JP3274213B2 - Electrophotographic color proofing master - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic color proofing master, and more particularly to an improvement in a photoconductive layer of the color proofing master.

[0002]

2. Description of the Related Art As a printing plate for multicolor printing, a PS plate is exclusively used from the viewpoints of quality, printing durability, dimensional stability, and resistance to contamination. The PS plate is a plate material in which a photosensitive layer mainly composed of a diazo resin or o-quinonediazide is provided on an aluminum support that has been subjected to a surface treatment for improving hydrophilicity. A printing plate can be prepared by exposing the exposed film to ultraviolet light, developing the exposed film and exposing the hydrophilic aluminum surface except for the photosensitive layer in the non-image area. A printing plate is prepared for each color by this process, and the printing plate is sequentially applied to a printing machine and printed on one sheet of printing paper using a corresponding ink, whereby a printed matter of a multicolor image can be obtained. In such a printing method, a series of editing operations such as character input, layout, and color designation, plate making, confirmation of work performed as specified in each process of printing, and ordering of an orderer for color tone reproduction and the like. After confirming that there is no difference, and making corrections if necessary, the process proceeds to actual printing. This step is called calibration. The former is called the inner school,
As described above, the purpose is to check each process inside the printing company. On the other hand, the latter is called a foreign school, which is a proofreading for obtaining printing permission from the orderer, uses the same ink, printing paper, and the like as this machine printing, and the printed result is almost the same as this machine printing. Here, performing proof printing on printing paper used for printing on the machine is called proofreading. Regarding color designation and color tone reproduction, it is necessary to confirm and correct each color. In particular, proof printing as a foreign school is actually repeated several times. Conventional proof printing uses a printing plate produced using color-separated and shaded film used for actual printing and a relatively inexpensive and low-durability PS plate called for proof printing. For example, printing is performed by a proofing machine having a mechanism similar to a printing machine called a flat table four-color proofing machine manufactured by Dainippon Screen. This is called press proof, but has the drawback that it takes a long time to produce a printing plate, and it is difficult to maintain a certain quality because of the skill required for the operation.

Several color proofing methods have been proposed which do not use a proofing machine having a mechanism close to such a printing press, and are therefore simple and free from unstable elements caused by printing. It is used as preferred from the point of view. This is called an off-press proof, and a typical system and system is the Journal of the Printing Society of Japan, Vol.
2 (1989). For example, it is a system that has been put to practical use under trade names such as Color Art (Fuji Photo Film Co., Ltd.), Cromarine (DuPont), and Match Print (3M). These are systems that use a color separation film but do not use the above-described proofing machine. Color separation films are often manufactured using a color scanner. This involves reading data from a manuscript, performing color separation, shading, and tone reproduction control, outputting it as digital data, and scanning and exposing the silver halide film with laser light modulated based on the data, and developing it. , Fixing and drying processes to produce a positive or negative film for a multicolor printing plate. In recent years, an electronic plate making system called a total color scanner has been further developed and put into practical use. This system can perform retouching or plate collection in the system, and requires an internal school that judges the quality of the finish more quickly than before. In other words, if the specifications and layout as a result of processing in the system, the suitability of the color separation quality of some pictures, the reproducibility of the tone, etc. were done by the conventional calibration method,
Because you have to wait for output to color separation film, press proof or off-press proof finish,
This will significantly reduce the utilization efficiency of the system. Since image data in the system can be used as digital information, some digital direct color proof systems that do not rely on the conventional calibration method have been proposed. Details of these are described in the “Printing Information” magazine, April 1991, page 2 and thereafter. Examples of the method include a silver salt method, an electrostatic toner method (wet electrophotographic method), an ink jet method, and a thermal sublimation transfer method.

[0004] In particular, in the wet electrophotography method, the photoconductive photoreceptor is charged, laser-exposed, and then developed with a color toner in which a pigment is dispersed in an electrically insulating liquid. Since the toner image can be transferred after repeating the four colors of M, Y, and Bk, high definition, high image quality, good color tone and tone reproducibility, and proofreading is possible because any paper is selected. Has the advantage of being However, it is extremely difficult to completely transfer the toner image directly from the surface of the photoreceptor to the actual paper, and the technique disclosed in Japanese Patent Application Laid-Open No. 2-272469, which can achieve this, requires several steps. Japanese Patent Application Laid-Open No. Sho 61-174557 (JP-B 2-43185) discloses a method in which a transferable layer is provided on the surface of a photoconductive layer, a toner image is formed on the transfer layer, and the entire transfer layer is transferred to the paper. This is described in Japanese Unexamined Patent Application Publication No. 1-112264, Japanese Patent Application Laid-Open No. 1-281464, and Japanese Patent Application Laid-Open No. 3-11347. Among them, the only one practically used is disclosed in JP-A-61-174557.
In this technique, the exposure is performed from the transparent support (polyethylene terephthalate film) side of the electrophotographic light-sensitive material, and the conductive layer must be transparent. It is disadvantageous in terms of terms. JP-A-1-112264, JP-A-1-281264
Has proposed an image forming method or a color printing method using a photosensitive paper in which a release layer and an adhesive layer are sequentially provided on the surface of a photoconductive layer. It is characterized by doing. However, it is difficult to form the structure of the photoconductive layer used in these methods uniformly with a practical area and to transfer the toner image without damaging the toner image.

The same can be said for the method using a recording medium in which a releasable overcoat layer is provided on a photoconductive layer in JP-A-3-11347. In addition to the problem of image deterioration related to transfer as described above, there are various problems in forming an image by an electrophotographic process, and the cause of such a problem is, in particular, the electrostatic characteristics of an electrophotographic photosensitive member. Can be A system using an electrophotographic photoreceptor composed of a known photoconductive layer was examined in detail by changing the environmental conditions at the time of imaging (high temperature / high humidity or low temperature / low humidity). (Particularly charge retention in the dark, light sensitivity, etc.) fluctuated, and a stable and good copied image could not be obtained. In addition, if a scanning exposure method using a semiconductor laser beam is adopted in an electrophotographic color proofing plate that can support today's digital direct conversion, the time will be longer than in the case of a full-surface simultaneous exposure method using visible light. Because there are restrictions on strength,
Higher performance is required for electrostatic characteristics, particularly dark charge retention characteristics and light sensitivity. On the other hand, in the above-mentioned known original plate, the electrophotographic characteristics are deteriorated, the ground fog is liable to occur in the actual copied image, and the thin lines are skipped and the characters are blurred. The printed image has dropped.

[0006]

SUMMARY OF THE INVENTION The present invention is to provide a color proofing original plate using an electrophotographic method in which the above problems are improved. SUMMARY OF THE INVENTION An object of the present invention is to easily and stably obtain a high-definition, high-quality color proof print without color shift. Another object of the present invention is to provide an electrophotographic color proofing original plate which can be easily manufactured and has a low manufacturing cost. Still another object is to provide a method for producing a color proof print which can easily transfer a toner image by a transfer device having a simple structure, and can perform proof printing on a printing paper sheet irrespective of transfer paper. It is in. Another object of the present invention is to provide a color proofing original plate capable of giving a color proof having a clear and high-quality image even when the environment at the time of forming a copy image fluctuates as low or low humidity or high temperature and high humidity. It is to be. Another object of the present invention is to provide a color proofing master which is hardly affected by the type of sensitizing dyes that can be used together and has excellent electrostatic characteristics even in a scanning exposure method using a semiconductor laser beam.

[0007]

According to the present invention, there is provided a support,
Electrophotography for producing a color proof by transferring a toner image of at least one color formed on the transfer layer by an electrophotographic process together with a transfer layer to a material to be transferred, including a photoconductive layer and a transfer layer. Formula master for color proofing, wherein the photoconductive layer is a resin (P) selected from the group consisting of the following resins (P ₁ ), (P ₂ ), (P ₃ ) and (P ₄ ); Resins (Q ₁ ) and (Q
₂ ) a resin [Q] selected from the group consisting of:
Or a resin [R] containing at least one structural unit containing at least one thermosetting group, and the resin [P] is present at least near the surface in contact with the transfer layer, and the JIS of the surface Z0237-1980 "Adhesive tape / sheet test method" has an adhesive strength of 15
Achieved by an electrophotographic color proofing master characterized by being less than or equal to 0 gram · force (g · f). (1) Resin (P ₁ ): a segment (X) containing 50% by weight or more of a constituent unit containing a fluorine atom and / or a silicon atom and a constituent unit containing at least one kind of light and / or thermosetting group. And a linear block copolymer containing a segment (Y). (2) Resin (P ₂ ): a segment (X) containing 50% by weight or more of a constituent unit containing a fluorine atom and / or a silicon atom and a constituent unit containing at least one kind of light and / or thermosetting group. AB containing segment (Y)
A star copolymer in which at least three type block polymer chains are bonded via an organic group (Z). (3) Resin (P ₃ ): a segment (X) containing 50% by weight or more of a constituent unit containing a fluorine atom and / or a silicon atom and a constituent unit containing at least one kind of light and / or thermosetting group. And a graft copolymer containing a segment (Y).

(4) Resin (P ₄ ): It contains a segment (X) containing 50% by weight or more of a structural unit containing a fluorine atom and / or a silicon atom and at least one kind of light and / or thermosetting group. An AB type or ABA type block copolymer containing a segment (Y) containing a structural unit, and at least one of the segments (X) is a graft type segment (X ′) shown below, or At least one of Y) is the following graft-type segment (Y '), or at least one of the segments (X) is the following graft-type segment (X'), and at least one of the segments (Y) is A copolymer having one of the following graft segments (Y '). Graft type segment (X '): weight average molecular weight 1 × 1
0 ³ a to 2 × 10 ^4, a fluorine atom and / or a structural unit containing a silicon atom 50 wt% or more, preferably contains macromonomer unit which contains more than 90% by weight of (M _A) as a copolymer component segment. Graft type segment (Y '): weight average molecular weight is 1 × 1
0 ³ a to 2 × 10 ^4, segment containing macromonomer unit consisting of structural units containing no structural units containing a fluorine atom and / or silicon atom (M _B) as a copolymerization component. (5) Resin (Q ₁ ): having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and having the following general formula (I):

[0009]

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Wherein b ¹ and b ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group, and R ³ represents a hydrocarbon group; and -PO ₃ H ₂
Group, -SO ₃ H group, -COOH group, -PO (OH) (R
¹ ) (wherein R ¹ represents a hydrocarbon group or —OR ² (R ² represents a hydrocarbon group)) and a cyclic acid anhydride group and contains at least one polar group. The following general formula (II) only at one end of the polymer main chain containing the united component

[0011]

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[Wherein V¹Is -COO-, -OCO-,
-CH_TwoOCO-, -CH_TwoCOO-, -O-, -SO
_Two-, -CO-, -CONHCOO-, -CONHCO
NH-, -CONHSO_Two-, -CON (T¹)-,-
SO_TwoN (T¹)-Or -C₆H_Four-(Where,
T¹Represents a hydrogen atom or a hydrocarbon group), b^ThreeAnd b^Four
Is hydrogen, halogen, cyano, hydrocarbon
Group, -COOZ¹Or -Z ^Two-COOZ¹(Z¹Is hydrogen
Z represents an atom or a hydrocarbon group;^TwoRepresents a hydrocarbon group)
Represents Represented by the following formula:
Weight average molecular weight 1 × 10^FourThe following monofunctional macromonomers
ー (M_CA) a graft copolymer comprising at least: (6) Resin (Q_Two): 1 × 10^Three~ 2 × 10^FourWeight average
Having a molecular weight of -PO_ThreeH_Two Group, -SO_ThreeH group, -CO
OH group, phenolic OH group, -PO (OH) (R¹)
(Where R ¹Has the same meaning as above.)
It contains at least one polar group selected from acid anhydride groups.
Block containing at least one polymer component having
And the following general formula (III):

[0013]

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[Wherein V^TwoIs -COO-, -OCO-,
− (CH_Two)_aOCO-,-(CH_Two)_aCOO- (a is 1
Represents an integer of ~ 3), -O-, -SO_Two-, -CO-,
−CON (T¹)-, -SO_TwoN (T¹)-, -CON
HCOO-, -CONHCONH- or -C₆H_Four-
Representation (where T¹Has the same meaning as described above), R
^FourRepresents a hydrocarbon group, b^FiveAnd b⁶Is b¹And b
^TwoHas the same meaning as Where V^TwoIs -C₆H_Four-
When represented, R^FourRepresents a hydrogen atom or a hydrocarbon group. 〕so
B block containing at least one polymer component shown
B block of AB block copolymer composed of
Consisting of a polymerizable double bond bonded to the terminal of the polymer main chain
Monofunctional macromonomer (M_D) At least one type
A graft copolymer contained as a combined component.

The photoconductive layer of the present invention may be any layer in which the photoconductive compound is dispersed in a binder resin such as resin [Q] and resin [R]. And a so-called laminated type (or a function separation type) including at least a charge generation layer and a charge transport layer which are photoconductive compound dispersion layers. What is important is that the resin [P] is unevenly distributed in the vicinity of the surface of the various photoconductive layers in contact with the transfer layer, and that the surface has improved release characteristics. For example, in a function-separated photoconductive layer composed of a charge generation layer and a charge transport layer, the charge transport layer adjacent to the transfer layer contains a resin [P] and a resin [R], and the charge generation layer is a resin. [Q] and a photoconductive compound. Further, in the function-separated type photoconductive layer including the charge generation layer and the charge transport layer, the charge transport layer adjacent to the transfer layer is formed of a resin [P], a resin [R], a resin [Q], and a photoconductive layer. Sexual compounds may also be included. Preferably, the resin [P] is contained in an amount of 1 to 30% by weight based on the total weight of the resin in the layer containing the resin. The amount of the resin [Q] is preferably the amount of the photoconductive compound 1
The amount is 1 to 100 parts by weight, more preferably 3 to 50 parts by weight, based on 00 parts by weight. The amount of the resin [R] is preferably 5 to 5% based on the total weight of the resin in the layer containing the resin.
９99.1% by weight. In the present invention, the binder resin is a resin that forms a matrix in which the photoconductive compound is dispersed, and the resin [P], the resin [Q], the resin [R] used in the present invention, and any other Including resin.
Also, preferably, the photoconductive layer of the present invention contains a light and / or thermosetting agent. In the present specification, “light and / or thermosetting agent” refers to a light and / or thermosetting compound, light and / or
Or a thermosetting oligomer, a light and / or thermosetting resin and a crosslinking agent.

[0016]

In the color proofing master of the present invention, the photoconductive layer is adjacent to the photoconductive layer when the photoconductive layer is a monodispersed layer type, and is adjacent to the transfer layer of the photoconductive layer when the photoconductive layer is a laminated type. When a coating film is formed by allowing a small amount of resin [P] to coexist in the layer, the resin [P] migrates to the surface of the film and concentrates after the application and before the drying step is completed, where the resin [P] is removed. Is expressed. On the other hand, the polymer segment (X) containing fluorine and / or silicon atoms in the resin [P] has a good compatibility with the resin [R] because the polymer segment (X) has a good compatibility with the resin [R]. It is arranged inside the photoconductive layer. As a result, releasability is exhibited on the surface of the photoconductive layer, and an interaction between the polymer segment (Y) and the resin [R] produces an anchor effect. Further, the segment (Y) of the resin [R] and the resin [P] contains a light and / or thermosetting group, and preferably, the photoconductive layer contains a light and / or thermosetting agent. When the layer is formed and then cured by light and / or heat, the layer is cured in a state where the resin [P] in the layer is oriented on the surface, so that the orientation state is sufficiently fixed. Is obtained. This further prevents the transfer of the resin [P] to the transfer layer when the transfer layer is formed as a coating film, and can maintain the interface between the transfer layer and the photoconductive layer clearly. Therefore, when the color proofing master of the present invention is used, in the proof printing, the toner image formed by the electrophotographic process is transferred well for each transfer layer, and there is no problem such as defective peeling of the transfer layer. In addition, a solvent for coating is selected depending on the type of the thermoplastic resin for the transfer layer. However, depending on the solvent, when forming the transfer layer, the solvation action with the binder resin of the photoconductive layer causes the light to be reduced. In some cases, this affects the dispersion state of the conductive layer and adversely affects the electrophotographic characteristics (for example, ground fogging is likely to occur and image quality is deteriorated). Such a problem is solved by imparting solvent resistance by crosslinking the photoconductive layer of the present invention.

Further, in the photoconductive layer of the present invention, the layer containing the photoconductive compound is a resin [Q] as a binder resin.
, The photoconductive compound is finely divided and uniformly dispersed. Furthermore, when sensitizing using a spectral sensitizing dye, even if the type of spectral sensitizing dye used in the photoconductive layer of the present invention is variously changed, these dyes sufficiently interact with the photoconductive compound. Can be. In particular, the interaction between the dye used for spectral sensitization for semiconductor laser light and the photoconductive compound is insufficient in the known binder resin system, but it is sufficient in the system of the present invention to interact. it can. Although the details are unknown, when the photoconductive compound and the spectral sensitizing dye are dispersed in the coexistence of the resin [Q], the resin [Q] causes the adsorption interaction between the dye and the photoconductive compound. This is probably because the resin [Q] adsorbs onto the surface of the photoconductive compound particles without hindrance, and keeps the coating of the surface of the photoconductive compound particles with the dye in an appropriate state. It is considered that, due to these, good and stable electrophotographic characteristics can be maintained even when environmental conditions such as low temperature / low humidity and high temperature / high humidity are significantly changed. On the other hand, when the photoconductive layer is a monodispersed layer type as described above, a system in which the resin [R] and a small amount of the resin [P] coexist with the photoconductive compound and the resin [Q]. Even in such a composite system, the resin [Q] sufficiently interacts with the photoconductive compound, and can maintain the above-described excellent electrostatic characteristics without being inhibited by the resin [R]. . At the same time, the surface uneven distribution resin [P]
Is concentrated on the surface portion and can sufficiently exhibit surface peelability.

As described above, the original plate for color proofing of the present invention is characterized in that the surface of the photoconductive layer in contact with the transfer layer has good releasability. JIS
Z0237 @ 1980 "Testing method for adhesive tape / sheet"
Judgment by the adhesive force tested by That is, the color proofing plate of the present invention has an adhesive force of 150 gram · force (g · f) or less, preferably 100 g · f or less, more preferably 5 g / f or less, of the surface of the photoconductive layer in contact with the transfer layer according to the above test method.
It must be 0 g · f or less. The adhesive strength was measured using the electrophotographic color proofing plate as the "test plate", the 6 mm wide adhesive tape as the "adhesive tape", and peeling off the adhesive tape at a peeling speed of 120 mm / min. It is expressed in proportion to a 10 mm wide adhesive tape. The adhesive strength of the photoconductive layer surface after the formation of the transfer layer is equal to the adhesive strength of the photoconductive layer surface before the formation of the transfer layer.

As described above, the color proofing plate of the present invention comprises:
It includes a support, a photoconductive layer and a transfer layer. Hereinafter, each will be described in detail. [Support] In the present invention, the photoconductive layer can be provided on a conventionally known support. The support is preferably conductive. As the conductive support, a support such as that conventionally used, for example, a substrate such as a metal, paper, or a plastic sheet is impregnated with a low-resistance substance to be conductive. Treated, 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 photoconductive layer is provided) and further preventing curling, A body provided with a water-resistant adhesive layer on the surface of the body, a body provided with at least one or more pre-coat layers as required on the surface layer of the support, or a sheet obtained by laminating a conductive plastic on which Al or the like is deposited on paper. Etc. can be used.

Specifically, as an example of a conductive substrate or a conductive material, Yukio Sakamoto, Electrophotography, 14, (No.
1), pp. 2-11 (1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry", Polymer Publishing Association (1975), MF
Hoover, J. Macromol. Sci. Chem. A-4 (6), 13
And the like described on pages 27 to 1417 (published in 1970) and the like. [Photoconductive layer] (Resin [P]) As described above, resin [P] is resin (P ₁ )
~ Selected from the group consisting of (P _4), which are copolymers containing both segments (X) and the segment (Y). Preferably, the segment (X) of the resin [P] contains at least 80% by weight of a structural unit containing a fluorine atom and / or a silicon atom, based on the total weight of the segment (X).
Particularly, the content is 90% by weight or more. In addition, segment (Y)
Is preferably 1 to 60 based on the total weight of the segment (Y),
% By weight, more preferably 5 to 40% by weight. The existence ratio of segment (X) and segment (Y) is 5-9
5/95 to 5 (weight ratio), preferably 10 to 90
/ 90 to 10 (weight ratio). Further, the number of fluorine atoms and / or silicon atoms contained in the structural unit having a fluorine atom and / or a silicon atom in the segment (X) is preferably 3 or more when only a fluorine atom is contained. And when it contains only silicon atoms, it is two or more, and when it contains both fluorine atoms and silicon atoms, it is one or more each. (Resin (P ₁ )) The resin (P ₁ ) contains a segment (X) containing 50% by weight or more of a structural unit containing a fluorine atom and / or a silicon atom and at least one kind of light and / or thermosetting group. And a segment (Y) containing the following structural unit. The resin (P ₁ )
May be any linear block copolymer,
For example, an AB type (that is, (X)-(Y)) block copolymer or a multi-block thereof, or an ABA type (that is, (X)-(Y)-(X), (Y)-(X) −
(Y)) a block copolymer. The weight average molecular weight of the resin (P ₁ ) is 5 × 10 ³ to 1 × 10 ⁶ , preferably 1 × 10 ^{4 to} 5 × 10 ⁵ . The weight average molecular weight of the segment (X) in the resin (P ₁ ) is preferably 1 × 10 ³ or more. (Resin (P ₂ )) The resin (P ₂ ) comprises at least one kind of a segment (X) containing 50% by weight or more of a structural unit containing a fluorine atom and / or a silicon atom and a light and / or thermosetting group. A star-type copolymer in which at least three AB-type block polymer chains containing a segment (Y) containing a constituent unit are bonded via an organic group (Z). In the AB type block polymer chain of the resin (P ₂ ), the sequence of the segment (X) and the segment (Y) in the polymer chain may be any order. That is, the polymer is schematically shown below.

[0021]

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(Where Z represents an organic group, (A) represents a segment (X), and (B) represents a segment (Y). The upper limit of the number of molecular chains is usually 15 and preferably 10.
The weight average molecular weight of the resin (P ₂ ) is 5 × 10 ³ to 1 × 10
⁶ , preferably 1 × 10 ^{4 to} 5 × 10 ⁵ . Also,
The weight average molecular weight of the segment (X) in the resin (P ₂ ) is preferably 1 × 10 ³ or more. The organic group (Z) is not particularly limited as long as it has a molecular weight of 1,000 or less. Examples include the following trivalent or higher valent hydrocarbon groups.

[0023]

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[Where r ^{1 to} r ⁶ are each a single bond,
Represents a hydrogen atom or a hydrocarbon group. However, at least one of r ¹ and r ² and at least one of r ^{3 to} r ⁶
One represents a single bond or a divalent or higher valent hydrocarbon group. These hydrocarbon groups are composed of a single or any combination thereof, and in the case of a combination, -O-, -S-, -N (r
^{7) -, - COO -,} - CON (r 7) -, - SO 2
_{-, - SO 2 N (r} 7) - ( wherein each represent r ⁷ hydrogen atom or a hydrocarbon group), - NHCOO -, - NH
Hetero atom-containing heterocycles such as CONH-, an oxygen atom, a sulfur atom and a nitrogen atom (e.g., thiophene ring, pyridine ring, pyran ring, imidazole ring, benzimidazole ring, furan ring, piperidine ring, pyrazine ring, pyrrole ring, piperazine And a bonding unit such as a ring. Examples of other linking groups that bind the polymer chain include those composed of a combination of a group selected from the following structures and the above-mentioned binding unit. However, the organic group (Z) in the present invention is not limited to these.

