JP5545051B2 - Intermediate transfer member - Google Patents

Description

  The present invention relates to an intermediate transfer member used in an electrophotographic image forming apparatus.

  As an image forming method in an image forming apparatus such as a copying machine or a laser printer, a toner image formed using a small diameter toner on a photosensitive drum is primarily transferred to an intermediate transfer member, and then transferred from the intermediate transfer member to a transfer material (for example, paper). A transfer system for secondary transfer is known.

  In recent years, colorization has been promoted. In particular, in a color image forming apparatus, toners of four colors of yellow, magenta, cyan, and black are used, and each toner image formed on the photoreceptor is primarily transferred to the intermediate transfer member. Since the four-color toner images transferred and formed are secondarily transferred onto a transfer material (for example, paper) simultaneously, there is a demand for higher image quality and higher speed. As an intermediate transfer body, an intermediate transfer body belt using an endless belt as a base material and an intermediate transfer body roll using a metal roll as a base material are known.

  In the case of the transfer method, the following items are known as typical items for achieving high image quality and high speed of the intermediate transfer member.

  1) A high transfer rate of a toner image formed on a surface of an intermediate transfer member by transfer from a photosensitive member to a transfer material is required.

  The transfer rate refers to the ratio of the toner image formed on the surface of the intermediate transfer member to the transfer material. If the transfer rate is low, the image transferred to the transfer material may be missing, or density unevenness may occur, resulting in poor image quality.

  2) High durability of the intermediate transfer member is required.

  Durability refers to the performance that enables transfer to a transfer material for a long time. The surface of the intermediate transfer body is secondarily transferred to a transfer material (for example, paper) and then cleaned by rubbing with a cleaning blade to remove the remaining toner. Cracks occur and stable transfer of the toner image from the photoconductor becomes impossible. Further, when the intermediate transfer member is an endless belt, cracks (cracks) are generated by the drawing.

  3) It is required that filming does not occur.

  Filming refers to a phenomenon in which, after secondary transfer onto a transfer material (for example, paper), the surface of the intermediate transfer member is cleaned with a cleaning blade, and toner remaining without being removed is gradually accumulated. As the cause of the toner remaining, the toner enters a crack generated on the surface of the intermediate transfer member, or the toner accumulated in the concave portion formed on the surface due to contact with the cleaning blade or the like remains. In a place where filming occurs, the transfer rate decreases, image streaks and unevenness occur, and image quality cannot be improved. Further, from the viewpoint of energy saving, a low-temperature fixing toner has recently been used. The low temperature fixing toner has a low glass transition point, so that filming is more likely to occur, and filming has become a big problem. In places where filming occurs, the transfer rate decreases, image streaks and unevenness occur, and this becomes a problem.

  4) It is required that bleeding does not occur.

  Bleed refers to a phenomenon in which a lipophilic component (for example, a plasticizer) contained in the lower layer constituting the intermediate transfer member oozes out into the surface layer. When the oleophilic component oozes out on the surface of the intermediate transfer member, the oleophilic component is transferred to the photosensitive member in contact with the intermediate transfer member, which affects the toner image formation on the photosensitive member. Further, when a crack occurs in the intermediate transfer member, the lipophilic component oozes out along the crack.

  The intermediate transfer member transfers the toner image formed on the surface of the photosensitive member from the photosensitive member to the surface of the intermediate transfer member and transfers the toner image formed on the surface of the intermediate transfer member to a transfer material (for example, paper). In order to increase the transfer rate when transferring the toner image and to uniformly transfer the toner image, a concentrated load prevention measure is taken in order to prevent image loss caused by a concentrated load applied to the toner image. The concentrated load prevention measure is said to be effective for the stress dispersion on the surface of the intermediate transfer member during cleaning by the cleaning blade and the stress dispersion applied to the intermediate transfer belt when the intermediate transfer belt is routed.

  As a measure against concentrated load, for example, in the case of an intermediate transfer belt, an elastic body is used for the base material, or an elastic layer is provided on the base material. A method of providing an elastic layer is known.

  Many studies have been made to meet the requirements 1) to 4) for the intermediate transfer member.

  For example, in order to prevent bleed generation, high durability, and high-quality image formation, EPDM (a diene monomer added as a third component to chloroprene rubber (CR), which is an elastic material, and ethylene-propylene rubber as a belt base material) An intermediate transfer member is known in which a diamond-like carbon (DLC) film is formed on the surface layer using Ethylene Propylene Diene Monomer (see, for example, Patent Document 1).

  The intermediate transfer member of Patent Document 1 is effective for preventing bleeding, forming high durability and high quality images for a short period of time. In some cases, since the surface layer is hard, even if an intermediate layer is provided between the substrate and the substrate is used for a long time (for example, 300,000 copies), cracks occur on the surface layer, and the generated cracks cause filming and bleeding. It was found that high quality image formation was not possible.

  An intermediate transfer belt is known in which a polyamide-based resin is used as a substrate and an elastic layer / silicon oxide is provided thereon to improve toner releasability (see, for example, Patent Document 2).

  In the intermediate transfer belt of Patent Document 2, the surface layer is composed of a silicon oxide layer, so that the transfer rate of the toner image from the intermediate transfer belt to the transfer material is good. It was found that cracks occurred and filming and bleeding occurred due to the cracks, and high quality image formation was not possible.

  The intermediate transfer body of Patent Document 3 is an intermediate transfer body having an elastic layer, and discloses a technique for preventing cracks by forming a resin layer and an inorganic surface layer on the elastic layer. However, simply laminating greatly reduces cracks, but it cannot be said that filming has completely disappeared. In addition, there are cases where surface peeling occurs in a high temperature and high humidity environment.

  Under these circumstances, there is no generation of cracks, surface deterioration due to the cleaning blade, and no filming after a long period of use, and it is an intermediate used for an electrophotographic image forming apparatus with high transfer efficiency and high durability. It is desired to develop an intermediate transfer member having high durability.

JP 2006-259581 A JP 2001-347593 A JP 2010-2567 A

  The present invention has been made in view of the above circumstances, and an object thereof is to provide an intermediate transfer member used in an electrophotographic image forming apparatus having high transfer efficiency and durability and no filming.

  The above object of the present invention has been achieved by the following constitution.

1. An intermediate transfer member having a substrate and an elastic layer,
Three-dimensionally crosslinked resin layer on the elastic layer has an inorganic compound layer in this order, and the three-dimensionally crosslinked resin layer surface has been subjected to stress adjusting means, said stress adjusting means, the three-dimensional cross-linking An intermediate transfer member characterized in that it is unevenly distributed near the surface of the conductive resin layer and contains inorganic fine particles .

2. 2. The intermediate transfer member according to 1 above, wherein the concentration of inorganic fine particles in the three-dimensional crosslinkable resin layer increases stepwise or continuously toward the interface with the inorganic compound layer .

3. An intermediate transfer member having a substrate and an elastic layer, comprising a three-dimensional crosslinkable resin layer and an inorganic compound layer in this order on the elastic layer, and stress adjusting means is applied to the surface of the three-dimensional crosslinkable resin layer. The intermediate transfer member , wherein the stress adjusting means is to introduce a silane coupling agent in the vicinity of the surface of the three-dimensional crosslinkable resin layer .

4). An intermediate transfer member having a substrate and an elastic layer, comprising a three-dimensional crosslinkable resin layer and an inorganic compound layer in this order on the elastic layer, and stress adjusting means is applied to the surface of the three-dimensional crosslinkable resin layer. An intermediate transfer member , wherein the stress adjusting means comprises coating an inorganic compound layer after coating with a three-dimensional crosslinkable resin and before curing, and thereafter performing curing .

5. 5. The intermediate transfer member according to any one of 1 to 4, wherein the three-dimensional crosslinkable resin layer contains an acrylate resin .

6). 5. The intermediate transfer member according to any one of 1 to 4, wherein the inorganic compound layer is made of silicon oxide or a laminate of carbon-containing silicon oxide and silicon oxide .

7). 7. The intermediate transfer member according to any one of 1 to 6, wherein the inorganic compound layer is formed by an atmospheric pressure plasma method .

8). 5. The intermediate transfer member according to any one of 1 to 4, wherein the inorganic compound layer is formed from a polysilazane coating layer .

9. 5. The intermediate transfer member according to any one of 1 to 4, wherein a protective layer containing an alkylsilane or a fluorine-containing silane compound is further provided on the inorganic compound layer .

  An intermediate transfer member used in an electrophotographic image forming apparatus having high transfer efficiency and durability and no filming can be provided.

1 is a schematic cross-sectional configuration diagram illustrating an example of an electrophotographic image forming apparatus that uses an intermediate transfer belt as an intermediate transfer member. 1 is a schematic cross-sectional configuration diagram illustrating an example of an electrophotographic image forming apparatus that uses an intermediate transfer roll as an intermediate transfer member. FIG. 3 is an enlarged schematic cross-sectional view of an intermediate transfer belt of the intermediate transfer member of the present invention. It is a schematic diagram of a manufacturing apparatus for forming an inorganic compound layer of an intermediate transfer belt, which is a belt-shaped intermediate transfer body, by an atmospheric pressure plasma CVD method.

  The embodiment of the present invention will be described with reference to FIGS. 1 to 4, but the present invention is not limited to this.

  FIG. 1 is a schematic sectional view showing an example of an electrophotographic image forming apparatus using an intermediate transfer belt as an intermediate transfer member. This figure shows the case of a full-color image forming apparatus.

  In the figure, reference numeral 1 denotes a full-color image forming apparatus. The full-color image forming apparatus 1 includes a plurality of sets of image forming units 10Y, 10M, 10C, and 10K, an endless belt-shaped intermediate transfer body forming unit 7 as a transfer unit, and an endless belt-shaped paper feeding conveyance for conveying a recording medium P. And a belt type fixing device 24 as fixing means. A document image reading device SC is arranged on the upper part of the main body A of the full-color image forming apparatus 1.

  An image forming unit 10Y that forms a yellow image as one of different color toner images formed on each of the photoreceptors 1Y, 1M, 1C, and 1K is a drum-like photoreceptor as a first image carrier. 1Y, a charging unit 2Y disposed around the photoreceptor 1Y, an exposure unit 3Y, a developing unit 4Y, a primary transfer roller 5Y as a primary transfer unit, and a cleaning unit 6Y.

  An image forming unit 10M that forms a magenta image as another different color toner image is disposed around a drum-shaped photoconductor 1M as a first image carrier, and the photoconductor 1M. A charging unit 2M, an exposure unit 3M, a developing unit 4M, a primary transfer roller 5M as a primary transfer unit, and a cleaning unit 6M.

  Further, an image forming unit 10C for forming a cyan image as one of different toner images of different colors is disposed around a drum-shaped photoreceptor 1C as a first image carrier, and the photoreceptor 1C. The charging unit 2C, the exposure unit 3C, the developing unit 4C, the primary transfer roller 5C as the primary transfer unit, and the cleaning unit 6C are provided.

  In addition, an image forming unit 10K that forms a black image as one of other different color toner images is disposed around a drum-shaped photosensitive member 1K as a first image carrier, and the photosensitive member 1K. It has a charging unit 2K, an exposure unit 3K, a developing unit 4K, a primary transfer roller 5K as a primary transfer unit, and a cleaning unit 6K.

