JPH0683079A - Electrophotographic color correcting original plate - Google Patents

Abstract

PURPOSE:To obtain a high-definition and high-quality color final copy with the transfer layer and photoconductive layer easily released, exhibiting an excellent electrophotographic characteristic and consequently without any color slurring. CONSTITUTION:This electrophotographic color correcting original plate contains a substrate, a photoconductive layer and a transfer layer, and at least a monochromatic toner image formed on the transfer layer by the electrophotographic process is transferred to a material along with the transfer layer to produce a color final copy. The photoconductive layer contains a resin P including a structural unit having fluorine atom and/or silicon atom, a low-mol.wt. resin Q having a polar group and a resin R including a structural unit having a photosetting and/or thermosetting groups and contains the resin P close to the surface in contact with the transfer layer. The adhesive force of the surface is controlled to <=150g.f when tested according to the JIS Z2037-1980 regarding the adhesive tape and sheet testing method.

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 original plate, and more particularly to improvement of a photoconductive layer of the color proofing original plate.

[0002]

2. Description of the Related Art As a printing plate for multicolor printing, a PS plate is exclusively used in terms of quality, printing durability, dimensional stability, stain resistance and the like. The PS plate is a plate material in which a photosensitive layer containing a diazo resin or o-quinonediazide as a main component is provided on an aluminum support which has been subjected to a surface treatment for improving hydrophilicity. It is possible to prepare a printing plate by exposing the hydrophilic aluminum surface except the photosensitive layer in the non-image area, after developing the film by exposing the film to ultraviolet light. A printing plate having a multicolor image can be obtained by producing a printing plate for each color by this process, sequentially applying the printing plate to a printing machine, and printing on one printing paper sheet using the corresponding ink. In such a printing method, a series of edits such as character input, layout, and color designation, confirmation that the work as specified in each process of plate making and printing has been performed, and the orderer's order regarding tone reproduction etc. After confirming that there is no difference between the two and making corrections if necessary, the actual printing is performed. This step is called calibration. The former is called the inner school,
As mentioned above, the purpose is to check each process inside the printing company. On the other hand, the latter is called out-of-school and is a proofreading to get the printing permission from the orderer, and the same ink, printing paper, etc. are used as in this machine printing, and the printed result is almost the same as this machine printing. Here, performing proofreading with the printing paper used for printing with this machine is called real paper proofing. For color specification and tone reproduction of color photographs, it is necessary to confirm and correct each color, and in particular, proof printing as an out-school is actually repeated several times. Conventional proof printing uses a printing plate produced by using a color-separated and shaded film used for actual printing and a PS plate with relatively low cost and low printing durability called proof printing, For example, printing is performed by a proofing machine having a mechanism similar to a printing machine called a flatbed four-color proofing machine manufactured by Dainippon Screen. This is called press proof, but it has the drawbacks that it takes time to prepare the printing plate and it is difficult to maintain a certain quality because it requires skill in operation.

Some color proofing methods have been proposed which do not use a proofing machine having a mechanism close to that of a printing machine, and are therefore simple and free of unstable elements caused by printing. It is used as preferable from the point of view. This is called off-press proof, and a typical method and system is Vol. 24, No. 3, 3 of the Journal of the Printing Society of Japan.
See page 2 (1989). For example, the system is put into practical use under the product names of color art (Fuji Photo Film Co., Ltd.), chromin (DuPont), match print (3M) and the like. These systems use a color separation film, but do not use the proofing machine as described above. Color separation films are often manufactured using color scanners. This is because the data is read from the original, the color separation, shading, and tone reproduction control are performed, then output as digital data, the silver salt film is scanned and exposed by the laser light modulated based on the data, and developed. It is an apparatus for producing a positive or negative film for a multicolor printing plate by performing a fixing process, a fixing process and a drying process. In recent years, an electronic plate-making system called a total color scanner has been further developed and started to be put into practical use. This allows retouching or plate collection within the system, and an internal school is required to judge the quality of the finished product more quickly than before. In other words, the specification format as a result of processing in the system, the layout, the suitability of the color separation quality of some patterns, the degree of reproducibility of the tone, etc. were performed with the proofreading method so far,
Since it is necessary to wait for output to color separation film, press proof or off press proof finish,
The utilization efficiency of the system will be significantly reduced. Since the 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. These details are published in "Printing Information" magazine April 1991 page 2 and subsequent pages. 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.

Each of them has its own characteristics. In particular, in the wet electrophotographic system, a photoconductive photosensitive member is charged and laser-exposed, and then developed with a color toner in which a pigment is dispersed in an electrically insulating liquid. The toner image can be transferred after repeating four colors of M, Y and Bk, so it has high definition, high image quality and good color tone and tone reproducibility. Also, since any paper can be selected, this paper can be proofed. Has the advantage of being However, it is extremely difficult to completely transfer the toner image directly from the surface of the photoconductor to the actual paper, and even the technique disclosed in Japanese Patent Laid-Open No. 272469/1990, which can achieve this, requires some steps. Further, there is a proposal that a peelable transfer layer is provided on the surface of a photoconductive layer, and a toner image is formed on the surface of the photoconductive layer and transferred to the main paper together with the transfer layer, as disclosed in JP-A-61-174557 (Japanese Patent Publication No. 2-43185). It is made in Kaihei 1-112264, JP-A-1-281464, and JP-A-3-11347. Of these, the only one that has been put to practical use is JP-A-61-174557.
However, this is a technique in which exposure is performed from the transparent support (polyethylene terephthalate film) side of the electrophotographic light-sensitive material, and the conductive layer must also be transparent. It is disadvantageous. JP-A 1-112264, JP-A 1-281464
Describes a method for forming an image 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 the photoconductive layer.These methods transfer a toner image after development to plain paper together with the release layer. It is characterized by doing. However, it is difficult to uniformly form the structure of the photoconductive layer used in these methods in a practical area and to transfer the toner image without impairing it.

The same can be said for the method of using a recording medium having a peelable overcoat layer on the photoconductive layer of JP-A-3-11347. In addition to the problem of image deterioration occurring at the transfer stage as described above, there is a problem occurring at the stage of forming an image by an electrophotographic process. The cause of such a problem is, in particular, the deterioration of the electrostatic characteristics of the electrophotographic color proofing original plate. A system using a known electrophotographic color proofing plate composed of a known photoconductive layer was examined in detail by changing the environmental conditions during imaging (high temperature / high humidity or low temperature / low humidity). The photographic characteristics, especially the charge retention in the dark, the photosensitivity, and the like fluctuate, and it may become impossible to stably obtain a good image. Moreover, in the direct digital system, when scanning exposure using semiconductor laser light is performed on the electrophotographic color proofing original plate, the scanning exposure method using semiconductor laser light has a longer exposure time than the full-time simultaneous exposure method using visible light. Therefore, the electrophotographic color proofing master plate is required to have higher electrostatic properties, particularly higher dark charge retention properties and photosensitivity. However, in the above-mentioned conventional color proofing original plate, since electrophotographic characteristics are deteriorated due to changes in environmental conditions, when exposed by a scanning exposure method using a semiconductor laser beam, the background fog on the obtained color proof, thin line skipping,
Character blurring etc. occurs. That is, the result is that the color proof image is deteriorated.

[0006]

SUMMARY OF THE INVENTION The present invention provides an original plate for color proofing using an electrophotographic system, which has solved the above problems. An object of the present invention is to easily and stably obtain a high-definition and high-quality color proof without any color shift. Another object of the present invention is to provide an electrophotographic color proofing original plate which can be easily manufactured and is low in manufacturing cost. Still another object is to provide a method for producing a color proof which allows a toner image to be easily transferred by a transfer device having a simple structure and allows proof printing on actual printing paper regardless of transfer paper. Especially. Another object of the present invention is to provide a color proofing original plate capable of providing a color proof having a clear and high-quality image even when the environment for forming a copy image changes such as low temperature and low humidity or high temperature and high humidity. It is to be. Another object of the present invention is to provide a color proofing original plate which is not easily affected by the types of sensitizing dyes that can be used in combination and which has electrostatic properties sufficient for use in a scanning exposure method using a semiconductor laser beam. Is.

[0007]

Means for Solving the Problems The above-mentioned problems are
It includes a photoconductive layer and a transfer layer, and an electrophotographic professional is formed on the transfer layer.
The toner image of at least one color formed by the process
Color proof by transferring to the material to be transferred together with the image layer
An original plate for electrophotographic color proofing for producing
The photoconductive layer is a resin (P₁), (P₂), (P₃)as well as
(P_Four[P] selected from the group consisting of
(Q₁) And (Q₂) Resin selected from the group consisting of
[Q], and a constitutional unit having a light and / or thermosetting group
Position-containing resin [R] and the resin [P] is small
At least in the vicinity of the surface in contact with the transfer layer,
JIS Z0237-1980 "Adhesive Tape / Sea
Adhesive strength tested by the "test method" is 150 gram-fo
An electrophotographic color school characterized by being less than rce (g ・ f)
Achieved by the original version. (1) Resin (P₁): Having a fluorine atom and / or a silicon atom
50 units for the weight of the segment (X)
Light and / or thermosetting with segment (X) containing more than amount%
A cell containing a structural unit containing at least one chemical group.
And a linear block type copolymer containing a pigment (Y). (2) Resin (P₂): Having a fluorine atom and / or a silicon atom
50 units for the weight of the segment (X)
Light and / or thermosetting with segment (X) containing more than amount%
A cell containing a structural unit containing at least one chemical group.
And a linear block type polymer chain containing
Star consisting of at least three bonded through an organic group (Z)
Type copolymer. (3) Resin (P₃): Having a fluorine atom and / or a silicon atom
50 units for the weight of the segment (X)
Light and / or thermosetting with segment (X) containing more than amount%
A cell containing a structural unit containing at least one chemical group.
A graft-type copolymer containing a pigment (Y). (4) Resin (P_Four): Having a fluorine atom and / or a silicon atom
50 units for the weight of the segment (X)
Light and / or thermosetting with segment (X) containing more than amount%
A cell containing a structural unit containing at least one chemical group.
And AB type or ABA type block containing cement (Y)
A polymer and at least one of the segments (X)
Is one of the following graft type segments (X '),
At least one of the
Segment (Y '), or the number of segments (X) is small.
At least one is the following graft type segment (X ')
And at least one of the segments (Y) is
A copolymer which is a graft type segment (Y '). Graft type segment (X '): Weight average molecular weight is 1 x 1
0³~ 2 x 10^FourAnd a fluorine atom and / or silicon
A structural unit having an atom is referred to as a macromonomer part (M _A) Heavy
50% by weight or more, preferably 90% by weight or more based on the amount
Macromonomer part (M_A) Containing
To. Graft type segment (Y '): Weight average molecular weight is 1 x 1
0³~ 2 x 10^FourAnd a fluorine atom and / or silicon
Consisting of structural units that do not contain structural units that contain atoms
Macromonomer part (M_B) Containing segments. (5) Resin (Q₁): 1 x 10³~ 2 x 10^FourWeight average of
Having a molecular weight of formula (I): --CH (a₁) −C (a₂) (COOR₃) − (Where a is₁And a₂Are hydrogen atom, halogen atom,
Represents a cyano group or a hydrocarbon group, R₃Is a hydrocarbon group
Represents the structural unit and -PO₃H₂, -SO₃H, -COOH
 , -PO (OH) (R₁) (Where R₁Is a hydrocarbon group or -OR₂(R₂ 
Represents a hydrocarbon group)) and a cyclic acid anhydride group
Randomly constituting units having polar groups selected from the group
At least 3 polymer chains contained in the organic group (Z)
And a structural unit represented by the above formula I.
Content of resin (Q₁30% by weight or more based on the total weight of
The content of the structural unit having the polar group is the resin (Q₁)
Star type copolymerization of 1 to 20% by weight based on the total weight of
body. (6) Resin (Q₂): 1 x 10³~ 2 x 10^FourWeight average of
It has a molecular weight and contains a structural unit represented by the above formula (I).
Segment (M) and -PO₃H₂, -SO₃H, -COOH,-
PO (OH) (R₁) (Where R₁Is a hydrocarbon group or -OR₂(R₂ Is carbonized
Represents a hydrogen group), and a cyclic acid anhydride group.
Seg containing a structural unit having a polar group selected from
Mention (N) containing a linear block type polymer chain
Star consisting of at least three bonded through an organic group (Z)
Type copolymer. In the photoconductive layer of the present invention, the photoconductive compound is a resin [Q] and
Any resin dispersed with a binder resin such as resin [R]
And consist only of a layer in which the photoconductive compound is dispersed.
It is a monodispersed layer type and a photoconductive compound dispersed layer.
A so-called product including at least a charge generation layer and a charge transport layer
Either layer type (or function separation type) may be used. Heavy
What is important is the vicinity of the surface of the various photoconductive layers in contact with the transfer layer.
The resin [P] is unevenly distributed on the surface, and the surface has improved peeling characteristics.
It is to be. For example, from the charge generation layer and the charge transport layer
In the separate functional photoconductive layer,
The charge transport layer which is a layer containing a resin [P] and a resin [R].
However, the charge generation layer contains a resin [Q] and a photoconductive compound.
be able to. It also consists of a charge generation layer and a charge transport layer.
In the function-separated photoconductive layer, the layer adjacent to the transfer layer
A certain charge transport layer is made of resin [P], resin [R], resin
[Q] and a photoconductive compound may also be included. Preferred
In other words, the above resin [P] is the resin of the layer containing the resin.
1 to 30% by weight based on the total weight of. resin
The amount of [Q] is preferably 100 parts by weight of the photoconductive compound.
With respect to 1 to 100 parts by weight, more preferably 3 to 50 parts
Parts by weight. The amount of resin [R] is preferably such that
5-99.1 layers based on the total weight of resin in the layer
The amount is%. In the present invention, the binder resin is a photoconductive compound.
A resin that forms a matrix in which materials are dispersed.
Resin [P], Resin [Q], Resin [R] and
And other resins optionally present. Also preferred
Preferably, the photoconductive layer of the present invention contains a light and / or heat curing agent.
Have. As used herein, "light and / or heat curing agent"
Is a light and / or thermosetting compound, a light and / or thermosetting compound
Functional oligomer, light and / or thermosetting resin and cross-linking agent
means.

[0008]

In the original plate for color proofing of the present invention, when the photoconductive layer is a monodispersed layer type, it is adjacent to the photoconductive layer, and when the photoconductive layer is a laminated type, it is adjacent to the transfer layer of the photoconductive layer. When a small amount of resin [P] coexists in the layer to form a coating film, the resin [P] migrates to the surface portion of the film and is concentrated until the drying step is completed after the coating, and the peeling property is there. Express. On the other hand, the polymer segment (X) containing fluorine and / or silicon atom in the resin [P] has good compatibility with the transfer layer side, and the other polymer segment (Y) has 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 anchor effect is exhibited by the interaction between the polymer segment (Y) and the resin [R]. 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 with the resin [P] in the layer being oriented on the surface, so that the orientation state is sufficiently fixed. Result is obtained. This further prevents transfer of the resin [P] to the transfer layer when the transfer layer is coated, and the interface between the transfer layer and the photoconductive layer can be clearly maintained. Therefore, when the color proofing original plate of the present invention is used, the toner image formed by the electrophotographic process is satisfactorily transferred together with the transfer layer in proof printing, and there is no problem such as peeling failure of the transfer layer. In addition, the solvent for coating is selected depending on the type of the thermoplastic resin for the transfer layer, but depending on the solvent, when the transfer layer is formed, the solvent is solvated with the binder resin of the photoconductive layer, so In some cases, it affects the dispersed state of the conductive layer and adversely affects the electrophotographic characteristics (e.g., easily causes background fog and deteriorates image quality). Such a problem is solved by imparting solvent resistance by crosslinking the photoconductive layer of the present invention.

In the photoconductive layer of the present invention, the layer containing the photoconductive compound is a resin [Q] as a binder resin.
Since it contains, the photoconductive compound is made into fine particles and uniformly dispersed. Furthermore, in the case of sensitizing with a spectral sensitizing dye, even if the kind of the spectral sensitizing dye used in the photoconductive layer of the present invention is changed, these dyes sufficiently interact with the photoconductive compound. You can In particular, the interaction between the dye used for the spectral sensitization for semiconductor laser light and the photoconductive compound becomes insufficient in the known binder resin system, but it may be sufficient in the system of the present invention. This is
The details are unknown, but when the photoconductive compound and the spectral sensitizing dye are dispersed in the coexistence of the resin [Q], the resin [Q]
Adsorb on the surface of the photoconductive compound particles without inhibiting the adsorption interaction between the dye and the photoconductive compound, and the resin [Q] makes the coating of the surface of the photoconductive compound particles with the dye suitable. Probably due to holding. It is considered that, as a result, good and stable electrophotographic characteristics can be maintained even when environmental conditions such as low temperature / low humidity and high temperature / high humidity change remarkably. On the other hand, when the photoconductive layer is of the monodispersed layer type as described above, the system is such that 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] can sufficiently interact with the photoconductive compound, and can retain the above-mentioned excellent electrostatic characteristics without being hindered by the resin [R]. . At the same time, the surface-unevenly distributed resin [P] is concentrated on the surface portion, and surface releasability can be sufficiently exhibited.

As described above, the original plate for color proofing of the present invention is characterized in that the surface of the photoconductive layer which is in contact with the transfer layer has a good releasability. JIS
Z0237-1980 "Adhesive tape / sheet test method"
It is judged by the adhesive strength tested by. That is, in the color proofing original plate of the present invention, the adhesive force of the surface of the photoconductive layer in contact with the transfer layer according to the above test method is 150 gram · force (g · f) or less, preferably 100 g · f or less, and more preferably 5 or less.
It must be 0 gf or less. For the adhesive strength, an electrophotographic color proofing original plate was used as the "test plate", an adhesive tape having a width of 6 mm was used as the "adhesive tape", and the adhesive tape was peeled off at a peeling speed of 120 mm / min. It is expressed in proportion to an adhesive tape having a width of 10 mm. The adhesive force on the surface of the photoconductive layer after forming the transfer layer is equivalent to the adhesive force on the surface of the photoconductive layer before forming the transfer layer.