[0025]

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(Resin (P ₃ )) The resin (P ₃ ) contains 50% by weight of a structural unit containing a fluorine atom and / or a silicon atom.
A graft copolymer containing the above-mentioned segment (X) and a segment (Y) containing a structural unit containing at least one kind of light and / or thermosetting group. In the resin (P ₃ ), the segment (X) and the segment (Y)
May be in any order in the polymer chain. That is, the polymer is schematically shown below.

[0027]

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The weight average molecular weight of the resin (P ₃ ) is 5 × 10
³ to 1 × 10 ⁶ , preferably 1 × 10 ^{4 to} 5 × 10 ⁵
It is. The weight average molecular weight of the segment (X) in the resin (P ₃ ) is preferably 1 × 10 ³ or more.

(Resin (P ₄ )) The resin (P ₄ ) contains 50% by weight of a structural unit containing a fluorine atom and / or a silicon atom.
An AB- or ABA-type block copolymer composed of a segment (X) containing the above and a segment (Y) containing a constituent unit containing a light and / or thermosetting group, and the segment (X) Is at least one of the following graft segments (X ′), at least one of the segments (Y) is the following graft segment (Y ′), or at least one of the segments (X) is And a copolymer in which at least one of the segments (Y) is the following graft segment (Y ′). Graft type segment (X ′): weight average molecular weight is 1 × 1
0 ³ a to 2 × 10 ^4, a fluorine atom and / or a structural unit containing a silicon atom 50 wt% or more, preferably contains macromonomer unit which contains more than 90% by weight of (M _A) as a copolymer component segment. Graft type segment (Y ′): weight average molecular weight is 1 × 1
0 ³ a to 2 × 10 ^4, segment containing macromonomer unit consisting of structural units containing no structural units containing a fluorine atom and / or silicon atom (M _B) as a copolymerization component. In the resin (P ₄ ), the arrangement order of the segment (X) and the segment (Y) may be any. Examples of the copolymer include those schematically shown below.

[0030]

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The proportion of the macromonomer portion (M _A ) in the segment (X) is 1 to 50% by weight, preferably 3 to 30% by weight, based on the total weight of the segment (X).
It is. The proportion of the segment (Y) of the macromonomer unit (M _B), based on the total weight of the segment (Y), 1 to 50% by weight, preferably 3 to 30 wt%. Preferably, the macromonomer unit (M _B)
It is a structural unit containing a photo and / or thermosetting group, 1 to 50% by weight relative to the total weight of the macromonomer unit (M _B), preferably in an amount of 3 to 20 wt% .

The weight average molecular weight of the resin (P ₄ ) is 5 × 10
³ to 1 × 10 ⁶ , preferably 1 × 10 ^{4 to} 5 × 10 ⁵
It is. The weight average molecular weight of the segment (X) in the resin (P ₄ ) is preferably 1 × 10 ³ or more.
Hereinafter, the segment (X) and the segment (Y) will be described in detail. (Segment (X)) The structural unit containing a fluorine atom and / or a silicon atom in the segment (X) has, for example, the following substituent having a fluorine atom and / or substituent having a silicon atom. The substituent may be incorporated in the polymer main chain of the resin [P] or may be bonded to a polymer side chain. Monovalent or divalent substituent having a fluorine atom:
-C _b F _{2b +} 1 _(b is an integer of 1~18), - (C
F ₂ ) _c CF ₂ H (c represents an integer of 1 to 17),-
CFH ₂ , -CF _2- , -CFH-,

[0033]

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Monovalent or divalent substitution having a silicon atom
Group: -Si (R^Five) (R⁶) (R⁷), −Si (R⁸) (R⁹)-Wherein R is^Five, R⁶, R⁷, R⁸, R⁹Are the same for each
And may be different and are substituted with 1 to 22 carbon atoms.
A hydrocarbon group, and a fluorine atom-containing monovalent compound as described above.
Group, -OR 'group (R' is substituted with 1 to 22 carbon atoms)
Represents an optionally substituted hydrocarbon group), or -OSi
(R^Five') (R⁶') (R⁷') (In the group, R^Five'~ R ⁷'Is the same for each
May be different and may be substituted having 1 to 22 carbon atoms.
Good hydrocarbon group, fluorine atom-containing monovalent organic as described above
Residue, -OR 'group (R' is a C1-22 substituted
Represents an optionally substituted hydrocarbon group). R^Five~ R⁹, R 'and R^Five'~ R⁷Examples of ': charcoal
An alkyl group which may be substituted and has a prime number of 1 to 22 (for example,
Tyl, ethyl, propyl, butyl, hexyl
Group, octyl group, decyl group, dodecyl group, hexadecyl
Group, 2-chloroethyl group, 2-bromoethyl group, 2,
2,2-trifluoroethyl group, 2-cyanoethyl group,
3,3,3-trifluoropropyl group, 2-methoxy
Tyl group, 3-bromopropyl group, 2-methoxycarbonyl
Ruethyl group, 2,2,2,2 ′, 2 ′, 2′-hexaf
Substituted with 4 to 22 carbon atoms
An alkenyl group (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-
Xenyl group, etc.), and may be substituted having from 7 to 12 carbon atoms.
Aralkyl groups (for example, benzyl group, phenethyl group,
3-phenylpropyl group, naphthylmethyl group, 2-naph
Tylethyl group, chlorobenzyl group, bromobenzyl group,
Methylbenzyl group, ethylbenzyl group, methoxybenzyl
Group, dimethylbenzyl group, dimethoxybenzyl group
Etc.), an optionally substituted alicyclic group having 5-8 carbon atoms
(For example, a cyclohexyl group, a 2-cyclohexyl group,
2-cyclopentylethyl group etc.) or having 6 to 12 carbon atoms.
An aromatic group which may be substituted (for example, a phenyl group,
Naphthyl group, tolyl group, xylyl group, propylphenyl
Group, butylphenyl group, octylphenyl group, dodecyl
Phenyl group, methoxyphenyl group, ethoxyphenyl
Group, butoxyphenyl group, decyloxyphenyl group,
Lorophenyl group, dichlorophenyl group, bromophenyl
Group, cyanophenyl group, acetylphenyl group, methoxy
Carbonylphenyl group, ethoxycarbonylphenyl
Group, butoxycarbonylphenyl group, acetamidophene
Nyl group, propioamidophenyl group, dodecylylamido
Dophenyl group etc.).

Further, the substituent having a fluorine atom and the substituent having a silicon atom may be constituted in combination. In this case, the substituent may be directly bonded or further via another linking group. May be combined. Linking group is, for example, a divalent organic group, -O -, - S -, - NR 5 -, - S
_{O -, - SO 2 -,} - COO -, - OCO -, - CON
HCO -, - NHCONH -, - CONR 5 -, - SO
It may be selected from ₂ NR ^5- and the like, and may be a divalent aliphatic group or a divalent aromatic group, or an organic group constituted by a combination of these divalent groups.
Here, R ⁵ has the above-mentioned meaning. Examples of the divalent aliphatic group include the following.

[0036]

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E ₁ and e ₂ may be the same or different and are each a hydrogen atom, a halogen atom (eg, a chlorine atom or a bromine atom) or an alkyl group having 1 to 12 carbon atoms (eg, a methyl group, an ethyl group). Group, propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.). Q is -O-,
-S- or -NR ¹⁰ - represents, R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms, a -CH ₂ Cl or -CH ₂ Br. Examples of the divalent aromatic group include a phenylene group, a naphthylene group, and a 5- or 6-membered heterocyclic group (at least a heteroatom selected from an oxygen atom, a sulfur atom, and a nitrogen atom as a heteroatom constituting a heterocycle). One type). These aromatic groups may have a substituent, for example, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a propyl group) , A butyl group, a hexyl group, an octyl group, etc.) and an alkoxy group having 1 to 6 carbon atoms (eg, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.).

Examples of the heterocyclic group include a furan ring, a thiophene ring, a pyridine ring, a pyrazine ring, a piperazine ring, a tetrahydrofuran ring, a pyrrole ring, a tetrahydropyran ring, and a 1,3-oxazoline ring. Next, specific examples of the structural unit having a substituent having a fluorine atom and / or a silicon atom as described above, that is, the structural unit having a fluorine atom and / or a silicon atom constituting the segment (X) are shown below. Show. However, these examples do not limit the invention. However, -R _f represents the following substituent. _{1) -C d F 2d + 1} 2) -CH 2 C d
F _{2d + 1} 3) -CH ₂ CH ₂ C _d F _{2d + 1} 4) -CH ₂ (C
_{F 2) d CFHCF 3 5)} -CH 2 CH 2 (CF 2) d CFHCF 3 6) -CH 2 CH 2 (CF 2) d CFHCF 2 H 7) -CH 2 (CFH) d CF 2 H 8) - CH (CF ₃ ) ₂

[0039]

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In the above formula and the following formula, d is 1 to 18
And e represents an integer of 1 to 5, and b represents a hydrogen atom or a methyl group.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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(A-34)-(N (COR_f) CH_TwoCH_Two)-Next, the macromonomer part (M_A) Will be described. Mc
Monomer part (M_A) Means that the weight average molecular weight is 1 × 10^Three~
2 × 10^Four, Preferably 3 × 10^Three~ 1 × 10^FourRange
It is something that is. Weight average molecular weight is 1 × 10^ThreeLess than
Has the effect of improving the releasability because the length of the graft is too short
Fades, 2 × 10^FourBeyond, the monofunctional macromono
Mer part (M_A) And the macromonomer part (M
_A) Copolymerization reactivity with monomers corresponding to structural units other than
And the desired graft polymer cannot be obtained.
It is because it becomes. The macromonomer part (M_A)
The structural unit having an elemental atom and / or a silicon atom is as described above.
It may be one of the constituent units of segment (X)
You. The macromonomer part (M_A) Is, for example,
The following general formula (IV) is added to one end of the polymer main chain comprising
Having a polymerizable double bond-containing group represented by
It may correspond to a monomer. CH (a¹) = C (a^Two) -V^Three-(IV) [wherein a¹And a^TwoRepresents a hydrogen atom, a halogen atom,
Represents trifluoromethyl, cyano or hydrocarbon groups
You. V^ThreeIs -COO-, -OCO-,-(CH_Two) _fO
CO-,-(CH_Two)_fCOO- (f is an integer of 1 to 3
), -O-, -SO_Two-, -CO-, -CON (T
¹)-, -SO_TwoN (T¹)-, -CONHCOO-,
-CONHCONH- or -C₆H_Four-(Here
And T¹Represents a hydrogen atom or a hydrocarbon group)]].

Examples of the hydrocarbon group as T ^{1 are} as follows: an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group) Octyl, decyl, dodecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2
-Methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group and the like, and an optionally substituted alkenyl group having 4 to 18 carbon atoms (eg, 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 and the like, and 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 optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms ( For example, phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, Dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, propioamidophenyl, dodecyloylamidophenyl, etc.) Can be

When V ³ represents —C ₆ H ₄ —, the benzene ring may have a substituent. Examples of the substituent include a halogen atom (eg, a chlorine atom, a bromine atom, etc.), an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group,
Chloromethyl group, methoxymethyl group, etc.) and alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.). Preferably, a ¹ and a ²
May be the same or different, and may be a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.), a trifluoromethyl group, a cyano group, or an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group) , propyl group, butyl group, etc.), - COOZ ³ or -Z ² -COOZ ³ (Z ³ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic or an aryl group, These may be substituted, and may specifically be as described for T ¹ above, and Z ² represents a hydrocarbon group).

As Z ² , a methylene group, an ethylene group,
And a propylene group. More preferably, in the general formula (IV), V ³ represents -COO-, -OCO-, -C
_{H 2 OCO -, - CH 2} COO -, - O -, - CONH
— Or —C ₆ H ₄ —, wherein a ¹ and a ² may be the same or different from each other and represent a hydrogen atom or a carbon atom having 1 to 6 carbon atoms.
(For example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc.). More preferably, ^one of a ¹ and a ² represents a hydrogen atom.

The polymerizable double bond-containing group represented by the general formula (IV) may be directly bonded, or may be bonded via an arbitrary linking group. Linking group, for example a divalent group, -O -, - S -, - N (d 1) -, - SO -, - S
O ₂ —, —COO—, —OCO—, —CONHCO—,
^{-NHCONH -, - CON (d 2} ) -SO
₂ (d ³ ), -Si (d ⁴ ) (d ⁵ )-, a divalent aliphatic group or a divalent aromatic group, or an organic group constituted by a combination of these divalent groups. Is also good. here,
d ^{1 to} d ⁵ may be those described for T ¹ in formula (IV). Examples of the divalent aliphatic group include, for example, -C (k
^{1) (k 2) -,} - C (k 1) = C (k 2) -, - C≡
_{C -, - C 6 H 10} -,

[0056]

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And the like. In the formula, k ¹ and k ² may be the same or different, and each is a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.)
Or an alkyl group having 1 to 12 carbon atoms (e.g., methyl, ethyl, propyl, chloromethyl, bromomethyl, butyl, hexyl, octyl, nonyl, decyl, etc.). As the divalent aromatic group, for example, a phenylene group, a naphthylene ring group and a 5- or 6-membered heterocyclic group (a heteroatom selected from an oxygen atom, a sulfur atom and a nitrogen atom as a heteroatom constituting a heterocyclic ring) Containing at least one). These aromatic groups may have a substituent, for example, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a propyl group) , A butyl group, a hexyl group, an octyl group, etc.) and an alkoxy group having 1 to 6 carbon atoms (eg, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.). As the heterocyclic group, for example, a furan ring group, a thiophene ring group, a pyridine ring group, a pyrazine ring group, a piperazine ring group,
Tetrahydrofuran ring group, pyrrole ring group, tetrahydropyran ring group, 1,3-oxazoline ring group, pyrrolidine ring group, piperidine ring group and the following formula:

[0058]

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(Wherein Q is —O—, —S— or —NR ¹⁰
And R ¹⁰ has the same meaning as described above). Specific examples of the polymerizable double bond group-containing portion represented by the general formula II of the macromonomer and the portion composed of the linking group linked thereto are as follows. In the following formula, P ₁ represents —H, —CH ₃ , —CH ₂
COOCH ₃ , —Cl, —Br, or —CN;
₂ represents -H or -CH _3, b represents -H or -CH _3, X represents a -Cl or -Br, n is an integer of 2 to 12, m is an integer of 1 to 4 Show.

[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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(Segment (Y)) Next, the segment (Y) will be described in detail. First, a structural unit containing a light and / or thermosetting group contained in the segment (Y) will be described. “Light and / or thermosetting group” refers to a functional group that causes a curing reaction of a resin by at least one of light and heat. Examples of the photocurable functional group include Hideo Inui, Mototaro Nagamatsu, "Photosensitive Polymer" (Kodansha, published in 1977), Takahiro Tsunoda, "New Photosensitive Resin" (publishing department of Printing Society, published in 1981), GEGreen
and BPStrak, J. Macro. Sci. Reas. Macro Chem., C2
1 (2), 187-273 (1981-82), CGRatte
y, `` Photopolymerization of Surface Coatings '' (A.
Examples of the photocurable resin include functional groups used in conventionally known photosensitive resins and the like described in reviews such as Wiley Inter Science Pub. 1982). Examples of the thermosetting functional group include, for example, Tsuyoshi Endo, "Precision of thermosetting polymer" (CMC Corporation, published in 1986), Yuji Harazaki (Handbook of Latest Binder Technology), Chapter II-I (Synthesis). Technical Center, 1985), Takatsu Otsu "Synthesis of acrylic resin
Design and New Application Development ”(Chubu Management Development Center Publishing Department, 1
985) and Eizo Omori "Functional Acrylic Resin" (Techno System, 1985) and the like. For example -COOH group, -PO ₃ H ₂
Group, -SO ₂ H group, -OH group, -SH group, -NH ₂ group,
-NHR ¹¹ group [R ¹¹ represents a hydrocarbon group, an alkyl group (e.g. methyl group having 1 to 8 carbon atoms, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a 2-chloroethyl group, 2- Methoxyethyl group, 2-cyanoethyl group, etc.), cyclic acid anhydride group, -CONHCH ₂ OR
¹² (R ¹² represents a hydrogen atom or an alkyl group (for example, those listed as R ¹¹ )), -N = C = O, a group represented by the following formula:

[0066]

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(Wherein Z ′ is a heterocyclic ring together with a nitrogen atom)
Represents a group of atoms necessary to form
= C = O group), a silane coupling group,
Titanate coupling group, -Cd⁶= CHd⁷｛D
⁶, D⁷Are a hydrogen atom and a halogen atom (for example, chlorine
Atom, bromine atom, etc.) or an alkyl group having 1 to 4 carbon atoms (eg,
Represents a methyl group, an ethyl group, etc.), polymerizable double bond
And a group containing a compound. Also, polymerizable double bond
Specific examples of the contained group include CH_Two= CH-, CH_Two= C
H-CH_Two-, CH_TwoＣＨCH—COO—, CH_Two= C
(CH_Three) -COO-, CH _Three-CH = CH-COO
-, CH_Two= CH-CONH-, CH_Two= C (CH_Three)
-CONH-, CH_ThreeCH = CH-CONH-, CH_Two
ＣＨCH—O—CO—, CH_Two= C (CH_Three) -O-CO
-, CH_Two= CH-CH_Two-O-CO-, CH_Two= CH
-NHCO-, CH_Two= CH-CH_Two-NHCO-, C
H_Two= CH-SO _Two-, CH_Two= CH-CO-, CH_Two
ＣＨCH—O—, CH_Two= CH-S-,

[0068]

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And the like. Next, the macromonomer unit (M _B) will be described. Macromonomer part (M
_B ) has a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , preferably 3 × 10 ³ to 1 × 10 ⁴ . When the weight average molecular weight is 1 × 10 ³ or less, the anchor effect is weakened. Further, in the 2 × 10 ⁴ or more, the copolymerization reactivity with a monomer corresponding to the other structural unit that constitutes the monomer and the segment (Y) corresponding to macromonomer unit (M _B) is lowered. Structural units constituting the macromonomer portion (M _B) may be any as long as it does not contain a fluorine atom and / or silicon atoms. More preferably, the macromonomer unit (M _B) is a light and / or heat-curable functional group structure unit containing, containing 1 to 50% by weight relative to the total weight of the macromonomer unit (M _B).

Specific examples of the photo- and / or thermosetting functional groups include the photo- and / or thermo-setting functional groups contained in the segment (Y) except for the polymerizable double bond-containing group. One. (Other Structural Units) Further, in the other structural units in the segment (X) and the segment (Y) in the resin [P] of the present invention, the monomer corresponds to the structural unit of each segment described above. Any one may be used as long as it copolymerizes with the monomer. Examples include an addition polymerization component, a polyester component, a polyether component, a polyimine component, and the like. Specific examples of the addition polymerization component include structural units selected from the repeating units represented by the following general formula (V). —CH (a ¹ ) —C (V ³ −T ¹ ) (a ² ) — (V) In the formula (V), a ¹ , a ² , V ³ and T ¹ have the same contents as in the formula (IV). Represent.

The content of the structural unit represented by the formula (V) in the segment (X) is usually at most 50% by weight, preferably at most 20% by weight, more preferably at all. The content of the structural unit is 50% by weight or less, preferably 20% by weight or less in the macromonomer part (M _A ), and more preferably it is not contained at all. On the other hand, the content of the structural unit in the segment (Y) is 0 to 95% by weight, preferably 5 to 90% by weight based on the total weight of the segment (Y).
The content of the structural units, the macromonomer unit (M _B)
In the composition, 40 to 100% by weight, preferably 50 to 100% by weight.
95% by weight. Further, as a structural unit which can be contained together with the structural unit represented by the formula (V), a monomer copolymerizable with a monomer corresponding to the structural unit of the formula (V), for example, acrylonitrile, methacrylonitrile, heterocyclic Vinyls (eg, vinylpyridine, vinylimidazole,
Structural units corresponding to vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine and the like. These other constituent units are used in an amount not exceeding 20 parts by weight based on 100 parts by weight of all the constituent units of the resin [P].

In the segment (Y) in the resin [P], -PO ₃ H ₂ ,-
SO ₃ H, —COOH, —P (＝ O) (OH) R ¹³ [R
¹³ represents a hydrocarbon group or —OR ¹⁴ (R ¹⁴ represents a hydrocarbon group)] and a structural unit containing, as a substituent, at least one polar group selected from cyclic acid anhydride groups,
It can also be used in an amount of less than 10% by weight, based on the total weight of the segment (Y). Preferably, R ¹³ and R ¹⁴ are each an optionally substituted hydrocarbon group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group,
Chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group, 3-chloropropyl group, 3-methoxypropyl group, 2-methoxybutyl group, benzyl group, phenyl group,
Propenyl group, methoxymethyl group, ethoxymethyl group,
2-ethoxyethyl group) and the like.

Examples of the cyclic acid anhydride group include residues such as aliphatic dicarboxylic acid anhydride and aromatic dicarboxylic acid anhydride. Examples of fatty acid dicarboxylic anhydrides include succinic anhydride, glutaconic anhydride, maleic anhydride, cyclopentane-1,2-dicarboxylic anhydride, cyclohexane-1,2-dicarboxylic anhydride, cyclohexene- 1,2-dicarboxylic anhydride, 2,3-
Examples thereof include bicyclo [2,2,2] octadicarboxylic anhydride and the like. These compounds include, for example, chlorine atom, halogen atom such as bromine atom, methyl group, ethyl group, butyl group,
It may be substituted with an alkyl group such as a hexyl group.
Examples of the aromatic dicarboxylic anhydride include phthalic anhydride, naphthalene-dicarboxylic anhydride, pyridine-dicarboxylic anhydride, thiophene-dicarboxylic anhydride, and the like. atom,
Halogen atom such as bromine atom, alkyl group such as methyl group, ethyl group, propyl group, butyl group, hydroxyl group, cyano group, nitro group, alkoxycarbonyl group (alkoxy group such as methoxy group, ethoxy group, etc.) May be substituted.

The copolymer component having a specific polar group as described above corresponds to, for example, a polar group-containing vinyl compound which can be copolymerized with a monomer corresponding to the repeating unit represented by the general formula (IV). Any of these may be used, for example, "Polymer Data Handbook (Basic)" edited by The Society of Polymer Science, Japan
It is described in Baifukan (1986) and the like. Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α-acetoxy form)
(2-amino) ethyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α-chloro-β
-Methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half-esters, itaconic acid half-amides, crotonic acid, 2-alkenylcarboxylic acids (eg, 2-pentenoic acid, 2-methyl- 2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4
-Ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzene carboxylic acid, vinylbenzene sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, vinyl group or allyl of dicarboxylic acids Structural units corresponding to half-ester derivatives of the groups, ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing the polar group in the substituents of the amide derivatives are exemplified.

(Synthesis of Resin [P]) Resin [P] of the present invention
The macromonomer corresponding to the macromonomer portion ((M _A ), (M _B )) can be synthesized according to a conventionally known polymerization method. For example, WJ Burlant, AS Hoffman
"Block and Graft polymers" (1960, Renhal
d), RJ Ceresa, "Block and Graft Polymers" (19
62, Butterworths), DC Allport, WH James
"Black Copolymers" (1972, Applied Sci), A.
Noshay, JF McGvath "Block Copolymers" (197
7 years, Academic press.), G. Huvtrez. DJ Wilson,
G. Riess, NATO ASI Sev. Sev E. 1985 , 149,
V. Percea, Applied. Polymer Sci. 285 , 95 (1
985), and the like.

For example, organometallic compounds (eg, alkyl lithiums, lithium diisopropylamide, alkali metal alcoholates, alkyl magnesium halides,
Ionic polymerization reaction using alkyl aluminum halides as polymerization initiators is described in TE Hogeu-Esch, J. S.
mid, "Recent Advances in Anionic Polymerization"
(1987, Elsevier New York) Yoshio Okamoto, Polymer,
38 , 912 (1989), Mitsuo Sawamoto, polymer, 38 ,
1018 (1989), Tadashi Narita, Polymer, 37 , 252
(1988), BC Anderson, et al, Macromolecule
s 14 , 1601 (1981), S. Aoshima, T. Hig
ashimura, Macromolecules 22 , 1009 (198
9) and the like. In addition, hydrogen iodide /
For the ionic polymerization reaction using iodine, etc., see T. Higas
himura et al, Makromol. Chem., Macromol. Symp., 1
3/14, 457 (1988), Higashimura Satoshinobe, Mitsuo Sawamoto,
Polymers, 46 , 189 (1989). For the group transfer polymerization reaction, DY
Sogah et al, Macromolecules 20 , 1473 (198
7), OW Webster, DY Sogah, polymer, 36 , 8
08 (1987), MT Reetg, et al, Angew. Chem.
Int. Ed. Eugl. 25 , 9108 (1986) JP-A-6
No. 3-97609.