  The endless belt-shaped intermediate transfer body unit 7 has an endless intermediate transfer belt 70 as a semiconductive endless belt-shaped second image carrier that is wound around a plurality of rollers and rotatably supported.

  Each color image formed by the image forming units 10Y, 10M, 10C, and 10K is sequentially transferred and synthesized on the rotating endless intermediate transfer belt 70 by the primary transfer rollers 5Y, 5M, 5C, and 5K. A color image is formed. A recording medium P such as paper as a recording medium accommodated in the paper feeding cassette 20 is fed by the paper feeding / conveying means 21, passes through a plurality of intermediate rollers 22 A, 22 B, 22 C, 22 D, and a registration roller 23, and is secondary. A color image is transferred onto the recording medium P at a time by being conveyed to a secondary transfer roller 5A as a transfer means.

  The recording medium P onto which the color image has been transferred is fixed by the fixing device 24 to which the heat roller fixing device 270 is attached, is sandwiched between the paper discharge rollers 25 and is placed on the paper discharge tray 26 outside the apparatus.

  On the other hand, after the color image is transferred to the recording medium P by the secondary transfer roller 5A, the residual toner is removed by the cleaning means 6A from the endless intermediate transfer belt 70 that has separated the curvature of the recording medium P.

  During the image forming process, the primary transfer roller 5K is always in pressure contact with the photoreceptor 1K. The other primary transfer rollers 5Y, 5M, and 5C are in pressure contact with the corresponding photoreceptors 1Y, 1M, and 1C, respectively, only during color image formation.

  The secondary transfer roller 5A comes into pressure contact with the endless belt-shaped intermediate transfer body 70 only when the recording medium P passes through the secondary transfer roller 5A and secondary transfer is performed.

  Further, the housing 8 can be pulled out from the apparatus main body A through the support rails 82L and 82R. The housing 8 includes image forming units 10Y, 10M, 10C, and 10K, and an endless belt-shaped intermediate transfer body forming unit 7.

  The image forming units 10Y, 10M, 10C, and 10K are arranged in tandem in the vertical direction. An endless belt-shaped intermediate transfer body unit 7 is disposed on the left side of the photoreceptors 1Y, 1M, 1C, and 1K in the figure. The endless belt-shaped intermediate transfer body unit 7 includes an endless intermediate transfer belt 70 that can be rotated by winding rollers 71, 72, 73, 74, and 76, primary transfer rollers 5Y, 5M, 5C, and 5K, and a cleaning unit 6A. have.

  The image forming units 10Y, 10M, 10C, and 10K and the endless belt-shaped intermediate transfer body unit 7 are integrally pulled out from the main body A by the drawer operation of the housing 8.

  In this manner, the outer peripheral surfaces of the photoreceptors 1Y, 1M, 1C, and 1K are charged and exposed to form a latent image on the outer peripheral surface, and then a toner image (developed image) is formed by development, and an endless belt-like intermediate transfer The toner images of the respective colors are superposed on the body 70, transferred to the recording medium P in a lump, and fixed and fixed by the belt-type fixing device 24 by pressure and heating. In the present invention, the time of image formation includes latent image formation and transfer of a toner image (developed image) to a recording medium P to form a final image.

  The photoreceptors 1Y, 1M, 1C, and 1K after the toner image is transferred to the recording medium P are transferred by the cleaning units 6Y, 6M, 6C, and 6K disposed on the photoreceptors 1Y, 1M, 1C, and 1K. After cleaning the toner remaining on the photoreceptor, the charging, exposure and development cycle described above is entered, and the next image formation is performed.

  In the color image forming apparatus, an elastic blade is used as a cleaning member of the cleaning unit 6A for cleaning the intermediate transfer member. Further, means (11Y, 11M, 11C, 11K) for applying a fatty acid metal salt to each photoconductor is provided. As the fatty acid metal salt, the same fatty acid metal salt as used in the toner can be used.

  FIG. 2 is a schematic sectional view showing an example of an electrophotographic image forming apparatus using an intermediate transfer roll as an intermediate transfer member.

  Reference numeral 1 'denotes a full-color image forming apparatus. The full-color image forming apparatus 1 ′ has a developing unit 2 ′, a photoreceptor 3 ′, a transfer unit 4 ′, a fixing device 5 ′, and a paper feed cassette 6 ′. The developing unit 2 'includes a magenta developing unit 2'M having magenta toner M, a cyan developing unit 2'C having cyan toner C, a yellow developing unit 2'Y having yellow toner Y, and a black having black toner K. And a developing unit black 2'K, which is disposed around the photoreceptor 3 '.

  The photoconductor 3 'is disposed so as to be rotationally driven at a predetermined peripheral speed in the direction of the arrow. In the course of rotation, the photosensitive member 3 'is uniformly charged to a predetermined polarity and potential by a primary charger (corona discharger) 7' disposed around the photosensitive member 3 '. By receiving the image exposure 8 'according to the figure, an electrostatic latent image corresponding to a first color component image of the target color image, for example, a magenta component image is formed. Next, the electrostatic latent image is developed by the magenta toner M, which is the first color, by the magenta developing unit 2'M.

  The transfer unit 4 ′ includes an intermediate transfer roller 401 ′, an intermediate transfer roller cleaner 402, and a transfer roller 403. The intermediate transfer roller 401 'is driven to rotate at the same peripheral speed as the photoconductor 3' in the opposite direction (arrow direction in the figure) to the photoconductor 3 '.

  The magenta toner image of the first color formed and supported on the photosensitive member 3 'passes through a nip portion N1 (primary transfer portion) between the photosensitive member 3' and the intermediate transfer roller 401 'in the process of power The intermediate transfer is sequentially performed on the outer peripheral surface of the intermediate transfer roller 401 ′ by an electric field formed by a primary transfer bias applied to the intermediate transfer roller 401 ′.

  The surface of the photoreceptor 3 ′ after the transfer of the first color magenta toner image to the intermediate transfer roller 401 ′ is cleaned by a cleaning device (not shown) disposed around the photoreceptor 3 ′. Similarly, a cyan toner image of the second color, a yellow toner image of the third color, and a black toner image of the fourth color are sequentially formed on the photosensitive member 3 ′, and these NATO images are sequentially formed on the intermediate transfer roller 401 ′. The toner images of the first to fourth colors are superimposed on the intermediate transfer roller 401 ′ to form a composite color toner image corresponding to the target color image.

  The composite color toner image superimposed and transferred onto the intermediate transfer roller 401 'is transferred to the transfer material 9' (secondary transfer) by the transfer roller 402 'that has been separated until then by a shift means (not shown). While being in contact with the intermediate transfer roller 401 ′, the transfer material 9 ′ is separated and fed from the paper feed cassette 6 ′ by the paper feed roller 601 ′, and the intermediate transfer roller 401 ′ and the transfer roller 403 are fed by the registration roller 602 ′. To the abutting nip portion N2 (secondary transfer portion) with ′, and at the same time, a secondary transfer bias is applied to the transfer roller 403 ′ from a bias power source (not shown). The composite color toner image is transferred from the intermediate transfer roller 401 ′ to the transfer material 9 ′ by the secondary transfer bias.

  The transfer material 9 'on which the composite color toner image has been transferred is separated from the intermediate transfer roller 401', introduced into the fixing device 5 'by a guide, and heated and fixed by the heat roller 501' and the pressure roller 502 '.

  After the transfer of the composite color toner image onto the transfer material 9 ', the transfer residual toner on the intermediate transfer roller 401' is applied to the intermediate transfer roller 401 'by an intermediate transfer roller cleaner 402' by a shift means (not shown). It is removed by contact (in the direction of the arrow in the figure).

  In the present invention, the intermediate transfer member refers to the endless intermediate transfer belt 70 shown in FIG. 1 and the intermediate transfer roll 401 ′ shown in FIG. 2, and the present invention refers to the endless intermediate transfer belt 70 shown in FIG. This relates to the transfer roll 401 '.

  FIG. 3 is an enlarged schematic cross-sectional view of the intermediate transfer belt of the intermediate transfer member of the present invention.

  In the figure, reference numeral 70 denotes an intermediate transfer member. The intermediate transfer member has a structure in which an elastic layer 70b, a three-dimensional crosslinkable resin layer 70c, and an inorganic compound layer 70d are sequentially laminated on a substrate 70a. Further, in the present invention, a three-dimensional crosslinkable resin layer is used. A stress adjusting means 70e is provided at the boundary between 70c and the inorganic compound layer 70d.

  The thickness of the substrate 70a is preferably 50 μm to 1000 μm in consideration of mechanical strength, image quality, manufacturing cost, and the like. The thickness of the elastic layer is preferably 50 μm to 500 μm, and more preferably 100 to 300 μm. The film thickness of the three-dimensional crosslinkable resin layer is preferably 1 μm to 100 μm, and more preferably 2 μm to 30 μm. The elastic modulus of the resin layer is higher than that of the elastic layer, and is preferably 0.1 GPa to 5 GPa. The thickness of the inorganic compound layer is preferably 10 nm to 1000 nm in consideration of durability, surface strength, adhesion to the resin layer, bending resistance, film formation time, and the like. More preferably, it is 200 nm-500 nm.

  In the conventional layer structure of elastic layer / resin layer / inorganic compound layer, the inorganic compound layer has finer defects than the cracks that are usually observed visually by long-term operation or storage in a high temperature and high humidity environment. As a result, it was found that filming occurs and durability deteriorates due to insufficient adhesion between the inorganic compound layer and the resin layer.

  As a result of diligent examination of the above problems, by providing a means for adjusting the stress between the elastic layer and the inorganic compound layer, that is, a means for adjusting the stress balance between the resin layer and the inorganic compound layer by the elastic balance in addition to the resin layer, this is a fine defect. It has been found that the influence on the generation and the use of a three-dimensional crosslinkable resin as the resin layer does not cause film peeling of the inorganic surface layer even under high temperature and high humidity, and the adhesiveness is good. . The present invention has a surface inorganic compound layer excellent in wear resistance and transferability, and can suppress fine defects in the inorganic compound layer by the elastic balance of the elastic layer, the three-dimensional crosslinkable resin layer, and the inorganic compound layer. Furthermore, it has been found that providing a low-friction protective layer on the inorganic compound layer has a great effect on improving the durability and cleaning properties of the inorganic compound layer.

  Each component will be described below.

[Constituent material of three-dimensional crosslinkable resin layer (hard coat (HC) layer)]
It is preferable to use an actinic ray curable resin as the three-dimensional crosslinkable resin according to the present invention.

(Actinic ray curable resin)
Typical examples of the actinic ray curable resin applicable to the present invention include an ultraviolet curable resin and an electron beam curable resin, but a resin that is cured by irradiation with an active ray other than an ultraviolet ray or an electron beam may be used. In particular, an ultraviolet curable resin is preferable.

  Examples of the three-dimensional crosslinkable resin according to the present invention include polyfunctional (meth) acrylates containing 3 or more (meth) acryloyl groups in one molecule, such as pentaerythritol tri (meth) acrylate. , Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, EO modified trimethylolpropane Tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO-modified phosphate tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (a Rirokishiechiru) isocyanurate and the like. In addition, the said polyfunctional (meth) acrylate can be used individually or in mixture of 2 or more types.