As described above, the original plate for color proofing of the present invention is
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, and as the conductive support, a conventionally used one, for example, a substrate such as metal, paper, or a plastic sheet is impregnated with a low-resistance substance so as 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, the above-mentioned support Water-resistant adhesive layer provided on the surface of the body, at least one precoat layer provided on the surface layer of the support, if necessary, laminated with electroconductive plastic such as Al 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 (published in 1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry," Polymer Publishing (1975), MF
Hoover, J. Macromol. Sci. Chem. A-4 (6), 13
Examples include those described on pages 27 to 1417 (published in 1970). [Photoconductive layer] (Resin [P]) As described above, the resin [P] is a resin (P ₁ )
To (P ₄ ), each of which is a copolymer containing a segment (X) and a segment (Y). Preferably, the segment (X) of the resin [P] has a structural unit containing a fluorine atom and / or a silicon atom of 80% by weight or more based on the total weight of the segment (X),
In particular, 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), which is a structural unit having a light and / or thermosetting group.
%, More preferably 5 to 40% by weight. The existence ratio of the segment (X) and the segment (Y) is 5 to 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. , Two or more when only silicon atoms are contained, and one or more when both fluorine atoms and silicon atoms are contained. (Resin (P ₁ )) The resin (P ₁ ) is a segment (X) containing a structural unit containing a fluorine atom and / or a silicon atom in an amount of 50% by weight or more based on the weight of the segment (X), and / or light and / or It is a linear block-type copolymer containing a segment (Y) containing a structural unit containing at least one thermosetting group. The resin (P ₁ ) may be any linear block type copolymer, for example, AB type (that is,
(X)-(Y)) block copolymer or its multiblock product, or ABA type (that is, (X)-(Y)-
It may be a (X), (Y)-(X)-(Y)) block copolymer. The weight average molecular weight of the resin (P ₁ ) is 5 × 10 ^3.
˜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 ) includes a segment (X) containing a structural unit containing a fluorine atom and / or a silicon atom in an amount of 50% by weight or more based on the weight of the segment (X), and light and / or Alternatively, a star-type co-polymer having at least three AB-type block polymer chains containing a segment (Y) containing a constitutional unit containing at least one thermosetting group and being bonded via an organic group (Z). It is united. In the AB type block polymer chain of the resin (P ₂ ), the order of arrangement of the segment (X) and the segment (Y) in the polymer chain may be any order. That is, the polymer is schematically shown as follows.

[0013]

[Chemical 1]

(Here, Z represents an organic group, (X) represents a segment (X), and (Y) 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 ×
It is 10 ⁶ , preferably 1 × 10 ^{4 to} 5 × 10 ⁵ . 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 its molecular weight is 1000 or less. The following trivalent or higher valent hydrocarbon groups may be mentioned as examples.

[0015]

[Chemical 2]

[Wherein r ^{1 to} r ⁶ are single bonds,
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
Represents a single bond or a divalent or higher valent hydrocarbon group. When the organic group (Z) is a hydrocarbon group, it may be composed of a single hydrocarbon group, or may be composed of a combination of a plurality of hydrocarbon groups. In the latter case, -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), - NHCO
O-, -NHCONH-, hetero atom-containing heterocycle such as oxygen atom, sulfur atom, nitrogen atom (for example, thiophene ring, pyridine ring, pyran ring, imidazole ring, benzimidazole ring, furan ring, piperidine ring, pyrazine ring,
(A pyrrole ring, piperazine ring, etc.) and the like. Other examples of the organic group (Z) include those composed of a group selected from the following formulas and the above-mentioned linking unit. However, the organic group (Z) in the present invention is not limited to these.

[0017]

[Chemical 3]

(Resin (P ₃ )) The resin (P ₃ ) is a segment (X) containing 50% by weight or more of a structural unit containing a fluorine atom and / or a silicon atom with respect to the weight of the segment (X). It is a graft-type copolymer containing a segment (Y) containing a structural unit containing at least one type of light and / or thermosetting group. In the resin (P ₃ ), the segment (X) and the segment (Y) may be arranged in any order in the polymer chain. That is, the polymer is schematically shown as follows.

[0019]

[Chemical 4]

The weight average molecular weight of the resin (P ₃ ) is 5 × 10 5.
^{It is 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 ₃ ) is preferably 1 × 10 ³ or more.

(Resin (P ₄ )) The resin (P ₄ ) is a segment (X) containing 50% by weight or more of a structural unit containing a fluorine atom and / or a silicon atom with respect to the weight of the segment (X). It is an AB type or ABA type block copolymer composed of a segment (Y) containing a structural unit containing a light and / or thermosetting group, and at least one of the segments (X) is the following graft type Segment (X '), at least one of the segments (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 the following graft type segment (Y ′). Graft type segment (X ′): Weight average molecular weight is 1 × 1
_A macromonomer having a content of 0 ^{3 to} 2 × 10 ⁴ and a structural unit containing a fluorine atom and / or a silicon atom in an amount of 50% by weight or more, preferably 90% by weight or more, based on the weight of the macromonomer part (MA). _A segment containing a part (MA). Graft type segment (Y '): Weight average molecular weight is 1 x 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). In the resin (P ₄ ), the segment (X) and the segment (Y) may be arranged in any order. Examples of the copolymer include those schematically shown below.

[0022]

[Chemical 5]

[0023] Segment (X ') The proportion of the macromonomer unit in the (M _A), the segment (X')
1 to 50% by weight, preferably 3 to 3 relative to the total weight of
It is 0% by weight. Segment (Y ') The proportion of the macromonomer unit in the (M _B), the segment (Y' relative to the total weight of), 1 to 50% by weight, preferably 3 to 30 wt%. Preferably, the macromonomer unit (M _B) 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 It is contained in an amount of 3 to 20% by weight.

The weight average molecular weight of the resin (P ₄ ) is 5 × 10 5.
³ to 1 × 10 ⁶ , preferably 1 × 10 ^{4 to} 5 × 10 ^5.
Is. The weight average molecular weight of the segment (X) in the resin (P ₃ ) 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 a substituent having a silicon atom. The substituent may be incorporated in the polymer main chain of the resin [P] or may be bonded to the polymer side chain. Monovalent or divalent substituent having a fluorine atom: —C _h F
_{2h +} 1 (h is an integer of _{1~18), - (CF 2)} j CF 2 H
(J is an integer of _{1~17), - CFH 2, -CF} 2 -,
-CFH-,

[0025]

[Chemical 6]

Monovalent or divalent substitution having a silicon atom
Group: -Si (R₁) (R₂) (R₃), −Si (R_Four) (R_Five)-. In the above formula, R
₁, R₂, R₃, R_Four, R_FiveAre the same or different
Good, hydrocarbon having 1 to 22 carbon atoms which may be substituted
Elementary groups, the above-mentioned fluorine atom-containing monovalent organic residues, -O
R'group (R 'may be substituted having 1 to 22 carbon atoms.
Represents a hydrocarbon group), or -OSi (R₁')
(R₂') (R₃') (Motochu, R₁'~ R ₃'Is R₁~ R_FiveAbout
Represents the groups listed above). R₁~ R_Five, R'and R
₁'~ R₃Examples of'are shown below: Substituted with 1 to 22 carbon atoms
Optionally substituted alkyl group (eg, methyl group, ethyl group,
Propyl group, butyl group, hexyl group, octyl group, decyl group
Group, dodecyl group, hexadecyl group, 2-chloroethyl
Group, 2-bromoethyl group, 2,2,2-trifluoroe
Cyl group, 2-cyanoethyl group, 3,3,3-trifluor
Ropropyl group, 2-methoxyethyl group, 3-bromopro group
Pill group, 2-methoxycarbonylethyl group, 2,2
2,2 ', 2', 2'-hexafluoroisopropyl group
Etc.), optionally substituted alkeny having 4 to 22 carbon atoms
Group (eg, 2-methyl-1-propenyl group, 2-butene group)
Tenyl group, 2-pentenyl group, 3-methyl-2-pente group
Nyl group, 1-pentenyl group, 1-hexenyl group, 2-hexyl group
Xenyl group, 4-methyl-2-hexenyl group, etc.), carbon
An optionally substituted aralkyl group of the formulas 7 to 12 (eg,
For example, benzyl group, phenethyl group, 3-phenylpropyl
Group, naphthylmethyl group, 2-naphthylethyl group, chloro
Benzyl group, bromobenzyl group, methylbenzyl group,
Cylbenzyl group, methoxybenzyl group, dimethylbenzyl
Group, dimethoxybenzyl group, etc.), substitution of 5 to 8 carbon atoms
Optionally cycloaliphatic radicals (eg cyclohexyl
Group, 2-cyclohexyl group, 2-cyclopentylethyl
Group) or an optionally substituted aroma having 6 to 12 carbon atoms
Group groups (eg phenyl group, naphthyl group, tolyl group, chi
Silyl group, propylphenyl group, butylphenyl group, o
Cutylphenyl group, dodecylphenyl group, methoxyphen
Nyl group, ethoxyphenyl group, butoxyphenyl group,
Syloxyphenyl group, chlorophenyl group, dichlorophenyl
Phenyl group, bromophenyl group, cyanophenyl group, acetone group
Cylphenyl group, methoxycarbonylphenyl group, eth
Xycarbonylphenyl group, butoxycarbonylphenyl
Group, acetamidophenyl group, propioamidophenyl
Group, dodecylylamidophenyl group, etc.).

Further, the substituent having a fluorine atom and the substituent having a silicon atom may be constituted in combination, and in that case, they may be directly bonded or further via another linking group. May be combined with each other. The linking group is, for example, a divalent group, and is —O—, —S—, —NR ₁ —, —SO.
_{-, - SO 2 -, -} COO -, - OCO -, - CONH
CO -, - NHCONH -, - CONR 1 -, - SO 2
It may be one selected from NR ₁ − and the like, and may be a divalent aliphatic group, a divalent aromatic group, or an organic group composed of a combination of these divalent groups. Here, R ₁ has the above-mentioned meaning. Examples of the divalent aliphatic group include the following.

[0028]

[Chemical 7]

E ₁ and e ₂ may be the same or different from each other, and each is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.) or an alkyl group having 1 to 12 carbon atoms (eg, methyl group, 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 ₂₀ - represents, R ₂₀ 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 hetero atom selected from an oxygen atom, a sulfur atom, and a nitrogen atom as a hetero atom forming the hetero ring). 1 type is contained). These aromatic groups may have a substituent, for example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, 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.) can be given as examples of the substituent.

Examples of the heterocyclic group include residues such as furan ring, thiophene ring, pyridine ring, pyrazine ring, piperazine ring, tetrahydrofuran ring, pyrrole ring, tetrahydropyran ring and 1,3-oxazoline ring. Next, specific examples of the constitutional unit having a substituent having a fluorine atom and / or a silicon atom as described above, that is, the constitutional 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 denotes the following represents a substituent. _{1) -C n F 2n + 1} 2) -CH 2 C n F 2n + 1 3) -CH 2 CH 2 C n F 2n + 1 4) -CH 2 (CF 2) m CFHCF 3 5) -CH 2 _{CH 2 (CF 2) m CFHCF} 3 6) -CH 2 CH 2 (CF 2) m CFHCF 2 H 7) -CH 2 (CFH) m CF 2 H 8) -CH (CF 3) 2

[0031]

[Chemical 8]

In the above formula and the following formula, n is 1 to 18
Represents an integer of 1, m represents an integer of 1 to 18, and l represents 1 to 5
Represents an integer of 1, p represents an integer of 1 to 12, and q represents 1 to 2.
0 represents an integer of 0, r represents an integer of 3 to 6, b represents a hydrogen atom or a methyl group, Rf ′ represents 1) to 8) above, and R ₁ ′, R ₂ ′ and R ₃ ′ represent represents an alkyl group having 1 to 12 carbon atoms, and R ₄ 'represents -Si (CH _{3) 3.}

[0033]

[Chemical 9]

[0034]

[Chemical 10]

[0035]

[Chemical 11]

[0036]

[Chemical 12]

[0037]

[Chemical 13]

[0038]

[Chemical 14]

[0039]

[Chemical 15]

[0040]

[Chemical 16]

[0041]

[Chemical 17]

[0042]

[Chemical 18]

[0043] (a-34) - (N (COR f) CH 2 CH 2) - Next, the macromonomer unit for (M _A) is described. Macromonomer unit (M _A) has a weight average molecular weight of 1 × 10
^{3 ~2} × 10 ^4, preferably those in the range of ^{3 × 10 3 ~1 × 10 4} . The weight average molecular weight is less than 1 × 10 ^3, the length of the graft portion is too short faded peelability enhancing effect, when it exceeds 2 × 10 ^4, corresponding to the monofunctional macromonomer unit (M _A) causes decreased copolymerization reactivity with a monomer corresponding with the structural unit other than the monomer and the macromonomer unit (M _a), because the desired graft polymer can not be obtained. The macromonomer unit (M _A)
The constituent unit having a fluorine atom and / or a silicon atom therein may be the one exemplified as the constituent unit of the segment (X). The macromonomer unit (M _A) are, for example,
It may correspond to a monofunctional macromonomer having a polymerizable double bond-containing group represented by the following general formula (II) at one end of the polymer main chain composed of the constituent units and the like. _{CH (a 1) = C (} a 2) -V 1 - (II) wherein (II), a ₁ and a ₂ each represents a hydrogen atom, a halogen atom, a trifluoromethyl group, a cyano group or a hydrocarbon group Represent V ₁ is -CO-O-, -O-CO-,-(CH
_{2) m 'O-CO -} , - (CH 2) m' CO-O- (m ' represents an integer of 1~3), - O -, - SO 2 -, - CO
^{-, - CON (T 1)} -, - SO 2 N (T 1) -, - C
ONHCO-O -, - CONHCONH- or -C ₆ H
₄ - represents a (wherein, T ¹ represents a hydrogen atom or a hydrocarbon group).

Examples of the hydrocarbon group as T ^{1 are} as follows: an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group). 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, etc.), C4-18 Optionally substituted alkenyl 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 (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.), alicyclic group having 5 to 8 carbon atoms which may be substituted. A group (for example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, etc.) or a carbon number of 6 to
12 optionally substituted aromatic groups (eg, 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, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group Group, dodecylylamidophenyl group, etc.).

[0045] V ₁ is -C ₆ H ₄ - may represent a benzene ring may have a substituent. As the substituent, 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.), alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) and the like. Preferably, a ₁ and a ₂
May be the same or different from each other, and are a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a trifluoromethyl group, a cyano group, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group). , Propyl group, butyl group, etc.), —COOZ ³ or —COOZ via a hydrocarbon group
³ (Z ³ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms,
It represents an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, and specifically,
Which may be the ones described for T ¹ above). Examples of the hydrocarbon group in —COOZ ³ via the above hydrocarbon group include a methylene group, an ethylene group, a propylene group and the like. More preferably, in the general formula (II),
V ₁ is -COO-, -OCO-, -CH ₂ OCO-,-.
_{CH 2 COO -, - O -} , - CONH- , or -C ₆ H ₄
- represents, a ₁ and a _2, which may be the same or different, each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.) . Even more preferably, a ₁ and a
_{In 2} , one of them represents a hydrogen atom.

Includes a polymerizable double bond represented by the general formula (II).
The group can be directly bonded or via an arbitrary linking group.
May be combined with each other. The linking group is, for example, a divalent group.
, -O-, -S-, -N (d₁)-, -SO-, -S
O₂-, -COO-, -OCO-, -CONHCO-,
-NHCONH-, -CON (d₂) -SO
₂(D₃), -Si (d_Four) (D_Five)-, Divalent aliphatic
Group or divalent aromatic group, or a combination of these divalent groups
It may be a group formed by combining. Where d₁
~ D _FiveIs T in the formula (II)₁About
Possible. Examples of the divalent aliphatic group include -C (k₁)
(K₂)-, -C (k₁) = C (k₂)-, -C≡C
-, -C₆H_Ten-,

[0047]

[Chemical 19]

And the like. In the formula, k ₁ and k ₂ may be the same or different from each other, and each is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.).
Alternatively, it represents an alkyl group having 1 to 12 carbon atoms (eg, methyl group, ethyl group, propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.). Examples of the divalent aromatic group include a phenylene group, a naphthylene group, and a 5- or 6-membered heterocyclic group (as a hetero atom forming the hetero ring, at least a hetero atom selected from an oxygen atom, a sulfur atom, and a nitrogen atom is used). 1 type is contained). These aromatic groups may have a substituent, for example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, 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.) can be given as examples of the substituent. Examples of the heterocyclic group include 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 formulas:

[0049]

[Chemical 20]

(In the formula, Q is --O--, --S-- or --NR ₂₀
Represents-, R ₂₀ is an alkyl group having 1 to 4 carbon atoms, -CH ₂
And a group represented by Cl or -CH ₂ Br). Specific examples of the portion composed of the polymerizable double bond-containing group represented by the general formula II of the macromonomer and a linking group linked to the group are as follows. In the following formulas, P ₁ is -H, -CH _3, -CH ₂ COO
CH _3, shows -Cl, -Br, or -CN, P ₂ is -
H or indicates -CH _3, X represents a -Cl or -Br,
n shows the integer of 2-12 and m shows the integer of 1-4.

