JPH10232516A - Making method of electrophotographic waterless planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrophotographic waterless planographic printing plate which can be applied to a scanning exposure system with low output laser light and provides high image quality in plate making and printing, excellent printing durability, further, simplification, quickening and power saving and is capable of removing a toner image part with a dry means and stably and faithfully reproducing an image of high quality, even with respect to the fluctuation of conditions in a removing process as well. SOLUTION: A transfer layer 12 is provided on the surface of an electrophotographic photoreceptor 11 and a nonfixed toner image 5 is formed on the transfer layer 12 by using a liquid developer by an electrophotographic process. The toner image 5 is transferred to a planographic printing plate substrate 20 together with the transfer layer 12 and further, a nonadhesive resin layer whose sticking force to the surface of the transfer layer 12 is greater than that of the toner image 5 to the surface of the substrate 20 by >=180g.f in tacky power is provided on the full surface of the transfer layer 12. After that, the nonadhesive resin layer on the toner image is selectively removed to make the electrophotographic waterless planographic printing plate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preparing a waterless lithographic printing plate of the electrophotographic type, and more particularly, it is applicable to a low output laser beam scanning exposure system, and has excellent plate making quality and printing quality. The present invention relates to a method for producing an electrophotographic waterless planographic printing plate having high printing durability.

[0002]

2. Description of the Related Art In conventional lithographic printing, an ink-philic image pattern is provided on a hydrophilic support, water and ink are alternately supplied, and water is attached to a hydrophilic non-image portion to prevent ink from attaching. In general, printing is performed by preventing the ink and attaching ink only to the image portion having ink affinity. However, with this printing method, it is difficult to maintain the balance between water and ink,
Requires skill. As a solution to these disadvantages,
A lithographic printing plate that does not require dampening water (hereinafter referred to as "waterless lithographic printing plate") is used.

[0003] A waterless planographic printing plate has an oleophobic portion and an oleophilic portion. By supplying ink, ink is applied only to the lipophilic portion to perform printing. Conventionally, using a photosensitive material consisting of a silicon rubber layer and a photosensitive layer made of a photosensitive resin sequentially laminated, the irradiation between the silicon rubber layer and the photosensitive layer is controlled by light irradiation, and the image area is removed by wet development processing. A method for producing a printing plate has been put to practical use. However, since the sensitivity of the photosensitive material is low, it is a system that requires contact exposure with a short wavelength, high output light source and wet processing, and thus has problems in simplicity, quickness, and labor saving. It has become extremely difficult to apply a printing plate suitable for an image forming system using digital signals (i.e., a digital direct printing plate).

On the other hand, a plate material having a silicon layer which is in close contact with a heat-sensitive layer containing a light-to-heat conversion material is subjected to scanning exposure with a laser beam corresponding to a digital signal output. A new system for forming a waterless printing plate by forming an image by destroying and dry-processing the layers together has been marketed by Heidelberg. Although this system was in the heat mode, writing by laser light and dry processing were realized. However, since the sensitivity is low, a high-output laser writing device is required, and an increase in the size of the device, a length of plate making time, an increase in the cost of the system, and the like are obstacles.

On the other hand, a silicon layer is provided on a photoreceptor by using an electrophotographic photoreceptor which can easily form an image with a small-sized apparatus and can be adapted to scanning exposure of a low-output semiconductor laser beam. A method of forming a toner image (oleophilic) by an electrophotographic process to obtain a waterless printing plate is disclosed in, for example, JP-A-47-19305 and JP-A-49-19.
No. 904, No. 59-125752, No. 62-1604
No. 66 and the like. However, when printing is actually performed, the adhesion between the image area and the silicon layer is insufficient, and the image area causes image loss immediately after printing due to the strong adhesive force of the ink, and only a small number of copies can be printed. Was.

Therefore, a method of curing silicone rubber after forming a toner image using an uncured silicone rubber layer to improve printing durability (for example, Japanese Patent Application Laid-Open Nos.
Or a method using a silicon rubber layer containing a reactive group (for example, JP-A-52-29305).
Nos. 56-83750, 57-178893) have been proposed to improve the adhesion between the toner image portion and the silicone rubber layer. It did not fit, and the adhesion was still insufficient.

On the other hand, an image using a dry toner is formed on a lithographic printing support by a PPC copying machine such as a laser printer using a low-output semiconductor laser beam or a thermal transfer printer, and a silicon layer is provided on the entire surface and cured. After that, the image portion and the silicon layer thereon are removed by a wet processing method using a solvent to form a printing plate (Japanese Patent Laid-Open No. 49-1).
21602) or a method in which a light absorbing agent-containing image or a non-adhesive image is formed, and a silicon layer is formed on the entire surface and cured, and then the image portion is removed by a dry method such as heat or mechanical force (Japanese Patent Laid-Open No. 3-118154) has been proposed.
These methods are considered to solve the problem of poor adhesion of the toner image to the silicon layer in a conventional printing plate manufactured by providing a toner image on the silicon layer. Further, the method described in JP-A-3-118154 is disclosed. Dry processing is possible for image formation with ink receptivity.

[0008]

However, in these methods, the adhesion between the silicon layer in the non-image area and the support is insufficient, or the peeling of the silicon layer is used as a material for the image area. The discrimination between the adhesion between the support and the silicon layer in the non-image area and the adhesion between the image area and the silicon layer is small due to the dependence on the light-to-heat conversion efficiency of the dye / pigment. However, it is difficult to selectively remove even small image portions by removing, and it is difficult to always provide a printing plate stably.

It is well known that the method of transferring from a PPC copier using dry toner or drawing an image by a thermal transfer printer described as an image forming means has a limit in producing a high-definition image. Therefore, it was difficult to produce a printing plate having a better plate image quality. In particular, in recent years, there has been a strong demand for a system for printing high-definition full-color images edited on a workstation or the like by digital signal processing in a simple, rapid, and labor-saving manner. Was not something that could be done.

Accordingly, an object of the present invention is to be applicable to a low-power laser beam scanning exposure method, to provide excellent plate making and printing image quality, good printing durability, and further simplicity, quickness, and labor saving. An object of the present invention is to provide a method of preparing a waterless lithographic printing plate that can be realized. Another object of the present invention is to
An object of the present invention is to provide a method of preparing an electrophotographic waterless planographic printing plate capable of faithfully reproducing a high-definition image. It is a further object of the present invention to create an electrophotographic waterless planographic printing plate capable of removing image portions by dry means and faithfully reproducing a high-definition image stably even when conditions change during the removal process. It is to provide a method.

[0011]

An object of the present invention is to provide a transfer layer (T) mainly containing a thermoplastic resin (A) on the surface of an electrophotographic photoreceptor, and forming an electron transfer layer on this layer. A non-fixed toner image is formed using a liquid developer by a photographic process, the toner image is transferred together with the transfer layer (T) onto a lithographic printing plate support, and further over the entire surface of the transfer layer (T) on the support. The adhesive force to the transfer layer (T) surface is
JIS Z0237-19 rather than adhesive strength between toner image and support surface
After providing a non-adhesive resin layer that is greater than 180 gram-force by the adhesive force measured based on the “Adhesive Tape / Adhesive Sheet Test Method” of 80, the transfer layer (T) and the non-adhesive resin layer on the toner image are removed. It has been found that this is achieved by a method of making an electrophotographic waterless lithographic printing plate characterized by selective removal.

The method for preparing a waterless lithographic printing plate of the present invention comprises:
It is performed through a process as shown in FIG. First, a transfer layer (T) 12 is formed on the surface of an electrophotographic photoreceptor (a),
After an unfixed toner image 5 is formed thereon by an electrophotographic process using a liquid developer (b), this toner image is transferred onto a lithographic printing plate support 20 together with a transfer layer (T) 12 (c). ).

Next, the transfer layer (T) on the lithographic printing plate support
12, a non-adhesive resin layer 6 is provided on the entire surface (d), and then the transfer layer and the non-adhesive resin layer of the toner image portion are selectively removed (e) to prepare a waterless planographic printing plate.

In the present invention, the adhesive force between the non-adhesive resin layer 6 and the transfer layer (T) 12 is larger than the adhesive force between the toner image 5 and the lithographic printing plate support 20. By utilizing the difference, the selective removal of the non-adhesive resin layer in the image area can be favorably achieved. Furthermore, by transferring the toner image together with the transfer layer onto the lithographic printing plate support, the toner image can be completely transferred as compared with the case where the toner image is transferred alone. Images can be faithfully reproduced.

According to the present invention, the adhesive strength between the transfer layer (T) and the support in the non-image area and the transfer between the non-adhesive resin layer and the non-adhesive toner layer are determined based on the adhesive strength between the non-fixed toner image and the surface of the lithographic printing support. Since the adhesive force with the layer (T) is larger, even a minute image portion can be selectively and easily removed.

Specifically, the force required to separate the interface between the non-adhesive resin layer and the transfer layer (T) on the lithographic printing plate support (the force required to separate the interface between the non-adhesive resin layer and the transfer layer (T)) Adhesion), JI
S Z0237-1980 Adhesive force measured based on “Adhesive tape / adhesive sheet test method” is 200 gram · force (g · f) or more, and the non-adhesive resin layer in the image area is lithographic printed together with the transfer layer (T). Force required for peeling from plate support (adhesion between toner image and lithographic printing plate support)
Is preferably adjusted so as to be 20 g · f or less in the above adhesive force. More preferably, the adhesive force between the non-adhesive resin layer and the transfer layer (T) is the same adhesive force of 300 g · f or more, and the adhesive force between the toner image and the lithographic printing plate support in the image area is the same adhesive force. Is 10 g · f or less.

Thus, the difference in adhesive strength between the non-image part and the image part with respect to the support can be remarkable, and the non-image part on the toner image part is not damaged without damaging the non-adhesive resin layer surface. The adhesive resin layer can be selectively removed.

The adhesive strength of the non-adhesive resin layer is JIS
Z0237-1980 `` Testing method for adhesive tape and adhesive sheet '', 8.3.
Measure according to the 180-degree peeling method of 1 with the following modifications. As the “test plate” of the non-image portion, a lithographic printing plate support having a transfer layer and a non-adhesive resin layer applied thereon is used. As a "test plate" for the image area, a lithographic printing plate support having a transfer layer and a non-adhesive resin layer coated thereon after being developed with toner on one side is used. As a “test piece”, a 3 mm silicone adhesive tape (# 851A) having a width of 25 mm is used. Peel off at a speed of 25 mm / min using a constant speed tension type tensile tester. That is, with the adhesive side of the test piece facing down on the test plate,
The roller is reciprocated one time at a speed of about 300 mm / min from above the test piece and pressed. The non-adhesive resin layer is peeled off by about 25 mm using a constant-speed tension type tensile tester for 20 to 40 minutes after the pressure bonding, and then peeled off at a rate of 25 mm / min. The force is read each time 5 mm is peeled off, and it is read four times in total. The test is performed on three test pieces, and an average value of twelve pieces measured from the three test pieces is obtained, and this is converted into a proportional value per 10 mm width.

In the present invention, the adhesiveness between the lithographic printing plate support and the transfer layer in the non-image portion is 200 g based on the above-mentioned adhesive force.
F or more, particularly preferably 500 g · f or more. The adhesive strength between the transfer layer and the non-adhesive resin layer is as described above. Since the adhesiveness is sufficient, the film strength of the non-image area is maintained with respect to the ink tacking force and printing pressure during printing. The printing durability is also significantly improved. In addition, since the adhesive force between the toner image and the lithographic printing plate support is small, the image portion can be easily removed, no extra steps or devices are required, and the speed of image formation, labor saving, and miniaturization of the device are reduced. realizable.

In the present invention, it is preferable to remove the toner image portion of the printing original plate provided with the non-adhesive resin layer by dry means. Thereby, the non-adhesive resin layer on the image portion can be more selectively and easily removed by cohesive failure of the toner image. For example, a non-adhesive resin layer pattern can be easily formed by applying an external force by peeling, brushing or the like.

Further, in the present invention, the surface of the transfer layer (T) on the lithographic printing plate support preferably contains a reactive group capable of chemically bonding at the interface with the non-adhesive resin layer. As a result, the transfer layer (T) on the lithographic printing plate support and the non-adhesive resin layer undergo a chemical reaction at least at the interface to form a crosslinked structure and further maintain good adhesiveness. The difference in adhesive strength between the image part and the non-image part becomes remarkable,
The film strength of the non-image area is maintained, and the printing durability can be improved.

Hereinafter, the present invention will be described in more detail. The configuration and materials of the electrophotographic photoreceptor (hereinafter, also referred to as photoreceptor) used in the present invention may be any of conventionally known ones, and are not limited. Examples of photoreceptors include “Basics and Applications of Electrophotographic Technology” (edited by the Electrophotographic Society of Japan) (Corona Publishing (1988)),
Edited by Hiroshi Komon “Recent development and practical application of photoconductive materials and photoconductors”
(Japan Science Information Co., Ltd., 1985), Ryuji Shibata and Jiro Ishiwatari, Polymer, Vol. 17, p. 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No. 8), Proceedings of the Current Symposium on Organic Photoconductors for Electrophotography (1985), RM Schaffert, "Electrophotograph"
y "Focal Press London (1980), SW Ing, MD Taba
k, WE Hass, "Electrophotography Fourth Internati
onal Conference "SPSE (1983), edited by Isao Shinohara, Hidetoshi Tsuchida, Hideaki Kusakawa," Recording Materials and Photosensitive Resins ", published by Gakkai Shuppan Center (1979), Hiroshi Komon, Chemistry and Industry, 39 (3), 161
(1986).

That is, a single layer composed of the photoconductive compound itself or a photoconductive layer in which the photoconductive compound is dispersed in a binder resin can be mentioned. The dispersed photoconductive layer can be either a single layer type or a laminated type. May be. Further, the photoconductive compound used in the present invention may be either an inorganic compound or an organic compound.

In the present invention, examples of the inorganic compound used as the photoconductive compound include conventionally known inorganic light sources such as zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, selenium, selenium-tellurium, amorphous silicon and lead sulfide. And a conductive compound. These may form the photoconductive layer together with the binder resin, or may form the photoconductive layer alone by vapor deposition or sputtering. When an inorganic photoconductive compound such as zinc oxide or titanium oxide is used, the binder resin is used in an amount of 10 to 100 parts by weight, preferably 15 to 40 parts by weight, based on 100 parts by weight of the inorganic photoconductive compound.

On the other hand, the organic compound may be any of the conventionally known compounds. Specifically, the organic compound has a photoconductive layer mainly composed of an organic photoconductive compound, a sensitizing dye, and a binding resin. Examples thereof include those having a photoconductive layer mainly composed of a charge generating agent, a charge transporting agent, and a binding resin, and a two-layered photoconductive layer containing a charge generating agent and a charge transporting agent in separate layers. The electrophotographic photoreceptor of the present invention may take any form of the above-described photoconductive layer.

In the case of the second example, the organic photoconductive compound functions as a charge transport agent. Examples of the organic photoconductive compound include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, arylamine derivatives, azurenium salt derivatives, amino-substituted chalcone derivatives, and N, N-bicarbazyl derivatives. Oxazole derivative, styryl anthracene derivative, fluorenone derivative, hydrazone derivative, benzidine derivative, stilbene derivative, polyvinyl carbazole and its derivatives, polyvinyl pyrene, polyvinyl anthracene, poly-2-vinyl-4- (4'-dimethylaminophenyl)
-5-phenyl-oxazole, poly-3-vinyl-N
-Polymers such as vinyl polymers such as ethylcarbazole, polyacenaphthylene, polyindene, copolymers of acenaphthylene and styrene, triphenylmethane polymer, pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin, etc. And condensation resins.

In the present invention, the organic photoconductive compound is not limited to these compounds, and all known organic photoconductive compounds can be used. These organic photoconductive compounds can be used in combination of two or more in some cases.

As the charge generator contained in the photoconductive layer, various kinds of organic and inorganic charge generators conventionally known in electrophotographic photoreceptors can be used. For example, selenium, selenium-tellurium, cadmium sulfide, zinc oxide and the organic pigments exemplified below can be used, and these are arbitrarily selected as charge generating agents having a spectral sensitivity suitable for the wavelength range of the light source of the printer. .

Examples of the organic pigment include azo pigments such as monoazo, bisazo, trisazo and tetraazo pigments, phthalocyanine pigments such as metal-free or metal phthalocyanine, perylene pigments, indigo and thioindigo derivatives.
Examples thereof include quinacridone pigments, polycyclic quinone pigments, bisbenzimidazole pigments, squarium salt pigments, and azurenium salt pigments, and these can be used alone or in combination of two or more.

When a charge transporting agent is further used in combination, a material having good compatibility with the kind of the charge generating agent used in combination is selected. Specifically, it is known as the above-mentioned organic photoconductive compound. Compounds that have been used.

The upper limit of the content ratio of the organic photoconductive compound is determined by the compatibility between the organic photoconductive compound and the binder resin. Crystallization of the photoconductive compound occurs, which is not preferable. Since the electrophotographic sensitivity decreases as the content of the organic photoconductive compound decreases, it is preferable that as much organic photoconductive compound as possible is contained as long as crystallization of the organic photoconductive compound does not occur. The content of the organic photoconductive compound is 5 to 100 parts by weight of the binder resin.
It is 120 parts by weight, preferably 10 to 100 parts by weight.

The binder resin that can be used for the photoreceptor is
Any of the resins used for conventionally known electrophotographic photoreceptors may be used, and the weight average molecular weight is preferably 5 × 10 ³ to 1 ×.
10 ⁶ , more preferably 2 × 10 ^{4 to} 5 × 10 ⁵ . The glass transition point of the binder resin is preferably -4.
0 ° C to + 200 ° C, more preferably -10 ° C to +140
° C.

As the binder resin, for example, review articles cited in the above photoreceptor, Koichi Nakamura, edited by Koichi Nakamura, Chapter 10, “Practical Technology of Binders for Recording Materials”, CMC Publishing (1985), Endo Tsuyoshi, “Thermosetting Polymer” Refinement "(CMC Corporation, 1986),
Yuji Harazaki, "Handbook of the Latest Binder Technologies", Chapter II-1 (General Technology Center, 1985), Takayuki Otsu "Synthesis, Design and New Application Development of Acrylic Resin" (Chubu Business Development Center, Publishing Division, 1985), Ei Omori Three “functional acrylic resin”
(Techno System, 1985), D. Tatt, SCHeidec
ker, Tappi, 49 , (No.10), 439 (1966), ES Baltazzi,
RG Blanclotte et al., Phot.Sci. Eng. 16 (No.
5), 354 (1972), Nguyen Chan K, Isamu Shimizu, Eiichi Inoue, and other books such as Journal of the Institute of Electrographic Photography 18 (No.2), 22 (1980).
Examples include the compounds described in the reviews.

Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and Polymers and copolymers of the derivatives, butadiene-styrene copolymer, isoprene-styrene copolymer, butadiene-unsaturated carboxylic acid ester copolymer, acrylonitrile copolymer, methacrylonitrile copolymer, alkyl vinyl ether copolymer Polymer, acrylate polymer and copolymer, methacrylate polymer and copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, itaconic diester polymer and copolymer , Maleic anhydride copolymer, acrylamide copolymer, methacrylamide Polymer, hydroxyl-modified silicone resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl and carboxyl group-modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylate copolymer, ring Rubber-acrylate copolymers, copolymers containing a nitrogen-free heterocycle (for example, as a heterocycle, a furan ring, a tetrahydrofuran ring, a thiophene ring, a dioxane ring, a dioxofuran ring, a lactone ring, a benzofuran ring, Benzothiophene ring, 1,3-dioxetane ring, etc.), epoxy resin and the like.

In particular, by using a resin having a relatively low molecular weight (about 10 ³ to 10 ⁴ ) containing an acidic group such as a carboxyl group, a sulfo group, or a phosphono group as a binder resin for the photoconductor, Electrical characteristics can be improved. For example, JP-A-64-70761, JP-A-2-67563, JP-A-3-181948, JP-A-3-24959 and the like can be mentioned.