  In addition, an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable epoxy resin, and the like can be given.

  In general, UV-curable acrylic urethane-based resins are obtained by further reacting 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate, methacrylate) with a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate (for example, see JP-A-59-151110).

  The UV curable polyester acrylate resin can be easily obtained by reacting polyester polyol with 2-hydroxyethyl acrylate or 2-hydroxy acrylate monomer (see, for example, JP-A-59-151112). .

  Specific examples of ultraviolet curable epoxy acrylate resins include those obtained by reacting epoxy acrylate with an oligomer, a reactive diluent and a photoreaction initiator added thereto (for example, JP-A-1- No. 105738).

In particular,
(1) A resin having a small number of (meth) acryloyl groups contained in the molecule, that is, a resin having small curing shrinkage is used. Specifically, monofunctional (meth) acrylates such as isobutyl (meth) acrylate and hydroxypropyl (meth) acrylate, 1,6-hexanediol-di (meth) acrylate, neopentyl glycol-di (meth) acrylate, etc. Bifunctional (meth) acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, and the like.
(2) Urethane (meth) acrylates containing 3 or more (meth) acryloyl groups in one molecule and having a shrinkage ratio after curing of less than 10%, which are industrially available, For example, UV-7600B, UV-7640B manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Unidic 17-806, Unidic 17-813, V-4030, V-4000BA manufactured by Dainippon Ink & Chemicals, Inc. EB-1290K manufactured by Daicel UCB Etc.
(3) Ring-opening polymerizable cyclic ether compounds include cyclic imino ethers such as epoxy derivatives, oxetane derivatives, tetrahydrofuran derivatives, oxazoline derivatives, and the like, and epoxy derivatives, oxetane derivatives, and oxazoline derivatives are particularly preferable.

These ring-opening polymerizable cyclic ether compounds are preferably compounds having 2 or more, preferably 3 or more of the above cyclic structures in the same molecule. For example, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, etc. as trifunctional glycidyl ether, sorbitol tetraglycidyl ether, pentaerythritol as tetrafunctional or higher glycidyl ether Examples of tri- or more functional epoxies such as tetraglycyl ether, polyglycidyl ether of cresol novolac resin, polyglycidyl ether of phenol novolac resin include Epolide GT-301, Epolide GT-401, EHPE (above, manufactured by Daicel Chemical Industries, Ltd.) ), Tri- or higher functional oxetanes such as phenol novolac resin polycyclohexyl epoxy methyl ether The Te OX-SQ, PNOX-1009 (manufactured by Toagosei Co.), and the like.
(4) Monofunctional monomers include alkyl esters of acrylic acid such as methyl (meth) acrylate and butyl (meth) acrylate, hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, etc. Examples include polar monomers-containing acrylic acid esters, acrylamides such as (meth) acrylamide and N-methylol (meth) acrylamide, and existing monomers such as N-vinylpyrrolidone, styrene, vinyl acetate and maleic anhydride.
(5) A compound having one or two ring-opening polymerizable groups in the same molecule can be used in combination as needed. Preferred compounds are monofunctional or bifunctional glycidyl ethers, monofunctional or 2 Functional alicyclic epoxies, monofunctional or bifunctional oxetanes can be mentioned, and various commercially available or known compounds can be used.

(Photopolymerization initiator)
In the three-dimensional crosslinkable resin layer according to the present invention, a polymerization initiator, a photoacid generator, or the like is used in order to cure the photopolymerizable resin by light irradiation.

  When the curable resin is a radical polymerization curable resin, a photo radical polymerization initiator is used. For example, acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α-acyloxime ester, tetramethylthiuram mono Sulfide, thioxanthone and the like are included. In addition to the photopolymerization initiator, a photosensitizer may be used. Examples of the photosensitizer include n-butylamine, triethylamine, triethanolamine, tri-n-butylphosphine, and thioxanthone.

When the cured resin is a cationic polymerization type cured resin, compounds such as triarylsulfonium salts, diaryliodonium salts, and nitrobenzyl esters of sulfonic acids can be cited as photoacid generators that generate cations. Various known photoacid generators such as compounds described in the study group, “Organic Materials for Imaging” published by Bunshin Publishing Co., Ltd. (1997) can be used. Among them, a sulfonium salt such as diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate or a diphenyliodonium salt is particularly preferable, and PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆ F _{5) 4} ^-, and the like.

(Method for providing a three-dimensional crosslinkable resin layer on a substrate)
In the present invention, as a method for forming the three-dimensional crosslinkable resin layer on the resin base material, a known method for forming a thin film can be applied, and it is particularly preferable to form the thin film by a wet coating method.

  The wet coating method refers to a three-dimensional crosslinkable resin layer obtained by dissolving a cured resin, a photopolymerization initiator, etc. in a solvent such as a hydrocarbon, alcohol, ketone, ester, glycol ether, or other solvent. In this method, a coating solution is prepared, and a wet thin film is formed on the substrate using the coating solution.

  Examples of coating methods used in such wet coating methods include spin coating, dip coating, extrusion coating, roll coating coating spray coating, gravure coating, wire bar coating, air knife coating, slide popper coating, and curtain coating. A coating method (coating apparatus) using a known solution can be applied.

  The three-dimensional crosslinkable resin layer formed on the substrate by the above coating method is irradiated with actinic rays for the purpose of curing the film.

  Examples of the active energy rays used to cure the three-dimensional crosslinkable resin layer include radiation, gamma rays, alpha rays, electron beams, ultraviolet rays, and the like. Ultraviolet rays are preferable, and the radicals or cations are generated by the ultraviolet rays. A method of adding a polymerization initiator and curing with ultraviolet rays is particularly preferable.

Examples of a light source that generates ultraviolet rays for curing a three-dimensional crosslinkable resin layer by a photocuring reaction to form a cured coating layer include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, A metal halide lamp, a xenon lamp, etc. can be mentioned. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may be any degree 20~10000mJ / cm ^2, preferably from 50~2000mJ / cm ^2. It can be used by using a sensitizer having an absorption maximum in the near ultraviolet region to the visible light region.

  The coating liquid containing the cured resin is coated and dried, and then cured by ultraviolet irradiation with an ultraviolet light source. The irradiation time is preferably 0.5 seconds to 5 minutes, and from the curing efficiency and working efficiency of the cured resin, 3 seconds to Two minutes is more preferable.

  As a method of forming a three-dimensional cured resin layer on an elastic body layer formed on an endless belt-like substrate, for example, in a tank containing a coating solution for the resin layer, a cylindrical core material is used. An annular endless belt-like resin substrate formed up to the elastic layer is set, put in a vertically standing state, and immersed. At this time, after dipping is repeated several times to form a coating film having a predetermined thickness, the coating solution is pulled up. Next, after drying and removing the solvent, heat treatment (for example, 60 ° C. × 60 minutes to 150 ° C. × 60 minutes) and curing treatment are performed to produce a three-dimensional crosslinkable resin layer.

  The film thickness of the three-dimensional crosslinkable resin layer is preferably 1 μm to 100 μm, and more preferably 2 μm to 30 μm.

(Stress adjustment means)
The present invention is characterized in that stress adjusting means is provided on the surface during or after the formation of the three-dimensional crosslinkable resin layer. This will be described.
(1) Method of providing inorganic fine particle-containing layer As a stress adjusting means, an inorganic fine particle-containing layer can be provided in the vicinity of the surface of the three-dimensional crosslinkable resin layer.

  The vicinity of the surface means that the layer within 30% by thickness from the surface of the entire three-dimensional crosslinkable resin layer is an inorganic fine particle-containing layer.

  Specifically, it is obtained by forming a three-dimensional crosslinkable resin containing inorganic fine particles after the formation of the lower layer of the three-dimensional crosslinkable resin layer, or by layering simultaneously.

  Examples of inorganic fine particles applicable to the three-dimensional crosslinkable resin layer according to the present invention include oxidation of a metal selected from Si, Ti, Mg, Ca, Zr, Sn, Sb, As, Zn, Nb, In, and Al. In particular, silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined Mention may be made of calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. In particular, in the present invention, it is preferable to use silicon oxide as the inorganic particles.

  The silicon oxide fine particles that can be preferably applied to the present invention include: Silicia manufactured by Fuji Silysia Chemical Co., Ltd., Nippon Sil manufactured by Nippon Silica Co., Ltd., Aerosil series manufactured by Nippon Aerosil Co., Ltd., Nissan Chemical Industries, Ltd. Colloidal silica, organosilica sol and the like manufactured by the method can be applied.

  The average particle size of the inorganic fine particles applicable to the three-dimensional crosslinkable resin layer according to the present invention is preferably 5 nm or more and 1.0 μm or less, more preferably 5 nm or more and 500 nm or less. The average particle diameter of the inorganic fine particles is obtained as a simple average value (number average) by observing the inorganic fine particles with an electron microscope and determining the particle diameter of 100 arbitrary primary particles. Here, each particle diameter is expressed by a diameter assuming a circle equal to the projected area.

  In the three-dimensional crosslinkable resin layer according to the present invention, the content of the inorganic fine particles in the inorganic fine particle-containing layer is preferably 0.1 to 50% by mass with respect to the three-dimensional crosslinkable resin (ultraviolet curable resin). Furthermore, 10-30% by mass is preferable. The fine particle-containing three-dimensional crosslinkable resin layer is preferably provided at 1 to 30% or less, more preferably 5 to 10% of the film thickness of the lower three-dimensional crosslinkable resin layer.

The fine particle-containing layer may have a multilayer structure, and it is preferable to provide a plurality of layers having different fine particle contents. The fine particle content may be continuously changed. It is preferable that the fine particle content increases as the surface layer increases.
(2) Method of providing a titanium oxide layer As another embodiment of the present invention, a titanium oxide thin film layer can be used as a stress adjusting means.

  The titanium oxide layer can be formed by either a vapor phase method or a liquid phase method. In the case of the gas phase method, the plasma CVD method is particularly preferable.

  Titanium compounds include organometallic compounds such as tetradimethylaminotitanium, metal hydrogen compounds such as monotitanium and dititanium, metal halogen compounds such as titanium dichloride, titanium trichloride, and titanium tetrachloride, tetraethoxy titanium, tetraisopropoxy titanium It is preferable to use a metal alkoxide such as tetrabutoxytitanium, but is not limited thereto.

Moreover, when forming by application | coating, you may form by the well-known sol-gel method using the alkoxide whose metal component is Ti. Specific examples of the titanium alkoxide include tetramethoxytitanium Ti (O—CH ₃ ) ₄ , tetraethoxytitanium Ti (O—C ₂ H ₅ ) ₄ , tetraisopropoxytitanium Ti (O-iso-C ₃ H ₇ ) _4. Tetra n-butoxy titanium Ti (O—C ₄ H ₉ ) ₄ or the like can be used as appropriate.

Here, the organic component derived from the raw material may remain in the titanium oxide layer.
(3) Method of providing silane coupling agent-containing layer As another embodiment of the present invention, a silane coupling agent-containing layer can be provided near the surface of the three-dimensional crosslinkable resin layer as a stress adjusting means.