[0051]

[Chemical 21]

[0052]

[Chemical formula 22]

[0053]

[Chemical formula 23]

[0054]

[Chemical formula 24]

[0055]

[Chemical 25]

(Segment (Y)) Next, the segment (Y) will be described in detail. First, the structural unit containing a light and / or thermosetting group contained in the segment (Y) will be described. The “light and / or thermosetting group” refers to a functional group that cures the 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 Society of Japan, 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.
Wiley Inter Science Pub. 1982) and other functional groups used in conventionally known photosensitive resins and the like as photocurable resins are described. Examples of the thermosetting functional group include Takeshi Endo, "Precision of thermosetting polymer" (CMC Co., Ltd., published in 1986), Yuji Harasaki (Latest binder technology handbook), Chapter II-I (General). Technology Center, 1985), Takayuki Otsu "Synthesis of Acrylic Resin
Design and new application development "(Chubu Business Development Center Publishing Department, 1
1985), Eizo Omori "Functional Acrylic Resin" (Techno System, 1985), and other functional groups described in reviews. For example -COOH group, -PO ₃ H ₂
Group, -SO ₂ H group, -OH group, -SH group, -NH ₂ group,
-NHR ₁₀₃ group [R ₁₀₃ represents a hydrocarbon group, for example, an optionally substituted alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, 2 -Chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, etc.], cyclic acid anhydride group, -CONHCH ₂ OR _{10 4} (R ₁₀₄ is a hydrogen atom or an alkyl group (for example, those listed as R ₁₀₃ )). Group), -N = C = O, a group represented by the following formula:

[0057]

[Chemical formula 26]

(In the formula, Z'represents an atomic group necessary for forming a heterocycle with a nitrogen atom, and the functional group is -N.
= C = O group protecting group), a silane coupling group,
Titanate coupling group, -Cd ₉ = CHd ₁₀ group {d
₉ and d ₁₀ each represent a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.) or an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, etc.)}, a polymerizable double bond-containing group Etc. can be mentioned. In addition, specific examples of the polymerizable double bond-containing group include CH ₂ ═CH— and CH ₂ ═C.
_{H-CH 2 -, CH 2} = CH-CO-O-, CH 2 = C
_{(CH 3) -CO-O-,} CH 3 -CH = CH-CO-
_{O-, CH 2 = CH-CONH-} , CH 2 = C (C
_{H 3) -CONH-, CH 3 CH} = CH-CONH-,
_{CH 2 = CH-O-CO-} , CH 2 = C (CH 3) -O
_{-CO-, CH 2 = CH-CH} 2 -O-CO-, CH 2
_{= CH-NHCO-, CH 2 =} CH-CH 2 -NHCO
_{-, CH 2 = CH-SO} 2 -, CH 2 = CH-CO-,
_{CH 2 = CH-O-, CH} 2 = CH-S-,

[0059]

[Chemical 27]

And the like. Next, the macromonomer part (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 . If the weight average molecular weight is 1 × 10 ³ or less, the anchor effect is weakened. On the other hand, when it is 2 × 10 ⁴ or more, the copolymerization reactivity between the monomer corresponding to the macromonomer part (M _B ) and the monomer corresponding to the other structural unit constituting the segment (Y) is lowered. The constitutional unit constituting the macromonomer part (M _B ) may be any as long as it does not contain a fluorine atom and / or a silicon atom. More preferably, the macromonomer unit (M _B) is a structural unit containing a photo and / or thermosetting group, containing 1 to 50% by weight relative to the total weight of the macromonomer unit (M _B). Specific examples of these photo- and / or thermo-curable functional groups include those excluding the polymerizable double bond-containing group among the groups listed as the photo- and / or thermo-curable functional groups contained in the segment (Y). Can be mentioned.

(Other Structural Units) The resin [P] of the present invention also contains other structural units, that is, structural units containing fluorine and / or silicon atoms, and photo- and / or thermosetting groups. You may contain a structural unit. Any other constituent unit may be used as long as the corresponding monomer corresponds to a monomer copolymerizable with the monomer corresponding to the constituent unit of each segment. Examples thereof include addition polymerization components, polyester components, polyether components, polyimine components and the like. Specific examples of the addition polymerization component include structural units selected from the repeating units represented by the following general formula (III). _{-CH (b 1) -C (V} 2 -R 11) (b 2) - (III)

In the formula (III), V ₂ is V ₁ in the formula (II).
And b ₁ and b ₂ respectively represent the same contents as a ₁ and a ₂ in the formula (II), R ₁₁ represents a hydrocarbon group,
Preferably a hydrocarbon group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group). Group, 2-chloroethyl group, 2-bromoethyl group, 2-
Cyanoethyl group, 2-methoxycarbonylethyl group, 2
-Methoxyethyl group, 3-bromopropyl group, 2-morpholinoethyl group, 2-furfurylethyl group, 2-thienylethyl group, 6-methoxyethyl-3-oxyethyl group, 2-ethoxyethyl group, 2- (N , N-dimethylamino) ethyl group, 2-methylthioethyl group, carbon number 4 to
18 optionally substituted alkenyl groups (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, 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, methyl Benzyl group, ethylbenzyl group, methoxybenzyl group, methyl-chlorobenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), having 5 to 5 carbon atoms
8 optionally substituted alicyclic groups (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.), and optionally substituted 6 to 12 carbon atoms.
Aromatic groups such as 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, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group Etc.) and the like.

The content of the constitutional unit represented by the formula (III) in the segment (X) is usually 50% by weight or less, preferably 20% by weight or less, and more preferably the weight of the segment (X). Is not contained at all. The content of the structural unit in the macromonomer unit (M _A) is
50 wt% or less based on the weight of the macromonomer (M _A), preferably 20 wt% or less, more preferably not contained at all. 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). Further, the content of the structural unit is the macromonomer part (M
_{In B} ), 40 to 100% by weight, preferably 5
It is 0 to 95% by weight. Furthermore, in the segment (X) or (Y), together with the structural unit represented by the formula (III),
A monomer copolymerizable with the monomer corresponding to the constitutional unit of the formula (III), for example, acrylonitrile, methacrylonitrile, heterocyclic vinyls (for example, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinyl There may be constitutional units corresponding to pyrazole, vinyldioxane, vinyloxazine, etc.). These other structural units are used within a range not exceeding 20 parts by weight based on 100 parts by weight of all the structural units of the resin [P]. Further, in the segment in the resin (P) (Y), with each of the structural units of the _{above, -PO 3 H 2, -SO 3} H, -COOH, -PO
(OH) R ¹⁰¹ [R ¹⁰¹ is a hydrocarbon group or -OR
¹⁰² (R ¹⁰² represents a hydrocarbon group)] and a structural unit containing at least one polar group selected from a cyclic acid anhydride group as a substituent relative to the total weight of the segment (Y). It can also be used in amounts of less than 10% by weight.
Preferably, R ¹⁰¹ and R ¹⁰² are each an optionally substituted hydrocarbon group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, 2-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 Group) and the like.

The cyclic acid anhydride group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride contained include aliphatic dicarboxylic acid anhydrides and aromatic dicarboxylic acid anhydrides. Is mentioned. Examples of fatty acid dicarboxylic acid anhydrides include succinic acid anhydride, glutaconic acid anhydride, maleic acid anhydride, cyclopentane-1,2-dicarboxylic acid anhydride, cyclohexane-1,2-dicarboxylic acid anhydride, cyclohexene- 1,2-dicarboxylic acid anhydride, 2,3-bicyclo [2,2,2] octadicarboxylic acid anhydride, and the like, and these compounds include, for example, halogen atoms such as chlorine atom and bromine atom, methyl group, It may be substituted with an alkyl group such as an ethyl group, a butyl group or a hexyl group.

Examples of aromatic dicarboxylic acid anhydrides include phthalic acid anhydride, naphthalene-dicarboxylic acid anhydride, pyridine-dicarboxylic acid anhydride, thiophene-dicarboxylic acid anhydride, and the like. , For example, a chlorine atom, a halogen atom such as a bromine atom, a methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (as the alkoxy group, for example, a methoxy group, Ethoxy group, etc.) and the like. The structural unit containing a specific polar group as described above may be, for example, a polar group-containing vinyl-based compound copolymerizable with a monomer corresponding to the structural unit represented by the formula (I). Any of them may be used, and for example, they are described in “Polymer Data Handbook (Basic Edition)” edited by Japan Society of Polymer Science, Baifukan (published in 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 compound, α-fluoro compound, α-tributylsilyl compound, α-cyano compound, β-chloro compound, β-bromo compound, α-
Chloro-β-methoxy, α, β-dichloro, 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 Containing the polar group in a substituent of a carboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, vinyl or allyl half-ester derivative of dicarboxylic acids, and the ester derivative or amide derivative of the above-mentioned carboxylic acid or sulfonic acid Structural units corresponding to compounds and the like can be mentioned.

(Synthesis of Resin [P]) Resin [P] of the Present Invention
And macromonomer unit _{((M A), (M} B)) macromonomer corresponding to can be synthesized in accordance with a conventionally known polymerization methods. 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) etc., and is described in reviews. For example, TE Hogeu-Esch, J. Smid describes an ionic polymerization reaction using an organometallic compound (for example, alkyllithium, lithium diisopropylamide, alkali metal alcoholate, alkylmagnesium halide, alkylaluminum halide, etc.) as a polymerization initiator. , "Recent Advances
in Anionic Polymerization "(1987, Elsevier Ne
w York), Yoshio Okamoto, High Polymer, 38 , 912 (198)
9), Mitsuo Sawamoto, Polymer, 38 , 1018 (1989).
, Tadashi Narita, Polymer, 37 , 252 (1988), BC
Anderson, et al, Macromolecules 14 , 1601
(1981), S. Aoshima, T. Higashimura, Macromol
ecules 22 , 1009 (1989) and the like. Regarding the ionic polymerization reaction using hydrogen iodide / iodine system, etc., see T. Higashimura et al, Makrom.
ol. Chem., Macromol. Symp ., 13/14, 457 (1
988), Toshinobu Higashimura, Mitsuo Sawamoto, Transactions on Polymers, 46 ,
189 (1989) and the like. For the group transfer polymerization reaction, see DY Sogah et al, Macro.
molecules 20 , 1473 (1987), OW Webste
r, DY Sogah, Polymer, 36 , 808 (1987),
MT Reetg, et al, Angew. Chem. Int. Ed. Eugl. 2
5 , 9108 (1986), JP-A-63-97609.

Regarding the living polymerization reaction using a metalloporphyrin complex, T. Yasuda, T. Aida, S. Inou
e, Macromolecules, 17 , 2217 (1984), M.
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) and the like. Furthermore, regarding ring-opening polymerization reaction of cyclic compounds, 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)
Etc. Furthermore, regarding the living photopolymerization reaction using a dithiocarbamate compound, a xanthate compound or the like as an initiator, Takayuki Otsu, Polymer, 37 ,
248 (1988), Shunichi Hinomori, Ryuichi Otsu, Polym. Re
p. Jap. 37 , 3508 (1988), JP-A-64-
111, JP-A 64-26619, M. Niwa, Macro
molecules, 189 , 2187 (1988) and the like. On the other hand, a method of synthesizing a block copolymer by a radical polymerization reaction using a polymer containing an azo group or a peroxide group as an initiator is described in Akira Ueda et al.
33 , 931 (1976), Akira Ueda, Osaka City Research Institute Report 84 , (1989), O. Nuyken et al, Macromo.
l. Chem., Rapid. Commun. 9 , 671 (1988), Yasuo Moriya et al., Reinforced plastics, 29 , 907 (19)
), Ryohei Oda, Science and Industry 61 , 43 (1987) and the like. Regarding the synthesis of the graft type block copolymer, in addition to the above-mentioned books and reviews, Fumio Ide, “Graft polymerization and its applications” (1977, Polymer Society of Japan), Polymer Society of Japan, “Polymer”・ Alloy ”(1
981, Tokyo Kagaku Dojin) and the like. For example, a method of grafting a polymer chain with a polymerization initiator, chemical actinic rays (radiation, electron beam, etc.), mechanochemical reaction in mechanical application, etc., using polymer chains and functional groups of polymer chains Then, a chemical reaction (so-called interpolymer reaction) and grafting method or a macromonomer is used to carry out a polymerization reaction,
A method of grafting is known.

The method of grafting using a polymer chain is as follows:
Specifically, T. Shiota et al, J. Appl. Polym. Sci.
13 , 2447 (1969), WH Buck, Rubber Che
mistry and Technology, 50 , 109 (1976), Takeshi Endo, Tsutomu Yokozawa, Journal of Japan Adhesion Society, 24 , 323 (198).
8), Takeshi Endo, ibid, 25 , 409 (1989) and the like. Further, the method of polymerizing and grafting using a macromonomer is specifically described in P. Dreyfuss.
& RP Quirk, Encycl. Polym. Sci. Eng., 7 , 551
(1987), PF Rempp, E. Franta, Adv. Polym.
Sci., 58 , 1 (1984), V. Percec, Appl. Poly.
Sci., 285 , 95 (1984), R. Asami, M. Takar
i, Macromol. Chem. Suppl., 12 , 163 (198)
5), P. Rempp., Et al, Macromol. Chem. Suppl.,
8, 3 (1984), Yusuke Kawakami, Chemical Industry, 38 , 56
(1987), Yuya Yamashita, Kobunshi, 31 , 988 (19)
82), Kobayashi Shiro, Kogaku, 30 , 625 (198).
1), Toshinobu Higashimura, Journal of Japan Adhesion Society, 18 , 536 (19)
82), Koichi Ito, Polymer Processing, 35 , 262 (198).
6), Kishiro Higashi, Takashi Tsuda, Functional Materials, 1987 , No. 1
0, 5, edited by Yuya Yamashita, "Chemistry and Industry of Macromonomers" (1989, IPC Corporation), edited by Takeshi Endo, "Molecular Design of New Functional Polymers" Chapter 4 (19)
1991, CMC, Y. Yamashita et al. Po
lym. Bull. 5 , 361 (1981) and the like. The method for synthesizing the star block copolymer is, for example, M.
T. Reetz, Angew. Chem. 1st. Ed. Engl 27 , 137
3 (1988), M. Sgwarc, "Carbanions, LivingPoly
mers and Electron Transfer Processes "(1968
Wiley.New York) B. Gordon et al, Polym. Bull.
11 , 349 (1984), RB Bates et al. J. Or.
g. Chem. 44 , 3800 (1979), Y. Sogah, A.
CS Polym. Repr. 1988 , No. 2, 3, JW May
s. Polym. Bull. 23 , 247 (1990), IM Kha
n. et al. Macromolecules, 21 , 2684 (198)
8), A. Morikawa, Macromolecules, 24 , 3469
(1991), Akira Ueda, Susumu Nagai, Kogaku, 39 , 202.
(1990), T. Otsu, Polym. Bull. 11 , 135.
(1984) and the like.

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.) And the like. More specifically, the star type 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 of synthesizing a star-shaped polymer from a monomer, for example, a polymerization reaction using a carbanion as an initiator, specifically M. Morton, TE Helminiak et al. . J.Polym. Sci., 5
7, 471 (1962), B. Gordon III, M. Blumethal, JELoftu
s. et al, Polym. Bull., 11,349 (1984), RBBates, W.
It can be synthesized according to the method described in A. Beavers, et al, J. Org, Chem., 44, 3800 (1979). When the segment (Y) in 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 monomer corresponding to the constituent unit containing the specific polar group, the polar group is set as a previously protected functional group, and an organometallic compound (eg, alkyllithium, lithium diisopropylamide, alkylmagnesium halide, etc.) or iodine After synthesizing a block copolymer by a so-called living polymerization reaction such as an ionic polymerization reaction with a hydrogen fluoride / iodine system, a photopolymerization reaction using a porphyrin metal complex as a catalyst, or a group transfer polymerization reaction, a functional group with a polar group protected is obtained. A deprotection reaction such as a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction or a photolysis reaction is performed to form a polar group. One example thereof is shown in the following reaction formula (I).

[0070]

[Chemical 28]

The macromonomer part (M_A) And (M
_B) Corresponding macromonomer and these macromonomers
AB type or ABA containing at least one of the nomer parts
Each of the block copolymers according to the related art is prepared by a conventionally known polymerization method.
Can be synthesized. These macromonomers
Is, for example, an organometallic compound (eg, alkyl lithium
, Lithium diisopropylamide, alkyl magnesi
Um halides, etc.) or hydrogen iodide / iodine, etc.
In the ionic polymerization reaction, the porphyrin metal complex is used as a catalyst.
Photopolymerization reaction, group transfer polymerization reaction, dithiocarba
Using a mate compound, dithioxanthate compound, etc. as an initiator
Photoinitiator polymerization method or polymerizable double bond group
Radical polymerization initiators containing functional groups that can introduce
For example, azobis compounds, peroxides, chain transfer agents (eg
Radicals using mercapto compounds, iodo compounds)
The weight average molecular weight is 2 × 1 by a known polymerization method such as a polymerization reaction.
0 ^FourAfter synthesizing the following polymer, one end of the polymer main chain
Introduce a polymerizable double bond group by reacting various reagents at the end
It can be synthesized.

For example, P. Lutz, P. Masson et al, Poly
m. Bull., 12 , 79 (1984) BC Anderson, G.
D. Andrews et al, Macromolecules, 14 , 1601
(1981) K. Hatada, K. Ute. Et al, Polym. J. 1
7 , 977 (1985), 18 , 1037 (198)
6), Koichi Right Hand, Koichi Hatada, Polymer Processing, 36 , 366
(1987) Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymers, 4
6 , 189 (1989) M. Kuroki, T. Aida, T. Am. Ch
em. Soc. 109 , 4737 (1987), Takuzo Aida,
Inoue Shohei, Synthetic Organic Chemistry, 43 , 300 (1985) D.
Y. Sogah, WR Hertler etal, Macromolecules, 2
0 , 1473 (1987), Takayuki Otsu, Polymer, 37 ,
248 (1988), Shunichi Hinomori, Ryuichi Otsu, Polym. Re
p. Jap. 37 , 3508 (1988), JP-A-64-1
The living polymer can be easily synthesized according to the synthesis method described in JP-A No. 11-26, JP-A 64-26619 and the like. As an example of using radical polymerization reaction, Y. Yamashi
ta, J. Appl. Polym. Sci, Appl. Polym. Symp. 36 , 1
93 (1981), KK Roy, et al, Makromol. Chem.
153 , 71 (1972), Y. Yamashita et al, Poly.
m. J., 14 , 255 (1982), Akira Ueda, Susumu Nagai,
The synthetic methods described in Science and Industry, 60 , 57 (1986) and the like can be mentioned. The method of introducing a polymerizable double bond group into the terminal of the polymer main chain may be a conventionally known method.
Specifically, P. Dreyfuss & RP Quirk, Encycl, Pol
ym. Sci. Eng., 7 , 51 (1987), PF Rempp,
E. Franta, Adu., Polym. Sci. 58 , 1 (198)
4), V. Per-cec, Appl., Polym. Sci., 285 , 95.
(1984), R. Asami, M. TakaRi, Makvamol. Chem.
Suppl. 12 , 163 (1985), P. Rempp. Et al.
Makvamol. Chem. Suppl. 8 , 3 (1984) Yusuke Kawakami,
Chemical Industry, 38 , 56 (1987), Yuya Yamashita, Polymer, 31 , 988 (1982), Kobayashi Shiro, Polymer, 3
0 , 625 (1981), Toshinobu Higashimura, Journal of Japan Adhesion Association,
18 , 536 (1982), Koichi Ito, Polymer processing, 3
5 , 262 (1986), Takashiro Higashi, Takashi Tsuda, Functional Materials, 1987 No. 10, Yuya Yamashita "Macromonomer Chemistry and Industry" Chapter 2, IPC Publishing (Published in 1989), etc. It can be synthesized according to the method described in the cited documents and patents.