Also, by using a specific medium to high molecular weight resin, stable performance can be maintained even when the environment fluctuates significantly. For example, Japanese Patent Application Laid-Open No. 3-29954
No. 3-77954, No. 3-92961 and No. 3
JP-A-353257 describes a resin which binds an acidic group to the end of a graft portion of a graft copolymer or a resin which contains an acidic group in a graft portion of a graft copolymer.
Graft copolymers containing an AB block copolymer comprising an acidic group-containing A block and an acidic group-free B block described in JP-A-066464 and JP-A-3-223762 in a graft portion. By using these resins, the photoconductor can be uniformly dispersed and a photoconductive layer having good smoothness can be formed, and in the case of using a scanning exposure method using environmental changes or semiconductor laser light. Also, excellent electrostatic characteristics can be maintained.

In the present invention, various dyes can be used as spectral sensitizers as needed depending on the type of light source such as exposure to visible light or exposure to semiconductor laser light. For example, the above-mentioned review and literature on electrophotographic photoreceptors, "Electrophotography" 12 , 9 (1973), "Synthetic Organic Chemistry" 24 (11), 1010
(1966), Harumiya Miyamoto, Hidehiko Takei; Imaging 1973 (N
o.8) Page 12, CJ Young et al .: RCA Review 15 , p. 469
(1954), Kohei Kiyota: IEICE Transactions , J63-C (N
o.2), p. 97 (1980), Yuji Harazaki et al., Industrial Chemistry Magazine, 6
6 , 78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 3
5 , 208 pages (1972), "Research Disclosure" 1982
Year, 216, 117-118, FM Hamer `` The Cyanine Dye
and carbon compounds, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.) ), Phthalocyanine dyes (which may contain metals) and the like.

Furthermore, various conventionally known electrophotographic photosensitive member additives can be used, if necessary. These additives include a chemical sensitizer for improving electrophotographic sensitivity, various plasticizers for improving film properties, and a surfactant.

Examples of the chemical sensitizer include halogen, benzoquinone, chloranil, fluoranyl, bromanyl,
Dinitrobenzene, anthraquinone, 2,5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, phthalic anhydride, maleic anhydride, N-hydroxymaleimide, N-hydroxyphthalimide, 2,
Electron-withdrawing compounds such as 3-dichloro-5,6-dicyanobenzoquinone, dinitrofluorenone, trinitrofluorenone, tetracyanoethylene, nitrobenzoic acid, dinitrobenzoic acid, etc .; Development and Practical Use ”Chapters 4-6: Japan Science Information Co., Ltd.
Examples include polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, and the like, which are reviewed in the publication section (1986). Further, Japanese Patent Application Laid-Open No. 58-65
No. 439, No. 58-102239, No. 58-1294
Compounds described in JP-A No. 39, 62-71965 and the like can also be mentioned.

Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, diphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalyl glycolate, dimethyl glycol phthalate Etc. can be added to improve the flexibility of the photoconductive layer. These plasticizers are preferably contained in a range that does not deteriorate the electrostatic properties of the photoconductive layer. The amount of these various additives is not particularly limited, but is usually 0.001 to 2.0 parts by weight based on 100 parts by weight of the photoconductor.

The thickness of the photoconductive layer is 1 to 100 μm, especially 10
~ 50μ is preferred. When a photoconductive layer is used as the charge generation layer of the photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is 0.01 to 5 μm, particularly 0.0 to 5 μm.
5-2μ is preferred.

The electrophotographic photosensitive layer can be provided on a conventionally known support. In general, the support of the electrophotographic photosensitive layer is preferably conductive. As the conductive support, a substrate such as a metal, paper, or a plastic sheet is impregnated with a low-resistance substance in the same manner as in the related art. The above-mentioned support, a substrate coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and further preventing curling, etc. A substrate provided with a water-resistant adhesive layer on its surface, a substrate provided with at least one or more precoat layers as required on the surface layer of the support, a substrate obtained by laminating a base conductive plastic on which aluminum or the like is deposited on paper. Etc. can be used.

Specifically, as an example of the conductive substrate or the conductive material, Yukio Sakamoto “Electrophotography” 14 (No. 1), 2-11
Page (1975), Hiroyuki Moriga "Introduction to Special Paper Chemistry" Polymer Publishing Association (1975), MF Hoover, J. Macromol. Sc
i. Chem. A-4 (6), pages 1327 to 1417 (published in 1970) and the like are used.

Further, the surface of the electrophotographic photosensitive member provided in the present invention preferably has a releasability. Specifically, JI
S Z0237-1980 20 gram · force (g · f) as the surface adhesive strength measured based on “Testing method of adhesive tape / adhesive sheet”
It is more preferably at most 10 g · f. By adjusting the adhesive strength in this manner, the transfer layer and the toner image formed on the photoreceptor can be easily and collectively peeled and transferred onto the printing plate support.

The surface adhesive strength of the above photoreceptor is JIS Z0237-19
80 “Adhesive tape / adhesive sheet test method”, 8.3.1-18
Measure according to the 0-degree peeling method with the following modifications. An electrophotographic photosensitive member on which a transfer layer is to be formed is used as a “test plate”. An adhesive tape having a width of 6 mm and manufactured according to JIS C 2338-1984 is used as a "test piece". Peel off at a speed of 120 mm / min using a constant speed tension type tensile tester.

That is, the roller is reciprocated from the top of the test piece at a speed of about 300 mm / min, with the adhesive side of the test piece facing down, by pressing the test piece downward. In a period of 20 to 40 minutes after the crimping, the film is peeled off at a speed of 120 mm / min after peeling off about 25 mm using a constant-speed tension type tensile tester. The force is read every 20 mm peeling, for a total of 4 readings. The test is performed on three test pieces, and an average value of twelve pieces measured from the three test pieces is obtained, and this is converted into a proportional value per 10 mm width.

Further, the transfer layer is more likely to be transferred as the surface smoothness of the photoreceptor becomes better, so that the “arithmetic mean roughness (Ra)” defined in JIS B0601 is defined as the contact height described in JIS B0651. The value obtained by measuring with a needle type surface roughness measuring device is 2.0 μm or less. However, the cut-off value (λ _c ) is 0.16 m.
m, evaluation length (l _n) 2.5mm}, it is preferable that especially 1.5μm or less. A photoreceptor having such good surface smoothness is particularly advantageous for obtaining a high-definition image.

In the present invention, an electrophotographic photosensitive member having a surface releasability in advance may be used, but the transfer layer (T)
Before forming the compound, a desired release property may be imparted to the surface of the photoconductor by applying a compound (S) containing at least a fluorine atom and / or a silicon atom to the surface of the photoconductor. As a result, an ordinary electrophotographic photoreceptor can be used without considering the releasability of the electrophotographic photoreceptor surface.

Further, when an electrophotographic photosensitive member having releasability in advance is repeatedly used in the present invention, the compound (S) may be applied when the releasability of the surface of the photoreceptor decreases. This makes it possible to easily maintain the releasability of the photoconductor surface. The imparting of the releasability to the electrophotographic photosensitive member is preferably performed in a toner image transfer device, and the means for applying the compound (S) to the surface of the electrophotographic photosensitive member can be appropriately set in an electrophotographic process device. .

In order to obtain a photoreceptor having a peelable surface, a method using a photoreceptor having a peelable surface in advance and a method of using the compound (S) on the surface of a commonly used electrophotographic photoreceptor are described in detail. A method of imparting peelability to the surface of the photoreceptor by applying the method is exemplified.

Examples of the photoreceptor having a peelable surface in advance which can be used in the former method include those using a photoconductor in which the surface of amorphous silicon is modified to be peelable. As a method for modifying the surface of an electrophotographic photoreceptor mainly containing amorphous silicon to have releasability, a coupling agent containing a fluorine atom and / or a silicon atom (such as a silane coupling agent or a titanium coupling agent) is used. There is a method of treating the surface of an amorphous silicon layer, which is disclosed in JP-A-55-89844 and JP-A-4-231.
No. 318, JP-A-60-170860 and JP-A-59-10
Nos. 2244 and 60-17750. Further, as another method, in particular, a compound containing a component containing a fluorine atom and / or a silicon atom as a substituent in a block (for example, a modified polydialkyl silicon such as polyether, carboxylic acid, amino group, carbinol, etc.) ) By adsorption (WO 94/507)
No. etc.).

Further, as another example of a photoreceptor having a peelable surface, an electrophotographic photoreceptor contains a silicon atom and / or a fluorine atom (containing a silicon atom and / or a fluorine atom) near its surface. Examples include a polymer containing a polymer containing a coalescing component. Here, the vicinity of the surface of the electrophotographic photoreceptor means the uppermost layer of the photoreceptor, and includes a cover coat layer provided on the photoconductive layer and the uppermost photoconductive layer. That is, an overcoat layer is provided as the uppermost layer of a photoconductor having a photoconductive layer, and the overcoat layer contains the polymer to impart releasability, or a photoconductive layer (a single photoconductive layer and a laminated photoconductive layer). The uppermost layer of any of the conductive layers may contain the above polymer, and the surface thereof may be modified so as to exhibit releasability.

In order to impart releasability to the overcoat layer or the uppermost photoconductive layer, a polymer containing silicon atoms and / or fluorine atoms may be used as a binder resin for the layer. Alternatively, it is also preferable to use a block copolymer (surface unevenly distributed copolymer) containing a polymer segment composed of a polymer component containing a silicon atom and / or a fluorine atom as described in detail below together with another binder resin. . Further, the resin containing a silicon atom and / or a fluorine atom can be used in the form of particles.

In particular, when an overcoat layer is provided, a method in which a surface uneven distribution type copolymer is used in combination with another binder resin is preferable because the adhesion between the photoconductive layer and the overcoat layer can be sufficiently maintained. . The surface uneven distribution type copolymer is usually contained in an amount of 0.1 part by weight in 100 parts by weight of the whole composition of the overcoat layer.
It can be used in a proportion of 1 to 95 parts by weight.

As such an overcoat layer, specifically, in a PPC photoreceptor using dry toner, it is known as one means for maintaining the durability of the photoreceptor surface against repeated use of the photoreceptor. A protective layer used for providing and protecting a surface layer on the photoreceptor is exemplified.

For example, as a technique relating to a protective layer using a silicone-based block copolymer, JP-A-61-953
No. 58, No. 55-83049, No. 62-87971
No. 61-189559, No. 62-75461,
Nos. 62-139556, 62-139557, and 62-208555. Further, as a protective layer using a fluorine-based block copolymer, JP-A-61-116362 and JP-A-61-11756.
3, No. 61-270768, and No. 62-14657. Further, as a protective layer in which a resin containing a fluorine atom-containing polymer component is used in the form of particles, JP-A-63-249152 and JP-A-63-22.
No. 1355. Further, a resin layer having the same content as the non-adhesive resin layer of the present invention described later can be used as the peelable overcoat layer.

The method of modifying the surface of the uppermost photoconductive layer to a state in which the releasability is developed is effective when a so-called dispersion type photoconductor using at least a photoconductor and a binder resin is used. Applied to That is, in the layer constituting the uppermost layer of the photoconductive layer, a resin of a block copolymer containing, as a block, a polymer segment containing a polymer component containing a silicon atom and / or a fluorine atom, and silicon atom and / or By coexisting at least one of the resin particles containing the fluorine-containing polymer component, these materials are concentrated and migrated to the surface and unevenly distributed, so that the surface can be modified into a peelable surface. Examples of the copolymer and resin particles include those described in JP-A-5-197169.

In order to further enhance the uneven distribution of the surface,
As a binder resin for the overcoat layer and the uppermost photoconductive layer,
It is possible to use a block copolymer obtained by bonding at least one type of polymer segment containing a silicon atom and / or fluorine atom and a polymer segment containing a heat and / or photocurable group-containing component with a block. it can. Examples of the polymer segment containing the heat and / or photocurable group-containing component include those described in JP-A-5-197169. Alternatively, a light and / or thermosetting resin may be used together with a fluorine atom and / or silicon atom containing resin.

The polymer containing a polymer component containing a silicon atom and / or a fluorine atom of the present invention, which is effective for modifying the surface of the photoreceptor by such a method, is a resin (hereinafter referred to as resin (P)). Or resin particles (hereinafter referred to as resin particles (PL)
).

When the polymer is a random copolymer, the proportion of the polymer component containing silicon atoms and / or fluorine atoms is preferably at least 60% by weight, more preferably at least 80% by weight of the total polymer components. It is. Preferably, the polymer component containing a silicon atom and / or a fluorine atom is 5
0 to 20% by weight of a polymer segment (α) containing 0% by weight or more and a polymer component containing silicon and / or fluorine atoms
It is a block copolymer in which the contained polymer segment (β) is bonded by blocks. More preferably, it is a block copolymer containing at least one polymer component containing a light and / or thermosetting functional group in the segment (β) in the block copolymer. In these block copolymers, it is preferable that the segment (β) does not contain any polymer component containing a fluorine atom and / or a silicon atom.

When a block copolymer containing the polymer segments (α) and (β) (a surface uneven distribution type copolymer) is used, the releasability of the surface itself is improved as compared with a random copolymer. Peelability is maintained. That is, when a coating film is formed in the presence of a small amount of a fluorine- and / or silicon-atom-containing block copolymer, these are easily transferred and concentrated to the surface of the film before the drying step after coating. Then, the surface of the film is modified so that the film can exhibit peelability. Further, such a copolymer is cross-linked at the surface portion of the membrane and is sufficiently fixed.

As described above, when the polymer segment (α) containing a fluorine atom and / or a silicon atom is blocked in the resin (P), the other polymer atom containing a fluorine atom and / or a silicon atom is blocked. Even if the transfer layer is formed, the polymer segment (β) containing a small amount of the polymer component has a good compatibility with the binder resin for forming the film because of its good compatibility with the binder resin. The transfer of the resin to the transfer layer is suppressed or eliminated, so that the interface between the transfer layer and the electrophotographic photosensitive member can be clearly formed and maintained (namely, the anchor effect). By using a polymer containing a curable group in the segment (β) of the block copolymer and crosslinking between the polymers at the time of film formation, an effect of further maintaining the interface with the photoreceptor clearly is exhibited. .

As described above, the polymer may be used as resin particles (PL). In the case of resin particles (PL),
Transfer and concentration to the surface are performed by the action of the insolubilized polymer segment (α), and the polymer segment (β) soluble in the non-aqueous solvent bound to the particles is, as in the case of the resin, It interacts with the binder resin to perform an anchor effect. Further, when the curable group is contained in the polymer or the binder resin, transfer to the transfer layer is eliminated.

The polymer component containing a substituent containing a fluorine atom and / or a silicon atom contains the substituent as a substituent on the side chain of the polymer even if the substituent is incorporated in the polymer main chain. It may be. Specific embodiments of the above compounds are described, for example, in JP-A-5-197169.

Next, in the latter method of obtaining a photoreceptor having a releasable surface, a releasable compound (S) is applied to the surface of a normal electrophotographic photoreceptor before the formation of a transfer layer. A method for making the surface peelable will be described.

The compound (S) includes a fluorine atom and / or
Or a compound containing at least a silicon atom, as long as it improves the releasability of the electrophotographic photoreceptor surface, the structure is not particularly limited, and may be any of a low-molecular compound, oligomer, or polymer. . In the case of an oligomer or polymer, the substituent containing a fluorine atom and / or a silicon atom may be incorporated into the main chain of the polymer, or may be present as a substituent on the side chain of the polymer. Preferably, an oligomer or a polymer containing a repeating unit containing such a substituent as a block is mentioned, and these are excellent in adsorptivity to the surface of the electrophotographic photoreceptor and particularly effectively exhibit releasability.

In the case of a block copolymer, a polymer component containing a fluorine atom and / or a silicon atom may be constituted by a block. Here, “constituting by a block” means that a component having a fluorine atom and / or a silicon atom
It means that the polymer has a polymer segment containing 0% by weight or more, for example, AB type block, AB
-A type block, BAB type block, graft type block or star type block.

As the compound (S) containing a fluorine atom and / or a silicon atom used in the present invention, specifically,
"New edition surfactant surfactant handbook" edited by Tokiyuki Yoshida, etc., published by Kogyo Tosho Co., Ltd. (1987), supervised by Takao Karimei "Latest surfactant application technology", CMC Corporation (1990), edited by Kunio Ito "Silicone Handbook" published by Nikkan Kogyo Shimbun (19
1990), supervised by Takao Karimei "Specially Functional Surfactant" C.
MC (1986), AM Schwartz et al., "Surface Ac
tive Agents and Detergents vol. II "and the like.

Further, Nobuo Ishikawa, "Synthesis and Function of Fluorine Compounds", CMC Co., Ltd. (1987), edited by Jiro Hirano et al., "Fluorine-Containing Organic Compounds-Synthesis and Application-", Technical Information Association, Ltd. (1991) , "Organic Silicon Strategic Materials", supervised by Mitsuo Ishikawa, No. 3
The compound (S) of the present invention that satisfies the above-mentioned properties can be synthesized using a synthesis method described in a literature such as Chapter Science Forum (1991).

By applying the compound (S) to the surface of the electrophotographic photosensitive member, the surface is modified so as to have a desired peeling property. Compound (S) on the surface of electrophotographic photoreceptor
Applying means that the compound (S) is supplied to the surface of the electrophotographic photosensitive member to form a state in which the compound (S) is adsorbed or adhered to the surface of the photosensitive member.

For applying the compound (S) to the surface of the electrophotographic photosensitive member, any conventionally known method may be applied. For example, Yuji Harasaki “Coating Engineering” Asakura Shoten (19
71), Yuji Harasaki “Coating Method” Maki Shoten (1979)
Air Doctor Coater, Blade Coater, Knife Coater, Squeeze Coater, Impregnation Coater, Reverse Roll Coater, Transfer Roll Examples include a coater, a gravure coater, a kiss roll coater, a spray coater, a curtain coater, and a calendar coater.

Further, cloth, paper, and the like impregnated with the compound (S)
A method of bringing felt or the like into close contact with the photoreceptor, a method of pressing a curable resin impregnated with the compound (S) against the photoreceptor, drying the solvent after wetting the photoreceptor with a non-aqueous solvent in which the compound (S) is dissolved And a method in which the non-aqueous solvent in which the compound (S) is dispersed is electrophoresed and adhered to the photoreceptor.

Further, after the non-aqueous solution of the compound (S) is uniformly wetted on the surface of the photoreceptor by an ink jet method, it can be adsorbed or adhered by drying.
The method using the ink jet method is described in, for example, "Non-impact Printing" edited by Shin Ohno, CMC (1986)
Annual publication). For example, continuous injection type Sweet method, Hertz type, intermittent injection type Wins
Examples include a ton method, an ink-on-demand type pulse jet method, a bubble jet method, and an ink mist type mist method.

Silicone rubber can be used as the compound (S). Preferably, a silicone rubber roller is wound around a metal core roller, which may be directly pressed against the surface of the photoreceptor. The nip pressure may be 0.5 to 10 kgf / cm ² , and the contact time may be 1 second to 30 minutes. At this time, the photoconductor and / or the silicone rubber roller may be heated to 150 ° C. or lower. It is considered that a part of the low molecular weight component in the silicone rubber is transferred from the roller surface to the photoreceptor surface by the pressing. The silicone rubber may be swollen with silicone oil. The silicone rubber may be in the form of a sponge, or the sponge roller may be further impregnated with a silicone oil, a silicone surfactant solution or the like.

In the present invention, these methods are not particularly limited, and various methods are selected depending on the state of the compound (S) to be used (liquid, waxy or solid). If necessary, a heating medium may be used in combination. Thus, the fluidity of the compound (S) used can be adjusted.

The amount of the compound (S) to be applied to the surface of the photoreceptor is not particularly limited, and it is sufficient that the adverse effect on the electrophotographic characteristics of the photoreceptor does not pose a practical problem. Usually, a film thickness of 1 μm or less is sufficient, and the expression of the releasability of the present invention is based on “Weakboundary Layer” (Bikerman “The Science of Ad
In the present invention, the compound (S) is applied to an electrophotographic photoreceptor to impart releasability to the surface, and is preferably used in the present invention, as defined by "Hesive Joints" Academic Press (published in 1961). Should be 20 g · f or less.

In the printing plate preparation step of the present invention, it is not necessary to repeat this step at all times, and it may be performed as appropriate according to the combination of the photoreceptor to be used and the ability to maintain the releasability by applying the compound (S) and the means thereof. About the specific example of such a compound (S) and the specific aspect of its application,
It is described in JP-A-7-5727.

In the present invention, a transfer layer (T) is formed on the surface-separable photosensitive member as described above. Preferably, it is performed in the same apparatus as the electrophotographic process or the transfer process.

