Electrophotographic image forming method and electrophotographic print

专利摘要:
PURPOSE: Provided are an electrophotographic method for forming images and an electrophotographic print produced thereby, which are capable of stably obtaining natural gloss texture equivalent to conventional silver salt photographic prints. CONSTITUTION: The image forming process comprises forming a toner image on an electrophotographic image-receiving sheet having at least one toner image-receiving layer on the support; and fixing the toner image on the electrophotographic image-receiving sheet using a belt fixing device, thereby outputting an electrophotographic print image, wherein a specular glossiness GsP(45°) and a reflected light scattering index GsP(*45±3°) of a black print image portion on the toner image-forming surface of the electrophotographic print satisfy the following conditions: (I) 30<=GsP(45°); (II) 0.1<=GsP(*45±3°)<=15; and (III) GsP(45°)/GsP(*45±3°)>=6 (III), wherein GsP(45°) is specular glossiness at an incident angle of 45° and an acceptance angle of 45°, and GsP(*45±3°) is an average of GsP(*42°) and GsP(*48°).
公开号:KR20040041059A
申请号:KR1020030078636
申请日:2003-11-07
公开日:2004-05-13
发明作者:이시즈카히로시；무라이아시타
申请人:후지 샤신 필름 가부시기가이샤；
IPC主号:

专利说明:

ELECTROPHOTOGRAPHIC IMAGE FORMING METHOD AND ELECTROPHOTOGRAPHIC PRINT}
[11] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic image forming method and an electrophotographic print, wherein an electrophotographic image forming in which "glossiness" such as good silver dye print is obtained by suppressing scattering of reflected light (corresponding to the sharpness of a glare of a light source, etc.). A method and an electrophotographic print obtained by the electrophotographic image forming method.
[12] In general, the glossiness of the reflective print is expressed using specular glossiness (hereinafter, abbreviated as "glossiness") specified in JIS (JIS Z8741 and JIS P8142) and the like. The measured value of 45 degree glossiness by JIS Z8741 of commercially available silver salt photograph print is about 90 degree normally. As means for improving the glossiness of an electrophotographic print to the level of a silver dye photoprint, an electrophotographic award sheet having a toner aqueous layer containing a thermoplastic resin on a support has been proposed (for example, Japanese Patent Laid-Open No. 8-A). 212168 and Japanese Patent Laid-Open No. 2001-183860.
[13] In addition, it has been proposed to improve the glossiness of electrophotographic frit obtained by having an electroluminescent frit having a toner water-receiving layer and having a predetermined glossiness or more and suppressing dispersion of reflected light (for example, Japanese Patent Laid-Open No. 2002). -23406).
[14] In addition, a method of improving gloss using a fritter is a belt fixing method, and a method of obtaining good gloss by pressing a smooth surface of a fixing belt on a surface of a fritter at the time of thermosetting is proposed (for example, Japanese patent). Publication 2002-91048).
[15] Japanese Patent Laid-Open No. 8-212168, Japanese Patent Laid-Open No. 2001-183860, Japanese Patent Laid-Open No. 2002-23406 and Japanese Patent Laid-Open No. 2002-91048 improve the specular gloss defined in JIS. Although it is possible to obtain mirror glossiness, such as silver-colored print, in some cases, even if glossiness similar to that of silver-printed print is achieved, it is often felt that the gloss of texture is clearly different. There is a problem in that it gives an unpleasant texture that is not smooth and not moist.
[16] As described above, even in the above-mentioned prior art, an electrophotographic printer having a sufficiently satisfactory performance has not been obtained, and it is a reality that further improvement and development are desired.
[17] This invention is made | formed in view of such a reality, and makes it a subject to solve the said various conventional problems and achieve the following objectives. That is, the present invention provides an electrophotographic image forming method capable of stably obtaining a natural and good gloss texture without discomfort even when compared to a conventional silver dye photo print, and an electrophotographic print obtained by the electrophotographic image forming method. It aims to do it.
[1] 1 is a graph showing the relationship between the specular glossiness GsP (45 °) and the scattering index GsP (* 45 ° ± 3 °).
[2] 2 is a graph showing the relationship between the light receiving angle and the glossiness measurement value.
[3] 3 is a schematic diagram showing the positional relationship between the light source L, the print sample P, and the subject M. FIG.
[4] 4 is a schematic view showing an example of an electrophotographic apparatus.
[5] 5 is a schematic view showing an example of a cooling release type belt fixed type smoothing processor.
[6] ******** Explanation of symbols for the main parts of the drawings *********
[7] 25 Belt Fusing Unit 71 Heating Roll
[8] 72 Pressure Roll 74 Peeling Roll
[9] 75 Tension Roll 73 Stepless Belt
[10] 77 Cooling Heatsink 100 Image Forming Device
[18] MEANS TO SOLVE THE PROBLEM In order to solve the said subject, when the present inventors repeated earnest examination, the following knowledge was acquired.
[19] Using a specific electrophotographic water-receiving sheet having at least one layer of toner water-receiving layer on a support, adopting a specific cooling peeling fixing method using a fixing belt, and applying a mirror glossiness in the image portion of the electrophotographic print. It was found that an electrophotographic print excellent in glossiness could be obtained by an electrophotographic image forming method in which a characteristic index defined in relation to reflected light dispersion was within a certain range.
[20] In addition, the present inventors have conducted a thorough analysis on the attitude and behavior when a subject observing electrophotographic prints determines that glossiness is desirable or undesirable for glossiness, and as a result, the subject observes the print from various angles and reflects it on the print. The observation light source was observed, and it was found that the good and bad glossiness was determined by whether the observation light source was clearly reflected or blurred. This can be said whether the reflected light on the print is (1) strong or weak, but (2) sharp or scattered light. However, the conventional mirror gloss measurement is that the light source is reflected, that is, the characteristics of the reflected light (1) It reflects whether it is strong or weak, but (2) It does not have a special relationship on whether it is sharp or contains a large amount of scattered light.
[21] Furthermore, it was found that the glossiness of the print is important from the viewpoint of obtaining a "glossy texture" in which the scattering of the reflected light (corresponding to the sharpness of the light source needle, etc.) is suppressed independently of the height of the conventional mirror glossiness. In addition, when the surface roughness of the fixing belt is set to a predetermined value or less and the thickness of the toner receiving layer is set to a predetermined value or more, by using a polyethylene resin coating layer formed by a laminating method as a support for the electrophotographic award sheet, the above characteristics are good. I knew it was accomplished.
[22] That is, as a means for solving the said subject, it is as follows.
[23] <1> A toner image is formed on an electrophotographic award sheet having one or more layers of toner receiving layers formed thereon, and the fixing belt is rotatably supported by a plurality of supporting members including a heating member. After pressurizing the rotating body to the heating member by means of a fixing belt to form a nip, and passing the electrophotographic water-receiving sheet in which the toner image is formed, the toner image is fixed and cooled to a temperature below a predetermined temperature. An electrophotographic image forming method of outputting an electrophotographic print image by performing a fixing process by using a belt fixing device that separates an electrophotographic award sheet from the fixing belt,
[24] The specular glossiness GsP (45 °) and reflected light dispersion GsP (* 45 ° ± 3 °) of the black print image portion of the toner image forming surface in the electrophotographic printing satisfy the conditions of the following formulas (I) to (III) It is an electrophotographic image forming method characterized in that.
[25] 30 ≦ GsP (45 °). (I)
[26] 0 GsP (* 45 ° ± 3 °) (II)
[27] GsP (45 °) / GsP (45 ° ± 3 °) (III)
[28] In the formulas (I) to (III), GsP (45 °) means mirror glossiness at an incident angle of 45 ° and a light receiving angle of 45 °. GsP (* 45 ° ± 3 °) means the average value of GsP (* 42 °) and GsP (* 48 °) (However, GsP (* 42 °) means mirror gloss at incident angle of 45 ° and light receiving angle of 42 °) GsP (* 48 °) refers to the measurement value of the specular gloss meter having an incident angle of 45 ° and a light receiving angle of 48 °.
[29] <2> In <1>, the specular glossiness GsP (45 °) and the reflected light dispersion GsP (* 45 ° ± 3 °) of the black print image portion of the toner image forming surface in the electrophotographic printing are represented by the following formula (I An electrophotographic image forming method that satisfies the conditions ') to (III').
[30] 60 ≦ GsP (45 °). (I ')
[31] 0≤GsP (* 45 ° ± 3 °) ≤10 (II ')
[32] GsP (45 °) / GsP (45 ° ± 3 °) (III ')
[33] <3> In <1> or <2>, the support body in the electrophotographic image receiving sheet is an electrophotographic image forming method which is a support body in which a thermoplastic resin layer is formed on one side or both sides of a base.
[34] <4> The electrophotographic image forming method according to any one of <1> to <3>, wherein the thickness of the toner aqueous layer is 5 µm or more and 20 µm or less.
[35] <5> The method of any one of <1> to <4>, wherein the fixing belt is an electrophotographic image forming method having a heat resistant support film and a release layer formed on the support film.
[36] <6> In <5>, a release layer is the electrophotographic image forming method which is 1 type, or 2 or more types chosen from the group which consists of a silicone rubber, a fluororubber, a fluorocarbon siloxane rubber, a silicone resin, and a fluororesin.
[37] &Lt; 7 > < 5 > or < 6 >, wherein the release layer is an electrophotographic image forming method containing a fluorocarbon siloxane rubber having a perfluoroalkyl ether group and / or a perfluoroalkyl group in the main chain.
[38] <8> The electrophotographic image forming method according to any one of <1> to <7>, wherein the belt surface roughness Rmax is 3 µm or less.
[39] <9> The mirror surface glossiness GsP (45 °) and the reflected light dispersion GsP (* 45 ° ± 3 °) of any one of <1> to <8> of the toner image forming surface in the electrophotographic water-receiving sheet before printing. ) Is an electrophotographic image forming method that satisfies at least one of the conditions selected from the following formulas (IV) to (VI).
[40] GsP (45 °) <30.. (IV)
[41] GsP (* 45 ° ± 3 °)> 15... (V)
[42] 1≤GsP (45 °) / GsP (45 ° ± 3 °) <6... (VI)
[43] However, in said Formula (IV)-(VI), GsP (45 degrees) and GsP (* 45 degrees +/- 3 degrees) show the same meaning as the above.
[44] <10> The specular glossiness GsP (45 °) and the reflected light dispersion GsP (* 45 ° ± 3 °) of the black printed image portion of the toner image forming surface in the electrophotographic printing are determined by the following formula (I) from (III). The electrophotographic print, characterized in that to satisfy.
[45] 30 ≦ GsP (45 °). (I)
[46] 0 GsP (* 45 ° ± 3 °) (II)
[47] GsP (45 °) / GsP (45 ° ± 3 °) (III)
[48] In the formulas (I) to (III), GsP (45 °) means mirror glossiness at an incident angle of 45 ° and a light receiving angle of 45 °. GsP (* 45 ° ± 3 °) means the average value of GsP (* 42 °) and GsP (* 48 °) (However, GsP (* 42 °) means mirror gloss at incident angle of 45 ° and light receiving angle of 42 °) GsP (* 48 °) refers to the measurement value of the specular gloss meter having an incident angle of 45 ° and a light receiving angle of 48 °.
[49] <11> An electrophotographic print obtained by the electrophotographic image forming method according to any one of <1> to <9>.
[50] <Electrophotographic image forming method>
[51] The electrophotographic image forming method of the present invention is a black print image of a toner image forming surface in an electrophotographic print obtained by fixing a toner to an electrophotographic water-receiving sheet using a cold peeling belt fixing smoothing processor. Negative mirror glossiness GsP (45 °) and reflected light dispersion GsP (* 45 ° ± 3 °) satisfy the condition regarding predetermined glossiness.
[52] In the electrophotographic image forming method of the present invention, the specular glossiness GsP (45 °) and the reflected light dispersion GsP (* 45 ° ± 3 °) of the black print image portion of the toner image forming surface in electrophotographic printing are represented by the following formula (I). ) To satisfy the conditions of (III).
[53] 30 ≦ GsP (45 °). (I)
[54] 0 GsP (* 45 ° ± 3 °) (II)
[55] GsP (45 °) / GsP (45 ° ± 3 °) (III)
[56] In the formulas (I) to (III), GsP (45 °) means mirror glossiness at an incident angle of 45 ° and a light receiving angle of 45 °. GsP (* 45 ° ± 3 °) means the average value of GsP (* 42 °) and GsP (* 48 °) (However, GsP (* 42 °) means mirror gloss at incident angle of 45 ° and light receiving angle of 42 °) GsP (* 48 °) refers to the measurement value of the specular gloss meter having an incident angle of 45 ° and a light receiving angle of 48 °.
[57] Specular glossiness GsP (45 degrees) prescribed | regulated by said formula (I) is 30 or more, 60 or more are preferable and 75 or more are more preferable.
[58] The reflected light dispersion GsP (* 45 ° ± 3 °) specified in the formula (II) is 0 or more and 15 or less, preferably 0 or more and 10 or less, and more preferably 0 or more and 6 or less.
[59] GsP (45 degrees) / GsP (45 degrees +/- 3 degrees) prescribed | regulated by said Formula (III) is 6 or more, 8 or more are preferable and 15 or more are more preferable.
[60] If the specular glossiness GsP (45 °) and the reflected light dispersion GsP (* 45 ° ± 3 °) do not meet the conditions of the above formulas (I) to (III), the print will look shiny, sink, and not clear. It does not give an unpleasant impression as a texture of the print luster.
[61] The specular glossiness GsP (45 °), the scattering index GsP (* 45 ° ± 3 °) can be measured using a specular gloss meter according to JIS Z8741, such as UGV-6P (trade name; manufactured by Suga Test Corp.).
[62] The specular glossiness is determined by measuring the incident angle and the reflection angle (= light receiving angle) in the same positional relationship, and measure the intensity of specularly reflected light. Here, 45 degree mirror glossiness by the conventional method is prescribed | regulated as intensity-index GsP (45 degree) of specular reflection light based on JISZ8741.
[63] The scattering index GsP (* 45 ° ± 3 °) is not prescribed by JIS Z8741, but after calibration under the measurement conditions of 45 ° mirror gloss (incident angle 45 °, light receiving angle 45 °) specified in JIS Z8741. It can be measured by changing only the light receiving angle to 42 ° or 48 °. Here, GsP (* 45 degrees +/- 3 degrees) means the average value of the measured value of 2 conditions of a light reception angle of 42 degrees and 48 degrees.
[64] Here, the conditions of the formulas (I) and (II) will be described in more detail. Silver Dye photo (A; 1 type), Thermal development diffusion type (B; 1 type), Direct thermal type (C; 3 type), Sublimation thermal transfer method (D; 3 type), Inkjet method (E; 5 type) Several types of uniform black image prints were made by changing the model or the material type by the conventional methods (F; 6 types), and the electrophotographic method. About the obtained print, specular glossiness GsP (45 degree) and scattering index GsP (* 45 degree +/- 3 degree) were measured, the sensory test by ten subjects was done, and the score evaluation by the following 5 steps was performed.
[65] [Evaluation standard]
[66] 5: very desirable
[67] 4: desirable
[68] 3: neither
[69] 2: undesirable
[70] 1: very undesirable
[71] The measurement result is shown in the graph prescribed | regulated by 2 axes of specular glossiness GsP (45 degree) and scattering index GsP (* 45 degree +/- 3 degree) in FIG. The average value of the scores of ten subjects regarding a sensory test is shown as a numerical value in a figure. At this time, it can be seen that a set of prints determined by the subject as a desirable glossiness appears in a specific area. The area A in FIG. 1 is a range judged to have an average score of 4 (&quot; preferred &quot;) or more in the sensory test and to obtain good glossiness.
[72] From the results in FIG. 1, it can be seen that the following three are important as a requirement for the subject to determine that the glossiness is good.
[73] (i) Mirror glossiness GsP (45 °) is not less than a certain (right side of line a in Fig. 1)
[74] (ii) Scattering index GsP (* 45 ° ± 3 °) is below fixed (lower line b in Fig. 1)
[75] (iii) The ratio of mirror glossiness GsP (45 °) / scattering index GsP (* 45 ° ± 3 °) is below a certain level (lower right side of line c in FIG. 1)
[76] This is the absolute value of the intensity of scattered light in addition to the intensity of the specular light (corresponding to (i)) in the process of the subject detecting the sharpness of the light source, i.e., determining whether the glossiness is good or poor. ), And the mirror gloss also strongly responds to the ratio of GsP (45 °) / scattering index GsP (* 45 ° ± 3 °) (corresponding to (iii)). It was found that it was judged to be good glossiness. In particular, it was confirmed that the ratio (iii) of GsP (45 °) and GsP (* 45 ° ± 3 °) has a close relationship with the glossiness of the print.
[77] This means that, for example, when the subject observes the print under the illumination of two parallel tubes, the image of the fluorescent lamp reflected on the print is clearly seen (corresponding to (i)), and the bokeh due to scattering is small (corresponding to (ii)). The other corresponds to the clear separation (corresponding to (iii)).
[78] In addition, "+/- 3 degree" in said GsP (* 45 degrees +/- 3 degree) is a measured value in 42 degrees and 48 degrees corresponded to the edge part of a profile, and the absolute value of the scattered light intensity in the position which deviated from the specular reflection To indicate. On the other hand, GsP (45 °) / GsP (* 45 ° ± 3 °) indicates the sharpness of the profile from the relative relationship between the specular and scattered light.
[79] Here, the conditions of the formula (III) will be described in more detail. Profiles of reflected light measurements at various light receiving angles for four representative prints A-1 (silver dye photo), E-1 (ink jet), E-2 (ink jet), and F-6 (conventional electrophotographic) Shown in All of them are almost symmetrical mountain shapes with a maximum of 45 °.
[80] In Fig. 2, the measured value when the light receiving angle is 45 ° is 45 ° ± 3 ° corresponding to the mirror glossiness GsP (45 °), which is defined in JIS Z8741, the end portion of the profile of the mountain, i.e. 42 °, 48 The average of the measured values at ° becomes the scattering index GsP (* 45 ° ± 3 °) specified in the present invention.
[81] Although the measured values at 45 ° of A-1 and F-6 or E-1 and E-2, that is, mirror glossiness GsP (45 °) are at close levels, respectively, there is a big difference in the glossiness received by the subject. It is judged that A-1 or E-2 is good. On the other hand, in view of the end portions of the profile at 42 ° and 48 °, that is, the scattering index GsP (* 45 ° ± 3 °), A-1 or E-2 judged to be good suppresses these characteristic values, The short cut is a sharp profile. It is understood that a sharp profile is important in obtaining a desirable glossiness.
[82] Moreover, FIG. 3 is a schematic diagram which shows the positional relationship of the light source L, the print sample P, and the test subject M. FIG. In this FIG. 3, it is assumed that the distance x (observation distance) between the print sample and the subject is a standard 30 cm, and that the light source is far enough. When the subject observes the light source image reflected on the print, the subject's eye detects scattered light a "and b" in addition to the specular light r '. At this time, the subject's eyes see the bokeh image at a position deviated by d from the normal immersion position of the light source. In other words, the intensity of the reflected light (scattered light) deviated by the angle θ from the specular reflection indicates the bokeh intensity at the position where the light from the light source is shifted by d from the normal position.
[83] There is a relationship shown in the following formula (VII) between the angle θ of the scattering at this time and the bokeh width d.
[84] d = ｘ · sin (θ) / sin (45-θ). (VII)