When the macromonomer contains a structural unit containing the specific polar group, the macromonomer is prepared by using a monomer in which the polar group is protected in advance in the polymerization reaction and It can be easily synthesized by introducing a polymerizable double bond group and then removing the protective group. Methods for protecting polar groups and removing them are known. For example, various references are given in the above cited references, and further, Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer", Kodansha Co., Ltd. (1977), TW Greene "Protective Gro".
ups in Organic Synthesis ”, John Wiley & Sons (19
81), JFW McOmie, "Protective Groups in Or
The method described in detail in the review of "Ganic Chemistry" Plenum Press, (1973) and the like can be appropriately selected and performed. The resin (P ₄ ) is described in Akira Ueda, Susumu Nagai, et al., Polymers, 33 131 (1976),
It can also be produced by a radical copolymerization reaction using a polymer azo initiator described in Science and Industry, 64 , 446 (1990) and the like. (Resin [Q]) Hereinafter, the resin [Q], that is, the resin (Q ₁ ) and the resin (Q ₂ ) will be described in detail. (Resin (Q ₁ )) The resin (Q ₁ ) is a star-type copolymer in which at least three polymer chains containing the structural unit of the formula I and the polar group-containing structural unit are bonded via an organic group. Is. That is, the polymer is represented as follows, for example.

[0074]

[Chemical 29]

In the above, Z represents an organic group, and [Po
is a polymer chain. Here, the polymer chains bonded to the organic group may be structurally identical or different, and each contains a structural unit of the formula (I) and a polar group-containing structural unit. The length of each polymer chain may be the same or different. The upper limit of the number of polymer chains to be bonded is 15, preferably 10
It is about an individual.

Resin (Q₁) Has a weight average molecular weight of 1 × 10³
~ 2 x 10^Four, Preferably 3 × 10 ³~ 1 x 10^FourAnd
Resin (Q₁The glass transition point of) is preferably −40 ° C.
110 degreeC, More preferably, it is -20 degreeC-90 degreeC. Tree
Fat (Q₁) Has a molecular weight of 1 × 10³Smaller, the film
The film forming ability is lowered and it is not possible to maintain sufficient film strength.
Square molecular weight is 2 × 10^FourLarger, especially near infrared
High temperature at the original plate for color proof using infrared spectral sensitizing dye
・ Dark decay retention rate under severe conditions such as high humidity, low temperature and low humidity
Also, the light sensitivity is reduced, making it difficult to obtain stable quality images.
Yes. The content of the polar group-containing constitutional unit is the resin (Q₁) Total weight
1-20% by weight, more preferably 3-15% by weight
The amount is%. The content of the polar group-containing structural unit is 1% by weight.
If the amount is too small, the initial potential will be low and sufficient image density will be obtained.
I can't. On the other hand, the content of the polar group-containing structural unit
Is more than 20% by weight, the resin (Q₁) Dispersible
However, the image quality of the obtained color proof will deteriorate and the background stain will increase.
To do. Two or more kinds of polar group-containing structural units are contained in the polymer chain.
It may be included. Also, the inclusion of the structural unit of formula (I)
The amount of resin (Q₁30% by weight or more based on the total weight of
It is preferably 30 to 9.95% by weight, more preferably 50 to
It is 99.5% by weight. Next, regarding the constitutional unit of the formula (I),
Explain. In formula I, a¹And a²Are hydrogen atom and
Rogen atom (eg fluorine atom, chlorine atom, bromine atom)
Etc.), cyano group or hydrocarbon group (for example, having 1 to 8 carbon atoms)
Aliphatic groups such as methyl, ethyl, propyl, bromo,
Chill group, pentyl group, hexyl group), benzyl group, carbon
It represents an aromatic group of formulas 6 to 12, for example, a phenyl group. a¹
Represents a hydrogen atom, and a²Is preferably a methyl group
Good

R ³ represents a hydrocarbon group, specifically an alkyl group, an aralkyl group or an aromatic group, preferably an aralkyl group or an aromatic group containing a benzene ring or a naphthalene ring. Further, R ³ preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. Examples of the substituent include a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom, etc.), —OZ ¹ , —CO—OZ ¹ ,
-O-COZ ¹ (Z ¹ represents an alkyl group having 1 to 22 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group,
Hexadecyl group, octadecyl group, etc.) and the like. The preferred hydrocarbon group is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, 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, etc.), optionally substituted carbon atoms 4 to 1
8 alkenyl groups (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, etc., 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 (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or optionally substituted aromatic group having 6 to 12 carbon atoms Groups (eg phenyl, naphthyl,
Tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group,
Methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, Acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.) and the like. When R ³ is an aliphatic hydrocarbon group, the structural unit of the formula (I) R ³ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms, the total weight of the structural unit of the formula (I) On the other hand, it is preferably contained in an amount of 60% by weight or more. As the constitutional unit of the formula (I), the formula (Ia) and / or the formula (Ib):

[0078]

[Chemical 30]

The structural unit represented by is particularly preferable. In formula (Ia), A ¹ and A ² are each independently a hydrogen atom, a chlorine atom, a bromine atom, a hydrocarbon group having 1 to 10 carbon atoms, —COR ¹⁴ or —CO—O—R ¹⁴ (R ¹⁴ Represents a hydrocarbon group having 1 to 10 carbon atoms), and B ¹ and B ²
Each represents a single bond connecting -COO- and the benzene ring or a linking group having 1 to 4 main chain atoms. Preferably, A ¹ and A ² are an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group), an optionally substituted aralkyl group having 7 to 9 carbon atoms (eg, benzyl). Base,
Phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloromethylbenzyl group) and optionally substituted aryl groups (eg phenyl group, tolyl group) , Xylyl group, bromophenyl group,
Methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and R in -COR ¹⁴ or -CO-OR ¹⁴
Mention may be made of the groups in which ¹⁴ represents a hydrocarbon radical mentioned as being preferred for A ¹ and A ² . Specific examples of B ₁ and B _2, a single _{bond, - (CH 2) a -} (a is an integer of _{1~3), - CH 2 O-} CO -, - CH 2 CH 2 O -CO- ,-(CH ₂
O) _b- (b represents an integer of 1 or 2) and -CH ₂ CH ₂ O-
And a single bond or a linking group having 1 to 2 main chain atoms is particularly preferable. Specific examples of the structural unit represented by the above formula (Ia) or (Ib) are given below. However, the scope of the present invention is not limited to this. The following (q-1)
To (q-20), c represents an integer of 1 to 4, and d
Represents an integer of 0 or 1 to 3, e is an integer of 1 to 3, R ⁶ is -C _C H _{2C + 1} or _{- (CH 2) d -C 6} H 5 ( except, c, d is Same as above), D ¹ and D ² may be the same or different and each represents a hydrogen atom, —Cl, —Br or —I.

[0080]

[Chemical 31]

[0081]

[Chemical 32]

Next, the polar group-containing structural unit will be described. Polar _{group, -PO 3 H 2, -SO 3} H, -COOH, -PO (OH)
It is a group selected from-(R ₁ ) and a cyclic acid anhydride group. In the above formula, R ₁ represents a hydrocarbon group or —OR ₂ (R ₂ represents a hydrocarbon group), and specifically R ₁ and R ₂ have 1 to 1 carbon atoms.
22 hydrocarbon groups (for example, methyl group, ethyl group, propyl group, butyl group, 2-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). Further, the cyclic acid anhydride group and its specific example may be those described for the resin [P]. The polar group-containing structural unit is exemplified below. Here, d ¹ represents H or CH ₃ , d ² represents H, CH ₃ or CH ₂ COOCH ₃ , R ²² represents an alkyl group having 1 to 4 carbon atoms, and R ²³ represents 1 to 6 carbon atoms. Represents an alkyl group, a benzyl group or a phenyl group, and f is 1 to 3
Represents an integer of 2, g represents an integer of 2 to 11, and h represents 1 to 1.
Represents an integer of 1, i represents an integer of 2 to 4, j represents 2-1
Represents an integer of 0.

[0083]

[Chemical 33]

[0084]

[Chemical 34]

[0085]

[Chemical 35]

[0086]

[Chemical 36]

[0087]

[Chemical 37]

[0088]

[Chemical 38]

[0089]

[Chemical Formula 39]

[0090]

[Chemical 40]

[0091]

[Chemical 41]

[0092]

[Chemical 42]

[0093]

[Chemical 43]

The polymer chain may contain a constitutional unit other than the above-mentioned polar group-containing constitutional unit and the constitutional unit of the formula (I). As such a constitutional unit, for example, a constitutional unit of the formula (IV)
The structural unit represented by

[0095]

[Chemical 44]

[In the formula (IV), X ¹ is —CO—O—, —O
_{-CO -, - (CH 2)} p -O-CO -, - (CH 2) P -
CO-O- (p represents an integer of 1 to 3), -O-, -S.
_{O 2 -, - CO -,} - CON (Z 3) -, - SO 2 N (Z
³ )-, -CONHCO-O-, -CONHCONH-
Or -C ₆ H ₄ - represents a (wherein Z ³ represents a hydrogen atom or a hydrocarbon group). R ¹² represents a hydrocarbon group. b ¹ and b ² may be the same as or different from each other and represent any of the groups mentioned for a ¹ and a ² in the formula (I). ]

Z ³ as a hydrocarbon group is preferably an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group). 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, etc.), 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.), optionally substituted carbon number 7 to 12
Aralkyl group of (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.), optionally substituted alicyclic group having 5 to 8 carbon atoms (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg, 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, bromophenyl Group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group and the like). X ¹ is -C ₆ H ₄ -
When represented, the benzene ring may have a substituent. As the substituent, 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.) and the like.

R ¹² is preferably an optionally substituted alkyl group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, Dodecyl group, tridecyl group, tetradecyl 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), 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 (eg, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chloro) Benzyl group,
(Bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted carbon atoms 5 to 5
8 alicyclic group (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.),
An optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxy group). Phenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, pro Pioamidophenyl group, dodecyloylamidophenyl group, etc.) and the like. Further preferably, in the formula (IV), X ¹ is —CO—O—, —O.
_{-CO -, - CH 2 -O-} CO -, - CH 2 -CO-O
-, - O -, - CONH -, - SO 2 NH-, or -C
Represents ₆ H ₄ −.

Further, the polymer chain may further contain other constitutional unit, and such constitutional unit is represented by the above formula.
A structural unit corresponding to a monomer copolymerizable with a monomer corresponding to the structural unit (IV), for example, a methacrylic acid ester or an acrylic acid ester containing a substituent other than those described in the formula (I) In addition to crotonic acid esters, α-olefins, vinyl carboxylates (for example, as carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, Itaconic acid esters (eg, dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrenes (eg, styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methane) Sulfonyloxystyrene, vinylnaphtha Ren, etc.), vinyl sulfone-containing compound, vinyl ketone-containing compound, heterocyclic compound having vinyl group, (for example, vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline, vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, Vinyloxazine etc.) and the like. The content of these other structural units is preferably within the range of not more than 20 parts by weight with respect to 100 parts by weight of all the structural units of the polymer chain. The organic group (Z) to which the polymer chain is bonded has a molecular weight of 1
If it is 000 or less, it is not particularly limited. Examples include those listed for the organic group (Z) of the resin (P ₂ ). The resin (Q ₁ ) is synthesized by using a conventionally known method for synthesizing a star polymer from a monomer having a polar group and a polymerizable double bond group, which has been described for explaining the resin (P). be able to. However, in this method, the polar group in the monomer is protected and the polymerization is performed, and then the protective group is removed. The protection of the polar group with the protecting group and the removal of the protecting group can be easily performed by a conventionally known method. For example, various references are given in the above cited document, and further, Yoshio Iwakura and Keisuke Kurita "Reactive Polymer"
Published by Kodansha Ltd. (1977), T.K. W. Greene
"Protective Groups in Org
anic Synthesis "John Wiley
& Sons (1981), J. F. W. McOm
ic "Protective Groups in Or
ganic Chemistry "Plenum Pr
The method described in detail in the review article such as ess (1973) can be appropriately selected and performed. In addition, resin (Q
₁ ) is synthesized, for example, by using a monomer that does not protect the polar group and using a compound containing a dithiocarbamate group and / or a compound containing a xanthate group as an initiator to carry out a polymerization reaction under light irradiation. You can also do it.
For example, Takayuki Otsu "Polymer" 37 , 248 (198).
8), Shunichi Hinomori, Ryuichi Otsu, Polym. Rep. Ja
p. 37 . 3508 (1988), JP-A-64-111
No. 64-26419, Nobuyuki Higashi, et al., Polym
er Preprints, Japan, 36 (6),
1511 (1987), M.A. Niwa, N.N. Higas
hi, et al. Macromol. Sci. C
hem. A24 (5), 567 (1987) and the like can be used for the synthesis.

The weight average molecular weight of the resin (Q ₁ ) of the present invention can be adjusted by adjusting the ratio of the total amount of monomers used in the polymerization to the amount of various polymerization initiators, the polymerization temperature, etc., as conventionally known in the polymerization reaction. This can be easily done by changing the parameters. Moreover, various resins [Q] can be produced by using an appropriate monomer and an initiator. (Resin (Q ₂ )) The resin (Q ₂ ) will be described below. The resin (Q ₂ ) is at least a linear block polymer chain containing a segment (M) containing the structural unit of the formula (I) and a segment (N) containing the polar group-containing structural unit. It is a star-type copolymer in which three are bonded via an organic group. Where segment (M)
The order of arrangement of the segment and the segment (N) in the polymer chain may be any. For example, the resin (Q ₂ ) is represented by the following schematic diagram.

[0101]

[Chemical formula 45]

In the above, Z represents an organic group, and (M)
Indicates segment (M), (N) indicates segment (N)
You In addition, the number of linear block type polymer chains to be bonded
The limit is about 15, preferably about 10. Resin (Q
₂) Has a weight average molecular weight of 1 × 10³~ 2 x 10^Four, Preferred
Kuha 3 × 10 ³~ 1 x 10^FourAnd the resin (Q₂) Gala
The transition point is preferably -40 ° C to 110 ° C, more preferably
The temperature is -20 ° C to 90 ° C. Resin (Q₂) Weight average
1 × 10³When it becomes smaller, the film forming ability decreases.
And cannot maintain sufficient film strength, while the weight average molecular weight is 2 ×
10^FourLarger, especially near-infrared to infrared spectral sensitized color
In the original plate for color proof using the element, high temperature, high humidity, low temperature
Electrophotographic characteristics under harsh conditions such as low humidity (especially initial charge)
Position, dark decay retention rate and light sensitivity)
It is difficult to obtain the specified copy image.

The content of the polar group-containing constitutional unit is the resin (Q ₂ ).
1 to 20% by weight, more preferably 3 to
It is 15% by weight. If the content of the polar group-containing constitutional unit is less than 1% by weight, the initial potential becomes low and a sufficient image density cannot be obtained. On the other hand, when the content of the polar group-containing structural unit is more than 20% by weight, the dispersibility of the resin (Q ₂ ) is lowered, the image quality of the obtained color proof is deteriorated, and the background stain is increased. Further, the content of the constituent unit of the formula (I) is preferably 30 to 100 relative to the total weight of the segment (M).
%, More preferably 50 to 100% by weight. The polar group-containing structural unit is not contained in the segment (M). Preferred examples of the substituents in formula I are resin (Q
It may be those mentioned as preferable substituents in formula I for ₁ ). The constitutional unit of the formula (I) is preferably the formula (Ia) or the formula (Ib) shown for the resin (Q ₁ ).
Can be a constituent unit of. Examples of preferred substituents in formula (Ia) and formula (Ib) are those given for resin (Q ₁ ). Specific examples of the structural unit represented by the formula (Ia) or (Ib) are also given for the resin (Q ₁ ). However, the scope of the present invention is not limited to these.

