic resin are measured by gel permeation chromatography (GPC) described later, and are measured as a molecular weight in terms of polystyrene. In the present invention, HLC-8220GPC (column: TSK gel Super HM-M) manufactured by Tosoh Corporation was used.

  From the viewpoint of obtaining the effects described in the present invention, the molecular weight of the thermoplastic resin is preferably a weight average molecular weight in the range of 50,000 to 2,000,000, and the molecular weight distribution is a weight average molecular weight / The number average molecular weight value is preferably 4.0 or more, and more preferably the weight average molecular weight / number average molecular weight value is 4.0 to 15.0.

  The thermoplastic resin having the molecular weight and molecular weight distribution described above can be synthesized by mixing resins having a plurality of molecular weight distributions or referring to a conventionally known synthesis method. After synthesizing a high molecular weight resin, it can be obtained by a known method such as block polymerization or graft polymerization in which a monomer is added to the reaction solution and further polymerized.

  The thermoplastic resin has a glass transition point of 30 ° C to 150 ° C, preferably 50 ° C to 120 ° C. Examples of these are polycarbonate, polyacrylonitrile, polystyrene, polyacrylate ester copolymer, polyvinyl alcohol, polymethacrylic acid, polyvinyl chloride-vinyl acetate copolymer, polyethylene, polyethylene-ethyl acetate copolymer, poly Vinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyester, polyamide, polyether, silicone, polybutadiene, styrene-butadiene copolymer, ABS rubber, acrylonitrile-butadiene copolymer, polyurethane, silicon-acrylic copolymer, acrylic modification A fluororesin etc. are mentioned.

  Also included are random copolymers, block copolymers, graft copolymers and the like obtained by copolymerizing these polymer compounds.

  Preferably, a thermoplastic resin obtained by polymerizing a monomer having a vinyl group is used. Preferred monomers include acrylonitrile, styrene, acrylates (acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, methacrylic acid, methyl methacrylate, butyl methacrylate), acetic acid Examples thereof include vinyl, polyvinyl alcohol, butadiene, vinyl chloride, and polyvinylidene chloride, and a copolymer in which two or more of these monomers are combined is preferable. Further, a thermoplastic resin, polyurethane, silicone-acrylic copolymer, or the like in which vinyl acetate incorporated in the copolymer is saponified and part or all of vinyl acetate is led to vinyl alcohol is preferably used.

  Polyester and polyurethane resins can also be used.

  The thermoplastic resin used in the present invention needs to be appropriately crosslinked. In order to produce a thermoplastic resin having a cross-linking agent, divinylbenzene, trimethanolpropane triacrylate, 1,6- What is necessary is just to superpose | polymerize, after adding a suitable quantity of crosslinking agents more than bifunctional, such as hexanediol diacrylate.

  In the case of a condensable polymer such as polyester and polyurethane, a condensation reaction may be performed using a trifunctional or higher functional alcohol such as trimethylolpropane and a trifunctional or higher functional isocyanate during the production of the polyester or polyurethane.

  In the present invention, after an image is formed on a recording medium, the ink pigment is embedded in a thermoplastic resin softened by pressure or heat by performing treatment with pressure or heat, whereby the ink is recorded on the recording medium. It is considered that the effect of the present invention can be obtained.

(Resin flow softening point)
The at least one resin contained in the adhesion improving layer according to the present invention preferably has a flow softening point of 130 ° C or higher, more preferably in the range of 130 ° C to 400 ° C, and particularly preferably. , 130 ° C to 300 ° C. Examples of the resin include a resin used as a compound having the reactive group described above, the thermoplastic resin described above, and the like.

  Here, the flow softening point according to the present invention was measured using an elevated flow tester CFT-500 (manufactured by Shimadzu Corporation).

"Base material"
The base material for the belt member used for the fixing belt according to the present invention and the respective base materials used for the heating roller and pressure roller of the fixing roller according to the present invention will be described.

  From the viewpoint of preferably obtaining the effects described in the present invention, the base material used for the belt member is preferably seamless nickel-plated brass, and the base material of the heating roller and pressure roller is preferably nickel. Moreover, it is preferable that the thickness of a base material is 10 micrometers-100 micrometers.

  In addition to nickel, aluminum, iron, polyethylene, or the like can be used as the base material.

The surface roughness of the base material of the fixing belt according to the present invention is preferably 0.1 μm or less, and more preferably 0.08 μm or less. Furthermore, the Young's modulus is preferably 50 kN / mm ² or more, and more preferably 50 kN / mm ^{2 to} 300 kN / mm ² .

"Surface roughness"
Here, measurement of the surface roughness of the releasable layer and the surface roughness of the base material of the fixing belt or the fixing roller will be described.

  In the present invention, the average surface roughness Ra was measured according to the following method.

  Using an Seismic Instruments SPI3800N probe station and SPA400 multifunctional unit as an atomic force microscope (AFM), a sample cut into a size of about 1 cm square is placed on a horizontal sample table on a piezo scanner. When the cantilever was approached to the sample surface and reached the region where the atoms were working, scanning was performed in the XY direction, and the unevenness of the sample at that time was detected by the displacement of the piezo in the Z direction. A piezo scanner that can scan XY 20 μm and Z 2 μm was used. The cantilever was a silicon cantilever SI-DF20 manufactured by Seiko Instruments Inc., which had a resonance frequency of 120 to 150 kHz and a spring constant of 12 to 20 N / m, and was measured in a DFM mode (Dynamic Force Mode). A measurement area of 2 μm square was measured with a 1 (or 2) field of view and a scanning frequency of 1 Hz. Further, the obtained three-dimensional data was approximated by least squares to correct a slight inclination of the sample and obtain a reference plane.

  To analyze the surface roughness, call the surface roughness analysis from the “Analysis” menu of the analysis software SPIwin (ver. 2.05D2, Seiko Instruments Inc.), and obtain the average surface roughness from the obtained three-dimensional data. It was.

The measurement surface represented by the measurement is represented by Z = F (X, Y). The range of (X, Y) is (0, 0) to (X _max , Y _max ). Assuming that it is a designated surface * to be subjected to roughness analysis, the surface area S ₀ is obtained by the following equation.

S ₀ = X _max · Y _max
When the average value of the Z data in the specified plane is Z ₀ , Z ₀ is obtained by the following equation when the plane where Z = Z ₀ is used as the reference plane.

  Separately, according to JIS B601, the centerline average roughness (Ra) is extracted from the roughness curve in the direction of the centerline by measuring the length L, the centerline direction of the extracted portion is the X axis, and the direction of the vertical magnification (X The vertical axis) is the Y axis, and the roughness curve is Y = F (X),

Is defined as the value given by.

  In the present invention, this center line average roughness Ra is defined as a surface roughness (also referred to as average roughness Ra) according to the present invention, which is three-dimensionally extended so that it can be applied to the measurement surface, The absolute value of the deviation from the surface to the specified surface was expressed as an average value, and the value obtained by applying the following equation was used.

  A method for manufacturing the fixing belt and the fixing roller according to the present invention will be described.

  In the manufacture of the fixing belt and the fixing roller according to the present invention, the surface of the fixing belt and the fixing roller on the side in contact with the recording material is coated with a dip coating method, a bar coating method, a blade coating method, an air knife method, a slide coating device, and a curtain. After applying and improving the adhesion improving layer by coating, etc., after the curable silicone such as solvent addition type silicone or solvent condensation type silicone is dip coated on the adhesion improving layer, the mold is released through heat curing. It is preferable that a conductive layer is formed.

  Among these, it is preferable to apply each of the adhesion improving layer and the release layer by a dip coating method. The viscosity of the coating solution when performing dip coating is preferably adjusted to a range of 0.01 Pa · s to 0.5 Pa / s.

  Moreover, in this invention, it is preferable to have the process of performing the aging process A and the process of performing the aging process B after coating of the said release layer.

  Here, the aging treatment A represents, for example, immersing the fixing belt or fixing roller after application of the releasable layer in water, spraying with steam, and storing with aging under high temperature and high humidity. The temperature range is 25 ° C. to 100 ° C., and the high humidity level is 50% RH or more, preferably 50% RH to 95% RH.

  The aging treatment B represents that the fixing belt or the fixing roller is treated under high temperature and low humidity after the aging treatment A. The high temperature is preferably in the range of 40 ° C. to 200 ° C., more preferably 40 ° C. It is the range of -150 degreeC, and low humidity represents relative humidity less than 50% RH.

  The recording material (also referred to as recording medium) according to the present invention will be described.

  The recording material is not particularly limited as long as it can receive pigment ink and form an image, but preferably has an ink absorbing layer on a support from the viewpoint of strength.

  As the support, a support conventionally used for ink jet recording materials, for example, a paper support such as plain paper, art paper, coated paper and cast coated paper, a plastic support, and a paper support coated with polyolefin on both sides. The composite support body which bonded the body and these can be used.

  For the purpose of increasing the adhesive strength between the support and the ink absorbing layer, the support is preferably subjected to corona discharge treatment, subbing treatment or the like prior to application of the ink absorbing layer. Furthermore, the recording paper of the present invention is not necessarily colorless, and may be a colored recording paper. In addition, it is particularly preferable to use a paper support in which both sides of the base paper support are laminated with polyethylene because the recorded image is close to photographic image quality and a high-quality image can be obtained at low cost.