  Here, the vicinity of the surface means that a layer within 30% by thickness from the surface of the all three-dimensional crosslinkable resin layer is a silane coupling agent-containing layer.

  Specifically, it is obtained by forming a three-dimensional crosslinkable resin containing a silane coupling agent in layers or simultaneously after forming a three-dimensional crosslinkable resin layer as a lower layer.

  There is no particular limitation on the silane coupling agent, and a silane coupling agent having a vinyl group, an epoxy group, an amino group, a methacryl group, a mercapto group, or the like as a reactive group can be appropriately selected. A silane coupling agent is preferred.

Specific examples of amino silane coupling agents include:
N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, γ- Examples thereof include aminopropyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N- (vinylbenzyl) -β-aminoethyl-γ-aminopropyltrimethoxysilane hydrochloride.

  The amino silane coupling agent according to the present invention can be used by mixing with an epoxy silane coupling agent. Specific examples of the epoxy silane coupling agent include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycid. Examples include xylpropyltriethoxysilane.

  In this invention, the addition amount of the silane coupling agent with respect to the three-dimensional crosslinkable resin in a silane coupling agent content layer shall be 0.1-10 mass% of a layer total amount. This is because when the addition amount of the silane coupling agent is less than 0.1% by mass, the adhesive strength is poor, and when it exceeds 10% by mass, it is difficult to form a coating film uniformly.

  The silane coupling agent-containing three-dimensional crosslinkable resin layer is preferably provided at 1 to 30% or less, more preferably 5 to 10% of the film thickness of the lower three-dimensional crosslinkable resin layer.

The silane coupling agent-containing layer may have a multilayer structure, and it is preferable to provide a plurality of layers having different fine particle contents. It is preferable that the fine particle content increases as the surface layer increases.
(4) Method of coating inorganic compound layer before curing of three-dimensional crosslinkable resin layer As another embodiment of the present invention, after forming a three-dimensional crosslinkable resin layer as a stress adjusting means, before curing treatment or during curing treatment By coating the inorganic compound-containing layer at the stage, and then performing a secondary curing treatment, a stress adjusting means can be obtained.

  More preferably, a three-dimensional crosslinkable resin layer is laminated for stress adjustment after the three-dimensional crosslinkable resin layer is formed (after curing), and a part of a surface layer (inorganic compound layer) described later can be formed before curing. . Since the interaction occurs at the interface during the curing process, the adhesion between the three-dimensional crosslinkable resin layer and the inorganic compound layer is strengthened, and the stress relaxation action between the upper and lower layers is brought about.

  As a specific embodiment, for example, an inorganic compound layer is formed by an atmospheric pressure plasma method, a sputtering method or the like after applying / drying the three-dimensional crosslinkable resin layer coating solution and before curing. This also partially cures the three-dimensional crosslinkable resin coating layer, but it is considered that the interaction of both layers at the interface occurs at the same time and the mutual mixing occurs in the vicinity of the interface. Adhesiveness is improved.

  The inorganic compound layer may be formed in the same manner as the inorganic compound layer described later, and may be a sputtering method, a plasma CVD method, or the like, but is not limited thereto, for example, a sol-gel method using a metal compound such as tetraalkoxysilane May be formed. Thereafter, a crosslinking treatment is performed by light irradiation to form a three-dimensional crosslinkable resin layer.

(Inorganic compound layer)
The inorganic compound layer is at least one metal oxide, metal nitride, or metal oxynitride selected from In, Sn, Cd, Zn, Al, Sb, Ge, W, Mo, Si, Zr, Ce, Mg, and Ti. Preferably, Al, Si, and Ti are preferable. Specific examples include silicon oxide, silicon nitride, silicon oxynitride, titanium oxide, titanium oxynitride, titanium nitride, and aluminum oxide. Furthermore, silicon oxide or silicon oxide containing carbon is most preferable.

  The thickness of the inorganic compound layer is preferably 50 nm to 1000 nm in consideration of durability, surface strength, adhesion to the resin layer, bending resistance, film formation time, and the like. More preferably, it is 200 nm-500 nm.

  The film thickness of the inorganic compound layer is a value obtained by measurement using “MXP21” (manufactured by Mac Science). A specific measurement of the film thickness can be performed by the following method. Copper is used as the target of the X-ray source and it is operated at 42 kV and 500 mA. A multilayer parabolic mirror is used for the incident monochromator. The incident slit is 0.05 mm × 5 mm, and the light receiving slit is 0.03 mm × 20 mm. Measurement is performed by the FT method with a step width of 0.005 ° and a step of 10 seconds from 0 to 5 ° in the 2θ / θ scan method. With respect to the obtained reflectance curve, Reflectivity Analysis Program Ver. Curve fitting is performed using 1, and each parameter is obtained so that the residual sum of squares of the actual measurement value and the fitting curve is minimized. The film thickness of the laminated film is obtained from each parameter.

The method for forming the inorganic compound layer is not particularly limited. For example, PVD method (physical vapor deposition method) such as sputtering method, vacuum vapor deposition method, ion plating method, CVD method (chemical vapor deposition method), plasma CVD method, atmospheric pressure plasma CVD. Law. Among these forming methods, the atmospheric pressure plasma CVD method is particularly preferable in consideration of adhesion to the resin layer.
(1) Formation of Inorganic Compound Layer by Atmospheric Pressure Plasma CVD Method Next, an apparatus for forming an inorganic compound layer according to the belt-like intermediate transfer member of the present invention by the atmospheric pressure plasma CVD method will be described. The atmospheric pressure in the present invention or a pressure in the vicinity thereof represents a pressure of 20 kPa to 200 kPa, but is preferably about 90 kPa to 110 kPa, and particularly preferably 93 kPa to 104 kPa in order to obtain the effects described in the present invention.

  FIG. 4 is a schematic view of a manufacturing apparatus for forming an inorganic compound layer of an intermediate transfer belt, which is a belt-shaped intermediate transfer body, by an atmospheric pressure plasma CVD method.

  In the figure, 9 indicates a manufacturing apparatus. The manufacturing apparatus 9 includes an atmospheric pressure plasma CVD apparatus 9a and a material supply apparatus 9b. The atmospheric pressure plasma CVD apparatus 9a includes a roll electrode 9a1, at least one set of fixed electrodes 9a2 arranged along the outer periphery of the roll electrode 9a1, a mixed gas supply device 9a3, a discharge vessel 9a4, a high-frequency power source 9a5, And an exhaust pipe 9a6. Reference numeral 9a7 denotes a discharge space where discharge is performed in a region where the fixed electrode 9a2 and the roll electrode 9a1 face each other. Although not shown, it is necessary to dispose a dielectric on the surface of at least one of the fixed electrode 9a2 and the roll electrode 9a1 in order to perform stable discharge, and it is more preferable to dispose them on both. As the dielectric, a ceramic such as aluminum oxide or titanium oxide can be appropriately selected. The surface of the fixed electrode 9a2 facing the roll electrode 9a1 is preferably the same as the curvature of the surface of the roll electrode 9a1 in order to keep the distance from the roll electrode 9a1 constant.

  From the mixed gas supply device 9a3, a mixed gas G of at least a raw material gas and a discharge gas is generated, and the mixed gas G is supplied to the discharge vessel 9a4. The discharge vessel 9a4 reduces the inflow of air into the discharge space 9a8.

  The high-frequency power source 9a5 is connected to the fixed electrode 9a2, and the used exhaust gas G 'is exhausted from the exhaust pipe 9a7.

  From the mixed gas supply device 9a3, a mixed gas obtained by mixing a raw material gas for forming an inorganic compound layer film and a rare gas such as nitrogen gas or argon gas is supplied to the discharge vessel 9a4. Moreover, it is more preferable to mix oxygen gas or hydrogen gas for promoting the reaction by the oxidation-reduction reaction.

  By applying a voltage to the high-frequency power source, the mixed gas G is turned into plasma (excited) between the electrodes of the fixed electrode 9a2 and the roll electrode 9a1, and a film (inorganic compound layer 70d) corresponding to the source gas contained in the mixed gas G (See FIG. 3) is deposited on the resin layer of the material F, and the intermediate transfer belt 70 which is a belt-like intermediate transfer member shown in FIG. 3 is manufactured. The inorganic compound layer formed in this way can also form a plurality of layers in which the carbon content gradually decreases from the lowermost layer to the uppermost layer.

  There is no limitation in particular as the high frequency power supply 9a5 which can be utilized, For example, CF-5000-13M by the pearl industry etc. can be used.

The power supplied to the high-frequency power source 9a5 supplies power (output density) of 1 W / cm ² or more to the fixed electrode 9a2, excites the discharge gas to generate plasma, and forms a thin film. The upper limit value of the power supplied to the fixed electrode 9a2 is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to an area in a range where discharge occurs in the electrode.

  Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called continuous mode and an intermittent oscillation mode called ON / OFF intermittently called pulse mode. Either of them can be used, but continuous sine wave is more precise It is preferable because a good quality film can be obtained.

  Of the plurality of fixed electrodes 9a2, the plurality of fixed electrodes 9a2 positioned on the downstream side in the rotation direction of the roll electrode 9a1 and the mixed gas supply device 9a3 are stacked so that the inorganic compound layers are stacked, and the thickness of the inorganic compound layer is set. You may make it adjust.

  Although not shown, the mixed gas from the mixed gas supply device 9a3 is directly supplied to the discharge space 9a8, and the fixed electrode 9a2 positioned on the most downstream side in the rotation direction of the roll electrode 9a1 and the mixed gas supply device 9a3 Other layers such as an adhesive layer that improves the adhesion between the inorganic compound layer and the resin layer, for example, may be formed by depositing the layers and using the other fixed electrode 9a2 and the mixed gas supply device 9a3 located further upstream. .

  Further, in order to improve the adhesion between the inorganic compound layer 70d (see FIG. 3) and the resin layer 70c (see FIG. 3), the fixed electrode 9a2 for forming the inorganic compound layer 70d (see FIG. 2) and the mixed gas supply device A gas supply device that supplies a gas such as argon or oxygen and a fixed electrode may be provided upstream of 9a3 to perform plasma treatment to activate the surface of the resin layer 70c (see FIG. 3).

  The material supply device 9b includes a driven roller 9b1 and tension applying means 9b2 that pulls the driven roller 9b1 (in the direction of the arrow in the drawing). The endless belt-shaped material F is held by the roll electrode 9a1 and the driven roller 9b1, is applied with a predetermined tension by the tension applying means 9b2, and is driven by the rotation of the roll electrode 9a1 (in the direction of the arrow in the drawing). It is in a state where it is stretched so as to rotate through. The tension applying means 9b2 cancels the application of the tension at the time of changing the material F, etc., so that the material F is easily changed. The material F shown in this figure shows a material in a state where the layers up to the stress adjusting means of the intermediate transfer belt 70 shown in FIG. 3 are formed (base 70a / elastic layer 70b / resin layer 70c / stress adjusting means 70e).