The living polymerization reaction using a metal porphyrin complex is described in T. Yasuda, T. Aida, S. Inou.
e, Macromolecules, 17 , 2217 (1984);
Kuroki, T. Aida, S. Inoue, J. Am. Chem. Soc. 10
9 , 4737 (1987); M. Kuroki et al, Macromo
lecules, 21 , 3115 (1988), M. Kuroki, I.
Inoue, Synthetic Organic Chemistry, 47 , 1017 (1989). Further, regarding ring-opening polymerization of cyclic compounds, see S. Kobayashi, T. Saegusa, "Ring Opening
Polymerization "(1984, Applied Science Publi
shors, Ltd.), W. Seeliger et al. Angew. Chem. In
t. Engl. 5 , 875 (1966), S. Kobayashi et a
l, Poly, Bull. 13 , 447 (1985), Y. Chujo
et al, Macromolecules, 22 , 1074 (1989)
And so on. Further, regarding a living photopolymerization reaction using a dithiocarbamate compound or a xanthate compound as an initiator, Takayuki Otsu, Polymer, 37 ,
248 (1988), Shunichi Hinomori, Ryuichi Otsu, Polym. Re
p. Jap. 37 , 3508 (1988);
No. 111, JP-A-64-26619, M. Niwa, Macro
molecules, 189 , 2187 (1988) and the like.

On the other hand, a radical polymerization reaction using a polymer containing an azo group or a peroxide group as an initiator is also possible.
A method of synthesizing a block copolymer is described in Akira Ueda et al., Journal of Polymers, 33 , 931 (1976), Akira Ueda, Report of Osaka Municipal Industrial Research Institute 84 , (1989), O. Nuyken et al, M.
acromol. Chem., Rapid. Commun. 9 , 671 (198
8), Yasuo Moriya, reinforced plastics, 29 , 907
(19), Ryohei Oda, Science and Industry 61 , 43 (19)
87). Regarding the synthesis of the graft type block copolymer, in addition to the above-mentioned books and reviews, Fumio Ide, “Graft Polymerization and Its Application” (1977)
Polymer Society of Japan, edited by The Society of Polymer Science, "Polymer Alloy" (1981, Tokyo Chemical Dojin). For example, a method of grafting a polymer chain by a polymerization initiator, a chemical actinic ray (radiation, electron beam, etc.), a mechanochemical reaction in mechanical application, etc., utilizing a polymer chain and a functional group of the polymer chain. Then, a method of performing a chemical bond (a so-called interpolymer reaction) and grafting, or a method of performing a polymerization reaction using a macromonomer and grafting is known.

The method of grafting using a polymer chain is as follows.
Specifically, T. Shiota et al, J. Appl. Polym. Sc
i.13, 2447 (1969), W. H. Buck, Rubber
Chemistry and Technology,50, 109 (197
6), Tsuyoshi Endo, Tsutomu Yokozawa, Journal of the Japan Adhesive Society,24, 323
(1988), Tsuyoshi Endo, ibid,25, 409 (198
9). Also, using macromonomer
Specifically, as a method of performing a polymerization reaction and grafting,
P. Dreyfuss & R. P. Quirk, Encycl. Polym. Sci. En
g.,7551 (1987); PF Rempp, E. Franta,
 Adv. Polym. Sci.,581 (1984), V. Perce
c, Appl. Poly. Sci.,285, 95 (1984), R.A.
sami, M. Takari, Macromol. Chem. Suppl.,12, 16
3 (1985), P. Rempp., Et al, Macromol. Chem. S
uppl., 8, 3 (1984), Yusuke Kawakami, Chemical Industry,3
8, 56 (1987), Yuya Yamashita, Polymer,31, 98
8 (1982), Shiro Kobayashi, Polymer,30, 625 (1
981), Toshinobu Higashimura, Journal of the Adhesive Society of Japan,18, 536
(1982), Koichi Ito, Polymer Processing,35, 262
(1986), Kishiro Higashi, Takashi Tsuda, Functional Materials,198
7No. 10, 5, edited by Yuya Yamashita, “Macromonomer
Chemistry and Industry "(1989, IPC
), Edited by Tsuyoshi Endo, “Molecular Design of New Functional Polymers
Chapter 4 (1991, CMC Corporation, Y. Yam
ashita et al. Polym. Bull.5, 361 (1981), etc.
It is described in.

The method of synthesizing the star block copolymer is as follows.
For example, M. T. Reetz, Angew. Chem. 1st. Ed. Engl2
71373 (1988), M. Sgwarc, "Carbanions,
LivingPolymers and Electron Transfer Processes "
(1968, Wiley. New York) B. Gordon et al, Pol
ym.bull.11349 (1984); R. B. Bates et.
 al. J. Org. Chem.44, 3800 (1979), Y.S.
ogah, A.C.S.Polym.Repr.1988, No. 2, 3,
J. W. Mays. Polym. Bull.23, 247 (1990),
I. M. Khan. Et al. Macromolecules,21, 2684
(1988), A. Morikawa, Macromolecules,24, 3
469 (1991), Akira Ueda, Susumu Nagai, Polymer,39,
202 (1990), T. Otsu, Polym. Bull.11, 1
35 (1984).

Further, for example, WJBurlant. AS Hoffma
n "Block and Graft Polymers" (1960, Renhold), R.
J. Ceresa, "Block and Graft Copolymers" (1962, Bu
tterwords) LCAllport, WHJames "Block copolymer
s "(1972 Applied Sci), A. Noshay, JEMcGrath" Block
Copolymers "(1977, Academic press.). More specifically, the star copolymer of the present invention has a conventionally known polar group-containing and polymerizable double bond-containing group. It can be synthesized by using a method for synthesizing a star polymer of a monomer, for example, a polymerization reaction using carbanion as an initiator.
M. Morton, TEHelminiak et al. J. Polym. Sci., 57, 47
1 (1962), B. Gordon III, M. Blumethal, JELoftus.
al, Polym. Bull., 11, 349 (1984), RBBates, WABeav.
ers, et al, J. Org, Chem., 44, 3800 (1979).

When the resin (P) of the present invention contains a structural unit containing a specific polar group such as the above-mentioned —COOH group in the segment (Y), the structure containing the specific polar group is used. In the monomer corresponding to the unit, the polar group is set as a functional group in which the polar group is protected in advance, and ionic polymerization is performed using an organometallic compound (eg, alkyl lithiums, lithium diisopropylamide, alkyl magnesium halides, etc.) or a hydrogen iodide / iodine system. After synthesizing a block copolymer by a so-called living polymerization reaction such as a reaction, a photopolymerization reaction using a porphyrin metal complex as a catalyst, or a group transfer polymerization reaction, a hydrolysis reaction, a hydrogenolysis reaction, and a polar group-protected functional group are performed. A deprotection reaction such as an oxidative decomposition reaction or a photodecomposition reaction is performed to form a polar group. One example is shown in the following reaction formula (I).

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Further, the macromonomer portions (M _A ) and (M
_B ) a macromonomer corresponding to AB) and an AB-type or ABA
Each of the block copolymers can be synthesized according to a conventionally known polymerization method. These macromonomers are, for example, photopolymerized by a porphyrin metal complex as a catalyst by an ionic polymerization reaction using an organometallic compound (eg, alkyl lithiums, lithium diisopropylamide, alkyl magnesium halides, etc.) or a hydrogen iodide / iodine system. Reaction, group transfer polymerization reaction, photoinitiator polymerization method using dithiocarbamate compound, dithioxanthate compound, etc. as an initiator, or radical polymerization initiator containing a functional group capable of introducing a polymerizable double bond group (for example, Azobis compound, peroxide) and a polymer having a weight average molecular weight of 2 × 10 ⁴ or less by a known so-called conventional polymerization method such as a radical polymerization reaction using a chain transfer agent (for example, a mercapto compound or an iodine compound). After that, by reacting various reagents on one end of the polymer main chain,
It can be synthesized by introducing a polymerizable double bond group.

For example, P. Lutz, P. Masson etal, Poly
m. Bull.,12, 79 (1984) B.C.Anderson, G.
D. Andrews etal, Macromolecules,14, 1601
(1981) K. Hatada, K. Ute. Etal, Polym. J.1
7977 (1985),18, 1037 (198
6), Koichi Ute, Koichi Hatada, Polymer Processing,36, 366
(1987) Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers,4
6189 (1989) M. Kuroki, T. Aida, T. Am. Ch.
em. Soc.109, 4737 (1987), Takuzo Aida,
Shohei Inoue, Synthetic Organic Chemistry,43, 300 (1985) D.
 Y. Sogah, W. R. Hertler etal, Macromolecules,2
0, 1473 (1987), Takayuki Otsu, Polymer,37,
248 (1988), Shunichi Hinomori, Ryuichi Otsu, Polym. Re
p. Jap.373508 (1988);
No. 11, the synthesis method described in JP-A-64-26619 and the like.
The living polymer can be easily synthesized according to
You. For an example using a radical polymerization reaction, see Y. Yamashi
ta, J. Appl. Polym. Sci, Appl. Polym. Symp.36, 1
93 (1981), K. K. Roy, etal, Makromol. Chem.
153, 71 (1972), Y. Yamashita etal, Poly
m. J.,14255 (1982), Akira Ueda, Susumu Nagai,
Science and industry,60, 57 (1986), etc.
Law. In addition, a polymerizable double bond is attached to the terminal of the polymer main chain.
A method for introducing a combined group may be a conventionally known method.

Specifically, P. Dreyfuss & RP Quirk,
Encycl, Polym. Sci. Eng., 7 , 51 (1987), P.
F. Rempp, E. Franta, Adu., Polym. Sci. 58 , 1
(1984), V. Per-cec, Appl., Polym. Sci., 28
5 , 95 (1984), R. Asami, M. TakaRi, Makvamo
l. Chem. Suppl. 12 , 163 (1985), P. Remp
p. etal, Makvamol. Chem. Suppl. 8 , 3 (1984)
Yusuke Kawakami, Chemical Industry, 38 , 56 (1987), Yuya Yamashita, Polymer, 31 , 988 (1982), Shiro Kobayashi, Polymer, 30 , 625 (1981), Toshinobu Higashimura, Journal of the Adhesive Society of Japan, 18, 536 (1982), Koichi Ito, Polymer Processing, 35 , 262 (1986), Kishiro Higashi, Takashi Tsuda,
Functional Materials, 1987 No. 10, edited by Yuya Yamashita, “Chemistry and Industry of Macromonomers”, Chapter 2, IPC Publishing (19
1989) and the methods described in the references and patents cited therein. Further, in the above-mentioned macromonomer, when a polymer component containing a specific polar group is contained, a polymerization reaction and polymerizable The compound can be easily synthesized by removing the protecting group after the introduction reaction of the double bond group.

The protecting group for protecting the specific polar group of the present invention and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing conventionally known knowledge. For example, various descriptions are given in the above-cited references, and furthermore, Yoshio Iwakura and Keisuke Kurita, "Reactive Polymers", published by Kodansha (1977), TW Greene "Protective Groups in"
Organic Synthesis ", John Wiley & Sons (1981
JFW McOmie, "Protective Groups in Organ
ic Chemistry ", Plenum Press, (1973) and the like. The resin (P ₄ ) can be easily produced by a known so-called living polymerization reaction such as an ionic polymerization reaction, a group transfer polymerization reaction, a metal porphyrin polymerization reaction, and a photoinitiator polymerization reaction. Furthermore, Akira Ueda, Susumu Nagai, et al., Journal of Polymers, 33 131 (197
6) It can also be produced by a radical copolymerization reaction using a high-molecular azo initiator described in Scientific and Industrial Science, 64 , 446 (1990) and the like.

<Resin (Q)> The resin (Q), that is, the resins (Q ₁ ) and (Q ₂ ) will be described in detail below. (Resin (Q ₁ )) As described above, the resin (Q ₁ ) comprises at least one monomer represented by the general formula (I) and a specific polar group-containing monofunctional macromonomer (M _C ). It is characterized by being a resin comprising a graft-type copolymer containing seeds. The weight average molecular weight of the resin (Q ₁ ) is 1 × 1
0 ^{3 to} 2 × 10 ⁴ , preferably 3 × 10 ³ to 1 × 10 ⁴
And the glass transition point of the resin (Q ₁ ) is preferably 1
It is 20 ° C. or lower, more preferably 90 ° C. or lower.
If the molecular weight of the resin (Q ₁ ) is smaller than 1 × 10 ³ or larger than 2 × 10 ⁴ , even if the resin of the present invention is used, the electrostatic properties are reduced and the effect of the present invention is lost. . Further, the resin macromonomers to be used in the _{(Q 1) (M C)} , the specific polar group and contains at least one, as a content in the resin (Q ₁₎ in the polar group 0. It is 5 to 15% by weight, preferably 1 to 10% by weight. If the amount exceeds the above range, the electrostatic properties (particularly, the dark decay retention and the photosensitivity) are reduced, and the photoreceptor using the near-infrared to infrared spectral sensitizing dye has a high temperature. The fluctuations in the dark decay retention and the light sensitivity under severe conditions of high humidity, low temperature and low humidity are slightly increased, and the effect of the present invention that a stable copied image is obtained is weakened.

Next, the monomer corresponding to the repeating unit represented by formula (I), which is contained in the resin (Q ₁ ) in an amount of 30% by weight or more, will be further described. b ¹ and b ² each preferably represent a hydrogen atom, a halogen atom (eg, a chlorine atom or a bromine atom), a cyano group, or an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, etc.). ), -COOZ ⁴ or -Z ² -COOZ ⁴ (where,
Z ⁴ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, specifically, the following R ³ described represent same contents as those, Z ²
Represents a hydrocarbon group).

R ³ is preferably an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group,
Propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, 2-chloroethyl, 2-bromoethyl,
A 2-cyanoethyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 3-hydroxypropyl group, etc., and an optionally substituted alkenyl group having 2 to 18 carbon atoms (eg, a vinyl group, an allyl group) Group, isopropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.) and optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, naphthylmethyl group, 2-naphthylethyl group) , A methoxybenzyl group, an ethoxybenzyl group, a methylbenzyl group, etc.), an optionally substituted cycloalkyl group having 5 to 8 carbon atoms (eg, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, etc.), Optionally substituted aryl groups (eg phenyl, tolyl, xylyl,
Naphthyl, methoxyphenyl, ethoxyphenyl, fluorophenyl, difluorophenyl, bromophenyl, chlorophenyl, dichlorophenyl, iodophenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, cyanophenyl, etc.) No.

The structural unit represented by the general formula (I), which is a component having the substituent R ³ , more preferably corresponds to the structural unit represented by the following general formulas (Ia) and / or (Ib) Monomers.

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[0093]

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In the formula (Ia), preferred A¹And A
^TwoAre independently a hydrogen atom, a chlorine atom and a odor
In addition to elemental atoms, preferred are hydrocarbon groups having 1 to 10 carbon atoms.
Preferably, an alkyl group having 1 to 4 carbon atoms (eg, a methyl group,
Ethyl group, propyl group, butyl group, etc.)
Aralkyl groups (e.g., benzyl, phenethyl, 3-
Phenylpropyl group, chlorobenzyl group, dichloroben
Zyl group, bromobenzyl group, methylbenzyl group, methoxy
Cibenzyl group, chloromethylbenzyl group) and aryl
Groups (eg, phenyl, tolyl, xylyl, bromo
Phenyl group, methoxyphenyl group, chlorophenyl group,
Dichlorophenyl group), and -COR ^FifteenAnd -COO
R^Fifteen(Preferred R^FifteenAre preferably those having 1 to 10 carbon atoms as described above.
Preferred hydrocarbon groups are listed below.
Cut).

In the formulas (Ia) and (Ib), B¹Passing
And B^TwoPreferably binds each of -COO- and a benzene ring
A single bond or-(CH_Two)_g-(G represents an integer of 1 to 3
), -CH_TwoOCO-, -CH_TwoCH_TwoOCO-,-
(CH_TwoO)_h-(H represents an integer of 1 or 2), -C
H_TwoCH_TwoA linking group having 1 to 4 linking atoms such as O-
And more preferably 1 to 2 linking groups
it can. The resin of the present invention (Q₁Formula (Ia) and
Specific examples of the structural unit represented by (Ib) and (Ib) are shown below.
You. However, the scope of the present invention is not limited to this.
Absent. In the following (a-1) to (a-20), c is
An integer of 1 to 4, d is 0 or an integer of 1 to 3, e is 1 to 3
Integer, R¹⁶Are all -C_cH_{2c + 1}Or-(CH_Two) _d−
C₆H_Five (Where c and d are the same as above),
D¹And D^TwoMay be the same or different, a hydrogen atom,-
Represents any of Cl, -Br and -I.

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[0097]

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Next, a low molecular weight resin (Q₁)
Functional macromonomer (M_C) Will be described in detail.
Monofunctional macromonomer (M_C) Is represented by the general formula (II)
At least a specific polar group
A polymer containing at least one kind of polymerization component
Weight average, consisting of only one end of the merging backbone
Molecular weight 1 × 10 ^FourThese are:

In the general formula (II) showing a polymerizable double bond group,
And V¹Is -COO-, -OCO-, -CH_TwoOCO
-, -CH_TwoCOO-, -O-, -SO_Two-, -CO
-, -CONHCOO-, -CONHCONH-, -C
ONHSO_Two-, -CON (T ¹)-, -SO_TwoN (T
¹)-Or -C₆H_FourRepresents-. Where T¹Is hydrogen
In addition to atoms, preferred hydrocarbon groups include those having 1 to 1 carbon atoms.
18 optionally substituted alkyl groups (eg, methyl
Group, ethyl group, propyl group, butyl group, heptyl group,
Xyl, octyl, decyl, dodecyl, hexa
Decyl group, octadecyl group, 2-chloroethyl group, 2-
Bromoethyl group, 2-cyanoethyl group, 2-methoxyca
Rubonylethyl group, 2-methoxyethyl group, 3-bromo
Propyl group etc.), and optionally substituted C 4-18
Lucenyl group (for example, 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
Etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms
(E.g., benzyl, phenethyl, 3-phenyl
Ropyl group, naphthylmethyl group, 2-naphthylethyl group,
Chlorobenzyl group, bromobenzyl group, methylbenzyl
Group, ethylbenzyl group, methoxybenzyl group, dimethyl
Benzyl group, dimethoxybenzyl group, etc.), having 5 to 8 carbon atoms
Optionally substituted alicyclic group (for example, cyclohexyl
Group, 2-cyclohexylethyl group, 2-cyclopentyl
Ethyl group) or a substituted or unsubstituted group having 6 to 12 carbon atoms.
Aromatic groups (eg, phenyl, naphthyl, tolyl,
Xylyl group, propylphenyl group, butylphenyl group,
Octylphenyl group, dodecylphenyl group, methoxyphenyl
Phenyl, ethoxyphenyl, butoxyphenyl,
Decyloxyphenyl group, chlorophenyl group, dichloro
Phenyl group, bromophenyl group, cyanophenyl group,
Cetylphenyl group, methoxycarbonylphenyl group, d
Toxylcarbonylphenyl group, butoxycarbonylphenyl
Nyl group, acetamidophenyl group, propioamidophen
Nyl group, dodecylylamidophenyl group, etc.)
You.

V¹Is -C₆H_Four-Represents Benze
The ring may have a substituent. As a substituent, halogen
Atom (for example, chlorine atom, bromine atom, etc.), alkyl group
(E.g., methyl, ethyl, propyl, butyl,
Chloromethyl group, methoxymethyl group, etc.), alkoxy group
(For example, methoxy, ethoxy, propoxy,
And the like). Preferably, b^ThreeAnd b
^FourMay be the same or different from each other, and represent a hydrogen atom,
Halogen atom (for example, chlorine atom, bromine atom, etc.), shea
And an alkyl group having 1 to 4 carbon atoms (for example, a methyl group,
Tyl, propyl, butyl, etc.), -COOZ¹Or
-Z^Two-COOZ¹(Z¹Is a hydrogen atom or carbon number 1
18 alkyl groups, alkenyl groups, alicyclic groups or aryl
And these may be substituted, and specifically,
Is the T¹Display the same contents as described for
Then Z^TwoHas the same meaning as described above). Z^TwoWhen
Examples include methylene, ethylene, and propylene.
I can do it. More preferably, in the general formula (II), V
¹Is -COO-, -OCO-, -CH_TwoOCO-, -C
H_TwoCOO-, -O-, -CONHCOO-, -CON
HCONH-, -CONH-, -SO_TwoNH- or -C
₆H_Four-, B^ThreeAnd b^FourAre the same but different
A hydrogen atom, a methyl group, -COOZ ¹or
Is -CH_TwoCOOZ¹[Z¹Is a hydrogen atom or carbon number 1
6 alkyl groups (for example, methyl group, ethyl group, propyl
Group, butyl group, hexyl group, etc.).
More preferably, b^ThreeAnd b^FourOne of which is water
Represents an elementary atom.

That is, the polymerizable double represented by the general formula (II)
As the linking group, CH_Two= CHCO-, CH_Two= C (C
H_Three) COO-, CH (CH_Three) = CHCOO-, CH
_Two= C (CH_TwoCOOCH_Three) COO-, CH_Two= C
(CH_TwoCOOH) COO-, CH_Two= CHCONH
-, CH_Two= C (CH_Three) CONH-, C (CH_Three) H
= CHCONH-, CH_Two= CHOCO-, CH_Two= C
HCH_TwoOCO-, CH_Two= CHO-, CH_Two= C (C
OOH) CH_TwoCOO-, CH_Two= C (COOCH _Three)
CH_TwoCOO-, CH_Two= C (CH_Three) CONHCOO
-, CH_Two= C (CH_Three) CONHCONH-, CH_Two
= CH-C₆H_Four-And the like.

The macromonomer (M _C ) of the present invention has a specific polar group (—CO
OH group, -PO ₃ H ₂ group, -SO ₃ H group, -OH group, -
CHO group, -PO (OH) R ¹ group and cyclic acid anhydride group)
And an addition-polymerizable copolymer component containing at least one polar group selected from the group consisting of: Here, R of —PO (OH) R ¹ group
¹ represents a hydrocarbon group or an —OR ² group (R ² represents a hydrocarbon group). Specifically, R ¹ is an optionally substituted aliphatic group having 1 to 22 carbon atoms (eg, a methyl group, Ethyl group,
Propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, 2-chloroethyl, 2-methoxyethyl, 3-ethoxypropyl,
An allyl group, a crotonyl group, a butenyl group, a cyclohexyl group), an optionally substituted aralkyl group having 7 to 22 carbon atoms (e.g., benzyl, phenethyl, 3-phenylpropyl, methylbenzyl, chlorobenzyl, fluoro) A benzyl group, a methoxybenzyl group or the like, or an optionally substituted aryl group having 6 to 22 carbon atoms (eg, phenyl, tolyl, ethylphenyl, propylphenyl, chlorophenyl, fluorophenyl, bromophenyl, A chloro-methyl-phenyl group, a dichlorophenyl group, a methoxyphenyl group, a cyanophenyl group, an acetamidophenyl group, an acetylphenyl group, a butoxyphenyl group, and the like, and R ² represents the same content as R ¹ .