[85] Therefore, when θ = 3 °, it can be calculated as the bokeh width d = 2.3cm, which corresponds exactly to the bokeh width that the subject actually judges that the light is bokeh in the sample.
[86] As described above, the present invention employs a specific electrophotographic award sheet having a toner aqueous layer, applies a specific fixing method using a fixing belt, and is combined well with an electrophotographic process, thereby providing good glossiness for post-print images. Although texture is obtained, it does not necessarily require that the electrophotographic award sheet before printing is high gloss and smooth.
[87] However, when the electrophotographic award sheet before printing is more glossy and smooth than necessary, the conveyance of the electrophotographic award sheet due to slip between the paper and the conveying member, or the occurrence of misalignment on the toner dot during toner transfer, etc. Since side effects may occur, it is preferable to reduce glossiness and smoothness to some extent from the viewpoint of the stability of ignition. That is, the mirror glossiness GsP (45 °) and the reflected light dispersion GsP (* 45 ° ± 3 °) of the electrophotographic water-receiving sheet before printing satisfy one or more of the conditions selected from the following formulas (IV) to (VI): It is preferable. On the other hand, needless to say, in this case, a print having good glossiness can be obtained by the method of the present invention.
[88] GsP (45 °) <30.. (IV)
[89] GsP (* 45 ° ± 3 °)> 15... (V)
[90] 1≤GsP (45 °) / GsP (45 ° ± 3 °) <6... (VI)
[91] However, in said Formula (IV)-(VI), GsP (45 degrees) and GsP (* 45 degrees +/- 3 degrees) show the same meaning as the above.
[92] The electrophotographic award sheet is formed by forming at least one toner award layer on a support. It is preferable to use the thing which provided the thermoplastic resin layer in the surface of a base as said support body at the time of fixation, and to achieve a favorable electrophotographic print, and to achieve the objective of this invention. In addition, the detail of the electrophotographic award sheet is mentioned later.
[93] In addition, the electrophotographic process used in the electrophotographic image forming method of the present invention forms a toner image on the electrophotographic award sheet, and rotatably supports the fixing belt by a plurality of support members including a heating member. In addition, the rotator is press-contacted to the heating member through a fixing belt to form a nip, and the electrophotographic award sheet is passed through the nip to fix the toner image, and after cooling to a predetermined temperature or lower, the electrophotograph from the fixing belt. By fixing the toner image by a belt fixing device which peels off the water receiving sheet for a print image, the process is performed using the electrophotographic water receiving sheet. You can get it.
[94] <Photo Printing>
[95] In the electrophotographic print of the present invention, the specular glossiness GsP (45 °) and the reflected light dispersion GsP (* 45 ° ± 3 °) of the black print image portion of the toner image forming surface in the electrophotographic print are represented by the following formulas (I) to: The condition of (III) is satisfied.
[96] 30 ≦ GsP (45 °). (I)
[97] 0 GsP (* 45 ° ± 3 °) (II)
[98] GsP (45 °) / GsP (45 ° ± 3 °) (III)
[99] In the formulas (I) to (III), GsP (45 °) means mirror glossiness at an incident angle of 45 ° and a light receiving angle of 45 °. GsP (* 45 ° ± 3 °) means the average value of GsP (* 42 °) and GsP (* 48 °) (However, GsP (* 42 °) means mirror gloss at incident angle of 45 ° and light receiving angle of 42 °) GsP (* 48 °) refers to the measurement value of the specular gloss meter having an incident angle of 45 ° and a light receiving angle of 48 °.
[100] Therefore, the electrophotographic print of the present invention is not particularly limited to the image forming method as long as it satisfies the conditions of the above formulas (I) to (III), and may of course be output by the image forming method of the present invention. It may be printed by any image forming method other than the image forming method of the present invention.
[101] The electrophotographic print of the present invention is of very high quality with a natural and good glossiness without any discomfort even when compared to silver-dyed photo prints.
[102] As described above, the electrophotographic image forming method of the present invention, as described above, mirror surface glossiness GsP (45 °) and reflected light dispersion GsP (* 45 ° ±) of the black print image portion of the toner image forming surface in electrophotographic printing. 3 °) satisfies the conditions of the above formulas (I) to (III). Hereinafter, the electrophotographic water-receiving sheet, the toner and the belt fixing type smoothing processor will be described in detail.
[103] << Electrophotography Award Sheet >>
[104] The electrophotographic water-receiving sheet is formed by forming a toner water-receiving layer on a support having a thermoplastic resin layer formed on one side or both sides of a base, and other layers suitably selected as necessary, such as an intermediate layer, a protective layer, a bottom layer, and a cushion. It has a layer, an antistatic control layer, a reflection layer, a colorant layer, a storage improvement layer, an anti-adhesion layer, a curl prevention layer, a smoothing layer, and the like. Each of these layers may have a single layer structure or a laminated structure.
[105] -gas-
[106] The gas can withstand the fixing temperature, and can satisfy the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic properties, and cruttering after fixing, and can be appropriately selected according to the purpose. have. In general, Japanese Society of Photography, "The Basics of Photographic Engineering-Silver-colored Photographs," published by Korona Co., Ltd. (54 years) pp. Photo-supports, such as the paper of 223-240, synthetic polymer (film), etc. are mentioned.
[107] Specific examples of the substrate include synthetic paper (synthetic paper such as polyolefin and polystyrene), fine paper, art paper, (double-sided) coated paper, (double-sided) cast coated paper, mixed paper made of natural pulp and synthetic pulp (such as polyethylene) I) paper, such as yankee paper, barita paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin impregnated paper, paperboard, cellulose fibrous paper, polyolefin, polyvinyl chloride , Polyethylene terephthalate, polystyrene methacrylate, polyethylene naphthalate, polycarbonate polyvinyl chloride, polystyrene, polypropylene, polyimide, various plastic films or sheets such as celluloses (such as triacetylcellulose), the plastic film or sheet Treatment to impart white reflectivity (e.g., to contain pigments such as titanium oxide in the film The film or sheet subjected to the process), textile, metal, glass, etc. are enumerated.
[108] These may be used individually by 1 type and may use together 2 or more types as a laminated body.
[109] As the gas, Japanese Patent Application Laid-Open No. 62-253159 pp. 29-31, Japanese Patent Laid-Open No. 1-61236 pp. The gas described in 14-17, Unexamined-Japanese-Patent No. 63-316848, Unexamined-Japanese-Patent No. 2-22651, Unexamined-Japanese-Patent No. 3-56955, US Pat. No. 5,001,033, etc. are also mentioned.
[110] It is preferable that the surface smoothness is high, specifically, the surface roughness (Oken type smoothness) is preferably 210 seconds or more, and more preferably 250 seconds or more.
[111] If the surface roughness (Oken type smoothness) is less than 210 seconds, the image quality in the image may be poor when the image is formed.
[112] On the other hand, in the present invention, the Oken smoothness is JAPAN TAPPI No. It is the smoothness prescribed | regulated by the 5B method, and about 600 second is preferable substantially, and about 500 second is more preferable.
[113] As thickness of the said base, it is 25-300 micrometers normally, 50-260 micrometers is preferable and 75-220 micrometers is more preferable.
[114] There is no particular restriction on the strength of the base, and it can be appropriately selected according to the purpose. However, as the base paper for photographic image quality, it is preferable to be close to the base for color silver dye photograph.
[115] The density of the gas is preferably 0.7 g / cm 3 or more from the viewpoint of fixing performance.
[116] The thermal conductivity of the gas is not particularly limited and can be appropriately selected depending on the purpose. However, in particular, when the image forming or image fixing material of the present invention is used as a support in an electrophotographic material, it is 20 ° C. in view of fixing performance. Is preferably 0.50 kcal / m · h · ° C or higher under a relative humidity of 65%.
[117] In addition, in this invention, thermal conductivity can be measured by the method of Unexamined-Japanese-Patent No. 53-66279 in the transfer paper which was moistened based on JISP8111.
[118] Various kinds of additives appropriately selected according to the purpose can be added to the above gas within a range not impairing the effects of the present invention.
[119] Examples of the additives include brighteners, conductive agents, fillers, pigments such as titanium oxide, ultramarine blue and carbon black, and dyes.
[120] In addition, various surface treatments and undercoating treatments may be performed on one side or both sides of the base for the purpose of improving the adhesion to the layer or the like formed thereon.
[121] As the surface treatment, for example, a glossy surface or a fine surface described in Japanese Patent Application Laid-open No. 55-26507, a mold surface treatment treatment, a corona discharge treatment, a flame treatment, a glow discharge treatment, an activation treatment such as plasma treatment, or the like, Listed.
[122] As the undercoat treatment, for example, the method described in JP-A-61-846443 is listed.
[123] As said undercoating, the method of Unexamined-Japanese-Patent No. 61-846443 is mentioned, for example.
[124] These treatments may be carried out alone, the activation treatment may be carried out after the mold-imparting treatment, or the like, and the undercoating treatment may be carried out after the surface treatment such as the activation treatment, or can be arbitrarily combined.
[125] Among the substrates, antistatic agents other than semiconducting metal oxides such as hydrophilic binders, alumina sol and tin oxide, and carbon black may be applied on the surface or the back surface of the substrate or a combination thereof. As such a gas, the support body specifically described in Unexamined-Japanese-Patent No. 63-220246 etc. is mentioned.
[126] Thermoplastic layer
[127] The thermoplastic resin is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, polycarbonate, polyimide, triacetyl cellulose, and the like. Among these, polyolefin is preferable. These resin may be used individually by 1 type, and may use 2 or more types together.
[128] The polyolefin is generally formed using low density polyethylene, but in order to improve the heat resistance of the support, it is preferable to use polypropylene, a mixture of polypropylene and polyethylene, a high density polyethylene, a mixture of high density polyethylene and low density polyethylene, and the like. . In particular, it is most preferable to use a mixture of high density polyethylene and low density polyethylene in view of cost and laminate suitability.
[129] The mixture of the said high density polyethylene and the said low density polyethylene is used, for example by mixing ratio (mass ratio) 1/9-9/1. As said mixing ratio, 2 / 8-8 / 2 are preferable and 3 / 7-7 / 3 are more preferable. When forming a thermoplastic resin layer on both surfaces of the said support body, it is preferable to form the back surface of a support body, for example using a high density polyethylene or a mixture of a high density polyethylene and a low density polyethylene. Although there is no restriction | limiting in particular as molecular weight of polyethylene, It is preferable that a melt index is 1.0-40 g / 10min for both high density polyethylene and low density polyethylene, and it has an extrusion property.
[130] In addition, you may perform the process which provides white reflectivity to these sheets or films. As such a processing method, the method of mix | blending pigments, such as a titanium oxide, in these sheets or films is mentioned, for example.
[131] In this invention, a double-side laminated paper is used as a support body, 25 micrometers-300 micrometers are preferable, as for the thickness of the said support body, 50 micrometers-260 micrometers are more preferable, 75 micrometers-220 micrometers are still more preferable. As the strength of the support, various kinds can be used according to the purpose thereof, and as the support for the photographic image electrophotographic award sheet, a support close to the support for color silver dye photography is preferable.
[132] <Toner Winner>
[133] The toner aqueous layer is an aqueous layer for accommodating color or black toner and forming an image. The toner water-receiving layer has a function of accommodating a toner which forms an image from a developing drum or an intermediate transfer member by (positive) electricity, pressure or the like in a transfer process, and immobilizing it by heat, pressure, or the like in a fixing process. The toner aqueous layer contains a thermoplastic resin as a main component, and contains a mold release agent and other components.
[134] In this case, it is preferable to have a toner layer containing a thermoplastic resin on at least one side of the support, and the thickness of the toner aqueous layer is preferably 5 µm or more and 20 µm or less, more preferably 7 µm or more and 15 µm or less. . Thereby, glossiness | photographic image quality is obtained.
[135] Thermoplastics
[136] The thermoplastic resin is not particularly limited as long as it can be deformed under temperature conditions such as fixing and can accommodate the toner. The thermoplastic resin can be appropriately selected depending on the purpose, but a binder resin of the toner and a resin of the same series are preferable. In most of the toners, polyester resins, copolymer resins such as styrene and styrene-butyl acrylate are used. In this case, polyester resins, styrene and styrene-butyl are also used as thermoplastic resins used in the electrophotographic image receiving sheet. It is preferable to use copolymer resins, such as an acrylate, It is more preferable to contain 20 mass% or more of copolymer resins, such as a polyester resin, styrene, and styrene butyl acrylate, Furthermore, styrene, styrene- butyl acrylate air Copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, etc. are also preferable.
[137] Specific examples of the thermoplastic resin include, for example, (a) a resin having an ester bond, (b) a polyurethane resin, (c) a polyamide resin, (d) a polysulfone resin, (e) a polyvinyl chloride resin, and the like. and (f) polyolefin resins, such as (f) polycaprolactone resins, such as (f) polyvinyl butyral, etc. are mentioned.
[138] Examples of the resin having an ester bond include dicarboxes such as terephthalic acid, isophthalic acid, maleic acid, fumaric acid, phthalic acid, adipic acid, sebacic acid, azelaic acid, abietinic acid, succinic acid, trimellitic acid and pyromellitic acid. Acid components (sulfonic acid groups, carboxyl groups, etc. may be substituted in these dicarboxylic acid components) and diether derivatives of ethylene glycol, diethylene glycol, propylene glycol, bisphenol A, bisphenol A (for example, ethylene of bisphenol A) Alcohol adducts such as oxide adducts, propylene oxide adducts of bisphenol A, and the like, bisphenol S, 2-ethylcyclohexyl dimethanol, neopentyl glycol, cyclohexyl dimethanol, and glycerin (they include Polyester resin, polymethyl methacrylate, polybutyl methacrylate, polymethacrylate obtained by the condensation of Polyacrylate resins such as acrylate and polybutyl acrylate or polymethacrylate resins, polycarbonate resins, polyvinylacetate resins, styrene acrylate resins, styrene-methacrylate copolymer resins, vinyl toluene acrylate resins, and the like. Listed.
[139] Specific examples include those described in JP-A-59-101395, JP-A 63-7971, JP-A 63-7972, JP-A 63-7973, JP-A 60-294862, and the like.
[140] Commercially available products of the above polyester resins include, for example, Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130; Turton NE-382, Turfton U-5, ATR-2009, ATR-2010; Eritel UE3500, UE3210, XA-8153 from Unitica; Nippon Gosei Chemical Co., Ltd. polyester TP-220, R-188, etc. are mentioned.
[141] Commercially available products of the above acrylic resins include, for example, Diamond SE-5437, SE-5102, SE-5377, SE-5649, SE-5466, SE-5482, HR-169, 124, HR-1127, and HR manufactured by Mitsubishi Rayon. -116, HR-113, HR-148, HR-131, HR-470, HR-634, HR-606, HR-607, LR-1065, 574, 143, 396, 637, 162, 469, 216, BR -50, BR-52, BR-60, BR-64, BR-73, BR-75, BR-77, BR-79, BR-80, BR-83, BR-85, BR-87, BR-88 , BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105, BR-106, BR-107, BR-108, BR-112, BR-113, BR -115, BR-116, BR-117; Selek Suigagaku Kogyo's Eresu P SE-0020, SE-0040, SE-0070, SE-0100, SE-1010, SE-1035; Haimer ST95, ST120 from Sanyo Kasei Kogyo Co., Ltd .; Sansei Chemical Co., Ltd. FM 601 etc. are listed.
[142] As said (e) polyvinyl chloride resin etc., polyvinylidene chloride resin, a vinyl chloride- vinyl acetate copolymer resin, a vinyl chloride- vinyl propionate copolymer resin, etc. are mentioned, for example.
[143] As said (f) polyvinyl butyral, cellulose resins, such as a polyol resin, an ethyl cellulose resin, a cellulose acetate resin, etc. are mentioned. Examples of commercially available products include Denki Chemical Co., Ltd., Sekisui Chemical Co., Ltd. products. The polyvinyl butyral preferably has a polyvinyl butyral content of 70% by mass or more and an average degree of polymerization of 500 or more, more preferably an average degree of polymerization of 1000 or more, and commercially available denkabutyral 3000-1, manufactured by Denki Chemical Co., Ltd. 4000-2, 5000A, 6000C; Esrek BL-1, BL-2, BL-3, BL-S, BX-L, BM-1, BM-2, BM-5, BM-S, BH-3, BX -1, BX-7 and the like.
[144] Examples of the (g) polycaprolactone resin include styrene-maleic anhydride resin, polyacrylonitrile resin, polyether resin, epoxy resin, phenol resin and the like.
[145] As said (h) polyolefin resin, polyethylene resin, a polypropylene resin, etc., copolymer resin of olefins, such as ethylene and a propylene, and other vinyl monomer, an acrylic resin, etc. are mentioned.
[146] The said thermoplastic resin may be used individually by 1 type, 2 or more types may be used, and in addition to these, these mixtures, these copolymers, etc. can also be used.
[147] The thermoplastic resin is preferably capable of satisfying the toner aqueous layer properties described later in the state where the toner aqueous layer is formed, and more preferably the resin alone can satisfy the toner aqueous layer properties described above. It is also preferable to use two or more resins with different toner aqueous layer physical properties.
[148] The thermoplastic resin is preferably one having a higher molecular weight than the thermoplastic resin used in the toner. However, the molecular weight does not necessarily mean that the relationship between the molecular weight is preferable depending on the relationship between the thermodynamic properties of the thermoplastic resin used for the toner and the resin used for the toner aqueous layer. For example, when the softening temperature of the resin used for the toner aqueous layer is higher than the thermoplastic resin used for the toner, the molecular weight may be equal or the molecular weight of the resin used for the toner aqueous layer may be smaller.