The segment (M) may contain another structural unit, for example, a structural unit of the formula (IV) shown for the resin (Q ₁ ). Preferred examples of the substituent in formula IV are those described for the resin (Q ₁ ). Further, the segment (M) is copolymerized with the structural unit represented by the formula (IV) and another structural unit, for example, a monomer corresponding to the structural unit of the formula (IV) described for the resin (Q ₁ ). Structural unit corresponding to a possible monomer, for example, acrylonitrile, methacrylonitrile, heterocyclic vinyls (for example, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.) Can be contained in an amount not exceeding 20% by weight, based on the total weight of the segment (M). The polar groups in segment (N) can be those mentioned for resin (Q ₁ ). Further, specific examples of the polar group-containing constitutional unit may be those given for the resin (Q ₁ ). The polar group-containing structural unit is a segment (N)
2 or more types may be contained therein, and in that case, the 2 or more types of polar group-containing constitutional units may be contained in the segment (N) in any mode of random copolymerization or block copolymerization. . Further, a structural unit other than the polar group-containing structural unit may be contained in the segment (N). Such constitutional units are preferably the constitutional units of the above formulas (I) and (IV). Furthermore, you may contain a structural unit other than these. Such other structural unit may correspond to, for example, a monomer copolymerizable with the monomer corresponding to the structural unit of the formula (IV) described for the resin (Q ₁ ). The organic group (Z) is not particularly limited as long as it has a molecular weight of 1000 or less. For example,
Include those described for the resin organic group (P ₂₎ (Z). The resin (Q ₂ ) can be synthesized and the molecular weight can be adjusted by the method described for the resin (Q ₁ ). (Resin [R]) Next, the resin [R] of the present invention containing at least one light and / or thermosetting group will be described. The light and / or thermosetting group contained in the resin [R] may be any, but specifically, those having the same contents as the light and / or thermosetting group contained in the resin [P] described above. Is mentioned. The resin [R] may be any resin as long as the above-mentioned light and / or thermosetting group is contained in the resin used for a conventionally known electrophotographic photoreceptor. These conventionally known binder resins for electrophotographic photoreceptors are described in the following documents, for example. Ryuji Shibata, Jiro Ishiwatari, Kogaku, Vol. 17, p. 278 (1968) Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No. 8) edited by Kouichi Nakamura "Practical Technology of Binders for Recording Materials" Chapter 10 , C.I.
H. C. Published (1985) Edited by The Electrophotographic Society, "Present Symposium on Organic Photoconductors for Electrophotography" (1985)
Year).

Hiroshi Komon, “Recent Developments and Practical Uses of Photoconductive Materials and Photoconductors”, Japan Science Information Co., Ltd. (1986), The Electrophotographic Society, “Basics and Applications of Electrophotographic Technology” Chapter 5 Corona Co., Ltd. (1988) D. Tatt, SC Heidecker, Tappi, 49 (No. 1
0), 439 (1966), E.I. S. Baltazzi, R.A.
G. Blanclotte et al, Phot. Sci. Eng. 16 (No.
5), 354 (1972), Nguyen Chan Kae, Isamu Shimizu, Eiichi Inoue, The Institute of Electrophotography, 18 (No. 2), 22.
(1980) and the like, compounds and the like described in reviews. Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and its derivatives, Polymers and copolymers, butadiene-styrene copolymers, isoprene-styrene copolymers, butadiene-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile copolymers, alkyl vinyl ether copolymers, Acrylic ester polymers and copolymers, methacrylic acid ester polymers and copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, itaconic acid diester polymers and copolymers, maleic anhydride Acid copolymer, acrylamide copolymer, methacrylamide copolymer, water Group-modified silicone resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl group- and carboxyl group-modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylic acid ester copolymer, cyclized rubber- Acrylic ester copolymer, copolymer containing a nitrogen ring-free heterocycle (as a heterocycle, for example, furan ring, tetrahydrofuran ring, thiophene ring,
Dioxane ring, dioxofuran ring, lactone ring, benzofuran ring, benzothiophene ring, 1,3-dioxetane ring, etc.), epoxy resin and the like.

The structural unit containing at least one type of light and / or thermosetting group is 0.1 parts by weight in 100 parts by weight of the resin [R].
-40 parts by weight, preferably 1-30 parts by weight. When the content is less than 0.1 part by weight, the curing after the film formation of the photoconductive layer does not proceed sufficiently, and the film interface with the surface portion of the photoconductive layer during the coating of the transfer layer is insufficiently retained, resulting in insufficient transfer. It adversely affects the peelability of the layer. On the other hand, if the content ratio exceeds 40 parts by weight, the electrophotographic properties of the photoconductive layer as the binder resin may deteriorate, the reproducibility of image lines may deteriorate, and the background fog in the non-image area may occur. is there. The resin [R] containing a light and / or thermosetting group is preferably used in an amount of 40 parts by weight or more based on 100 parts by weight of the total binder resin. This is because if the content of the resin [R] is less than 40 parts by weight, the electrophotographic properties will deteriorate. The photoconductive layer may contain other binder resins in addition to the resin [P], the resin [Q] and the resin [R], if necessary. For example, the conventionally known binder resin for an electrophotographic photoreceptor described with respect to the resin [R] is used. (Light and / or heat curing agent) In the present invention, the photoconductive layer (in the case of a laminated type, a layer adjacent to the transfer layer) is further provided with a light and / or heat curing agent in order to improve the curability of the film. It is preferable to contain The term "light and / or heat curing agent" includes light and / or heat curable compounds, light and / or
Or thermosetting oligomer, light and / or thermosetting resin,
And a cross-linking agent. The amount used is resin [P],
Based on 100 parts by weight of the total amount of resin [Q] and resin [R]
The amount is 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight. If the amount used 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, electrophotographic characteristics are adversely affected. The light and / or thermosetting resin may be any conventionally known curable resin,
For example, a resin having a functional group similar to the curable group described for the segment (Y) of the resin [P] of the present invention can be given as an example.

As the cross-linking agent, a compound usually used as a cross-linking agent can be used. Specifically, compounds described in "Crosslinking agent handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taisei (1981), "Polymer Data Handbook Basic Edition", edited by The Society of Polymer Science, Baifukan (1986), etc. are used. be able to.

For example, organic silane compounds (for example, vinyltrimethoxysilane, vinyltributoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, and other silane coupling agents), polyisocyanate compounds (eg, toluylene diisocyanate, o-toluy) Diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, high molecular polyisocyanate, etc.), polyol compounds (for example, 1, 4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane, etc., polyamine compounds (for example, ethylenediamine, γ-hydroxypropyl) Pill of ethylene diamine,
Phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.),
Titanate coupling compounds (such as tetrabutoxy titanate, tetrapropoxy titanate, isopropyl tristearoyl titanate), aluminum coupling compounds (such as aluminum-butyrate, aluminum acetyl acetate, aluminum oxide octate, aluminum tris (acetyl acetate)) Polyepoxy group-containing compounds and epoxy resins (for example, "Epoxy Resins", edited by Hiroshi Kakiuchi, Shokoido (19
1985), "Epoxy Resins" edited by Kuniyuki Hashimoto, compounds described in Nikkan Kogyo Shimbun (1969) and others, melamine resins (e.g., Ichiro Miwa, Hideo Matsunaga "Yuria.
"Melamine resin", compounds described in Nikkan Kogyo Shimbun (1969), poly (meth) acrylate compounds (for example, Shin Okawara, Takeo Saegusa, Toshinobu Higashimura "Oligomer" Kodansha (1976), Omori. Examples thereof include compounds described in Eizo "Functional Acrylic Resin" Techno System (published in 1985), etc. Also, a monomer having a polyfunctional polymerizable group (for example, vinyl methacrylate, allyl methacrylate, ethylene glycol diacrylate). , Polyethylene glycol diacrylate, divinyl succinate, divinyl adipate, diallyl succinate, 2-methylvinyl methacrylate, trimethylolpropane trimethacrylate, divinylbenzene, pentaerythritol polyacrylate and the like).

As described above, since the layer adjacent to the transfer layer of the photoconductive layer of the present invention is cured after film formation, the resin [P],
The resin [Q], the resin [R] and the light and / or heat curing agent are
It is preferable to use a combination of functional groups in which polymers are easily chemically bonded to each other. Such combinations are well known in polymer reactions, and examples thereof include, but are not limited to, combinations of functional groups of group A and functional groups of group B as shown in the table below.

[0110]

[Table 1]

In Table 1, R represents a hydrocarbon group,
R ¹⁵ and R ¹⁶ represent an alkyl group, R ^{17 to} R ¹⁹ represent an alkyl group or an alkoxy group, and at least one of R ^{17 to} R ¹⁹ represents an alkoxy group, and B ¹ and B ² represent electron withdrawing groups. represents sex groups, for example ^{_{-CN, -CF 3, -COR 20,}} -CO
OR ^20, is _{^{-SO 2 OR 20 (R 20 C}} n H 2n + 1 (n is an integer of 1 to 4), - represents a _{CH 2 C 6 H 5, -C} 6 hydrocarbon group H ₅ etc. ) Etc. (Reaction Accelerator) In order to accelerate the crosslinking reaction in the photoconductive layer, a reaction accelerator may be added to the binder resin of the photoconductive layer, if necessary. When the crosslinking reaction is a reaction mode in which a chemical bond between functional groups is formed, 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 (diethyldithiocarbamic acid) Salt, etc.), thiuram disulfide compound (tetramethyl thiuram disulfide etc.), carboxylic acid anhydride (phthalic anhydride, maleic anhydride, succinic anhydride, butyl succinic anhydride,
3,3 ′, 4,4′-tetracarboxylic acid benzophenone dianhydride, trimellitic acid anhydride, etc.) and the like.
When the crosslinking reaction is a polymerizable reaction mode, 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 the heat curing, for example, the drying conditions are set to be more strict than the drying conditions at the time of producing the conventional electrophotographic color proofing original plate. For example, the drying conditions are high temperature and / or long time. Alternatively, it is preferable to further heat-treat after drying the coating solvent. For example, 60 ° C to 150
Treat for 5 to 120 minutes. When the above reaction accelerator is used in combination, the treatment can be performed under milder conditions.

As a method for curing the specific functional group in the resin of the present invention by irradiation with light, a step of irradiating with "chemically active light" may be included. The "chemically actinic ray" used in the present invention may be any of visible ray, ultraviolet ray, far ultraviolet ray, electron beam, X-ray, γ ray, α ray, and the like, and preferably ultraviolet ray. It is more preferable to emit light in the wavelength range of 310 nm to 500 nm, and low-pressure, high-pressure or ultra-high-pressure mercury lamps, halogen lamps and the like are generally used. The light irradiation treatment can usually be performed sufficiently by irradiation for 10 seconds to 10 minutes from a distance of 5 cm to 50 cm. (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 zinc oxide, titanium oxide, zinc sulfide,
Conventionally known inorganic photoconductive compounds such as cadmium sulfide and lead sulfide are mentioned, and zinc oxide and titanium oxide are preferable from the viewpoint of pollution. When an inorganic compound such as zinc oxide or titanium oxide is used as the photoconductive compound, the inorganic compound 10
The binder resin is used in an amount of 10 to 100 parts by weight, preferably 15 to 40 parts by weight, based on 0 parts by weight. On the other hand, the organic compound may be any conventionally known compound. For example, as a first example, Japanese Patent Publication No. 37-
17162, 62-51462, and JP-A-52-243.
7, 54-19803, 56-107246, 57.
Examples of the materials used in the photoconductive layer mainly composed of the organic photoconductive compound, the sensitizing dye, and the binder resin described in JP-A-161863 and the like. Further, as a second example, JP-A-56-146145 and JP-A-60-1775.
1, the same 60-17752, the same 60-17760, the same 60
No. 254142 and No. 62-54266, and the like, those used in the photoconductive layer mainly composed of the charge generating agent, the charge transporting agent, and the binder resin are described.
Further, JP-A-60-230147 and 60-23011
48 and 60-238853, etc., those used in a two-layered photoconductive layer containing a charge generating agent and a charge transporting agent in separate layers.

The organic photoconductive compound used in the present invention includes: (a) triazole derivatives described in US Pat. No. 3,121,197, etc., and (b) oxadiazoles described in US Pat. No. 3,189,447. Derivatives, (c) imidazole derivatives described in JP-B-37-16096, (d) U.S. Pat. Nos. 3,615,402 and 3,820,982.
9, No. 3542544, Japanese Patent Publication No. 45-55
5, 51-10983, JP-A-51-932.
24, ibid. 55-108667, ibid. 55-156953,
Polyarylalkane derivatives described in JP-A-56-36656, (e) U.S. Pat. Nos. 3,180,729 and 4;
278746, JP-A-55-88064, JP-A-55-88065, JP-A-49-105537, and JP-A-55-5.
1086, 56-80051, 56-88141,
57-45545, 54-112637, 55-
Pyrazoline derivatives and pyrazolone derivatives described in JP-A-74546, (f) U.S. Pat. ,
Phenylenediamine derivatives described in JP-A-54-110836, JP-A-54-119925 and the like, (g) US Patent Nos. 3567450, 3180703, and 324059.
7, 3658520, 4232103, 4175
961 and 4012376, Japanese Patent Publication No. 49-3
5702, West German Patent (DAS) 111051
8, Japanese Patent Publication No. 39-27577, Japanese Patent Laid-Open No. 55-1
44250, 56-119132, 56-2243.
7 arylamine derivatives described in each publication, (h) amino-substituted chalcone derivatives described in US Pat. No. 3,526,501, etc., (i) US Patent 354.
2546, etc., N, N-bicarbazyl derivatives,

(J) Oxazole derivatives described in US Pat. No. 3,257,203, etc., (k) JP-A-56-
Styrylanthracene derivatives described in JP-A-46234, (l) Fluorenone derivatives described in JP-A-54-110837, and (m) US Pat. No. 3,717,462.
No. 54-59143 (corresponding to U.S. Pat. No. 4,150,987), JP-A-55-520.
63, 55-52064, 55-46760, 5
5-85495, 57-11350, 57-148.
749, 57-104144 and the like, (n) US Pat. No. 404794.
8, same 4047949, same 4265990, same 4273
Nos. 846, 4299897, 4306008 and the like, and (o) JP-A-58-
190953, 59-95540, 59-9714.
8, 59-195658, 62-36674 and the like, stilbene derivatives described in (p) Japanese Patent Publication No. 34-10966 and its derivatives, (q) Japanese Patent Publication No. 43-18674. ,
Polyvinyl pyrene described in each of the same 43-19192 publications,
Polyvinyl anthracene, poly-2-vinyl-4-
Vinyl polymers such as (4′-dimethylaminophenyl) -5-phenyl-oxazole and poly-3-vinyl-N-ethylcarbazole; (r) polyacenaphthylene and polyindene described in JP-B-43-19193. Polymers such as copolymers of acenaphthylene and styrene, (s) condensation resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin described in JP-B-56-13940 and the like, (t) characteristics Kaisho 56-90833 and 56-16
Various triphenylmethane polymers described in each publication of 1550 are listed.

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. Two or more kinds of these organic photoconductive compounds may be used in combination depending on the case. As the charge generating agent contained in the photoconductive layer, various organic and inorganic charge generating agents known in the prior art for electrophotographic photoreceptors can be used. For example, selenium, selenium-tellurium, cadmium sulfide, zinc oxide, and the organic pigments shown in the following (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 Nos. 148453, 61-238063, JP-B-60-5941 and JP-B No. 60-45664, and (2) U.S. Pat. No. 3,397,086, 46668.
02 each specification, JP-A-51-90827, 52-5
Phthalocyanine pigments such as metal-free or metal phthalocyanines described in Japanese Patent Publication No. 5643 and the like, (3) US Patent No. 3
No. 371884, Japanese Patent Application Laid-Open No. 47-30330, and the like, (4) British Patent No. 2237
680, indigo and thioindigo derivatives described in JP-A-47-30331, and (5) quinacridone pigments (6) described in British Patent No. 2237679, JP-A-47-30332 and the like. ) British Patent No. 22
Polycyclic quinone pigments described in JP-A-376789, JP-A-59-184348, JP-A-62-28738 and JP-A-47-18544, and (7) JP-A-47-3033.
1, bisbenzimidazole-based pigments described in JP-A-47-18543 and (8) US Pat. No. 4,396,661.
No. 0, No. 4644082, and the like, Squalium salt-based pigments, (9) JP-A-59-53850, and No. 61-
The azurenium salt-based pigments described in JP-A-212542 and the like. These may be used alone or in combination of two or more.

The mixing ratio of the organic photoconductive compound and the binder resin is such that the upper limit of the content ratio of the organic photoconductive compound is determined by the compatibility of the organic photoconductive compound and the binder resin, and the amount exceeds the upper limit. Is not preferable 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 to include as many organic photoconductive compounds as possible within the range where 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 of the organic photoconductive compound, relative to 100 parts by weight of the binder resin. 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 together as a spectral sensitizer depending on the kind of light source such as visible light exposure or semiconductor laser light exposure. For example, Harumi Miyamoto, Hidehiko Takei: Imaging 1973 (No.
8) Page 12, CJ Young et al., RCA Review 15 , 4,
69 (1954), Kyohei Kiyota: The Institute of Electrical Communication, J63-C (No. 2), 97 (1980), Yuji Harasaki, et al., Journal of Industrial Chemistry, 66 , 78 and 188 (1
963), Tadaaki Tani, Journal of the Photographic Society of Japan, 35 , p. 208 (1972), and the like, carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (eg, oxonol). Dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, and the like), phthalocyanine dyes (which may contain a metal), and the like.

More specifically, those mainly containing carbonium type dyes, triphenylmethane type dyes, xanthene type dyes and phthalein type dyes are disclosed in Japanese Examined Patent Publication No. 51-4.
52, JP-A-50-90334, 50-11422.
7, JP-A-53-39130, JP-A-53-82353, US Pat. Nos. 3,052,540 and 4,054,450, and JP-A-57-16456. Further, as polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes, FM Harmmer “The Cyanine Dyes a
The dyes described in "nd Related Compounds" and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384, 3,110,591, 3,121008, and 31,544.
7, Same 3128179, Same 3132942, Same 3622
317, British Patents 12268892, 13
09274, 140545898, Japanese Patent Publication No. 4
The dyes described in JP-A-8-7814, JP-A-55-18892 and the like are mentioned. Further, as polymethine dyes for spectrally sensitizing the near-infrared to infrared light region having a long wavelength of 700 nm or more, JP-A-47-840, 47-44180 and JP-B-51-
41061, 49-5034, 49-45122,
57-46245, 56-351141, 57-1
57254, 61-26044, 61-27551
Publications, US Patent Nos. 3619154 and 417595.
6 Specifications, "Research Disclosure" 1982,
216, pages 117 to 118, and the like.