  The discharge gas used in the manufacturing apparatus formed by the atmospheric pressure plasma CVD method shown in FIG. 4 means a gas that is plasma-excited under the above conditions, such as nitrogen, argon, helium, neon, krypton, xenon, and the like. A mixture etc. are mentioned. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  As the raw material gas for forming the inorganic layer, a gaseous or liquid organometallic compound, particularly an alkyl metal compound, a metal alkoxide compound, or an organometallic complex compound is used at room temperature. The phase state in these raw materials does not necessarily need to be a gas phase at normal temperature and normal pressure, and any liquid phase or solid phase can be used as long as it can be vaporized through heating, decompression, etc. through melting, evaporation, sublimation, etc. But it can be used.

  The source gas contains a component that is in a plasma state in the discharge space and forms a thin film, and is an organometallic compound, an organic compound, an inorganic compound, or the like.

  For example, as a silicon compound, silane, tetramethoxysilane, tetraethoxysilane (TEOS), tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetra t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane , Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethyl Silane, bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimi , Diethylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane , Tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsila , Propargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethyl Examples include, but are not limited to, cyclotetrasiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  Titanium compounds include organometallic compounds such as tetradimethylaminotitanium, metal hydrogen compounds such as monotitanium and dititanium, metal halogen compounds such as titanium dichloride, titanium trichloride, and titanium tetrachloride, tetraethoxy titanium, tetraisopropoxy titanium And metal alkoxides such as tetrabutoxytitanium, but are not limited thereto.

  As aluminum compounds, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum diisopropoxide ethyl acetoacetate, aluminum ethoxide, aluminum hexafluoropentanedionate, aluminum isopropoxide, 4-pentanedionate Dimethylaluminum chloride and the like, but are not limited thereto.

  These raw materials may be used alone, or two or more kinds of components may be mixed and used.

  In the present invention, it is preferable to use silicon oxide formed by these atmospheric pressure plasma methods as the inorganic compound layer.

  The inorganic compound layer may be formed of at least two layers. In the case of two layers, the thickness of the upper layer is preferably 10 nm to 300 nm. The thickness of the lower layer is preferably 10 nm to 500 nm. In this way, a further durability effect can be obtained.

  When the inorganic compound layer is composed of two layers, the lower layer carbon content (carbon atom number concentration) is 0.5 atom concentration% to 10 atom concentration%, and the uppermost layer carbon content (carbon atom concentration). ) Is preferably 0.1 atomic percent concentration% or less.

  The atomic number concentration indicating the carbon content in the present invention is calculated by the following XPS method and is defined below.

Atomic concentration% = number of carbon atoms / number of all atoms × 100
In the present invention, the XPS surface analyzer used ESCALAB-200R manufactured by VG Scientific. Specifically, Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA). The energy resolution was set to be 1.5 eV to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak.

  As a measurement, first, the range of the binding energy of 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what elements were detected.

  Next, with respect to all the detected elements except the etching ion species, the data acquisition interval was set to 0.2 eV, and the photoelectron peak giving the maximum intensity was subjected to narrow scan, and the spectrum of each element was measured.

  The obtained spectrum is COMMON DATA PROCESSING SYSTEM manufactured by VAMAS-SCA-JAPAN (preferably Ver. 2.3 or later) in order not to cause a difference in the content calculation result due to a difference in measuring apparatus or computer. After being transferred to the top, the processing was performed with the same software, and the content value of each analysis target element (carbon, oxygen, silicon, titanium, etc.) was determined as the atomic concentration (at%).

  Before performing the quantitative process, a calibration of the Scale Scale was performed for each element, and a 5-point smoothing process was performed. In the quantitative process, the peak area intensity (cps * eV) from which the background was removed was used. For the background treatment, the method by Shirley was used. For the Shirley method, see D.C. A. Shirley, Phys. Rev. , B5, 4709 (1972).

  The silicon oxide formed by these atmospheric pressure plasma CVD methods can be selected by selecting conditions so that the silicon oxide film containing carbon derived from the raw material (carbon content (carbon atom number concentration) is 0.5 atom number concentration% to 10%. A silicon oxide film having an atomic number concentration%) and a carbon content (carbon atom number concentration) of 0.1 atomic number concentration% or less can be formed.

  As the inorganic compound layer, not only a two-layer film of a silicon oxide and a carbon-containing silicon oxide layer but also an inorganic compound layer obtained by alternately laminating a plurality of layers may be used.

Those made of a laminate of carbon-containing silicon oxide and silicon oxide are less prone to cracks and have excellent durability.
(2) Formation of Inorganic Compound Layer from Polysilazane Film The inorganic compound layer according to the present invention can also be formed by applying a coating liquid containing a polysilazane compound as a hydrolyzable silicon compound. Preferably, the intermediate transfer member coated with a solution in which polysilazane is dissolved can be obtained by treatment in air or in an oxidizing atmosphere. In the present invention, perhydropolysilazane having a structure of (SiN _a H _b ) _n (a = 1 to 3, b = 0 to 1) is preferable. The polysilazane can be dissolved in a solvent such as benzene, toluene, xylene, ether, THF, methylene chloride, carbon tetrachloride, and the silicon oxide layer can be obtained by coating and heating after dissolving the polysilazane. At this time, a low-temperature treatment can be performed by adding a catalyst such as amine or transition metal. Specific examples include Aquamica NAX120-20, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials.

  The molecular weight (Mn) of polysilazane can be used in the range of 100 to tens of thousands, but those having a molecular weight of 5000 or less are preferable for coating.

  As for the film thickness of the inorganic compound layer formed from the solution containing polysilazane, 0.1-2 micrometers is preferable, More preferably, it is 0.2-1 micrometers. If the film thickness is much thinner than 0.1 μm, a uniform silicon oxide layer cannot be obtained, and a film thicker than 2 μm is cracked due to internal stress of the film. It is not preferable.

  The coating method is not particularly limited, and examples thereof include spin coating, roll coating, spray coating, and dip coating.

(3) Formation by Sol-Gel Method The inorganic compound layer of the present invention may be formed by a sol-gel method.

  The sol-gel method is obtained by hydrolyzing and / or hydrolyzing and polycondensing a hydration complex (sol) of a metal hydroxide with an acid catalyst. First, a sol is prepared by hydrolyzing an alkoxide or acetate compound such as methoxide, ethoxide, propoxide, or butoxide of a metal such as titanium, zirconium, lead, or zinc with an acid or the like.

  The prepared sol is then applied. After applying the sol, it is dried at a constant temperature for a certain period of time to evaporate the solvent of the sol. The drying temperature is preferably 100 ° C. or more and 200 ° C. or less, and the drying time is preferably 5 minutes or more and 120 minutes or less.

  Hereinafter, the metal oxide obtained by the sol-gel reaction will be described.

  In the sol-gel reaction, alkoxysilane and / or metal alkoxide other than alkoxysilane is used. As the metal alkoxide other than alkoxysilane, it is preferable to use zirconium alkoxide, titanium alkoxide, aluminum alkoxide or the like. These can also be used in combination. Examples of preferable combinations include, for example, alkoxysilane alone, alkoxysilane and alkoxyzirconium, and a combination of aluminum alkoxide and / or titanium alkoxide.

  The acid catalyst used in the sol-gel reaction is preferably a mineral acid such as sulfuric acid, hydrochloric acid or nitric acid, and an organic acid such as acetic acid or tartaric acid. The amount of the acid catalyst used is 0.001 to 0.005 mol per 1 mol of metal alkoxide (alkoxysilane and other metal alkoxide, when alkoxysilane and other metal alkoxide are contained), preferably about 0.01 mole.

  As the metal alkoxide of the metal compound, alkoxysilane and / or metal alkoxide other than alkoxysilane can be preferably used. As the metal alkoxide other than alkoxysilane, zirconium alkoxide, titanium alkoxide, aluminum alkoxide and the like are preferable.

  Further, the polymer used in combination during the sol-gel reaction preferably has a hydrogen bond forming group.

  Examples of resins having hydrogen bond-forming groups include hydroxyl group-containing polymers and derivatives thereof (polyvinyl alcohol, polyvinyl acetal, ethylene-vinyl alcohol copolymers, phenol resins, methylol melamine, and derivatives thereof); carboxyl groups Polymers and derivatives thereof (mono or copolymers containing units of polymerizable unsaturated acids such as poly (meth) acrylic acid, maleic anhydride, itaconic acid, and esterified products of these polymers (vinyl esters such as vinyl acetate, Homo- or copolymers containing units such as (meth) acrylic acid esters such as methyl methacrylate)); polymers having an ether bond (polyalkylene oxide, polyoxyalkylene glycol, polyvinyl ether, silicon resin, etc.); amide bond Having a polymer (> N COR) -bond (wherein R represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent) N- of polyoxazoline or polyalkyleneimine Acylated product);> polyvinylpyrrolidone having a NC (O) -bond and derivatives thereof; polyurethane having a urethane bond; polymer having a urea bond, and the like. A silyl group-containing polymer may also be used. The silyl group-containing polymer is composed of a main chain polymer, and at least one, preferably two silyl groups having a hydrolyzable group and / or a silicon atom bonded to a hydroxyl group at the terminal or side chain in one molecule of the polymer. It contains above. Particularly preferred as the silyl group-containing polymer is a silyl group-containing vinyl polymer whose main chain is a vinyl polymer.

《Protective layer》
As a further aspect of the present invention, a protective layer (low friction layer) can be provided on the inorganic compound layer. The protective layer preferably contains an alkyl silane or a fluorine-containing silane compound.

  First, the alkylsilane compound used for the protective layer will be described.

(Alkylsilane compound)
In order to impart antifouling properties to the protective layer, it is particularly preferable that an alkyl group is present on the outermost surface of the film, and a silicon compound (alkylsilane) having an alkyl group as a raw material used for layer formation (also referred to as film formation) Compound) is preferably used. In addition, it is important for the alkyl group to be low in price and to maintain the hardness of the film. In this sense, it is preferably an ethyl group or a methyl group, and more preferably a methyl group. Moreover, as long as said functional group is provided, the compound may contain two or more silicon atoms.

  More preferably, an organosilicon compound having both a hydrolyzable group and an alkyl group is used. The hydrolyzable group is not particularly limited, and preferably includes an alkoxy group, but having an ethoxy group is particularly preferable from the viewpoint of reactivity and adjustment of physical properties of the raw material.

  Specific examples of the organosilicon compound include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane. , Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltri Ethoxysilane, γ-chloropropyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl Pyrtriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, Chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β- Glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane , Β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane , Γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxy Silane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glyoxydoxybutyltrimethoxysilane, δ-glyoxydoxybutyltriethoxy Silane, (3,4-epoxy Cyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, γ- (3 , 4-epoxycyclohexyl) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) )Professional Trialkoxysilanes such as rutriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, triacyloxysilanes, triphenoxysilanes; dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldi Ethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxy Silane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, Ruvinyldimethoxysilene, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β -Glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane , Β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycid Xylpropylmethyldibutoxyethoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane Γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyl Dialkoxysilanes such as diethoxysilane, diphenoxysilane, diacyloxysilane, trimethylethoxysilane, trimethylmethoxysilane, hexamethyldisilane, hexamethyldisiloxanes, etc. , But it is not limited to these.

  Moreover, even if it uses said compound independently, 2 or more types which are different can also be used simultaneously. In addition, organosilicon compounds other than the above compounds can be used in combination.