  Such a paper support laminated with polyethylene will be described below.

  The base paper used for the paper support is made from wood pulp as a main raw material, and if necessary, paper is made using synthetic pulp such as polypropylene or synthetic fiber such as nylon or polyester in addition to wood pulp. As wood pulp, for example, any of LBKP, LBSP, NBKP, NBSP, LDP, NDP, LUKP, NUKP can be used, but more LBKP, NBSP, LBSP, NDP, LDP with more short fibers are used. Is preferred. However, the ratio of LBSP or LDP is preferably 10% by mass or more and 70% by mass or less.

  As the pulp, chemical pulp (sulfate pulp or sulfite pulp) with less impurities is preferably used, and a pulp whose whiteness is improved by bleaching is also useful.

  In the base paper, for example, sizing agents such as higher fatty acids and alkyl ketene dimers, white pigments such as calcium carbonate, talc and titanium oxide, paper strength enhancers such as starch, polyacrylamide and polyvinyl alcohol, fluorescent whitening agents, polyethylene Water retaining agents such as glycols, dispersants, softening agents such as quaternary ammonium, and the like can be added as appropriate.

  The freeness of the pulp used for papermaking is preferably 200 to 500 ml as defined by CSF, and the fiber length after beating is 24% by mass as defined in JIS-P-8207, and 42 mesh residue. 30 to 70% is preferable. In addition, it is preferable that the mass% of 4 mesh remainder is 20 mass% or less.

  The basis weight of the base paper is preferably 30 to 250 g, and particularly preferably 50 to 200 g. The thickness of the base paper is preferably 40 to 250 μm.

The base paper can be given a high smoothness by calendering at the paper making stage or after paper making. The density of the base paper is generally 0.7 to 1.2 g / m ² (JIS-P-8118). Furthermore, the base paper stiffness is preferably 20 to 200 g under the conditions specified in JIS-P-8143.

  A surface sizing agent may be applied to the surface of the base paper. As the surface sizing agent, a sizing agent such as a higher fatty acid or an alkyl ketene dimer that can be added to the base paper can be used.

  The pH of the base paper is preferably 5 to 9 when measured by a hot water extraction method defined in JIS-P-8113.

  The polyethylene covering the front and back surfaces of the base paper is mainly low-density polyethylene (LDPE) and / or high-density polyethylene (HDPE), but some other LLDPE, polypropylene, etc. can also be used.

  In particular, the polyethylene layer on the ink absorbing layer side is preferably one in which rutile or anatase type titanium oxide is added to polyethylene to improve opacity and whiteness, as is widely done in photographic paper. The titanium oxide content is usually 3 to 20% by mass, preferably 4 to 13% by mass, based on polyethylene.

  Polyethylene-coated paper can be used as glossy paper. Also, when polyethylene is melt-extruded on the surface of the base paper and coated, a so-called molding process is performed to form a matte or silky surface that can be obtained with ordinary photographic paper. These can also be used in the present invention.

  The amount of polyethylene used on the front and back of the base paper is selected so as to optimize curling under low and high humidity after providing a void layer and a back layer. Usually, the polyethylene layer on the void layer side is 20 μm to 40 μm and the back layer side is in the range of 10 μm to 30 μm.

  Further, the polyethylene-coated paper support preferably has the following characteristics.

1. Tensile strength: The strength specified in JIS-P-8113 is preferably 2 to 30 kg in the vertical direction and 1 to 20 kg in the horizontal direction. 2. Tear strength: 10 to 200 g in the longitudinal direction and 20 to 200 g in the lateral direction are preferred according to the stipulated method according to JIS-P-8116. Compression modulus ≧ 98.1 MPa
4). Surface Beck smoothness: 20 seconds or more is preferable as a glossy surface under the conditions specified in JIS-P-8119, but it may be less than this for a so-called molded product. Surface roughness: The surface average roughness specified in JIS-B-0601 preferably has a maximum height of 10 μm or less per reference length of 2.5 mm. Opacity: when measured by the method defined in JIS-P-8138, 80% or more, particularly 85 to 98% is preferable. Whiteness: L *, a *, and b * specified in JIS-Z-8729 are preferably L * = 80 to 95, a * = − 3 to +5, and b * = − 6 to +2. 8. Surface glossiness: 60 degree specular glossiness defined in JIS-Z-8741 is preferably 10 to 95%. Clark stiffness: Clark stiffness in the conveying direction of the recording sheet, the support is 50~300cm ^2/100 is preferably 10. Moisture content of middle paper: usually 2 to 100% by weight, preferably 2 to 6% by weight, based on the middle paper
The ink absorbing layer of the recording material is roughly divided into a swelling type and a void type.

  As the swelling type, as the hydrophilic binder, for example, gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide or the like applied alone or in combination and used as an ink absorbing layer can be used.

  As the void type, fine particles and a hydrophilic binder are mixed and applied, and particularly glossy ones are preferable. As the fine particles, alumina or silica is preferable, and those using silica having a particle diameter of 0.1 μm or less are particularly preferable. As the hydrophilic binder, for example, gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide and the like are preferably used alone or in combination.

  In order to give suitability to continuous or high-speed printing, it is suitable that the ink absorption speed of the recording material is fast. From this point, a void type can be particularly preferably used.

  The void-type ink absorbing layer used in the present invention will be described.

  The void layer is mainly formed by soft aggregation of a hydrophilic binder and inorganic fine particles. Conventionally, various methods for forming voids in a film are known. For example, a uniform coating solution containing two or more kinds of polymers is coated on a support, and these polymers are phase-separated from each other in the drying process. A method of forming voids by applying a coating liquid containing solid fine particles and a hydrophilic or hydrophobic binder on a support, and after drying, the ink jet recording paper is immersed in water or a liquid containing an appropriate organic solvent. A method of creating voids by dissolving solid fine particles, a method of forming voids in the film by foaming this compound in the drying process after applying a coating solution containing a compound that foams during film formation, porous A coating liquid containing porous solid fine particles and a hydrophilic binder on a support to form voids in the porous fine particles or between the fine particles, approximately equal to or more than the hydrophilic binder The coating solution containing the solid particles and or particulate oil and a hydrophilic binder having a volume and coated on a support, and a method of making an air gap between the solid particles are known. In the present invention, it is particularly preferable that the void layer is formed by containing various inorganic solid fine particles having an average particle diameter of 100 nm or less.

  Examples of the inorganic fine particles used for the above purpose include light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc hydroxide, zinc sulfide. , Zinc carbonate, hydrotalcite, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, pseudoboehmite, aluminum hydroxide, lithopone, zeolite, magnesium hydroxide, etc. A white inorganic pigment etc. can be mentioned.

  The average particle size of the inorganic fine particles is obtained by observing the particles themselves or the particles appearing on the cross section or surface of the void layer with an electron microscope, obtaining the particle size of 1,000 arbitrary particles, and calculating the simple average value (number average). As required. Here, the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.

  As the solid fine particles, it is preferable to use solid fine particles selected from silica and alumina or alumina hydrate, and silica is more preferable.

  As the silica, silica synthesized by a usual wet method, colloidal silica, silica synthesized by a gas phase method, or the like is preferably used, and the fine particle silica particularly preferably used in the present invention is a colloidal silica or a gas phase method. Synthesized fine particle silica, especially fine particle silica synthesized by the vapor phase method not only provides high porosity, but also adds coarse aggregates when added to the cationic polymer used to immobilize the dye. It is preferable because it is difficult to form. Alumina or alumina hydrate may be crystalline or amorphous, and any shape such as amorphous particles, spherical particles, and acicular particles can be used.

  The fine particles are preferably in a state where the fine particle dispersion before mixing with the cationic polymer is dispersed to the primary particles.

  The inorganic fine particles preferably have a particle size of 100 nm or less. For example, in the case of the above vapor phase method fine particle silica, the average particle size of primary particles of inorganic fine particles dispersed in a primary particle state (particle size in a dispersion state before coating) is preferably 100 nm or less, More preferably, it is 4-50 nm, Most preferably, it is 4-20 nm.

  As the silica synthesized by the vapor phase method in which the average particle diameter of primary particles is 4 to 20 nm, which is most preferably used, for example, Aerosil manufactured by Nippon Aerosil Co., Ltd. is commercially available. The vapor phase fine particle silica can be dispersed to primary particles relatively easily by sucking and dispersing in water using, for example, a jet stream inductor mixer manufactured by Mitamura Riken Kogyo Co., Ltd.

  Examples of the hydrophilic binder include polyvinyl alcohol, gelatin, polyethylene oxide, polyvinyl pyrrolidone, polyacrylic acid, polyacrylamide, polyurethane, dextran, dextrin, color ginan (κ, ι, λ, etc.), agar, pullulan, water-soluble polyvinyl butyral. , Hydroxyethyl cellulose, carboxymethyl cellulose and the like. Two or more of these water-soluble resins can be used in combination.