[149] It is also preferable to use a mixture of resins having the same composition as the thermoplastic resin and having different average molecular weights from each other. As the relationship between the molecular weight of the thermoplastic resin used in the toner, a relationship disclosed in Japanese Patent Laid-Open No. 8-334915 is preferable.
[150] The molecular weight distribution of the thermoplastic resin is preferably wider than that of the thermoplastic resin used in the toner.
[151] As the thermoplastic resin, Japanese Patent Application Laid-Open No. 5-127413, Japanese Patent Application Laid-Open No. 8-194394, Japanese Patent Application Laid-Open No. 8-334915, Japanese Patent Application Laid-Open No. 8-334916, and Japanese Patent Application Laid-Open No. 9 It is preferable to satisfy the physical properties disclosed in Japanese Patent Laid-Open No. 171265, Japanese Patent Laid-Open No. 10-221877, and the like.
[152] As a thermoplastic resin used for the said toner receiving layer, it is especially preferable that it is water-based resin, such as a water-soluble resin and a water-dispersible resin, for the following (i)-(ii) reasons.
[153] (i) There is no discharge of organic solvent in the coating and drying process, so it is excellent in environmental and workability.
[154] (ii) Release agents such as waxes are often difficult to dissolve in solvents at room temperature, and are often dispersed in solvents (water, organic solvents) during use. In addition, the water dispersion form is more stable and the manufacturing processability is excellent. In addition, the aqueous coating is more likely to cause wax to spread to the surface during the coating and drying process, and the effect of the release agent (offset resistance, adhesive resistance, etc.) is easily obtained.
[155] The water-based resin is not particularly limited as long as it is a water-soluble resin or a water-decomposable resin, its composition, bonding structure, molecular structure, molecular weight, molecular weight distribution, and form. Examples of the water-based group of the polymer include sulfonic acid groups, hydroxyl groups, carboxylic acid groups, amino groups, amide groups or ether groups. Examples of such water-soluble resins include those described in p. 26, p. 18,716. 651, pp. 307,105. Pp. 873-874 and Japanese Patent Laid-Open No. 64-13546. The thing of 71-75 is mentioned.
[156] Specifically, for example, vinylpyrrolidone-vinylacetate copolymer, styrene-vinylpyrrolidone copolymer, styrene-maleic anhydride copolymer, water-soluble polyester, water-soluble acrylic, water-soluble polyurethane, water-soluble nylon, water-soluble epoxy resin Can be used. In addition, the gelatin may be selected from so-called degreased gelatin having a reduced content of lime-treated gelatin, acid-treated gelatin, calcium and the like according to various purposes, and is preferably used in combination. Commercially available products are water-soluble polyesters, plus various coats of Kaoga Gaku Kogyo Co., Ltd., Finetex ES series from Dainippon Ink, Kagaku Kogyo Co., Ltd., Jurima AT series from Nippon Kayaku Co., Ltd. The products include Finetex 6161, K-96, Seiko Chemical Co., Ltd. Hiros NL-1189, BH-997L, and the like.
[157] As the water-dispersible resin, water-dispersible resins such as a water-dispersible acrylic resin, a water-dispersed polyester resin, a water-dispersed polystyrene-based resin, and a water-dispersed urethane resin; Emulsions such as acrylic resin emulsions, polyvinylacetate emulsions, SBR (styrene, butadiene and rubber) emulsions, resins or emulsions obtained by dispersing the thermoplastic resins of (a) to (h), or copolymers, mixtures and cations thereof Two or more kinds can be combined by selecting suitably among denaturation things.
[158] Commercially available products of the water-dispersible resins include, for example, polyester-based Vironal series manufactured by Toyobo Co., Ltd., Pes resin A series manufactured by Takamatsu Yuji Co., Ltd., Toughton UE series manufactured by Kao Corp., and Nippon Kosei Co., Ltd. Examples include the ester WR series, the Eriel series from Unitika, and the acrylic series Hirose XE, KE, PE series from Sekogaku Kogyo Co., Ltd., and the Jurima ET series from Nippon Juyaku Corporation.
[159] The film formation temperature (MFT) of the polymer to be used is preferably room temperature or higher for pre-printing storage, and 100 ° C. or lower for fixing of toner particles.
[160] In this invention, it is preferable to use the self-dispersion type water-based polyester resin emulsion which satisfy | fills the characteristic of following (1)-(4) as said thermoplastic resin. Since it is a self-dispersing type that does not use a surfactant, the hygroscopicity is low even in a high humidity atmosphere, the softening point decreases due to moisture, and the occurrence of offset during fixation and the occurrence of adhesion failure between sheets during storage can be suppressed. Moreover, since it is an aqueous system, it is excellent in environment and workability. In addition, since a polyester resin which has a high molecular energy having a high cohesive energy is used, the polyester resin has a sufficient hardness in the storage environment and becomes a low elastic (low viscosity) molten state in the electrophotographic fixing step, and the toner is an aqueous layer. It is embedded in the can be achieved a sufficient high picture quality.
[161] (1) 5000-10000 are preferable and, as for number average molecular weight (Mn), 5000-7000 are more preferable.
[162] (2) The molecular weight distribution (weight average molecular weight / number average molecular weight) is preferably ≦ 4, and more preferably Mw / Mn ≦ 3.
[163] (3) 40-100 degreeC is preferable and, as for glass transition temperature (Tg), 50-80 degreeC is more preferable.
[164] (4) 20-200 nm (phi) is preferable and, as for a volume average particle diameter, 40-150 nm (phi) is more preferable.
[165] As content in the said toner aqueous layer of the said thermoplastic resin, 10-90 mass% is preferable, and 30-90 mass% is more preferable.
[166] Release Agent
[167] The release agent of this invention is mix | blended with a toner aqueous layer in order to prevent the offset of a toner aqueous layer. The release agent used in the present invention is heated and melted at a fixing temperature, precipitates on the surface of the toner aqueous layer, is localized on the surface of the toner aqueous layer, and is cooled and solidified to form a release agent material layer on the surface of the toner aqueous layer. It does not limit kind.
[168] The mold release agent exhibiting such an effect includes at least one mold release agent selected from the group consisting of a silicone compound, a fluorine compound, a wax and a mat agent. Preferred are one or more release agents selected from the group consisting of silicone oils, polyethylene waxes, carnauba waxes and silicone particles and polyethylene wax particles.
[169] Specifically, as the mold release agent used in the present invention, for example, a compound based on the silicone handbook published by Saiwai Shobo, "Properties and Applications of Revised Wax", and published by Japan Daily Newspaper, can be used. Further, Japanese Patent Publication No. 59-38581, Japanese Patent Publication No. Hei 4-32380, Japanese Patent No. 2838498, 2949558, Japanese Patent Publication No. 50-117433, 52-52640, 57-148755 , 61-62056, 61-62057, 61-118760, Japanese Patent Laid-Open No. 2-42451, 3-41465, 4-212175, 4-214570, 4-263267 No. 5-34966, No. 5-119514, No. 6-59502, No. 6-161150, No. 6-175396, No. 6-219040, No. 6-230600, No. 6-295093, East 7-36210, East 7-43940, East 7-56387, East 7-56390, East 7-64335, East 7-199681, East 7-223362, East 7-287413, East 8 -184992, East 8-227180, East 8-248671, East 8-248799, East 8-248801, East 8-278663, East 9-152739, East 9-160278, East 9-185181 No. 9-319139, No. 9-319143, No. 10-20549, No. 10-48889, No. 10-198069, No. 10-207116, No. 11-2917, No. 11-44969, 11-65156, 11-73049, and 11-194542 are used for the toners described in each publication. It can be preferably used also a silicon-based compound, a fluorine compound or a wax. Moreover, you may use combining these compounds in multiple numbers.
[170] Specifically, the silicone compound is a silicone oil as a silicone oil (specifically, dimethylsiloxane oil, methylhydrogensilicone oil, phenylmethylsilicone oil, or commercially available products manufactured by Shin-Etsu Chemical Co., Ltd., KF-96, KF). -96L, KF-96H, KF-99, KF-50, KF-54, KF-56, KF-965, KF-968, KF-994, KF-995, HIVAC F-4, F-5; Toray Dow Corning Silicon Products SH200, SH203, SH490, SH510, SH550, SH710, SH704, SH705, SH7028A, SH7036, SM7060, SM7001, SM7706, SH7036, SH8710, SH1107, SH8627; TSF400, TSF401, TSF404, TSF405, TSF431, TSF433, TSF434, TSF437, TSF450 Series, TSF451 Series, TSF456, TSF458 Series, TSF483, TSF484, TSF4045, TSF4300, TSF4600, YF33 Series, YF-3057, YF-3800, YF-3802, YF- 3804, YF-3807, YF-3897, XF-3905, XS69-A1753, TEX100, TEX101, TEX102, TEX103, TEX104, TSＷ831, etc., amino modified silicone oil (KF-8 from Shin-Etsu Chemical Co., Ltd. as a commercially available product) 57, KF-858, KF-859, KF-861, KF-864, KF-880, SF8417, SM8709 from Toray Dow Corning Silicon, TSF4700, TSF4701, TSF4702, TSF4703, TSF4704 from Toshiba Silicon TSF4705, TSF4706, TEX150, TEX151, TEX154, etc.), carboxy-modified silicone oils (commercially available BY16-880 from Toray, Dow Corning, Silicon, TSF4770, XF42-A9248 from Toshiba Silicone, etc.), carbinol-modified silicone oils Commercially available products such as XF42-B0970 from Toshiba Silicone Co., Ltd., vinyl modified silicone oil (XF40-A1987 from Toshiba Silicone Co., Ltd. as commercially available product), epoxy modified silicone oil (SF8411 from Toray Dow Corning Silicon Co., Ltd. as commercially available products). SF8413; TSF3965, TSF4730, TSF4732, XF42-A4439, XF42-A4438, XF42-A5041, XC96-A4462, XC96-A4463, XC96-A4464, and TEX170 from Toshiba Silicone Co., Ltd., polyether modified silicone oils (Shin-Etsu Chemical Co., Ltd. as a commercially available product) KF-351 (A), KF-352 (A), KF-353 (A), KF-354 (A), KF-355 (A), KF-615 (A), KF-618, KF-945 (A); SH3746, SH3771, SF8421, SF8419, SH8400, SF8410 from Toray, Dow Corning, and Silicon; TSF4440, TSF4441, TSF4445, TSF4446, TSF4450, TSF4452, TSF4453, TSF4460, etc., manufactured by Toshiba Silicon, Inc.); , Silanol-modified silicone oil, methacryl-modified silicone oil, mercapto-modified silicone oil, alcohol-modified silicone oil (commercially available products such as Toray, Dow Corning, and Silicon Industries Co., Ltd. (SF8427, SF8428, Toshiba Silicone Co., Ltd.) B0970, etc.), alkyl modified silicone oil (commercially available as SF8416 from Toray, Dow Corning, and Silicon, TSF410, TSF411, and TSF4 from Toshiba Silicone, Inc.). 420, TSF4421, TSF4422, TSF4450, XF42-334, XF42-A3160, XF42-A3161, etc., fluorine-modified silicone oil (commercially available FS1265 from Toray, Dow Corning, and Silicon, FQF501 from Toshiba Silicone) Rubber and silicone fine particles (commercially available from Toray, Dow Corning, and Silicon Corporation, SH851U, SH745U, SH55UA, SE4705U, SH502UA & B, SRX539U, SE6770U-P, DY38-038, DY38-047, Trefill F-201, F-202, F-250, R-900, R-902A, E-500, E-600, E-601, E-506, BY29-119; Tospur 105, 120, 130, 145, 240, 3120 from Toshiba Silicone Silicone modified resin (specifically, olefin resin, polyester resin, vinyl resin, polyamide resin, cellulose resin, phenoxy resin, vinyl chloride-vinylacetate resin, urethane resin, acrylic resin, styrene-acrylic resin, etc.) Dies manufactured by Daiichi Seika Co., Ltd. Aroma SP03V, SP712, SP2105, SP3023; Modifa FS700, FS710, FS720, FS730, FS770 from Nippon Oil Industries; Cymac US-270, US-350, US-352, US-380, US-413, US-450, Rejeda GP-705, GS-30, GF-150, GF- 300; SH997, SR2114, SH2104, SR2115, SR2202, DCI-2577, SR2317, SE4001U, SRX625B, SRX643, SRX439U, SRX488U, SH804, SH840, SR2107, SR2115 manufactured by Toray Dow Corning Silicon; Toshiba Silicon Corporation YR3370, TSR1122, TSR102, TSR108, TSR116, TSR117, TSR125A, TSR127B, TSR144, TSR180, TSR187, YR47, YR3187, YR3224, YR3232, YR3270, YR3286, YR3340, YR3365, TEX152, TEX152, TEX152 Etc.) and reactive silicone compounds (specifically, there are an addition reaction type, a peroxide curable type, and an ultraviolet curable type, and commercially available products include TSR1500, TSR1510, TSR1511, TSR1515, TSR1520, YR3286, YR3340, PSA6574, TPR6500, and TPR6501 manufactured by Toshiba Silicone Co., Ltd.). TPR6600, TPR6702, TPR6604, TPR6700, TPR6701, TPR6705, TPR6707, TPR6708, TPR6710, TPR6712, TPR6721, TPR6722, UV9300, UV9315, UV9425, UV9430, XS56-A2775, XS56-A2982, XS56-56-30 A5730, XS56-A8012, XS56-B1794, SL6100, SM3000, SM3030, SM3200, # SR3022, etc.) are mentioned.
[171] Examples of the fluorine compound include fluorine oil (Difluoroyl # 1, # 3, # 10, # 20, # 50, # 100 from Daikin Kogyo Co., Ltd., commercially available TG-440, TG-452, TG-490, TG-560, TG-561, TG-590, TG-652, TG-670U, TG-991, TG-999, TG-3010, TG-3020, TG-3510; , MF-110, MF-120, MF-130, MF-160, MF-160E; Saflon S-111, S-112, S-113, S-121, S-131, S- from Asahi Glass 132, S-141, S-145; Sansei Fluoro Chemical Co., Ltd. FC-430, FC-431, etc.), fluororubber (commercially available as Toray, Dow Corning, Silicon, LS 63U, etc.), fluorine-modified resin ( As a commercial item, Modifa F200, F220, F600, F2020, F3035 of Nippon Yuji Co., Ltd .; Diaroma FF203, FF204 of Dainichi Seika Co .; Supron S-381, S-383, S-393 of Asahi Glass Co., Ltd. SC-101, SC-105, KH-40, SA-100; EF-351, EF-352, EF-801, EF-802, EF-601, TFE, TFEA, TFEMA, PDFOH, manufactured by Tochem Produk. TH from Sumitomo 3M V-200P, etc.) and a fluorine sulfonic acid compound (commercially available products such as EF-101, EF-102, EF-103, EF-104, EF-105, EF-112, EF-121, and EF-122A manufactured by Tochem Produk. , EF-122B, EF-122C, EF-123A, EF-123B, EF-125M, EF-132, EF-135M, EF-305, FBSA, KFBS, LFBS, etc.), fluorosulfonic acid, fluoric acid compounds or salts (Specifically, fluoric anhydride, dilute hydrofluoric acid, boron fluoric acid, zinc fluoride, nickel fluoride, tin borofluoride, lead fluoride, copper fluoride, silicon fluoride, potassium fluoride titanate, perfluorocaprylic acid, Perfluoro phthalate, etc.), inorganic fluorides (specifically aluminum fluoride, potassium silicon fluoride, potassium zirconate fluoride, zinc fluoride tetrahydrate, calcium fluoride, lithium fluoride, barium fluoride, tin fluoride, potassium fluoride, acidic potassium fluoride) , Magnesium fluoride, titanium fluoride, zirconic fluoride, ammonium hexafluorophosphate, potassium hexafluorophosphate, and the like.
[172] The wax is petroleum wax, paraffin wax (paraffin wax 155, 150, 140, 135, 130, 125, 120, 115, HNP-3, HNP-5, HNP-9, HNP- 10, HNP-11, HNP-12, HNP-14G, SP-0160, SP-0145, SP-1040, SP-1035, SP-3040, SP-3035, NPS-8070, NPS-L-70, OX- 2151, OX-2251, EMUSTAR-0384, EMUSTAR-0136; Cerrozol 686, 428, 651-A, A, H-803, B-460, E-172, 866, K-133, Hi D-337, E-139; 125 ° paraffin, 125 ° FD, 130 ° paraffin, 135 ° paraffin, 135 ° H, 140 ° paraffin, 140 ° N, 145 ° paraffin and paraffin from Nippon Seki Yumitsubishi Seiki Co., Ltd. Wax M, etc.), microcrystalline wax (commercially available Hi-Mic-2095, Hi-Mic-3090, Hi-Mic-1080, Hi-Mic-1070, Hi-Mic-2065, Hi- Mic-1045, Hi-Mic-2045, EMUSTAR-0001, EMUSTAR-042X; Cerrosol 967 from Nakagyo oil company, M; 155 microwax, 180 microwax from Nippon Seki Yumitsubishi Seiki Co., Ltd.), Petro Tom (commercially available product OX-1749, OX-0450, OX-0650B, OX-0153, OX-261BN, OX-0851, OX-0550, OX-0750B, JP-1500, JP-056R, available from Nippon Seiro Co., Ltd.) JP-011P and the like); Commercially available products such as Fischer Tropsch Wax (FT100, FT-0070 from Nippon SEIRO, etc.), acid amide compounds or acid imide compounds (specifically, stearic acid amide, phthalic anhydride imide, etc.) 920, B-495, high micron G-270, G-110, hydrin D-757 and the like).
[173] Examples of the modified wax include amine-modified polypropylene (QN-7700 from Sanyo Kasei Co., Ltd. as a commercially available product), acrylic acid-modified and fluorine-modified wax, olefin-modified wax, and urethane type wax (NPS-6010, HAD-5090 from Nippon Seiro Co., Ltd. as a commercially available product). ) And alcohol type waxes (NPS-9210, NPS-9215, OX-1949, XO-020T, etc., available from Nippon Shiroi Co., Ltd.) as commercially available products.
[174] As hydrogenated wax, hardened castor oil (casta wax manufactured by Itosei Co., Ltd. as a commercially available product), castor oil derivative (dehydrated castor oil DCO, DCO Z-1, DCO Z-3 from Itosei Co., Ltd. as a commercially available product, castor oil fatty acid CO -FA, ricinoleic acid, dehydrated castor oil fatty acid DCO-FA, dehydrated castor oil fatty acid epoxy ester D-4 ester, castor oil urethane acrylate CA-10, CA-20, CA-30, castor oil derivative MINERASOL S- 74, S-80, S-203, S-42X, S-321, special castor oil condensed fatty acid MINERASOL RC-2, RC-17, RC-55, RC-335, special castor oil condensed fatty acid ester MINERASOL LB-601 , LB-603, LB-604, LB-702, LB-703, # 11, L-164, etc.), stearic acid (such as 12-hydroxy stearic acid from Itosei Co., Ltd., commercially available), lauric acid, myristic acid , Palmitic acid, behenic acid, sebacic acid (sevacinic acid from Itosei Co., Ltd. as commercially available products), undecylenic acid (as commercially available Itoseiyu) Undecylenic acid, etc. of the product), heptyl acid (heptylic acid, etc., manufactured by Itosei Co., Ltd.), maleic acid, highly maleated oil (HIMALEIN DC-15, LN-10, 00-15, manufactured by Itosei Co., Ltd., commercially available) DF-20, SF-20, etc.), blown oil (commercially available selbonol # 10, # 30, # 60, R-40, S-7, etc.), cyclopentadienated oil (commercially available) Synthetic waxes such as CP oil, CP oil-S, and the like manufactured by Itosei Corporation.
[175] The natural wax is preferably at least one of a vegetable wax and a mineral wax, and a vegetable wax is particularly preferable. As the natural wax, in particular, a water-dispersible wax is preferable in view of compatibility with the case of using an aqueous thermoplastic resin as the thermoplastic resin of the toner aqueous layer.
[176] Examples of the plant waxes include carnauba wax (EMUSTAR-0413 from Nippon Shiroi Co., Cesol 524 from Nakagyo Oil Co., Ltd.), castor oil (purified castor oil from Itosei Oil Co., Ltd., etc.), Rape Seed Oil, Soybean Oil, Beeswax, Cotton Wax, Rice Wax, Sugar Cane Wax, Candelilla Wax, Japanese Wax, Jojoba Oil, Animal Wax, Beeswax, Lanolin, Horned Lobster, Stelap (Whale Oil), Wool Wax, etc. This is listed. Among them, melting points of 70 to 70 are particularly excellent in that they can provide an electrophotographic water-receiving sheet which is excellent in offset resistance, adhesiveness, noticeability, glossiness, hardly cracks, and can form high quality images. Carnauba wax at 95 ° C. is particularly preferred.
[177] Examples of the mineral waxes include natural waxes such as montan wax, montan ester wax, ground wax and ceresin, and fatty acid esters (oxygen sizers DOA, AN-800, DINA, DIDA, DOZ, DOS, available from Shin Nippon Rica Co., Ltd.). , TOTM, TITM, E-PS, nE-PS, E-PO, E-4030, E-6000, E-2000H, E-9000H, TCP, C-1100, etc., polyethylene wax (Naka as a commercially available product) Polylon A, 393, H-481 from the branch offices; Sanwax E-310, E-330, E-250P, LEL-250, LEL-800, LEL-400P, etc. from Sanyo Kasei Co., Ltd., polypropylene wax (Biscol 330-P, 550-P, 660-P by Sanyo Kasei Co., Ltd. as a commercial item), etc. are mentioned. Among them, in particular, the melting point is 70 because it is excellent in offset resistance, adhesion resistance, noticeability, glossiness, hardly cracks, and can provide an electrophotographic award sheet capable of forming a high quality image. Montan wax which is -95 degreeC is especially preferable.
[178] As content (g / m <2>) in the said toner aqueous layer (surface) of the said natural wax, 0.1-4 g / m <2> is preferable and 0.2-2 g / m <2> is more preferable.
[179] 0.1g / m <2> of the said content If less than this, the offset resistance and the adhesion resistance may be particularly insufficient, while if it exceeds 4 g / m 2, the amount of wax may be excessively large, resulting in poor image quality of the formed image.