  Among the above compounds, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, trimethylethoxysilane, etc. are preferred, and further against silicon. A compound having two alkyl groups is preferred, and dimethyldiethoxysilane, dimethyldimethoxysilane and the like are particularly preferred examples.

(Fluorine-containing silane compound)
An organic silicon compound having an organic group containing a fluorine atom is preferable as a protective layer containing a fluorine-containing silane compound.

  In the organic silicon compound having an organic group containing a fluorine atom, examples of the organic group containing a fluorine atom include an organic group having an alkyl group, an alkenyl group, an aryl group, etc. having a fluorine atom. For example, when the compound having a plurality of silicon atoms such as siloxane has these organic groups, at least one silicon atom may have an organic group containing a fluorine atom. The position does not matter.

  According to the method for forming a protective layer using an organic silicon compound having an organic group containing a fluorine atom, the organic silicon compound having an organic group containing a fluorine atom is bonded to an inorganic compound layer under the protective layer. It is presumed that it is easy to form and that the excellent effects of the present invention can be achieved.

  Although there is no restriction | limiting in particular as an organosilicon compound which has an organic group containing the fluorine atom used in this invention, The compound represented by following General formula (1) is preferable.

In the formula, M represents Si. R _{1 to} R ₆ each represents a hydrogen atom or a monovalent group, and at least one of the groups represented by R _{1 to} R ₆ is an organic group containing a fluorine atom. An organic group having an alkyl group, an alkenyl group or an aryl group is preferred. Examples of the alkyl group containing a fluorine atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, 1 , 1,2,2,3,3,4,4-octafluorobutyl group and the like, as the alkenyl group containing a fluorine atom, for example, 3,3,3-trifluoro-1-propenyl group, etc. Examples of the aryl group containing a fluorine atom include groups such as a pentafluorophenyl group. In addition, an alkyl group, an alkenyl group, an alkoxy group formed from an aryl group, an alkenyloxy group, an aryloxy group, or the like can also be used.

  In the alkyl group, alkenyl group, aryl group, etc., any number of fluorine atoms may be bonded to any position of the carbon atoms in the skeleton, but at least one or more fluorine atoms may be bonded. preferable. The carbon atom in the skeleton of the alkyl group or alkenyl group includes, for example, other atoms such as oxygen, nitrogen and sulfur, and divalent groups containing oxygen, nitrogen and sulfur, such as a carbonyl group and a thiocarbonyl group. It may be substituted with a group.

  More preferably, the protective layer of the present invention contains at least a fluoroether polymer silicon compound having a reactive silyl group.

  Hereinafter, a fluoroether polymer silicon compound having a reactive silyl group (hereinafter also simply referred to as a fluorine-containing polymer) that forms the protective layer according to the present invention will be described.

  The fluoroether polymer silicon compound according to the present invention is characterized in that a fluorohydrocarbon is ether-bonded and has a reactive silyl group. The weight average molecular weight of the fluoropolymer is preferably 1500 or more, preferably 1500 to 200000, and more preferably 2000 to 100000. Moreover, it preferably has 2 to 50 reactive silyl groups in the molecule. The weight average molecular weight Mw can be measured by gel permeation chromatography using, for example, a calibration curve with 13 samples of standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 500 to 1000000.

  The fluoroether high molecular silicon compound having a reactive silyl group can be obtained, for example, by introducing a reactive silyl group by reacting a fluoroether polymer having a hydroxy group with a silane modifier. A fluoroether-based polymer having a hydroxy group is obtained by copolymerizing a fluoroolefin and a hydroxy group-containing monomer such as hydroxyalkyl vinyl ether or allyl alcohol as a main monomer component. In this case, in addition to these components, an alkyl group is used. It may be obtained by copolymerizing a mixture of other monomer components such as vinyl ether, vinyl ester, allyl ether, isopropenyl ether and the like.

  The fluoroolefin is not particularly limited, and those commonly used as monomers for fluororesins are used, and perfluoroolefin is preferred, and among them, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoroolefin, Fluoropropyl vinyl ether and mixtures thereof are particularly preferred.

  The reactive silyl group is preferably a reactive silyl group selected from an alkoxy group, a chloro group, an isocyanate group, a silazane group, a carboxyl group, a hydroxyl group and an epoxy group. Of these, an alkoxy group is preferred.

  As the fluorine-containing silane compound according to the present invention, a fluoroether high molecular silicon compound having a reactive silyl group represented by the following general formula (2) is preferably used.

In the general formula (2), R _f is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is an iodine atom or a hydrogen atom, Y is a hydrogen atom or a lower alkyl group, and Z is a fluorine atom or A trifluoromethyl group, R ¹ is a hydrolyzable group, R ² is a hydrogen atom or an inert monovalent organic group, a, b, c, d are integers from 0 to 200, e is 0 or 1, f Represents an integer of 0 to 10, m and n each represents an integer of 0 to 2, and p represents an integer of 1 to 10.

  The fluoroether polymer silicon compound having a reactive silyl group represented by the general formula (2) preferably used in the present invention can be produced by, for example, the method described in Japanese Patent No. 28747715. In addition, the following compounds can be obtained as commercial products.

  For example, OPTOOL AES-2 (average molecular weight of about 2000), OPTOOL AES-4 (average molecular weight of about 4000), OPTOOL AES-4E (average molecular weight of about 4000), OPTOOL AES-6 (average molecular weight of about 6000) manufactured by Daikin Industries, Ltd. DOW CORNING 2603 COATING (average molecular weight of about 2000), DOW CORNING 2604 COATING (average molecular weight of about 4000), DOW CORNING 2634 COATING (average molecular weight of about 4000), DOW CORNING 260 manufactured by Toray Dow Corning Co., Ltd. Average molecular weight of about 6000).

  As a method of forming a protective layer on an inorganic compound layer using a fluoroether high molecular silicon compound having such a reactive silyl group, these materials are used as they are or dissolved in a solvent, and a dip method, a spray method or a spin method is used. This is a method of removing excess fluoroether-based polymeric Si compound by applying with a wet method such as a coating method, heating and drying, and then treating with a solvent.

  The film thickness of the protective layer according to the present invention can be measured by the X-ray reflectivity method shown below.

  Specifically, as a measuring apparatus, MXP21 manufactured by Mac Science Co., Ltd. is used, copper is used as a target of the X-ray source, and it is operated at 42 kV and 500 mA. A multilayer parabolic mirror is used for the incident monochromator. The incident slit is 0.05 mm × 5 mm, the light receiving slit is 0.03 mm × 20 mm, and the 2θ / θ scan method is used to measure from 0 to 5 ° by the FT method with a step width of 0.005 ° and a step of 10 seconds. . With respect to the obtained reflectance curve, Reflectivity Analysis Program Ver. 1 is used to obtain the parameters such that the residual sum of squares of the actual measurement value and the fitting curve is minimized, and the film thickness can be obtained from each parameter.

  The film thickness of the protective layer can also be measured by the same method as described above. The film thickness of the protective layer according to the present invention is not particularly limited, but is preferably 1.0 nm or more and 50 nm or less.

  Moreover, in the protective layer which concerns on this invention, it is a preferable aspect that the surface dynamic friction coefficient (micro | micron | mu) of a protective layer is 0.3 or less.

  The dynamic friction coefficient can be measured according to JIS-K-7125 (1987).

Using a reciprocating wear tester (HEIDON-14DR) manufactured by Shinto Kagaku Co., under the conditions of a load of 100 g / cm ² and a speed of 1 cm / sec, the protective layer surface is polyester fiber as a reference material, and the sample moving speed Horizontal pulling is performed under the conditions of 100 mm / min and a contact area of 80 mm × 200 mm, the average load (F) while the polyester fiber is moving is measured, and the dynamic friction coefficient (μ) is obtained from the following formula.

Coefficient of dynamic friction = F (gf) / weight of weight (gf)
(Elastic layer)
The elastic layer is not particularly limited, and any rubber material or thermoplastic elastomer can be used. For example, styrene-butadiene rubber (SBR), high styrene rubber, polybutadiene rubber (BR), polyisoprene rubber (IIR), ethylene-propylene copolymer, nitrile butadiene rubber, chloroprene rubber (CR), ethylene-propylene-diene rubber (EPDM) ), Butyl rubber, silicone rubber, fluorine rubber, nitrile rubber, urethane rubber, acrylic rubber (ACM, ANM), epichlorohydrin rubber, norbornene rubber, and the like. These may be used alone or in combination of two or more.

  On the other hand, as the thermoplastic elastomer, polyester, polyurethane, styrene-butadiene triblock, polyolefin, or the like can be used.

  The elastic layer may be a layer formed using a material obtained by blending a resin material used for the substrate and an elastic material.

  For example, as a material for silicone rubber, a polyorganosiloxane composition containing a vinyl group is used. As the silicone rubber, a two-component liquid silicone rubber that can be cured by an addition reaction catalyst or a heat vulcanized silicone rubber that can be vulcanized (cured) by a vulcanizing agent made of a peroxide is used. In addition, the elastic layer may contain various compounding agents such as a filler, an extended filler, a vulcanizing agent, a colorant, a conductive material, a heat-resistant agent, and a pigment depending on the purpose of use and design of the seamless belt. Can be added. Moreover, although the plasticity of a synthetic resin changes with the addition amount etc. of a compounding agent, the thing of 120 or less is used suitably as a plasticity of the rigid resin before hardening.

The elastic layer can be prepared to have an electric resistance value (volume resistivity) of 10 ⁵ to 10 ¹¹ Ω · cm by dispersing a conductive substance in the elastic material.

  Carbon black, zinc oxide, tin oxide, silicon carbide, etc. can be used as the conductive substance added to the elastic layer. As carbon black, neutral or acidic carbon black can be used. The amount of the conductive material used varies depending on the type of the conductive material to be used, but may be added so that the volume resistance value and the surface resistance value of the elastic layer are within a predetermined range. It is 10-20 mass parts with respect to it, Preferably it is 10-16 mass parts.

Method for forming elastic body layer The elastic body layer may be formed by a known coating method, for example, dip coating described in JP-A No. 2006-255615, circular amount regulation type coating described in JP-A No. 10-104855, JP-A 2007- Although it can be produced by providing a coating film by combining the annular coating method described in Japanese Patent No. 136423 or the dip coating and the circular amount regulation type coating, it is not limited thereto.

  Specifically, as a method of forming an elastic body layer on an endless belt-shaped resin substrate, for example, in a tank in which a coating liquid for an elastic layer is stored, a cylindrical endless belt-shaped cylindrical core material is used. The resin substrate is set and immersed in a vertically standing state. At this time, after dipping is repeated several times to form a coating film having a predetermined thickness, the coating solution is pulled up. Next, after drying and removing a solvent, heat processing (for example, 60-150 degreeC x 60 minutes) are performed, and an elastic layer is produced.

  The method of forming an elastic body layer on a metal cylindrical substrate is the same as in the case of an endless belt-shaped resin substrate, such as melt molding, injection molding, dip coating or spraying on a metal roll. It can be provided by molding by coating or the like.

  The thickness of the elastic layer is preferably 50 μm to 500 μm. Further, 100 to 300 mμ is more preferable.