  The water-soluble resin preferably used in the present invention is polyvinyl alcohol. The polyvinyl alcohol preferably used in the present invention includes, in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate, modified polyvinyl alcohol such as polyvinyl alcohol having a cation-modified terminal and anion-modified polyvinyl alcohol having an anionic group. Alcohol is also included.

  The polyvinyl alcohol obtained by hydrolyzing vinyl acetate preferably has an average polymerization degree of 1,000 or more, and particularly preferably has an average polymerization degree of 1,500 to 5,000. The saponification degree is preferably 70 to 100%, particularly preferably 80 to 99.5%.

  Examples of the cation-modified polyvinyl alcohol have primary to tertiary amino groups and quaternary ammonium groups in the main chain or side chain of the polyvinyl alcohol as described in JP-A-61-110483. Polyvinyl alcohol, which is obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.

  Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl) ammonium chloride. N-vinylimidazole, N-vinyl-2-methylimidazole, N- (3-dimethylaminopropyl) methacrylamide, hydroxylethyltrimethylammonium chloride, trimethyl- (2-methacrylamidopropyl) ammonium chloride, N- (1, 1-dimethyl-3-dimethylaminopropyl) acrylamide and the like.

  The ratio of the cation-modified group-containing monomer of the cation-modified polyvinyl alcohol is 0.1 to 10 mol%, preferably 0.2 to 5 mol%, relative to vinyl acetate.

  Examples of the anion-modified polyvinyl alcohol include polyvinyl alcohols having an anionic group as described in JP-A-1-2060888, vinyls as described in JP-A-61-237681 and JP-A-63-3079799. Examples thereof include a copolymer of an alcohol and a vinyl compound having a water-soluble group, and modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.

  Nonionic modified polyvinyl alcohol is, for example, a polyvinyl alcohol derivative obtained by adding a polyalkylene oxide group to a part of vinyl alcohol as described in JP-A-7-9758, and described in JP-A-8-25595. And a block copolymer of a vinyl compound having a hydrophobic group and vinyl alcohol.

  Polyvinyl alcohol can be used in combination of two or more, such as the degree of polymerization and the type of modification.

The amount of inorganic fine particles used in the colorant receiving layer depends largely on the required ink absorption capacity, the porosity of the void layer, the type of inorganic fine particles, and the type of water-soluble resin, but generally per 1 m ² of recording paper. Usually, 5 to 30 g, preferably 10 to 25 g.

  Further, the ratio of the inorganic fine particles and the water-soluble resin used in the colorant receiving layer is usually 2: 1 to 20: 1 by mass ratio, and preferably 3: 1 to 10: 1.

The colorant-receiving layer may contain a cationic water-soluble polymer having a quaternary ammonium base in the molecule, and is usually 0.1 to 10 g, preferably 0.2 to 5 g, per 1 m ^{2 of} inkjet recording paper. Used in a range.

In the void layer, the total amount of voids (void volume) is preferably 20 ml or more per 1 m ² of recording paper. When the void volume is less than 20 ml / m ² , the ink absorbency is good when the amount of ink at the time of printing is small, but when the amount of ink increases, the ink is not completely absorbed and the image quality deteriorates, Problems such as delay in drying are likely to occur.

  In the void layer having ink retention ability, the void volume relative to the solid content volume is referred to as a void ratio. In the present invention, it is preferable to set the porosity to 50% or more because the voids can be efficiently formed without unnecessarily increasing the film thickness.

  As another type of void type, in addition to forming an ink solvent absorption layer using inorganic fine particles, a polyurethane resin emulsion and a water-soluble epoxy compound and / or acetoacetylated polyvinyl alcohol are used in combination, and further an epichlorohydrin polyamide resin is used in combination. The ink solvent absorption layer may be formed using the applied coating liquid. The polyurethane resin emulsion in this case is preferably a polyurethane resin emulsion having a polycarbonate chain, a polycarbonate chain and a polyester chain and a particle diameter of 3.0 μm, and the polyurethane resin of the polyurethane resin emulsion is a polyol having a polycarbonate polyol, a polycarbonate polyol and a polyester polyol. More preferably, the polyurethane resin obtained by reacting with an aliphatic isocyanate compound has a sulfonic acid group in the molecule, and further has an epichlorohydrin polyamide resin, a water-soluble epoxy compound and / or an acetoacetylated vinyl alcohol. .

  In the ink solvent absorption layer using the polyurethane resin, it is estimated that weak aggregation of cations and anions is formed, and accordingly, voids having ink solvent absorption ability are formed, so that an image can be formed.

  In the present invention, it is preferable to provide a layer containing a thermoplastic resin on the surface layer of the ink absorbing layer in order to achieve the object of the present invention.

  The layer containing a thermoplastic resin may be a layer made of only a thermoplastic resin or may be added with a water-soluble binder or the like as required. The thermoplastic resin is preferably in the form of fine particles from the viewpoint of ink permeability.

  Examples of the thermoplastic resin or fine particles include polycarbonate, polyacrylonitrile, polystyrene, polyacrylic acid, polymethacrylic acid, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyester, polyamide, polyether, and copolymers thereof. And styrene-acrylic acid ester copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylic acid ester copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester. A copolymer and SBR latex are preferred. As the thermoplastic resin or fine particles, a plurality of polymers having different monomer compositions, particle sizes, and polymerization degrees may be mixed and used.

  In selecting a thermoplastic resin or fine particles, ink acceptability, glossiness of an image after fixing by heating and pressing, image fastness, and releasability should be taken into consideration.

  Regarding the ink receptivity, when the particle diameter of the thermoplastic fine particles is less than 0.05 μm, the separation of the pigment particles and the ink solvent in the pigment ink is slowed, resulting in a decrease in the ink absorption rate. On the other hand, when the thickness exceeds 10 μm, it is not preferable from the viewpoint of the adhesiveness with the solvent absorbing layer adjacent to the ink receiving layer when coated on the support and the coating strength of the ink jet recording material after coating and drying. For this reason, the preferable thermoplastic resin fine particle diameter is preferably 0.05 μm to 10 μm, more preferably 0.1 μm to 5 μm. More preferably, it is 0.1 micrometer-1 micrometer.

  Further, the glass transition point (Tg) may be mentioned as a criterion for selecting the thermoplastic resin or fine particles. When Tg is lower than the coating and drying temperature, for example, the coating and drying temperature at the time of recording material production is already higher than Tg, and voids due to thermoplastic fine particles for allowing the ink solvent to pass through disappear.

  Also, if Tg is higher than the temperature at which the support is denatured by heat, a fixing operation at a high temperature is required for melt film formation after ink jet recording with pigment ink, and the load on the apparatus and the heat stability of the support are stable. Sex is a problem. The preferable Tg of the thermoplastic fine particles is 50 ° C to 150 ° C. Moreover, as minimum film-forming temperature (MFT), the thing of 50 to 150 degreeC is preferable.

  The thermoplastic fine particles are preferably dispersed in an aqueous system from the viewpoint of environmental suitability, and an aqueous latex obtained by emulsion polymerization is particularly preferable. At this time, the emulsion polymerized type using a nonionic dispersant as an emulsifier is a form that can be preferably used.

  The thermoplastic fine particles to be used are preferably less residual monomer components from the viewpoint of odor and safety, preferably 3% or less, more preferably 1% or less, particularly preferably 0. 1% or less is preferable.

  As the water-soluble binder, polyvinyl alcohol or polyvinyl pyrrolidone can be used in the range of 1 to 10% of the thermoplastic fine particles.

  As the recording material according to the present invention, a recording material having an ink absorbing layer on a support and a surface layer containing at least an inorganic pigment and thermoplastic fine particles is preferably used.

  In particular, the following points can be given as preferable reasons.

(A) High ink absorption speed, low image quality degradation such as beading and color bleeding, and high-speed printing suitability (b) High image surface strength (c) Fusing in overlapping during image storage (D) Excellent coating productivity of the ink absorption layer (e) Excellent writing property In this case, the mass ratio of the thermoplastic fine particles of the surface layer to the inorganic pigment is the thermoplastic fine particles and the inorganic fine particles. It is preferably determined individually depending on the pigment and other additives, and is not particularly limited, but the thermoplastic fine particles / inorganic pigment is preferably selected in the range of 2/8 to 8/2, more preferably 3/7 to 7/3, and more preferably 4/6 to 6/4.

  Next, the colorant used in the present invention will be described.

  As the colorant that can be used in the present invention, conventionally known colorants can be used without particular limitation, and are water-soluble dyes, water-dispersible dyes, water-dispersible pigments, solvent-soluble dyes, solvent-dispersible dyes, solvent-dispersible pigments. Any of these can be used, but among these, solvent-dispersible pigments are preferably used in the present invention.

  These may be used alone or in combination. Among these, particularly preferred colorants are dispersed particles of a dispersible dye or a dispersible pigment. Representative colorants are listed below, but the present invention is not limited to these.