[180] As melting | fusing point (degreeC) of the said natural wax, 70-95 degreeC is especially preferable at the point of offset resistance and noticeability, and 75-90 degreeC is more preferable.
[181] Various well-known things are mentioned as said mat agent. Solid particles used as a mat agent can be classified into inorganic particles and organic particles. Specific examples of the inorganic mat material include oxides (such as silicon dioxide, titanium oxide, magnesium oxide, alumina), alkaline earth metal salts (such as barium sulfate, calcium carbonate, magnesium sulfate), silver halides (such as silver chloride, silver bromide), and glass. Can be mentioned.
[182] As the inorganic mat agent, for example, West German Patent No. 2529321, British Patent No. 760775, No. 1260772, US Patent No. 1201905, No. 2192241, No. 3053662, No. 3026249, No. 3257206, No. 3322555, No. 3353958, No. 3370951, No. 3411907, No. 3437484, No. 3302302, No. 3515554, No. 3635714, No. 3769020, No. 4021245, The thing described in each specification of the said heading 4029504 is mentioned.
[183] The organic mattress material includes starch, cellulose esters (such as cellulose acetate propionate), cellulose ethers (such as ethyl cellulose), and synthetic resins. It is preferable that the synthetic resin is water insoluble or poorly water soluble. Examples of water-insoluble or poorly water-soluble synthetic resins include poly (meth) acrylic acid esters (such as polyalkyl (meth) acrylates, polyalkoxyalkyl (meth) acrylates, polyglycidyl (meth) acrylates), poly (meth) Acrylamide, polyvinyl ester (such as polyvinyl acetate), poly acrylonitrile, polyolefin (such as polyethylene), polystyrene, benzoguanamine resin, formaldehyde condensation polymer, epoxy resin, polyamide, polycarbonate, phenol resin, polyvinyl Carbazole and polyvinylidene chloride.
[184] You may use the copolymer which combined the monomer used for the above polymer.
[185] In the case of the copolymer, a small amount of hydrophilic repeating unit may be included. Examples of monomers forming the hydrophilic repeat unit include acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate and styrenesulfonic acid.
[186] Examples of the organic matting agent include, for example, British Patent No. 1055713, US Patent No. 1939213, No. 22227373, No. 22628662, No. 222037, No. 2376005, No. 2311851, No. 2712, 45 2992101, 3079257, 32,627, 82, 3438,46, 35,168, 32,344, 35,379, 79,349,437, 37,448, 337, Japanese Patent Publication No. 49 The thing of -106821 and Unexamined-Japanese-Patent No. 57-14835 can be mentioned.
[187] Moreover, you may use together 2 or more types of solid particle. The average particle diameter of the solid particles is, for example, 1 to 100 µm, preferably 4 to 30 µm. The amount of the solid particles used is 0.01 to 0.5 g / m 2, preferably 0.02 to 0.3 g / m 2.
[188] As the release agent added to the toner aqueous layer of the present invention, derivatives thereof, oxides, tablets, and mixtures may be used. In addition, these may have a reactive substituent.
[189] As melting | fusing point (degreeC) of the said mold release agent, 70-95 degreeC is especially preferable at the point of offset resistance and noticeability, and 75-90 degreeC is more preferable.
[190] In particular, the release agent is preferably a water-dispersing release agent in view of compatibility with the case of using an aqueous thermoplastic resin as the thermoplastic resin of the toner aqueous layer.
[191] As content in the said toner aqueous layer of a mold release agent, 0.1-10 mass% is preferable, 0.3-8.0 mass% is more preferable, 0.5-5.0 mass% is further more preferable.
[192] Other Ingredients
[193] Examples of the other components include various additives added for the purpose of improving the thermodynamic properties of the toner aqueous layer, such as colorants, plasticizers, fillers, crosslinking agents, charge control agents, emulsions, and dispersions. The other components contained in these toner aqueous layers are preferably hollow particles in view of excellent thermal conductivity (low thermal conductivity) of the toner aqueous layer upon image fixing, and particularly preferably the pigments are hollow particles. .
[194] --coloring agent--
[195] Examples of the colorant include fluorescent brighteners, white pigments, colored pigments, and dyes.
[196] The fluorescent brightener is a compound that is absorbed in the near ultraviolet and fluoresces at 400 to 500 nm, and known fluorescent brighteners can be used in various ways without particular limitation. As said fluorescent brightener, the compound described in V. Chapter 8 of "The Chemistry of Synthetic Dyes" of K. Veen Rataraman is mentioned preferably. Specific examples include stilbene compounds, coumarin compounds, biphenyl compounds, benzooxazoline compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, and the like. Examples thereof include Whitepulpa PSN, PHR, HCS, PCS, B from Tumitomokagaku Co .; And UNITEX-OG manufactured by Ciba-Geigy.
[197] As the white pigment, the inorganic pigment (for example, titanium oxide, calcium carbonate, etc.) described above for the filler may be used. As pigments, various pigments and azo pigments described in Japanese Patent Application Laid-Open No. 63-44653 (eg, Azo Lake; Carmine 6B, Red 2B, Insoluble Azo; Monoazo Yellow, Disazo Yellow, Pyrazolo Orange, Balkan) Orange, condensed azo; chromophthal yellow, chromophthal red), polycyclic pigments (e.g., phthalocyanine; copper phthalocyanine blue, copper phthalocyanine green, oxazine; dioxazine violet, isoindolinone; isoindolinone Yellow, styrene-based, perylene, perinone, flavanthrone, thioindigo, lake pigments (e.g. malachite green, rhodamine B, rhodamine G, victoria blue B), and inorganic pigments (e.g. oxides, dioxides) Titanium, bengal, sulfate; precipitated barium sulfate, carbonate; precipitated calcium carbonate, silicate; hydrous silicate, anhydrous silicate, metal powder; aluminum powder, copper powder, zinc powder, carbon black, sulfur lead, Eavesdropping;
[198] These may be used individually by 1 type and may use 2 or more types together. Among these, titanium oxide is particularly preferable as the pigment.
[199] Although there is no restriction | limiting in particular as a shape of the said pigment, It is preferable that it is hollow particle form from the point which is excellent in the heat transfer property (low thermal conductivity) at the time of image fixation.
[200] As the dye, various known dyes can be used.
[201] Examples of the oil-soluble dyes include anthraquinone compounds and azo compounds.
[202] Specific examples of the water insoluble dye include C.I. Vat Violet 1, C.I. Vat Violet 2, C.I. Vat Violet 9, C.I. Vat Violet 13, C.I. Vat Violet 21, C.I. Vat blue 1, C.I. Vat Blue 3, C.I. Vat Blue 4, C.I. Vat Blue 6, C.I. Vat blue 14, C.I. Vat blue 20, C.I. Dye dyes such as Vat Blue 35, CI Disperse Violet 1, CI Disperse Violet 4, CI Disperse Violet 10, CI Disperse Blue 3, CI Disperse Blue 7 and CI Disperse Blue 58 Oil-soluble dyes such as Violet 13, CI Solvent Violet 14, CI Solvent Violet 21, CI Solvent Violet 27, CI Solvent Blue 11, CI Solvent Blue 12, CI Solvent Blue 25, and CI Solvent Blue 55.
[203] Moreover, the coloring coupler used by silver salt photograph can also be used preferably.
[204] As content (g / m <2>) in the said toner aqueous layer (surface) of the said coloring agent, 0.1-8 g / m <2> is preferable and 0.5-5 g / m <2> is more preferable.
[205] When content of the said coloring agent is less than 0.1 g / m <2>, the light transmittance in a toner aqueous layer becomes high, while when content of a coloring agent exceeds 8 g / m <2>, handleability, such as a crack and adhesion resistance, may be bad.
[206] --Plasticizer--
[207] As the plasticizer, a known plasticizer for resin can be used without particular limitation. The plasticizer has a function of adjusting the flow or softening of the toner aqueous layer by heat and / or pressure when fixing the toner.
[208] As said plasticizer, "chemical handbook" (Japanese chemical society edition, Maruzen) and "plasticizer-the theory and application-" (Murai Koichi edition, Hangseobang) and "research of plasticizer" "under the study of plasticizer" It can be selected by referring to (Polymer Chemistry Association) or "Handbook Rubber / Plastic Compound Chemicals" (Lover Digest).
[209] Although the said plasticizer is described as a high boiling point organic solvent, a thermal solvent, etc., For example, Unexamined-Japanese-Patent No. 59-83154, 59-178451, 59-178453, 59-178454, 59-178455 No. 59-178457, No. 62-174754, No. 62-245253, No. 61-209444, No. 61-200538, No. 62-8145, No. 62-9348, No. 62-30247, East 62-136646, East 62-174754, East 62-245253, East 61-209444, East 61-200538, East 62-8145, East 62-9348, East 62-30247, East 62 Esters (e.g., phthalic acid esters, phosphoric acid esters, fatty acid esters, abietinic acid esters, adipic acid esters, sebacic acid) Esters, azelaic acid esters, benzoic acid esters, lactic acid esters, epoxidized fatty acid esters, glycolic acid esters, propionic acid esters, trimel Acid esters, citric acid esters, sulfonic acid esters, carboxylic acid esters, succinic acid esters, maleic acid esters, fumaric acid esters, phthalic acid esters, stearic acid esters, and the like, amides (e.g., fatty acid amides, Compounds such as sulfoamides), ethers, alcohols, lactones, polyethyleneoxy, and the like.
[210] The said plasticizer can be mixed and used for resin.
[211] As the plasticizer, a relatively low molecular weight polymer can be used. In this case, the molecular weight of the plasticizer is preferably lower than the molecular weight of the binder resin to be plasticized, and the molecular weight is preferably 15,000 or less, preferably 5,000 or less. In addition, in the case of the polymer plasticizer, it is preferable that the polymer is the same kind as the binder resin to be plasticized. For example, low molecular weight polyester is preferable for plasticizing the polyester resin. Oligomers can also be used as plasticizers. In addition to the above-listed compounds, commercially available products include, for example, adecaizers PN-170 and PN-1430 manufactured by Asahi Denka Kogyo; C. PARAPLEX-G-25, G-30, G-40 from P. HALL; Ester gum 8L-JA, ester R-95, pentaline 4851, FK115, 4820, 830, leusol 28-JA, picolastic A75, picotex LC, Crystallex 3085, etc., manufactured by Rika Hacures.
[212] The plasticizer stresses or skews caused when the toner particles are embedded in the toner aqueous layer (physical skew such as elastic force or viscosity, skew due to material resin such as molecular or binder backbone or pendant portion). Can be used arbitrarily to mitigate.
[213] The plasticizer may be in a state dispersed in micro in the toner aqueous layer, may be in a phase separated into micro in the islands, or may be sufficiently mixed and dissolved with other components such as a binder.
[214] As content in the said toner aqueous layer of the said plasticizer, 0.001-90 mass% is preferable, 0.1-60 mass% is more preferable, 1-40 mass% is more preferable.
[215] Such plasticizers include adjustment of slipperiness (improvement of conveyability by lowering friction), improvement of fixing unit offset (separation of toner or layer to the fixing unit), adjustment of curl balance, charge adjustment (formation of toner electrostatic image), and the like. You may use it for the purpose.
[216] --Fillers--
[217] Examples of the filler include organic or inorganic fillers, and known binders may be used as binder resin reinforcing agents, fillers, or reinforcing materials. The filler can be selected with reference to "Handle rubber and plastic compounding chemicals" (Luber digest), "New plastic compounding agent basics and applications" (Daesung), "Filler handbook" (Daesung).
[218] In addition, various inorganic fillers (or pigments) can be used as the filler. As inorganic pigments, for example, silica, alumina, titanium dioxide, zinc oxide, zirconium oxide, mica iron oxide, lead white, lead oxide, cobalt oxide, strontium chromate, molybdenum pigment, smectite, magnesium oxide, calcium oxide, calcium carbonate, mullite Etc. can be mentioned. Especially as a filler, silica and alumina are preferable. These fillers may be used individually by 1 type, and may use 2 or more types together. In addition, the filler is preferably one having a small particle diameter. If the particle diameter is large, the surface of the toner aqueous layer is likely to be roughened.
[219] The silica includes circular silica and amorphous silica. The silica can be synthesized by a dry method, a wet method or an air gel method. The surface of the hydrophobic silica particles may be surface treated with trimethylsilyl group or silicon. As silica, colloidal silica is preferable. As average particle diameter of a silica, 4-120 nm is preferable and 4-90 nm is more preferable.
[220] It is preferable that the said silica is porous. The average pore size of the porous silica is preferably 50 to 500 nm. In addition, the average pore volume per mass of the porous silica is preferably, for example, 0.5 to 3 ml / g.
[221] The alumina includes anhydrous alumina and alumina hydrate. As the crystal form of the anhydrous alumina, α, β, γ, δ, ζ, η, θ, κ, ρ or χ may be used. Alumina hydrate is more preferable than anhydrous alumina. Monohydrate or trihydrate can be used as an alumina hydrate. Monohydrates include boehmite aggregates and diaspores. Trihydrates include gibbsite and bayerite. As an average particle diameter of alumina, 4-300 nm is preferable and 4-200 nm is more preferable. It is preferable that alumina is porous. As average pore diameter of porous alumina, 50-500 nm is preferable. The average pore volume per mass of the porous alumina is preferably about 0.3 to 3 ml / g.
[222] The alumina hydrate can be synthesized by a sol-gel method in which ammonia is added to an aluminum salt solution to precipitate, or a method of hydrolyzing an alkali aluminate. Anhydrous alumina can be obtained by dehydrating alumina hydrate by heating.
[223] It is preferable that the said filler is 5-2000 mass% with respect to the dry mass of the binder of the layer to add.
[224] --Bridge
[225] The said crosslinking agent can be mix | blended in order to adjust the storage stability, thermoplasticity, etc. of a toner aqueous layer. As such a crosslinking agent, a compound having an epoxy group, an isocyanate group, an aldehyde group, an active halogen group, an active methylene group, an acetylene group, and other known reactors in two or more molecules can be used as the reactor.
[226] Different from this, the compound which has 2 or more groups which can form a bond by a hydrogen bond, an ionic bond, a coordination bond, etc. can also be used as said crosslinking agent.
[227] As the crosslinking agent, a compound known as a coupling agent for a resin, a curing agent, a polymerization agent, a polymerization accelerator, a coagulant, a film forming agent, a film forming aid, or the like can be used. Examples of the coupling agent include, for example, chlorosilanes, vinylsilanes, epoxysilanes, aminosilanes, alkoxyaluminum chelates, titanate coupling agents, etc., and the like listed in "Handbook Rubber / Plastic Compounding Chemicals" (Luber Digest Part). Known ones can be used.
[228] --Charge control agent--
[229] It is preferable to include a charge adjuster in the toner water repellent layer of the present invention in order to adjust transfer or adhesion of the toner, or to prevent charge adhesion of the toner water repellent layer. As the charge adjuster, various charge adjusters conventionally known can be used. As such a charge control agent, a polymer electrolyte, a conductive metal oxide, etc. can be used besides surfactant, such as a cationic surfactant, anionic surfactant, an amphoteric surfactant, a nonionic surfactant, etc., for example. For example, quaternary ammonium salts, cationic antistatic agents such as polyamine derivatives, cationic modified polymethylmethacrylates, and cationic modified polystyrenes, anionic antistatic agents such as alkyl phosphates and anionic polymers, fatty acid esters, polyethylene oxides, and the like Although an ionic antistatic agent is mentioned, It is not limited to these.
[230] In the case where the toner has a negative charge, for example, a cation or a nonionic is preferable as the charge adjusting agent to be blended in the toner aqueous layer.
[231] Examples of the conductive metal oxide include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , and the like. These electroconductive metal oxides may be used independently and may be used as these complex oxides. In addition, the metal oxide may further contain a hetero element, and may contain (dope) Al, In, etc. for ZnO, Nb, Ta, etc. for TiO ₂ , and Sb, Nb, halogen elements, etc. for SnO ₂ . .
[232] -Other additives--
[233] The material that can be used for the toner aqueous layer of the present invention may contain various additives for improving the stability of the output image and for improving the stability of the toner aqueous layer itself. Examples of additives for this purpose include various known antioxidants, anti-aging agents, anti-aging agents, ozone anti-aging agents, ultraviolet absorbers, metal complexes, light stabilizers, preservatives, mold inhibitors, and the like.
[234] As said antioxidant, a chromman compound, a coumaran compound, a phenol compound (for example, a hindered phenol), a hydroquinone derivative, a hindered amine derivative, a spiro indane compound is mentioned, for example. On the other hand, about antioxidant, it is described in Unexamined-Japanese-Patent No. 61-159644.
[235] Examples of the anti-aging agent include those described in "Handbook Rubber / Plastic Compounded Chemical Revision 2nd Edition" (1993, manufactured by Louver Die) p.76 to 121.
[236] As the ultraviolet absorber, for example, a benzotriazole compound (described in the specification of US Patent No. 3533794), a 4-thiazolidone compound (described in the specification of US Patent No. 3352681), and a benzophenone compound (Japanese Patent Application Laid-Open No. 46-2784) Base material) and an ultraviolet-ray absorption polymer (it describes Unexamined-Japanese-Patent No. 62-260152).
[237] Examples of the metal complex include, for example, US Patent Nos. 4241155, 4245018, and 4254195, Japanese Patent Laid-Open Nos. 61-88256, 62-174741, 63-199248, and Japanese Patent Application Laid-Open No. 1-75568. It is suitable to describe in each publication of No. 1-74272.
[238] Moreover, the ultraviolet absorber and light stabilizer as described in "the handbook rubber-plastic compound revised 2nd edition" (1993, made by Louver Die) p. 122-137 can also be used preferably.
[239] As the above-mentioned material which can be used for the toner aqueous layer of this invention, a well-known photographic additive can be added. As a photographic additive, for example, research and closure (hereinafter abbreviated as RD) No. 17643 (December 1978), No.18716 (November 1979), and No.307105 (November 1989), and the corresponding points are collectively shown below.
[240] Type of additiveRD17643RD18716RD307105 Brightener 2. Stabilizer 3. Light absorbers (ultraviolet absorbers) 4. Pigment image stabilizer 5. Dural film 6. Binder 7. Plasticizer, lubricant 8. Coating aids (surfactants) 9. Antistatic Agent 10. Matp.24pp.24 ~ 25pp.25 ~ 26p.25p.26p.26p.27pp.26 ~ 27p.27p.648 right p.649 right p.649 right p.650 right p.651 left p.651 left p.650 right p.650 right p.650p.868pp.868 ~ 870p.873p.872pp.874 ~ 875pp.873 ~ 874p.876pp.875 ~ 876pp.876 ~ 877pp.878 ~ 879
[241] The toner aqueous layer of the present invention is formed by applying a coating liquid containing a polymer used for the toner aqueous layer to the support using a wire coater or the like and drying. Coating liquid is prepared by dissolving additives, such as a thermoplastic polymer and a plasticizer, in organic solvents, such as alcohol and a ketone, or disperse | distributing uniformly, for example. As an organic solvent used here, methanol, isopropyl alcohol, methyl ethyl ketone, etc. are mentioned, for example. If the polymer used for the toner aqueous layer is water-soluble, the toner aqueous layer can be prepared by applying an aqueous polymer solution on the support. Moreover, it is also possible to apply | coat on a support body with an aqueous dispersion about the polymer which is not water-soluble.