The original plate for color proofing of the present invention is excellent in that its performance is hardly changed by the sensitizing dye even when various sensitizing dyes are used in combination. (Various Additives) Furthermore, if necessary, various conventionally known additives for electrophotographic photoreceptors can be used in combination. These additives include chemical sensitizers for improving electrophotographic sensitivity, various plasticizers for improving film properties, surfactants and the like. As a chemical sensitizer,
For example, halogen, benzoquinone, chloranil, fluoranyl, bromanil, dinitrobenzene, anthraquinone, 2,5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, 2,3-dichloro-
Electron-withdrawing compounds such as 5,6-dicyanobenzoquinone, dinitrofluorenone, trinitrofluorenone and tetracyanoethylene, Hiroshi Komon et al. "Recent Developments and Practical Uses of Photoconductive Materials and Photoconductors" Chapters 4-6 : Polyarylalkane compounds, hindered phenol compounds, which are cited in the review article of Japan Science Information Publishing Co., Ltd. (1986).
Examples thereof include p-phenylenediamine compounds. Also,
JP-A-58-65439, 58-102239, 5
Compounds and the like described in each of 8-129439 and 62-71965 can also be mentioned. Photoconductive of plasticizers such as dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, triphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalyl ethyl glycolate and dimethyl glycol phthalate. It can also be added to improve the flexibility of the layer. These plasticizers can be contained in a range that does not deteriorate the electrostatic properties of the photoconductive layer.

The addition amount of these various additives is not particularly limited, but is usually 0.00 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. Grinding and dispersion are carried out in a system in which a binder resin, a solvent thereof and various additives coexist, for example, a ball mill as shown in "Paint Chemistry" by Solomon and others,
It is common to use a kedi mill, sand mill, dyno mill, paint shaker, roll mill, ultrasonic disperser or the like. Then, 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,
Any solvent may be used to disperse the photoconductive substance, and it is selected in consideration of the solubility of the binder resin used. They may be used alone or in combination of two or more. The thickness of the photoconductive layer is preferably 1 to 100 μm, particularly preferably 10 to 50 μm. Also,
When 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 μm,
It is particularly preferably 0.05 to 2 μ. The thickness of the charge transport layer is
It is preferably 0.99 to 99.9μ, and particularly preferably 9 to 90μ. The stacking order of the charge transport layer and the charge generation layer may change depending on whether the color proofing original plate is negatively charged or positively charged. [Transfer Layer] Next, the transfer layer will be described.

The resin forming the transfer layer is a thermoplastic resin having a weight average molecular weight of 5 × 10 ³ to 1 × 10 ⁶ , preferably 1 × 10 ^{4 to} 5 × 10 ⁵ , and a glass transition point of 0 ° C. to 1 °.
It is in the range of 00 ° C, preferably 20 ° C to 85 ° C. The resin is used in a proportion of 70% by weight or more, preferably 90% by weight or more, based on the total amount of all compositions for forming the transfer layer.

Any thermoplastic resin may be used as long as it satisfies the above-mentioned physical properties. Specifically, vinyl chloride resin, polyolefin resin, olefin-styrene copolymer, vinyl alkanoate resin, polyester resin, polyether resin, Acrylic resins, cellulose resins, fatty acid-modified cellulose resins and the like can be mentioned. For example, "Plastic Materials Lecture Series" Volumes 1 to 18, published by Nikkan Kogyo Shimbun, (1961) "Polyvinyl Chloride" edited by the Kinki Chemical Society Vinyl Section, Nikkan Kogyo Shimbun (1988) Eizo Omori "Function Acrylic Resin "Techno System Co., Ltd. (1985) Eiichiro Takiyama" Polyester Resin Handbook ", Nikkan Kogyo Shimbun (1988) Kazuo Yuki" Saturated Polyester Resin Handbook "Nikkan Kogyo Shimbun (1989) Polymer Society of Japan "Polymer data handbook, application",
Chapter 1, Baifukan (1986) Yuji Harasaki "Latest Handbook of Binders", Chapter 2,
Compounds specifically exemplified by General Technology Center Co., Ltd. (1985) are listed. These thermoplastic resins can be used alone or in combination of two or more kinds. Further, other additives may be used in combination with the transfer layer in order to improve various physical properties such as coating property, film forming property and film strength. For example, the same plasticizers as those used in the photoconductive layer described above can be used. The thickness of the transfer layer is 0.1 to 10 μm, preferably 0.5 to 5
μm. The transfer layer can be formed by using an ordinary coating film forming method. For example, a coating solution containing any of the compounds as described above can be used and the same means as the means for forming the photoconductive layer can be used. Furthermore, a spray drying method which is a known method can also be used. The method for forming the layer is not particularly limited. [Method for producing color proof] A method for producing a color proof by using the electrophotographic original plate for color proof of the present invention will be described below. First, a copy image is formed on an electrophotographic color proofing original plate by a normal electrophotographic process. That is, each process of charging-exposure-developing-fixing is performed by a conventionally known method. The developer used in the development process may be any conventionally known developer, and examples thereof include a dry developer and a liquid developer. Specifically, for example, Gen Machida, “Recording Material and Photosensitive Resin,” p107-127 (1983).
The specific modes are shown in "Annual Publication", Academic Society Publishing Center, Electrophotographic Society, "Imaging No. 2-5 Development, Fixing, Charging, Transfer of Electrophotography".

A combination of the scanning exposure method using laser light which is exposed on the basis of digital information and the 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 original plate of the present invention (hereinafter, referred to as a color proofing original 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. To do. Next, for example, the basic plate for color proofing is charged by a charging device described on and after page 212 of "Basics and Applications of Electrophotographic Technology" (edited by the Electrophotographic Society, published by Corona, June 15, 1988). The corotron or scorotron method is common. At this time, it is preferable to apply feedback based on the information from the means for detecting the charging potential of the color calibration original plate and control the charging conditions so that the surface potential is always within a predetermined range. afterwards,
For example, scanning exposure with a laser light source is performed using the method described on page 254 and after of the above cited material. First, an image corresponding to a yellow plate, which is obtained by separating a color image 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 original plate for color proofing is removed from the flat bed and developed by the direct wet development method shown on page 275 and after of the above cited document. The exposure mode at this time is
It is determined according to the toner development mode. For example, in the case of reversal development, negative exposure is performed, that is, laser light is radiated to the image area, and toner having the same charge polarity as when charged is used. Is electrodeposited. Details of the principle are described on page 157 and after of the above cited material. After the development, in order to remove the excess developing solution, squeeze as shown on page 283 of the above cited reference material is performed, and then dried. It is also preferable to rinse only with the carrier liquid of the developer before squeezing. By repeating the above process for each color of magenta, cyan, and black, four full-color images can be obtained on the same original plate for color calibration. As a final step, the toner image on the original plate for color proof is thermally transferred together with the transfer layer to the main printing paper to obtain a color proof, that is, a color proof.

FIG. 1 shows an example of an apparatus for thermally transferring the transfer layer onto the main paper. This is driven while applying a predetermined nip pressure between a pair of rubber-coated metal rollers having a built-in heating means. The roller surface temperature at this time is 50 to 150.
° C., more preferably 80 to 120 ° C., a roller nip between pressure 0.2~20 kgf / cm ^2, more preferably 0.5
-10 kgf / cm ² , transport speed 0.1-100 mm /
Seconds, more preferably 1 to 30 mm / second. These conditions are appropriately set according to the physical properties of the materials of the transfer layer, the photoconductive layer and the support of the original plate for color proof used to obtain the optimum results. The roller surface temperature is preferably kept within a predetermined range by a known means. Further, it is also possible to provide a preheating means for the color calibration original plate in front of the heating roller portion and a cooling means after the heating roller portion. Although not shown in FIG. 1, an air cylinder using a spring or compressed air may be used as 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 peeled off extremely well,
As a result, it is possible to obtain a high-quality color proof without any toner color misregistration or transfer failure.

Examples of the present invention will be illustrated 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 block-bonded.

【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 polymeric azobis initiator [I-1] having the following structure was added and reacted for 8 hours. After the reaction was completed, the obtained reaction product 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]
Got

[0125]

[Chemical formula 46]

Synthesis Example of Resin [P ₁ ] 102: A mixed solution of 63 g of methyl methacrylate, 12.8 g of tri (dipropyl) silyl methacrylate and 200 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream and cooled to -20 ° C. Add 0.8 g of 1,1-diphenylbutyllithium to 1
The reaction was carried out for 2 hours. Furthermore, 30 g of the monomer (M-1) having the following structure and 60 g of tetrahydrofuran were added to this mixed solution.
After thoroughly degassing the mixed solution of under a nitrogen stream, add it,
The reaction was continued for 8 hours. After the mixture was heated to 0 ° C., 10 ml of methanol was added and the mixture was reacted for 30 minutes to terminate the polymerization and deprotect the silyl ester. The resulting polymer solution was heated to a temperature of 30 ° C. under stirring, and
3 ml of 0% hydrogen chloride ethanol solution was added and stirred for 1 hour. Then, the solvent was distilled off from the reaction mixture under reduced pressure until the total amount was halved, followed by reprecipitation 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.
It was g.

[0127]

[Chemical 47]

Synthesis Example of Resin [P ₁ ] 103: 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 under a nitrogen stream is 30 ° C.
And This was irradiated with 300 W-xenon lamp light from a distance of 25 cm through a glass filter and reacted for 20 hours. The following monomer [M-
2] 25 g was added, and after similarly irradiating with light for 12 hours, 3 g of methanol was added to this reaction mixture and stirred for 30 minutes to stop the reaction. Next, 50 g of a 5 wt% tetrahydrofuran solution of p-toluenesulfonic acid was added to the reaction mixture for hydrolysis. Next, it was re-precipitated in 2 liters of methanol and the precipitate was collected and dried. Obtained resin [P
-103] had a yield of 70 g and Mw of 7 × 10 ⁴ .

[0129]

[Chemical 48]

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
The mixture was sealed in a container under a nitrogen stream and heated to a temperature of 50 ° C. This was irradiated with light from a high-pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 6 hours for photopolymerization. This was dissolved in 100 g of tetrahydrofuran, 40 g of the monomer (M-3) having the following structure was further added, the atmosphere was replaced with nitrogen, and light irradiation was again performed for 10 hours. The obtained reaction product was reprecipitated in 1 liter of methanol, collected, and dried. The obtained polymer [P-104] had a yield of 73 g and Mw of 8 ×.
It was 10 ⁴ .

[0131]

[Chemical 49]

Synthesis Example of Resin [P ₁ ] 105: 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,
The temperature was raised to 50 ° C. This was irradiated with light from a high pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 6 hours for 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 and the atmosphere was replaced with nitrogen, and light was again irradiated 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 .

[0133]

[Chemical 50]

Synthesis Examples 106 to 114 of Resin [P ₁ ]: The following copolymers were synthesized in the same manner as in Synthesis Example 105. Obtained Resin [P-106] to [P-114]
Had an Mw of 6 × 10 ⁴ to 8 × 10 ⁴ .

[0135]

[Chemical 51]

[0136]

[Chemical 52]

[0137]

[Chemical 53]

[0138]

[Chemical 54]

[0139]

[Chemical 55]

Synthesis Example 115 of Resin [P ₁ ]: Synthesis Example 10 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 No. ⁴ , resin with Mw 8.3 × 10 ⁴ [P-
115] was obtained.

[0141]

[Chemical 56]

Synthesis Example 116 of Resin [P ₁ ]: Mw 9.3 by the same method as Synthesis Example 105 except that 12 g of an initiator [I-3] having the following structure was used instead of benzylisopropylxanthate. A resin [P-116] of × 10 ⁴ was obtained.

[0143]

[Chemical 57]

Synthesis Examples 117 to 125 of Resin [P ₁ ]: Benzyl-N, N-diethyldithiocarbamate was replaced by 14 g of an initiator [I-4] having the following structure, and the composition shown in Table 2 below was used. Other than using each monomer corresponding to the unit,
By the same method as in Synthesis Example 104, Mw 7 × 10 ^{4 to} 9
Resins [P-117] to [P-125] of × 10 ⁴ were obtained.

[0145]

[Chemical 58]

[0146]

[Table 2]

[0147]

[Table 3]

[0148]

[Table 4]

Synthesis Examples 126 to 134 of Resin [P ₁ ]: Instead of the initiator [I-3], compounds [I-
5] A resin having a Mw of 8 × 10 ⁴ to 10 × 10 ^{4 was} prepared by the same method as in Synthesis Example 116 except that 9.6 g was used and each of the monomers corresponding to the constitutional units shown in Table 3 below was used. P-12
6] to [P-134] were obtained.

[0150]

[Chemical 59]

[0151]

[Table 5]

[0152]

[Table 6]

[0153]

[Table 7]

[0154]

[Table 8]

Synthesis Examples 135 to 138 of Resin [P ₁ ]: 40 g of a monomer corresponding to the constitutional unit shown in Table 4 below, 11 g of a compound [I-6] having the following structure and 40 tetrahydrofuran.
The mixture of g was sealed in a container under a nitrogen stream and heated to a temperature of 50 ° C. This was subjected to photopolymerization by irradiating it with a 400 W high-pressure mercury lamp from a distance of 10 cm through a glass filter for 12 hours. A solution of 23 g of methyl methacrylate, 22 g of methyl acrylate, and 15 g of glycidyl methacrylate in 50% by weight of tetrahydrofuran was added thereto, and the atmosphere was replaced with nitrogen, followed by irradiation with light 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] have Mw
It was 6 × 10 ⁴ to 8 × 10 ⁴ .

[0156]

[Chemical 60]

[0157]

[Table 9]

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

[0159]

[Chemical formula 61]

[0160]

[Chemical formula 62]

Synthesis Examples 202 to 214 of Resin [P ₂ ]:
[P-202] to [P-214] Under the same conditions as in Synthesis Example 201, except that 0.031 mol of the initiator shown in Table 5 below was used instead of 17.5 g of the initiator [I-7]. Operated. The obtained resins [P-202] to [P-202]
-214] has a yield of 70 to 80 g and Mw of ⁴ × 10 ^{4 to} 6
It was × 10 ⁴ .

[0162]

[Table 10]

[0163]

[Table 11]

[0164]

[Table 12]

[0165]

[Table 13]

[0166]

[Table 14]

Synthesis Examples 215 to 233 of Resin [P ₂ ]:
[P-215] to [P-233] Synthesis Example 20 except that 60 g of each monomer corresponding to the constitutional unit shown in Table 6 below was used instead of 60 g of the monomer (M-5).
Operate in the same manner as in No. 1 to make each resin [P-215] to [P-2]
33] was obtained. Mw of each resin is 6 × 10 ^{4 to} 7 × 10 ⁴
Was in the range.

[0168]

[Table 15]

[0169]

[Table 16]

[0170]

[Table 17]

[0171]

[Table 18]

[0172]

[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 constitutional unit of the following Table-7, each monomer 3 corresponding to the constitutional unit Y of the following Table-7
80 g of a polymer having Mw of 6 × 10 ^{4 to} 7 × 10 ⁴ was obtained by the same method as in Synthesis Example 201 except that a mixed solution of 0 g, 15 g of the initiator [I-13] and 100 g of tetrahydrofuran was used. Next, 50 g of this polymer, Synthesis example 201
50 g of the monomer [M-5] and tetrahydrofuran 10
A 0 g mixed solution was prepared, and the polymerization reaction was carried out in the same manner as in Resin Synthesis Example 201. However, the reprecipitation solvent was diethyl ether instead of methanol. Obtained resin [P-
234] to [P-240] have Mw of 8 × 10 ⁴ to 10 ×.
It was in the range of 10 ⁴ .

[0174]

[Table 20]

[0175]

[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].
Resins [P-241] to [P-2] represented by the following formulas were 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. The Mw of the obtained resin is 7 × 10 ⁴ to
The range was 9 × 10 ⁴ .

[0177]

[Chemical formula 63]

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

[0179]

[Chemical 64]

[0180]

[Chemical 65]

[0181]

[Chemical formula 66]

[0182]

[Chemical formula 67]

[0183]

[Chemical 68]

Synthesis Example 301 of Resin [P ₃ ]: [P-30
1] 60 g of methyl methacrylate, 30 g of macromonomer [M-6] having the following structure, 10 of glycidyl methacrylate
g, and a mixed solution of 150 g of toluene were heated to 70 ° C. under a nitrogen stream. 1.0 g of 2,2'-azobisisobutyronitrile (abbreviation: AIBN) was added and reacted for 4 hours, and 0.5 g of AIBN was further added and reacted for 4 hours. The obtained resin [P-301] has Mw (weight average molecular weight) of 6.5 × 1.
It was 0 ⁴ .

[0185]

[Chemical 69]

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 corresponding to the constitutional unit shown in Table 8 below was used instead of 30 g of macromonomer [M-6]. Others are Synthesis Example 3
In the same manner as in 01, each of the resins [P-302] to [P-302]
-314] was synthesized. The Mw of the obtained resin is 5 × 10.
It was in the range of ⁴ to 8 × 10 ⁴ . The Mw of the macromonomer used is shown in Table 8 below.

[0187]

[Table 22]

[0188]

[Table 23]

[0189]

[Table 24]

[0190]

[Table 25]

Synthesis Examples 315 to 325 of Resin [P ₃ ]:
[P-315] to [P-325] Monomers corresponding to the constitutional units shown in Table 9 below, macromonomer FM-0721 having a polysiloxane structure (Chisso Corporation)
A mixed solution of 25 g of Mw1 × 10 ⁴ ) and 200 g of toluene was heated to a temperature of 80 ° C. under a nitrogen stream. afterwards,
2,2'-azobisisobutyronitrile (abbreviation: AIB
N) 1.0 g was added and reacted for 4 hours, and AIBN 0.5 g was further added and reacted for 4 hours.