<Direct dye>
C. I. Direct Yellow 1, 4, 8, 11, 12, 24, 26, 27, 28, 33, 39, 44, 50, 58, 85, 86, 100, 110, 120, 132, 142, 144;
C. I. Direct Red 1, 2, 4, 9, 11, 13, 17, 20, 23, 24, 28, 31, 33, 37, 39, 44, 47, 48, 51, 62, 63, 75, 79, 80, 81, 83, 89, 90, 94, 95, 99, 220, 224, 227, 243;
C. I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 71, 76, 78, 80, 86, 87, 90, 98, 106, 108, 120, 123, 163, 165, 192, 193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 236, 237;
C. I. Direct Black 2, 3, 7, 17, 19, 22, 32, 38, 51, 56, 62, 71, 74, 75, 77, 105, 108, 112, 117, 154
<Acid dye>
C. I. Acid Yellow 2, 3, 7, 17, 19, 23, 25, 29, 38, 42, 49, 59, 61, 72, 99;
C. I. Acid Orange 56, 64;
C. I. Acid Red 1, 8, 14, 18, 26, 32, 37, 42, 52, 57, 72, 74, 80, 87, 115, 119, 131, 133, 134, 143, 154, 186, 249, 254, 256;
C. I. Acid Violet 11, 34, 75;
C. I. Acid Blue 1, 7, 9, 29, 87, 126, 138, 171, 175, 183, 234, 236, 249;
C. I. Acid Green 9, 12, 19, 27, 41;
C. I. Acid Black 1, 2, 7, 24, 26, 48, 52, 58, 60, 94, 107, 109, 110, 119, 131, 155
<Reactive dye>
C. I. Reactive Yellow 1, 2, 3, 13, 14, 15, 17, 37, 42, 76, 95, 168, 175;
C. I. Reactive Red 2, 6, 11, 21, 22, 23, 24, 33, 45, 111, 112, 114, 180, 218, 226, 228, 235;
C. I. Reactive Blue 7, 14, 15, 18, 19, 21, 25, 38, 49, 72, 77, 176, 203, 220, 230, 235;
C. I. Reactive Orange 5, 12, 13, 35, 95;
C. I. Reactive Brown 7, 11, 33, 37, 46;
C. I. Reactive Green 8, 19;
C. I. Reactive violet 2, 4, 6, 8, 21, 22, 25;
C. I. Reactive Black 5, 8, 31, 39
<Basic dye>
C. I. Basic yellow 11, 14, 21, 32;
C. I. Basic Red 1, 2, 9, 12, 13;
C. I. Basic violet 3, 7, 14;
C. I. Basic blue 3, 9, 24, 25
Examples of the dye for ink used in the present invention include chelate dyes and azo dyes used in so-called silver dye bleaching photosensitive materials (for example, Cibachrome manufactured by Ciba Geigy).

  With respect to the chelate dye, for example, the description of British Patent 1,077,484 can be referred to.

  Regarding the azo dyes for silver dye bleaching photosensitive material, for example, British Patent Nos. 1,039,458, 1,004,957, 1,077,628, and U.S. Pat. No. 2,612,448 are described. It can be helpful.

  The content of the water-soluble dye used in the ink of the present invention is preferably 1 to 15% by mass with respect to the total mass of the ink.

Examples of the disperse dye preferably used in the present invention include C.I. I. Disperse Yellow 3, 4, 5, 7, 9, 13, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68, 71, 74 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 114, 116, 118, 119, 122, 124, 126, 135, 140, 141, 149 160, 162, 163, 164, 165, 179, 180, 182, 183, 186, 192, 198, 199, 202, 204, 210, 211, 215, 216, 218, 224;
C. I. Disperse Orange 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 47, 48, 49, 50 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130, 139, 142 ;
C. I. Disperse Red 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 288, 298, 302, 303, 310, 311, 312, 320, 324, 328;
C. I. Disperse Violet 1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69 77;
C. I. Disperse Green 9;
C. I. Disperse Brown 1, 2, 4, 9, 13, 19;
C. I. Disperse Blue 3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 79, 81 , 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143, 146 148, 149, 153, 154, 158, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214 224, 225, 257, 259, 267, 268, 270, 284, 285, 287, 288, 291, 293, 295, 2 97, 301, 315, 330, 333;
C. I. Disperse Black 1, 3, 10, 24;
Etc.

  As the colorant used in the present invention, it is preferable to use a pigment from the viewpoint of obtaining good glossiness. Further, for example, as pigments used in pigment ink, organic pigments such as insoluble pigments and lake pigments, carbon black, and the like can be preferably used.

  The insoluble pigment is not particularly limited. Dioxazine, thiazole, phthalocyanine, diketopyrrolopyrrole and the like are preferable.

  Specific pigments that can be preferably used include the following pigments.

  Examples of the magenta or red pigment include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. And CI Pigment Red 222.

  Examples of the pigment for orange or yellow include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. And CI Pigment Yellow 138.

  Examples of the pigment for green or cyan include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Green 7.

  In addition, for example, carbon black pigment (CI Pigment Black 7); I. Pigment Yellow 12, 13, 14, 16, 17, 73, 74, 75, 83, 108, 109, 110, 180, 182; C.I. I. Pigment Red 5, 7, 12, 112, 123, 168, 184, 202; I. Pigment Blue 1, 2, 3, 15: 3, 16, 22, 60; I. Vat Blue 4, 60; and the like.

In addition to the above, when red, green, blue and intermediate colors are required, the following pigments are preferably used alone or in combination. I. Pigment Red 209, 224, 177, 194;
C. I. Pigment Orange 43;
C. I. Vat Violet 3;
C. I. Pigment Violet 19, 23, 37;
C. I. Pigment Green 36, 7;
C. I. Pigment Blue 15: 6;
Etc. are used.

  The pigments and disperse dyes used in the present invention are preferably used after being dispersed by a disperser together with a dispersant and other additives necessary for various desired purposes. As the disperser, a conventionally known ball mill, sand mill, line mill, high-pressure homogenizer, or the like can be used.

  A surfactant is used as the dispersant. As the surfactant used in the present invention, any of cationic, anionic, amphoteric and nonionic can be used. Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Examples of the anionic surfactant include fatty acid soap, N-acyl-N-methylglycine salt, N-acyl-N-methyl-β-alanine salt, N-acyl glutamate, acylated peptide, alkyl sulfonate, Alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl sulfoacetate, α-olefin sulfonate, N-acylmethyl taurine, sulfated oil, higher alcohol sulfate, secondary higher alcohol Sulfate ester, alkyl ether sulfate, secondary higher alcohol ethoxy sulfate, polyoxyethylene alkyl phenyl ether sulfate, monoglyculate, fatty acid alkylolamide sulfate, alkyl ether phosphate ester, alkyl phosphate ester Examples include tellurium salts. Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine and the like. Nonionic activators include polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, Oxyethylene castor oil, hydrogenated castor oil, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, fatty acid alkanolamide, polyoxyethylene Fatty acid amide, polyoxyethylene alkylamine, alkylamine oxide, acetyl Glycol, acetylene alcohol, and the like.

  Further, for example, when the above colorant is used as an inkjet ink, it is preferable to use a surfactant in order to accelerate the penetration of ink droplets after ink discharge into the medium. The activator is not limited as long as it does not have an adverse effect on the ink, such as storage stability, and the same surfactant as that used as the dispersant is used.

  In the present invention, an electrical conductivity regulator can also be used. Examples of the electrical conductivity regulator include inorganic salts such as potassium chloride, ammonium chloride, sodium sulfate, sodium nitrate, and sodium chloride, and aqueous solutions such as triethanolamine. There are sex amines.

  In the ink used in the present invention, according to the purpose of improving discharge stability, print head and ink cartridge compatibility, storage stability, image storage stability, and other various performances, a viscosity adjusting agent, a specific resistance adjusting agent, Film forming agents, ultraviolet absorbers, antioxidants, anti-fading agents, rust inhibitors, preservatives, and the like can also be added.

  The ink used in the present invention contains water and a water-soluble organic solvent as main liquid medium components. Examples of the water-soluble organic solvent include alkyl alcohols having 1 to 4 carbon atoms (for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, etc. ), Amides (eg, dimethylformamide, dimethylacetamide, etc.), ketones or ketoalcohols (eg, acetone, diacetone alcohol, etc.), ethers (eg, tetrahydrofuran, dioxane, etc.), polyalkylene glycols (eg, polyethylene glycol, polypropylene glycol) Etc.), alkylene glycols in which the alkylene group contains 2 to 6 carbon atoms (eg ethylene glycol, propylene glycol, butylene glycol, Tylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol, etc.), glycerin, polyhydric alcohol lower alkyl ethers (ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, triethylene Glycol monomethyl (or ethyl) ether) and the like.

  Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether are preferred.

  The content of the water-soluble organic solvent in the ink is generally 10 to 70%, preferably 30 to 65%, and particularly preferably 40 to 60% by mass% with respect to the total mass of the ink.