(Substrate of intermediate transfer member)
As the substrate used in the present invention, it is preferable to use a seamless belt in which a conductive agent is dispersed in a resin.

<Resin substrate>
The resin substrate has rigidity that prevents the intermediate transfer body from being deformed by a load applied to the intermediate transfer belt from the cleaning blade as a cleaning member, and reduces the influence on the transfer portion. The resin base is preferably formed using a material having a Young's modulus measured by the nanoindentation method in the range of 5.0 GPa to 15.0 GPa, and more preferably in the range of 8.0 GPa to 15.0 GPa. .

  In consideration of mechanical strength, image quality, manufacturing cost, etc., the thickness of the substrate is preferably in the range of 50 μm to 1000 μm.

  As materials that exhibit such performance, for example, so-called engineering plastic materials such as polycarbonate, polyphenylene sulfide, polyvinylidene fluoride, polyimide, polyether, ether ketone, ethylene tetrafluoroethylene copolymer, polyamide, and polyphenylene sulfide are used. In these, polyimide, polycarbonate, and polyphenylene sulfide are preferable. The Young's modulus of these resin materials measured by the nanoindentation method exceeds 5.0 GPa, and has a thickness of 50 to 200 μm and satisfies the mechanical properties as a resin substrate. Furthermore, it is also possible to use a material obtained by blending the above-mentioned resin material and the following elastic material. Examples of the elastic material include polyurethane, chlorinated polyisoprene, NBR, chloropyrene rubber, EPDM, hydrogenated polybutadiene, butyl rubber, and silicone rubber. These may be used alone or in combination of two or more.

  Among these, it is preferable to contain polyphenylene sulfide or a polyimide resin. The polyimide resin is formed by heating polyamic acid that is a precursor of the polyimide resin. The polyamic acid can be obtained by dissolving tetracarboxylic dianhydride or an approximately equimolar mixture of its derivative and diamine in an organic polar solvent and reacting in a solution state.

  In the present invention, when a polyimide resin is used for the resin substrate, the content of the polyimide resin in the resin substrate is preferably 51% or more.

The resin substrate according to the present invention is preferably a seamless belt or drum in which a conductive substance is added to a resin material and an electric resistance value (volume resistivity) is adjusted to 10 ⁵ Ω · cm to 10 ¹¹ Ω · cm.

  Carbon black can be used as the conductive substance added to the resin material. As carbon black, neutral or acidic carbon black can be used. The amount of the conductive material used varies depending on the type of the conductive material used, but may be added so that the volume resistance value and the surface resistance value of the intermediate transfer member are within a predetermined range. 10 parts by mass to 20 parts by mass, preferably 10 parts by mass to 16 parts by mass.

  The substrate used in the present invention can be produced by a conventionally known general method. For example, a resin as a material can be melted by an extruder, formed into a cylindrical shape by an inflation method using an annular die, and then cut into a ring to produce an annular endless belt-like substrate.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1
(Preparation of intermediate transfer belt)
(Preparation of endless belt-like substrate 1)
A seamless-less belt made of polyimide (PI) containing a conductive material having a thickness of 100 μm was prepared as an endless belt-like substrate 1.

(Production of elastic layer)
An elastic layer made of chloroprene rubber having a thickness of 150 μm is provided on the outer periphery of the prepared endless belt-shaped substrate 1 by dipping coating to form an elastic layer. 1-a.

<Preparation of Intermediate Transfer Belt 1>
(Formation of resin surface)
The prepared endless belt-shaped substrate No. 1-a was fitted with a core material, and a fluorine-based coating agent ("TR304" manufactured by Dainippon Ink & Chemicals, Inc. was diluted with a MEK / butyl acetate mixed solvent and dipped. It was dried by heating at 130 ° C for 1 hour. A resin surface layer having a thickness of 5 μm was formed to obtain an intermediate transfer belt 1.

<Preparation of Intermediate Transfer Belt 2>
Endless belt base No. An inorganic compound layer was formed on 1-a as described below to obtain an intermediate transfer belt 2.

(Formation of inorganic compound layer)
The prepared endless belt-shaped substrate No. The intermediate transfer belt 2 was produced by forming a single inorganic compound (silicon oxide) layer having a thickness of 150 nm on the 1-a using a manufacturing apparatus based on atmospheric pressure plasma CVD shown in FIG. . In addition, the film thickness of an inorganic compound (silicon oxide) layer is a value obtained by measuring by the method described in the specification text using “MXP21” (manufactured by Mac Science).

  The carbon content (carbon atom number concentration) of the inorganic compound (silicon oxide) layer was 0.1 atom number concentration%.

  The carbon content (carbon atom number concentration) indicates a value measured using an ESCALAB-200RXPS surface analyzer manufactured by VG Scientific.

Atmospheric pressure plasma CVD conditions Silicon oxide was used as a material for forming the inorganic compound layer. As the dielectric covering each electrode of the plasma discharge processing apparatus at this time, both electrodes facing each other were coated with alumina by ceramic spraying. The metal base material coated with a dielectric has a stainless steel jacket specification having a cooling function by cooling water, and was performed while controlling the electrode temperature with cooling water during discharge.

  Each source gas was heated to generate steam, mixed and diluted with a discharge gas and a reaction gas that had been preheated so that the source material did not aggregate in advance, and then supplied to the discharge space.

Discharge gas: Ar gas 98.6% by volume
Reaction gas: 1.0% by volume of O ₂ gas with respect to the total gas
Source gas: Tetraethoxysilane (TEOS) 0.4% by volume with respect to the total gas
High frequency power supply (Pearl Industries high frequency power supply (13.56 MHz)): 10 W / cm ²
<Preparation of Intermediate Transfer Belt 3>
Endless belt base No. As shown below, a three-dimensional crosslinkable resin layer and an inorganic compound layer were formed on 1-a to obtain an intermediate transfer belt 3.

Preparation of coating solution for three-dimensional crosslinkable resin layer Dipentaerythritol hexaacrylate monomer 60 parts by mass Dipentaerythritol hexaacrylate dimer 20 parts by mass Dipentaerythritol hexaacrylate trimer or higher component 20 parts by mass Diethoxybenzophenone (UV photoinitiator) 2 parts by mass Methyl ethyl ketone 50 parts by mass Ethyl acetate 50 parts by mass Isopropyl alcohol 50 parts by mass The above composition was dissolved while stirring to obtain a coating solution No. 3 for the three-dimensional crosslinkable resin layer. It was set to 1. This coating solution No. 1 was applied by extrusion so that the dry film thickness was 5 μm, and dried at 80 ° C. for 5 minutes. Next, an 80 W / cm high pressure mercury lamp was irradiated for 4 seconds from a distance of 12 cm to be cured.

  Subsequently, an inorganic compound layer was formed on the three-dimensional crosslinkable resin layer by the same method as the inorganic compound layer of the intermediate transfer belt 2 to obtain an intermediate transfer belt 3.

<Preparation of Intermediate Transfer Belt 4>
The same procedure as that for the intermediate transfer belt 3 was performed until the three-dimensional crosslinkable resin layer was formed.

Subsequently, ethyl acetate 50 parts by mass methyl ethyl ketone 50 parts by mass isopropyl alcohol 50 parts by mass Aerosil R972V (average particle size 16 nm, made by Nippon Aerosil Co., Ltd.) 4 parts by mass High-speed stirrer (TK Homomixer, Special Machine Industries, Ltd.) ) And then dispersed with a collision-type disperser (Manton Gorin, manufactured by Gorin Co., Ltd.), the following components were added, and the coating composition No. 2 was prepared.

Dipentaerythritol hexaacrylate monomer 60 parts by weight Dipentaerythritol hexaacrylate dimer 20 parts by weight Dipentaerythritol hexaacrylate trimer or higher component 20 parts by weight Diethoxybenzophenone (UV photoinitiator) 4 parts by weight This coating Liquid No. 2 was applied by extrusion so that the dry film thickness was 1 μm, and dried at 80 ° C. for 5 minutes. Next, an 80 W / cm high-pressure mercury lamp was irradiated for 2 seconds from a distance of 12 cm to be cured.

  Subsequently, an inorganic compound layer was formed on the three-dimensional crosslinkable resin layer by the same method as the inorganic compound layer of the intermediate transfer belt 2 to obtain an intermediate transfer belt 4.

<Preparation of Intermediate Transfer Belt 5>
The same procedure as that for the intermediate transfer belt 3 was performed until the three-dimensional crosslinkable resin layer was formed.

Subsequently, on this layer, the following composition for stress adjusting layer was applied with a bar coater, then dried at 80 ° C. for 5 minutes, and then irradiated with ultraviolet rays at an irradiation intensity of 300 mJ / cm ² , stress adjusting means (layer) Was provided. The dry thickness of the stress adjusting means (layer) was 0.1 μm, and the refractive index was 1.85.

(Stress adjusting layer composition)
Titanium tetrabutoxide 14.5g
γ-methacryloxypropyltrimethoxysilane 0.25 g
Cationic curable resin (KR56-39 manufactured by Asahi Denka Kogyo Co., Ltd.) 0.25 g
1-butanol 75ml
Dimethylformamide 3ml
10% hydrochloric acid 3ml
(Formation of inorganic compound layer)
On the stress adjusting layer, a polysilazane coating layer was formed as the outermost layer (inorganic compound layer) in accordance with the following method to obtain an intermediate transfer belt 5.

  That is, polysilazane (manufactured by AZ Electronic Materials, Aquamica NAX-120-20) was applied on the stress adjusting layer using a micro gravure coater so that the film thickness after curing was 1.0 μm. After coating and drying, it was allowed to stand for 7 days in an environment of 40 ° C. and cured as a siloxane bond layer.

<Preparation of Intermediate Transfer Belt 6>
<Formation of polymer layer>
Endless belt base No. A coating solution having the composition shown in Table 1 below was applied onto 1-a.

As a coating method, a microgravure coater was used so that the film thickness after curing was 5 μm. After evaporating and drying the solvent, the solvent was cured by irradiation with ultraviolet rays of 0.4 J / cm ² using a high pressure mercury lamp to form a three-dimensional crosslinkable resin layer.

Subsequently, 0.5% by mass of KBM-903 (manufactured by Shin-Etsu Silicone) is added as a silane coupling agent to a polymer liquid of a photocurable resin of JSR Z7535 (manufactured by JSR Corporation) as a coating liquid for a stress adjustment layer. Thus, a stress adjusting layer coating solution was prepared. It applied using the micro gravure coater so that the film thickness after hardening might be set to 5 micrometers. After the solvent was evaporated and dried, the polymer layer 1 (stress adjusting layer) was formed by curing with 0.4 J / cm ² ultraviolet irradiation using a high-pressure mercury lamp.

(Formation of inorganic compound layer)
On the stress adjusting layer, a polysilazane coating layer was formed as the outermost layer according to the following method.

  An inorganic compound layer was formed on the polymer layer 1 in the same manner as in the production of the intermediate transfer belt 5. This was designated as an intermediate transfer belt 6.

<Preparation of Intermediate Transfer Belt 7>
The three-dimensional crosslinkable resin layer coating solution used in the production of the intermediate transfer belt 3 was applied by extrusion so that the dry film thickness was 5 μm, and dried at 80 ° C. for 5 minutes. Subsequently, the following coating composition was extruded and applied to a dry film thickness of 1 μm before the curing treatment, and further dried at 80 ° C. for 5 minutes.