The cyclic acid anhydride groups include aliphatic dicarboxylic acid anhydrides and aromatic dicarboxylic acid anhydrides. Examples of the aliphatic dicarboxylic anhydride include a succinic anhydride ring, a glutaconic anhydride ring, a maleic anhydride ring, a cyclopentane-1,2-dicarboxylic anhydride ring,
Cyclohexane-1,2-dicarboxylic anhydride ring, cyclohexene-1,2-dicarboxylic anhydride ring, 2,3-
Bicyclo [2,2,2] octadicarboxylic anhydride rings and the like. These rings are, for example, halogen atoms such as chlorine atom and bromine atom, and alkyl groups such as methyl group, ethyl group, butyl group and hexyl group. And so on. Examples of the aromatic dicarboxylic anhydride include phthalic anhydride, naphthalene-dicarboxylic anhydride, and pyridine-
Examples thereof include dicarboxylic anhydrides, thiophene-dicarboxylic anhydrides, and the like. These compounds include, for example, chlorine atoms, halogen atoms such as bromine atoms, methyl groups, ethyl groups, propyl groups, alkyl groups such as butyl groups, and hydroxyl groups. , A cyano group, a nitro group, an alkoxycarbonyl group (for example, a methoxy group, an ethoxy group and the like as the alkoxy group) and the like.

As the copolymer component containing a specific polar group as described above, any copolymer component which can be copolymerized with the polar group-containing vinyl compound can be used. For example, it is described in “Polymer Data Handbook (Basic Edition)” edited by The Society of Polymer Science, Baifukan (1986), etc. Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy) Form, α-acetoxymethyl form, α- (2-amino) ethyl form, α-chloro form,
α-bromo, α-fluoro, α-tributylsilyl, α-cyano, β-chloro, β-bromo, α-
Chloro-β-methoxy, α, β-dichloro, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid semiamides, crotonic acid, 2-alkenylcarboxylic acids (for example, 2-pentenoic acid, -Methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzene Carboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, half-ester derivatives of vinyl or allyl groups of dicarboxylic acids, and the polar groups in the substituents of ester derivatives of these carboxylic acids or sulfonic acids and amide derivatives And a structural unit corresponding to a compound or the like.

Examples of the copolymer component containing a polar group are described below.
Show. Where b¹Is H or CH _ThreeAnd b^TwoIs
H, CH_ThreeOr CH_TwoCOOCH_ThreeAnd R¹⁷Is carbon
R 1 represents an alkyl group represented by Formulas 1 to 4,¹⁸Is a group having 1 to 6 carbon atoms.
Represents a alkyl group, a benzyl group or a phenyl group, and f is 1 to
3 represents an integer, g represents an integer of 2 to 11, and h represents 1 to
11 represents an integer, i represents an integer of 2 to 4, and j represents 2 to
Indicates an integer of 10.

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[0108]

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The macromonomer (M _C ) of the present invention contains another copolymerization component together with the specific polar group-containing component. The copolymer component includes a structural unit represented by the following general formula (VI).

[0115]

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In the general formula (VI), V ⁴ represents —COO
-, - OCO -, - ( CH 2) m OCO -, - (C
H _{2) m} COO- _(m is an integer of 1 to 3), - O
_{-, - SO 2 -, -} CO -, - CON (T 1) -, - S
O ₂ N (T ¹ )-, -CONHCOO-, -CONHC
Represents ONH— or —C ₆ H ₄ — (where T ¹ has the same meaning as described above). R ¹⁹ represents a hydrocarbon group.
However, when V ⁴ in the general formula (VI) represents —C ₆ H ₄ —, R ¹⁹ represents a hydrogen atom or a hydrocarbon group. Preferred hydrocarbon groups include alkyl groups having 1 to 22 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group,
Butyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-methoxycarbonylethyl, 2 -Methoxyethyl group, 3-bromopropyl group and the like, an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 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, 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.), having 5 to 8 carbon atoms
An optionally substituted alicyclic group (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) and an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl Group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, A bromophenyl group, a cyanophenyl group, an acetylphenyl group, a methoxycarbonylphenyl group, an ethoxycarbonylphenyl group, a butoxycarbonylphenyl group, an acetamidophenyl group, a propioamidophenyl group, and a dodecyloylamidophenyl group.

V^FourIs -C₆H_Four-Represents Benze
The ring may have a substituent. As a substituent, halogen
Atom (for example, chlorine atom, bromine atom, etc.), alkyl group
(E.g., methyl, ethyl, propyl, butyl,
Chloromethyl group, methoxymethyl group, etc.), alkoxy group
(For example, methoxy, ethoxy, propoxy,
And the like). Preferably, b⁷And b
⁸May be the same or different from each other, and represent a hydrogen atom,
Halogen atom (for example, chlorine atom, bromine atom, etc.), shea
And an alkyl group having 1 to 4 carbon atoms (for example, a methyl group,
Tyl, propyl, butyl, etc.), -COOZ^FiveOr
-Z^Two-COOZ^Five(Z^FiveIs a hydrogen atom or carbon number 1
18 alkyl groups, alkenyl groups, aralkyl groups, alicyclic groups
Represents a formula or an aryl group, which may be substituted
Well, specifically, the above T¹It is a description of
, Z ^TwoHas the same meaning as described above). Z^Two
As methylene group, ethylene group, propylene group, etc.
No. More preferably, in the general formula (IV),
V^FourIs -COO-, -OCO-, -CH_TwoOCO-,-
CH_TwoCOO-, -O-, -CONH-, -SO_TwoNH
-Or -C₆H_Four-, B⁷And b⁸Are the same as each other
Hydrogen atom, methyl group, -C
OOZ^FiveOr -CH_TwoOOZ^Five[Z^FiveIs preferably hydrogen
An atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group,
Ethyl, propyl, butyl, hexyl, etc.)
]. Still more preferably, b⁷And b⁸In
One of them represents a hydrogen atom.

These copolymer components are the same as those of the macromonomer (M
It is 50 to 99% by weight, preferably 70 to 95% by weight, based on all polymer components of _C ). If the proportion of the copolymer component exceeds the above range, the electrostatic properties will be reduced. Further, as a polymer component of the macromonomer (M _C ), another polymer component can be further contained. As another polymer component that can be contained, for example, a polymer other than that described in the general formula (I) can be used. In addition to methacrylates, acrylates, crotonic esters containing substituents, α-olefins, vinyl carboxylates or allyls (for example, carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid) Acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic esters (eg, dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrenes (eg, styrene, vinyltoluene, chlorostyrene, Hydroxystyrene, N, N-dimethylaminomethylstyre , Methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinylsulfone-containing compounds, vinylketone-containing compounds, heterocyclic vinyls (eg, vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline, vinylpyrazole, vinyl Dioxane,
Vinylquinoline, vinyltetrazole, vinyloxazine, etc.). These other monomers are preferably used in an amount not exceeding 20% by weight of the total polymer components of the polymer chain.

(Resin (Q ₂ )) The binder resin (Q ₂ ) has a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , preferably 3 × 10 3.
10 ³ to 1 × 10 ⁴ , and the glass transition point of the resin (Q ₂ ) is preferably −40 ° C. to 110 ° C., and more preferably −
20 ° C to 90 ° C. The molecular weight of the binder resin (Q ₂ ) is 1
Becomes smaller than × 10 ^3, can not be maintained a sufficient film strength and decrease film forming ability, whereas the molecular weight is greater than 2 × 10 ⁴ the even resin of the present invention, in particular near-infrared to infrared spectral sensitization In photoreceptors using dye-sensitive dyes, fluctuations in electrophotographic characteristics (especially initial potential, dark decay retention and photosensitivity) under severe conditions of high temperature / high humidity, low temperature / low humidity are somewhat large, and stable copying is possible. The effect of the present invention that an image can be obtained is weakened.

In the binder resin (Q ₂ ) of the present invention, the ratio of the macromonomer (M _D ) to the other monomer (for example, the monomer of the formula (VII)) is 1-60 / 99-40. (Weight ratio)
And preferably 5 to 40/95 to 60 (weight ratio). When the content of the macromonomer in the binder resin (Q ₂ ) is less than 1.0% by weight, the electrophotographic properties (particularly, dark decay rate and photosensitivity) decrease, and the fluctuation of the electrophotographic properties under environmental conditions is particularly close. It increases in combination with infrared to infrared spectral sensitizing dyes. This is considered to be due to the fact that the composition becomes almost the same as that of a conventional homopolymer or random copolymer due to a small amount of macromonomer serving as a graft portion. On the other hand, when the content of the macromonomer exceeds 60% by weight, the copolymerizability between the monomer corresponding to the other copolymerization component and the macromonomer according to the present invention is not sufficient, and the macromonomer is not sufficiently used as a binder resin. Electrophotographic characteristics cannot be obtained.

The macromonomer (M _D ) in the binder resin (Q ₂ ) of the present invention may contain a polar group-containing component. The amount of the polar group-containing component contained is determined by the binder resin (Q ₂ )
The amount is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, per 100 parts by weight. That is, the binder resin existing ratio of polar group in (Q ₂₎ in the macromonomer (M _D) in the macromonomer (M _D) A block of the composition ratio and binder resin in (Q ₂₎ Can be adjusted to a preferable ratio by the copolymerization ratio of
If the content of the polar group in the binder resin (Q ₂ ) is less than 1% by weight, a sufficient initial image potential cannot be obtained due to a low initial potential. On the other hand, if the content of the polar group is more than 20% by weight, the dispersibility of even a low molecular weight substance is reduced,
Further, when used as an offset master, background contamination increases.

The monofunctional macromonomer (M _D ) used in the graft copolymer of the present invention will be described more specifically. The copolymer component in the macromonomer (M _D ) in the binder resin (Q ₂ ) of the present invention is composed of an A block and a B block as described above. The ratio is preferably 1-70 / 9
9 to 30 (weight ratio), more preferably 3 to 50 /
97 to 50 (weight ratio). Macromonomer (M _D )
Examples of the polar group contained in the components constituting the A block of, -PO ₃ H ₂ group, -COOH group, -SO ₃ H group,
A phenolic OH group, —P (＝ O) (OH) R ¹ ｛R ¹ represents a hydrocarbon group or —OR ² (R ² is a hydrocarbon group) group, and / or a cyclic acid anhydride-containing group. the recited, preferably, -COOH group, -SO ₃ H group, a phenolic O
It is an H group or a —P (＝ O) (OH) R ¹ group.

R ¹ represents a hydrocarbon group or —OR ² (R ² represents a hydrocarbon group), and R ¹ and R ² are preferably an optionally substituted aliphatic group having 1 to 22 carbon atoms. For example, methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, 2-chloroethyl, 2-methoxyethyl, 3-
An ethoxypropyl group, an allyl group, a crotonyl group, a butenyl group, or a cyclohexyl group);
To 22 aralkyl groups (benzyl group, phenethyl group, 3
A phenylpropyl group, a methylbenzyl group, a chlorobenzyl group, a fluorobenzyl group, a methoxybenzyl group or the like, or an optionally substituted aryl group having 6 to 22 carbon atoms (for example, a phenyl group, a tolyl group, an ethylphenyl group,
Propylphenyl, chlorophenyl, fluorophenyl, bromophenyl, chloro-methyl-phenyl, dichlorophenyl, methoxyphenyl, cyanophenyl, acetamidophenyl, acetylphenyl, butoxyphenyl, etc.). Examples of the cyclic acid anhydride-containing group include the same groups as those described in the description of the binder resin (Q ₁ ). The “polymer component containing a specific polar group” as described above is, for example, a polymer component constituting another block component of the macromonomer (M _D ) of the present invention, that is, a methacrylate represented by the general formula (III) Any vinyl compound containing the polar group and copolymerizing with the corresponding vinyl compound such as a component can be used.

For example, it is described in “Polymer Data Handbook [Basic Edition]” edited by The Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α and / or β
Substituted acrylic acid (for example, α-acetoxy, α-acetoxymethyl, α- (2-amino) methyl, α-chloro, α-bromo, α-fluoro, α-tributylsilyl, α-cyano) Form, β-chloro form, β-bromo form,
α-chloro-β-methoxy, α, β-dichloro, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid semiamides, crotonic acid, 2-alkenylcarboxylic acids (eg, 2-pentenoic acid) , 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-
Hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinyl benzene carboxylic acid, vinyl benzene sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, dicarboxylic acid Examples include a half-ester derivative of a vinyl group or an allyl group, and a compound containing the polar group in a substituent of an ester derivative or an amide derivative of a carboxylic acid or a sulfonic acid thereof. The following are specific examples of these compounds. However, in the following examples, p ¹ is _{-H, -CH 3, -Cl, -Br} , -CN,
-CH ₂ COOCH ₃ or indicates -CH ₂ COOH, p
² represents -H or -CH _3, b represents an integer of 2 to 18, c represents an integer of 1 to 12, d is an integer of 1-4.

[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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Two or more polar group-containing components as described above may be contained in the A block. These two or more polar group-containing components may be contained in the A block by either random copolymerization or block copolymerization. It may be. Further, a component not containing a polar group (for example, a component represented by the above formula (III)) may be contained in the A block together with the polar group-containing component. Preferably it is present in an amount of up to 100% by weight. Next, in the above-mentioned macromonomer, a component constituting the B block, that is, a repeating unit represented by the general formula (III) will be described. In the general formula (III), V
The ^{2 -COO -, - OCO -,} - (CH 2) a OCO
_{-, - (CH 2) a} COO- (a is an integer of 1~3), - O -, - SO 2 -, - CO -, - CON
(T ¹ )-, -SO ₂ N (T ¹ )-, -CONHCOO
-, - CONHCONH or -C ₆ H ₄ - represents a. Here, T ¹ has the same meaning as defined in the general formula (II), and specific examples thereof are also the same as those described in the description of V ^{1 in} the general formula (II).

R ⁴ represents a hydrocarbon group, and is preferably the same as the above-mentioned preferred hydrocarbon group for T ¹ . When V ² represents —C ₆ H ₄ —, R ⁴ represents a hydrogen atom in addition to the above hydrocarbon, and the benzene ring may have a substituent. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group, Ethoxy group, propoxy group, butoxy group, etc.). b ⁵ and b ⁶ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (eg, a chlorine atom or a bromine atom), a cyano group, an alkyl group having 1 to 4 carbon atoms (eg, a methyl group) , Ethyl group,
Propyl group, butyl group, etc.), -COOZ ⁵ or -Z ^2-
COOZ ⁵ (Z ⁵ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted; ¹ has the same meaning as described above, and Z ² has the same meaning as described above).

As Z ² , a methylene group, an ethylene group,
And a propylene group. More preferably, in the general formula (III), V ² is -COO-, -OCO-, -C
_{H 2 OCO -, - CH 2} COO -, - O -, - CONH
—, —SO ₂ NH— or —C ₆ H ₄ —, wherein b ⁵ and b ⁶ may be the same or different and each represent a hydrogen atom, a methyl group, —COOZ ⁵ or —CH ₂ COOZ ⁵ [Z ⁵ is More preferably, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group,
Hexyl group). Even more preferably, one of b ⁵ and b ⁶ represents a hydrogen atom. Further, a polymer component other than the polymer component of the formula (III) may be contained in the B block. As monomers corresponding to the other polymer components, acrylonitrile, methacrylonitrile, heterocyclic vinyl (For example, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.). These other monomers are used in an amount not exceeding 20 parts by weight per 100 parts by weight of the total polymer components of the B block. In the B block, the A
It is preferable not to contain a polymer component containing a polar group which is a component of the block. When two or more copolymer components are present in the B block, these two or more copolymer components may be contained in the B block by either random copolymerization or block copolymerization. More preferably, it is contained at random. Next, in the macromonomer (M _D ) of the present invention, the above-mentioned A
A description will be given of a polymerizable double bond group in which a block and a B block containing a polymer component represented by the general formula (III) are connected in an AB form and connected to the other end of the B block connected to the A block. I do. Specific examples include a polymerizable double bond group represented by the following general formula (VIII).

[0138]

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(Wherein b^Five, B⁶And V^TwoIs in formula (III)
B^Five, B⁶And V^TwoRepresents the same content as. That is, a polymerizable double bond group represented by the general formula (VIII)
More specifically, CH_Two= CH-COO-, CH_Two
= C (CH_Three) OCOO-, CH (CH_Three) = CHCO
O-, CH_Two= C (CH_TwoCOOCH_Three) COO-, C
H_Two= C (CH _TwoCOOH) COO-, CH_Two= CHC
ONH-, CH_Two= C (CH_Three) CONH-, CH (C
H_Three) = CHCONH-, CH_Two= CHOCO-, CH
_Two= CHCH_TwoOCO-, CH_TwoＣＨCH—O—, CH_Two
= C (COOH) CH_TwoCOO-, CH_Two= C (COO
CH_Three) CH_TwoCOO-, CH_Two= CH-C₆H_Four−,
CH_Two= CH (CH_Two)_TwoCOO-, CH_Two= CH-C
O-, CH_Two= CH (CH _Two)_TwoOCO- and the like.
You.

The macromonomer (M _D ) used in the present invention
Is a compound having a chemical structure in which a polymerizable double bond group represented by the general formula (VIII) is directly bonded to one end of the B block as described above, or is bonded by an arbitrary connecting group. . Examples of the linking group include a carbon-carbon bond (single bond or double bond), a carbon-hetero atom bond (for example, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc.), a hetero atom-hetero atom. It is composed of any combination of bonding atomic groups. That is, specifically, a simple bond or -C (Z ⁶ ) (Z ⁶ )-
[Z ⁶ may be the same or different and include a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.),
A cyano group, a hydroxyl group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.)],-(CH =
_{CH) -, - C 6 H} 10 -, - C 6 H 4 -, - O -, - S
-, - CO -, - N (Z 7) -, - COO -, - C (=
_{S) -, - SO 2 -} , - CON (Z 7) -, - SO 2 N
(Z ⁷ )-, -NHCOO-, -NHCONH-, -C
(Z ⁷ ) (Z ⁷ )-[Z ⁷ is a hydrogen atom;
[III] represents a hydrocarbon group or the like having the same contents as R ⁴ in (III)], or a single linking group selected from atomic groups or an arbitrary combination thereof.

The macromonomer (M_D) Weight average molecular weight
Is 2 × 10^FourExceeds, other monomers (for example,
Copolymerizability with the monomer of formula (VII))
Therefore, it is not preferable. On the other hand, the weight average molecular weight is too small
And the effect of improving the electrophotographic properties of the photosensitive layer is reduced.
1 × 10^ThreeIt is preferable that it is above. The present invention
Chromonomer (M_D) Is, specifically, the following compound
Examples can be given. However, the scope of the present invention is:
It is not limited to these. However, the following compound examples
At p^Three, P^FourAnd p^FiveAre -H and -C, respectively.
H_ThreeOr -CH_TwoCOOCH_ThreeAnd p⁶Is -H or
-CH_ThreeAnd R²⁰Is -C _pH_{2p + 1}(P is 1-18
Integer),-(CH_Two)_qC₆G_Five(Q is 1-3
Number), -C₆H_Four-Y¹(Y¹Is -H, -Cl, -B
r, -CH_Three, -OCH_ThreeOr -COCH_ThreeTo indicate)
Is-(CH_Two)_r-C_TenH₇(R is an integer of 0 or 1-3
Number) and R^{twenty one}Is -C_FiveH_{2s + 1}(S is an integer from 1 to 8)
Or-(CH_Two)_qC₆H_FiveAnd Y^TwoIs -OH,-
COOH, -SO_ThreeH, -OP (= O) (OH) _TwoOr
-OP (= O) (OH) OCH_ThreeAnd Y^ThreeIs -CO
OH, -SO_ThreeH, -OP (= O) (OH)_TwoOr -O
P (= O) (OH) OCH_ThreeAnd t = 2 to 12
U represents an integer of 2 to 6.

[0142]

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[0143]

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[0144]

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[0145]

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Further, in the resin (Q ₂ ), as a component copolymerized with the macromonomer (M _D ),
The monomers represented by II) are preferred.

[0147]

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(Wherein b ⁹ and b ¹⁰ each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R
²² represents a hydrocarbon group. In the formula (VIII), b ⁹ and b ¹⁰ are each a hydrogen atom, a halogen atom (for example, a chlorine atom or a bromine atom), a cyano group or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, Butyl group). R ²² represents a hydrocarbon group, specifically, an alkyl group, an aralkyl group or an aromatic group, preferably an aralkyl group or an aromatic group which is a hydrocarbon group containing a benzene ring or a naphthalene ring.

Further, R ²² preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. During the polymer backbone, -PO ₃ H ₂ group, -SO ₃ H group, -COOH
It is preferred that the resin (Q ₂ ) does not contain a copolymer component containing a polar group of a group, —OH group, —SH group and —PO ₃ R ¹ H group. polymeric component can be contained include the substituents other than the polar group, for example, a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), - OZ ^8, -C
OOZ ^8, -OCOZ ⁸ (Z ⁸ represents an alkyl group having 1 to 22 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl Etc.)
And the like. Preferred hydrocarbon groups include alkyl groups having 1 to 18 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, Hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2
-Methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group and the like, and an optionally substituted alkenyl group having 4 to 18 carbon atoms (eg, 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 and the like, and 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 optionally substituted alicyclic group having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group and the like) or an optionally substituted aromatic group having 6 to 12 carbon atoms ( For example, phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, Dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, propioamidophenyl, dodecylylamidophenyl, etc.) Be mentioned

[0150] In the repeating unit of the general formula such substituent R ²² is a component having a ring (VII), more preferably at methacrylate component represented by the following formulas (VIIa) and / or general formula (VIIb) It is preferable (hereinafter, this low molecular weight compound is particularly referred to as resin (QQ)).

[0151]

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[0152]

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[In the formulas (VIIa) and (VIIb), A ^{1 ′} and A ^{2 ′} each independently represent a hydrogen atom or a carbon atom of 1 to 1;
0 represents a hydrocarbon group, a chlorine atom, a bromine atom, —COZ ⁹ or —COOZ ⁹ (Z ⁹ represents a hydrocarbon group having 1 to 10 carbon atoms). Each B ¹ and B ² bind the -COO- and the benzene ring, represents a single bond or a linking atoms 1-4 linking groups. ] The more electrophotographic characteristics than the particular resin (QQ) the use the resin (Q ₂₎ (in particular V _10, D.R.R,
E _1/10 ) can be improved. The reason for this is unknown, but one reason is that, due to the effect of the planar benzene ring or naphthalene ring having a substituent at the ortho position, which is an ester component of methacrylate, these compounds are present at the zinc oxide interface in the film. This may be due to the proper arrangement of the polymer molecular chains.

In the formula (VIIa), preferred A^{1 '}And A
^{2 '}Are each independently a hydrogen atom, a chlorine atom and a odor
In addition to the hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms is preferable.
Preferably, an alkyl group having 1 to 4 carbon atoms (eg, a methyl group,
Ethyl group, propyl group, butyl group)
Aralkyl groups (for example, benzyl group, phenethyl group,
Phenylpropyl group, chlorobenzyl group, dichlorobenzene
Group, bromobenzyl group, methylbenzyl group, methoxy
Benzyl group, chloromethylbenzyl group) and aryl group
(For example, phenyl group, tolyl group, xylyl group, bromo group
Phenyl, methoxyphenyl, chlorophenyl, di
Chlorophenyl group), and -COOZ ⁹And -COO
Z⁹(Preferred Z⁹Are preferably those having 1 to 10 carbon atoms as described above.
Preferred hydrocarbon groups are listed below.
Cut).

In the formulas (VIIa) and (VIIb), B ¹
And B ² are each a single bond connecting —COO— and a benzene ring or — (CH ₂ ) _e — (e represents an integer of 1 to 3);
_{-CH 2 OCO -, - CH 2} CH 2 OCO -, - (CH
_{2) f} - _(f is an integer of 1 or _2), - CH 2 CH
It is a linking group having 1 to 4 linking atoms such as ₂ O-, and more preferably a single bond or a linking group having 1 to 2 linking atoms. Specific examples of the repeating unit represented by the formula (VIIa) or (VIIb) used in the resin (Q ₂ ) of the present invention are shown below. However, the scope of the present invention is not limited to this.