  The ink-jet ink used in the present invention is preferably added with thermoplastic resin particles for the purpose of increasing adhesion to the transfer medium and image strength on the transfer medium. It is particularly preferable to coat the dispersed particles of the colorant with a resin. As a combination with the colorant, the thermoplastic resin particles can be preferably used in any of the dissolved dye system, the disperse dye system, and the dispersed pigment system, and the resin coat can be particularly preferably used in the disperse dye system and the dispersed pigment system. . The thermoplastic resin particles preferably have a melting point of 30 ° C. or higher, more preferably 40 ° C. or higher, in order to stabilize liquid properties at room temperature. As a thermoplastic resin, what is used for the transfer layer mentioned later can be mentioned. As the coating agent for the particles used for the resin coating, a conventionally known thermoplastic resin having a melting point of 40 ° C. or higher can be used without any particular limitation, and more preferably, the melting point is 50 ° C. or higher. Acid ester, methacrylate ester, styrene, styrene-acrylic copolymer, styrene butadiene copolymer, acrylonitrile butadiene copolymer, polybutadiene, vinyl acetate, polyvinyl chloride, polyvinylidene chloride, ethylene vinyl acetate copolymer Homopolymerized or copolymerized resin emulsions such as olefins and monomers having hydrophilic functional groups such as amino groups, amide groups, carboxyl groups, hydroxyl groups, microemulsions, internal three-dimensionally crosslinked organic fine particles, paraffin wax, polyethylene wax, carnauba Natural such as wax Synthetic wax emulsion, can be mentioned a latex, a colloidal solution, a suspension or the like.

  As the ink used for image formation, a water-based ink composition, an oil-based ink composition, a solid (phase change) ink composition, or the like can be used, but a water-based ink composition (for example, 10% by mass or more per total ink mass) A water-based inkjet recording liquid containing the above water can be particularly preferably used.

  These pigments may use a pigment dispersant as needed. Examples of the pigment dispersant that can be used include higher fatty acid salts, alkyl sulfates, alkyl ester sulfates, alkyl sulfonates, and sulfosuccinates. , Naphthalene sulfonate, alkyl phosphate, polyoxyalkylene alkyl ether phosphate, polyoxyalkylene alkyl phenyl ether, polyoxyethylene polyoxypropylene glycol, glycerin ester, sorbitan ester, polyoxyethylene fatty acid amide, amine oxide, etc. Activators, or styrene, styrene derivatives, vinyl naphthalene derivatives, acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, fumaric acid derivatives. Block copolymer comprising a body, a random copolymer and can be exemplified salts thereof.

  The method for dispersing the pigment is not particularly limited, but various methods such as ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, paint shaker, etc. Can be used.

  In order to remove the coarse particles of the pigment dispersion according to the present invention, it is also preferable to use a centrifugal separator or a filter.

  The average particle size of the pigment in the pigment ink is selected in consideration of stability in the ink, image density, glossiness, light resistance, etc. In addition, the inkjet pigment image forming method of the present invention improves glossiness. From the viewpoint of improving the texture, it is preferable to select the particle size. In the present invention, the reason for improving gloss and texture is not clear, but it is presumed that the pigment is related to the state that the thermoplastic fine particles are dispersed in the melted film in the image. For the purpose of high-speed processing, it is necessary to form thermoplastic fine particles into a melt film in a short time and to sufficiently disperse the pigment in the film. At this time, the surface area of the pigment has a great influence, and therefore it is assumed that an optimum region exists in the average particle diameter.

  The water-based ink composition which is a preferable form as the pigment ink preferably uses a water-soluble organic solvent in combination.

  Examples of water-soluble organic solvents include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols (For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ether (E.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Tylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono Butyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc.), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine) , Ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.) ), Heterocyclic rings (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone), sulfoxides (for example, dimethyl sulfoxide) , Sulfones (for example, sulfolane), urea, acetonitrile, acetone and the like. Preferable water-soluble organic solvents include polyhydric alcohols. Furthermore, it is particularly preferable to use a polyhydric alcohol and a polyhydric alcohol ether in combination.

  The water-soluble organic solvent may be used alone or in combination. The total amount of the water-soluble organic solvent added to the ink is 5% by mass to 60% by mass, and preferably 10% by mass to 35% by mass.

  The ink composition is suitable for the purpose of improving ejection stability, print head and ink cartridge compatibility, storage stability, image storage stability, and other various performances, thermoplastic fine particles, viscosity modifiers, surface tension modifiers, ratios. Resistance adjusting agents, film forming agents, dispersants, surfactants, ultraviolet absorbers, antioxidants, fading inhibitors, antifungal agents, rust inhibitors, and the like can be added as appropriate.

  In particular, the addition of thermoplastic fine particles is preferable for obtaining the effects of the present invention. As the thermoplastic fine particles, the types described in the description of the thermoplastic resin or fine particles that can be added to the surface layer of the recording material can be used. In particular, it is preferable to apply those which do not cause thickening or precipitation even when added to the ink. The average particle size of the thermoplastic fine particles is preferably 0.5 μm or less, and more preferably selected from the range of 0.2 to 2 times the average particle size of the pigment in the ink from the viewpoint of stability. The thermoplastic fine particles to be added are preferably those that melt and soften in the range of 50 ° C to 200 ° C.

  The ink composition has a viscosity at the time of flight of preferably 40 mPa · s or less, and more preferably 30 mPa · s or less.

  The ink composition preferably has a surface tension at the time of flight of 20 mN / m or more, more preferably 30 mN / m to 45 mN / m.

  The pigment solid content concentration in the ink can be selected in the range of 0.1% by mass to 10% by mass, and in order to obtain a photographic image, it is preferable to use so-called dark and light inks having different pigment solid content concentrations. It is particularly preferable to use magenta, cyan, and black dark and light inks. It is also preferable from the viewpoint of color reproducibility to use special color inks such as red, green, and blue as necessary.

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

  In order to obtain the effect described in the present invention, that is, to obtain an image exhibiting good gloss after fixing, the heat fixing device according to the present invention has at least one fixing belt according to the present invention as a component. It is a feature.

  In addition, for the heat fixing process, it is sufficient to give the image energy sufficient to exert the effect of the present invention, but the heating temperature may be any temperature that can smooth the image, particularly in the case of a pigment image. The range of 60 ° C to 200 ° C is preferable, and the range of 80 ° C to 160 ° C is more preferable.

  Heating may be performed by a heater built in the printer or by a separate heater. As the heating means, it is preferable to use a heating roller even when a fixing belt is used, because unevenness is eliminated and continuous processing can be performed in a small space. In addition, these apparatuses can be used as an electrophotographic heat fixing machine, and are advantageous in terms of cost.

  The heating roller has a hollow roller as a constituent component and is rotated by a driving means. A heating element such as a halogen lamp heater, a ceramic heater, or a nichrome wire is incorporated in the hollow portion as a heat source. It is preferable.

  In addition, the roller is preferably made of a material having high thermal conductivity, particularly a metal roller, and nickel is preferably used.

  The recording material conveyance speed when the fixing belt is used is preferably in the range of 1 mm / second to 100 mm / second, more preferably in the range of 10 mm / second to 50 mm / second. This is preferable from the viewpoint of image quality in addition to the viewpoint of high-speed processing.

In order to obtain a higher texture and gloss, it is preferable to apply pressure at the same time as or immediately after heating. The pressure applied is preferably in the range of 9.8 × 10 ⁴ Pa to 4.9 × 10 ⁶ Pa because filming is promoted.

  The image forming method of the present invention will be described.

  The image forming method of the present invention is characterized in that the heat fixing device of the present invention is used during image fixing processing. In the present invention, for example, when an inkjet pigment image is formed, a commercially available printer is used. There is no particular limitation as long as it has a recording material storage unit, a transport unit, an ink cartridge, and an inkjet print head, but at least a roll-shaped recording material storage unit, a transport unit, an inkjet print head, a cutting unit, and necessary Accordingly, a series of printer sets including a heating unit, a pressurizing unit, and a recording / printing storage unit are useful when an inkjet photograph is used commercially.

  The recording head may be any of a piezo method, a thermal method, and a continuous method, but the piezo method is preferable from the viewpoint of stability with pigment ink.

  It is preferable to improve the C value described later by some processing after printing. As the processing, the image is heated or pressed, or both heated and pressed, or a solvent or a plasticizer is applied and further heated, or a thermoplastic resin component is supplied to the image and then heated. Further, these processes may be combined or performed multiple times.

  The image forming method of the present invention is characterized in that after the pigment ink is printed on the recording material, the recording material is heat-fixed by the heat-fixing device of the present invention. It is preferable to heat-fix the pigment image in which the resin and the thermoplastic resin are mixed or present in the vicinity. In this case, it is preferable to partially or completely melt the thermoplastic resin and further form a film.

  As a method for allowing a thermoplastic resin to coexist with a pigment image, 1) a recording material containing a thermoplastic resin, preferably thermoplastic fine particles is used, and 2) a thermoplastic resin is supplied to the recording material before or after printing. ) A method using an ink in which a thermoplastic resin coexists in a pigment ink.

  In the present invention, it is preferable that the image definition called C value is 60 or more. Here, the C value is defined as a measure of image clarity, with a value measured by the reflection method using an optical comb of 2 mm among the image sharpness defined in JIS K7105 as a C value.