[0192]

[Table 26]

[0193]

[Table 27]

[0194]

[Table 28]

[0195]

[Table 29]

Resin [P₃] Synthesis Examples 326 to 337:
[P-326] to [P-337] correspond to the following monomer [M-7] and the structure shown in Table 10 below.
Using a mixed solution of macromonomer and 200g of toluene
Otherwise, show in the table by the same method as in Synthesis Example 301.
Resins [P-326] to [P-337] were obtained. Of each resin
Mw is 6 × 10 ^Four~ 8 × 10^FourWas in the range.

[0197]

[Chemical 70]

[0198]

[Table 30]

[0199]

[Table 31]

[0200]

[Table 32]

[0201]

[Table 33]

Synthesis Example 401 of Resin [P ₄ ]: 50 g of monomer [M-8] having the following structure, initiator [I-2] having the following structure
1] A mixed solution of 0.5 g and tetrahydrofuran 50 g was sealed in a container under a nitrogen stream and heated to a temperature of 60 ° C. This was irradiated with light from a high-pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 10 hours for photopolymerization.
To this reaction solution, a mixed solution of 25 g of methyl methacrylate, 15 g of glycidyl methacrylate, 10 g of macromonomer [M-9] having the following structure and 50 g of tetrahydrofuran was added, and then the atmosphere was replaced with nitrogen and light irradiation was carried out for 16 hours again.
The resulting reaction mixture was reprecipitated in 1.0 liter of methanol, collected and dried. Obtained resin [P-401]
Had a Mw of 6 × 10 ⁴ at 68 g.

[0203]

[Chemical 71]

[0204]

[Chemical 72]

Synthesis Example 402 of Resin [P ₄ ]: 36 g of the monomer [M-10] having the following structure, siloxane macromonomer Praxel FM-725 (Mw 1 × 1 manufactured by Nissin Corporation)
0 ⁴ ) 4 g, a mixed solution of 1.0 g of the initiator [I-22] having the following structure and 50 g of tetrahydrofuran was sealed in a container under a nitrogen stream and heated to 50 ° C. In addition to this, Synthesis Example 4
Under the same light irradiation conditions as 01, light irradiation was carried out for 12 hours for photopolymerization. To this polymer solution, 24 g of methyl methacrylate,
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 carried out again for 10 hours. The resulting reaction mixture was reprecipitated in 1 liter of methanol, collected and dried. The yield of the obtained resin [P-402] was 7
The Mw was 8 × 10 ⁴ at 0 g.

[0206]

[Chemical formula 73]

[0207]

[Chemical 74]

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
After degassing a mixed solution of g, 2.5 g of an initiator [I-23] having the following structure and 50 g of tetrahydrofuran under a nitrogen stream, photopolymerization was carried out for 12 hours under the same conditions as in Synthesis Example 401. A monomer having the following structure [M-1
2] After adding a mixed solution of 50 g and 60 g of tetrahydrofuran, the atmosphere was replaced with nitrogen, and light was irradiated again for 12 hours to polymerize. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. 72 g of resin [P-403] having an Mw of 5.3 × 10 ⁴ was obtained.

[0209]

[Chemical 75]

[0210]

[Chemical 76]

Synthetic Examples 404 to 416 of Resin [P ₄ ]: The same procedure as in Synthetic Example 402 was repeated except that macromonomers corresponding to the constitutional units shown in Table 11 below were used as macromonomers. 404] to [P-416] were synthesized. The Mw of the obtained resin is 5 × 10 ⁴ to 8 × 10 ^4.
It was in the range of. The Mw of the macromonomer used is shown in Table 11 below.

[0212]

[Table 34]

[0213]

[Table 35] Table 11 (continued) Synthesis Example P Macromonomer M _A portion chemical structure of the macromonomer -X- M _W ───────────────────── _{─────────────── 404 P- 404 M A -4 6.5} × 10 3 405 P- 405 M A -5 8 × 10 3 406 P- 406 M A -6 6 × 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 -11 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 ───────────────────────────── ──────

[0214]

[Chemical 77]

[0215]

[Chemical 78]

[0216]

[Chemical 79]

[0217]

[Chemical 80]

Synthesis Examples 417 to 429 of Resin [P]: By the same method as Synthesis Example 401 of Resin [P], the following Table 1
Each resin of 2 was synthesized. The Mw of the obtained resin is 4 × 10.
It was in the range of ⁴ to 8 × 10 ⁴ . The Mw of the monofunctional macromonomer used was 6 × 10 ³ to 1 × 10 ⁴ .

[0219]

[Table 36]

[0220]

[Table 37]

[0221]

[Table 38]

[0222]

[Table 39]

[0223]

[Chemical 81]

[0224]

[Chemical formula 82]

[0225]

[Chemical 83]

[0226]

[Chemical 84]

[0227]

[Chemical 85]

[0228]

[Chemical 86]

[Synthesis of Resin [Q]] Synthesis Example of Resin (Q ₁ ) 1: 66 g of methyl methacrylate,
A mixed solution of 30 g of methyl acrylate, 4 g of acrylic acid, 28 g of an initiator [I-24] having the following structure, and 150 g of tetrahydrofuran was heated to a temperature of 50 ° C. under a nitrogen stream.

[0230]

[Chemical 87]

[0231] 10 cm of this solution with a 400 W high pressure mercury lamp
Photopolymerization was carried out by irradiating with light from the distance of 10 hours through a glass filter. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to obtain a Mw of 72 g.
8 × 10 ³ of resin (Q-1) was obtained (Mw is the weight average molecular weight by the GPC method in terms of polystyrene).

[0232]

[Chemical 88]

[0233] Synthesis examples of the resin (Q ₁₎ 2: Synthesis Example 1 of Resin (Q _1), instead of the initiator [I-24] 28 g,
Except for using 36.3 g of the initiator [I-25] having the following structure,
By the same method as in Synthesis Example 1 of resin (Q ₁ ), resin (Q-
2) was synthesized. The yield of the obtained resin (Q-2) is 75.
The Mw was 7.5 × 10 ³ in g.

[0234]

[Chemical 89]

[0235]

[Chemical 90]

Synthesis Examples 3 to 9 of Resin (Q ₁ ): 95 g of 2-chlorophenyl methacrylate, 5 g of methacrylic acid, 0.10 mol of the initiator shown in Table 13 below, and tetrahydrofuran 1
Synthesis Example 1 of resin (Q ₁ ) except that a mixed solution of 00 g was used.
Resins (Q-3) to (Q-9) were obtained by the same method as. The Mw of each resin obtained was in the range of 6 × 10 ³ to 8 × 10 ³ .

[0237]

[Table 40]

[0238]

[Table 41]

[0239]

[Table 42]

Synthesis Examples 10 to 25 of Resin (Q ₁ ): Resin (Q
Synthesis example 1 of ₁ ) except that each monomer corresponding to the constitutional unit shown in Table 14 was used in place of methyl methacrylate, methyl acrylate, and acrylic acid in Synthesis Example _{1 of 1} ) Resin (Q-10) by the same method as 1
~ (Q-25) were synthesized. Mw of each resin obtained is 6
It was in the range of × 10 ^{3 to} 9 × 10 ³ .

[0241]

[Table 43]

[0242]

[Table 44]

[0243]

[Table 45]

Synthesis Examples 26 to 30 of Resin (Q ₁ ): 33.9 g of the above-mentioned initiator [I-25] and a mixture of monomers corresponding to the respective constitutional units shown in Table 15 below were mixed with a nitrogen stream. under,
The temperature was raised to 40 ° C. This was irradiated with light and polymerized by the same method as in Synthesis Example 1. Take out the solids,
After dissolving in 250 ml of tetrahydrofuran, methanol
The precipitate was reprecipitated in 1.5 liters, and the precipitate was collected by filtration and dried. The yield of the obtained resins (Q-26) to (Q-30) was 60.
˜75 g, Mw ranged from 6 × 10 ³ to 8 × 10 ³ .

[0245]

[Table 46]

[0246]

[Table 47]

Synthesis Example 31 of Resin (Q ₂ ): A mixture of 47.5 g of benzyl methacrylate, 24.8 g of the following initiator [I-27] and 70 g of tetrahydrofuran was heated to a temperature of 40 ° C. under a nitrogen stream. This solution was passed through a glass filter from a distance of 10 cm with a high pressure mercury lamp of 400 W for 10
Photopolymerization was carried out by irradiation with light for an hour.

[0248]

[Chemical Formula 91]

Then, methacrylic acid 2.
A mixed solution of 5 g and 5 g of tetrahydrofuran was added, and light irradiation was further carried out for 10 hours at a temperature of 40 ° C. under a nitrogen stream in the same manner as above. The obtained polymer was mixed with water / methanol (2
The precipitate was collected by reprecipitation in 800 ml of the mixed solution of (1/1) and dried. The yield of the obtained resin (Q-31) is 38.
Mw was 8.5 × 10 ³ in g.

[0250]

[Chemical Formula 92]

Synthesis Examples 32 to 40 of Resin (Q ₂ ): In place of 47.5 g of benzyl methacrylate and 2.5 g of methacrylic acid, each monomer corresponding to the constitutional unit shown in Table 16 below was used. In the same manner as in Synthesis Example 31 of Resin (Q ₂ ), Resins (Q-32) to (Q-40) were synthesized.
The Mw of each resin obtained was in the range of 7 × 10 ³ to 1 × 10 ⁴ .

[0252]

[Table 48]

[0253]

[Table 49]

[0254]

[Table 50]

Synthesis Examples 41-46 of Resin (Q ₂ ): A mixed solution of 40 g of 2-chlorophenyl methacrylate, 0.02 mol of an initiator shown in Table 17 below and 50 g of tetrahydrofuran was added to a temperature of 40 ° C. under a nitrogen stream. Warmed. This solution was irradiated with light by the same method as in Example 31 for 8 hours. Next, to this reaction product, benzyl methacrylate 7.
5 g, methacrylic acid 2.5 g and tetrahydrofuran 10
After adding g of the mixed solution, light irradiation was performed for 10 hours by the same method as in Synthesis Example 31. The obtained polymer is water /
Reprecipitation in 800 ml of a mixed solution of methanol (2/1),
The precipitate was collected and dried. Obtained resin (Q-41)
The Mw of (Q-46) was in the range of 5 × 10 ^{3 to} 9 × 10 ³ .

[0256]

[Table 51]

[0257]

[Table 52]

Synthesis Examples 47 to 55 of Resin (Q ₂ ): 52.5 g of methyl methacrylate, 17.5 g of methyl acrylate,
A mixed solution of 44 g of the above-mentioned initiator [I-25] and 75 g of tetrahydrofuran was irradiated with light at a temperature of 50 ° C. for 15 hours under a nitrogen stream in the same manner as in Synthesis Example 31 of Resin (Q ₂ ). To this polymer were added each monomer corresponding to the constitutional unit in Table 18 below and 25 g of tetrahydrofuran,
Again, light irradiation was performed for 15 hours by the same method as above.
The Mw of the obtained resins (Q-47) to (Q-55) is 5 ×.
It was in the range of 10 ³ to 8 × 10 ³ .

[0259]

[Table 53]

[0260]

[Table 54]

[0261]

[Table 55]

Synthesis Examples 56 to 61 of Resin (Q ₂ ): Table-
A resin was prepared in the same manner as in Synthesis Example 31 of Resin (Q ₂ ) except that each monomer corresponding to the constitutional unit described in 19 and 0.03 mol of an initiator [I-28] having the following structure were used. (Q-5
6) to (Q-61) were synthesized. Mw of each resin obtained
Was in the range of 4 × 10 ^{3 to} 9 × 10 ³ .

[0263]

[Chemical formula 93]

[0264]

[Table 56]

[0265]

[Table 57]

Example 1 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 1.
5 g, resin [R-1] of the following structure 8.5 g, resin [Q-1
0] 1.5 g, the resin [P-104] of the present invention 0.3 g, the compound [A] of the following structure 0.15 g and tetrahydrofuran 8
Put 0g of the mixture into a 500ml glass container with glass beads and paint shaker (Toyo Seiki Seisakusho)
Dispersion for 60 minutes, and 0.04 g of phthalic anhydride and o
-After adding 0.001 g of chlorophenol and dispersing for 2 minutes, the glass beads were filtered to obtain a photoconductive layer dispersion liquid. This dispersion was then subjected to conductivity treatment and solvent resistance treatment.
It is coated with a wire bar on a 0.2 mm thick master plate for base material, dried by touching with a finger, and then in a 110 ° C circulating oven for 2 minutes.
It was dried for 0 seconds. Furthermore, it heated at 140 degreeC for 1 hour. The film thickness of the obtained photoconductive layer was 10 μm.

[0267]

[Chemical 94]

Further, the following thermoplastic resin solution was prepared in order to form a transfer layer on the photoconductive layer. Poly (vinyl acetate / crotonic acid) (95/5, Mw5 × 10 ⁴ ) ··· 3g ammonia (28% aqueous solution) ··· 1g ethanol ··· 97g This solution should have a thickness of 1.3μm with a wire bar. It was applied and oven dried at 120 ° C. for 20 seconds. Comparative Example A1 An electrophotographic color proofing original plate was prepared in the same manner as in Example 1 except that 0.3 g of the random copolymer having the following structure was used instead of 0.3 g of the resin [P-104]. .

[0269]

[Chemical 95]

Comparative Example B1 In Example 1, instead of 8.5 g of the resin [R-1] and 1.5 g of the resin [Q-10], only the resin [R-1] was 1 g.
An electrophotographic color proofing original plate was prepared in the same manner as in Example 1 except that 0 g was used. Test Example The electrostatic characteristics, transferability and image reproducibility of the electrophotographic color proof original plates prepared in Example 1, Comparative Example A1 and Comparative Example B1 were examined, and the results are shown in Table 20.

[0271]

Table 58 Table 20 ─────────────────────────────────── Example 1 Comparative Example A1 Comparative Example B1 ─────────────────────────────────── Electrostatic characteristics Note 1) V ₁₀ (-V) ｜ (20 ℃, 65% RH) 580 570 560 ─────────────────────────────‖ (30 ℃, 80% RH) 555 550 515 ────────────────────────────────── DRR (%) ｜ (20 ℃, 65% RH) 86 85 81 ───────────────────────────── ‖ (30 ℃, 80% RH) 81 80 71 ───────── _{^{───────────────────────── E 1/10 | (20}} ℃, 65% RH) 15 17 23 (erg / cm 2) ─── ────────────────────────── ‖ (30 ℃, 80% RH) 17 20 28 ────── ────────────────────────────── Transferability Note 2) ○ × ○ Very good Uneven transfer Very good Remarkably ─── ──────────────────────────────── Image reproducibility Note 3) ○ × × ○ ｜ (20 ° C, 65% RH ) Good Remarkable image unevenness Good ─────────────────────────────‖ (30 ℃, 80% RH) ○ × × × ~ △ Good Image unevenness Low density, remarkable thin lines and fine characters missing ────────────────────────────────────

The evaluation items shown in Table 20 were tested by the following methods. Note 1) Electrostatic characteristics: In a dark room at a temperature of 20 ° C. and 65% RH, a paper analyzer (Paper Analyzer-SP-428 type manufactured by Kawaguchi Electric Co., Ltd.) was used for each color calibration original plate at −6 kV.
After corona discharge for 2 seconds, the surface potential V ₁₀ at this time was measured after leaving for 10 seconds. Then, the potential V ₁₃₀ after standing for 120 seconds in the dark was measured, and the potential retention after dark decay for 120 seconds, that is, the dark decay retention rate [DRR
(%)] To DRR (%) = (V ₁₃₀ / V ₁₀ ) × 100
It was calculated by the formula (%). 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 gives a surface potential (V ₁₀ ) of 1
Calculate the time until it attenuates to / 2,
Calculate _1/2 (erg / cm ² ). Also, temperature 30 ℃, 80% R
Under the environmental conditions of H, the same operation as above was carried out to examine each characteristic. The environmental conditions (20 ° C., 65% RH) were condition I, and (30 ° C., 80% RH) were condition II. Note 2) Transferability The sample on which the transfer layer was formed and the coated paper were overlapped and passed between a pair of heating rollers in which an infrared lamp heater was incorporated inside a hollow metal roller coated with silicone rubber. At this time, the roller surface temperature was set to 120 ° C. both above and below, the nip pressure between the rollers was set to 5 kgf / cm ² , and the conveyance speed was set to 5 mm / sec. After passing, the sample and the coated paper were separated after cooling to room temperature while overlapping the coated paper. At this time, the state of the transfer layer transferred to the coated paper side was visually evaluated. Note 3) Image reproducibility Under each environmental condition (I) and (II),
A copied image was actually formed, and the image reproducibility of the color proof plate after transfer was evaluated.

Each color proofing original plate was corona charged to +450 V in a dark place, then read from a document with a color scanner in advance, color-separated, and some system-specific corrections related to color reproduction were performed. Was stored in the hard disk in the system as
Based on the information about yellow among the colors of yellow, magenta, cyan, and black, using a negative mirror image mode, a 5 mW output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm) on the surface of the original plate for color calibration. 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 the signature system (Eastman Kodak (manufactured)) is diluted 75 times (polymerization ratio) with Isopar H (manufactured by Esso Standard Petroleum) and used to have a pair of planographic developing electrodes. By applying a bias voltage of + 400v to the electrode on the side of the original plate for color proofing by the developing device, the reversal development was carried out so that the toner was electrodeposited on the exposed portion, and then rinsed in a bath of Isopar H alone to wash the non-image portion. I removed the dirt. The above process was repeated for each color of magenta, cyan and black. The image of the original plate for color proof 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, and the original plate for color proofing after four-color development are overlaid, and a pair of rubber rollers whose surface temperature is constantly controlled to 120 ° C are in contact with each other under a pressure of 15 kgf / cm ^2. It was passed at a speed of 10 mm / sec.
Then, the coated paper and the original plate for color proofing were peeled off after being cooled to room temperature while being piled up, and the image (fog, image quality of the image) formed on the obtained coated paper was visually evaluated. Table 20
As shown in FIG. 7, the electrostatic characteristics of Example 1 (the present invention) and Comparative Example A1 showed good results even when the environmental conditions changed.