[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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Further, in the graft copolymer of the present invention, the component copolymerized with the macromonomer (M _D ) is a monomer other than the general formula (VII), (VIIa) or (VIIb). For example, in addition to methacrylates, acrylates, crotonates containing substituents other than those described in the general formula (VII), α-olefins, vinyl carboxylate or allyl esters (Such as carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalene carboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic esters (for example, dimethyl ester,
Diethyl ester, etc.), acrylamides, methacrylamides, styrenes (eg, styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), Vinylsulfone-containing compounds, vinylketone-containing compounds, heterocyclic vinyls (eg, vinylpyrrolidone,
Vinyl pyridine, vinyl imidazole, vinyl thiophene, vinyl imidazoline, vinyl pyrazole, vinyl dioxane, vinyl quinoline, vinyl tetrazole, vinyl oxazine, etc.). Preferred examples include vinyl or allyl carboxylate having 1 to 3 carbon atoms, acrylonitrile, methacrylonitrile, styrene and styrene derivatives (for example, vinyltoluene, butylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, ethoxy, and the like). Styrene and the like).

(Method for Producing Binder Resin (Q)) The method for producing the resin (Q) of the present invention and the method for producing the macromonomer (M _C ) or (M _D ) used therein will be described below. The resin (Q) or the macromonomer (M _C ) or (M
_D ) can be produced by a conventionally known synthesis method. For example, in a monomer corresponding to the polymer component containing the specific polar group, a polar group is previously protected as a functional group, and an organometallic compound (eg, alkyl lithiums, lithium diisopuramide, alkyl magnesium halide) is used. AB block copolymer was synthesized by a known so-called living polymerization reaction such as a photopolymerization reaction using a porphyrin metal complex as a catalyst, or a group transfer polymerization reaction by an ionic polymerization reaction using hydrogen iodide, iodine, or the like. Thereafter, various reagents are reacted with the terminal of the living polymer to introduce a polymerizable double bond group. After this, the hydrolysis of the functional group protecting the polar group, the hydrogenolysis reaction,
A method in which a deprotection reaction is performed by an oxidative decomposition reaction or a photodecomposition reaction to form a polar group may be mentioned.
One example is shown in the following reaction schemes (2) and (3). Scheme (2) relates to the macromonomer (M _C ) and scheme (3) relates to the macromonomer (M _C ).
_D ).

[0166]

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[0167]

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For example, P. Luta, P. Masson etal, Polym.
Bull., 12 , 79 (1984), BC Anderson, GD Andrews et
al, Macromolecules, 14 , 1601 (1981) K. Hatada, K. Ut
e, etal, Polym.J. 17 , 977 (1985), 18 , 1037 (1986), Koichi Ute, Koichi Hatada, Polymer Processing, 36 , 366 (1987) Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymer Papers, 46 , 189 (1989) M. Kuro
ki, T. Aida, T. Am. Chem. Soc. 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43 , 300 (1985), D.
Y. Sogah, WRHertler etal, Macromolecules, 20 , 147
Living polymers can be easily synthesized according to the synthesis method described in 3 (1987) and the like. Further, as a method of introducing a polymerizable double bond group at the terminal of the living polymer,
The macromonomer of the present invention can be easily prepared according to a conventionally known synthesis method of a macromonomer method. Specifically, P. Dreyfuss & RPQuirk, Encycl. Polym. Sci. En
g., 7 , 51 (1987), PFRempp, E. Franta, Adu., Poly
m.Sci. 58 , 1 (1984), V.Per-cec, Appl., Polym.Sci.,
285 , 95 (1984), R. Asami, M, Takari, Makvamol.Chem.Su
ppl. 12 , 163 (1985), P. Rempp. et al., Makvamol. Chem.
Suppl. 8 , 3 (1984) Yusuke Kawakami, Chemical Industry, 38 , 56 (198
7), Yuya Yamashita, High Polymer, 31 , 988 (1982), Shiro Kobayashi, High Polymer, 30 , 625 (1981), Toshinobu Higashimura, Journal of the Adhesion Society of Japan 18 ,
536 (1982), Koichi Ito, Polymer Processing, 35 , 262 (1986), Kiyoshiro Higashi, Takashi Tsuda, Functional Materials, 1987 , No. 10, 5, etc. It can be synthesized according to the method.

The protecting group for protecting the specific polar group of the present invention and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing conventionally known knowledge. For example, various descriptions are given in the above cited references, and furthermore, Yoshio Iwakura and Keisuke Kurita, “Reactive Polymers”, published by Kodansha (1977), TW Greene “Protective Groups in
Organic Synthesis, John Wiley & Sons (1981)
, JFWMcOmie, `` Protective Groups in Organic Ch
emistry ", Plenum Press (1973), and the like. As another method of synthesizing the AB type block copolymer, it can be synthesized by a photoiniferter polymerization method using a disiocarbamate compound as an initiator. For example, Takatsu Otsu, Polymer, 37 , 248 (1988), Shunichi Himori, Ryuichi Otsu,
Polym. Rep. Jap. 37 , 3508 (1988), JP-A-64-111
And JP-A-64-26619. The macromonomers (M _C ) and (M _D ) of the present invention can be obtained by utilizing the above-mentioned macromonomer synthesis method.

The binder resin (Q) of the present invention comprises the above-mentioned macromonomer and other monomers (for example, the macromonomer (M _C ) is represented by the general formula (I), the macromonomer (M _D ) can be produced by copolymerizing at least one compound selected from each of the monomers represented by the general formula (VII) at a desired ratio. As the polymerization method, it can be produced by using a known method such as solution polymerization, suspension polymerization, precipitation polymerization, and emulsion polymerization. For example, in the solution polymerization, a macromonomer and a monomer are added at a predetermined ratio in a solvent such as benzene and toluene, and then polymerized with an azobis compound, a peroxide compound, and a radical polymerization initiator to obtain a copolymer solution. . By drying this or adding it to a poor solvent, a desired copolymer can be obtained. In the suspension polymerization, a monomer can be suspended in the presence of a dispersant such as polyvinyl alcohol and polyvinylpyrrolidone, and then copolymerized in the presence of a radical polymerization initiator to obtain a copolymer.

(Resin [R]) Next, the resin [R] of the present invention containing at least one kind of light and / or thermosetting group
Will be described. The light and / or thermosetting group contained in the resin [R] may be any, but specific examples include those having the same contents as the curable group contained in the resin [P]. The resin [R] may be any resin as long as the above-mentioned curable group is contained in a resin used for a conventionally known electrophotographic photoreceptor. These conventionally known binder resins for an electrophotographic photosensitive layer are described, for example, in the following documents. Ryuji Shibata, Jiro Ishiwatari, Polymer, Vol. 17, pp. 278 (1968) Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No. 8) Koichi Nakamura, Ed. "Practical Technology of Binders for Recording Materials", Chapter 10 , C.I. H. C. Publishing (19
1985) Edited by the Society of Electrophotography, pre-edited by "Current Symposium on Organic Photoconductors for Electrophotography" (1985).

"Recent Development and Practical Use of Photoconductive Materials and Photoconductors", edited by Hiroshi Komon, "Japan Science Information Co., Ltd. (1986)" Co., Ltd. (1988) Tatt, SC Heidecker, Tappi, 49 (No. 1
0), 439 (1966); S. Baltazzi, R.A.
G. FIG. Blanclotte et al, Phot. Sci. Eng. 16 (No.
5), 354 (1972), Nguyen Chan K, Isamu Shimizu, Eiichi Inoue, Journal of the Society of Electrographic Photography 18 (No. 2), 22
(1980), etc., and the like. Specifically, olefin polymers and copolymers,
Vinyl chloride copolymer, vinylidene chloride copolymer, vinyl alkanoate polymer and copolymer, allyl alkanoate polymer and copolymer, styrene and its derivatives, polymer and copolymer, butadiene-styrene copolymer , Isoprene-styrene copolymer, butadiene-unsaturated carboxylic acid ester copolymer, acrylonitrile copolymer, methacrylonitrile copolymer, alkyl vinyl ether copolymer, acrylic ester polymer and copolymer, methacrylic ester Polymers and copolymers, styrene-acrylate copolymers, styrene-methacrylate copolymers, itaconic diester polymers and copolymers,
Maleic anhydride copolymer, acrylamide copolymer, methacrylamide copolymer, 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, cyclized rubber-acrylate copolymer, nitrogen-free heterocycle (E.g., a heterocycle such as a furan ring, a tetrahydrofuran ring, a thiophene ring, a dioxane ring, a dioxofuran ring, a lactone ring, a benzofuran ring, a benzothiophene ring, a 1,3-dioxetane ring), an epoxy resin, and the like. No.

The structural unit containing at least one light and / or thermosetting group contained in these polymers is 0.1 to 40% by weight, preferably 1 to 40% by weight, per 100 parts by weight of the resin [R]. ３０30% by weight. If the abundance is less than 0.1% by weight, the curing after the formation of the photoconductive layer does not proceed sufficiently, and the retention of the film interface with the photoconductive layer surface during coating of the transfer layer becomes insufficient. This has an adverse effect on the peelability of the layer. On the other hand, if the abundance exceeds 40% by weight, the electrophotographic characteristics of the binder resin of the photoconductive layer are deteriorated, and the reproducibility of the original of the copy image is reduced, and the fogging of the non-image portion is caused. It happened. These light and / or thermosetting group-containing resins [R] are 40% by weight of the total binder resin.
It is preferable to use it by weight% or more. When the content of the resin [R] is less than 40% by weight, the electrophotographic properties are deteriorated. The photoconductive layer may contain other binder resins as necessary in addition to the resin [P], the resin [Q] and the resin [R]. For example, a conventionally known binder resin for an electrophotographic photosensitive member described for the resin [R] is used. (Light and / or thermosetting agent) In the present invention, the photoconductive layer (the layer adjacent to the transfer layer in the case of the laminated type) further comprises a light and / or thermosetting agent in order to improve the curability of the film. Is preferable. The term “light and / or thermosetting agent” includes light and / or thermosetting compounds, light and / or
Or thermosetting oligomers, light and / or thermosetting resins,
As well as a crosslinking agent. The amount used is resin [P],
Based on 100 parts by weight of the total amount of resin [Q] and resin [R]
It is 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight. If the amount is less than 0.01 parts by weight, the effect of improving the curability of the film will be diminished. On the other hand, if it exceeds 20 parts by weight, the electrophotographic properties are adversely affected. The light and / or thermosetting resin may be any of conventionally known curable resins,
For example, a resin having the same functional group as the curable group described for the segment (Y) of the resin [P] of the present invention is mentioned as an example. As the cross-linking agent, a compound usually used as a cross-linking agent can be used. Specifically, compounds described in Shinzo Yamashita, Tosuke Kaneko, “Crosslinking Agent Handbook”, Taiseisha Publishing Co., Ltd. (1981), edited by The Society of Polymer Science, “Basic Polymer Data Handbook,” Baifukan (1986), etc. are used. be able to.

For example, organic silane compounds (for example, vinyltrimethoxysilane, vinyltributoxysilane,
silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, etc.), polyisocyanate-based compounds (eg, toluylene diisocyanate, O-toluene) Range isocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymer polyisocyanate, etc.), polyol compound (for example, 1, 4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane, etc.), polyamine-based compounds (for example, ethylenediamine, γ-hydroxyp Pill of ethylene diamine,
Phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.),
Titanate coupling compounds (eg, tetrabutoxytitanate, tetrapropoxytitanate, isopropyl tristearoyl titanate, etc.) Aluminum coupling compounds (eg, aluminum-butyrate, aluminum acetyl acetate, aluminum oxide octate, aluminum tris (acetyl acetate), etc.) Polyepoxy group-containing compounds and epoxy resins (for example, "Epoxy Resins" edited by Hiroshi Kakiuchi, Shokodo (19
1985), "Epoxy Resins" edited by Kuniyuki Hashimoto, compounds described in Nikkan Kogyo Shimbun (published in 1969), etc., and melamine resins (for example, "Julia
Compounds described in "Melamine Resin", Nikkan Kogyo Shimbun (1969), etc.) Poly (meth) acrylate compounds (for example, "Oligomer" Kodansha (1976), edited by Shin Okawara, Takeo Saegusa, Toshinobu Higashimura, Omori, Compounds described in Eizo “Functional Acrylic Resin” Techno System (published in 1985), etc. In addition, polyfunctional polymerizable monomers (eg, vinyl methacrylate, allyl methacrylate, ethylene glycol diacrylate, polyethylene) Glycol diacrylate, divinyl succinate, divinyl adipate, diallyl succinate, 2-methylvinyl methacrylate, trimethylolpropane trimethacrylate, divinylbenzene,
Pentaerythritol polyacrylate, etc.).

As described above, the layer adjacent to the transfer layer of the photoconductive layer of the present invention is characterized in that it is cured after the film is formed, but the resin [P], the resin [Q], the resin [R], Light and / or
Alternatively, it is preferable to use the thermosetting agent in a combination of functional groups that are easily chemically bonded between polymers. Such combinations are well known in macromolecular reactions, for example, A
Combinations of group B and group B functional groups are illustrated.
(But not limited to this).

[0176]

[Table 1]

In Table 1, R represents a hydrocarbon group,
R^Fifteen, R¹⁶Represents an alkyl group; ¹⁷~ R¹⁹Is alkyl
Or an alkoxy group, and R¹⁷~ R¹⁹Few of
At least one represents an alkoxy group;¹, B^TwoIs electron absorption
Represents an attractive group, for example, -CN, -CF_Three, -CO
R²⁰,, -COOR²⁰, -SO_TwoOR²⁰(R²⁰Is C_nH
_{2n +1}(N: an integer from 1 to 4), -CH_TwoC₆ H_Five, -C₆ 
H_FiveAnd the like). (Reaction accelerator) To promote the crosslinking reaction in the photoconductive layer
A reaction accelerator, if necessary, to the binder resin of the photoconductive layer.
May be added.

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, acetylacetozirconium salt, acetylacetocobalt salt, etc., dibutoxytin dilaurate, etc.), dithiocarbamic acid compound ( Thiuram disulfide compound (such as tetramethylthiuram disulfide), carboxylic anhydride (such as phthalic anhydride, maleic anhydride, succinic anhydride, and butyl succinic anhydride);
3 ', 4,4'-tetracarboxylic acid benzophenone dianhydride,
Trimellitic anhydride) and the like.

When the cross-linking reaction is of the polymerizable reaction type, a polymerization initiator (peroxide, azobis compound, etc.) may be used. In the present invention, after coating the photoconductive layer, the binder resin is cured by light and / or heat. In order to carry out thermosetting, for example, the drying conditions are made stricter than the drying conditions at the time of preparing a conventional electrophotographic color proofing master. For example, the drying conditions are high temperature and / or long time. Alternatively, it is preferable to further perform a heat treatment after drying the coating solvent. For example, 6
Treat at 0 ° C to 150 ° C for 5 to 120 minutes. When the above-mentioned reaction accelerator is used in combination, the treatment can be performed under milder conditions. As a method of curing a specific functional group in the resin of the present invention by light irradiation, a step of light irradiation with “chemically active light rays” may be included. The "chemically active light" used in the present invention may be any of visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, γ-ray, α-ray,
Preferably, ultraviolet light is used. More preferably, wavelength 3
Those capable of emitting light in the wavelength range of 10 nm to 500 nm are preferred, and low-pressure, high-pressure or ultra-high-pressure mercury lamps, halogen lamps and the like are generally used. The light irradiation treatment can be sufficiently performed by irradiation from a distance of 5 cm to 50 cm for 10 seconds to 10 minutes.

(Photoconductive Compound) The photoconductive compound used in the present invention may be either an inorganic compound or an organic compound. Examples of the inorganic compound used as the photoconductive compound of the present invention include conventionally known inorganic photoconductive compounds such as zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, and lead sulfide. Zinc and titanium oxide are preferred. When an inorganic compound such as zinc oxide or titanium oxide is used as the photoconductive compound, the above-mentioned binder resin is added to 100 parts by weight of the inorganic compound.
It is used in a proportion of 0 to 100 parts by weight, preferably 15 to 40 parts by weight. On the other hand, the organic compound may be any of conventionally known compounds. For example, as a first example,
Japanese Patent Publication Nos. 37-17162 and 62-51462, JP-A-52-2437, 54-19803, and 56-1072.
46 and 57-161863, and those used in a photoconductive layer mainly composed of an organic photoconductive compound, a sensitizing dye, and a binding resin. As a second example, JP-A-56-146145 and JP-A-56-146145
0-17775, 60-17752, 60-177
No. 60, No. 60-254142 and No. 62-54266, which are used in a photoconductive layer mainly composed of a charge generating agent, a charge transporting agent, and a binding resin. Further, JP-A-60-230147 and JP-A-6-230147
Nos. 0-230148 and 60-238853, which are used in a two-layered photoconductive layer containing a charge generating agent and a charge transporting agent in separate layers.

Examples of the organic photoconductive compound used in the present invention include: (a) a triazole derivative described in US Pat. No. 3,121,197 and the like; and (b) an oxadiazole described in US Pat. No. 3,189,447. Derivatives, (c) imidazole derivatives described in JP-B-37-16096, and (d) U.S. Patent Nos. 3,615,402 and 3,820,098.
9, JP 3542544, JP-B-45-55
5, JP-A-51-10983 and JP-A-51-993.
24, 55-108667, 55-56953,
Polyarylalkane derivatives described in JP-A-56-36656 and (e) US Pat.
278746, JP-A-55-88064, JP-A-55-88065, JP-A-49-105537 and JP-A-55-5
1086, 56-80051, 56-88141,
57-55545, 54-112637, 55-
Pyrazoline derivatives and pyrazolone derivatives described in each of the 74546 publications,

(F) US Pat. No. 3,615,404, Japanese Patent Publication Nos. 51-10105, 46-3712, and 4
Phenylenediamine derivatives described in JP-A-7-28336, JP-A-54-83435, JP-A-54-110836 and JP-A-54-119925; (g) U.S. Pat. Nos. 3,567,450, 3,180,703 and 3,24059
7, 3658520, 4232103, 4175
Nos. 961, 401,376, JP-B-49-3
No. 5702, West German Patent (DAS) 111051
No. 8, JP-B-39-27577, JP-A-55-1
44250, 56-119132, 56-2243
7, an arylamine derivative described in each publication, (h) an amino-substituted chalcone derivative described in US Pat. No. 3,526,501, etc., and (i) a US patent 354
An N, N-bicarbazyl derivative described in JP-A-2546, etc.,

(J) Oxazole derivatives described in US Pat. No. 3,257,203, and (k) JP-A-56-203.
No. 46234, etc., styryl anthracene derivatives, (1) fluorenone derivatives described in JP-A-54-110837, etc., and (m) U.S. Pat. No. 3,717,462.
JP-A-54-59143 (corresponding to U.S. Pat. No. 4,150,987) and JP-A-55-520.
63, 55-52064, 55-46760, 5
5-85495, 57-11350, 57-148
749, 57-104144, and the like. (N) U.S. Patent No. 404794
8, 4047949, 4265990, 4273
No. 846, No. 4299897, No. 4306008, and the like.
190953, 59-95540, 59-9714
8, stilbene derivatives described in JP-A-59-195658, JP-A-62-36674, and the like;

(P) Polyvinylcarbazole and derivatives thereof described in JP-B-34-10966, and (q) Polyvinylpyrene, polyvinylanthracene, and poly-2- described in JP-B-43-18874 and JP-B-43-19192. Vinyl-4- (4'-dimethylaminophenyl)-
Vinyl polymers such as 5-phenyl-oxazole and poly-3-vinyl-N-ethylcarbazole;
No. -19193, polymers such as polyacetalene, polyindene, copolymers of acenaphthylene and styrene, and (s) pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, ethylcarbazole-formaldehyde described in JP-B-56-13940. Condensation resins such as resins, (t) JP-A-56-90833,
Various triphenylmethane polymers described in JP-A-56-161550 can be exemplified.

In the present invention, the organic photoconductive compound is not limited to the compounds listed in (a) to (t).
All known organic photoconductive compounds can be used. These organic photoconductive compounds may optionally be 2
It is also possible to use more than one kind in combination. As the charge generator contained in the photoconductive layer, various organic and inorganic charge generators conventionally known in electrophotographic photoreceptors can be used. For example, selenium, selenium-tellurium, cadmium sulfide, zinc oxide, and the following organic pigments (1) to (9) can be used. (1) U.S. Pat. Nos. 4,436,800 and 4,439,506, JP-A-47-37543 and JP-A-58-1235.
41, 58-192042, 58-219263,
59-78356, 60-179746, 61-
Azo pigments such as monoazo, bisazo and trisazo pigments described in JP-B-148453, JP-A 61-238063, JP-B-60-5941 and JP-B-60-45664; (2) U.S. Pat.
02, JP-A-51-90827, JP-A-52-5
Phthalocyanine pigments such as metal-free or metal phthalocyanines described in JP-A-5643, and the like; (3) US Pat.
No. 3,718,884, perylene pigments described in JP-A-47-30330, etc.

(4) Indigo and thioindigo derivatives described in British Patent No. 2237680, JP-A-47-30331, and the like; (5) British Patent No. 22376
No. 79, JP 47-30332, etc., quinacridone pigments (6) British Patent No. 2237678
No. 9, JP-A-59-184348, JP-A-62-28
738 and 47-18544, and polycyclic quinone pigments described in (7) JP-A-47-30331 and 47-47.
Bisbenzimidazole pigments described in JP-A-18543 and (8) U.S. Patent Nos. 4,396,610 and 4,644.
082 squarium salt pigments described in the specification, etc.,
(9) JP-A-59-53850, JP-A-61-212542
And azurenium salt-based pigments described in each publication. These can be used alone or in combination of two or more.

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. Is undesirable because crystallization of the organic photoconductive compound occurs. 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 120 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the binder resin. Further, the organic photoconductive compounds may be used alone or in combination of two or more.

(Spectral Sensitizer) In the present invention, various dyes can be used in combination as a spectral sensitizer, if necessary, depending on the type of light source such as exposure to visible light or exposure to semiconductor laser light. For example, Harumi Miyamoto, Hidehiko Takei: Imaging 1
973 (No. 8), page 12, CJ Young et al., RCA Revi
ew 15 , 469 (1954), Kohei Kiyota: IEICE Transactions, J63-C (No. 2), 97 (198).
0), Yuji Harasaki et al., Industrial Chemistry Magazine, 66 , 78 and 1
88 pages (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35 ,
208 (1972), such as carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (eg, oxonol dyes, merocyanine dyes, etc.)
Cyanine dye, rhodacyanine dye, styryl dye, etc.),
And a phthalocyanine dye (which may contain a metal).

More specifically, those mainly comprising carbonium dyes, triphenylmethane dyes, xanthene dyes and phthalein dyes are described in JP-B-51-4.
52, JP-A-50-90334 and 50-11422
7, 53-39130 and 53-82353, U.S. Pat. Nos. 3,052,540, 4,054,450, and JP-A-57-16456. Polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include FM Harmmer "The Cyanine Dyes and
Related Compounds ”and the like can be used, and more specifically, US Pat.
110591, 312008, 312547,
3128179, 3132942, 362231
7, each specification, British Patent Nos. 1226892 and 1309.
274, 14045898, JP-B-48-
And the dyes described in JP-A Nos. 7814 and 55-18892. Furthermore, near-infrared light having a long wavelength of 700 nm or more
Examples of polymethine dyes that spectrally sensitize the infrared region include JP-A-47-840 and JP-A-47-44180, and JP-B-51-41.
061, 49-5034, 49-45122, 5
7-46245, 56-51441, 57-157
Nos. 254, 61-26044, 61-27551, U.S. Pat. Nos. 3,619,154 and 4,175,956, "Research Disclosure", 1982, 21.
6, pages 117 to 118 and the like.
The original plate for color proofing of the present invention is also excellent in that even if various sensitizing dyes are used in combination, the performance is hardly changed by the sensitizing dyes.