The transfer layer of the present invention is mainly composed of the thermoplastic resin (A), is light-transmissive, and has transparency to at least a part of the wavelength light in the spectral sensitivity region of the electrophotographic photosensitive member. What is necessary is just to have, and it may be colored. When it is necessary to inspect the transferred image on the lithographic printing plate support, the color needs to be different from the color of the colored toner image.

Since the transfer layer (T) is provided on the surface of the electrophotographic photosensitive member, the electrophotographic characteristics (chargeability, charge retention in darkness, photosensitivity) are not deteriorated until a toner image is formed by an electrophotographic process. It is important to form a good copy image and to have thermoplasticity to be easily transferred in the next thermal transfer process.

The transfer layer of the present invention may be transferred at a temperature of 150 ° C. or less and / or a pressure of 20 kgf / cm ² or less, more preferably a temperature of 140 ° C. or less and / or a pressure of 10 kgf / cm ² or less. Is preferably performed. If the value is equal to or less than the above value, there is almost no need to increase the size of the transfer device in order to maintain the heat capacity and pressure of the transfer device in order to peel and transfer the transfer layer from the photoreceptor surface. It can be done without any practical problems. Although the lower limit is not particularly limited, it is usually a temperature equal to or higher than room temperature or 100 g ·
It is preferable that the film can be peeled off under a transfer condition of a pressure of f / cm ² or more. Therefore, the resin (A) as the main component constituting the transfer layer of the present invention is preferably a glass transition point of 90 ° C. or lower or a softening point of 100 ° C. or lower, more preferably a glass transition point of 80 ° C.
It is a thermoplastic resin having a softening point of 90 ° C. or lower.

The resin (A) may be used alone or in combination of two or more. In particular, it is preferable to use at least two resins having different glass transition points or softening points in combination. In particular, a resin having a glass transition point of 25 ° C. to 70 ° C. or a softening point of 35 ° C. to 100 ° C. (hereinafter sometimes referred to as resin (AH)) and a resin having a glass transition point of 30 ° C. or less or a softening point of 45 ° C. or less (hereinafter referred to as “resin ( AL), and the difference between the glass transition point or the softening point of the resin (AH) and the resin (AL) is preferably 2 ° C or more. As a result, the adhesive force at the interface between the surface of the photoreceptor and the transfer layer (T) is reduced, and even when the transfer layer is thinned, the transfer to the lithographic printing plate support is performed well. The pressure (transport speed, transport speed, etc.) can be further increased, and transfer can be easily performed regardless of the type of the printing plate support.

The resin (AH) preferably has a glass transition point of 28 ° C. to 60 ° C. or a softening point of 38 ° C. to 80 ° C., more preferably a glass transition point of 30 ° C. to 50 ° C. or a softening point of 40 ° C. to 70 ° C. ° C, and the resin (AL) preferably has a glass transition point of -50 ° C to + 28 ° C or a softening point of -30 ° C.
To + 40 ° C., more preferably a glass transition point of −20.
° C to + 23 ° C or a softening point of 0 ° C to 35 ° C. The glass transition point or softening point of the resin (AL) is determined by the resin (AH)
It is preferably lower by at least 5 ° C. Here, the resin (A
H) or the difference in the glass transition point or softening point when two or more resins (AL) are contained, the difference between the resin (AH) having the lowest glass transition point or the softening point and the resin (AL)
Among them, the difference from the one having the highest glass transition point or softening point.

The resin (AH) and the resin (A) in the transfer layer
The proportion of L) present is preferably 5 to 90/95 to 10 (weight ratio), particularly preferably 10 to 70/90 to 30 (weight ratio). When the ratio of the resin (AH) / (AL) is out of the above range, the effect of the combined use is reduced.

As a preferred embodiment of the transfer layer (T) in the present invention, after the transfer layer is transferred onto a lithographic printing plate support, a state in which the transfer layer is chemically bonded at the interface with a non-adhesive resin layer provided thereon is formed. Is preferred. That is, on the surface portion of the transfer layer, there is a component containing a reactive group capable of chemically bonding to a reactive group present in the resin constituting the non-adhesive resin layer, and the non-adhesive resin layer is exposed to light and heat. Alternatively, a bridge is formed by a chemical reaction due to moisture.

As these chemically reactive groups, those similar to the curable reactive groups of the non-adhesive resin described below can be mentioned.
The transfer layer contains the reactive group-containing resin. These reactive groups can be used alone or in combination of two or more of them by arbitrarily combining groups capable of chemically reacting with the reactive group in the non-adhesive layer. The proportion of the polymer component containing these reactive groups was 1% by weight in all the components of the copolymer.
Or more, preferably 5% by weight or more.

Further, when these reactive group-containing resins are used in the transfer layer, it is preferable that the resin contains a polymer component containing a fluorine atom and / or a silicon atom. The fluorine atom and / or silicon atom may be contained in the reactive group-containing polymer component or may be contained in another polymer component. As a result, these reactive group-containing resins are concentrated on the surface of the transfer layer during the transfer layer formation or non-adhesive resin layer installation process due to a difference in surface free energy, and as a result, the transfer layer and the non-adhesive Promotes interfacial crosslinking between the conductive resin layers.

The polymer component containing a fluorine atom and / or a silicon atom may be contained at random or as a block. More preferably, it is a block copolymer resin in which a polymer segment containing a fluorine atom and / or a silicon atom is contained in a block. Examples of the random polymer and block copolymer containing a fluorine atom and / or a silicon atom include those described in JP-A-5-197169.

In the case of a random copolymer, the amount of the polymer component containing a fluorine atom and / or a silicon atom is preferably at least 40% by weight, more preferably at least 60% by weight of the total polymer component. is there. More preferably, the polymer contains 0 to 20% by weight of a polymer segment (α) containing 50% by weight or more of a polymer component containing a fluorine atom and / or a silicon atom and a polymer component containing a fluorine and / or silicon atom. % Of the polymer segment (β) is linked by a block. The reactive group is a polymer segment (α) or a segment (β)
May be present in either one or both.

The reactive group-containing polymer is preferably used in such a manner that the reactive group-containing polymer component is present in an amount of 1 to 30% by weight based on all the constituent components of the transfer layer. When a resin (AH) and a resin (AL) having different thermophysical properties are used in combination as described above, a resin containing such a reactive group is contained in one or both of these resins. Good.

Specific examples of the resin (A) that can be used in the transfer layer include thermoplastic resins, resins known as adhesives and pressure-sensitive adhesives, and include, for example, olefin polymers or copolymers, and chlorides. Vinyl copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers or copolymers, allyl alkanoate polymers or copolymers, polymers and copolymers of styrene and its derivatives, olefin-styrene copolymers, Olefin-unsaturated carboxylic acid ester copolymer, acrylonitrile copolymer, methacrylonitrile copolymer, alkyl vinyl ether copolymer, acrylate ester polymer and copolymer, methacrylate ester polymer and copolymer, styrene -Acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, itaconic acid ester Polymers and copolymers, maleic anhydride copolymers, acrylamide copolymers, methacrylamide copolymers, hydroxyl-modified silicone resins, polycarbonate resins, ketone resins, polyester resins, silicone resins, amide resins, hydroxyl and carboxyl group modifications Polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylic acid ester copolymer, cyclized rubber-acrylic acid ester copolymer, heterocyclic-containing copolymer (for example, a furan ring, tetrahydrofuran as a heterocyclic ring) Ring, thiophene ring, dioxane ring, dioxofuran ring, lactone ring, benzofuran ring, benzothiophene ring, 1,3-dioxetane ring, etc.), cellulose resin,
Fatty acid-modified cellulose resins, epoxy resins, and the like.

For example, "Plastic Materials Lecture Series", Vol. 1-18 (1981), published by Nikkan Kogyo Shimbun, "Polyvinyl Chloride" edited by Kinki Chemical Association Vinyl Subcommittee, published by Nikkan Kogyo Shimbun (1988), Ei Omori III "Functional Acrylic Resin" published by Techno System Co., Ltd. (1985), Eiichiro Takiyama "Polyester Resin Handbook" Published by Nikkan Kogyosha (1988), Kazuo Yuki "Saturated Polyester Resin Handbook" published by Nikkan Kogyo Shimbun (1989) ), Edited by The Society of Polymer Science, “Polymer Data Handbook <Application>”, Chapter 1, Baifukan (1986), Yuji Harasaki, “Latest Binder Technology Handbook”, Chapter 2, Integrated Technology Center (1985), Okudadaira, Polymer Processing, Separate Volume, 8
Volume 20 Extra Number "Adhesive" Polymer Publishing Association (1976), Keiji Fukuzawa "Adhesion Technology" Polymer Publishing Association (1987), Mamoru Nishiguchi "Adhesion Handbook 14th Edition" Polymer Publishing Association (1985) ), Various adhesives described in "Adhesion Handbook 2nd Edition" edited by The Japan Adhesion Association, Nikkan Kogyo Shimbun (1980) and the like.

The resin (A) may further comprise a polymer component (f) containing a fluorine-containing and / or silicon-containing substituent having the effect of improving the releasability of the resin (A) itself. It may further be contained as a polymer component therein.
This improves the releasability from the electrophotographic photoreceptor,
As a result, the transferability becomes better. This fluorine atom /
The silicon atom-containing substituent may be incorporated into the polymer main chain of the polymer or may be contained as a substituent on the side chain of the polymer. Preferably, the fluorine / silicon-containing polymer component (f) is contained as a block in the thermoplastic resin (A). The polymer component (f) is preferably 3 to 40% by weight, more preferably 5 to 25% by weight, based on all polymer components.
contains.

Further, as described above, when the resin (A) constituting the transfer layer is composed of two or more resins having different glass transition points or softening points, these fluorine-containing and / or silicon-containing polymer components ( f) may be contained in any of the resin (AH) and the resin (AL). The polymer component (f) having the function of improving the releasability of the resin (A) itself is specifically a fluorine / silicon-containing polymer which can be contained in the resin used for the photosensitive layer having the releasability. Those having the same contents as the coalesced component can be mentioned.

In the resin (A) used for the transfer layer,
As a preferable embodiment of the so-called block copolymer, any block copolymer may be used as long as the polymer component (f) containing a fluorine atom and / or a silicon atom is composed of blocks. Here, the term "composed of blocks" means that the polymer has a polymer segment containing at least 70% by weight of a fluorine atom and / or a silicon atom in the polymer, for example, as described in the resin (P). , A
-B type block, ABA type block, BAB type block, graft type block, star type block and the like.

These various block copolymers can be synthesized according to a conventionally known polymerization method. Specifically, a fluorine atom and / or a silicon atom that imparts releasability to the surface of the electrophotographic photosensitive member are used. The same method as that cited for the resin (P) containing the polymer component as a block can be used. However, it is not limited to these methods.

Further, other additives may be used in the transfer layer, if necessary, in order to improve various physical properties such as adhesiveness, film formability and film strength. For example, rosin, petroleum resin, silicone oil, etc. for adjusting the adhesiveness. Polybutene, DOP, DBP, low molecular weight styrene resin, low molecular weight as a plasticizer and softener for improving the wettability to the photoreceptor and lowering the melt viscosity. Polyethylene wax, microcrystalline wax, paraffin wax and the like, and high molecular weight hindered polyhydric phenol, triazine derivative and the like as an antioxidant can be added. For details, see "Hot Melt Adhesion in Practice" (by Hiroshi Fukada, published by the Society of Polymer Publishing, 1983).
On page 107.

The thickness of the transfer layer is 0.1 to 5 μm as a whole.
Is suitable, and preferably in the range of 0.5 to 3 μm. If the film thickness is too small, transfer failure tends to occur. If the film thickness is too large, the toner image after transfer may be distorted due to the expansion and contraction of the resin of the transfer layer.

In the present invention, a transfer layer is first provided on a photoreceptor. This transfer layer is preferably formed on the photoreceptor each time in an apparatus for performing an electrophotographic process. As described above, by incorporating the transfer layer forming apparatus into the electrophotographic apparatus, it becomes possible to repeatedly use the photoreceptor after the toner image is peeled together with the transfer layer in the same apparatus, and the plate making process is continuously performed. And the cost of the printing plate can be significantly reduced.

In order to provide the transfer layer on the photoreceptor, a known layer forming method can be used. For example, a solution or dispersion of the composition for a transfer layer may be applied by a known method. In particular, it is preferable to form the transfer layer on the photoreceptor by at least one of a hot melt coating method, an electrodeposition coating method, a transfer method, and an inkjet method. In particular, it is preferable to use an electrodeposition coating method, whereby a thin transfer layer having a uniform thickness can be easily formed on the surface of the photoreceptor in the transfer device.

The hot-melt coating (hot-melt) method is a method in which the transfer layer composition is hot-melt-coated by a known method. The mechanism of the hot melt adhesive hot melt coating apparatus (hot melt coater) described on page 215 is
It can be diverted to drum application specifications for photoreceptors. Examples include direct roll coaters, offset gravure roll coaters, lot coaters, extrusion coaters, slot orifice coaters, curtain coaters, and the like.

The melting temperature of the thermoplastic resin at the time of coating is optimized depending on the composition of the thermoplastic resin used, but is usually in the range of 50 to 180 ° C. It is desirable that the preheating is performed using a sealed preheating device having an automatic temperature control means, and then the temperature is raised to an appropriate temperature in a short time at a position where the photoconductor is coated. By doing so, it is possible to prevent deterioration and coating unevenness due to thermal oxidation of the thermoplastic resin.

The coating speed depends on the fluidity of the thermoplastic resin at the time of thermal melting, the coater method, the amount of coating, and the like.
0 mm / sec is appropriate, more preferably 10 to 100 mm
/ Second range.

In the electrodeposition coating method, the above-mentioned thermoplastic resin (A) is electrodeposited or electrostatically adhered (hereinafter sometimes simply referred to as electrodeposition) on the surface of the photosensitive member in the form of resin particles. A uniform thin film is formed by heating or the like to form a transfer layer. Therefore, the particles of the thermoplastic resin (A) (hereinafter sometimes referred to as resin particles (AR)) need to have either a positive charge or a negative charge, and the Is arbitrarily determined by the chargeability of the photoconductor to be combined.

The resin particles can contain two or more resins as desired. For example, the glass transition point or softening point differs by at least 2 ° C., preferably by at least 5 ° C.
Kind of resin (for example, the resin having a high glass transition point (A)
By using resin particles containing at least two of H) and the resin (AL) having a low glass transition point in the same particle (hereinafter referred to as resin particles (ARW) in particular), the transferability is good, The transfer layer is excellent in durability, and the printing durability as a waterless printing plate can be improved.

In the resin particles (ARW), the resin (AH) /
It is preferable that the resin (AL) is contained in an existing ratio of 10 to 95/90 to 5 (weight ratio), particularly 30 to 90/70 to 10 (weight ratio). Resin (AH) presence ratio is 10
Weight percent or more, when performing offset printing as a waterless printing plate, maintain sufficient strength against ink touchness, mechanical force of the impression cylinder, etc. It is possible to obtain a printed material that does not cause a missing.
When the content ratio of the resin (AL) is 5% by weight or more, the transferability of the transfer layer is more favorably exhibited.

Further, at least two kinds of resins (AH) and resin (AL) contained in the resin particles (ARW) may exist in a simple mixed state in the particles, or the core portion and the shell portion may be mixed. The laminate may be formed like a core / shell structure made of different resins. The core is resin (AL)
And a resin particle having a core / shell structure in which the shell portion is made of one of the other resin and the resin (AH), whereby the transfer layer can be rapidly transferred under milder conditions. Can be implemented.

The resin particles (AR) are in a range satisfying the above-mentioned physical properties, and the average particle diameter is usually 0.01%.
μm to 1.0 μm, preferably 0.05 μm
m to 0.5 μm, more preferably 0.1 μm to 0.4 μm
m. The particles may be either resin particles dispersed in a non-aqueous system (wet type) or resin particles dispersed in an electrically insulating organic substance which is solid at room temperature and becomes liquid by heating (pseudo wet type). Preferably, non-aqueous dispersed resin particles that can easily and uniformly adjust the thickness of the transfer layer are used.

The resin particles can be produced by a conventionally known mechanical pulverization method or polymerization granulation method. For example, a method in which a dispersing polymer is used in combination and further dispersed by a wet disperser (for example, a ball mill, a paint shaker, a Keddy mill, a Dyno mill, etc.), and a material serving as a resin particle component and a dispersion assisting polymer (or a coating polymer) are previously kneaded. And then pulverized, and then dispersed in the presence of a dispersing polymer. Specifically, a method for producing a paint or a developer for electrostatography can be used,
For example, Kenji Ueki, “Paint Flow and Pigment Dispersion” Kyoritsu Shuppan (1971), DHSolomon “The Chemistry of Organic”
Film Formers, John Wiley (1967), Paintand Surfac
e Coating Theory and Practice ”, Yuji Harasaki“ Coating Engineering ”Asakura Shoten (1971), and Yuji Harasaki“ Basic Science of Coating ”(1977).

Further, as a polymerization granulation method, it can be easily produced by using a dispersion polymerization method. Specifically, the aforementioned “Advanced Technology of Ultrafine Polymers”, Chapter 2, “Recent Development of Electrophotographic Development Systems and Toner Materials”
Chapter 3, KEJ Barvett "Dispersion Polymerizatio
n in Organic Media, "John Wiley (1975) and other publications.

At least two different glass transition points are used.
In the case of obtaining resin particles (ARW) containing the same type of resin in the same particle, the resin can be easily produced by using, for example, a seed polymerization method. Specifically, first, fine particles are synthesized by the above-described conventionally known non-aqueous dispersion polymerization method, and then the fine particles are used as seeds. It can be produced by a method in which monomers are fed and polymerized.

In the polymerization granulation method, the polymer component (f) for improving the releasability is introduced into the resin (A) by dissolving in an organic solvent to be a thermoplastic resin and polymerizing the resin. The resin (A) is obtained by performing a polymerization reaction in the presence of a monomer corresponding to the polymer component (f) together with the insolubilized monomer.
Random copolymer resin particles (AR) copolymerized in
Can be easily obtained. Also, when a reactive group capable of undergoing a chemical reaction at the interface with the non-adhesive resin layer is introduced, a polymerization reaction is carried out in the presence of the reactive group-containing monomer in the same manner as described above, and a copolymer is formed in the resin (A). What is necessary is just to polymerize.

Further, to introduce the polymer component (f) into the polymer as a block, a method using a block copolymer containing the polymer component (f) as a block as a dispersion stabilizing resin to be used, or a method using a polymer. The monofunctional macromonomer having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ (preferably 3 × 10 ^{3 to} 1.5 × 10 ⁴ ) containing the united component (f) as a main repeating unit is used alone. By copolymerizing with the monomers, resin particles of a block copolymer can be easily obtained.
Another method is to use a polymer initiator (azobis polymer initiator or peroxide polymer initiator) containing the polymer component (f) as a main repeating unit, similarly to the block copolymerization. The combined resin particles can be obtained.

The non-aqueous solvent used in the production of the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or lower, and may be used alone or as a mixture of two or more. . Specific examples of such organic solvents include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol and benzyl alcohol, ketones such as acetone, methyl ethyl ketone, cyclohexanone and diethyl ketone, ethers such as diethyl ether, tetrahydrofuran and dioxane. ,
Carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, hexane, octane,
Aliphatic hydrocarbons having 6 to 14 carbon atoms such as decane, dodecane, tridecane, cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, methylene chloride, dichloroethane, tetrachloroethane, chloroform and methyl Halogenated hydrocarbons such as chloroform, dichloropropane, and trichloroethane are exemplified. However, the present invention is not limited to the compound examples described above.

By synthesizing the dispersed resin particles by a dispersion polymerization method in these non-aqueous solvent systems, the average particle diameter of the resin particles can be easily reduced to 1 μm or less, and the particle diameter distribution is very narrow and monodispersed. It can be.

These non-aqueous dispersion resin particles are subjected to a wet electrostatographic development method or a method of being electrophoresed by electrophoresis in an electric field, so that the dispersion medium used at the time of electrodeposition is electroless. It is preferable to adjust to a non-aqueous solvent system having a resistance of 10 ⁸ Ω · cm or more and a relative dielectric constant of 3.5 or less.