[242] The film formation temperature of the polymer used in the present invention is preferably room temperature or higher for pre-printing storage, and preferably 100 ° C. or lower for fixing of toner particles.
[243] [Properties of Toner Water Layer]
[244] It is appropriate that the toner aqueous layer has a peel strength of 180 ° C. at a fixing temperature with the fixing member of 0.1 N / 25 mm or less, more preferably 0.041 N / 25 mm or less. The 180 degree peeling strength can be measured based on the method of JISK6887 using the surface material of a fixing member.
[245] It is preferable that the toner aqueous layer has a high whiteness. The said white road is measured by the method of JIS P 8123, and 85% or more is preferable. In the wavelength range of 440 nm to 640 nm, the spectral reflectance is preferably 85% or more, and the difference between the maximum spectral reflectance and the lowest spectral reflectance in the same wavelength range is preferably within 5%. It is more preferable that the spectral reflectance is 85% or more in the wavelength region of 400 nm to 700 nm, and the difference between the maximum spectral reflectance and the lowest spectral reflectance in the wavelength region is less than 5%.
[246] In the CIE 1976 (L * a * b *) color space, specifically, the L * value is preferably 80 or more, more preferably 85 or more, and even more preferably 90 or more. In addition, it is preferable that the color taste of white is as neutral as possible. White color maze L * in the a * b * space, (a *) is ² + (b *) and more preferably a value of ²⁵⁰ or less is preferable, more preferably 18 or less, 5 or less.
[247] It is preferable that the toner aqueous layer has high smoothness. As the smoothness, the arithmetic mean roughness Ra is preferably 3 µm, more preferably 1 µm or less, and even more preferably 0.5 µm or less in the entire region from white without toner to black of maximum density.
[248] On the other hand, arithmetic mean roughness can be measured based on JIS B 0601, B 0651, and B 0652.
[249] It is preferable that the toner aqueous layer has the physical properties of one of the following items, more preferably a plurality of items, most preferably all of the items.
[250] (1) The Tm (melting temperature) of the toner aqueous layer is 30 ° C or more and the Tm of the toner is 20 ° C or less.
[251] (2) The temperature at which the viscosity of the toner aqueous layer becomes 1 × 10 ⁵ CP is 40 ° C. or higher and lower than that of the toner.
[252] (3) The storage modulus (G ′) at the fixing temperature of the toner aqueous layer is 1 × 10 ^{2 to} 1 × 10 ⁵ Pa, and the loss modulus (G ″) is 1 × 10 ^{2 to} 1 × 10 ⁵ Pa.
[253] (4) Loss tangent (G "/ G ') which is the ratio of the loss modulus (G") and storage modulus (G ") at the fixing temperature of the toner aqueous layer is 0.01 to 10.
[254] (5) The storage modulus G 'at the fixing temperature of the toner aqueous layer is -50 to +2500 with respect to the storage modulus G "at the fixing temperature of the toner.
[255] (6) The inclination angle of the molten toner on the toner aqueous layer is 50 degrees or less, particularly 40 degrees or less.
[256] The toner aqueous layer preferably satisfies the physical properties disclosed in Japanese Patent No. 2788358, Japanese Patent Laid-Open No. 7-248637, Japanese Patent Application No. 8-305067, Japanese Patent Application Publication No. 10-239889, and the like.
[257] The physical property of (1) may be measured by a differential scanning calorimetry (DSC). The physical property of said (2)-(3) can be measured using the flow tester CFT-500 or 500D of Shimadzu Corporation product, for example. The physical property of said (5)-(7) can be measured using a rotatable rheometer (for example, the dynamic analyzer RADII made from a rheometric company). The physical properties of the above (8) can be measured by the method disclosed in Japanese Patent Application Laid-open No. Hei 8-334916 using a contact angle measuring apparatus of Kyowa Kaimen Kagaku Co., Ltd. product.
[258] [Other layers]
[259] As the other layers, for example, the surface protective layer, the white layer, the intermediate layer, the adhesion improvement layer, the undercoat layer, the cushion layer, the charge control (prevention) layer, the reflection layer, the color preparation layer, the preservation improvement layer, the anti-adhesion layer, the anti-cal layer and the smoothing Layer etc. are mentioned. These layers may have a single layer structure or may be constituted by two or more layers.
[260] Surface protective layer
[261] The surface protective layer is the toner aqueous layer for the purpose of protecting the surface of the electrophotographic water-receiving sheet of the present invention, improving storage properties, improving handleability, imparting handwriting property, improving device permeability, and imparting anti-offset property. Can be formed on the surface of the. One surface may be sufficient as the said surface protection layer, and it may consist of two or more layers. Various thermoplastic resins, heat-changeable resins, etc. can be used as a binder for a surface protection layer, It is preferable to use resin of the same kind as the said toner aqueous layer. However, thermodynamic characteristics, electrostatic characteristics, and the like do not need to be the same as the toner aqueous layer, and can be optimized respectively.
[262] The surface protective layer may be blended with the above-described various additives usable for the toner aqueous layer. In particular, the surface protective layer may be mixed with a release agent used in the present invention, other additives such as a mat agent. In addition, various well-known things can be mentioned as said mat agent.
[263] The outermost surface layer (e.g., surface protective layer or the like when the surface protective layer is formed) in the electrophotographic water-receiving sheet of the present invention is preferably compatible with toner in terms of fixability. Specifically, it is preferable that the contact angle with the melted toner is, for example, 0 to 40 degrees.
[264] Back floor
[265] In the electrophotographic award sheet of the present invention, the back layer is preferably formed on the opposite side of the toner receiving layer with respect to the support for the purpose of granting backside output aptitude, improving backside output image quality, improving balance, and improving device permeability. Do.
[266] Although there is no restriction | limiting in particular as a color of the said white layer, When the electrophotographic image receiving sheet of this invention is a double-sided output type image paper which forms an image also on the back surface, it is preferable that a white layer is also white. Whiteness and spectral reflectance are preferably 85% or more like the surface.
[267] In addition, in order to improve double-sided output suitability, the structure of the back layer may be the same as that of the toner receiving layer side. The various additives mentioned above can be used for a back layer. Especially as such an additive, it is suitable to mix | blend a mat agent, a charge control agent, etc. Single layer structure may be sufficient as a back layer, and the laminated structure of two or more layers may be sufficient as it.
[268] In addition, when release mold oil is used for a fixing roller etc. in order to prevent the offset at the time of fixation, a back layer may make oil absorption.
[269] -Adhesive improvement layer
[270] The adhesion improving layer is preferably formed for the purpose of improving the adhesion between the support and the toner receiving layer in the electrophotographic water receiving sheet of the present invention. It is preferable to mix | blend the said various additives with an adhesive improvement layer, and especially mix | blend a crosslinking agent. In the electrophotographic award sheet of the present invention, a cushion layer or the like is preferably further formed between the adhesion improving layer and the toner receiving layer in order to improve the water solubility of the toner.
[271] Middle layer
[272] The intermediate layer can be formed, for example, between the support and the adhesion improving layer, between the adhesion improving layer and the cushion layer, between the cushion layer and the toner aqueous layer, between the toner aqueous layer and the storage improvement layer, and the like. Of course, in the case of the electrophotographic award sheet composed of the support, the toner aqueous layer and the intermediate layer, the intermediate layer can be present between the support and the toner aqueous layer, for example.
[273] In addition, there is no restriction | limiting in particular as thickness of the said electrophotographic water receiving sheet of this invention, Although it can select suitably according to the objective, For example, 50-350 micrometers is preferable and 100-280 micrometers is more preferable.
[274] << toner >>
[275] The electrophotographic award sheet of the present invention is used by receiving toner in a toner receiving layer during printing or copying.
[276] The toner contains at least a binder resin and a colorant, and a mold release agent and other components as necessary.
[277] Toner binding resin
[278] As a binder resin, Styrene, such as styrene and parachlor styrene; Vinyl esters such as vinyl naphthalene, vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl benzoate and vinyl lactate; Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-chloroacrylate, methyl methacrylate, ethyl methacrylate, meta Methylene aliphatic carboxylic acid esters such as butyl acrylate; Vinyl nitriles such as acrylonitrile, methacrylonitrile and acrylamide; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; Homopolymers of vinyl monomers such as vinyl carboxylic acids such as methacrylic acid, acrylic acid and cinnamic acid, copolymers thereof, and various polyesters can be used, and various waxes can also be used in combination.
[279] Among these resins, it is particularly preferable to use resins of the same type as those used for the toner aqueous layer of the present invention.
[280] Toner Colorant
[281] As the colorant, those used in toners can be used without limitation, such as carbon black, chrome yellow, kanji yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazoron orange, balkan orange, watch young red, Permanent Tread, Brillly Cumin 3B, Brillly Cumin 6B, Dayon Oil Red, Pyrazololone Red, Resolred, Rhodamine B Lake, Lake Red C, Rose Bengal, Aniline Blue, Ultramarine Blue, Chaco Oil Blue, Methylene And various pigments such as blue chloride, phthalocyanine blue, phthalocyanine green and malachite green oxalate. In addition, acridine series, xanthene series, azo series, benzoquinone series, azine series, anthraquinone series, thioindico series, dioxadine series, thiazine series, azomethine series, indico series, thioindico series, phthalocyanine series, And various dyes such as aniline black, polymethine, triphenylmethane, diphenylmethane, thiazine, thiazole and xanthene. These coloring agents may be used individually by 1 type, and may use multiple types together.
[282] As for content of a coloring agent, the range of 2-8 mass% is preferable. If the content of the colorant is 2% by mass or more, the coloring power is not weakened, while if it is 8% by mass or less, transparency is not impaired.
[283] Toner Release Agent
[284] In principle, all known waxes may be used as the release agent, but relatively low molecular weight, highly crystalline polyethylene waxes, Fischer-Tropsch waxes, amide waxes, polar waxes containing nitrogen such as urethane compounds, and the like. This is especially valid. About polyethylene wax, the thing of molecular weight 1000 or less is especially effective, and the range of 300-1000 is more preferable.
[285] The compound having a urethane bond is preferable because the compound has a low molecular weight because it can be maintained in the solid state by the strength of the cohesion force due to the polar group, and the melting point can be set higher than the molecular weight. The preferable range of molecular weight is 300-1000. As a raw material, various combinations can be selected, such as a combination of diisocyanate compounds and monoalcohols, a combination of monoisocyanate and monoalcohols, a combination of dialcohols and monoisocyanic acid, and a combination of triisocyanate compounds and monoalcohols. In order not to make high molecular weight, it is preferable to combine the compound of a polyfunctional group and a monofunctional group, and it is important to make it equivalent functional group amount.
[286] Examples of monoisocyanate compounds in the specific raw material compounds include dodecyl isocyanate, phenyl isocyanate and derivatives thereof, naphthyl isocyanate, hexyl isocyanate, benzyl isocyanate, butyl isocyanate and isocyanate. And allyl.
[287] As the diisocyanate compound, diisocyanate toylene, diisocyanate 4,4'-diphenylmethane, diisocyanate toluene, diisocyanate 1,3-phenylene, diisocyanate hexamethylene, diisocyanate 4- Methyl-m-phenylene, diisocyanate isophorone, etc. are mentioned.
[288] As monoalcohols, it is possible to use very common alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol and heptanol.
[289] Examples of the dialcohols among the starting compounds include glycols such as ethylene glycol, diethylene glycol, triethylene glycol and trimethylene glycol; As trialcohols, trimethylolpropane, trietholpropane, trimethanol ethane and the like can be used, but are not necessarily limited to this range.
[290] These urethane compounds can be used together with a resin or a colorant at the time of kneading like a conventional mold release agent, and can also be used as a kneaded powder toner. In addition, when used as the emulsion polymerization flocculation toner, it is dispersed in water with a polymer electrolyte such as an ionic surfactant, a polymer acid or a polymer base, heated to a melting point or higher, and subjected to strong shear by a homogenizer or a pressure discharge type disperser. It can be added to fine particles to prepare a release agent particle dispersion of 1 μm or less, and can be used together with a resin particle dispersion, a colorant dispersion, and the like.
[291] Ingredients other than toner
[292] In addition, the toner of the present invention can be blended with other components such as internal additives, charge control agents, and inorganic fine particles. As the internal additive, magnetic bodies such as metals such as ferrite, magnetite, reduced iron, cobalt, nickel, and manganese, alloys or compounds containing these metals can be used.
[293] As the charge control agent, various charge control agents commonly used, such as quaternary ammonium salt compounds, nigrosine compounds, dyes made of complexes such as aluminum, iron, and chromium, and triphenylmethane pigments, can be used. On the other hand, materials that are less likely to dissolve in water are preferable from the viewpoint of controlling the ionic strength that affects the stability at the time of flocculation and melting and reducing wastewater pollution.
[294] As the inorganic fine particles, silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, etc., all of the external additives on the surface of the toner are usually used, and they are dispersed and used in an ionic surfactant, a polymer acid, or a polymer base. It is preferable.
[295] Moreover, surfactant can be used for emulsion polymerization, seed polymerization, pigment dispersion, resin particle dispersion, mold release agent dispersion, aggregation, and stabilization thereof. For example, anionic surfactants such as sulfate ester salts, sulfonates, phosphate esters and soaps, cationic surfactants such as amine salts and quaternary ammonium salts, polyethylene glycols, alkylphenol ethylene oxide adducts, and polyalcohols. It is also effective to use the nonionic surfactant of together. As the dispersing means at this time, a general type such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, a dyno mill or the like can be used.
[296] On the other hand, you may add an external additive further to the said toner as needed. Examples of the external additives include inorganic powders and organic particles. As the inorganic particles, SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , Fe ₂ O ₃ , MgO, BaO, CaO, K ₂ O, Na ₂ O, ZrO ₂ , CaO · SiO ₂ , K ₂ O and (TiO ₂₎ and the like can be given _{n, Al 2 O 3, 2SiO} 2, CaCO 3, MgCO 3, BaSO 4, MgSO 4. As the organic particles, fatty acids or derivatives thereof, powders such as metal salts such as these, resin powders such as fluorine resin, polyethylene resin and acrylic resin can be used. The average particle diameter of these powders is, for example, 0.01 to 5 mu m, preferably 0.1 to 2 mu m.
[297] Although the manufacturing method of the said toner is not specifically limited, (i) forming agglomerated particles in a dispersion formed by dispersing the resin particles to prepare an aggregated particle dispersion, and (ii) a fine particle dispersion formed by dispersing fine particles in the aggregated particle dispersion. And adhering and mixing the fine particles to form the adherent particles, and (iii) heating the adherent particles to fuse the attached particles to form toner particles. desirable.
[298] Toner property, etc.
[299] The volume average particle diameter of the toner of the present invention is preferably 0.5 µm or more and 10 µm or less.
[300] If the volume average particle diameter of the toner is too small, adverse effects may occur on the handleability (supplyability, cleaning property, fluidity, and the like) of the toner, and the particle productivity may sometimes decrease. On the other hand, if the volume average particle diameter of the toner is too large, it may adversely affect the image quality and resolution due to granularity and transferability.
[301] Further, the toner of the present invention preferably satisfies the volume average particle diameter range of the toner, and the volume average particle size distribution index (GSDv) is preferably 1.3 or less.
[302] The ratio (GSDv / GSDn) of the volume average particle size distribution index (GSDv) and the number average particle size distribution index (GSDn) is preferably at least 0.95.
[303] In addition, the toner of the present invention satisfies the volume average particle diameter range of the toner, and the average value of the shape coefficient represented by the following formula is preferably 1.00 to 1.50.
[304] Shape factor = (π × L ² ) / (4 × S)
[305] (Where L is the maximum length of the toner particles and S is the projection area of the toner particles)
[306] When the toner satisfies the above conditions, the toner is effective in image quality, in particular, granularity and resolution, and it is difficult to cause omission or blur due to transfer, and it is difficult to adversely affect handleability even if the average particle size is not small.
[307] On the other hand, the storage modulus G '(measured at an angular frequency of 10 rad / sec) at 150 DEG C of the toner itself is 10 to 200 Pa, which is suitable for improving image quality and preventing offset in the fixing process.
[308] << belt fixing type smoothing processor >>
[309] The belt mounting type smoothing processor has a heating pressurizing means, a cooling device and a cooling peeling part, and further includes other members as necessary.
[310] Since the smoothness of the fixing belt greatly affects the finish print smoothness and the glossiness of the finished print image, it is preferable to use a good smoothness. As the belt surface roughness, Rmax is preferably 3 µm or less, more preferably 2 µm or less.
[311] The belt in the belt fixing type smoothing processor has a heat resistant support film and a release layer formed on the support film.