  The image clarity referred to in the present invention represents the performance of the film surface to which an image of an object facing the film surface is transferred, and is a value indicating how accurately an incident image is reflected or projected on the image surface. The more accurately the reflected image is given to the incident image, the higher the image clarity and, as a result, the C value increases. The C value shows the effect of combining the specular gloss and the smoothness of the surface. The higher the reflectivity and the higher the smoothness, the larger the C value.

  As a result of examining various ink jet pigment images having different C values, it was found that as the C value increased, glossiness was obtained and an image approximate to a silver salt photograph could be obtained. Furthermore, it has been surprisingly found that the bronzing phenomenon peculiar to pigment inks is suppressed as the C value increases. Furthermore, it has been found that image storability such as water resistance and acid gas resistance is improved as the C value increases.

  A pigment image having a C value of 60 or more can obtain the intended effect of the present invention, but is preferably 70 to 90, more preferably 75 to 90.

  The method for setting the C value specified in the present invention to 60 or more is not particularly limited. For example, after printing an ink pigment on a recording material, the image is heated or pressed, or both heating and pressing are performed. Alternatively, it is achieved by adding a solvent or a plasticizer and further heating, or by appropriately selecting and combining methods such as heating after supplying a thermoplastic resin component to an image, or performing these treatments a plurality of times. can do.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Example 1
<Manufacture of fixing belt>
(Manufacture of fixing belt sample 1)
(Preparation of release layer coating composition 1: 5 liters)
Release agent KS830E for release paper (Shin-Etsu Chemical Co., Ltd.) 1250g
Curing catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) 12.5 ml
Toluene 3750ml
The above materials were mixed and stirred to obtain a release layer coating composition 1.

  This liquid is put into a cylindrical beaker having an inner diameter of 15 cm and a height of 50 cm, and a seamless nickel electroformed belt (diameter 65 mm, length 240 mm, wall thickness 40 μm: manufactured by Nitto Kogyo Co., Ltd.) is set in a commercially available dip type coating machine. The belt was lowered and immersed in the beaker. Next, the application was performed with the pulling speed set to 15 mm per second. After 5 minutes at room temperature, heating was performed in an oven at 100 ° C. for 1 hour to produce a fixing belt sample 1 having a release layer as shown in FIG.

(Manufacture of fixing belt sample 2)
An elastic layer (a layer containing a commercially available silicon rubber) is provided on a belt base material (seamless nickel electroformed belt) used in the preparation of the fixing belt sample 1, and the following adhesive improvement layer coating composition is applied on the elastic layer. A fixing belt sample 2 was prepared by coating an adhesive property improving layer and then coating a release layer.

(Preparation of coating composition for improving adhesion layer: 5 liters)
Denkabu tyral 6000C (manufactured by Denki Kagaku Kogyo) 5g
Ethyl acetate 4500ml
500 ml of n-butanol
The above materials were mixed and stirred for 3 hours to completely dissolve Denkabutyral.

(Application of adhesion improving layer on elastic layer)
A seamless nickel electroforming belt in which 5 liters of an adhesive layer coating solution is placed in a cylindrical beaker having an inner diameter of 15 cm and a height of 50 cm, and the elastic layer is provided in a commercially available dip type applicator. Was set, the belt was lowered and immersed in the beaker.

  Next, the application was performed with the lifting speed set to 15 mm / sec. After leaving at room temperature for 5 minutes, it was heated in an oven at 100 ° C. for 30 minutes to apply an adhesion improving layer.

(Coating of release layer)
On the adhesive improvement layer, using the release layer coating composition 1, a release layer was applied in the same manner as the fixing belt sample 1, and a fixing belt sample 2 was produced.

(Manufacture of fixing belt sample 3)
In the production of the fixing belt sample 2, the fixing belt sample 3 was produced in the same manner except that the elastic layer was not provided.

  Each of the obtained fixing belt samples 1 to 3 was evaluated as follows.

<Evaluation of fixing belt>
The evaluation of the fixing belt is performed by evaluating the film peeling as an evaluation of the belt alone, and the image evaluation using the fixing belt is performed by preparing an ink jet recording material and an ink jet ink as described later. The described fixing belt was arranged as shown in FIG. 1, and the image clarity (C value) of the fixed image was evaluated.

(Evaluation of film peeling: adhesion test)
Evaluation of film peeling of the fixing belt samples 1 to 3 obtained above was performed according to the method described in JIS K 6854 (1977).

  The state of film peeling was visually observed, and the rank was evaluated as follows.

○: No change in film surface ×: Film peeling has occurred In evaluating a fixed image using the fixing belt samples 1 to 3 obtained above, an ink jet recording material and an ink jet ink as described below Were prepared respectively.

<Production of inkjet recording material>
After preparing each dispersion with the following formulation, an inkjet recording material was prepared using these dispersions.

<Preparation of silica dispersion-1>
125 kg of vapor phase method silica (manufactured by Tokuyama Co., Ltd .: QS-20) having an average primary particle size of about 0.012 μm is mixed with nitric acid using a jet stream inductor mixer TDS manufactured by Mitamura Riken Kogyo Co., Ltd. After suction-dispersing in 620 L of pure water adjusted to pH = 2.5 at room temperature, the total amount was finished to 694 L with pure water to prepare silica dispersion-1.

<Preparation of silica dispersion-2>
While stirring 69.4 L of silica dispersion-1 in 18 L of an aqueous solution (pH = 2.3) containing 1.14 kg of cationic polymer (P-1), 2.2 L of ethanol, and 1.5 L of n-propanol. Then, 7.0 L of an aqueous solution containing 260 g of boric acid and 230 g of borax was added, and 1 g of an antifoaming agent SN381 (manufactured by San Nopco Co., Ltd.) was added.

  This mixed solution was dispersed with a high-pressure homogenizer manufactured by Sanwa Kogyo Co., Ltd., and the entire amount was finished to 97 L with pure water to prepare silica dispersion-2.

<Preparation of silica coating solution>
Next, using the silica dispersion-2 obtained as described above, the following silica coating solution was prepared.

The following additives were sequentially mixed in 600 ml of silica dispersion-2 while stirring at 40 ° C.
(1) 10% aqueous solution of polyvinyl alcohol (Kuraray Industrial Co., Ltd .: PVA203): 6 ml
(2) 7% aqueous solution of polyvinyl alcohol (Kuraray Industries, Ltd .: PVA235): 185 ml
(3) Finish the whole volume with pure water to 1000 ml.

<Preparation of thermoplastic fine particle coating solution>
A styrene-acrylic latex polymer (Tg 78 ° C., average particle size 250 nm, solid content concentration 40%) obtained by emulsion polymerization using polyvinyl alcohol as a nonionic emulsifier is adjusted to pH 4.7 with a 6% nitric acid aqueous solution, and styrene-acrylic. A thermoplastic fine particle coating solution was prepared.

<Preparation of composite fine particle coating solution>
A composite fine particle coating solution was prepared by setting the solid content mass ratio of the thermoplastic fine particle coating solution and the silica coating solution to 2/1.

(Preparation of inkjet recording material 1)
Polyethylene-coated paper both sides of thick 170 g / m ² base paper coated with polyethylene (the ink-receiving layer side 8 wt% in the polyethylene of anatase titanium oxide containing; ink-receiving layer surface of 0.05 g / m ² on the side of gelatin The undercoat layer has a latex polymer with a Tg of about 80 ° C. on the opposite side as a back layer of 0.2 g / m ² ), and the silica coating solution and the composite fine particle coating solution from the polyethylene-coated paper side have a wet film thickness of 120 μm. The ink-jet recording material 1 was prepared by simultaneously applying the film to 120 μm and cooling it to about 7 ° C., followed by drying by blowing air at 20 ° C. to 65 ° C.

<Preparation of inkjet ink>
An ink composition was prepared as follows.

(Yellow pigment dispersion)
C. I. Pigment Yellow 74 95g
Demall C (Kao Corporation) 65g
Ethylene glycol 100g
Ion exchange water 120g
Were dispersed using a sand grinder filled with 50% by volume of 0.5 mm zirconia beads to obtain a yellow pigment dispersion. The average particle diameter of the obtained pigment dispersion was 122 nm. The particle size was measured using a Zetasizer 1000 manufactured by Malvern.

(Magenta pigment dispersion)
C. I. Pigment Red 122 105g
Jonkrill 61 (acrylic-styrene resin, manufactured by Johnson) 60g
Glycerin 100g
Ion exchange water 130g
Were dispersed using a sand grinder filled with 50% by volume of 0.5 mm zirconia beads to obtain a magenta pigment dispersion. The average particle diameter of the obtained pigment dispersion was 85 nm.

(Cyan pigment dispersion)
C. I. Pigment Blue 15: 3 100g
DEMAL C 68g
Diethylene glycol 100g
125g of ion exchange water
Were dispersed using a sand grinder filled with 50% by volume of 0.5 mm zirconia beads to obtain a cyan pigment dispersion. The average particle diameter of the obtained pigment dispersion was 105 nm.

<Preparation of yellow ink>
113g yellow pigment dispersion
Ethylene glycol 100g
Glycerin 72g
Perex OT-P (manufactured by Kao Corporation) 3g
Proxel GXL (Zeneca) 0.2g
This was finished to 1000 g with ion-exchanged water, sufficiently stirred, and then passed through a Millipore filter having a pore size of 1 micron twice to prepare a yellow ink. The pH was 8.2.