Specific examples of the insulating solvent include linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons, and halogen-substituted products thereof. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoper E, isoper G, isoper H, isoper L
(Isoper; trade name of Exxon), Shersol 7
0, Shelsol 71 (Shelsol; trade name of Shell Oil), Amsco OMS, Amsco 460 solvent (Amsco; trade name of American Mineral Spirits) or the like can be used alone or in combination. As the solvent used during polymerization granulation, it is preferable to use the above-mentioned insulating organic solvent from the beginning, but it is also possible to prepare by granulating with a solvent other than these solvents and then replacing the dispersion medium.

As another method for synthesizing a non-aqueous latex, a polymer component soluble in a non-aqueous solvent having an electric resistance of 10 ⁸ Ωcm or more and a dielectric constant of 3.5 or less and an insoluble in the solvent are used. The block copolymer composed of the polymer component can be provided as fine resin particles by wet dispersion in this solvent. That is, a block copolymer consisting of a soluble polymer component and an insoluble polymer component was converted into a polymer by using the above-described block polymer synthesis method in an organic solvent in which the block copolymer was previously dissolved. Then, it is a method of dispersing in a non-aqueous solvent for electrodeposition.

In order to electro-deposit the dispersed particles in the dispersion medium by electrophoresis, the resin particles are positively or negatively charged electro-detectable particles. Providing the resin particles with an electric detecting property can be achieved by appropriately utilizing the technique of a developer for wet electrostatography. Specifically, the above-mentioned “Recent development and practical application of electrophotographic development systems and toner materials”, pp. 139-148, edited by the Society of Electrophotography, “Basics and Application of Electrophotographic Technology”, pp. 497-505 (Corona Corporation,
1988), Yuji Harasaki "Electrophotography" 16 (No.2), 44 pages (19
77 years) and other additives. For example, British Patent Nos. 893,429 and 934,038, U.S. Pat. Nos. 1,122,397, 3,900,412, 4,606,989, and JP-A-60-179751, 60 -185963 and JP-A-2-13965.

The composition of the non-aqueous resin particle dispersion (latex) to be subjected to electrodeposition generally includes 0.1 to 30 g of particles mainly containing a thermoplastic resin in at least 1 liter of an electrically insulating dispersion medium. Dispersion stabilizing resin is 0.0
1 to 100 g, and the charge control agent to be added as needed is 0.1 g.
The range is from 0001 to 10 g.

Further, other additives may be added in order to maintain the dispersion stability and charge stability of the particles.
Rosin, petroleum resin, higher alcohols, polyethers, silicone oils, paraffin waxes, triazine derivatives and the like are mentioned. However, it is not limited to these. The upper limit of the total amount of these additives is regulated by the electrical resistance of the latex for electrodeposition. That is, if the electric resistance is lower than 10 ⁸ Ωcm, it is difficult to obtain a sufficient amount of the thermoplastic resin particles. Therefore, the amount of each additive is controlled within this limit.

The thermoplastic resin particles dispersed in the electrically insulating liquid after being formed into fine particles and charged as described above exhibit the same behavior as the electrophotographic wet developer. Thus, for example, electrophoresis can be performed on the surface of the photoreceptor using a developing device, for example, a slit developing electrode device described in “Basics and Application of Electrophotographic Technology”, pp. 275 to 285, supra. That is, particles mainly containing the thermoplastic resin (A) are supplied between the opposing electrodes provided so as to face the photoreceptor, and adhere to or adhere to the photoreceptor by electrophoresis according to a potential gradient applied from an external power supply. The film is formed by electrodeposition.

In general, when the particles are charged positively, a voltage is applied from an external power source between the conductive support of the photoreceptor and the developing electrode of the developing device so that the photoreceptor side has a negative potential. Then, the particles are electrostatically electrodeposited on the surface of the photoreceptor. Electrodeposition can also be performed by wet toner development using a normal electrophotographic process. That is, as shown in the prerequisite "Basics and Application of Electrophotographic Technology", pp. 46-79, the photosensitive member is uniformly charged, and then the normal wet toner development is performed.

On the other hand, when a resin particle dispersed in a medium which is liquefied by heating is used, a preferred medium is a solid at ordinary temperature, and a heating temperature of 30 to 80 ° C., preferably 4 to 80 ° C.
It is an electrically insulating organic compound which becomes a liquid at 0 to 70 ° C, and suitable compounds therefor have a freezing point of 30 to 80 ° C.
Paraffins, waxes, low molecular weight polypropylene having a freezing point of 20 to 80 ° C, tallow having a freezing point of 20 to 50 ° C, and hardened oil having a freezing point of 30 to 80 ° C. These can be used alone or in combination. Other necessary characteristics are the same as those of the electrodeposited resin particle dispersion used in the wet development method.

Further, the resin particles subjected to the pseudo-wet method include a so-called core in which a resin component having a high glass transition point or a high softening point which does not soften at a temperature at which the medium to be supplied is liquefied forms an outer shell of the particles. A state in which the dispersed resin particles are stably dispersed without being fused by heating by using shell-type particles (a resin having a low glass transition point in the core and a resin having a high glass transition point in the shell). Can be maintained.

The adhesion amount of the thermoplastic resin particles on the photoreceptor can be arbitrarily adjusted by the applied voltage of the external bias, the charging potential of the photoreceptor, the processing time and the like. After the electrodeposition, the developer is wiped off with a squeeze using a known rubber roller, gap roller, reverse roller, or the like. Methods such as corona quiz and air squeeze are also known. In addition, cold or warm air,
Alternatively, it is dried by an infrared lamp or the like, and preferably a thermoplastic resin particle is formed into a film to form a transfer layer.

Next, formation of a transfer layer by a transfer method will be described. The transfer method is to transfer a transfer layer formed on a peelable support represented by release paper to the surface of a photoreceptor.

The release paper on which the transfer layer is formed is usually in the form of a roll or a sheet and can be easily supplied to an electrophotographic plate making apparatus. As the release paper, any conventionally known release papers can be used. For example, a new adhesive (adhesive) technology and its use / development materials of various applied products (publishing;
May 20, 2013), Product Encyclopedia of All Paper Guide Papers, Volume 1, Cultural Industry Edition (Published by Paper Industry Times, Inc.
On December 1, 1983).

More specifically, the release paper is formed by applying a release agent mainly composed of silicone, unbleached clupak paper laminated with a polyethylene resin, high-grade paper or kraft paper precoated with a solvent-resistant resin, or undercoat. Or a PET film coated on glassine paper. Silicone is generally used in the form of a solvent.
After applying and drying with a gravure roll, reverse roll, wire bar, etc. at a concentration of 7%, it is heat-treated at 150 ° C or higher,
Is cured. The coating amount is about 1 g / m ² .

As the release paper, those commercially available from paper manufacturers for tapes, labels, for the forming industry and for the cast coat industry can be used. For example, Separate Paper (Oji Paper Co., Ltd.), King Leeds (Shikoku Paper Co., Ltd.), Sun Release (Sanyo Kokusaku Pulp Co., Ltd.)
And NK High Release (manufactured by Nippon Kaishi Paper Co., Ltd.).

In order to form a transfer layer on release paper, a transfer layer composition containing a thermoplastic resin (A) as a main component is applied and formed by bar coating, spin coating, spray coating, or the like according to a conventional method. This is easily done. Further, the hot melt coating method or the electrodeposition coating method may be used.

In order to thermally transfer the transfer layer on the release paper onto the photoreceptor, a usual thermal transfer method can be used. That is, the release paper holding the transfer layer may be pressed against the photoreceptor on which the toner image has been formed, and the transfer layer may be thermally transferred. The conditions for transferring the transfer layer from the release paper to the photoreceptor surface are preferably as follows. Roller nip pressure is preferably 0.1-10 kg
f / cm ² , more preferably 0.2 to 8 kgf / cm ² , and the temperature at the time of transfer is preferably 25 ° C to 100 ° C, more preferably 40 ° C to 80 ° C. The transport speed is preferably 0.5 to 200 mm / sec, more preferably 10 to 150 mm
/ Sec.

Next, formation of a transfer layer by the ink jet method will be described. In the ink-jet method, a non-aqueous solution of a thermoplastic resin (A) or a non-aqueous dispersion of resin particles dispersed in a thermoplastic resin (A) is uniformly applied to the surface of a photoreceptor by an ink-jet method, and then adsorbed or adhered by drying. It is done by letting it. The ink-jet method is achieved, for example, by the principle and means described in Shin Ono, “Non-impact Printing”, CMC (1986). For example, continuous injection type Sweet method, Hertz
Systems, intermittent jet type Winston system, ink-on-demand type pulse jet system, bubble jet system, ink mist type mist system and the like.

In each case, a solution or dispersion containing the resin (A) instead of the ink is used by filling the ink tank and / or the ink head cartridge. Normal ink viscosity is 1-10 cP, surface tension is 30-60 dyne / cm
If necessary, a surfactant or the like may be added, and the ink may be heated. Conventional ink jet printers use a three-head orifice system for finer character drawing.
Although it is about 0 to 100 μm and the particle size of the flying ink is about the same, in the present invention, it may be larger. In this case, the amount of ink to be ejected increases, so that the time required for application can be reduced. Further, the use of a multi-nozzle is extremely effective for shortening the coating time.

A non-fixed toner image is formed on the electrophotographic photosensitive member provided with the above-described transfer layer by using a liquid developer by a usual electrophotographic process.

In the present invention, the non-fixed toner image is
It refers to a toner image in which the adhesive force to the transfer layer (T) on the lithographic printing plate support is smaller than the adhesive force of the non-adhesive resin layer provided later to the transfer layer (T). Any configuration having such characteristics can be used. Preferably, the non-fixed toner image has an adhesive strength with the lithographic printing plate support of 20 g · f or less, particularly 10 g · f or less, based on the aforementioned adhesive strength.

The formation of a non-fixed toner image can be easily achieved by omitting the fixing process by heat using a conventionally known liquid developer. Further, by improving the toner image forming material, it is possible to satisfy the above physical properties. It is particularly advantageous when a certain amount of heat is conducted from the viewpoint of the electrophotographic process or the subsequent process of forming the non-adhesive resin layer. Specifically, the following methods (1) to (5) are mentioned.

The glass transition point of the resin constituting the toner particles is selected to be at least 40 ° C. or higher, preferably 80 ° C. or higher. Cured resin particles having an internal crosslinked structure are used as toner particles (for example, see JP-A-5-34998 and JP-A-5-15).
No. 0562). The proportion of the pigment in the colored toner particles composed of the pigment and the binder resin is 50% by weight or more, preferably 80% by weight or more (particles containing only the pigment may be used).

As long as the above conditions are satisfied, toner image formation by an electrophotographic process may be performed by any conventionally known method and is not limited. For specific aspects,
Examples include the methods described in books and reviews exemplified in the description of the photoreceptor.

As the developer used in the present invention, a conventionally known liquid developer for electrophotography can be used. For example,
"Basics and Application of Electrophotographic Technology", pp. 497-505, supervised by Koichi Nakamura, "Development and Practical Use of Toner Materials", Chapters 3 and 4
Chapter (published by Nippon Kagaku Kagaku Co., Ltd., 1985), Moto Machida, "Recording Materials and Photosensitive Resins", pp. 107-127 (1983), Gakkai Shuppan Center, Electrographic Society of Japan, "Imaging No. 2-5, "Development / Fixing / Electrification / Transfer of Electrophotography", edited by the Society of Electrophotography, "Imaging No. 1, Development of Electrophotography", pp. 34-42, The Society of Electrophotography (1977), Ed. 397-408, Management Development Center (1989), Yuji Harasaki "Electrophotography" 16 (No.2), 44 pages (1977)
Etc. are shown.

The basic structure of a specific liquid developer is as follows: an electrically insulating organic solvent such as an isoparaffinic aliphatic hydrocarbon: Isopar H, Isopar G (manufactured by Esso Corporation), Shellsol 70, and Shellsol 71 (manufactured by Shell Corporation). ), IP
-Solvent 1620 (manufactured by Idemitsu Petrochemical) or the like as a dispersion medium, and using an inorganic or organic pigment or dye as a colorant in combination with a resin for imparting dispersion stability and chargeability as necessary. Thus, various additives are added as required to enhance the charge characteristics or improve the image characteristics.

As the colorant, known dyes and pigments are arbitrarily selected. For example, benzidine, azo (including metal-containing), azomethine, xanthene, anthraquinone, triphenylmethane, phthalocyanine System (including metals), titanium white, zinc white, nigrosine, aniline black, carbon black and the like.

As the resin, a resin insoluble in the above-mentioned solvent,
A resin soluble in the above-mentioned solvent for stabilizing the dispersion of the above-mentioned dye / pigment or insoluble resin may be mentioned, but polymers in which an insoluble resin component and a soluble resin component are bonded in the same polymer chain are also used. These resins are not particularly limited, and are arbitrarily selected from conventionally known resins. For example, various resins described as the binder resin for the photoconductor can be used. The size of the colored particles or the dispersed resin particles dispersed in the dispersion medium is preferably 0.05 to 5 μm, more preferably 0.1 to 3 μm in terms of the average particle size.

The particles are positively or negatively chargeable electrophoretic particles for electrophoresis of the dispersed particles in the dispersion medium. In order to impart or adjust the electrostatic property, other additives are used. Is also performed. For example, a metal salt of an alkyl sulfosuccinic acid, a metal salt of a naphthenic acid, a metal salt of a higher fatty acid, a metal salt of an alkyl benzene sulfonic acid, a metal salt of an alkyl phosphate, a copolymer containing a lecithin, poly (vinylpyrrolidone), a hemimaleamide component, Malon indene resin, petronate metal salt, abietic acid-modified maleic resin and the like can be mentioned.

Further, for example, British Patent 893,429
No. 934,038, U.S. Pat. No. 1,122,397
No. 3,900,412, 4,606,989
No., JP-A-60-179751, JP-A-60-18596
No. 3, JP-A-2-13965, JP-A-60-6176
No. 5, etc. may be used.

Further, other additives may be added in order to maintain the dispersion stability and charge stability of the particles and to improve the transferability. For example, rosin, petroleum resins, higher alcohols, polyethers, Polyethylene glycols, polypropylene glycols, silicone oils, paraffin waxes, triazine derivatives, fluororesins, acrylate resins containing organic bases described in JP-A-59-95543, JP-A-59-160152 and the like. No.
The upper limit of the total amount of these additives is regulated by the electric resistance of the liquid developer. That is, the electric resistance is 10 ⁸ Ω · c
If it is lower than m, it is difficult to obtain a sufficient amount of toner particles attached, so the amount of each additive is controlled within this limit.

The amounts of the main components of the liquid developer are generally as follows. The amount of the toner particles containing a resin (and a colorant used as desired) as a main component is preferably 0.5 parts by weight to 50 parts by weight with respect to 1000 parts by weight of the carrier liquid. If the amount is less than 0.5 parts by weight, the image density becomes insufficient, and if it exceeds 50 parts by weight, fogging to a non-image portion is apt to occur. The carrier liquid-soluble resin for dispersion stabilization is also used as needed, and 0.5 parts by weight to 1000 parts by weight of the carrier liquid is used.
About 100 parts by weight can be added. The charge control agent is preferably used in an amount of 0.001 to 1.0 part by weight based on 1,000 parts by weight of the carrier liquid. If desired, various additives may be added. The upper limit of the total amount of these additives is regulated by the electric resistance of the liquid agent. That is, the electric resistance of the liquid developer from which the toner particles have been removed is 10 ⁹ Ωcm.
When the value is lower, it is difficult to obtain a high quality continuous tone image. Therefore, the amount of each additive is controlled within this limit.

As specific examples of the method for producing a liquid developer,
A method of producing colored particles by mechanically dispersing a colorant and a resin using a disperser such as a sand mill, a ball mill, a jet mill, and an attritor is disclosed in, for example, Japanese Patent Publication No. 35-55.
No. 11, 35-13424, and 50-40017
No. 49-98634, No. 58-129438,
It is described in JP-A-61-180248.

There is also a method in which dispersed resin particles are produced by using a conventionally known non-aqueous dispersion polymerization method, and separately mixed with coloring particles obtained by wet-dispersing a pigment together with a dispersant. Specific examples using the dispersed resin particles by the non-aqueous dispersion polymerization method are described in, for example, U.S. Pat. No. 3,990,980, JP-B-4-31109, and JP-A-6-40229. As another method for producing the colored particles, a method for further coloring the dispersed resin particles may be mentioned.

As one method of coloring, JP-A-57-4
As described in No. 8738 and the like, there is a method of dyeing a dispersion resin with a preferable dye. Also, JP-A-53-5
No. 4029, a method of chemically bonding a dispersing resin and a dye, and a method of preliminarily containing a pigment in the production by polymerization granulation as described in JP-B No. 44-22955. There is a method of using a monomer to obtain a dye-containing copolymer.

The thickness of the non-fixed toner image is at least 0.5
μm, and preferably about 2 to 3 μm. Within this range, the removal of the non-adhesive resin layer in the toner image area is facilitated, and it is advantageous without wasting an excessive amount of toner.

In the present invention, the toner image area formed on the transfer layer on the electrophotographic photosensitive member is transferred together with the transfer layer onto a lithographic printing plate support by a contact transfer method. That is, the toner image formed on the photoreceptor is peeled and transferred onto the lithographic printing plate support by contact transfer under heating and / or pressure conditions together with the transfer layer. For this transfer, a known method and apparatus can be used.

For example, thermal transfer is performed by passing a lithographic printing support between a photoreceptor, a transfer backup roller and a peeling backup roller. The nip pressure between the photoreceptor and the transfer backup roller is preferably 0.1 to 10 kgf / cm ² , more preferably 0.2 to 10 kgf / cm ² .
It is 5 kgf / cm ² . As the roller pressing means, an air cylinder using a spring or compressed air at both ends of the roller shaft can be used. The transport speed is preferably 10 to 300 mm / sec, more preferably 50 to 200 mm / sec.
mm / sec. The transport speed may be different between the electrophotographic process and the thermal transfer process. The temperature at the time of transfer is preferably 30 to 80C, more preferably 35 to 60C, on the surface of the photoreceptor. The photoconductor may be heated to a desired temperature in advance. For this purpose, it is preferable to use non-contact heating means such as an infrared line heater or a flash heater.

The surface temperature of the transfer backup roller is preferably from 50 ° C. to 140 ° C., more preferably from 70 ° C. to
120 ° C. On the other hand, the peeling backup roller may be cooled (preferably at a temperature of 10 to 50 ° C.) to make the transfer from the photoreceptor to the printing plate support easier.

As the lithographic printing plate support used in the present invention, a support conventionally used for offset printing plates can be used as it is. Specifically, a bimetal plate such as a plastic sheet, paper with printing durability, paper laminated with a plastic sheet or metal foil, aluminum plate, zinc plate, copper-aluminum plate, copper-stainless plate, chrome-copper plate, Chrome-copper-aluminum plate, chrome-lead-iron plate,
A substrate such as a trimetal plate such as a chromium-copper-stainless plate is used. Its thickness is 0.1 ~ 3mm, especially 0.1 ~
1 mm is preferred.

On the surface of the lithographic printing support, an adhesive layer made of a resin such as a thermoplastic resin, an adhesive or an adhesive similar to that used for the transfer layer (T) can be provided. As a result, the contact between the transfer layer (T) and the transfer layer (T) becomes an adhesion layer, so that the adhesion between the two layers is improved, and the transfer of the toner image and the transfer layer (T) from the photoreceptor regardless of the type of the support. The transferability is improved, the transfer temperature is lowered, and the transfer speed is further improved.

The resin constituting the adhesive layer provided on the lithographic printing plate support preferably has a glass transition point of 80 ° C. or lower or a softening point of 90 ° C. or lower. Specifically, the resins described in the transfer layer (T) satisfying these thermophysical properties are exemplified. The thickness of the adhesion layer is preferably 0.1 to 10 μm,
More preferably, it is in the range of 0.2 to 2 μm. The adhesion layer may be coated in advance, or may be provided in an apparatus for performing the method of the present invention by using the same method as that for forming the transfer layer described above.

After transferring the transfer layer and the toner image layer onto the lithographic printing plate support as described above, a non-tacky resin layer is provided on the transfer layer. The non-adhesive resin layer used in the present invention is a non-adhesive resin layer having an adhesive force to the transfer layer (T) larger than the adhesive force between the toner image and the lithographic printing support (preferably, the adhesive force to the transfer layer is 200 g · f). This is a resin layer that forms an ink repellent surface that does not cause background stain due to ink adhesion when printed as a waterless printing plate and has good rub resistance.