(Various Additives) If necessary, various conventionally known additives for electrophotographic photosensitive members can be used in combination. 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, 2,3-dichloro-5,6-dicyano Electron-withdrawing compounds such as benzoquinone, dinitrofluorenone, trinitrofluorenone, and tetracyanoethylene; Hiroshi Komon et al. "Recent development and commercialization of photoconductive materials and photoreceptors" Chapters 4 to 6: Japan Science Information ( Polyarylalkane compounds, hindered phenol compounds, p-
And phenylenediamine compounds. Further, Japanese Patent Application Laid-Open Nos. 58-65439, 58-102239, 58-
Compounds described in JP-A-129439 and JP-A-62-71965 can also be mentioned. Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, triphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalyl ethyl glycolate, dimethyl glycol phthalate and the like. Can be added to improve the flexibility of the photoconductive layer. These plasticizers can be contained in a range that does not deteriorate the electrostatic properties of the photoconductive layer.

The amount of each of these additives is not particularly limited, but is usually 0.000 per 100 parts by weight of the photoconductor.
It is 1 to 2.0 parts by weight. The photoconductive substance is pulverized and finely dispersed by a known means. Pulverization and dispersion in a system in which the binder resin, its solvent and each additive coexist, for example, a ball mill as shown in Solomon's "Coating Chemistry" and others,
It is common to use a Keddy mill, a sand mill, a dyno mill, a paint shaker, a roll mill, an ultrasonic disperser, or the like. Thereafter, this is applied with a bar coater, a reverse coater, a die coater or the like at an optimum application amount, and dried to form a photoconductive layer. or,
The solvent in which the photoconductive material is dispersed may be any solvent, and is selected in consideration of the solubility of the binder resin to be used. They may be used alone or in combination of two or more. The thickness of the photoconductive layer is preferably from 1 to 100 µ, particularly preferably from 10 to 50 µ. In the case of forming a laminated type photoconductive layer including a charge generation layer and a charge transport layer, the thickness of the charge generation layer is 0.01 to 5 mm.
μ, particularly 0.05 to 2 μ, is preferred. Further, the thickness of the charge transport layer is preferably 0.99 to 99.9 μm, particularly preferably 9 to 90 μm. The stacking order of the charge transport layer and the charge generation layer can be changed depending on whether the color proofing plate is charged negatively or positively.

[Transfer Layer] Next, the transfer layer will be described. The resin forming the transfer layer is a thermoplastic resin and has a weight average molecular weight of 5 × 10 ³ to 1 × 10 ⁶ , preferably 1 × 10 ^3.
10 ^{4 to} 5 × 10 ⁵ , a glass transition point of 0 ° C. to 100 ° C.,
Preferably, it is in the range of 20 ° C to 85 ° C. The resin is used in an amount of 70% by weight or more, preferably 90% by weight or more based on the total amount of the entire composition of the transfer layer.

Any thermoplastic resin which satisfies the above physical properties may be used. Specific examples thereof include vinyl chloride resin, polyolefin resin, olefin-styrene copolymer, vinyl alkanoate resin, polyester resin, polyether resin, and the like. An acrylic resin, a cellulose resin, a fatty acid-modified cellulose resin, and the like can be given. For example, Nikkan Kogyo Shimbun, "Plastic Materials Course Series" Vol. 1-18, (1961) Kinki Chemical Association Vinyl Subcommittee, "Polyvinyl Chloride", Nikkan Kogyo Shimbun (1988) Eizo Omori, ""Functional Acrylic Resin" published by Techno System Co., Ltd. (1985) Eiichiro Takiyama, "Polyester Resin Handbook" published by Nikkan Kogyo Shimbun (1988) Kazuo Yugi, edited by "Saturated Polyester Resin Handbook" Nikkan Kogyo Shimbun (1989) The Society of Polymer Science, “Polymer Data Handbook <Applications”
Chapter 1 Baifukan (1986) Yuji Harazaki, "Latest Binder Technology Handbook", Chapter 2
Compounds specifically exemplified in the General Technology Center (1985) and the like. These thermoplastic resins can be used alone or in combination of two or more.

Further, other additives may be used in the transfer layer in order to improve various physical properties such as coating properties, film forming properties, and film strength. For example, a plasticizer or the like may be used as in the above-described photoconductive layer. The thickness of the transfer layer is 0.1 to 10 μm, preferably 0.5 to 5 μm. The formation of the transfer layer can be performed by using a usual coating film forming method, for example, using a coating solution containing an arbitrary compound as described above, using the same means as that for coating the photoconductive layer. Can do it. Further, a spray drying method which is a known method can also be used. The method for forming the layer is not particularly limited.

[Production Method of Color Proof Printing] A method of producing a color proof printing using the electrophotographic color proof original plate of the present invention is described below. First, by the usual electrophotographic process,
A copy image is formed on an electrophotographic color proofing master. That is, each process of charging, exposure, development, and fixing is performed by a conventionally known method. As the developer used in the developing process, any conventionally known developer may be used, and examples thereof include a dry developer and a liquid developer. Specifically, for example, Moto Machida, “Recording Materials and Photosensitive Resins”, pp. 107-127
Specific examples are shown in, for example, "Development / Fixing / Electrification / Transfer of Electrophotography Nos. 2 to 5".

A combination of a scanning exposure method using a laser beam for exposing based on digital information and a developing method using a liquid developer is preferable because a high-definition image can be formed. An example is shown below. First, an electrophotographic color proofing plate of the present invention (hereinafter, simply referred to as a color proofing plate) is placed on a flat bed, positioned by a register pin method, and then fixed by suction from the back surface by air suction. . Next, for example, "Basic and Application of Electrophotographic Technology" (edited by the Society of Electrophotographic Engineers, Corona, June 1, 1988)
The original for color proofing is charged by the charging device described on page 212 et seq. Corotron or scorotron systems are common. At this time, it is preferable to control the charging conditions so that the surface potential is always within a predetermined range based on the information from the charging potential detecting means of the color proofing master.

Thereafter, for example, scanning exposure with a laser light source is performed by using the method described on page 254 and subsequent pages of the above cited document. First, an image corresponding to a yellow plate in a color image separated into four colors is converted into a dot pattern and exposed. Next, toner development is performed using a liquid developer. For example, the charged and exposed color proofreading master is removed from the flatbed and developed by the direct wet development method described on page 275 and thereafter of the above-cited reference material. The exposure mode at this time is determined according to the toner development mode. For example, in the case of reversal development, negative exposure, that is, irradiation of laser light to the image area is performed, and a toner having the same charge polarity as that when charged is used, and the toner is applied to the exposed area by applying a developing bias voltage. Is electrodeposited. Details of the principle are described on page 157 and thereafter of the cited reference. After development, squeezing is performed as shown on page 283 of the above-cited reference material in order to remove excess developer, and then drying is performed. It is also preferable to rinse only the carrier liquid of the developer before squeezing. By repeating the above process for each color of magenta, cyan, and black, a full-color image of four colors can be obtained on the same color proofing master. As a final step, the toner image on the color proofing plate is thermally transferred together with the transfer layer to the printing paper to obtain a color proof, that is, a color proof print.

FIG. 1 shows an example of an apparatus for thermally transferring the transfer layer to the paper. This is to drive while applying a predetermined nip pressure between a pair of rubber-coated metal rollers with built-in heating means. The roller surface temperature at this time is 50 to 150
° C, more preferably 80 to 120 ° C, the nip pressure between the rollers is 0.2 to 20 kgf / cm ² , more preferably 0.5 to 20 kgf / cm ² .
10 kgf / cm ² , transport speed 0.1-100 mm /
Seconds, more preferably in the range of 1 to 30 mm / sec. These conditions are appropriately set according to the physical properties of the material of the transfer layer, photoconductive layer, and support of the color proofing master used so as to obtain optimum results. The roller surface temperature is preferably maintained within a predetermined range by a known means. Further, it is also possible to provide a means for preheating the color proofing master in front of the heating roller section, and to provide a cooling means after the heating roller section. Although not shown in FIG. 1, a spring or an air cylinder using compressed air may be used at both ends of the shaft of at least one of the rollers as the inter-roller pressing means. As described above, by adding a small amount of the resin [P] to the photoconductive layer adjacent to the transfer layer, the surface releasability of the layer can be satisfactorily modified. This allows the transfer layer provided on the layer to be remarkably peeled off,
As a result, it is possible to obtain a high-quality color proof print free of toner color shift and transfer failure. Examples of the present invention will be described below, but the contents of the present invention are not limited to these. In the following formula, the symbol "-b-"
Means that the segments on both sides of the symbol are bollocked.

【Example】

Synthesis Example 101 of Resin [P ₁ ]: Methyl Methacrylate 7
A mixed solution of 0 g, 20 g of methyl acrylate, 10 g of glycidyl methacrylate and 200 g of toluene was heated to a temperature of 80 ° C. under a nitrogen stream. To this, 10 g of a polymer azobis initiator [I-1] having the following structure was added and reacted for 8 hours. After completion of the reaction, the obtained reactant was treated with methanol 1.
The 5 liters precipitate was obtained and reprecipitated in and scavenged and drying, M _W 3 × 10 ⁴ of the resin in a yield 75g [P-101]
I got

[0199]

Embedded image

Synthesis Example 102 of Resin [P ₁ ]: A mixed solution of 63 g of methyl methacrylate, 12.8 g of tri (dipropyl) silyl methacrylate and 200 g of tetrahydrofuran was sufficiently degassed under a nitrogen stream and cooled to -20 ° C. 0.8 g of 1,1-diphenylbutyllithium was added and 1
The reaction was performed for 2 hours. Further, 30 g of a monomer (M-1) having the following structure and 60 g of tetrahydrofuran were added to this mixed solution.
The mixed solution of was added after sufficiently degassing under a nitrogen stream,
The reaction was continued for another 8 hours. After the mixture was cooled to 0 ° C., 10 ml of methanol was added and reacted for 30 minutes to terminate the polymerization and deprotect the silyl ester. The obtained polymer solution was brought to a temperature of 30 ° C. under stirring,
3 ml of a 0% ethanol solution of hydrogen chloride was added, and the mixture was stirred for 1 hour. Next, the solvent was distilled off under reduced pressure until the total amount of the reaction mixture was reduced to half, and the reaction mixture was reprecipitated in 1 liter of petroleum ether. The precipitate was collected and dried under reduced pressure. The Mw of the obtained resin [P-102] was 6.8 × 10 ⁴ and the yield was 76.
g.

[0201]

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Synthetic Example 103 of Resin [P ₁ ] 103: A mixture of 63.8 g of methyl methacrylate, 19.7 g of 2- (trifluoroacetyloxy) ethyl methacrylate, 0.5 g of (tetraphenylporphinato) aluminum methyl and 200 g of methylene chloride The temperature of the solution is 30 ° C under a nitrogen stream.
And This was irradiated with light of 300 W-xenon lamp through a glass filter from a distance of 25 cm, and reacted for 20 hours. The mixture was further added with the following monomer [M-
2] 25 g was added, and the mixture was similarly irradiated with light for 12 hours. Thereafter, 3 g of methanol was added to the reaction mixture, and the mixture was stirred for 30 minutes to stop the reaction. Next, 50 g of a 5% by weight solution of p-toluenesulfonic acid in tetrahydrofuran was added to the reaction mixture to carry out a hydrolysis treatment. Next, the precipitate was reprecipitated in 2 liters of methanol, and the precipitate was collected and dried. The obtained resin [P
-103] had a yield of 70 g and Mw of 7 × 10 ⁴ .

[0203]

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Synthesis Example 104 of Resin [P ₁ ]: 48 g of ethyl methacrylate, 12 g of glycidyl methacrylate and 2.4 g of benzyl N, N-diethyldithiocarbamate
Was sealed in a container under a stream of nitrogen and heated to a temperature of 50 ° C. This was irradiated with light through a glass filter from a distance of 10 cm with a 400 W high-pressure mercury lamp for 6 hours to carry out photopolymerization. This was dissolved in 100 g of tetrahydrofuran, and 40 g of a monomer (M-3) having the following structure was further added, followed by nitrogen replacement and light irradiation again for 10 hours. The obtained reaction product was reprecipitated in 1 liter of methanol, collected and dried. The obtained polymer [P-104] was obtained in a yield of 73 g and Mw 8 ×
It was 10 ⁴ .

[0205]

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Synthesis Example 105 of Resin [P ₁ ] A mixture of 55 g of methyl methacrylate, 20 g of 3- (trimethoxysilyl) ethyl methacrylate, and 1.0 g of benzyl isopropyl xanthate was sealed in a container under a nitrogen stream.
Heated to a temperature of 50 ° C. This was irradiated with light through a glass filter from a distance of 10 cm with a 400 W high-pressure mercury lamp for 6 hours to carry out photopolymerization. The obtained reaction product was made into a solution having a concentration of 40% with tetrahydrofuran, and the following monomer [M-
4] 25 g was added, the atmosphere was replaced with nitrogen, and light irradiation was performed again for 10 hours. The obtained reaction product was reprecipitated in 2 liters of methanol, collected, and dried. The obtained resin [P-105] had a yield of 63 g and Mw of 6 × 10 ⁴ .

[0207]

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Synthesis Examples 106 to 114 of Resin [P ₁ ] The following copolymers were synthesized in the same manner as in Synthesis Example 105. The obtained resins [P-106] to [P-114]
Mw ranged from 6 × 10 ⁴ to 8 × 10 ⁴ .

[0209]

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[0210]

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[0211]

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[0212]

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[0213]

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Synthesis Example 115 of Resin [P ₁ ] Synthesis Example 115 was repeated except that 10 g of an initiator [I-2] having the following structure was used in place of benzyl N, N-diethyldithiocarbamate.
In the same manner as in Example ^4, a resin having Mw of 8.3 × 10 ⁴ [P-
115] was obtained.

[0215]

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Synthetic Example 116 of Resin [P ₁ ]: Mw 9.3 was obtained in the same manner as in Synthetic Example 105 except that 12 g of an initiator [I-3] having the following structure was used in place of benzyl isopropyl xanthate. × 10 ⁴ resin [P-116] was obtained.

[0219]

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Synthesis Examples 117 to 125 of Resin [P ₁ ]: In place of benzyl-N, N-diethyldithiocarbamate, 14 g of an initiator [I-4] having the following structure was used. Mw 7 × 10 ⁴ was obtained in the same manner as in Synthesis Example 104 except that each monomer corresponding to the unit was used.
To 9 × 10 ⁴ resins [P-117] to [P-125] were obtained.

[0219]

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[0220]

[Table 2]

[0221]

[Table 3]

[0222]

[Table 4]

Synthesis Examples 126 to 134 of Resin [P ₁ ]: In place of the initiator [I-3], a compound [I-
5] A resin having Mw of 8 × 10 ⁴ to 10 × 10 ^{4 was} prepared in the same manner as in Synthesis Example 116 except that 9.6 g was used and each monomer corresponding to the structural unit shown in Table 104 below was used. P-1
26] to [P-134].

[0224]

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[0225]

[Table 5]

[0226]

[Table 6]

[0227]

[Table 7]

[0228]

[Table 8]

Synthesis Examples 135 to 138 of Resin [P ₁ ]: A mixture of 40 g of a monomer corresponding to the structural unit shown in Table 105 below, 11 g of a compound [I-6] having the following structure, and 40 g of tetrahydrofuran was placed under a nitrogen stream. Seal in a container, temperature 50
g. 10C with a 400W high pressure mercury lamp
Light irradiation was performed for 12 hours through a glass filter from a distance of m for photopolymerization. In addition, methyl methacrylate 23
g, 22 g of methyl acrylate and 15 g of glycidyl methacrylate in 50% by weight of tetrahydrofuran, followed by nitrogen replacement and light irradiation again for 10 hours. The obtained reaction product was reprecipitated in 1 liter of methanol, collected and dried. The obtained resins [P-135] to [P-138]
Mw was 6 × 10 ⁴ to 8 × 10 ⁴ .

[0230]

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[0231]

[Table 9]

Synthesis Example 201 of Resin [P ₂ ]: 57 g of methyl methacrylate, 28 g of methyl acrylate, 15 g of glycidyl methacrylate, and an initiator [I-
7] A mixed solution of 17.5 g and 150 g of tetrahydrofuran was heated to a temperature of 50 ° C. under a nitrogen stream. Add this solution to 4
Light irradiation was performed for 10 hours through a glass filter from a distance of 10 cm with a high-pressure mercury lamp of 00 W to carry out photopolymerization. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to obtain a polymer having an Mw of 4.0 × 10 ^{4 in} a yield of 72 g. 40 g of this polymer, a monomer having the following structure (M-5)
A mixed solution of 60 g and 100 g of tetrahydrofuran is
The temperature was set to 50 ° C. in a nitrogen stream, and light irradiation was performed under the same conditions as above for 15 hours. Next, this reaction product was reprecipitated in 1.5 liters of methanol, and the precipitate was collected and dried to give a yield of 78 g of Mw.
6 × 10 ⁴ resin [P-201] was obtained.

[0233]

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[0234]

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Synthesis Examples 202 to 214 of Resin [P ₂ ]:
[P-202] to [P-214] In place of 17.5 g of the initiator [I-7], the following Table 202 was used.
The procedure was performed under the same conditions as in Synthesis Example 201, except that 0.031 mol of the initiator was used. Each of the obtained resins [P-202] to
The yield of [P-214] is 70 to 80 g and Mw ⁴ × 10 ^4.
６6 × 10 ⁴ .

[0236]

[Table 10]

[0237]

[Table 11]

[0238]

[Table 12]

[0239]

[Table 13]

[0240]

[Table 14]

Synthetic Examples 215 to 233 of Resin [P ₂ ]
[P-215] to [P-233] In the same manner as in Synthesis Example 201, except that 60 g of each monomer corresponding to the structural unit shown in Table 203 below was used instead of 60 g of the monomer [M-5]. Operate each resin [P-215]-[P
-233] was obtained. Mw of each resin is 6 × 10 ^{4 to} 7 × 1
0 was ⁴ of range.

[0242]

[Table 15]

[0243]

[Table 16]

[0244]

[Table 17]

[0245]

[Table 18]

[0246]

[Table 19]

Synthesis Examples 234 to 240 of Resin [P ₂ ]:
[P-234] to [P-240] 70 g of a methacrylate monomer corresponding to the structural unit of Table-204 below, 30 g of each monomer corresponding to the structural unit Y of Table-204 below, and an initiator [I-13] Synthesis Example 2 except that a mixed solution of 15 g and 100 g of tetrahydrofuran was used.
Mw 6 × 10 ^{4 to} 7 × 10 ⁴
80 g of a polymer was obtained. Next, a mixed solution of 50 g of this polymer, 50 g of the monomer [M-5] of Synthesis Example 201, and 100 g of tetrahydrofuran was used, and the polymerization reaction was carried out in the same manner as in Synthesis Example 201 of resin. However, diethyl ether was used as the reprecipitation solvent instead of methanol. Mw of the obtained resins [P-234] to [P-240] is 8 × 10 ⁴
It was in the range of 〜１０10 × 10 ⁴ .

[0248]

[Table 20]

[0249]

[Table 21]

Synthesis Examples 241 to 254 of Resin [P ₂ ]
[P-241] to [P-254] Initiator [I-9] instead of 17.5 g of initiator [I-7]
Each of the resins [P-241] to [P-2] represented by the following formulas was prepared in the same manner as in Synthesis Example 201 except that 10 g was used, and diethyl ether was used instead of the reprecipitation solvent methanol.
54] was synthesized. Mw of the obtained resin is 7 × 10 ⁴ or more.
The range was 9 × 10 ⁴ .

[0251]

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In the formula, [P] is a polymer chain having the following structure.

[0253]

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[0254]

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[0255]

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[0256]

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[0257]

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Synthesis Example 301 of Resin [P ₃ ]: [P-30]
1] 60 g of methyl methacrylate, 30 g of a macromonomer [M-6] having the following structure, and glycidyl methacrylate 10
g and a mixed solution of 150 g of toluene were brought to a temperature of 70 ° C. under a nitrogen stream. 1.0 g of 2,2'-azobisisobutyronitrile (abbreviation: AIBN) was added and reacted for 4 hours.
0.5 g of IBN was added and reacted for 4 hours. Mw (weight average molecular weight) of the obtained resin [P-301] is 6.5 × 10
^{Was 4} .

[0259]

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Synthesis Examples 302 to 314 of Resin [P ₃ ]:
[P-302] to [P-314] In Synthesis Example 1 of resin [P-301], 30 g of macromonomer [M-6] was used in place of 30 g of macromonomer [M-6]. Otherwise, in the same manner as in Synthesis Example 301, each of the resins [P-302] to
[P-314] was synthesized. Mw of the obtained resin is 5 ×
The range was from 10 ⁴ to 8 × 10 ⁴ . The Mw of the used macromonomer is shown in Table-302 below.

[0261]

[Table 22]

[0262]

[Table 23]

[0263]

[Table 24]

[0264]

[Table 25]

Synthesis Examples 315 to 325 of Resin [P ₃ ]:
[P-315] to [P-325] 25 g of a monomer corresponding to the structural unit shown in Table 303 below, 25 g of a macrosiloxane FM-0721 (manufactured by Chisso Corporation, Mw 1 × 10 ⁴ ) having a polysiloxane structure, and 200 parts of toluene
g of the mixed solution was heated to a temperature of 80 ° C. under a nitrogen stream. Thereafter, 2,2′-azobisisobutyronitrile (abbreviation: AI
BN), and react for 4 hours.
0.5 g was added and reacted for 4 hours.

[0266]

[Table 26]

[0267]

[Table 27]

[0268]

[Table 28]

[0269]

[Table 29]

Synthetic Examples 326 to 337 of Resin [P ₃ ]:
[P-326] to [P-337] The same as Synthesis Example 301 except that a mixed solution of the following monomer [M-7], a macromonomer corresponding to the structure in Table-304 below, and 200 g of toluene was used. According to the method, resins [P-326] to [P-337] shown in the table were obtained. The Mw of each resin ranged from 6 × 10 ⁴ to 8 × 10 ⁴ .

[0271]

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[0272]

[Table 30]

[0273]

[Table 31]

[0274]

[Table 32]

[0275]

[Table 33]

Synthesis Example 401 of Resin [P ₄ ] 50 g of a monomer (M-8) having the following structure, and an initiator [I-2] having the following structure
1] A mixed solution of 0.5 g and 50 g of tetrahydrofuran was sealed in a vessel under a nitrogen stream, and heated to a temperature of 60 ° C. This was irradiated with light through a glass filter from a distance of 10 cm with a 400 W high-pressure mercury lamp for 10 hours to carry out photopolymerization.
To this reaction product solution was added a mixed solution of 25 g of methyl methacrylate, 15 g of glycidyl methacrylate, 10 g of a macromonomer [M-9] having the following structure, and 50 g of tetrahydrofuran.
The resulting reaction mixture was re-precipitated in 1.0 liter of methanol, collected and dried. Obtained resin [P-401]
Mw was 6 × 10 ⁴ at 68 g.

[0277]

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[0278]

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Synthesis Example 402 of Resin [P ₄ ]: 36 g of monomer (M-10) having the following structure, siloxane macromonomer Praxel FM-725 (Mw1 × 1 manufactured by Nitrogen Co., Ltd.)
0 ⁴⁾ 4g, a mixed solution of the initiator [I-22] 1.0g and tetrahydrofuran 50g of the following structure was sealed in a container under a stream of nitrogen, was heated to a temperature of 50 ° C.. In addition, Synthesis Example 4
Light irradiation was performed for 12 hours under the same light irradiation conditions as in Example 01 to carry out photopolymerization. 24 g of methyl methacrylate was added to the polymer solution.
After adding a mixed solution of 18 g of methyl acrylate, 18 g of glycidyl methacrylate and 60 g of tetrahydrofuran, the atmosphere was replaced with nitrogen, and light irradiation was performed again for 10 hours. The obtained reaction mixture was reprecipitated in 1 liter of methanol, collected, and dried. The obtained resin [P-402] has a yield of 7
Mw was 8 × 10 ⁴ at 0 g.