<Preparation of cyan ink>
Cyan pigment dispersion 113g
Ethylene glycol 100g
Glycerin 72g
Perex OT-P (manufactured by Kao Corporation) 3g
Proxel GXL (Zeneca) 0.2g
After finishing this to 1000 g with ion-exchanged water and stirring sufficiently, a cyan ink was prepared by passing twice through a Millipore filter with a pore size of 1 micron. The pH was 8.3.

<Preparation of magenta ink>
113 g of magenta pigment dispersion
Ethylene glycol 100g
1,2-hexanediol 100g
Perex OT-P (manufactured by Kao Corporation) 3g
Proxel GXL (Zeneca) 0.2g
This was finished to 1000 g with ion-exchanged water, sufficiently stirred, and then passed twice through a Millipore filter with a pore size of 1 micron to prepare a magenta ink. The pH was 8.5.

<Preparation of black ink>
Hostfine Black T 167g
(Clariant Co., Ltd., average particle size 50 nm)
1,2-hexanediol 150g
Ethylene glycol 220g
Diethylene glycol 90g
Lebenol WX (manufactured by Kao Corporation) 3g
Proxel GXL (Zeneca) 0.2g
After finishing this to 1000 g with ion-exchanged water and stirring sufficiently, a black ink was prepared by passing twice through a Millipore filter having a pore size of 1 micron. The pH was 8.6.

(Preparation of image samples 1 to 3)
The fixing belt samples 1 to 3 obtained above are set in the ink jet printer with the heat fixing device shown in FIG. 1, and after printing a solid black image on the ink jet recording material 1 using the ink for ink jetting, the device A heat fixing process was performed with the fixing device in the inside, and image samples 1 to 3 were obtained. Here, the temperature of the heating roller for applying heat to the fixing belt was set to 120 ° C.

(Glossiness evaluation)
The glossiness of each of the image samples 1 to 3 was measured by the image clarity measuring device ICM-IDP (manufactured by Suga Test Machine Co., Ltd.) at 60 degrees reflection and image clarity at 2 mm optical comb (gloss value C value%). . As a criterion for evaluation, 60 or more was made practical.

  The obtained results are shown in Table 1.

  From Table 1, it is clear that Sample 3 of the present invention has no film peeling of the fixing belt and good gloss (C value) as compared with Comparative Samples 1 and 2. More specifically, in the fixing belt sample 1 in which the release layer is directly coated on the nickel base material, the peeling of the release layer is significant, and between the nickel base material and the release layer. In the fixing belt sample 2 provided with the elastic layer and the adhesive layer, it was found that the release layer was not peeled off, but the glossiness (C value) did not reach a practical level.

  From the above, it can be seen that only the fixing belt sample 3 of the present invention in which an adhesive layer is provided between the nickel base and the releasable layer does not peel off the releasable layer and exhibits sufficient gloss. .

Example 2
(Manufacture of fixing belt sample 4)
In the production of the fixing belt sample 3 of Example 1, the fixing belt sample 4 was prepared in the same manner except that the adhesion improving layer coating composition was a hard coat silicone primer (PC-7A, manufactured by Shin-Etsu Chemical Co., Ltd.). Manufactured.

(Manufacture of fixing belt sample 5)
In the production of fixing belt sample 4, the composition for coating the adhesion improving layer was replaced with 5 liters of primer for hard coat silicone (PC-7A, manufactured by Shin-Etsu Chemical Co., Ltd.), and further a silane coupling agent (KBM503, Shin-Etsu Chemical). A fixing belt sample 5 was produced in the same manner except that 1 g of Kogyo Co., Ltd. was added.

(Manufacture of fixing belt sample 6)
In the production of fixing belt sample 4, the composition for coating the adhesion improving layer was replaced with 5 liters of a primer for hard coat silicone (PC-7A, manufactured by Shin-Etsu Chemical Co., Ltd.), and a titanium coupling agent (TOG, Nippon Soda). A fixing belt sample 6 was produced in the same manner except that 1 g of (made by Co., Ltd.) was added.

(Manufacture of fixing belt samples 7 to 9)
Fixing belt sample 7 was similarly prepared except that Denkabutyral 6000C (manufactured by Denki Kagaku Kogyo Co., Ltd.) was replaced with the following member in the composition for coating an adhesion improving layer used in the production of fixing belt sample 3 of Example 1. ~ 9 were each produced.

Fixing belt sample 7: PVA224 (manufactured by Kuraray Co., Ltd.)
Fixing belt sample 8: ESREC BL-1 (manufactured by Sekisui Chemical Co., Ltd.)
Fixing belt sample 9: Denkabutyral 3000K (manufactured by Denki Kagaku Kogyo Co., Ltd.)
<Evaluation of fixing belt>
For each of the obtained fixing belt samples 4 to 9 and fixing belt samples 1 and 3 described in Example 1, film peeling test (forced deterioration test) and film thickness uniformity evaluation were performed as evaluation of the belt alone. .

(Film peeling test: forced deterioration test (also called acceleration test))
The fixing belt is cut into a 2 cm × 5 cm strip, and the image forming surface of the thermoplastic resin particle layer media cut into the same size is applied with pigment ink, and the ink is separated from the belt. The laminate was sandwiched between the mold layer and the image forming surface of the medium, and placed in an oven at 120 ° C. for 3 days and nights under a pressure of ² kg / 10 cm ² . Thereafter, the sample is taken out and cooled to room temperature, and then an adhesive tape (Knit-Polyester Tape No. 31B (manufactured by Nitto Denko Corporation)) is attached so that air does not enter between the releasability and the adhesive part. Peeling was performed at an angle.

  The evaluation was made visually and ranked as follows.

◎: No peeling at all between the adhesive layer and the release layer ○: Some peeling was observed between the adhesive layer and the release layer (practical)
×: Many peeled portions (5 or more) between the adhesive layer and the release layer
(Thickness uniformity evaluation)
After applying the fixing belt, the belt was cut into a strip shape in the application direction, and the change in film thickness in the application direction was measured with a micrometer. In the measurement, 10 samples were randomly sampled from a plurality of belts, evaluated by the average, and ranked as follows.

A: Film thickness difference between upper and lower ends of application is less than 2 μm ○: Film thickness difference between upper and lower ends of application is 2 μm or more and less than 5 μm Δ: Film thickness difference between upper and lower ends of application is 5 μm or more and less than 10 μm ×: Table 2 shows the results obtained when the film thickness difference was 10 μm or more.

  From Table 2, it is clear that the sample of the present invention is excellent in film thickness uniformity and the film peeling is remarkably reduced as compared with the comparison.

Example 3
(Bending and stretching evaluation)
The fixing belt sample 3 described in Example 1 and the fixing belt samples 7 to 9 described in Example 2 were each installed in a fixing device as illustrated in FIG. 1, and the belt rotation speed was set to 750 m / hour. An empty operation was performed without heating. After 100 hours of idling, the film surface of the belt was observed with the naked eye, and cracks on the film surface due to bending and stretching of the belt were evaluated.

  In addition, the bending / elongation resistance was evaluated as follows.

◎: Less than 3 cracks per 1 cm in the belt circumferential direction ○: 3 or more cracks per 1 cm in the belt circumferential direction △: 10 cracks per 1 cm in the belt circumferential direction Less than 20 or more ×: Table 3 shows the results of obtaining 20 or more cracks per 1 cm in the belt circumferential direction.

  From Table 3, in the repeating unit of the resin (polyvinyl butyral) constituting the adhesive improvement layer, the composition ratio of the repeating unit having a hydroxyl group is 20% or less, and the flow softening point of the resin is adjusted to 130 ° C. or less. In addition, it can be seen that the fixing belt samples 9 and 3 have improved resistance to bending and stretching of the fixing belt as compared with samples outside the range.

Example 4
(Manufacture of fixing belt sample 10)
In the production of the fixing belt sample 3 described in Example 1, 1 g of a silane coupling agent (KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the composition for coating an adhesive improvement layer as an additive for the adhesive improvement layer. A fixing belt sample 10 was produced in the same manner except for the above.

(Manufacture of fixing belt samples 11 to 20)
Fixing belt samples 11 to 11 were prepared in the same manner except that the coating speed was adjusted so that the kind of the adhesive improving layer additive used in the production of fixing belt sample 10 and the film thickness of the adhesive improving layer were as shown in Table 4. 20 was produced.

  Each of the obtained fixing belt samples 10 to 20 and the fixing belt sample 3 described in Example 1 is subjected to the following brushing (presence or absence of cloudiness of the film surface after the release layer coating of each fixing belt sample), gloss Degree (C value) evaluation and long run durability were evaluated.

(Brushing evaluation)
The degree of white turbidity of the film surface of the fixing belt after the release layer coating was visually evaluated, and the rank was evaluated as follows.

◯: No brushing △: Brushing is slightly present and the metallic luster of the nickel base is cloudy ×: Strong brushing and no metallic luster of the nickel base (Glossiness evaluation)
The glossiness was evaluated in the same manner as described in Example 1.