Specific means for providing a difference in adhesive strength between the image area and the non-image area include, for example, the following. I. The non-adhesive resin layer has a specific configuration. i) The non-adhesive resin layer contains a specific component. ii) The non-adhesive resin layer contains an adhesive resin other than the non-adhesive resin. iii) A laminated structure in which the non-adhesive resin layer is functionally separated into an adhesive layer and an ink repellent layer.

II. A transfer layer having good affinity with the non-adhesive resin layer is used. III. The non-adhesive resin layer and the transfer layer are chemically bonded at the interface.

The above means may be used alone or in combination of two or more. These specific means will be described later.

The ink repellent surface of the non-adhesive resin layer may be any as long as it forms a surface state having a coating film surface energy of 30 erg · cm ⁻¹ or less. By adjusting to this range, it is possible to obtain a clear print without fogging in the non-image portion without causing ink adhesion. The surface energy of the coating film is preferably 28 erg · cm ⁻¹ or less, more preferably 25 erg · cm ⁻¹ or less, and even more preferably 15 to 2 erg · cm ^−1.
It is 5 erg · cm ⁻¹ .

One method for adjusting the surface energy of the coating film on the ink repellent surface of the non-adhesive resin layer to the above range is to include a non-adhesive resin such as a silicone resin or a fluorine resin in the layer. It is mentioned. In the present invention, a resin containing both a fluorine atom and a silicon atom can be used as the non-adhesive resin. The non-adhesive resin of the present invention is preferably a silicone resin.

The fluororesin is a resin mainly containing a polymer component containing a substituent containing a fluorine atom.
This substituent may be incorporated into the polymer main chain of the polymer, or may be contained as a substituent on the side chain of the polymer.

Examples of the substituent containing a fluorine atom include the following monovalent or divalent organic residues. _{-C n (F) 2n + 1} (n is 1 to 22 integer), - CFH _2, integer _{-CF 2) m CF 2 H (} m is 1 to 17), - CF
_2- , -CFH-

These fluorine-containing organic residues may be constituted in combination, and in that case, they may be directly bonded or combined via another linking group. Specific examples of the linking group include divalent organic residues, and include —O—, —S—, —N (d ¹ ) —, and —CO—.
-, - SO -, - SO 2 -, - COO -, - OCO-,
-CONHCO -, - NHCONH -, - CON (d 1)
A divalent aliphatic group or a divalent aromatic group, which may have a bonding group selected from —, —SO ₂ N (d ¹ ) — and the like,
Or an organic residue composed of a combination of these divalent residues is exemplified. Here, d ¹ represents an alkyl group having 1 to 3 carbon atoms. The fluorine atom-containing polymer component is preferably contained in an amount of 80 to 100 parts by weight based on all polymer components of the resin.

Further, the fluororesin may contain a curable functional group, and its content is 1 to 20% by weight. Examples of the curable functional group to be contained include those described for a silicon-based resin described below. The weight average molecular weight of the fluororesin is preferably 5 × 10 ³ to 1 × 10 ⁶ , more preferably 2 × 10 ^{4 to} 5 × 10 ⁵ .

The silicone resin is a resin mainly containing a polymer component containing a silicon atom. In the present invention, a polymer mainly composed of a component having a repeating unit of an organosiloxane structure represented by the following general formula (I) can be mentioned as a specific example.

[0169]

Embedded image

In the formula (I), R ₁ and R ₂ may be the same or different and each represents an aliphatic group, an aromatic group or a heterocyclic group.

R ₁ and R ₂ may be the same or different from each other, and are preferably a linear or branched alkyl group having 1 to 18 carbon atoms which may be substituted, for example, a methyl group, an ethyl group, a propyl group. , Butyl group, hexyl group, heptyl group,
Octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, 2-fluoroethyl, trifluoromethyl, 2-
Chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, 2-methylcarbonylethyl group, 2,3-dimethoxypropyl group,-(CH
_{2) p C r F 2r +} 1 group (wherein p is an integer of 1 or 2, r is 1 to 1
2 represents an integer) _{group, - (CH 2) p -} (CF 2) s -R '
Group (wherein s is an integer from 1 to 12, R 'is -CFHCF ₃ or -CFHCF represent ₂ H), etc.}, an optionally substituted alkenyl group having 4 to 18 carbon atoms (e.g., 2-methyl -
1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, decenyl group , A dodecenyl group, a tridecenyl group, a hexadecenyl group, an octadecenyl group, a linoleyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-
Phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.),
An alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, cyclopentyl group, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, polyfluorohexyl group, methylcyclohexyl group, methoxycyclohexyl group, etc.) An aromatic group having 6 to 12 carbon atoms which may be substituted (for example, a phenyl group, a naphthyl group, a tolyl group,
Xylyl group, propylphenyl group, butylphenyl group,
Octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group,
Fluorophenyl, chlorophenyl, difluorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, propioamidophenyl, A fluoromethylphenyl group), or a nitrogen atom,
A heterocyclic group which contains at least one atom selected from an oxygen atom and a sulfur atom and which may be substituted and may be condensed (for example, a heterocyclic ring includes a pyran ring, a furan ring, a thiophene ring, a morpholine ring , A pyrrole ring, a thiazole ring, an oxazole ring, a pyridine ring, a piperidine ring,
Pyrrolidone ring, benzothiazole ring, benzoxazole ring, quinoline ring, tetrahydrofuran ring, etc.).

Particularly preferably, R ₁ and R ₂ are methyl groups. The dimethylsiloxane unit in which R ₁ and R ₂ are methyl groups is preferably 60% by weight or more, more preferably 7% by weight, based on the total amount of all organosiloxane units in the silicone resin.
5% by weight or more. As a result, the resilience of the printing ink is sufficiently maintained, and the occurrence of background contamination is suppressed.

Further, it is preferable to contain a specific component for improving the adhesion between the non-tacky resin layer and the transfer layer (T) on the lithographic printing plate support. As such a specific component, R ₁ or a substituent selected from the above-mentioned substituted alkyl group (for example, a halogen or cyano group substituent), an optionally substituted aralkyl group, an aromatic group, and a heterocyclic group in the silicon-based resin may be used. Those having as R ₂ can be mentioned. Further, those containing a polar group such as a carboxyl group, a hydroxyl group, a mercapto group, a phosphono group, an amide group in the substituents of R ₁ and / or R ₂ , or a ureido group (—NH
Examples thereof include those containing a divalent linking group such as CONH-), a thioether group (-S-), and a urethane group (-NHCOO-).

The content of the organosiloxane unit having such a substituent is preferably less than 40% by weight, more preferably 25% by weight, of the total amount of the organosiloxane units.
Is less than. A good dimethylsiloxane unit as a printing ink repellent component and the other organosiloxane unit for improving the adhesiveness described above may be present in the above-described ratio. It is possible to improve the performance. Each polymerization unit may be any of a random copolymer, a block copolymer, and a star copolymer, and is not limited. The weight average molecular weight of the silicone resin is preferably 5 × 10 ³ to 1 × 10 ⁶ , more preferably 2 × 10 ^{4 to} 5 × 10 ⁵ .

In the non-adhesive resin layer of the present invention, the resin layer forms a crosslinked structure before the step of selectively removing the transfer layer (T) and the non-adhesive resin layer in the toner image area, and is cured. Preferably, the conductive resin layer is formed. As a result, the mechanical strength of the resin layer film is improved, the non-image portion is not lost in the step of removing the toner image portion, the durability against mechanical external force during printing is maintained, and the printing durability is improved. Is improved.

In the present invention, in order to obtain a cured non-adhesive resin layer, there are a method of providing a resin layer containing a previously cured non-adhesive resin and a method of curing after forming the non-adhesive resin layer. In the above curing method, any conventionally known method can be used for curing the non-adhesive resin layer to form a crosslinked structure inside the layer. Less than,
A description will be given using a silicone resin as an example.

For example, a method of self-crosslinking the silicone resin itself, a method of crosslinking the silicone resin with various crosslinking agents or curing agents, and the like, and a combination of some of these methods may be used. In addition, the reaction mode of the crosslinking reaction between the polymers of the resins may be any conventionally known chemical bonding reaction, or may be a combination of several reaction modes.

Specific examples of these reaction modes include the following reactions i) to iv).

I) Polyvalent metal ions (eg, Ca, Mg, Ba, Al, Zn, F) which coexist with acidic groups (carboxyl group, sulfo group, phosphono group, etc.) contained in the resin.
e, a cation of a polyvalent metal such as Sn, Zr, Ti, etc.) and crosslinking by ionic bonding by a chelate reaction.

Ii) Organic reactive groups [specifically, a hydroxyl group, a thiol group, a halogen atom (for example, a chlorine atom,
Bromine atom, iodine atom), carboxyl group, acid anhydride group, amino group, isocyanate group, protected isocyanate group (blocked isocyanate group), acid halide group, epoxy group, imino group, formyl group, diazo group Combination of reactive groups selected from, azide groups and the like]], cross-linking by chemical bond by addition reaction, substitution reaction or elimination reaction.

Iii) A self-coupling group [eg, -CON
HCH_TwoOR₁'Group (R₁'Represents a hydrogen atom or an alkyl group
The following groups (R_Two', R_Three′ Is the same but different
Each represents a hydrogen atom or an alkyl group, or
Is R_Two'And R_Three'Combine to form a 5- to 6-membered alicyclic ring
Cinnamoyl group, -Si (R_Four′)_s(OR
_Five′)_tBase ｛R_Four'Is an alkyl group, alkenyl group, aryl
A group represented by R_Five'Represents an alkyl group, and s is 0 or 1-2.
And t represents an integer of 1 to 3. Where s + t = 3｝
Self-crosslinking.

[0182]

Embedded image

Iv) Polymerizable double bond group or triple bond group
Crosslinking by addition polymerization reaction. As a polymerizable double bond group
For example, CH_Two= C (p) COO-, C (CH_Three)
H = CHCOO-, CH_Two= C (CH_TwoCOOH) COO
-, CH_Two= C (p) CONH-, CH_Two= C (p) CO
NHCOO-, CH_Two= C (p) CONHCONH-,
C (CH_Three) H = CHCONH-, CH_Two= CHCO-,
CH_Two= CH (CH_Two) _nOCO- (n is an integer of 0 or 1 to 3
Number), CH_Two= CHO-, CH_Two= CHC₆H_Four-, CH_Two
= CH-S- and the like (p is -H or -CH_Three
Represents). Further, as the polymerizable triple bond group, the same as above
And those having a linking group of

These arbitrarily selected reactive groups can be contained in the silicone resin. As the content form, specifically, (a) one or both of the substituents R _{1 and} R ₂ of the siloxane unit represented by the repeating unit of the general formula (I) are directly substituted with a reactive group, Or contained in either or both of R _{1 and} R ₂ of the substituent,
(b) contained in a copolymer component of another polymer chain bonded to the polymer chain of the siloxane unit by a block, and (c) bonded to the terminal of the polymer chain of the silicone resin (other linking groups are May be combined via the same).

Further, a conventionally known bridging reaction inherent to organosiloxane polymers is also an effective reaction. For example, "Silicone Handbook" edited by Kunio Ito, Nikkan Kogyo Shimbun (1990)
Annual), edited by Makoto Kumada and Tadashi Wada, "Latest Silicone Technology-
Development and Application- "CMC Co., Ltd., published in 1986). Examples thereof include the following groups (where R ₁ ″ to R ₅ ″ each represent an alkyl group).

[0186]

Embedded image

As described above, the curable reactive group may be contained in the polymer chain as a random copolymer together with the siloxane unit represented by the general formula (I) exhibiting ink repellency, It may be a block copolymer in which a polymer is formed by combining an ink repellent block and a curable block. Examples of the block copolymer include a graft type, an AB type block (including an ABA type) and a star type. In the case of these block copolymers, the ink-repellent block component is preferably contained in an amount of at least 30% by weight, more preferably at least 50% by weight, based on all the polymer components.

As the crosslinking agent or curing agent capable of forming a crosslinked structure with the silicone resin, any of low molecular compounds, oligomers and polymers known as heat, light or moisture curable compounds can be used. Or two or more of them may be used in combination.

Specific examples of the compounds used as the crosslinking agent or the curing agent are described in Shinzo Yamashita and Tosuke Kaneko, “Handbook of Crosslinking Agents” Taiseisha (1981), edited by the Society of Polymer Science, “Polymer Data Handbook, Basic Edition”. Baifukan (1986),
Tsuyoshi Endo “Refinement of thermosetting polymer” CMC Corporation (1986)
Annual), Yuji Harasaki, "The latest binder technology handbook" No. II-1
Chapters, General Technology Center (1985), Takayuki Otsu "Synthesis and Design of Acrylic Resins and Development of New Applications", Chubu Management Development Center Publishing Division (1985), Compounds cited in the reviews such as "Silicone Handbook" mentioned above. Can be

For example, organic silane compounds (for example, vinyltrimethoxysilane, vinyltriethoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, vinyltrichlorosilane, vinyltris (t-butylperoxide) silane, γ-
(Β-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, silane coupling agent, etc.), polyisocyanate-based compounds (for example,
Toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate,
Polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
High-molecular-weight polyisocyanate, etc.), polyblocked isocyanate-based compound protecting the isocyanate of the above-mentioned polyisocyanate-based compound (examples of compounds used for protecting isocyanate groups include alcohols, β-diketones, β- Ketoesters, amines, etc.), polyol compounds (eg, 1,4-butanediol, polyoxypropylene glycol, polyoxyethylene glycol, 1,1,1-trimethylolpropane, etc.), polyamine compounds (eg, ethylenediamine) , Γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), titanate coupling compounds (eg, tetrabutoxytitanate, tetrapropoxytitanate) Isopropyl tristearoyl titanate), aluminum coupling compounds (eg, aluminum butyrate, aluminum acetyl acetate, aluminum oxide octate, aluminum tris (acetyl acetate), etc.), polyepoxy group-containing compounds, and epoxy resins (eg, edited by Hiroshi Kakiuchi) "New epoxy resin" Shokodo (1985), "Epoxy resin" edited by Kuniyuki Hashimoto "Compounds described in Nikkan Kogyo Shimbun (1969)", melamine resin (for example, Ichiro Miwa,
Edited by Hideo Matsunaga, “Urea Melamine Resin”, compounds described in Nikkan Kogyo Shimbun (1969), etc., and poly (meth) acrylate compounds (eg, Shin Okawara, Takeo Saegusa, Toshinobu Higashimura “Oligomers” Kodansha (1976), Emori Omori “Functional Acrylic Resins”, compounds described in Techno System (1985), and the like.

The polyfunctional monomer (also referred to as polyfunctional monomer (d)) containing two or more polymerizable functional groups to be coexistent or the polymerizable functional group of the polyfunctional oligomer may be, for example, Specifically, CH ₂ ＣＨCHCH ₂ —, CH ₂ ＣＨCH
_{COO-, CH 2 = CH-, CH} 2 = C (CH 3) -COO
_{-, CH (CH 3) =} CHCOO-, CH 2 = CHCON
_{H-, CH 2 = C (CH} 3) -CONH-, CH (CH 3)
_{= CHCONH-, CH 2 = CHOCO-,} CH 2 = C
_{(CH 3) -OCO-, CH 2} = CHCH 2 OCO-, CH
_{2 = CHNHCO-, CH 2 = CHCH} 2 NHCO-, C
_{H 2 = CHSO 2 -, CH} 2 = CHCO-, CH 2 = CHO
—, CH ₂ ＣＨCHS— and the like. The same or different ones of these polymerizable functional groups are
Any number of monomers or oligomers may be used.

Specific examples of the monomer having two or more polymerizable functional groups include, as monomers or oligomers having the same polymerizable functional group, styrene derivatives such as divinylbenzene and trivinylbenzene: polyhydric alcohols. (For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 20
0, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc., or polyhydroxyphenol (eg, hydroquinone, resorcin, catechol) And their derivatives)
Methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers: dibasic acids (eg, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) Vinyl esters, allyl esters, vinyl amides or allyl amides: polyamines (eg, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) and carboxylic acids containing vinyl groups (eg, methacrylic acid, acrylic Acid, crotonic acid, allyl acetic acid, etc.).

Examples of monomers or oligomers having different polymerizable functional groups include, for example, carboxylic acids containing vinyl groups (eg, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, allyloyl) Ester derivatives or amide derivatives containing a vinyl group such as a reactant of propionic acid, itaconiloyl acetic acid, itaconiloyl propionic acid, carboxylic anhydride and the like or an alcohol or amine (for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate) , Allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloyl propionate, allyl methacryloyl propionate, vinyl oxycarbonyl methyl methacrylate, vinyl acrylate Loxycarbonylmethyloxycarbonyl ethylene ester, N-allylacrylamide, N-allylmethacrylamide, N-allylitaconamide, methacryloylpropionylallylamide, etc.) or amino alcohols (for example, aminoethanol, 1-aminopropanol, 1-amino) Butanol,
Condensates of 1-aminohexanol, 2-aminobutanol, etc.) with a carboxylic acid having a vinyl group.

In the present invention, a reaction accelerator may be added as necessary in order to accelerate the crosslinking reaction of the non-adhesive resin layer. In the case of a reaction mode in which a crosslinking reaction forms a chemical bond between functional groups, for example, organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), phenols (phenol, chlorophenol, Nitrophenol, cyanophenol, bromophenol, naphthol, dichlorophenol, etc.), organometallic compounds (acetylacetonato zirconium salt, acetylacetone zirconium salt, acetylacetocobalt salt, dibutoxytin dilaurate, etc.), dithiocarbamic acid compounds (diethyldithiocarbamate, etc.) ), Thiuram disulfide compounds (such as tetramethylthiuram disulfide), carboxylic anhydrides (phthalic anhydride, maleic anhydride, succinic anhydride, butylsuccinic anhydride, 3,
3 ', 4,4'-tetracarboxylic acid benzophenone dianhydride, trimellitic anhydride, etc.). When the crosslinking reaction is a polymerization reaction mode, a thermal polymerization initiator (a peroxide, an azobis compound, a photopolymerization initiator and a sensitizer (for example, P. Walker, NJ Webers et al., J. Phot.
Sci. 18, 150 (1970), Katsumi Tokumaru, Shin Okawara, "Sensitizers"
It is described in reviews and books such as Kodansha (1987), and specifically, carbonyl compounds, organic sulfur compounds,
Examples thereof include azine compounds and azo compounds.

Examples of the silicone resin curing accelerator or reaction control agent include a platinum catalyst, methylvinyltetrasiloxane, and acetylene alcohols.

The curing conditions for curing these films are, of course, appropriately selected according to the characteristics of the combined materials. In order to perform heat curing, for example, 60 ° to 15 °
Treat at 0 ° C. for 5 to 120 minutes. When the above-mentioned reaction accelerator is used in combination, the treatment can be performed under milder conditions.

In order to cure a specific functional group in the resin by light irradiation, a step of irradiating light with a chemically active light ray may be included. The chemical actinic ray may be any of visible ray, ultraviolet ray, far ultraviolet ray, electron beam, X-ray, γ ray, α ray, etc., but is preferably ultraviolet ray, more preferably wavelength 31
It is a light ray in the range of 0 nm to 500 nm. Generally, a low-pressure, high-pressure or ultra-high-pressure mercury lamp, a halogen lamp, or the like is used. The light irradiation treatment can usually be performed sufficiently by irradiation from a distance of 5 cm to 50 cm for 10 seconds to 10 minutes.

The non-adhesive resin preferably accounts for 60% by weight or more, particularly 80% by weight or more of the non-adhesive resin layer.

The non-adhesive resin layer used in the present invention contains, together with the above-mentioned non-adhesive resin, another resin within a range that does not impair the ink repellency, thereby improving the adhesion between the transfer layer and the non-adhesive resin layer. It can also be done. As other resins that can be used in combination, conventionally known various resins can be used as long as the resins have a softening point of 30 ° C. or higher.

More specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and Polymers and copolymers of the derivatives, butadiene-styrene copolymer, isoprene-styrene copolymer, butadiene-unsaturated carboxylic acid ester copolymer, acrylonitrile copolymer, methacrylonitrile copolymer, alkyl vinyl ether copolymer Polymer, acrylate polymer and copolymer, methacrylate polymer and copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, itaconic diester polymer and copolymer , Maleic anhydride copolymer, acrylamide copolymer, methacrylamide Polymers, polycarbonate resins, ketone resins, polyester resins, amide resins, alkyl-modified nylon resin, a hydroxyl group and a carboxyl group-modified polyester resins, butyral resins, polyvinyl acetal resins, cyclized rubber - methacrylic acid ester copolymer,
Cyclic rubber-acrylic ester copolymer, cellulose acetate resin, urethane resin, copolymer containing a nitrogen-free heterocycle (for example, as a heterocycle, a furan ring, a tetrahydrofuran ring, a thiophene ring, a dioxane ring, a dioxofuran) Ring, lactone ring, benzofuran ring, benzothiophene ring, 1,3-dioxetane ring, etc.), epoxy resin and the like. Among these resins, particularly preferred examples include vinyl alkanoate polymers and copolymers, acrylic resins, methacrylic resins, vinyl chloride resins, cellulose acetate resins, urethane resins, and epoxy resins.

The preferred proportion of these other resins in the non-adhesive resin layer is less than 40% by weight, more preferably less than 20% by weight of the total resin. Further, these other resins may contain the above-mentioned reactive group which is cured by heat, light or moisture.

As a method of making these other resins compatible with a non-adhesive resin to achieve both ink resilience and adhesion, for example, "Compatibility and Evaluation Technology of Polymers" edited by Technical Information Association (1992) ), Seiichi Nakahama, etc. "High performance polymer alloy"
The contents described in a copy such as Maruzen (1991) edited by the Society of Polymer Science, etc. can be applied.

Further, in a film in which a non-adhesive resin is mixed with another resin, a method may be used which utilizes the property that the non-adhesive resin is concentrated on the surface side of the film. Further, in order to enhance the interaction between the two resins and improve the cohesive strength of the film, one of the resins is a copolymer in which a polymer component containing a silicon and / or fluorine atom similar to the non-adhesive resin is block-bonded. Small amounts of coalescence can be used.

The non-adhesive resin layer used in the present invention may have a multilayer structure. For example, a resin layer having good adhesion (adhesion functional layer) is provided on the side of the lithographic printing support in contact with the transfer layer (T).
Is provided, and a non-adhesive resin layer having good ink repellency is provided thereon. The maintenance of the adhesion between the adhesion functional layer and the non-adhesive resin layer having good ink repellency is achieved by the above-mentioned polymer components having good compatibility with the resin for adhesion and the polymer components having good compatibility with the non-adhesive resin. It is possible to make the copolymer in which the above is bonded by a block preferably coexist in the adhesion functional layer.

Further, as described above, it is preferable that the transfer layer (T) on the support forms a chemical bond at the interface with the non-adhesive resin layer. That is, on the surface portion of the transfer layer, there is a component containing a reactive group capable of chemically bonding to a reactive group present in the resin constituting the non-adhesive resin layer, and the non-adhesive resin layer is exposed to light and heat. Alternatively, a bridge is formed by a chemical reaction due to moisture, whereby the adhesion is sufficiently maintained.

The method of providing the non-adhesive resin layer on the entire surface of the transfer layer is not limited to any conventionally known method. Specifically, as long as the resin for the non-adhesive layer is liquid or solvent-soluble, it can be applied by a conventionally known means. For example, Yuji Harasaki "Coating Engineering" Asakura Shoten Co., Ltd. (1971), Yuji Harasaki "Coating Method" Maki Shoten Co., Ltd. (1979), Hiroshi Fukada "Hot Melt Bonding", Polymer Publishing Co., Ltd. (1979) ), Etc., such as air doctor coater, blade coater, knife coater, squeeze coater, impregnation coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, spray coater, curtain coater, calendar coater, etc. For example, Shin Ono “Non-impact printing” CM
C. (1986) Ink jet method, continuous jet type Sweet method, Hertz type, intermittent jet type Winston type, ink on demand type pulse jet type, bubble jet type, ink mist type It can be provided by a mist method or the like.

A non-adhesive resin layer held on a release support represented by release paper (hereinafter referred to as release paper) may be provided on the transfer layer by transferring and sticking it. In this method, the release paper having the non-adhesive layer formed thereon can be easily supplied to an apparatus for transferring in the form of a roll or a sheet.

As the release paper, any of conventionally known release papers can be used. For example, "New adhesive (adhesive) technology and its use / development materials of various applied products" (published by Management Development Center Publishing Division, May 20, 1978), "Product Encyclopedia of All Paper Guide Paper, Volume 1, Cultural Industry" (Published by Co., Ltd.)
Papers, Times, December 1, 1983) and the like.

Specifically, the release paper is a silicone-based release agent, a bleached clupak paper laminated with a polyethylene resin, a high-grade paper pre-coated with a solvent-resistant resin,
Examples thereof include kraft paper, undercoat-coated PET base, glassine paper and the like applied on a substrate. The silicone is generally of a solvent type, and is coated on the above substrate at a concentration of 3 to 7% with a gravure roll, a reverse roll, a wire bar, or the like, dried, and then heat-treated at 150 ° C. or more to be cured. The application amount is about 1 g / m ² .

As the release paper, those commercially available from paper manufacturers, for tapes, labels, for the forming industry and for the cast coat industry can be used. For example, Separate Paper (Oji Paper Co., Ltd.), King Leeds (Shikoku Paper Co., Ltd.), Sun Release (Sanyo Kokusaku Pulp Co., Ltd.)
And NK High Release (manufactured by Nippon Kaishi Paper Co., Ltd.).

The formation of the non-adhesive resin layer on the release paper is easily carried out by applying a film by bar coating, spin coating, spray coating or the like according to a conventional method. In order to thermally transfer the non-adhesive resin layer on the release paper onto the transfer layer on the lithographic printing support, a usual thermal transfer method can be used.
That is, the release paper holding the non-adhesive resin layer may be pressed against a lithographic printing support, and the non-adhesive resin layer may be thermally transferred onto a transfer layer on the support.

The conditions for transferring the non-adhesive resin layer from the release paper to the surface of the transfer layer on the support are preferably as follows. The nip pressure of the roller is 0.1 to 20 kgf / cm ² , more preferably 0.2 to 10 kgf / cm ² , and the temperature at the time of transfer is 25 to 200 ° C., more preferably 40 to 150 ° C.
° C.

As described above, the non-adhesive resin layer is preferably cured so as to withstand the printing pressure at the time of printing. Is preferred. Such a film state is achieved by appropriately performing heating and / or light irradiation during each operation in either the coating method or the transfer method. After the film is set on the support, heating and / or light irradiation may be performed again. These conditions are as described above.

After the non-adhesive resin layer is provided on the transfer layer on the support, an operation for selectively removing the non-adhesive resin layer in the toner image area is performed. For selective removal, either a wet system or a dry system may be used, but a dry process is preferred from the viewpoint of easy operation. In order to remove the non-adhesive resin layer by swelling with a solvent, the non-adhesive resin layer in the image area may be removed by applying a mechanical force such as rubbing, if necessary. Kaisho 49-1216
02).

[0215] In the present invention, the non-adhesive resin layer is easily and selectively removed by applying a mechanical external force, and thus the method of the dry treatment is not limited. Specific examples include a peel apartment method using an adhesive sheet, a brushing method using a brush, and a friction method using an eraser.

Further, when the non-adhesive resin layer provided on the release paper is provided on the transfer layer by the transfer method, the releasability between the release paper and the non-adhesive resin layer is adjusted, so that the toner image can be obtained. Only parts can be selectively removed. That is, after the non-adhesive resin layer is pressed against the transfer layer, when the release paper is peeled off, the non-adhesive resin layer in the non-image area is transferred to the surface of the transfer layer of the support,
By removing the non-adhesive resin layer of the toner image portion while adhering to the release paper, the toner image portion can be simultaneously removed (so-called peel-apart development).

The separation of the non-adhesive resin from the support in the image area is achieved by the interface between the surface of the support and the toner image, the transfer layer (T)
May occur at the interface between the toner image and the toner image or inside the toner image (due to so-called cohesive failure). As a result of removing the non-adhesive resin layer and the transfer layer in the image area, the toner image may be removed together with the resin layer, or may remain on the support.

The printing plate of the present invention obtained as described above can be printed by various offset printing machines without using immersion water, similarly to a conventionally known printing plate without water.

Hereinafter, a method for preparing an electrophotographic waterless planographic printing plate of the present invention will be described in detail with reference to the accompanying drawings. FIG. 2 is a schematic diagram of an electrophotographic plate making apparatus suitable for carrying out the method of the present invention.

First, the transfer layer (T) 12 is formed on the photoreceptor 11.
Is provided by the transfer layer forming unit 13. Here, the formation of the transfer layer will be described by taking the case of the electrodeposition coating method as an example. A charge is applied to the thermoplastic resin particles (AR) to form a thermoplastic resin particle dispersion, which is used as the transfer layer forming unit 1
3 and the liquid developing unit set 14 is
And fix it so that the distance from the transfer layer forming unit 13 to the developing electrode is 1 mm. The resin particle dispersion is supplied from the transfer layer forming unit 13 between the gaps and rotated while applying a voltage from the outside, so that the resin particles are adsorbed on the entire surface of the photoconductor 11. If necessary, the dispersion medium adhered to the surface of the photoreceptor is removed by a squeeze device incorporated in the liquid developing unit set, and then the resin particles are thermally melted by a heating device to obtain a transfer layer formed into a film.

At this time, the exhaust of the dispersion solvent of the dispersion can be performed by using the suction / exhaust unit 15 provided for the electrophotographic process of the electrophotographic photosensitive member. Transfer layer forming unit 1
3 may be provided in the liquid developing unit set 14 as shown in FIG. 2, or may be provided separately from the developing unit set.

Next, a toner image is formed on the photoreceptor 11 by a normal electrophotographic process. First, after the photosensitive member 11 is uniformly charged, for example, positively by a corona charging device 18, image exposure is performed based on image information by an exposure device (for example, a semiconductor laser) 19. , A potential contrast is obtained. A toner image forming unit 14T containing a liquid developer in which resin particles having a positive electrostatic charge are dispersed in an electrically insulating dispersion medium is brought close to the surface of the photoreceptor from the liquid developing unit set 14 and fixed with a gap of 1 mm. .

The photoreceptor 11 is pre-bused by pre-bus means provided in the developing unit, and then the photoreceptor 11 is supplied with a bias power supply and an electric connection (not shown).
The liquid developer is supplied to the surface of the photoreceptor while applying a developing bias voltage between the photoconductor and the developing electrode. The bias voltage at this time is connected so that the developing electrode side is positive and the photoconductor side is negative, and the applied voltage is slightly lower than the surface potential of the unexposed portion. If the applied voltage is too low, a sufficient toner image density cannot be obtained.

Thereafter, the developing solution adhering to the surface of the photoreceptor is washed away by rinsing means 14R built in the liquid developing unit set 14, and then the rinsing liquid adhering to the surface of the photoreceptor is removed by squeezing means. 15 to dry.

After the transfer layer is formed, a predetermined preheating is performed by the heating means 16 for thermal transfer as necessary, and the lithographic printing plate support 20 is also preheated by the transfer backup roller 31 as necessary. After pressing the toner image on the photoreceptor together with the transfer layer onto the lithographic printing plate support 20, while cooling it with the peeling backup roller 32,
The toner image is peeled and transferred on the lithographic printing plate support 20 together with the transfer layer, and a series of steps is completed.

A series of steps from the formation of the transfer layer to the transfer to the lithographic printing plate support 20 can be carried out by previously heating the surface temperature of the photoreceptor. In such a case, the heating temperature of the photoreceptor surface is 70 ° C. or less, preferably 60 ° C. or less.
At such a temperature, the photoconductor can be used repeatedly without causing damage to the photoconductor. As a result, it is possible to reduce the burden and time required for temperature adjustment in each process.

[0227]

The present invention will be described in more detail with reference to the following examples.

[Synthesis Example of Resin Particles] Synthesis Example 1 of Resin Particles (AR): (AR-1) A mixed solution of 16 g of a dispersion stabilizing resin (Q-1) having the following structure and 550 g of Isopar H was stirred under a nitrogen stream. While heating to a temperature of 50 ° C. To this, 50 g of benzyl methacrylate, 40 g of 2-butoxyethyl methacrylate,
10 g of a monomer (a-1) having the following structure, 2.6 g of methyl 3-mercaptopropionate and 2,2'-azobis (2
-Cyclopropylpropionitrile) (ACPP)
1.2 g of the mixed solution was added dropwise over 1 hour. After stirring for 1 hour as it was, 0.8 g of ACPP was added and reacted for 2 hours.
Furthermore, 2,2'-azobis (isobutyronitrile) (abbreviation)
(AIBN) 0.5g, set the temperature to 80 ℃, 3
Reacted for hours. After cooling, the white dispersion obtained was passed through a 200-mesh nylon cloth and had a conversion of 97% and an average particle size of 0.1%.
It was a 19 μm monodisperse latex. Particle size is CA
PA-500 (manufactured by Horiba, Ltd.) (measured hereinafter).

A part of the white dispersion was centrifuged (rotation speed: 1 × 10 ⁴ rpm, rotation time: 1 hour), and the sedimented resin particles were collected and dried, and the weight average molecular weight of the resin particles was measured. Mw) (measured in terms of polystyrene by GPC; the same applies hereinafter) and a glass transition point (Tg) were measured. As a result, Mw was 5 × 10 ⁴ and Tg was 34 ° C.

[0230]

Embedded image

Synthesis Example 2 of Resin Particles (AR): (AR-
2) A macromonomer having dimethylsiloxane as a repeating unit (Silaprene FM-725, Mw 1.0 × 1
0 ^4, manufactured by Chisso (Ltd.)) 18 g, a mixed solution of vinyl acetate 100g of Isopar G 382 g was heated to 75 ° C. under nitrogen gas stream with stirring. In addition, AIBN
1.5 g was added and reacted for 3 hours. Next, AIBN 0.
After adding 8 g, immediately raise the temperature to 80 ° C. for 2 hours, and further
0.5 g of AIBN was added and reacted for 2 hours. Temperature 10
At 0 ° C, unreacted monomer was distilled off, and after cooling, 2
The resulting white dispersion was passed through a 00 mesh nylon cloth, and was a monodisperse latex having a conversion of 98% and an average particle size of 0.22 μm. Mw of resin particles is 9 × 10 ⁴
And Tg was 38 ° C.

Synthesis Example 3 of Resin Particles (AR): (AR-
3) A mixed solution of 12 g of a dispersion stabilizing resin (Q-2) having the following structure, 65 g of vinyl acetate, 30 g of vinyl valerate, 5 g of crotonic acid and 275 g of Isopar H was heated to a temperature of 80 ° C. while stirring under a nitrogen stream. . 1.6 g of 2,2'-azobis (isovaleronitrile) (abbreviated as AIVN) was added,
After reacting for 1.5 hours, 0.8 g of AIVN was added and the reaction was continued for 2 hours, and 0.5 g of AIBN was further added for 4 hours. Then
The temperature was raised to 100 ° C., and the mixture was stirred for 2 hours. After unreacted monomers were distilled off, the mixture was cooled and passed through a 200-mesh nylon cloth to obtain a white dispersion at a polymerization rate of 93%. Average particle size 0.
It was a 25 μm monodisperse latex. The Mw of the resin particles was 8 × 10 ⁴ , and the Tg was 24 ° C.

[0233]

Embedded image

Synthesis Examples 4 to 9 of Resin Particles (AR): (AR
-4) to (AR-9) A mixed solution of 20 g of the dispersion stabilizing resin (Q-3) having the following structure and 480 g of Isopar G was heated to a temperature of 50 ° C. while stirring under a nitrogen stream. To this, a mixed solution of a predetermined amount of each monomer shown in Table A below, 2.6 g of methyl 3-mercaptopropionate and 1.5 g of AIVN was added for 1 hour.
The reaction was continued for 1 hour. Then
After adding 1.0 g of AIVN and keeping the temperature at 70 ° C. for 2 hours, further adding 0.8 g of AIBN and immediately setting the temperature at 80 ° C. and reacting for 3 hours.

To the above reaction product, 60 g of Isopar H was added, and the remaining monomer was distilled off at a temperature of 50 ° C. under reduced pressure of a water jet pump, followed by cooling and passing through a 200-mesh nylon cloth to obtain a white dispersion. Each of the obtained latexes had good monodispersity in the range of an average particle diameter of 0.18 to 0.25 μm. The Mw of the resin particles of each latex was in the range of 9 × 10 ^{3 to} 1.5 × 10 ⁴ . Tg was as shown in Table-A.

[0236]

Embedded image

[0237]

[Table 1]

Synthesis Examples 10-14 of Resin Particles (AR)
(AR-10-14) 8 g of a dispersion stabilizing resin (Q-4) having the following structure, Table-B below
Of a macromonomer and 392 g of Isopar H was heated to a temperature of 50 ° C. while stirring under a nitrogen stream. To this, phenethyl methacrylate 50 g, ethylene glycol propyl ether methacrylate 38 g,
3 g of initiator ACPP and 150 g of methyl ethyl ketone
Was added dropwise over a period of 1 hour, and the mixture was reacted for 1 hour. Further, 1.0 g of ACPP was added and the mixture was reacted for 2 hours. Then, immediately after adding 1.0 g of AIVN, the temperature was set to 75 ° C., and the reaction was carried out for 2 hours.
8 g was added and reacted for 2 hours. After cooling, a white dispersion was obtained by passing through a 200-mesh nylon cloth. The polymerization rate of each resin particle is 93 to 99%, and the average particle size is 0.15 to
The latex had a narrow particle size distribution in the range of 0.25 μm. The Mw of the resin component of each particle was about 2.5 × 10 ⁴ , and the Tg was in the range of 30 to 35 ° C.

[0239]

Embedded image

[0240]

[Table 2]

Synthesis Example 15 of Resin Particles (AR): (AR-
15) As the resin (A), a vinyl acetate / ethylene (46/54 weight ratio) copolymer (Evaflex 45) at Tg-25 ° C
X, manufactured by Mitsui DuPont Chemical Co., Ltd.) and Tg 38 ° C
And polyvinyl acetate at a ratio of 1/1 weight ratio and melt-kneaded at 120 ° C. in a three-roll mill. The kneaded material is roughly pulverized by a tribender of a pulverizer.
g, 4 g of a dispersion stabilizing resin (Solprene 1205, manufactured by Asahi Kasei Corporation) and 51 g of Isopar H are about 4 mm in diameter.
Was placed in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) using the glass beads as a medium, and preliminarily dispersed for 20 minutes. The predispersion was wet-dispersed at 4500 rpm for 6 hours using a Dynomill KDL type (Shinmaru Enterprises Co., Ltd.) using glass beads having a diameter of 0.75 to 1 mm as a media. A white dispersion obtained by passing these through a 200 mesh nylon cloth was a latex having an average particle size of 0.4 μm.

Synthesis Example 1 of Resin Particles (ARW)
-1) A mixture of 8 g of the dispersion stabilizing resin (Q-1), 70 g of vinyl acetate, 30 g of vinyl propionate and 388 g of Isopar H was heated to a temperature of 80 ° C. while stirring under a nitrogen stream. To this, 1.5 g of AIBN was added as an initiator, and 2
React for 2 hours, then add 0.8 g of AIBN every 2 hours
The reaction was performed by adding once. After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth was a latex having a polymerization degree of 93% and an average particle diameter of 0.14 μm and having good monodispersibility. The Mw of the resin particles was 8 × 10 ⁴ , and the Tg was 17 ° C. The resin particles obtained here are designated as (AR-16).

A mixed solution of the entire resin particle dispersion (ie, seed particles) and 10 g of the dispersion stabilizing resin (Q-1) was heated to a temperature of 60 ° C. while stirring under a nitrogen stream.
To this, 50 g of benzyl methacrylate, 40 g of 2-butoxyethyl methacrylate, 10 g of monomer (a-1)
g, 2.6 g of methyl 3-mercaptopropionate, AI
VN. A mixture of 1.0 g and 400 g of Isopar G is
It was added dropwise over 2 hours, and the reaction was continued for another 2 hours. Next, 0.8 g of an initiator was added, the temperature was raised to 70 ° C., and the mixture was reacted for 2 hours. Further, 0.6 g of an initiator was added and reacted for 3 hours. After cooling, 20
After passing through a 0-mesh nylon cloth, the obtained white dispersion was a latex having a degree of polymerization of 98% and an average particle diameter of 0.25 μm and having good monodispersibility. Here, the components reacted for lamination of the resin particles are the same as those of the resin particles (AR-1).