[312] The support film is not particularly limited as long as it has heat resistance, and examples thereof include polyimide (PI), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyether ether ketone (PEEK), and polyether sulfone (PES). , Polyetherimide (PEI), polyparavanic acid (PPA), and the like.
[313] As the release layer, one kind or two or more kinds selected from the group consisting of silicone rubber, fluororubber, fluorocarbon siloxane rubber, silicone resin, and fluororesin are preferable. Among these, the form of forming a fluorocarbon siloxane rubber layer of uniform thickness on the surface of the fixing belt, the silicone rubber layer of uniform thickness on the surface of the belt member, and the fluorocarbon on the surface of the silicone rubber layer The form which forms the layer of siloxane rubber is preferable.
[314] Thereby, belt contamination in offset generation and long-term operation (about 100,000 sheets) can be suppressed, and the fall of glossiness can be prevented.
[315] It is preferable that the fluorocarbon siloxane rubber has a perfluoroalkyl ether group and / or a perfluoroalkyl group in the main chain.
[316] Such fluorocarbon siloxane rubbers include (A) a fluorocarbon siloxane of the following general formula (1) as a main component, a fluorocarbon polymer having an aliphatic unsaturated group, and (B) one or more ≡SiH groups in one molecule. And organopolysiloxane and / or fluorocarbonsiloxane of 1 to 4 times the molar amount of the SiH group with respect to the amount of aliphatic unsaturated groups in the fluorocarbon siloxane rubber composition, (C) filler, (D) effective amount of catalyst Hardened | cured material of the fluorocarbonsiloxane rubber composition containing is used preferably.
[317] The fluorocarbon polymer of the said (A) component has a fluorocarbonsiloxane which has a repeating unit represented by following General formula (1) as a main component, and has an aliphatic unsaturated group.
[318]
[319] In the formula (1), R ¹⁰ is unsubstituted or substituted, preferably a C 1-8 monovalent hydrocarbon group, preferably a C 1-8 alkyl group or a C 2-3 alkenyl group In particular, it is preferable that it is a methyl group. a and e are each 0 or 1, b and d are the integers of 1-4, respectively, and c is an integer of 0-8. In addition, x is an integer of 1 or more, Preferably it is 10-30.
[320] As such (A) component, what is represented by following formula (2) is mentioned.
[321]
[322] In the said (B) component, organohydrogenpolysiloxane which has at least 2 hydrogen atoms couple | bonded with a silicon atom in a molecule | numerator as an organopolysiloxane which has XSiH group is mentioned.
[323] Moreover, in the fluorocarbon siloxane rubber composition used by this invention, when the fluorocarbon polymer of (A) component has an aliphatic unsaturated group, the said organohydrogen polysiloxane can be used as a hardening | curing agent. That is, in this case, hardened | cured material is formed by addition reaction which arises between the aliphatic unsaturated group in fluorocarbon siloxane, and the hydrogen atom couple | bonded with the silicon atom in organohydrogenpolysiloxane.
[324] As such organohydrogenpolysiloxane, various organohydrogenpolysiloxanes used in the addition-curable silicone rubber composition can be used.
[325] It is preferable to mix | blend the said organohydrogenpolysiloxane generally at the rate which will become at least 1, especially 1-5 with respect to 1 aliphatic unsaturated hydrocarbon group in the number of (Si) fluorocarbonsiloxane of (A) component. Do.
[326] In addition, as a fluorocarbon which has a SiSi group, in the unit of said Formula (1), or in Formula (1), R <^10> is a dialkyl-hydrogensiloxy group, the terminal is a dialkyl-hydrogensiloxy group, a silyl group, etc. It is preferable that it is SiH group of, and what is represented by following formula (3) is mentioned.
[327]
[328] As a filler of the said (C) component, the various filler used for the general silicone rubber composition can be used. For example, reinforcing fillers such as aerosol silica, precipitated silica, carbon powder, titanium dioxide, alumina, quartz powder, talc, sericite and bentonite, fibrous fillers such as asbestos, glass fibers, organic fibers and the like can be exemplified.
[329] As the catalyst of the component (D), chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and olefins, platinum black or palladium supported on a carrier such as alumina, silica or carbon, known as a catalyst for addition reaction, rhodium Examples of periodic table group VIII elements or compounds thereof, such as a complex of an olefin, a chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst), and a rhodium (III) acetylacetonate, are exemplified, but these complexes are alcohols, ethers, hydrocarbons. It is preferable to use it, melt | dissolving in solvents, such as these.
[330] In the fluorocarbon siloxane rubber composition used in the present invention, various compounding agents can be added within a range not impairing the object of the present invention of improving solvent resistance. For example, diphenylsilanediol, low-polymerization molecular chain terminal hydroxyl group-blocked dimethylpolysiloxane, dispersant such as hexamethyldisilazane, heat resistance improvers such as ferrous oxide, ferric oxide, cerium oxide, iron octylate, pigments and the like A coloring agent etc. can be mix | blended as needed.
[331] The fixing belt of the present invention can be obtained by coating the surface of the heat resistant support film with the fluorocarbon siloxane rubber composition and heat curing it, but diluting it with a solvent such as m-xylene hexafluoride or benzotrifluoride as necessary. The coating liquid can be further applied by a general coating method such as spray coat, dip coat and knife coat. In addition, the temperature and time of heat hardening can be selected suitably, Usually, it selects according to the kind of support film, manufacturing method, etc. in the range of temperature 100-500 degreeC, time 5 second-5 hours.
[332] The thickness of the release layer formed on the surface of the belt is not particularly limited, but is preferably 1 to 200 µm, particularly 5 to 150 µm, in order to prevent peeling of the toner or offset of the toner component to obtain good fixability of the image. Do.
[333] As the belt fixing method, for example, the oilless belt fixing method described in Japanese Patent Application Laid-Open No. Hei 11-352819, the second transfer and fixing described in Japanese Patent Application Laid-Open No. Hei 11-231671 and Japanese Patent Application Laid-open No. Hei 5-341666 It is known how to achieve this at the same time. The electrophotographic apparatus having the fixing belt according to the present invention includes, for example, a heating and pressing unit capable of melting and pressurizing at least the toner, a fixing belt capable of conveying the receiving material with toner in contact with the toner receiving layer, and And an electrophotographic apparatus having a belt-type toner fixing portion having a cooling portion capable of cooling in a state in which a heated water phase material is attached to a fixing belt. By using the electrophotographic award sheet having the toner award layer in the electrophotographic apparatus having such a fixing belt, the toner adhered to the toner award layer is finely fixed without spreading to the award material. At the same time, the melted toner is cooled and fixed in a state of being in close contact with the fixing belt, so that the toner is completely contained in the toner receiving layer and accommodated in the toner receiving layer. Therefore, a smooth toner image having no glossiness and having a gloss can be obtained.
[334] The electrophotographic water-receiving sheet formed in the present invention is particularly preferable for an image forming method by an oilless belt fixing method, whereby the offset is greatly improved. However, other various image forming methods can be used similarly.
[335] For example, by using the electrophotographic water-receiving sheet of the present invention, a full-color image can be preferably formed while improving image quality and preventing cracks. The color image can be formed by using an electrophotographic apparatus capable of forming a full color image. A conventional electrophotographic apparatus has an image paper conveying portion, a latent image forming portion, and a developing portion provided in proximity to the latent image forming portion, and depending on the model, the toner near the latent image forming portion and the image paper conveying portion in the center of the apparatus main body. It has a middle and middle transfer part.
[336] Moreover, as a method for improving image quality, an adhesive transfer or a heat support transfer method is known instead of or in combination with electrostatic transfer or bias roller transfer. For example, Japanese Patent Laid-Open No. 63-113576 and Japanese Patent Laid-Open No. 5-341666 describe the specific structure thereof. In particular, the method of using the intermediate transfer belt of the thermal support transfer method is preferable. It is also preferable to provide a cooling device in the intermediate belt after toner transfer to the electrophotographic award sheet or in the latter half of the transfer. By the above cooling apparatus, the toner (toner image) is cooled below the softening temperature of the binder resin or the glass potential temperature of the toner used therein, and is efficiently transferred to the electrophotographic water-receiving sheet to allow peeling from the intermediate belt.
[337] Fixation is an important process that influences the gloss or smoothness of the final image. As a fixing method, fixing by a heating and pressing roller, belt fixing using a belt, and the like are known. However, the belt fixing method is preferable in terms of image quality such as gloss and smoothness. As for the belt fixing method, the secondary transfer and fixing described in, for example, the oilless belt fixing method described in Japanese Patent Application Laid-Open No. Hei 11-352819, Japanese Patent Application Laid-Open No. Hei 11-231671 and Japanese Patent Application Laid-open No. Hei 5-341666. At the same time, a method of achieving the same is known. In addition, before fixing and heating by the fixing belt and the fixing roller, the primary fixing by the heat roller may be performed.
[338] Fig. 5 shows an example of a belt-separated smoothing processor, and can be used, for example, as an electrophotographic apparatus shown in Fig. 4 (e.g., as a full-color laser printer belt-shaped fixing unit made by Fuji Xerox).
[339] In Fig. 4, reference numeral 100 denotes an image forming apparatus, 37 a photosensitive drum, 9 a developing apparatus, 31 an intermediate transfer belt, 16 a recording sheet, and 25 a belt-shaped fixing unit.
[340] 5 illustrates a belt type fixing unit 25 installed in the image forming apparatus 100 of FIG. 4.
[341] As shown in Fig. 5, the belt-type fixing device 25 is endlessly supported rotatably by a heating roll 71, a peeling roll 74 including the heating roll 71, and a tension roll 75. The belt 73 and the press roll 72 which press-contact with the said heating roll 71 through the endless belt 73 are provided.
[342] In addition, a cooling heat sink 77 for forcibly cooling the endless belt 73 between the heating roll 71 and the peeling roll 74 is provided on the inner surface side of the endless belt 73. The heat sink 77 constitutes a cooling / sheet conveying unit for cooling the electrophotographic water-receiving sheet and conveying the sheet.
[343] As shown in Fig. 5, the belt type fixing device 25 has an electrophotographic water-receiving sheet on which a color toner image is transferred and fixed on a surface thereof. The color toner image is introduced into the pressure contact portion (nip) of the pressure roll 72 press-contacted through 73 so as to be positioned on the heating roll 71 side, and the pressure contact portion of the heating roll 71 and the pressure roll 72 is introduced. During passing, the color toner image T is melted and fixed on the electrophotographic award sheet.
[344] Thereafter, in the pressure-contacting portion of the heating roll 71 and the pressing roll 72, for example, the toner is heated to a temperature of about 120 to 130 ° C. and melted so that the color toner image is fixed to the aqueous layer. The water receiving sheet for the dragon is conveyed together with the endless belt 73 in a state in which the water receiving layer on the surface is in close contact with the surface of the endless belt 73. In the meantime, the endless belt 73 is forcibly cooled by the cooling heat sink 77, and the color toner image and the aqueous layer are cooled and fixed, and then the release sheet 74 itself is subjected to the electrophotographic water sheet. It peels off by elasticity (stiffness) of.
[345] On the other hand, after the peeling step is completed, the surface of the endless belt 73 is removed with residual toner or the like by a cleaner (not shown) to prepare for the next fixing step.
[346] Example
[347] Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples at all. In addition, below, "%" and "part" represent a "mass%" and a "mass part", respectively.
[348] (Examples 1-7 and Comparative Examples 1-3)
[349] <Production of Electrophotographic Award Sheet>
[350] Support
[351] Support A: Smooth base with a basis weight of 180 g / m 2
[352] Support B: A polyethylene resin coating layer having a thickness of 20 µm is formed on both sides of a smooth base paper having a basis weight of 160 g / m 2 by the laminating method.
[353] Toner Water Level
[354] On each of the supports shown in Table 1, the coating liquid for the toner aqueous layer having the following composition was coated with a wire coater and dried, whereby six kinds of electrophotographic water-based sheets P-1 to P having the toner aqueous layer having the thickness shown in Table 1 were formed. -6 was written.
[355] [Coating Liquid for Toner Water Layer]
[356] 100 parts of water-dispersed polyester resin
[357] (Unitica Eritel KZA-1449, solid content mass 30%)
[358] Carnava wax 10 part water
[359] (Cellazole 524 from Nakagyo oil and fat, 30% solids mass)
[360] White pigment (TiO ₂ ) water dispersion 7.5 parts
[361] (Taipec A-220 of Ishihara Sangyo Bridge, 40% by mass)
[362] 4 parts of coating aid
[363] (Alcox E30 from Akishige Kagaku)
[364] For each of the obtained electrophotographic award sheets, GsP (45 °), GsP (* 45 ° ± 3 °), GsP (45 °) / GsP (* 45 ° ±), which are characteristic values relating to glossiness before printing, were obtained by the following method. 3 °) was measured. The results are shown in Table 1.
[365] Gloss evaluation
[366] About the glossiness of the center part of each electrophotographic award sheet, mirror glossiness GsP (45 degree) and reflected light dispersion GsP (* 45 degree ±) using gloss meter UGV-6P (brand name; product made by Suga Test Corp.) according to JIS Z8741 3 °) was measured.
[367] Here, in the measurement opening of 8mm diameter and the setting of the high sensitivity mode, the mirror surface glossiness measurement conditions according to JIS of 45 degree setting were previously performed using the standard plate, and the mirror glossiness GsP (45 degree) of the light receiving angle of 45 degree was performed in advance. After the measurement, only the light receiving angle was changed to 42 ° and 48 ° to measure the reflected light dispersion GsP (* 45 ° ± 3 °).
[368] Award SheetSupportPolyethylene resin coating layerToner Water Layer ThicknessMeasured value of award sheet before printing GsP (45 °)GsP (* 45 ° ± 3 °)GsP (45 °) / GsP (* 45 ° ± 3 °) P-1Anone8㎛20.518.81.1 P-2Anone12㎛24.017.31.4 P-3Bhas exist4㎛75.626.02.9 P-4Bhas exist8㎛91.318.64.9 P-5Bhas exist12㎛94.014.26.6 P-6Anonenone6.56.31.0
[369] <Photo Printing>
[370] Next, the fixing unit (two roll fixing machine formed of two pressurized heating rolls) of the electrophotographic printer DocuCenterColor 500 (trade name; manufactured by Fuji Xerox Co., Ltd.) shown in Fig. 4 was removed, and the fixing unit shown in Fig. 5 was attached instead. Using a retrofit machine, the toner image was electrostatically transferred onto the electrophotographic water-receiving sheet by photosensitive, developing and transferring processes.
[371] Thereafter, the electrophotographic award sheet is provided in the fixing unit shown in Fig. 5 to fix the toner image to obtain a print image.
[372] <Creation of electrophotographic print and sensory evaluation test>
[373] The same black image of 8-bit (0 to 255) full color R / G / B = 0/0/0 was created by a PC, and this was sent to a printer to create a control postcard size (100 mm x 148 mm) print.
[374] At this time, as the fixing belt, as shown in Table 2, the belt surface roughness Rmax was prepared differently, and electrophotographic printing was performed using the electrophotographic award sheet shown in Table 1.
[375] After application of DY-115, a silicone rubber primer made by Toray Dow Corning and Silicon, to a base layer made of polyimide as a fixing belt base material, after 30 minutes of air drying, 100 parts of DY35-796AB, which is a silicone rubber precursor, and n- The coating liquid adjusted to 30 parts of hexane formed the coating film with the immersion coating cloth, and 10-minute primary vulcanization was performed at 120 degreeC, and 40 micrometers of silicone rubbers were obtained.
[376] On this silicone rubber layer, 100 parts of SiFEL 610, a fluorocarbon siloxane rubber precursor manufactured by Shin-Etsu Chemical Co., Ltd., and a fluorine solvent (m-xylene hexafluoride, perfluoroalkane, perfluoro (2-butyltetrahydrodofuran) After mixing the coating liquid adjusted to 20 parts) with a immersion cloth, the coating film was formed by immersion coating, and the secondary vulcanization was carried out at 120 ° C. for 10 minutes and secondary vulcanization at 180 ° C. for 4 hours. A fixing belt having a siloxane rubber was used.
[377] About the obtained electrophotographic print, the characteristic values regarding the glossiness of GsP (45 degrees), GsP (* 45 degrees +/- 3 degree), GsP (45 degrees) / GsP (* 45 degrees +/- 3 degree) by the said method, and Sensory evaluation was performed by the following method. The results are shown in Table 2.
[378] Sensory Evaluation Score
[379] The sensory evaluation score is an average score of five subjects scored by ten subjects.
[380] 5: highly desirable
[381] 4: desirable
[382] 3: neither
[383] 2: undesirable
[384] 1: highly undesirable
[385] Award SheetHow to settleBelt Surface Roughness RmaxPrint measurement resultSensory Evaluation Score GsP (45 °)GsP (* 45 ° ± 3 °)GsP (45 °) / GsP (* 45 ° ± 3 °) Example 1P-4Belt fixation3 μm90.35.416.74.5 Example 2P-4Belt fixation2 μm96.43.032.14.8 Example 3P-4Belt fixation1 μm97.42.834.84.8 Example 4P-1Belt fixation2 μm88.07.511.74.3 Example 5P-2Belt fixation2 μm90.55.815.64.5 Example 6P-3Belt fixation2 μm86.212.27.14.0 Example 7P-5Belt fixation2 μm97.82.933.74.8 Comparative Example 1P-42 roll fixing-86.217.45.03.2 Comparative Example 2P-6Belt fixation2 μm32.014.22.31.8 Comparative Example 3P-62 roll fixing-10.19.21.11.8
[386] From the results in Table 2, the mirror glossiness GsP (45 °) is high and the scattering index GsP (* 45 ° ± 3 °) is suppressed, so that GsP (45 °) / GsP (* 45 ° ± 3 °) is sufficiently secured. In the case, it is confirmed that the texture of the gloss is remarkably improved.
[387] In addition, when the surface roughness of the fixing belt is set to be constant or less and the thickness of the toner receiving layer is set to be greater than or equal to the support of the electrophotographic award sheet, the polyethylene resin coating layer is formed by the laminating method. It was confirmed that it became remarkable.
[388] As described above, according to the present invention, it is possible to provide an electrophotographic image forming method capable of stably obtaining a natural and good glossiness without discomfort even when compared to a conventional silver dye photo print.