(Long run durability evaluation)
Each of the fixing belt samples 10 to 20 and the fixing belt sample 3 is set in an ink jet printer with a heat fixing device as shown in FIG. 1, and the ink for ink jet as described in Example 1 is used. After printing a normal photographic image on the ink jet recording material, a heat fixing process was performed with a fixing device in the apparatus. The belt temperature was set to 120 ° C. The pressure was 3.14 MPa. The fixing speed was set at a belt rotation speed of 25 m / hour.

  The fixing operation was continuously performed, and the fixing was performed within 5 minutes at the latest after printing.

  The film surface was observed every time 50 sheets were fixed, and the number of fixed sheets when film peeling of 5 mm square or more occurred was recorded.

  Table 4 shows the obtained results.

  From Table 4, at least one of a titanium coupling agent, a silane coupling agent, and an isocyanate compound (Coronate L: manufactured by Nippon Polyurethane Industry Co., Ltd.) is added as an additive to the adhesion improving layer, and the adhesion is improved. It was found that by increasing the film thickness to 1 μm, 3 μm, and then 10 μm, the long run durability was improved and an image having a good gloss (C value) was obtained. In addition, it can be seen that addition of a titanium coupling agent, a silane coupling agent, and an isocyanate compound is preferable as an additive to the adhesion improving layer, but a more preferable effect can be obtained by using a titanium coupling agent or a silane coupling. It is clear that the titanium coupling agent has the best effect.

Example 5
(Manufacture of fixing belt samples 21 and 22)
In the production of the fixing belt samples 10 and 11 of Example 4, 1 g each of thermoplastic resin register tops 2205 and 2206 (phenol resin: manufactured by Gunei Chemical Industry Co., Ltd.) was added as an additive for the adhesive improvement layer. Except for the above, fixing belt samples 21 and 22 were produced in the same manner.

  For the obtained fixing belt samples 21 and 22, and the four fixing belts 10 and 11 described in Example 4, the long run durability was evaluated in the same manner as described in Example 4. The results obtained are shown in Table 5.

  It can be seen from Table 5 that the long run durability is further improved in the fixing belt samples 21 and 22 in which the thermoplastic resin is added to the adhesion improving layer as compared with the fixing belt samples 10 and 11 in which the thermoplastic resin is not added.

1 is a schematic configuration diagram illustrating an example of an ink jet recording apparatus used in the present invention. FIG. 3 is a schematic configuration diagram illustrating another example of an ink jet recording apparatus used in the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Recording material 2 Recording material conveyance means 21 Conveying roller pair 3 Recording head 34 Recording material holding part 4 Heat fixing means 41 Heating roller 42 Pressure roller 43 Heat generating body 44 Fixing belt 45 Lower belt 46 Driven roller 5 Temperature sensor 6 Recording material Cutting means 61, 62 Cutter 7 Slack forming means 71 First roller pair 72 Second roller pair

Claims (29)

In a fixing belt for fixing by passing a recording material and a surface of a fixing belt having at least a releasing layer on a substrate while facing each other between a heating unit and a pressing unit. The release layer contains a silicone resin made of solvent-added silicone, and an adhesive improvement layer is provided so as to be adjacent to the release layer and the substrate, A compound in which the adhesion improving layer has at least one reactive group selected from the group consisting of a hydroxyl group, a carboxyl group, a group represented by the following general formula (a) and a group represented by the following general formula (b) These compounds include polyvinyl alcohol resins, butyral resins, ethylene-vinyl acetate copolymers, olefin resins such as vinylidene chloride and polybutadiene, urethane resins, and polyester resins. Fixing belt characterized in that at least one resin selected from the group consisting of acrylic resins, epoxy resins and polyethylenimine resins.
General formula (a)
-Si- (OH) _m
General formula (b)
-Ti- (OH) _n
[Wherein, m represents an integer of 1 to 3, and n represents an integer of 1 to 4. ] 2. The fixing belt according to claim 1, wherein the releasable layer contains a silicone resin formed by dip-coating a curable silicone on a substrate and then heat-curing the curable silicone. The fixing belt according to claim 1, wherein the base material is a seamless nickel belt. The fixing belt according to claim 1, wherein the content of the compound having a reactive group in the adhesion improving layer is 20% by mass or less. The fixing belt according to claim 1, wherein the adhesion improving layer contains at least one kind of resin, and the flow softening point of the resin is 130 ° C. or higher. The fixing according to claim 1, wherein the adhesion improving layer contains at least one compound selected from the group consisting of a silane coupling agent, a titanium coupling agent, and an isocyanate. belt. The fixing belt according to claim 1, wherein the adhesion improving layer contains at least one thermosetting resin. The fixing belt according to claim 1, wherein the adhesive improvement layer has a thickness of 1 μm or more. 9. A method for producing a fixing belt, wherein the adhesion improving layer and the release layer are each applied by dip coating in producing the fixing belt according to claim 1. The method for producing a fixing belt according to claim 9, further comprising a step of performing the following aging treatment A after the release layer coating, and then a step of performing the following aging treatment B.
Aging treatment A: Represents treatment in which the temperature range is 25 ° C. to 100 ° C. and the relative humidity is 50% RH to 95% RH.
Aging process B: represents a process of storing with aging at a temperature range of 40 ° C. to 200 ° C. and a relative humidity of less than 50% RH. A fixing belt manufactured using the manufacturing method according to claim 9. In a fixing roller for fixing by passing a recording material and a surface of a fixing roller having at least a release layer on a substrate while facing each other between a heating unit and a pressurizing unit. The release layer contains a silicone resin made of solvent-added silicone, and an adhesive improvement layer is provided so as to be adjacent to the release layer and the substrate, A compound in which the adhesion improving layer has at least one reactive group selected from the group consisting of a hydroxyl group, a carboxyl group, a group represented by the following general formula (a) and a group represented by the following general formula (b) These compounds include polyvinyl alcohol resins, butyral resins, ethylene-vinyl acetate copolymers, olefin resins such as vinylidene chloride and polybutadiene, urethane resins, and polyester resins. Fixing roller, characterized in that at least one resin selected from the group consisting of acrylic resins, epoxy resins and polyethylenimine resins.
General formula (a)
-Si- (OH) _m
General formula (b)
-Ti- (OH) _n
[Wherein, m represents an integer of 1 to 3, and n represents an integer of 1 to 4. ] The fixing roller according to claim 12, wherein the releasable layer contains a silicone resin formed by dip-coating curable silicone on a substrate and then heat-curing the curable silicone. The fixing roller according to claim 12 or 13, wherein the base material is a seamless nickel belt. The fixing roller according to claim 12, wherein the content of the compound having a reactive group in the adhesion improving layer is 20% by mass or less. The fixing roller according to any one of claims 12 to 15, wherein the adhesion improving layer contains at least one resin, and a flow softening point of the resin is 130 ° C or higher. The fixing roller according to any one of claims 12 to 16, wherein the adhesion improving layer contains at least one compound selected from the group consisting of a silane coupling agent, a titanium coupling agent and an isocyanate. . The fixing roller according to claim 12, wherein the adhesion improving layer contains at least one thermosetting resin. The fixing roller according to claim 12, wherein the film thickness of the adhesion improving layer is 1 μm or more. 21. A method for manufacturing a fixing roller, wherein, when the fixing roller according to claim 12 is manufactured, the adhesion improving layer and the release layer are each applied by dip coating. 21. The method of manufacturing a fixing roller according to claim 20, further comprising: a step of performing the following aging treatment A after the release layer coating, and a step of performing the following aging treatment B.
Aging treatment A: Represents treatment in which the temperature range is 25 ° C. to 100 ° C. and the relative humidity is 50% RH to 95% RH.
Aging process B: represents a process of storing with aging at a temperature range of 40 ° C. to 200 ° C. and a relative humidity of less than 50% RH. A fixing roller manufactured using the manufacturing method according to claim 20 or 21. A heat fixing apparatus for an ink jet recording material, comprising the fixing belt according to any one of claims 1 to 8 and 11, or the fixing roller according to any one of claims 12 to 19 and 22. The recording material on which printing has been performed by ejecting ink uses the fixing belt according to any one of claims 1 to 8 and 11, or the fixing roller according to any one of claims 12 to 19 and 22. And a heat fixing device for an ink jet recording material. The heat fixing apparatus for ink jet recording material according to claim 24, wherein the ink is a pigment ink. The ink jet recording material according to any one of claims 23 to 25, wherein the recording material has a surface layer containing thermoplastic resin particles and an ink absorbing layer containing inorganic fine particles adjacent to the surface layer. Heat fixing device. 27. An image forming method, wherein a recording material on which printing has been performed by ejecting ink is subjected to a fixing process using the heat fixing device for an inkjet recording material according to any one of claims 23 to 26. 28. The image forming method according to claim 27, wherein the ink is a pigment ink. 29. The image forming method according to claim 27 or 28, wherein the recording material has a surface layer containing thermoplastic resin particles and an ink absorbing layer containing inorganic fine particles adjacent to the surface layer.

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