Next, whether or not the obtained resin particles were formed as single particles was examined by observing the state of the particles using a scanning electron microscope (SEM). On a PET film, a film prepared by dispersing resin particles was prepared by heating a sample not heated and 5 ° C at 60 ° C.
JEOL's JSL
-Observed at 20,000 times using a T330 Scanning Microscope. Particles were observed in the sample that was not heated, but no particles were observed in the sample at 60 ° C.
That is, the particles were melted by heating.

Similarly, resin particles (AR-1) made of each of the two kinds of resins (copolymers) constituting the above resin particles.
6), the resin particles (AR-1) and these two types of particles were 1 /
The resin particles mixed at a weight ratio of 1 were examined. In the case of the resin particles (AR-16), no particles were already observed in the sample not heated, while in the case of the resin particles (AR-1), the particles were observed in the sample not heated, whereas in the sample at 60 ° C., the particles were not observed. I disappeared. Furthermore, in the case of mixed particles, particles were observed in the sample not heated,
Particles disappeared in the sample at ° C.

As a result of the visual observation of the thermal behavior of the particles as described above, the resin particles (ARW-1) were not a mixture of two types of resin particles, but contained two types of resin in one particle. In this case, it was confirmed that the high Tg resin was core / shell particles in which the low Tg resin was distributed in the outer layer and the low Tg resin was distributed in the inner layer.

Synthesis Examples 2 to 7 of Resin Particles (ARW): (A
RW-2) to (ARW-7) In Synthesis Example 1 of the resin particles (ARW), the following Table-
Resin particles (ARW-2) to (ARW-7) were produced in the same manner except that each monomer described in C was used. The polymerization rate of each of the obtained latex particles was 95 to 99%, the average particle size was in the range of 0.20 to 0.30 μm, and the monodispersity was good.

[0248]

[Table 3]

Example 1 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 2
g, 14.4 g of the following binder resin (B-1), 3.6 g of the following binder resin (B-2), 0.15 g of the following compound (A), and 80 g of cyclohexanone were mixed with glass beads in a 500 ml glass container. The mixture was dispersed with a paint shaker (manufactured by Toyo Seiki Seisakusho) for 60 minutes, and then the glass beads were separated by filtration to obtain a photosensitive layer dispersion.

[0250]

Embedded image

Next, this dispersion was subjected to a degreasing treatment.
Apply on a 2mm thick aluminum plate with a wire bar,
After drying to the touch, it was heated in a circulating oven at 110 ° C. for 20 seconds. The thickness of the obtained photosensitive layer was 8 μm.

Formation of Releasable Surface Layer A coating material containing 10 g of the following silicone resin, 1 g of the following crosslinking agent and 0.1 g of platinum for crosslinking catalyst in 100 g of n-hexane was applied using a wire round rod, and touched with a finger. After drying, it was further heated at 120 ° C. for 10 minutes. The thickness of the surface layer was 1.5 μm. The surface tackiness of the obtained photoreceptor was 1 g · f or less.

[0253]

Embedded image

The photoreceptor having surface releasability thus obtained was mounted on an apparatus as shown in FIG. 2 as an electrophotographic photoreceptor.

A transfer layer (T) was formed on the surface of the photoreceptor. While rotating the photosensitive drum at a peripheral speed of 100 mm / sec, and using a slit electrodeposition device on the surface of the photosensitive member, while supplying the following dispersion (L-1) of resin (A) for electrodeposition,
Ground the photoconductor side and +13 on the electrode side of the slit electrodeposition device
A voltage of 0 V was applied to electrodeposit resin particles. Next, the dispersion was removed by air squeezing, and the film was formed with an infrared line heater to form a transfer layer. The thickness was 1.5 μm.

Dispersion (L-1) of resin (A) Resin particles (AR-3) 20 g (as solid content) Charge control agent (CD-1) Octadecyl vinyl ether / half maleic acid 0.08 g dodecylamide (1 (1 / molar ratio) copolymer was added to 1 liter of Isopar G (manufactured by Esso Corporation).

Next, a toner image was formed on the photosensitive member by an electrophotographic process. +4 photoconductor in dark place
After corona charging to 80V, the original was read in advance from a document by a color scanner, color-separated, subjected to some system-specific color reproduction corrections, and stored as digital image data on a hard disk in the system. Based on the information, the wafer was exposed to light of 788 nm using a semiconductor laser drawing apparatus so that the exposure amount on the photoconductor was 30 erg / cm ² .

On the other hand, a positively chargeable liquid developer (LD-1) was prepared by the following method. -Synthesis of dispersed resin particles 90 g of methyl methacrylate, 10 of methyl acrylate
g, 20 g of the following dispersed polymer and 680 g of Isopar H
Was heated to 65 ° C. while stirring under a nitrogen stream.

[0259]

Embedded image

To this, 1.0 g of 2,2'-azobisisovaleronitrile (AIVN) was added and reacted for 4 hours.
Add 0.5 g of IVN and react for 2 hours.
0.5 g was added and reacted for 2 hours. Next, the reaction temperature was set to 9
The temperature was raised to 0 ° C., and the mixture was stirred under a reduced pressure of 30 mmHg for 1 hour to remove unreacted monomers. After cooling to room temperature, a white dispersion was obtained through a 200-mesh nylon cloth. The reaction rate of the monomer in the dispersion was 98% by weight, and the average particle size of the resin particles measured by CAPA-500 (manufactured by HORIBA, Ltd.) was 0.25 μm.
m, and the dispersibility was also good. The Tg of the resin is 108
° C.

Synthesis of Colored Particles Tetradecyl methacrylate / methacrylic acid (95/5
(Weight ratio) 10 g of the copolymer, 10 g of nigrosine and 30 g of Isopar G were placed together with glass beads in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

Production of Liquid Developer 45 g of the above-mentioned toner resin particle dispersion, 25 g of the above-mentioned nigrosine dispersion, 0.6 g of hexadecene / half-maleic acid octadecylamide (1/1 molar ratio) copolymer, and branched octadecyl alcohol (FOC) A liquid developer for electrostatic photography (LD-1) was obtained by diluting 10 g of -1800 (manufactured by Nissan Chemical Industries, Ltd.) into 1 liter of Isopar G.

Using a liquid developer (LD-1), a developing device having a developing electrode is applied with a bias voltage of +400 V to the electrode to perform reversal development in which toner is electrodeposited on the exposed portion. Rinsing was performed in a single bath to remove stains on non-image areas.

Next, an electrophotographic printing original plate (ELP-IX, Fuji Photo Film Co., Ltd.) was used as the lithographic printing plate support 20.
Photosensitive member 1 whose surface temperature was adjusted to 60 ° C.
A nip pressure of 8 kg was guided between the drum 1 and the transfer backup roller 31 whose surface temperature was adjusted to 130 ° C. and the peeling backup roller 32 set to 25 ° C.
When heating and pressurization were performed at f / cm ² and a drum peripheral speed of 60 mm / sec, all the toner images were transferred onto the support together with the transfer layer. The adhesion between the transfer layer and the surface of the support is 1 kg
f or more, and the adhesiveness was sufficient.

Observation of the transferred image on the support with a 200 × optical microscope revealed that there was no fine line, no disorder of fine characters, no bleeding and the reproducibility of halftone dots of 150 lines / inch was good, and the solid portion was uniform. The image was also excellent in properties. The adhesive force between the toner image area and the support surface was 10 g · f.

Next, a condensation type silicone rubber (K
S705F, manufactured by Shin-Etsu Silicon Co., Ltd.) 6 g, CAT-P
S-1 (Shin-Etsu Silicon Co., Ltd.) 240mg, CAT-P
D (manufactured by Shin-Etsu Silicon Co., Ltd.) 120 mg, vinyl acetate / crotonic acid (99/1 molar ratio) copolymer 2 g, and heptane / tetrahydrofuran (3/1 weight ratio) mixed solvent 34 g
The solution was uniformly applied with a wire bar, dried by heating at 80 ° C. for 2 minutes, and crosslinked to form a non-adhesive resin layer made of silicone rubber (hereinafter sometimes referred to as a silicone rubber layer). At this time, the thickness of the silicon rubber layer is 2.12.
μm. Adhesion between transfer layer and silicone rubber layer is 50
It was 0 g · f.

Next, by using a PS sponge (manufactured by Fuji Photo Film Co., Ltd.), the silicon rubber layer on the toner image portion is selectively removed by uniformly rubbing the silicon rubber layer over the entire surface. A lithographic printing plate was prepared by leaving the silicone rubber layer in the pattern of the non-image area.

Using this printing plate, a printing machine (TOKO OFFSET)
810L, manufactured by Tokyo Aviation Instrument Co., Ltd.) with black ink (DRI-O-COLO)
R, manufactured by Dainippon Ink and Chemicals Co., Ltd.) without printing dampening water, clear images with no missing fine lines and fine characters and no background stains on non-image areas 3000 or more good prints were obtained.

Further, in Example 1, 20 g of resin particles (ARW-7) was used in place of 20 g of resin particles (AR-3) in the dispersion for electrodeposition of the transfer layer (T). A printing plate was prepared and printed in the same manner as in Example 1.
The result was equivalent to.

Next, the transfer speed is increased from 60 mm / sec to 100 mm / sec.
/ Sec, the transfer was somewhat insufficient with the transfer layer of Example 1. On the other hand, the core / shell type particles (AR
In the transfer layer using W-7), 100% transfer was performed, and the image on the support was good without deformation such as distortion. In the present invention, it can be seen that the resin of the transfer layer and the resin of the non-adhesive resin layer interact sufficiently at the interface between the two layers, and the adhesion is sufficiently maintained.

Comparative Example 1 In Example 1, the support on which the toner image was transferred was heated at 140 ° C. for 3 minutes to fix the toner layer. At this time, the adhesive strength between the toner image portion and the support was 250 g · f. Subsequently, a silicon rubber layer was formed in the same manner as in Example 1. The thickness of the silicone rubber layer was 2.15 μm.

When the silicon rubber layer in the image area was removed under the same conditions as in Example 1, and printing was performed, the image area was not sufficiently deposited, and only a printed matter having poor image reproducibility was obtained. Scan the printing plate with a scanning electron microscope (JSM-T33).
0, manufactured by JEOL Ltd.), it was found that the silicon rubber layer on the image area was not sufficiently removed. The silicon rubber layer on the image area could be sufficiently removed by making the rubbing conditions with a sponge more severe, but under such conditions, many fine scratches occurred on the silicon rubber layer on the non-image area, resulting in printing stains. Was.

In Comparative Example 1, the reason why the silicone rubber layer in the image area was not easily removed was that the difference in adhesion between the transfer layer in the non-image area and the fixed toner image area on the support surface was not sufficient. It seems to be because. Therefore, it is difficult to sufficiently remove the silicon rubber layer in the image area without leaving any damage to the silicon rubber layer. Even if it is possible, the condition is very narrow. On the other hand, in Example 1, the toner in the image area was not fixed to the extent that it could be said at all, and the apparent adhesion to the surface of the support was almost nil. Therefore, the silicone rubber layer in the image part can be easily removed without damaging the silicone rubber layer in the non-image part at all.

Comparative Example 2 A toner image was formed in the same manner as in Example 1 except that the transfer layer (T) was not provided on the surface of the photoreceptor, and the transfer of the toner image to a lithographic printing plate support was carried out. Done. The obtained toner image on the support was largely missing and could not be used practically as a copied image. Further, toner residue was observed on the photoreceptor. That is, without using a transfer layer,
It was impossible to completely transfer the non-fixable toner image from the photoreceptor.

Comparative Example 3 A printing plate was prepared in the same manner as in Example 1 except that the vinyl acetate / crotonic acid copolymer was not used. When an attempt was made to remove the silicone rubber layer in the image area in the same manner as in Example 1, the silicone rubber layer in the non-image area was partially peeled off, and it was impossible to selectively remove only the image area. Was. In Comparative Example 3, the adhesion at the interface between the transfer layer on the support and the non-adhesive resin layer made of only the silicone polymer was insufficient, and the adhesive strength of the transfer layer to the non-adhesive resin layer and the toner to the support This is probably because the difference in adhesive strength between the image areas was insufficient.

Example 2 5 g of 4,4'-bis (diethylamino) -2,2'-dimethyltriphenylmethane was used as an organic photoconductive substance.
6 g of the following binder resin (B-3) and the following methine dye (D-
1) 40 mg of the compound (A) 0.2 as a chemical sensitizer
g was dissolved in a mixture of 30 ml of methylene chloride and 30 ml of ethylene chloride to obtain a photosensitive layer dispersion.

[0277]

Embedded image

This photosensitive layer dispersion was applied on a conductive transparent support (a polyethylene terephthalate support having a thickness of 100 μm and a vapor-deposited film of indium oxide; surface resistance: 10 ³ Ω) using a wire round rod. After doing
By heating at a temperature of 70 ° C. for 2 hours, the film was crosslinked to form a photosensitive layer of about 5 μm. An ultraviolet-curable silicone rubber (TFC7700, manufactured by Toshiba Silicon Corp.) is applied to the surface of this photosensitive layer.
Is applied with a wire bar, and a high-pressure mercury lamp (UM10
2, Ushio Inc.) from a distance of 5 cm for 30 seconds. The thickness of the surface layer was 0.6 μm. The surface tackiness of the obtained photoreceptor was 1 g · f.

The photoreceptor thus prepared was mounted on an apparatus as shown in FIG. Surface temperature of photoreceptor drum is 50 ℃
Then, a transfer layer was formed on the surface of the photoreceptor by wet electrodeposition using the following dispersion (L-2) of resin (A) in the same manner as in Example 1. However, a voltage of 150 V was applied to the developing electrode. The thickness was 1.6 μm.

Dispersion of Resin (A) (L-2) Resin Particles (AR-1) 20 g (as solid content) Charge control agent (CD-1) 0.08 g of isopar so that the total amount becomes 1 liter. G.

With the surface temperature of the photoreceptor kept at 50 ° C., a toner image was formed on the photoreceptor and rinsed in the same manner as in Example 1, and then the photoreceptor and a transfer backup roller adjusted to 120 ° C. OK as a lithographic printing plate support between the peeling backup roller adjusted to 25 ° C
Nip pressure 8kgf / cm ²
The transfer layer and the toner image were collectively transferred onto the OK master at a transfer speed of 50 mm / sec.

The copied image formed on the OK master in this manner was visually observed using an optical microscope of 200 times. No background staining due to toner was observed in the non-image area. Further, the toner image and the transfer layer were all transferred without remaining on the photoreceptor.
A high-definition image area of 3% to 95% of the halftone dot of 0 line / inch was faithfully reproduced without causing fattening, dropout or bending, and was excellent. In this plate-making method, the adhesive strength of the toner image area to the support surface was 8 g · f, and the adhesive strength of the non-image area to the transfer layer was 800 g · f.

Next, an ultraviolet-curable silicone rubber (TFC7
70, manufactured by Toshiba Silicon Co., Ltd.) with a wire bar, and a high-pressure mercury lamp (UM102, USHIO INC.)
Was irradiated from a distance of 5 cm for 30 seconds. The thickness of the silicone rubber layer was 2.2 μm. The adhesive strength between the transfer layer (T) made of the resin (AR-1) and the non-adhesive resin layer is 400.
At g · f or more, it was sufficiently adhered.

Next, by uniformly brushing the entire surface of the silicon rubber layer, the silicon rubber layer in the image area is selectively removed, and the silicon rubber layer is left in a non-image area pattern. Created a version. Using the printing plate thus obtained, printing was carried out in the same manner as in Example 1. As a result, it was possible to obtain 10,000 or more printed materials having good inking in the image area and good stainability in the non-image area. Was completed.

Example 3 5 g of the following bisazo pigment, 95 g of tetrahydrofuran and a polyester resin (Vylon 200, Toyobo Co., Ltd.)
5 g of the mixture was thoroughly pulverized in a ball mill. The mixture was taken out and stirred with tetrahydrofuran 52
0 g was added. This dispersion was coated on the conductive transparent support used in Example 2 using a wire round rod to form a charge generation layer of about 0.7 μm.

[0286]

Embedded image

A mixed solution of 20 g of the following hydrazone compound, 30 g of a polycarbonate resin (Lexane 121, manufactured by GE) and 160 g of tetrahydrofuran was applied on the charge generation layer using a wire round rod, and dried at 60 ° C. for 30 seconds. Further, the resultant was heated at a temperature of 100 ° C. for 20 seconds to form a charge transporting layer having a thickness of about 18 μm, thereby obtaining an electrophotographic photosensitive member having a two-layered photosensitive layer.

[0288]

Embedded image

30 g of a room temperature tack-free silicone adhesive (TSR1520 [A], manufactured by Toshiba Silicon Co., Ltd.), 300 mg of a crosslinking agent (TSR1520 [B], manufactured by Toshiba Silicon Co., Ltd.) and heptane 90 g of the mixed solution was applied with a wire bar, and then 125
Heating at 2 ° C. for 2 minutes formed a surface layer having a thickness of 5 μm. The surface tackiness of the photoreceptor was 2 g · f.

The photosensitive member obtained as described above was mounted on an apparatus as shown in FIG. Set the surface temperature of the photoreceptor surface to 50
° C, and rotating the photosensitive drum at a peripheral speed of 100 mm / sec., While supplying a dispersion (L-3) of the following resin (A) to the surface of the photosensitive member using a slit electrodeposition device, It was grounded, and a voltage of 180 V was applied to the electrode side of the slit electrodeposition device to electrodeposit and fix the resin particles. The thickness of the transfer layer was 2 μm.

Dispersion of resin (A) (L-3) Resin particles (AR-5) 20 g (as solid content) Charge regulator (CD-2) 0.16 g of zirconium naphthenate in 1 liter of Isopar G Was prepared in addition to

With the surface temperature kept at 50 ° C., the surface was charged to −550 V, and a 5 mW output H was obtained based on information previously read from a document by a color scanner and stored as digital image data on a hard disk in the system.
The surface of the photoreceptor was exposed at a dose of 25 erg / cm ² using an e-Ne laser (oscillation wavelength: 633 nm). Using the following liquid developer (LD-2), a bias voltage of 50 V was applied to perform development, and rinsing was performed with Isopar G.

Preparation of Liquid Developer (LD-2) A mixture having the following composition was kneaded in a kneader at 100 ° C. for 2 hours to obtain a mixture. The mixture was cooled in a kneader and then ground in the same kneader. 10 g of this pulverized material and 40 g of Isopar H were dispersed with a paint shaker for 6 hours to obtain a dispersion. This dispersion is diluted with Isopar G so that the toner solid content is 6 g per liter, and at the same time, zirconium naphthenate (CD-2) is contained as a charge control agent in an amount of 0.1 g per liter. LD
-2).

Kneading composition Ethylene / methacrylic acid copolymer 5 g (Nucrel N-699, manufactured by Du Pont-Mitsui) Polyvinyl acetate (glass transition point 38 ° C.) 0.8 g Alkaline blue pigment 6 g Isopar L (manufactured by Exxon) 30g

Next, a transfer film backup roller was adjusted so that the surface temperature became 110 ° C., and a 150 μm-thick PET film was used as a lithographic printing plate support as a lithographic printing plate support without adjusting the temperature of the peeling backup roller. The transfer layer and the toner image were collectively transferred on the PET film by passing the nip pressure of 7 kgf / cm ² and the transfer speed of 80 mm / sec between the transfer layer and the backup roller.

The copy image thus formed on the PET film was visually observed using an optical microscope of 200 times. No background staining due to toner was observed in the non-image area. Further, the toner image and the transfer layer were all transferred without remaining on the photoreceptor.
The high-definition image area of 3% to 95% of the halftone dot of 0 line / inch was faithfully reproduced without any fattening, dropout or bending, and was excellent.

A mixed solution of 6 g of addition type silicone rubber (KS774, manufactured by Shin-Etsu Silicone Co., Ltd.), 180 mg of CAT-PL-4 (manufactured by Shin-Etsu Silicone Co., Ltd.) and 34 g of heptane was uniformly spread on the transfer layer by a wire bar. And dried by heating and crosslinking at 90 ° C. for 2 minutes to form a silicone rubber layer. The thickness of the silicone rubber layer was 2.1 μm. The adhesion between the transfer layer and the silicon rubber layer formed thereon was sufficient, and the adhesive strength was 800 g · f or more. The adhesive force between the toner image area and the support surface was 12 g · f.