[0280]

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[0281]

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Synthesis Example 403 of Resin [P ₄ ]: [P-40]
3] 25 g of methyl methacrylate, 15 g of glycidyl methacrylate, macromonomer (M-11) 10 having the following structure
g, a mixed solution of 2.5 g of an initiator [I-23] having the following structure and 50 g of tetrahydrofuran were degassed under a nitrogen stream, and then photopolymerized for 12 hours under the same conditions as in Synthesis Example 401. A monomer having the following structure (M-1) was added to this polymerization solution.
2) After adding a mixed solution of 50 g and 60 g of tetrahydrofuran, the atmosphere was replaced with nitrogen, and the mixture was irradiated with light again for 12 hours to carry out polymerization. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. 72 g of a resin [P-403] having an Mw of 5.3 × 10 ⁴ was obtained.

[0283]

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[0284]

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Synthesis Examples 404 to 416 of Resin [P ₄ ]: Each of the resins [P ₄ ] was prepared in the same manner as in Synthesis Example 402 except that macromonomers corresponding to the structural units shown in Table 402 below were used as macromonomers. 404] to [P-416] were synthesized. Mw of the obtained resin is 5 × 10 ⁴ to 8 × 10
It was in the range of ⁴ . The Mw of the used macromonomer is shown in Table-402 below.

[0286]

[Table 34]

[0287]

Table 35 (Continued) Synthesis Example P Macromonomer M Part _A Chemical Structure of -X- of Macromonomer M _W ───────────────────── ─────────────── 404 P- 404 M _A -4 6.5 x 10 ³ 405 P- 405 M _A- 58 8 x 10 ³ 406 P- 406 M _A- 66 6 x 10 _{^{3 407 P- 407 M A -7 8}} × 10 3 408 P- 408 M A -8 5 × 10 3 409 P- 409 M A -9 8 × 10 3 410 P- 410 M A -10 7 × 10 3 411 P- 411 M _A− 116 6 × 10 ³ 412 P− 412 M− _A 12 9 × 10 ³ 413 P− 413 M _A− 13 1.5 × 10 ⁴ 414 P− 414 M _A− 14 1.2 × 10 ⁴ 415 P− 415 M _A- 15 1.5 × 10 ⁴ 416 P-416 M _A- 16 1.0 × 10 ⁴ ───────────────────────────── ──────

[0288]

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[0289]

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[0290]

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[0291]

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Synthesis Examples 417 to 429 of Resin [P]: In the same manner as in Synthesis Example 401 of Resin [P], the following Table-4
No. 03 were synthesized. Mw of the obtained resin is 4 × 1
0 ranged from ^{4 ~8} × 10 ^4. The Mw of the monofunctional macromonomer used was 6 × 10 ³ to 1 × 10 ⁴ .

[0293]

[Table 36]

[0294]

[Table 37]

[0295]

[Table 38]

[0296]

[Table 39]

[0297]

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[0298]

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[0299]

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[0300]

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[0301]

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[0302]

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Synthesis Example 1 of Resin [Q ₁ ]: [Q-1] 80 g of benzyl methacrylate, malomonomer [weight average molecular weight (Mw) 6 corresponding to a repeating unit having the following structure:
× 10 ³ ] a mixed solution of 20 g and 100 g of toluene,
The mixture was heated to a temperature of 80 ° C. under a nitrogen stream. 3 g by adding 6 g of 2,2-azobis (valeronitrile) (abbreviation: AIVN)
After reacting for 1 hour, 1 g of AIVN was further added and reacted for 4 hours. Mw of the obtained copolymer was 9.5 × 10 ³ .

[0304]

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Synthesis Example 2 of Resin [Q ₁ ]: [Q-2] 60 g of methyl methacrylate, macromonomer (Mw 5 × 10 ³ ) 25 corresponding to a repeating unit having the following structure
g, 15 g of methyl acrylate, 130 g of toluene and 20 g of ethanol at 80 ° C. under a nitrogen stream.
Warmed to ° C. 2,2'-azobis (cyanovaleric acid) (AC
V.) 7 g was added and reacted for 4 hours, and 1 g of ACV was further added and reacted for 4 hours. Mw of the obtained copolymer is 1 × 10
^{Was 4} .

[0306]

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Synthesis Example 3 of Resin [Q ₁ ]: [Q-3] 70 g of 2-chlorophenyl methacrylate, a macromonomer (Mw 6.5 ×) corresponding to a repeating unit having the following structure
10 ³ ] 25 g, thioglycolic acid 2 g and toluene 1
50 g of the mixed solution was heated to a temperature of 75 ° C. under a nitrogen stream. 2,2'-azobis (isobutyronitrile) (AI
1 g of BN) and reacted for 4 hours.
Add 8 g for 3 hours, then add 0.5 g of AIBN and add 4
Reacted for hours. Mw of the obtained copolymer was 7.8 × 10 ⁴
Met.

[0308]

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Synthesis Examples 4 to 11 of Resin [Q ₁ ]: [Q-
4] to [Q-11] Resin [Q] was synthesized in the same manner as in Synthesis Example 1 of resin [Q ₁ ], using methacrylate and macromonomer corresponding to Table 2 below. Mw of each resin [Q] is 7 × 10
It was in the range of ³ to 1 × 10 ⁴ . The Mw of the used macromonomer was in the range of 5 × 10 ^{3 to} 7 × 10 ³ .

[0310]

[Table 40]

[0311]

[Table 41]

Synthetic Examples 12 to 19 of Resin [Q ₁ ]: [Q-
12] to [Q-19] Resin [Q] shown in Table 3 below was synthesized in the same manner as in Synthesis Example 2 of resin [Q ₁ ], except that methacrylate, macromonomer, and azobis-based compound were each replaced. The Mw of each resin [Q] was in the range of 8 × 10 ³ to 1 × 10 ⁴ . The Mw of each macromonomer used was 4 × 10
³ ranged to 6 × 10 ^3.

[0313]

[Table 42]

[0314]

[Table 43]

Synthesis Examples 20 to 27 of Resin [Q ₁ ]: [Q-
20] to [Q-27] Resins [Q] shown in Table 4 below were synthesized in the same manner as in Synthesis Example 3 of resin [Q ₁ ], except that methacrylate, macromonomer, and mercapto compound were each replaced. Mw of each resin [Q] was in the range of 7 × 10 ³ to 1 × 10 ⁴ . The Mw of each macromonomer used was 3 × 10
The range was from ^{3 to} 6 × 10 ⁴ .

[0316]

[Table 44]

[0317]

[Table 45]

Synthesis Examples 28 to 35 of Resin [Q ₁ ]: [Q-
28] to [Q-35] Macromonomer (Mw 4 × 10 ³ ) 20 corresponding to the following repeating unit in the same manner as in Synthesis Example 3 of resin [Q ₁ ].
g, 2 g of thiosalicylic acid, a mixed solution of 80 g of a monomer corresponding to Table 5 below, 130 g of toluene and 20 g of ethanol were polymerized to synthesize resins [Q] shown in Table 5 below. Mw of each resin [Q] is 6 × 10 ^{3 to} 8.5 × 10 ³
Was in the range.

[0319]

[Table 46]

[0320]

[Table 47]

Synthesis Example 1 of Macromonomer (M _D )
-13) A mixed solution of 30 g of triphenylmethyl methacrylate and 100 g of toluene was sufficiently degassed under a stream of nitrogen to obtain -20.
Cooled to ° C. 1,1-diphenylbutyllithium 1.0
g was added and reacted for 10 hours. Further, to this mixed solution, a mixed solution of 70 g of ethyl methacrylate and 100 g of toluene was sufficiently degassed under a nitrogen stream, and then added.
The reaction was performed for 0 hours. After the mixture was cooled to 0 ° C., carbon dioxide gas was bubbled at a flow rate of 60 ml / min for 30 minutes to terminate the polymerization reaction. The obtained reaction solution was stirred at a temperature of 25 ° C., and 6 g of 2-hydroxyethyl methacrylate was added.
Furthermore, dicyclohexylcarbodiimide 12g, 4-
A mixed solution of 1.0 g of N, N-dimethylaminopyridine and 20 g of methylene chloride was added dropwise over 30 minutes, and the mixture was stirred for 3 hours. After filtering out the precipitated insoluble matter, 10 ml of a 30% ethanol solution of hydrogen chloride was added to the mixed solution, and
Stirred for hours. Next, the solvent was distilled off under reduced pressure until the total amount of the reaction mixture was reduced to half, and the reaction mixture was reprecipitated in 1 liter of petroleum ether. The precipitate was collected and dried under reduced pressure to give a polymer having an Mw of 6.5 × 10 ³ and a yield of 56 g.

[0322]

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Synthesis Example 2 of Macromonomer (M _D )
-14) A mixed solution of 5 g of benzyl methacrylate, 0.1 g of (tetraphenylporphinato) aluminum methyl and 60 g of methylene chloride was heated to a temperature of 30 ° C. under a nitrogen stream. This was irradiated with light from a 300 W-xenon lamp through a glass filter from a distance of 25 cm, and reacted for 12 hours. 45 g of butyl methacrylate was further added to this mixture, and the mixture was similarly irradiated with light for 8 hours.
10 g of bromomethylstyrene was added, and the mixture was stirred for 30 minutes to stop the reaction. Next, Pd-C was added to the reaction mixture, and a catalytic reduction reaction was performed at a temperature of 25 ° C for 1 hour. After filtering off the insoluble matter, the precipitate was reprecipitated in 500 ml of petroleum ether, and the precipitate was collected and dried. The obtained polymer had a yield of 33 g and Mw of 7 × 10 ³ .

[0324]

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Synthesis Example 3 of Macromonomer (M _D ): (M
-15) A mixed solution of 20 g of 4-vinylphenyloxytrimethylsilane and 100 g of toluene was sufficiently degassed under a nitrogen stream and cooled to 0 ° C. 2 g of lithium 1,1-diphenyl-3-methylpentyl was added and stirred for 6 hours. Further, to this mixture, a mixed solution of 2-chloro-6-methylphenyl methacrylate (80 g) and toluene (100 g) was sufficiently degassed under a nitrogen stream, and then added, followed by a reaction for 8 hours. Ethylene oxide was bubbled through the reaction mixture at a flow rate of 30 ml / min for 30 minutes with sufficient stirring.
After cooling to ° C., 12 g of methacrylic acid chloride was added dropwise over 30 minutes, and the mixture was further stirred for 3 hours. Next, 10 g of a 30% ethanol solution of hydrogen chloride was added to the reaction mixture,
After stirring at 5 ° C. for 1 hour, the mixture was reprecipitated in 1 liter of petroleum ether, and the collected precipitate was collected in 300 ml of diethyl ether.
And dried twice. The obtained polymer had a yield of 55 g.
Mw was 7.8 × 10 ³ .

[0326]

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Synthesis Example 4 of Macromonomer (M _D )
-16) A mixed solution of 40 g of triphenylmethyl methacrylate and 100 g of toluene was sufficiently degassed under a nitrogen stream, and -2.
Cooled to 0 ° C. 2 g of sec-butyllithium was added and reacted for 10 hours. Next, 60 g of styrene was added to this mixed solution.
Then, a mixed solution of 100 g of toluene and 100 g was sufficiently degassed under a nitrogen stream and then added, followed by a reaction for 12 hours. This mixture
After that, 11 g of benzyl bromide was added and reacted for 1 hour, and further reacted at a temperature of 25 ° C. for 2 hours. To this reaction mixture was added 10 g of a 30% hydrogen chloride-containing ethanol solution,
Stir for 2 hours. After filtering off the insoluble matter, the precipitate was reprecipitated in 1 liter of n-hexane, and the precipitate was collected and dried under reduced pressure. The yield of the obtained polymer was 58 g and Mw was 4.5 × 10 ³ .

[0328]

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Synthesis Example 5 of Macromonomer (M _D )
-17) A mixture of 70 g of phenyl methacrylate and 4.8 g of benzyl-N-hydroxylethyl-N-ethyldithiocarbamate was sealed in a vessel under a stream of nitrogen and heated to a temperature of 60 ° C. This was irradiated with light through a glass filter from a distance of 10 cm with a 400 W high-pressure mercury lamp for 10 hours to carry out photopolymerization. After 30 g of acrylic acid and 180 g of methyl ethyl ketone were added thereto, the atmosphere was replaced with nitrogen and light irradiation was performed again for 10 hours. 12 g of 2-isocyanatoethyl methacrylate was added dropwise to the obtained reaction mixture at a temperature of 30 ° C. for 1 hour, and the mixture was further stirred for 2 hours. The obtained reaction product was treated with hexane 1.
Reprecipitated to 5 liters, collected and dried. The obtained polymer had a Mw of 6.0 × 10 ³ in 68 g.

[0330]

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Synthesis Example 1 of Resin [Q ₂ ]: [Q-36] 80 g of ethyl methacrylate, macromonomer (M-1)
3) A mixed solution of 120 g and 150 g of toluene was heated to a temperature of 95 ° C. under a nitrogen stream. 6 g of 2,2'-azobis (isobutyronitrile) (AIBN) was added and reacted for 3 hours.
Further, every 2 hours, 2 g of AIBN was added and reacted. Mw of the obtained copolymer was 9 × 10 ³ .

[0332]

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Synthesis Example 2 of Resin [Q ₂ ]: [Q-37] 70 g of 2-chlorophenyl methacrylate, 30 g of macromonomer (M-14), n-dodecyl mercaptan 2
g and 100 g of toluene were heated to a temperature of 80 ° C. under a nitrogen stream. 3 g of 2,2'-azobis (isovaleronitrile) (AIVN) was added and reacted for 3 hours.
1 g of IVN was added and reacted for 2 hours. Next, 1 g of AIVN was added, and the mixture was heated to a temperature of 90 ° C. and reacted for 3 hours. The Mw of the obtained copolymer was 7.6 × 10 ³ .

[0334]

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Synthesis Examples 3 to 18 of Resin [Q ₂ ]: [Q-3]
8] to [Q-53] Copolymers shown in Table 6 below were synthesized under the same polymerization conditions as in Synthesis Example 1 of Resin [Q ₂ ], except that ethyl methacrylate was replaced by another monomer. The Mw of each of the obtained polymers is 5 × 10 ³ to
It was 9 × 10 ³ .

[0336]

[Table 48]

[0337]

[Table 49]

[0338]

[Table 50]

Synthesis Examples 19 to 35 of Resin [Q ₂ ]: [Q-
54] to [Q-70] In Synthesis Example 2 of the resin [Q ₂ ], the macromonomer (M
-14) was used other macromonomer (M _D) in place of the copolymer of Table -7 were synthesized under the same polymerization conditions as in Synthesis Example 2. The Mw of each polymer obtained was 2 × 10 ³
１1 × 10 ⁴ .

[0340]

[Table 51]

[0341]

[Table 52]

[0342]

[Table 53]

[0343]

[Table 54]

Example 1 X-type metal-free phthalocyanine (Dainippon Ink Co., Ltd.) 1.
5 g, 8.5 g of resin [R-1] having the following structure, and resin [Q-
5] 1.5 g, 0.3 g of the resin [P-104] of the present invention, 0.15 g of the compound [A] having the following structure, and tetrahydrofuran 8
0 g of the mixture is placed in a 500 ml glass container together with glass beads, and the mixture is placed on a paint shaker (manufactured by Toyo Seiki Seisakusho).
For 60 minutes, and 0.04 g of phthalic anhydride and o
After adding 0.0001 g of chlorophenol and dispersing for 2 minutes, the glass beads were filtered to obtain a photoconductive layer dispersion. Then, this dispersion was subjected to a conductive treatment and a solvent resistance treatment.
It is applied on a 0.2 mm thick paper plate master paper with a wire bar, dried by touch, and then dried in a 110 ° C. circulating oven.
Dry for 0 seconds. Further heating was performed at 140 ° C. for 1 hour. The thickness of the obtained photoconductive layer was 10 μm.

[0345]

Embedded image

Further, in order to form a transfer layer on the photoconductive layer, the following thermoplastic resin solution was prepared. Poly (vinyl acetate / crotonic acid) (95/5, Mw 5 × 10 ⁴ ) 3 g Ammonia (28% aqueous solution) 1 g Ethanol 97 g This solution was adjusted to a thickness of 1.3 μm with a wire bar. Coated and oven dried at 120 ° C. for 20 seconds. Comparative Example A1 Example 1 was repeated except that 0.3 g of the random copolymer [RP-1] having the following structure was used in place of 0.3 g of the resin [P-104].
An electrophotographic color proofreading master was prepared in the same manner as in the above.

[0347]

Embedded image

Comparative Example B1 In Example 1, instead of 8.5 g of the resin [R-1] and 1.5 g of the resin [Q-1], only the resin [R-1] was used.
An electrophotographic color proofreading master was prepared in the same manner as in Example 1 except that g was used. Test Example The electrostatic characteristics, transferability and image reproducibility of the electrophotographic color proofing plates prepared in Example 1, Comparative Example A1 and Comparative Example B1 were examined, and the results are shown in Table-8.

[0349]

[Table 55] Example 1 Comparative Example A1 Comparative Example B1 静電 Electrostatic characteristics Note 1) V ₁₀ (-V) | ( (20 ° C, 65% RH) 580 570 560 ───────────────────────────── 30 (30 ° C, 80% RH) 555 550 515 ────────────────────────────────── DRR (%) ｜ (20 ℃, 65% RH) 86 85 81 ───────────────────────────── ‖ (30 ° C, 80% RH) 82 81 72 ──────── _{^{────────────────────────── E 1/2 | (20}} ℃, 65% RH) 16 18 22 (erg / cm 2) ── ─────────────────────────── ‖ (30 ° C, 80% RH) 18 20 25転 写 Transferability Note 2) ○ × ○ Very good Transfer unevenness Very good Notable ──── ─────────────────────────────── Image reproducibility Note 3) ○ ×× ○ │ (20 ℃, 65% RH) Good Remarkable image unevenness Good ───────────────────────────── 30 (30 ° C, 80% RH) ○ ×× × ~ △ Good Image unevenness Low density, remarkable fine lines and fine characters are missing.

The evaluation items described in Table 8 were tested by the following methods. Note 1) Electrostatic characteristics In a dark room at a temperature of 20 ° C. and 65% RH, use a paper analyzer (Paper Analyzer-SP-428, manufactured by Kawaguchi Electric Co., Ltd.) for each color calibration master at −6 kV.
Seconds and left 10 seconds After corona discharge was measured surface potential V ₁₀ at this time. Then measuring the potential V ₁₃₀ after leaving 120 seconds in as dark, retention of potential after being 120 seconds dark decay, i.e., dark decay retention rate [DRR
DRR (%) = (V ₁₃₀ / V ₁₀ ) × 100
(%). After charging the surface of the photoconductive layer in contact with the transfer layer to −500 V by corona discharge,
Irradiation with monochromatic light having a wavelength of 780 nm has a surface potential (V ₁₀ ) of 1
/ 2, the time required to decay to / 2, and the exposure E
Calculate _1/2 (erg / cm ² ). In addition, temperature 30 ℃, 80% R
The same operation as described above was performed under the environmental conditions of H, and each characteristic was examined. Environmental conditions (20 ° C., 65% RH) were defined as condition I, and (30 ° C., 80% RH) were defined as condition II.

Note 2) Transferability The sample on which the transfer layer was formed and the coated paper were passed over a pair of heating rollers in which an infrared lamp heater was incorporated inside a hollow metal roller covered with silicone rubber. . At this time, the surface temperature of the roller was set to 120 ° C. in both directions, the nip pressure between the rollers was set to 5 kgf / cm ² , and the transport speed was set to 5 mm / sec. After the passage, the sample was cooled to room temperature while being overlapped with the coated paper, and then the sample and the coated paper were separated. At this time, the state of the transfer layer transferred to the coated paper side was visually evaluated. Note 3) Image reproducibility Under the environmental conditions (I) and (II),
A copied image was actually formed, and the image reproducibility of the color proof plate after transfer was evaluated.

Each color calibration master was corona-charged to +450 V in a dark place, read in advance from a manuscript with a color scanner, color-separated, and corrected for some system-specific color reproduction. Was stored on the hard disk in the system as
On the surface of the color calibration master using a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength: 780 nm) with a 5 mW output in the negative mirror image mode based on information on yellow in each color of yellow, magenta, cyan, and black. At 30er
Exposure was performed at a pitch of 25 μm and a scan speed of 300 m / sec under an irradiation amount of g / cm ² . Subsequently, a yellow liquid developer for a signature system (Eastman Kodak (manufactured by)) diluted 75 times (polymerization ratio) with Isopar H (manufactured by Esso Standard Petroleum) is used, and has a pair of planographic developing electrodes. In the developing device, a bias voltage of +400 V is applied to the electrode on the side of the color proofing original plate, and reversal development is performed so that the toner is electrodeposited on the exposed portion. Dirt was removed. The above processing was repeated for each color of magenta, cyan, and black. The image of the color proofing plate after plate making obtained as described above was fixed by a fixing method using a heat roll.

Next, the coated paper, which is the actual printing paper, is superimposed on the color proofreading plate after the four-color development, and a pair of rubber rollers in contact with a pressure of 15 kgf / cm ² , the surface temperature of which is constantly controlled at 120 ° C. At a speed of 10 mm / sec. Thereafter, the coated paper and the color proofreading master were peeled off after being cooled to room temperature while being stacked, and an image (fog, image quality) formed on the obtained coated paper was visually evaluated. As shown in Table 8, the electrostatic characteristics of Example 1 (the present invention) and Comparative Example A1 showed good results even when environmental conditions were changed.

However, in Comparative Example B1 using only the conventional resin as the binder resin for the photoconductive layer, the electrostatic characteristics were deteriorated (in particular, the charge retention in the dark: DRR and the photosensitivity: E
_1/2 ), and the resulting color proof copy image was not satisfactory. This difference is that, in the color proofing plate of the present invention, the resin [Q] is sufficiently adsorbed to the photoconductive compound, and enables uniform dispersion of the photoconductive compound.
It is presumed that the compound [A], which is a chemical sensitizer, and the photoconductive compound form a state in which the interaction can be performed sufficiently and uniformly. Also, the resin [P] of the present invention
The transfer layers of Example 1 and Comparative Example B1 using the resin were completely transferred to the material to be transferred. However, in Comparative Example A1 using the conventional resin, the peeling of the coated paper and the color proofreading master was satisfactory. No, the transfer layer or the photoconductive layer was damaged.

The difference is that, in the color proofing masters of the present invention and Comparative Example B1, the resin [P], which is a fluorine atom-containing copolymer coexisting in the photoconductive layer, has a surface portion at the time of forming the photoconductive layer. To the resin [R] and resin [P]
Are sufficiently chemically bonded to each other by a crosslinking agent to form a cured film, whereby an interface having good releasability is clearly formed, whereas Comparative Example A1 using a conventional random copolymer is used. It is considered that such a clear interface is difficult to be formed in the color proofing master. Also,
The color proofing plate of the present invention was able to provide color proofing of a good color image, even when environmental conditions fluctuated.
The color proofing master of Comparative Example A1 was insufficient in transferability and could not provide a satisfactory image, and the color proofing master of Comparative Example B1 had significantly reduced image reproducibility under high humidity. Further, in order to examine the releasability of the photoconductive layer formed in Example 1 and Comparative Example A1, the adhesive strength of the surface of the photoconductive layer was measured before forming the transfer layer. The adhesive strength is as described in JISZ0237-
1980 "Adhesive tape / sheet test method". The adhesive strength of the photoconductive layer formed in Example 1 is 6 g · f
The adhesive force of the photoconductive layer formed in Comparative Example A1 was 33.
It was 0 g · f. As described above, only the color proofing master of the present invention showed good performance.