<Coating composition>
Synthetic silica fine particles (average particle size 16 nm) 13 parts UV curable acrylic urethane resin 99 parts (Unidic 17-806 (Dainippon Ink Co., Ltd.)
Coronate L 100 parts (polyisocyanate compound, manufactured by Nippon Polyurethane Co., Ltd.)
3 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy Co., Ltd.) was mixed with a solvent (methyl ethyl ketone) by a homogenizer to prepare a homogeneous dispersion having a volatile content of 60% by mass.

  After coating the coating composition, a 90 W / cm high-pressure mercury lamp was irradiated for 5 seconds from a distance of 12 cm to perform a curing treatment, thereby forming a stress adjusting means (layer).

(Formation of inorganic compound layer)
On the stress adjusting means (layer), a polysilazane coating layer was formed as the outermost layer (inorganic compound layer) according to the following method.

  A polysilazane coating layer was formed as the outermost layer on the stress adjusting means (layer).

  An inorganic compound layer was formed on the polymer layer 1 in the same manner as in the production of the intermediate transfer belt 5. This was designated as an intermediate transfer belt 7.

<Preparation of Intermediate Transfer Belt 8>
Instead of the coating composition applied after the application of the three-dimensional cross-linked resin layer on the intermediate transfer belt 7, a mixed solution of 100 parts of polysilazane (manufactured by AZ Electronic Materials, Aquamica NAX-120-20) and 30 parts of methyl ethyl ketone was cured. It applied using the micro gravure coater so that a film thickness might be set to 1.0 micrometer. Thereafter, a 90 W / cm high-pressure mercury lamp was irradiated for 5 seconds from a distance of 12 cm to perform a curing treatment, and used as a stress adjusting means. Thereafter, a polysilazane coating layer was further formed in the same manner as the intermediate transfer belt 7.

<Preparation of intermediate transfer belt 9>
The process was the same as that for the intermediate transfer belt 4 until the formation of the stress adjusting means (layer). Subsequently, formation of the surface layer (inorganic compound layer) was performed as follows.

(Formation of inorganic compound layer)
On the stress adjustment layer means (layer), a manufacturing apparatus using atmospheric pressure plasma CVD shown in FIG. 4 is used to form a silicon oxide layer in which the carbon content (carbon atom number concentration) is changed between the upper layer and the lower layer. A transfer belt was prepared and used as a sample. The film thickness of the upper layer was 150 nm, and the film thickness of the lower layer was 200 nm. The film thickness indicates a value measured by the same method as in Example 1.

  The method of dividing the inorganic compound layer into two layers was formed by laminating the upper layer after forming the lower layer. In addition, the silicon oxide layer in which the carbon content (carbon atom number concentration) is changed does not change the ratio of the discharge gas, the reaction gas, and the raw material gas, and the supply rate of all the gases is changed. Formed in the same manner as

  Next, a protective layer (alkylsilane protective layer) was formed.

(Preparation of methyltriethoxysilane hydrolyzate)
380 parts of ethanol was added to 250 parts of methyltriethoxysilane, and an aqueous hydrochloric acid solution prepared by diluting 4 parts of concentrated hydrochloric acid with 235 parts of water was slowly added dropwise to this solution at room temperature. After dropping, the mixture was stirred at room temperature for 3 hours to prepare a methyltriethoxysilane hydrolyzate.

<Protective layer composition>
Methyltriethoxysilane hydrolyzate 180 parts γ-methacryloxypropyltrimethoxysilane 5 parts Cyclohexanone 3200 parts Coating with a bar coater and drying at 80 ° C. for 30 minutes to produce an intermediate transfer belt 9.

<Preparation of Intermediate Transfer Belt 10>
The process was the same as that of the intermediate transfer belt 6 until the stress adjusting means (layer) was formed.

  The surface layer (inorganic compound layer) was formed in the same manner as the intermediate transfer belt 9.

  Subsequently, the protective layer (alkylsilane protective layer) of the intermediate transfer belt 9 was changed to the following protective layer.

(Formation of protective layer)
As a fluoroether polymer Si compound, 1 g of OPTOOL AES (manufactured by Daikin Industries) was diluted with 100 g of Novec HFE7100 (manufactured by Sumitomo 3M) to adjust the solid concentration to 0.2% to prepare a protective layer coating solution. Next, the water repellent layer coating solution 1 is applied to the surface layer by a dipping method, dried, stored in a room temperature and humidity environment for one day and night, and then the excess water repellent layer is removed by alcohol washing to obtain an intermediate transfer belt 10. It was.

<Evaluation>
<Image forming device>
The intermediate transfer member produced above was evaluated by attaching it to an image forming apparatus “bizhub PRO C6500 (manufactured by Konica Minolta Business Technologies)”.

  For image formation, a two-component developer comprising a toner having a median particle diameter (D50) of 4.5 μm on a volume basis and a coat carrier of 60 μm was used.

The printing environment was 160,000 printed at low temperature and low humidity (10 ° C., 20% RH) and high temperature and high humidity (33 ° C., 80% RH). As the transfer material, high-quality paper (64 g / m ² ) of A4 size was used.

  A printed document has a character image with a printing rate of 7% (3 point characters and 5 point characters are 50% each), a color human face image (dot image including a halftone), a solid white image, and a solid image each 1/4. The original image (A4 version) in equal parts was used.

<Evaluation>
(Occurrence of cracks)
Cracks are generated in a room temperature and humidity environment (20 ° C., 50% RH) by placing the back surface of the intermediate transfer body on the resin substrate side of the intermediate transfer body on a round bar having a different diameter on the back side of the intermediate transfer body. The surface on the side was observed with a microscope and evaluated based on the occurrence of cracks. Level 1 and level 2 are acceptable.

Level 1: No crack at 15 mm rod diameter Level 2: No crack at 15 mm rod diameter, no crack at 25 mm Level 3: No crack at 25 mm rod diameter, no crack at 45 mm Level 4: Rod Crack generation at a diameter of 45 mm Level 5: Crack generation on a flat surface.

(Generation of minute cracks)
After printing with the image forming apparatus, the surface of the intermediate transfer belt was observed using a scanning electron microscope (S-5000 manufactured by Hitachi), and the presence or absence of a shell-like crack having a diameter of about 1 to 50 μm was confirmed. .

○: No microcracks are observed △: Microcracks are present in the region ×: Microcracks are present on almost the entire surface (cleaning property)
Evaluation of the cleaning property is obtained by performing printing in a low-temperature and low-humidity (10 ° C., 20% RH) environment, visually observing the surface of the intermediate transfer member after cleaning, and printing the degree of toner remaining on the surface. Evaluation was made based on the degree of occurrence of image contamination due to poor cleaning on the printed image.

Evaluation Criteria A: Up to 160,000 sheets, no cleaning residual toner is observed on the intermediate transfer body, and there is no image contamination due to poor cleaning in the printed image. ○: At 160,000 sheets, residual cleaning toner is present on the intermediate transfer body. Although it is recognized, there is no image contamination due to poor cleaning in the printed image ×: 100,000 remaining sheets, cleaning residual toner is recognized on the intermediate transfer body, and there is image contamination due to poor cleaning in the printed image, which is a practical problem .

(Toner filming)
The evaluation of toner filming was performed by printing 160,000 sheets in an environment of high temperature and high humidity (33 ° C., 90% RH), and then visually observing the surface of the intermediate transfer member to determine the state of toner filming and 160,000 sheets. The fog and white streaks generated in the printed image at the time of printing were evaluated.

Evaluation criteria A: No gloss unevenness on the surface of the intermediate transfer member due to toner filming was observed, and no fogging or white streaks due to toner filming occurred in the printed image. No fogging or white streaks were observed in a place corresponding to the fading, or no occurrence of fogging or white streaks was observed on the surface of the intermediate transfer member due to toner filming. Occurred.

(durability)
The durability was evaluated by the image density at the end of printing 160,000 sheets at high temperature and high humidity (33 ° C., 80% RH).

  The image density was evaluated by measuring the density of a solid black image portion at 12 points using a reflection densitometer “RD-918” (manufactured by Macbeth).

Evaluation criteria A: Excellent when image density is 1.35 or more B: Practical problem when image density is 1.20 or more and less than 1.35 ×: Practical value when image density is less than 1.20 The level at issue.

  It can be seen that those having the stress adjusting means of the present invention are good in any evaluation.

1, 1 'full-color image forming apparatus 10Y, 10M, 10C, 10K image forming unit 4' transfer unit 401 'intermediate transfer roller 7 endless belt-like intermediate transfer body unit 70 intermediate transfer belt 70a substrate 70b elastic layer 70c resin layer 70d inorganic compound Layer 70e Stress adjusting means 9 Manufacturing device 9a Atmospheric pressure plasma CVD device 9a1 Roll electrode 9a2 Fixed electrode 9a3 Mixed gas supply device 9a4 Discharge vessel 9a5 First power source (high frequency power source)
9a6 Second power supply (high frequency power supply)
9a7 Exhaust pipe 9a8 Discharge space 9b Material supply device

Claims (9)

An intermediate transfer member having a substrate and an elastic layer,
The elastic layer has a three-dimensional crosslinkable resin layer and an inorganic compound layer in this order, and the surface of the three-dimensional crosslinkable resin layer is subjected to stress adjusting means ,
The intermediate transfer member , wherein the stress adjusting means is unevenly distributed near the surface of the three-dimensional crosslinkable resin layer to contain inorganic fine particles . 2. The intermediate transfer member according to claim 1 , wherein the concentration of the inorganic fine particles in the three-dimensional crosslinkable resin layer increases stepwise or continuously toward the interface with the inorganic compound layer. An intermediate transfer member having a substrate and an elastic layer,
The elastic layer has a three-dimensional crosslinkable resin layer and an inorganic compound layer in this order, and the surface of the three-dimensional crosslinkable resin layer is subjected to stress adjusting means,
The intermediate transfer member , wherein the stress adjusting means is to introduce a silane coupling agent in the vicinity of the surface of the three-dimensional crosslinkable resin layer . An intermediate transfer member having a substrate and an elastic layer,
The elastic layer has a three-dimensional crosslinkable resin layer and an inorganic compound layer in this order, and the surface of the three-dimensional crosslinkable resin layer is subjected to stress adjusting means,
An intermediate transfer member , wherein the stress adjusting means comprises coating an inorganic compound layer after coating with a three-dimensional crosslinkable resin and before curing, and thereafter performing curing . The intermediate transfer member according to claim 1, wherein the three-dimensional crosslinkable resin layer contains an acrylate resin. The intermediate transfer member according to any one of claims 1 to 4, wherein the inorganic compound layer comprises silicon oxide or a laminate of carbon-containing silicon oxide and silicon oxide. The intermediate transfer member according to claim 1, wherein the inorganic compound layer is formed by an atmospheric pressure plasma method. The intermediate transfer member according to claim 1, wherein the inorganic compound layer is formed of a polysilazane coating layer. The intermediate transfer member according to any one of claims 1 to 4, wherein a protective layer containing an alkylsilane or a fluorine-containing silane compound is further provided on the inorganic compound layer.

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