Next, a printing plate was prepared by removing the silicone rubber layer in the image portion by brushing. When the toner image portion of the printing plate was visually observed using a 200-fold optical microscope, a 3- to 95-dot thin line of 10 μm or a halftone dot of 150 lines was observed.
% Was clearly formed without any loss, and the image was extremely high-definition. When printing was performed using this printing plate, 50,000 or more excellent printed matter having a high-definition image almost equivalent to the image on the printing plate and having no background stain on the non-image portion could be obtained.

This means that the resin (AR-
A chemical bond is formed by the reaction between 5) and the silicone rubber layer, whereby the adhesion between the two layers is remarkably improved. As a result, a fine image portion is easily removed, and even when actually printed, It is considered that a high-definition image was obtained and printing durability was improved.

Example 4 An amorphous silicon photoreceptor (manufactured by Kyocera Corporation) was used as an electrophotographic photoreceptor, and releasability was imparted to the photoreceptor as follows. That is, the following compound (S-
1) The above-mentioned photoreceptor was immersed in a bath containing a solution of 1.0 g dissolved in 1 liter of Isopar G (manufactured by Esso Corporation), taken out and dried. The surface tackiness of the photoreceptor thus obtained was 250 g · f before the treatment, but was reduced to 3 g · f, indicating good releasability.

[0301]

Embedded image

The photosensitive member was mounted on an apparatus as shown in FIG. A transfer layer having a thickness of 1 μm was formed on a photoreceptor having a surface temperature set at 55 ° C. by an electrodeposition coating method using a dispersion (L-4) of the following resin (A). -Dispersion (L-4) of resin (A) 20 g of resin particles (AR-7) 0.07 g of charge control agent (CD-1) was added to 1 liter of Isopar G to prepare.

Next, the above-mentioned photoreceptor was corona-charged to +700 V with the surface temperature kept at 55 ° C., read in advance from a manuscript with a color scanner, color-separated, and subjected to some system-specific color reproduction corrections. 780 using a semiconductor laser based on information stored in a hard disk in the system as digital image data.
Exposure with nm light. The potential of the exposed part was +220 V, and that of the unexposed part was +600 V.

Subsequently, after pre-bathing by Isopar G (manufactured by Esso Standard Petroleum) using a pre-bath device incorporated in the developing unit, the following liquid developer (L
D-3) was supplied from the developing unit to the surface of the photoreceptor. At this time, a developing bias voltage of +500 V was applied to the developing unit to perform reversal development so that the toner was electrodeposited on the exposed portion. Next, rinsing was carried out in a bath of Isobar G alone to remove stains on the non-image area, and dried with a suction / exhaust unit.

Preparation of Liquid Developer (LD-3) A methyl methacrylate / octadecyl methacrylate (95/5 weight ratio) copolymer (glass transition point 100 ° C.) as a coating resin and carbon black (# 40, After sufficient mixing at a weight ratio of 1: 1, the mixture was melted and kneaded in a three-roll mill heated to 150 ° C. 12 g of this kneaded material, styrene / butadiene copolymer (Solprene 1205, manufactured by Asahi Kasei Corporation) 4
g and 76 g of Isopar G were dispersed in a Dynomill. The toner concentrate thus obtained was diluted with Isopar G so that the solid content concentration became 6 g / liter, and sodium dioctyl sulfosuccinate was further added to 1 × 10 6
^-4 mol / l was added to obtain a liquid developer.

Next, a SUS-430 plate having a thickness of 100 μm as a support for a lithographic printing plate (between a transfer backup roller whose surface temperature was adjusted to 100 ° C. and a peeling back roller whose temperature was not adjusted and a photoreceptor). Kawasaki Steel Corporation
Was passed at a nip pressure of 7 kgf / cm ² and a transfer speed of 80 mm / sec to collectively transfer the transfer layer and the toner image onto the support. The adhesive strength between the toner image area and the surface of the support is 10 g · f
In a small, non-fixing state.

Next, an ultraviolet curing silicone rubber (UV9300, manufactured by Toshiba Silicon Co., Ltd.) was used using an applicator incorporating a suitable transport system and liquid feed system in the head and control sections of a small ink jet printer manufactured by EPSON. 6g, UV9
A mixed solution of 60 mg of 310C (manufactured by Toshiba Silicon Co., Ltd.) and 34 g of heptane is applied to the entire surface, and irradiated online with a high-pressure mercury lamp (UM102, manufactured by Ushio Inc.) for 7 seconds from a distance of 3 cm for 7 seconds. A 5 μm silicon rubber layer was formed.

When the silicone rubber layer in the image area was removed and printed in the same manner as in Example 1, a good printed matter having the same level of inking and non-image area in the image area as in Example 1 was obtained. More than 50,000 sheets could be obtained.

Example 5 Photoconductive zinc oxide SAZEX-2000 (manufactured by Sakai Chemical Co., Ltd.) 100
g, the following binder resin (B-4) 2 g, and the following binder resin (B-
5) 20 g, 0.020 g of the following methine dye (D-2),
A mixture of 0.25 g of phthalic anhydride and 300 g of toluene was mixed with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 1 × 10 5
^The dispersion was performed at a rotation speed of ⁴ rpm for 20 minutes. This dispersion for forming a photosensitive layer was coated on a support for ELP-IIX with a dry adhesion amount of 25%.
g / m ² was applied with a wire bar and dried at 110 ° C. for 1 minute to prepare an electrophotographic photosensitive member.

[0310]

Embedded image

On the surface of this photoreceptor, a peelable surface layer having the following content was provided. A mixed solution of 9 g of a silicon polymer having the following structure, 400 mg of a crosslinking agent having the following structure, 40 mg of catalyst X92-1114 (manufactured by Shin-Etsu Silicon Co., Ltd.), and 150 g of heptane is uniformly applied by a wire bar, and heated at 90 ° C. for 2 minutes. Then, drying and crosslinking were performed to form a surface layer. At this time, the thickness of the surface layer was 1.0 μm. The surface adhesive strength was 1 g · f or less.

[0312]

Embedded image

Next, using a dispersion (L-5) of the following resin (A), a voltage of -120 V was applied on the photoreceptor to electrodeposit resin particles, and a temperature of 60 ° C. was applied for 1 minute. The film was heated to form a transfer layer. At this time, the film thickness was 2 μm. -Dispersion liquid (L-5) of resin (A) 8 g of resin particles (AR-13) (as solid content) 12 g of resin particles (AR-9) (as solid content) 0.09 g of the following positive charge control agent isoper Prepared by adding in 1 liter of G.

[0314]

Embedded image

Next, the photoreceptor was corona-charged to -600 V, and then exposed to light of 833 nm using a semiconductor laser drawing apparatus so that the exposure amount on the photoreceptor became 30 evg / cm ² . Developing was performed using the liquid developer (LD-1) and the bias voltage of the developing section was set to 100 V, followed by rinsing with Isopar G.

Next, an aluminum metal foil was laminated as a printing support between the transfer backup roller having the surface temperature of the photosensitive member of 50 ° C. and the surface temperature of 120 ° C. and the photosensitive member, and subjected to water resistance treatment. The paper support thus obtained was passed at a nip pressure of 8 kgf / cm ² and a transfer speed of 70 mm / sec to transfer the transfer layer and the toner image onto the support.

When the plate thus obtained was visually observed using a 200-fold optical microscope, no transfer layer remained in the non-image area, and high resolution such as fine lines and fine characters in the image area was observed. No loss of territory was noted. The adhesive strength between the toner image portion and the support was 12 g · f, which was a non-fixing state, and the adhesive strength between the support and the transfer layer was 800 g · f or more.

Next, additional silicone rubber (KS774,
A mixed solution of 6 g of Shin-Etsu Silicon Co., Ltd., 180 mg of CAT-PL-4 (Shin-Etsu Silicon Co., Ltd.) and 34 g of heptane was uniformly applied on the transfer layer with a wire bar,
Heat drying and cross-linking were performed at 2 ° C. for 2 minutes to form a silicone rubber layer. At this time, the thickness of the silicon rubber layer is 2.1 μm.
Met. The removal and printing of the silicon layer in the image area were performed in the same manner as in Example 1. As a result, 10,000 or more good prints with clear images and no stains in the non-image area could be obtained.

Example 6 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 1
g, 7.5 g of the following binder resin (B-6), 0.15 g of the following compound (B), and 80 g of cyclohexanone were put into a 500 ml glass container together with glass beads.
The mixture was dispersed for 60 minutes using a paint shaker (manufactured by Toyo Seiki Seisaku-sho, Ltd.), and 1.5 g of the following resin (B-7), 0.03 g of phthalic anhydride and 0.002 of o-chlorophenol were further added thereto.
g was added and dispersed for 2 minutes, and then the glass beads were filtered off to obtain a photosensitive layer dispersion.

[0320]

Embedded image

Next, this dispersion was subjected to a degreasing treatment.
Apply on a 2mm thick aluminum plate with a wire bar,
After drying to the touch, it was heated in a circulating oven at 120 ° C. for 30 minutes. The thickness of the obtained photoreceptor was 8 μm. The surface tackiness of the photoreceptor was 8 g · f.

In the photosensitive layer composition, the resin (B
Except that -7) was not used, the photoreceptor produced in the same manner as described above had a surface adhesive strength of 400 g · f or more and showed no releasability. The photoreceptor was mounted on an apparatus as shown in FIG. 2, and the surface temperature of the photoreceptor was set at 50 ° C.

In the same manner as in Example 1, a transfer layer having a thickness of 3 μm was formed using the following dispersion (L-6) of resin (A). -Dispersion liquid (L-6) of resin (A) 20 g of resin particles (ARW-1) (as solid content) 0.09 g of charge control agent (CD-1) 1 g of the following charge imparting auxiliary agent was added to 1 liter of Isopar G Prepared.

[0324]

Embedded image

With the surface temperature of the photosensitive member kept at 50 ° C., a toner image was formed in the same manner as in Example 1.
(Exxon). Next, the temperature 120
A 150 μm-thick aluminum plate is passed as a printing support between the transfer backup roller heated to ℃ and the photoreceptor under the conditions of a nip pressure of 7 kgf / cm ² and a transfer speed of 80 mm / sec. Then, the transfer layer and the toner image were collectively transferred onto the support. No transfer residue was observed on the photoreceptor. Here, the adhesive strength between the transfer layer and the printing support was 1 kg · f or more, which was a level at which no peeling occurred.

The copied image formed on the support is
Even in a high-resolution area and a high-definition area such as a 12 μm fine line, a Mincho character class 5 or higher, and a 4-95% area of a halftone dot area of 150 lines / inch, there is no missing or distortion, and extremely good. Was something.

A silicone rubber layer was uniformly formed on the transfer layer having the toner image thus obtained by the following process. A 100 μm-thick PET film (Fuji Photo Film Co., Ltd.) whose surface was treated with polyvinyl acetate was added to an additional silicone rubber for release paper (X56-
A5730, Toshiba Silicon Co., Ltd.) (6 g) and heptane (36 g) were coated with a wire bar at 90 ° C. for 2 hours.
After drying for a minute, a donor sheet (DS-1) was prepared.
The thickness of the silicon rubber layer was 2.2 μm.

On the other hand, a cross-linking agent (CM620, manufactured by Toshiba Silicon Co., Ltd.) was applied on the transfer layer having the toner image with a wire bar so as to have a concentration of 30 μg / cm ² . Next, the above-mentioned donor sheet (DS-1) was affixed so that the application surfaces thereof were overlapped, and the silicone rubber layer was transferred onto a printing plate support through a roller. At this time, the roller pressure was set to 5 kgf / cm ² , the roller temperature was set to 90 ° C. for both upper and lower sides, and the transport speed was set to 40 cm / min. Then, the donor sheet P
When only the ET film was peeled off, a silicon rubber layer was formed on the support. The adhesive strength between the non-adhesive resin layer and the transfer layer was 800 g · f or more. The removal and printing of the silicone rubber layer in the image area were performed in the same manner as in Example 1. As a result, 50,000 or more good prints with high-definition images and no stain on the non-image area could be obtained.

Example 7 In the same manner as in Example 6, a transfer layer and a toner image were transferred onto an aluminum plate. On the transfer layer having the toner image, the donor sheet (DS-2) was adhered with a roller so that the silicon rubber surface of the donor sheet (DS-2) overlapped. At this time,
Roller pressure 5kg / cm ² , Roller temperature up and down 11
At 0 ° C., the transport speed was set at 20 cm / min.

Preparation of Donor Sheet (DS-2) 100 μm-thick PET whose surface was treated with polyvinyl acetate
A film (manufactured by Fuji Photo Film Co., Ltd.), 6 g of additional silicone rubber (KS774, manufactured by Shin-Etsu Silicon Co., Ltd.),
A mixed solution of 180 mg of CTA-PL-4 (manufactured by Shin-Etsu Silicon Co., Ltd.) and 34 g of heptane was applied with a wire bar,
Heat drying and crosslinking at 90 ° C. for 2 minutes were performed to form a silicone rubber layer. At this time, the thickness of the silicon rubber layer is 2.0
μm.

Next, when the donor sheet support (PET film) was peeled off at a rate of 10 cm / min in the direction of 150 °, the silicone rubber layer in the non-image area was transferred to the printing plate support. On the other hand, the silicone rubber layer in the image area remained on the donor sheet support. That is, when the PET film of the donor sheet is peeled off, the silicone rubber layer is transferred onto the printing plate support by the adhesive force with the transfer layer in the non-image area, while the toner image area is masked by toner. Therefore, the silicone rubber layer is not substantially adhered to the support together with the transfer layer, and is easily peeled off while being in close contact with the PET film surface when the donor sheet is peeled off.
The adhesive strength between the transfer layer and the printing support is 1 kg · f or more, and the adhesive strength between the non-adhesive resin layer and the transfer layer is 800 g · f.
That was all.

When printing was performed in the same manner as in Example 1 using this printing plate, 50,000 or more good prints with clear images and no stain on the non-image area could be obtained. In addition, the contours of fine lines and characters of the printed matter were sharper than those of the printed matter of Example 6. It is clear by observation with an electron microscope and the like that this is because the phenomenon that the silicon rubber layer at the edge of the non-image portion is obliquely scraped by rubbing the silicon rubber layer does not occur in the peel-apart method of this embodiment. Was.

Examples 8 to 19 In Example 2, the resin particles (A) for forming the transfer layer (T) were used.
A printing plate was prepared and printed in the same manner except that the resin particles shown in Table-D were used instead of R-1).

[0334]

[Table 4]

In each of the embodiments, there is no loss or disturbance in the high-resolution area such as thin lines and thin characters, and no loss or disturbance of the halftone dots in the high-definition image area of the halftone halftone portion. More than 10,000 prints having print images were obtained.

Example 20 In Example 6, 15 g of resin particles (AR-8) (AR-8) was used instead of 20 g of resin particles (ARW-1) of the dispersion (L-6) of the resin (A) for forming a transfer layer. A 2.8 μm-thick transfer layer was formed in the same manner except that 5 g (as a solid content) of the resin particles (AR-9) and 5 g of the resin particles (AR-9) were used.

The following silicone rubber layer was provided by using a printing plate support to which a toner image was transferred and formed in the same manner as in Example 6. On the transfer layer, 9 g of the following silicone rubber base polymer (SB-1) and the following crosslinking agent (SV-
1) A mixed solution of 400 mg, catalyst X92-1114 (Shin-Etsu Silicon Co., Ltd.) 40 mg and heptane 60 g was uniformly applied by a wire bar, dried at 90 ° C. for 2 minutes and crosslinked to form a silicone rubber layer. did. At this time, the thickness of the silicon rubber layer was 2.21 μm.

[0338]

Embedded image

According to the above method, the adhesion between the transfer layer and the silicone rubber layer can be improved. When the image portion silicone rubber layer was removed and printed in the same manner as in Example 6, a clear image was obtained. 50,000 or more good prints with no background stain on the non-image area were obtained. In this example, the adhesive strength between the transfer layer and the printing plate support was 1 kg · f or more, and the adhesive strength between the non-adhesive resin layer and the transfer layer was 800 g · f or more. The same performance was obtained by using the resin particles (ARW-2) instead of the resin particles (AR-9).

Example 21 In Example 20, a silicone rubber-based polymer (S
When the same procedure as in Example 20 was carried out except that a silicone rubber-based polymer (SB-2) having the following structure was used instead of B-1), it was possible to obtain at least 50,000 good printed matter equivalent to that of Example 20. Was completed.

[0341]

Embedded image

Example 22 A printing plate was prepared in the same manner as in Example 1, except that the transfer layer and the non-adhesive resin layer were changed as follows.

<Transfer Layer> Dispersion of Resin (A) (L-1)
In the same manner as in Example 1, except that 20 g (as the solid content) of the resin particles (AR-6) was used instead of 20 g (as the solid content) of the resin particles (AR-3).

<Non-adhesive resin layer> 5 g of the following silicone rubber base polymer (SB-3) and 5 g of the following silicone polymer, 400 mg of crosslinking agent (SV-1), Catalyst X92-11
14 (manufactured by Shin-Etsu Silicon Co., Ltd.) 40 mg and heptane 60
g of the mixture is uniformly applied with a wire bar,
Heat drying and crosslinking were performed for a minute to form a silicone rubber layer. At this time, the thickness of the silicon rubber layer was 2.50 μm.

[0345]

Embedded image

When the silicone rubber layer in the image area was removed and printed in the same manner as in Example 1, 3,000 or more excellent printed matters with clear images and no background smear in the non-image area were obtained. Similar results were obtained when resin particles (ARW-6) were used instead of the resin particles (AR-6) in the transfer layer.

[0347]

According to the present invention, an electrophotographic waterless planographic printing plate which is applicable to a low output laser beam scanning exposure system, has excellent plate making and printing quality, and has high printing durability is produced. be able to.

[Brief description of the drawings]

FIG. 1 is a schematic diagram for explaining the present invention.

FIG. 2 shows an example of an apparatus for performing the method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Photoconductor support 2 Photosensitive layer 5 Toner image 6 Non-adhesive resin layer 10 Compound (S) application apparatus 11 Photoconductor 12 Transfer layer 13 Transfer layer forming unit 14 Liquid developing unit set 14T Toner image forming unit 14R Rinse means 15 Absorption Exhaust unit 15a Intake section 15b Exhaust section 16 Heating means 18 Corona charging device 19 Exposure device 20 Lithographic printing plate support 31 Transfer backup roller 32 Peeling backup roller

Claims (5)

[Claims] An electrophotographic photoreceptor is provided on a surface thereof with a peelable transfer layer (T) mainly containing a thermoplastic resin (A), and a non-fixed layer is formed on this layer by an electrophotographic process using a liquid developer. A toner image is formed, and the toner image is transferred together with the transfer layer (T) onto a lithographic printing plate support. Further, the adhesive force to the transfer layer (T) surface is applied to the entire surface of the transfer layer (T) on the support. After providing a non-adhesive resin layer larger than 180 gram-force by the adhesive force measured based on `` Adhesive tape / adhesive sheet test method '' of JIS Z0237-1980 than the adhesive force between the toner image and the support surface, A method for preparing an electrophotographic waterless planographic printing plate, comprising selectively removing a transfer layer (T) and a non-adhesive resin layer on a toner image. 2. The adhesive force between a toner image and the surface of a lithographic printing plate support is 20 gram · forc as an adhesive force measured based on “Testing method of adhesive tape / adhesive sheet” of JIS Z0237-1980.
e or less, and the adhesive force between the non-adhesive resin layer and the transfer layer (T) and the adhesive force between the transfer layer (T) and the surface of the lithographic printing plate support are 200 gram-force or more at the same adhesive force. 2. The method for preparing an electrophotographic waterless planographic printing plate according to claim 1, wherein: 3. The method according to claim 1, wherein the non-adhesive resin layer on the toner image is removed by dry means. 4. The transfer layer (T) according to claim 1, wherein the transfer layer (T) contains a reactive group capable of chemically bonding at an interface between the transfer layer (T) and the non-adhesive resin layer. The method for producing an electrophotographic waterless planographic printing plate described in 1 above. 5. The electrophotographic photosensitive member according to claim 1, wherein the surface of the electrophotographic photosensitive member has a peelability of JIS.
The electrophotographic waterless lithographic plate according to any one of claims 1 to 4, wherein the surface adhesive strength measured based on "Adhesive tape / adhesive sheet test method" of Z0237-1980 is 20 gram / force or less. How to make a printing plate.