Example 2 200 g of photoconductive zinc oxide, 10 g of resin [Q-2], 40 g of resin [R-2] having the following structure, and resin [P-1] of the present invention
03] 8 g, dye [D-1] 0.018 g having the following structure, N
-0.20 g of hydroxysuccinimide and 30 of toluene
0 g of the mixture is homogenized (manufactured by Nippon Seiki Co., Ltd.).
And dispersed at a rotation speed of 9 × 10 ³ rpm for 10 minutes. 1 g of propylene glycol and 0.02 g of tetrabutoxytitanate were added to this dispersion, and the number of revolutions was 1 × 10 ³
Dispersed for 1 minute at rpm. Then, this dispersion was applied with a wire bar onto a 0.2 mm-thick stencil master paper subjected to a conductive treatment and a solvent resistance treatment, and then dried by touch.
Heated in a circulating oven at 90 ° C. for 1 hour. The thickness of the obtained photoconductive layer was 15 μm.

[0357]

Embedded image

Further, in order to form a transfer layer on the photoconductive layer, the same thermoplastic resin solution as in Example 1 was prepared, applied and dried. Comparative Example C1 A color proofreading master was prepared in the same manner as in Example 2 except that only 50 g of the resin [R-2] was used instead of 10 g of the resin [Q-2] and 40 g of the resin [R-2]. Created. Test Example The smoothness, electrostatic properties, transferability and image reproducibility of each color proofing master were evaluated, and the results are shown in Table-9.

[0359]

[Table 56] Table 9 {Example 2 Comparative Example C1} ─────────────────────────────── Smoothness of photoconductive layer surface Note 1) 1,100 1050 ───────静電 Electrostatic characteristics V ₁₀ (-V) ｜ 710 550 ─────────── ─────────────── ‖ 685 510 ─────────────────────────────── DRR (%) ｜ 88 75 ────────────────────────── ‖ 85 76 ─────────────── _{^{──────────────── E 1/2 | 10 25}} (erg / cm 2) ───────────────────── ───── ‖ 12 26 ────────────────── ──────── Transferability ○ ○ Very good Very good ──────────────────────────────── ── Image reproducibility Note 2) ○ △ ～ ○ ｜ Good Good The density is slightly low. Fine lines and missing small characters Slightly generated ────────────────────────── ‖ ○ ×× Good No density, fog on ground, fine lines , Small characters are missing ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

In Table 9, the transferability was tested by the method of Table 8 above, and the other evaluation items were tested by the following methods. Note 1) Smoothness of photoconductive layer: The smoothness (see / cc) of the obtained color proofreading master was measured using a Beck smoothness tester (manufactured by Kumagaya Riko Co., Ltd.) under the condition of an air capacity of 1 cc. It was measured. Note 2) Image Reproducibility After the color proofreading master was corona-charged to −600 V in a dark place, the same digital image data as in Example 1 was used. Exposure was performed using a semiconductor laser with light of 780 nm so that the plate surface exposure amount became 25 erg / cm ² . The residual potential of the exposed part was -120v. Next, Versatech 300
A yellow toner for 0 (Xerox color electrostatic plotter) diluted with 50 times Isopar H (manufactured by Esso Standard Petroleum) is used, and a developing device having a pair of flat plate developing electrodes is used as an electrode on the color calibration original plate side. A bias voltage of 200 V was applied to perform normal development so that the toner was electrodeposited on the unexposed area, and then rinsed in a single bath of Isopar H to remove stain on the non-image area. The above processing was repeated for each color of magenta, cyan, and black.

Next, the coated paper, which is the printing paper, is superimposed on the color proofreading plate after four-color development, and a pair of rubber rollers in contact with a pressure of 10 kgf / cm ² , the surface temperature of which is constantly controlled to 120 ° C. At a speed of 6 mm / sec. Thereafter, the coated paper and the original plate for color proofreading were peeled off after being cooled to room temperature while being overlapped, and an image as a color proof print was visually evaluated. As shown in Table-9, the color proofing master of Example 2 had extremely good electrostatic characteristics and
Even if the environmental conditions change, the change in those characteristics was suppressed to a small value. Even when the imaging performance was actually examined, there was no background stain and the reproducibility of fine images such as fine lines and fine characters was good. On the other hand, the color proofing master of Comparative Example C1 had significantly reduced electrostatic properties, especially under high humidity conditions, and the actual image reproducibility was not practical. That is, the ground fog in the non-image area,
The image density was reduced, and thin lines were missing.
The transferability of the transfer layer is good, and the release property of the resin [P] can be improved not only in the photoconductive layer made of the organic photoconductive compound but also in the photoconductive layer containing the inorganic photoconductive compound. It became clear. Further, in order to examine the releasability of the photoconductive layer formed in Example 2 and Comparative Example C1, the adhesive strength of the photoconductive layer surface was measured before forming the transfer layer. The adhesive strength is as described in JISZ0237-198.
0 The adhesive tape / sheet test method was used. The adhesive strength of the photoconductive layer formed in Example 2 was 8 g · f, and the adhesive strength of the photoconductive layer formed in Comparative Example C1 was 400 g · f.
g · f or more. As described above, only the color proofreading master of Example 2 exhibited good transferability and good image reproducibility regardless of environmental changes.

Example 3 As an organic photoconductive compound, 4,4′-bis (diethylamino) -2,2′-dimethyltriphenylmethane (5 g), resin [Q-32] 1 g, resin [R-3 3 g, 0.8 g of the resin [P-119] of the present invention, 40 mg of the dye (D-2) having the following structural formula, 0.2 g of the anilide compound (B) having the following structural formula as a chemical sensitizer, and 30 ml of methylene chloride.
And 30 ml of ethylene chloride to obtain a photoconductive layer solution. This photoconductive layer solution was applied to 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) by using a wire round rod to obtain about 4 μm.
A μm photoconductive layer was formed.

[0363]

Embedded image

In order to confirm the uneven distribution of the resin [P] of the present invention on the surface of the photoconductive layer, the adhesive strength of the pressure-sensitive adhesive tape was measured, and the resin [P-119] was not added. Except that the resin [R-3] was used in Example 3, except that the adhesive strength of the color proofreading master produced by the same method as in Example 3 was 7%.
It turned out that it reduced to 1/0. Further, in order to form a transfer layer on the photoconductive layer, the same thermoplastic resin solution as in Example 1 was prepared, applied, and dried. When the pressure-sensitive adhesive tape was applied to the surface of the transfer layer and peeled off, only the transfer layer was easily peeled off without feeling resistance as in Example 1. Next, the image-capturing property and transfer property of this color proofing master were examined in a dark place by the same method as in Example 1. However, helium-neon laser light having an oscillation wavelength of 630 nm was used instead of the semiconductor laser light having an oscillation wavelength of 780 nm used in Example 1. The color copy image transferred to the coated paper was clear with no background fog, and the image intensity was sufficiently high.

Example 4 5 g of a bisazo pigment having the following structure, 95 of tetrahydrofuran
g, 1.5 g of resin [Q-17], 3.5 g of polyester resin Byron 200 (manufactured by Toyobo Co., Ltd.) and 30 g of a tetrahydrofuran solution were sufficiently pulverized in a ball mill. Next, the mixture was taken out, and 520 g of tetrahydrofuran was added with stirring. This dispersion was coated on the conductive transparent support used in Example 1 using a wire round rod to form a charge generation layer of about 0.7 μm.

[0366]

Embedded image

Next, a hydrazone compound 20 of the following structural formula
g, 20 g of polycarbonate resin (manufactured by GE, trade name: Lexan 121), 2 g of resin [P-102], 0.04 g of isophorone diisocyanate, tetrabutoxy titanate
A mixed solution of 0.001 g and 160 g of tetrahydrofuran is applied on the charge generating layer using a wire round rod, dried at 60 ° C. for 30 seconds, and further heated at 120 ° C. for 1 hour to form a charge transporting layer of about 18 μm. Thus, a color proofreading master having a photoconductive layer composed of two layers was obtained.

[0368]

Embedded image

Further, in order to form a transfer layer on the photoconductive layer, the same thermoplastic resin solution as in Example 1 was prepared, applied and dried. When the pressure-sensitive adhesive tape was applied to the surface of the transfer layer and peeled off, only the transfer layer was easily peeled off without feeling resistance as in Example 1. Next, the color proofreading master was operated in a dark place in the same manner as in Example 1 to examine the image capturing property and the transfer property. However, 780 nm used in Example 1 was used.
This was performed using a helium-neon laser beam having an oscillation wavelength of 630 nm instead of the semiconductor laser beam having the oscillation wavelength. The obtained color copied image of the coated paper after the transfer was clear without fog, and the image strength was sufficiently high. Examples 5 to 7 In Example 1, 0.3 g of resin [P-104] was used. In place of the above, 0.3 g of each resin [P] shown in Table 10 below was used, and an electrophotographic color calibration original plate was produced in the same manner as in Example 1. The electrostatic properties, transferability, and image reproducibility of each master thus obtained were evaluated in the same manner as in Example 1, and the results are shown in Table-10.

[0370]

Table 57 Table 5 Example 5 Example 6 Example 7 樹脂 Resin of the present invention [P] [P-209] [P −308] [P-421] 静電 Electrostatic characteristics 580 585 580 V ₁₀ (−V) I ──────────────────────────────── II 560 560 565 ──────── ─────────────────────────── D. R. R (%) I 87 86 86 {II 83 84 82} ───────────────────────────── E _1/2 I 16 15 17 (evg / cm ² ) ─────── ───────────────────── II 17 18 20 ───────────────────────── ────────── Transferability ○ ○ ○ Very good Very good Very good ────────────────────────── ───────── Image reproducibility I ○ ○ ○ Good ───────────────────────────── II ○ ○ ○ Good good good ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

As shown in Table 10, all of the color proofreading masters of Examples 8 to 10 exhibited good performance equivalent to that of Example 1 in terms of electrostatic characteristics, transferability and image reproducibility.
The adhesive strength of the photoconductive layers of the color proofing masters of Examples 5 to 7 was all in the range of 5 to 8 g · f, indicating that the peelability was extremely good. On the other hand, a color proofing master produced by the same method as in Example 1 except that the resin [P] was not added and the same amount of the resin [R-1] was used instead. Resulted in poor transfer, and uniform peeling at the interface between the photoconductive layer and the transfer layer could not be obtained. Further, a resin [Q-5] 1.5 prepared for comparison was prepared.
g and the resin [R-1] 8.5 g instead of the resin [R-1]
An original plate for color proofing produced by the same method as in Example 1 except that only 10 g was used and the resin [P] of Examples 5 to 7 was used instead of 0.3 g of the resin [P-104]. Then
When the environmental conditions fluctuate, the electrostatic characteristics deteriorate particularly under high-temperature and high-humidity conditions, and the actual image reproducibility is not practical. That is, the density was reduced, and thin lines and characters were missing. From the test examples described above, it was found that the color proofing plate of the present invention can provide very good color proofing. Examples 8 to 27 In the same manner as in Example 1, except that 1.5 g of each resin [Q] in Table 11 below was used instead of 1.5 g of the resin [Q-5], Each color proofing master was manufactured.

[0372]

[Table 58] Table-11 {Example resin [Q] Example resin [Q]} ８ 8 Q-1 18 Q-23 ━━━━━━━━━━━━━ ９ 9 Q-3 19 Q-29 10 Q-6 20 Q-33 11 Q-9 21 Q-40 12 Q-11 22 Q-46 13 Q-13 23 Q-52 14 Q-16 24 Q-59 15 Q-18 25 Q-65 16 Q-20 26 Q-68 17 Q-22 27 Q-70 ━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━

The imaging performance and transferability of these color proofing masters were examined in a dark place in the same manner as in Example 1. The color copy image of the coated paper after the transfer was clear without background fog, and the image intensity was sufficiently high. Examples 28 to 50 In Example 1, instead of 1.5 g of the binder resin [Q-5], 0.3 g of the resin [P-104] and the crosslinking compound, each resin [Q] 1 in Table 12 below was used. Each electrophotographic color proofing master was produced in the same manner as in Example 1 except that 0.5 g, 0.3 g of the resin [P] and a predetermined amount of the crosslinking compound were used.

[0374]

[Table 59] Example 12 Resin [Q] Resin [ P] Compound for crosslinking ２８28 Q-2 P-202 Gluconic anhydride Product 0.15 g o-cresol 0.01 g 29 Q-4 P-301 {30 Q-7 P-214 ethylene glycol 0.03 g diglycidyl ether zinc stearate 0.001 g 31 Q-10 P-315} 32 Q-17 P-419 {} 33 Q-19 P-207 1,6-dihexane 0.20 g Diamine 34 Q-21 P-423 Gluconic acid 0.18 g Phenol 0.0002 g 35 Q-30 P-421 anhydrous phthalate Acid 0.2g o-chlorophenol 0.001g 36 Q-25P 210 3-aminopropyl trimethoxysilane 0.1 g 37 Q-24 P-321 〃 ３８ 38 Q-35 P-417 〃 ３９ 39 Q-41 P-212 Propylene glycol 0.8 g Tetrabutoxy titanate 0.001 g 40 Q- 45 P-323 〃 ４１ 41 Q-48 P-213 Trimethylolpropane 1.0 g Dibutoxy dilaurate 0.001 g Tin salt 42 Q-49 P-125 〃 ４３ 43 Q-50 P-215 Phthalic anhydride 0.3 g Acetylacetone Co 0.001 g Baltic salt 44 Q-55 P-329 〃 〃 45 Q-56 P-421 〃 ４６ 46 Q-58 P-322 Propylene glycol 0.05 g Diglycidyl ether o-chlorophenol 0.002 g 47 Q-60 P-222 ROOCNH (CH ₂ ) ₆ NHCOOR 0.2 g Tetrapropoxy titanate 0.0 01g 48 Q-64 P-122 〃 ４９ 49 Q-66 P-335 γ-glycidopropyl trimethoxysilane 0.1 g 50 Q-67 P-118 〃 ━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━

In the formula, R represents an m-methylphenyl group.
The imaging and transfer properties of the obtained color proofing master in a dark place
Investigation was performed in the same manner as in Example 1. The color copy image of the coated paper after transfer is clear without ground fog,
And the image intensity was sufficiently high. Examples 51 to 58 In Example 1, the resin [Q] 2 shown in Table 13 below was used.
g, a resin [R] 9 g, a resin [P] 0.3 g, and a color proofing master were produced in the same manner as in Example 1 except for using a crosslinking compound.

[0376]

[Table 60] Table 13 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example Resin Resin Resin Resin Bridge compound [Q] [R] [P] ─────────────────────────────────── 51 Q-8 R-4 P-429 Benzoyl peroxy 0.008 g Side 52 Q-12 R-5 P-116 1,4-butanedio 0.3 g Dibutyl dibutyrate 0.001 g Xitin 53 Q-28 R- 6 P-428 Ethylene glycol 2.0 g Dimethacrylate 2,2'-azobis 0.03 g (isovaleronitrile) 54 Q-34 R-6 P-325 〃 〃 55 Q-35 R-7 P-129 Divinyl adipate 2 0.2 g 2,2'-azobis 0.01 g (isovaleronitrile) 56 Q-38 R-7 P 336 〃 ５７ 57 Q-50 R-8 P-422 Block isocyanate 3 g Nato Aditol VXL 81 (manufactured by Hoechst) Butyl titanate 0.02 g Dimer 58 Q-56 R-8 P-126 〃 ━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

In the table, resins R-4 to R-8 are represented by the following formulas.

[0378]

Embedded image

When a color proof was produced using a color proof master having a transfer layer formed by the method of Example 1, the obtained color proof print color copy image was free of background smear. , Was clear. Examples 59-66 The transfer layer was coated with poly (vinyl acetate / crotonic acid) (95/5
Each of the color proofreading masters was manufactured in the same manner as in Example 1 except that the resin and the coating solvent shown in Table 14 below were used instead of (weight ratio).

[0380]

[Table 61] Table 14 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Examples Thermoplastic resin Coating solvent ５９ 59 Cellulose acetate butyrate: cellidor Bsp Ethyl acetate (Bayer AG) 60 Polyvinyl butyral resin: Esrec Ethanol (manufactured by Sekisui Chemical Co., Ltd.) 61 Cellulose propionate: ethyl ceridria acetate (manufactured by Daicel Chemical Industries, Ltd.) 62 Poly (vinyl acetate) methyl ethyl ketone 63 Poly (vinyl acetate / crotonic acid) 1% ammonia water (95/5) copolymer and containing Cellidor Bsp used at (8/2) weight ratio Ethanol solution 64 Methyl methacrylate / methyl acrylate copolymer (6/4) weight ratio Tetrahydrofuran 6 Styrene / butadiene copolymer Sorprene 1205 (manufactured by Asahi Kasei Corporation) Toluene 66 Poly (vinyl acetate) and poly (ethyl methacrylate) are used in a weight ratio of (6/4) Methyl ethyl ketone ━━━━━━━━━━━━━━━━━━━━━━━━━━━━

When the electrostatic properties, transferability and image reproducibility of each of the obtained color proofreading masters were examined in the same manner as in Example 1, all of them showed the same level of performance as in Example 1.

[Brief description of the drawings]

FIG. 1 shows a thermal transfer device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Rubber-coated metal roller 2 Built-in heater 3 Surface temperature detecting means 4 Temperature controller

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-204739 (JP, A) JP-A-4-179962 (JP, A) JP-A-4-67151 (JP, A) JP-A-4- 37857 (JP, A) JP-A-4-22961 (JP, A) JP-A-2-244146 (JP, A) JP-A-2-278276 (JP, A) JP-A 64-52135 (JP, A) JP-A-3-11347 (JP, A) JP-A-61-174557 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 5/00

Claims (9)

(57) [Claims] 1. A method comprising: a support; a photoconductive layer; and a transfer layer.
At least the electrophotographic process formed on the transfer layer
Also transfers the one-color toner image to the transfer-receiving material together with the transfer layer.
Electrophotographic colors to produce color proofs
A calibration master, wherein the photoconductive layer is formed of the following resin (P₁),
(P_Two), (P_Three) And (P_Four) Resin selected from the group consisting of
[P], the following resin (Q₁) And (Q_Two)
Resin [Q] and light and / or thermosetting groups
A tree containing at least one kind of structural unit containing at least one kind
Fat [R], and the resin [P] is at least
Exists in the vicinity of the surface in contact with the photoconductive layer, and the JIS Z of the surface
0237-1980 "Testing method for adhesive tape and sheet"
Adhesive strength to be tested is 150gram ・ force (g ・ f) or less
An electrophotographic color proofing master, characterized in that: (1) Resin (P₁): Contains fluorine atom and / or silicon atom
Containing 50% by weight or more of structural units
Contains (X) and at least one light and / or thermosetting group
Including the segment (Y) containing the structural unit
Block copolymer. (2) Resin (P_Two): Contains fluorine atom and / or silicon atom
Containing 50% by weight or more of structural units
Contains (X) and at least one light and / or thermosetting group
Comprising a segment (Y) containing a structural unit
At least three type block polymer chains and an organic group (Z)
Star-type copolymers that are bonded via a polymer. (3) Resin (P_Three): Contains fluorine atom and / or silicon atom
Containing 50% by weight or more of structural units
Contains (X) and at least one light and / or thermosetting group
And a segment (Y) containing a structural unit
Ft-type copolymer. (4) Resin (P_Four): Contains fluorine atom and / or silicon atom
Containing 50% by weight or more of structural units
Contains (X) and at least one light and / or thermosetting group
Comprising a segment (Y) containing a structural unit
Type or ABA type block copolymer, and
At least one of the following graft-type segments (X)
(X ') or at least the segment (Y)
One is the following graft type segment (Y '), or
Is a graph in which at least one of the segments (X) is
Segment (X ') and the segment (Y)
At least one of the following graft-type segments (Y ')
Is a copolymer. Graft type segment (X '): weight average molecular weight 1 × 1
0^Three~ 2 × 10^FourAnd a fluorine atom and / or silicon
Mac containing 50% by weight or more of constituent units containing atoms
Monomer part (M_A) As a copolymer component
Ment. Graft type segment (Y '): weight average molecular weight is 1 × 1
0^Three~ 2 × 10^FourAnd a fluorine atom and / or silicon
Consists of constituent units that do not contain constituent units containing atoms
Macromonomer part (M_B) As a copolymer component
segment. (5) Resin (Q₁): 1 × 10^Three~ 2 × 10^FourWeight average
Having a molecular weight of the following general formula (I):[Where b¹And b^TwoRepresents a hydrogen atom, a halogen atom,
Represents a cyano group or a hydrocarbon group;^ThreeRepresents a hydrocarbon group
And -PO_ThreeH_Two Group, -SO_Three
H group, -COOH group, -PO (OH) (R¹) (Where
R¹Is a hydrocarbon group or -OR^Two(R^TwoRepresents a hydrocarbon group
Group) and cyclic anhydride groups.
A polymer containing at least one kind of polar group-containing polymer component
Only at one end of the coalesced main chain is the following general formula (II):[Where V¹Is -COO-, -OCO-, -CH_TwoOC
O-, -CH_TwoCOO-, -O-, -SO_Two-, -CO
-, -CONHCOO-, -CONHCONH-, -C
ONHSO_Two-, -CON (T¹)-, -SO_TwoN (T
¹)-Or -C₆H_Four-(Where T¹Is hydrogen field
Represents a child or a hydrocarbon group), b^ThreeAnd b^FourAre hydrogen sources
, Halogen atom, cyano group, hydrocarbon group, -COOZ
¹Or -Z ^Two-COOZ¹(Z¹Is a hydrogen atom or hydrocarbon
Represents a radical, Z^TwoRepresents a hydrocarbon group). ]
Weight average molecular weight formed by bonding polymerizable double bond groups
1 × 10^FourThe following monofunctional macromonomer (M_C)And
At least a graft copolymer. (6) Resin (Q_Two): 1 × 10^Three~ 2 × 10^FourWeight average
Having a molecular weight of -PO_ThreeH_Two Group, -SO_ThreeH group, -CO
OH group, phenolic OH group, -PO (OH) (R¹)
(Where R ¹Has the same meaning as above.)
It contains at least one polar group selected from acid anhydride groups.
Block containing at least one polymer component having
And the following general formula (III):[Where V^TwoIs -COO-, -OCO-,-(CH_Two)_a
OCO-,-(CH_Two)_aCOO- (a is an integer of 1 to 3
), -O-, -SO_Two-, -CO-, -CON (T
¹)-, -SO_TwoN (T¹)-, -CONHCOO-,
-CONHCONH- or -C₆H_FourRepresents-(here
And T¹Has the same meaning as described above), R ^FourIs hydrocarbon
Represents a radical, b^FiveAnd b⁶Is b¹And b^TwoSimilar to
Meaningful. Where V^TwoIs -C₆H_FourWhen expressing-,
R^FourRepresents a hydrogen atom or a hydrocarbon group. ]
A B block containing at least one coalescing component.
AB block copolymer to be formed
Monofunctional polymer consisting of a polymerizable double bond attached to the chain end
Chromonomer (M_D) As at least one copolymer component
A graft-type copolymer. 2. The electrophotographic color proofing master according to claim 1, wherein the resin [P] is a resin (P ₁ ) and the resin [Q] is a resin (Q ₁ ). 3. The electrophotographic color proofing master according to claim 1, wherein the resin [P] is a resin (P ₂ ) and the resin [Q] is a resin (Q ₁ ). 4. The electrophotographic color proofing master according to claim 1, wherein the resin [P] is a resin (P ₃ ) and the resin [Q] is a resin (Q ₁ ). 5. The electrophotographic color proofing master according to claim 1, wherein the resin [P] is a resin (P ₄ ) and the resin [Q] is a resin (Q ₁ ). 6. The electrophotographic color proofing master according to claim 1, wherein the resin [P] is a resin (P ₁ ) and the resin [Q] is a resin (Q ₂ ). 7. The electrophotographic color proofing master according to claim 1, wherein the resin [P] is a resin (P ₂ ) and the resin [Q] is a resin (Q ₂ ). 8. The electrophotographic color proofing master according to claim 1, wherein the resin [P] is a resin (P ₃ ) and the resin [Q] is a resin (Q ₂ ). 9. The electrophotographic color proofing master according to claim 1, wherein the resin [P] is a resin (P ₄ ) and the resin [Q] is a resin (Q ₂ ).