权利要求:
Claims (11)
[1" claim-type="Currently amended] A toner image is formed on an electrophotographic award sheet having at least one layer of toner receiving layers formed on a support, and the support belt is rotatably supported by a plurality of supporting members including a heating member. The pressurized rotating body was pressed through a fixing belt to form a nip, and the toner image was fixed by passing the electrophotographic water-receiving sheet having the toner image formed thereon, and the toner image was cooled to a temperature below a predetermined temperature. An electrophotographic image forming method of outputting an electrophotographic print image by performing a fixing process by using a belt fixing device that separates an electrophotographic award sheet from a
The specular glossiness GsP (45 °) and reflected light dispersion GsP (* 45 ° ± 3 °) of the black print image portion of the toner image forming surface in the electrophotographic printing satisfy the conditions of the following formulas (I) to (III) An electrophotographic image forming method, characterized in that.
30 ≦ GsP (45 °). (I)
0 GsP (* 45 ° ± 3 °) (II)
GsP (45 °) / GsP (45 ° ± 3 °) (III)
(In the above formulas (I) to (III), GsP (45 °) means mirror glossiness at an incident angle of 45 ° and a light receiving angle of 45 °. GsP (* 45 ° ± 3 °) means GsP (* 42 °) and mean value of GsP (* 48 °) (GsP (* 42 °) means the measurement value of the specular gloss meter at the incident angle of 45 °, light receiving angle 42 °.) The GsP (* 48 °) Denotes a measurement of the specular glossmeter having an incident angle of 45 ° and a light receiving angle of 48 °)
[2" claim-type="Currently amended] The specular glossiness GsP (45 °) and reflected light dispersion GsP (* 45 ° ± 3 °) of the black print image portion of the toner image forming surface in the electrophotographic printing are the following formulas (I ') to: An electrophotographic image forming method characterized by satisfying the condition of (III ').
60 ≦ GsP (45 °). (I ')
0≤GsP (* 45 ° ± 3 °) ≤10 (II ')
GsP (45 °) / GsP (45 ° ± 3 °) (III ')
[3" claim-type="Currently amended] The electrophotographic image forming method according to claim 1 or 2, wherein the support in the electrophotographic water receiving sheet is a support having a thermoplastic resin layer formed on one or both sides of the substrate.
[4" claim-type="Currently amended] The electrophotographic image forming method according to claim 1 or 2, wherein the toner image receiving layer has a thickness of 5 µm or more and 20 µm or less.
[5" claim-type="Currently amended] The electrophotographic image forming method according to claim 1 or 2, wherein the fixing belt has a heat resistant support film and a release layer formed on the support film.
[6" claim-type="Currently amended] 6. The electrophotographic image forming method according to claim 5, wherein the release layer is one or two or more selected from the group consisting of silicone rubber, fluorine rubber, fluorocarbon siloxane rubber, silicone resin and fluorine resin.
[7" claim-type="Currently amended] The electrophotographic image forming method according to claim 5, wherein the release layer contains a fluorocarbon siloxane rubber having a perfluoroalkyl ether group and / or a perfluoroalkyl group in the main chain.
[8" claim-type="Currently amended] The electrophotographic image forming method according to claim 1 or 2, wherein the belt surface roughness Rmax is 3 µm or less.
[9" claim-type="Currently amended] The mirror glossiness GsP (45 °) and the reflected light dispersion GsP (* 45 ° ± 3 °) of the toner image forming surface in the electrophotographic award sheet before printing are the following formulas (IV): Electrophotographic image forming method characterized by satisfying at least one of the conditions selected from (VI) to (VI).
GsP (45 °) <30.. (IV)
GsP (* 45 ° ± 3 °)> 15... (V)
1≤GsP (45 °) / GsP (45 ° ± 3 °) <6... (VI)
(However, in the formulas (IV) to (VI), GsP (45 °), GsP (* 45 ° ± 3 °) has the same meaning as above)
[10" claim-type="Currently amended] The specular glossiness GsP (45 °) and reflected light dispersion GsP (* 45 ° ± 3 °) of the black printed image portion of the toner image forming surface in electrophotographic printing satisfy the conditions of the following formula (I) to (III). Electrophotographic print, characterized in that.
30 ≦ GsP (45 °). (I)
0 GsP (* 45 ° ± 3 °) (II)
GsP (45 °) / GsP (45 ° ± 3 °) (III)
(In the above formulas (I) to (III), GsP (45 °) means mirror glossiness at an incident angle of 45 ° and a light receiving angle of 45 °. GsP (* 45 ° ± 3 °) means GsP (* 42 °) and mean value of GsP (* 48 °) (GsP (* 42 °) means the measurement value of the specular gloss meter at the incident angle of 45 °, light receiving angle 42 °.) The GsP (* 48 °) Denotes a measurement of the specular glossmeter having an incident angle of 45 ° and a light receiving angle of 48 °)
[11" claim-type="Currently amended] An electrophotographic print obtained by the electrophotographic image forming method according to claim 1.

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同族专利:

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公开号 | 公开日

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US20040091296A1|2004-05-13|

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CN1501181A|2004-06-02|

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JP2004157412A|2004-06-03|

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EP1418474A1|2004-05-12|

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US6985688B2|2006-01-10|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2002-11-07|Priority to JP2002324441A

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2002-11-07|Priority to JPJP-P-2002-00324441

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2003-11-07|Application filed by 후지 샤신 필름 가부시기가이샤

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2004-05-13|Publication of KR20040041059A

优先权:

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申请号 | 申请日 | 专利标题

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JP2002324441A|JP2004157412A|2002-11-07|2002-11-07|Electrophotographic image forming method and electrophotographic print|

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JPJP-P-2002-00324441|2002-11-07|