However, Comparative Example B1 using only the conventional resin as the binder resin for the photoconductive layer resulted in a decrease in electrostatic characteristics (particularly, dark charge retention ratio: DRR and photosensitivity: E
_1/2 ), and the resulting color proof copy image was also unsatisfactory. In the original plate for color proofing of the present invention, such a difference is that the resin [Q] is sufficiently adsorbed to the photoconductive compound, and the photoconductive compound can be uniformly dispersed.
It is presumed that this is because the compound [A], which is a chemical sensitizer, and the photoconductive compound are allowed to interact with each other sufficiently and uniformly. Further, the resin of the present invention [P]
The transfer layers of Example 1 and Comparative Example B1 using No. 1 were completely transferred to the transfer target material, but in Comparative Example A1 using the conventional resin, peeling of the coated paper and the color proofing original plate was not good. However, the transfer layer or the photoconductive layer was damaged. The difference is that in the color proofing original plates of the present invention and Comparative Example B1,
The resin [P], which is a fluorine atom-containing copolymer coexisted in the photoconductive layer, is concentrated and transferred to the surface portion when the photoconductive layer is formed,
Further, the resin [R] and the resin [P] are sufficiently chemically bonded to each other between the polymers by a cross-linking agent to form a cured film, which clearly forms an interface with good releasability. It is considered that such a clear interface is unlikely to be formed in the color proofing original plate of Comparative Example A1 using the random copolymer of No. 1. Further, the color proofing original plate of the present invention was able to provide a good color proofing image of a color image even if environmental conditions changed, but the color proofing original plate of Comparative Example A1 had insufficient transferability. No satisfactory image could be provided, and the color proofing original plate of Comparative Example B1 remarkably deteriorated in image reproducibility under high humidity. Further, in order to investigate the peeling property of the photoconductive layer formed in Example 1 and Comparative Example A1, the adhesive force on the surface of the photoconductive layer was measured before forming the transfer layer. The adhesive strength was measured by the aforementioned JIS Z0237-1980 “Adhesive tape / sheet test method”. The photoconductive layer formed in Example 1 had an adhesive force of 6 g · f, and the photoconductive layer formed in Comparative Example A1 had an adhesive force of 330 g · f. As described above, only the original plate for color proofing 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, a dye [D-1] having the following structure: 0.018 g, N
-Hydroxysuccinimide 0.20 g and toluene 30
0 g of the mixture was homogenized (manufactured by Nippon Seiki Co., Ltd.)
The mixture was placed in a flask and dispersed at a rotation speed of 9 × 10 ³ rpm for 10 minutes. To this dispersion, 1 g of propylene glycol and 0.02 g of tetrabutoxy titanate were added, and the rotation speed was 1 × 10 ³
Dispersed at r pm for 1 minute. Then, this dispersion liquid is applied with a wire bar onto a 0.2 mm-thick base paper for a master for a printing plate which has been subjected to a conductive treatment and a solvent resistance treatment, and after being touch-dried,
Heated in a circulating oven at 90 ° C. for 1 hour. The film thickness of the obtained photoconductive layer was 15 μm.

[0276]

[Chemical 96]

Further, in order to form a transfer layer on this photoconductive layer, the same thermoplastic resin solution as in Example 1 was prepared, coated and dried. Comparative Example C1 An original plate for color proofing 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 Each color proofing original plate was evaluated for smoothness, electrostatic properties, transferability and image reproducibility, and the results are shown in Table 21.

[0278]

Table 59 Table 21 ────────────────────────────────── Example 2 Comparative Example C1 ──── ────────────────────────────── Smoothness of photoconductive layer surface Note 1) 1100 1050 ──────── ────────────────────────── Electrostatic characteristics V ₁₀ (-V) I 730 550 ───────────── ────────────── II 710 505 ─────────────────────────────── DRR ( %) I 88 72 ────────────────────────── II 85 48 ──────────────── _{^{─────────────── E 1/10 I 12 30}} (erg / cm 2) ────────────────────── ──── II 15 33 ───────────────────── ───────────── Transferability ○ ○ Very good Very good ─────────────────────────── ─────── Image reproducibility Note 2) ○ △ to ○ I Good Good density is slightly low. Fine lines, missing fine characters Occurred a little ────────────────────────── II ○ × × Good No density, ground fogging, fine lines , Missing thin characters ───────────────────────────────────

In Table 21, transferability was tested by the method of Table 20 above, and other evaluation items were tested by the following methods. Note 1) Smoothness of photoconductive layer: The smoothness (see / cc) of the obtained original plate for color proofing was measured with a Beck smoothness tester (Kumagaya Riko Co., Ltd.) under the condition of an air capacity of 1 cc. It was measured. Note 2) Image reproducibility After the color calibration original plate was corona charged to -600v in a dark place, the same digital image data as in Example 1 was used, and first, based on the information about yellow, in the positive mirror image mode, Exposure was carried out using a semiconductor laser with light of 780 nm so that the exposure amount on the plate surface would be 25 erg / cm ² . The residual potential of the exposed portion was -120v. Then Versatech 300
0 (Xerox color electrostatic plotter) yellow toner diluted with 50 times Isopar H (made by Esso Standard Petroleum) was used, and a color proofing plate side electrode was used with a developing device having a pair of flat plate developing electrodes. A bias voltage of 200 v was applied to perform positive development so that the toner was electrodeposited on the unexposed area, and then rinsed in a bath of Isopar H alone to remove stains on the non-image area. The above process was repeated for each color of magenta, cyan and black. Next, the coated paper, which is the actual printing paper, is overlaid with the original plate for color proofing after four-color development, and the surface temperature in contact with a pressure of 10 kgf / cm ² is maintained between 120 ° C and a pair of rubber rollers. , At a speed of 6 mm / sec. Then, the coated paper and the original plate for color proofing were peeled off after being cooled to room temperature while being piled up, and the image as a color proof was visually evaluated. As shown in Table 21, the color proofing original plate of Example 2 was
The electrostatic characteristics are extremely good, and even if the environmental conditions change,
The changes in these characteristics were suppressed to a small level, and even when the image pickup property 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 original plate for color proof of Comparative Example C1 had remarkably deteriorated electrostatic properties particularly under high humidity conditions, and the actual image reproducibility was not practical. That is, the background fog in the non-image area, the decrease in image density, and the lack of fine lines became remarkable. The transferability of the transfer layer is good, and not only in the photoconductive layer made of an organic photoconductive compound, but also in the photoconductive layer containing an inorganic photoconductive compound, the release property can be improved by the resin [P]. It became clear. Further, in order to investigate the peeling property of the photoconductive layer formed in Example 2 and Comparative Example C1, the adhesive force on the surface of the photoconductive layer was measured before forming the transfer layer. The adhesive strength was measured by the aforementioned JIS Z0237-1980 “Adhesive tape / sheet test method”. The adhesive force of the photoconductive layer formed in Example 2 was 8 g · f, and the adhesive force of the photoconductive layer formed in Comparative Example C1 was 400 g · f or more. As described above, only the color proofing original plate of Example 2 showed 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 was used.
g, resin [Q-32] 1 g, resin [R-3] having the following structure
3 g, resin [P-119] of the present invention 0.8 g, dye (D-2) 40 mg of the following structural formula, anilide compound (B) 0.2 g of the following structural formula as a chemical sensitizer, and methylene chloride 30 ml. It was dissolved in a mixture with 30 ml of ethylene chloride to obtain a photoconductive layer solution. This photoconductive layer solution was applied to a conductive transparent support (100 μm) using a wire round rod.
m polyethylene terephthalate support on which a vapor deposited film of indium oxide is provided. It was coated on a surface resistance of 10 ³ Ω) to form a photoconductive layer of about 4 μm.

[0281]

[Chemical 97]

In order to confirm the uneven distribution of the resin [P] of the present invention on the surface of the photoconductive layer, the adhesive force with an adhesive tape was measured. The resin [P-119] was not added and the same amount was used instead. Except that the resin [R-3] of No. 1 was used, and the adhesive strength of the color proofing original plate produced by the same method as in Example 3 was 7%.
It was found that it was reduced to 1/0. Further, in order to form a transfer layer on this photoconductive layer, the same thermoplastic resin solution as in Example 1 was prepared, applied and dried. When the adhesive tape was attached to the surface of the transfer layer and peeled off, as in Example 1, only the transfer layer was easily peeled off without feeling resistance. Next, the image pick-up property and the transfer property of this color proof plate were examined in the dark by the same method as in Example 1. However, helium-neon laser light having an oscillation wavelength of 630 nm was used in place 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 without background fog, and the image strength was sufficiently high.

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

[0284]

[Chemical 98]

Next, the hydrazone compound 20 of the following structural formula
g, polycarbonate resin (manufactured by GE Corporation, trade name Lexan 121) 20 g, resin [P-102] 2 g, isophorone diisocyanate 0.04 g, tetrabutoxy titanate
A mixed solution of 0.001 g and 160 g of tetrahydrofuran was applied on the charge generation 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 transport layer of about 18 μm. A master plate for color proofing having a photoconductive layer composed of two layers was obtained.

[0286]

[Chemical 99]

Further, in order to form a transfer layer on the photoconductive layer, the same thermoplastic resin solution as in Example 1 was prepared, coated and dried. When the adhesive tape was attached to the surface of the transfer layer and peeled off, as in Example 1, only the transfer layer was easily peeled off without feeling resistance. Next, this original plate for color proofing was operated in a dark place in the same manner as in Example 1, and the image pickup property and the transfer property were examined. However, 780 nm used in Example 1
Instead of the semiconductor laser light having the oscillation wavelength, helium-neon laser light having the oscillation wavelength of 630 nm was used. The obtained color copied image of the coated paper after transfer was clear without background fog and the image strength was sufficiently high. Examples 5 to 7 In Example 1, resin [P-104] 0.3 g was used. Instead of using 0.3 g of each resin [P] shown in Table 22 below,
In the same manner as in Example 1, electrophotographic color proofing original plates were produced. The electrostatic characteristics, transferability and image reproducibility of each of the original plates thus obtained were evaluated in the same manner as in Example 1, and the results are shown in Table 22.

[0288]

Table 60 Table 22 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 5 Example 6 Example 6 Example 7 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ The resin of the present invention [P] [P-209] [P- 308] [P-421] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Electrostatic characteristics 580 575 585 V ₁₀ (−V) I ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ II 565 560 570 ━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━ D. R. R (%) I 87 86 86 86 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ II 84 84 83 ━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ E _1/10 I 16 15 17 (evg / cm ² ) ━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━ II 17 17 19 19 ━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━ Transferability ○ ○ ○ Very good Very good Very good ━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━ Image reproducibility I ○ ○ ○ Good ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ II ○ ○ ○ Good Good Good ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ As shown in Table 22, Any of the color correction precursor 施例 5-7, electrostatic properties, transfer properties, and showed good performance equivalent to that in Example 1 for image reproducibility. Further, the adhesive force of the photoconductive layer of the color proofing plates of Examples 5 to 7 was 5 to 8 g in all cases.
-It is the range of f, and this shows that the releasability is extremely good. On the other hand, a color proofing original plate 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 as a comparative example. Caused a transfer failure, and uniform peeling at the interface between the photoconductive layer and the transfer layer was not obtained. Furthermore, 1.5 g of resin [Q-10] produced as a comparison and resin [R-1]
Example except that 10 g only of the resin [R-1] was used instead of 8.5 g and the resin [P] of Examples 5 to 7 was used instead of 0.3 g of the resin [P-104]. In the original plate for color proofing manufactured by the same method as 1), when the environmental conditions fluctuate, the electrostatic characteristics are deteriorated especially under the conditions of high temperature and high humidity, and the actual image reproducibility cannot be put to practical use. It was That is,
There was a decrease in density and loss of fine lines and letters. From the above test examples, it was found that the original plate for color proofing of the present invention can provide a very good color proof. Examples 8 to 27 By the same method as in Example 1 except that 1.5 g of each resin [Q] shown in Table 23 below was used in place of 1.5 g of the resin [Q-10] in Example 1, each color was obtained. An original plate for calibration was manufactured.

[0289]

[Table 61] Table 23 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example Resin [Q] Example Resin [Q] ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 8 Q-1 18 Q-26 9 Q-4 19 Q-28 10 Q-6 20 Q -30 11 Q-9 21 Q-39 12 Q-11 22 Q-41 13 Q-13 23 Q-42 14 Q-14 24 Q-48 15 Q-16 25 Q-53 16 Q-20 26 Q-60 17 Q-23 27 Q-58 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ In the dark,
It investigated by the method similar to Example 1. The color copy image of the coated paper after transfer is clear without background fog.
Moreover, the image intensity was sufficiently high. Examples 28 to 50 In Example 1, instead of the binder resin [Q-10] 1.5 g, the resin [P-104] 0.3 g and the crosslinking compound, each resin [Q] 1. Each electrophotographic color proofing original plate was produced in the same manner as in Example 1 except that 5 g, resin [P] 0.3 g and a predetermined amount of the crosslinking compound were used.

[0290]

[Table 62] Table 24 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example Resin [Q] Resin [P ] Crosslinking compound ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 28 Q-2 P-202 Gluconic anhydride 0.15 g o-cresol 0.01 g 29 Q-5 P-301 〃 30 Q-7 P-214 ethylene glycol 0.03 g diglycidyl ether zinc stearate 0.001 g 31 Q-12 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 0.002 g 35 Q-27 P-421 Phthalic anhydride 0.2 g o-chlorophenol 0.001 g 36 Q-29 P- 10 3-Aminopropyl trimethoxysilane 0.1 g 37 Q-34 P-321 〃 〃 38 Q-36 P-417 〃 〃 39 Q-43 P-212 Propylene glycol 0.8 g Tetrabutoxy titanate 0.001 g 40 Q- 44 P-323 〃 〃 41 Q-49 P-213 trimethylolpropane 1.0 g Dibutoxy dilaurate 0.001 g Tin salt 42 Q-52 P-125 〃 43 Q-50 P-215 Phthalic anhydride 0.3 g Acetylacetone Co 0.001 g Baltic salt 44 Q-55 P-329 〃 〃 45 Q-53 P-421 〃 〃 46 Q-54 P-322 Propylene glycol 0.055 g Diglycidyl ether o-chlorophenol 0.002 g 47 Q-58 P-222 ROOCNH (CH ₂ ) ₆ NHCOOR 0.2 g tetrapropoxy titanate 0.00 1 g 48 Q-59 P-122 〃 〃 49 Q-61 P-335 γ-glycidpropyl trimethoxysilane 0.1 g 50 Q-32 P-118 〃 〃 ━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━ In the formula, R represents an m-methylphenyl group. The image pick-up property and transfer property of the obtained master plate for color proof were examined in a dark place by the same method as in Example 1. The color copied image of the coated paper after transfer was clear without background fog and the image strength was sufficiently high. Examples 51 to 58 In Example 1, the resin [Q] 2 shown in Table 25 below was used.
An original plate for color proofing was produced in the same manner as in Example 1 except that g, resin [R] 9 g, resin [P] 0.3 g and a crosslinking compound were used.

[0291]

[Table 63] Table 25 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example Examples Trees Fats Trees Fats Trees Fats Racks Bridge compound [Q] [R] [P] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 51 Q-8 R-4 P-429 Benzoyl Peroxy 0.008 g Side 52 Q-19 R-5 P-116 1,4-Butanedio 0.3 g Dibutilauric acid dibut 0.001 g Xisutin 53 Q-28 R-6 P-428 ethylene glycol 2.0 g dimethacrylate 2,2'-azobis 0.03 g (isovaleronitril) 54 Q-21 R-6 P-325 〃 〃 55 Q-33 R-7 P-129 divinyl adipate 2. 2 g 2,2'-azobis 0.01 g (isovaleronitrilyl) 56 Q-37 R-7 P- 36 〃 57 -40 R-8 P-422 Block Isocyanate 3 g Nato Aditol VXL 81 (manufactured by Hoechst) Butyl titanate 0.02 g Dimer 58 Q-45 R-8 P-126 〃 〃 ━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ In the table, resins R-4 to R-8 are represented by the following formulas. .

[0292]

[Chemical 100]

A color proof was prepared by using the original plate for color proof having the transfer layer formed according to the method of Example 1. The obtained color copied image of the color proof had no background stain. It was clear. Examples 59-66 The transfer layer was made of poly (vinyl acetate / crotonic acid) (95/5
An original plate for each color proof was manufactured in the same manner as in Example 1 except that the resins and coating solvents shown in Table 26 below were used instead of the (weight ratio).

[0294]

[Table 64] Table 26 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example Example Thermoplastic plastic resin coating Cloth Solvent ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 59 Cellulose acetate butyrate: cellidor Bsp Ethyl acetate (Bayer AG 60) Polyvinyl butyral resin: S-REC 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% aqueous ammonia (95/5) copolymer and Cellidor Bsp contained at (8/2) weight ratio are used Ethanol solution 64 Methyl methacrylate / methyl acrylate copolymer (6/4) weight ratio Tetrahydrofuran 65 Styrene / Butadiene Copolymer Sorprene 1205 (Asahi Kasei Corp.) Toluene 66 Poly (vinyl acetate) and poly (ethyl methacrylate) in a (6/4) weight ratio Methyl ethyl ketone ━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━ The obtained electrostatic properties, transferability, and image reproducibility of each color calibration original plate were measured by When examined by the same method as in Example 1, all showed the same level of performance as in Example 1.

[Brief description of drawings]

FIG. 1 shows a thermal transfer device.

[Explanation of symbols]

 1 Rubber-coated metal roller 2 Built-in heater 3 Surface temperature detection means 4 Temperature controller

Claims (9)

[Claims] 1. A support, a photoconductive layer, and a transfer layer, comprising:
At least the electrophotographic process formed on the transfer layer.
Also transfers the toner image of one color to the transfer material together with the transfer layer.
Electrophotographic colors for producing color proofs by
An original plate for calibration, wherein the photoconductive layer is a resin
(P₁), (P₂), (P₃) And (P_Four) Selected from the group consisting of
Resin [P], the following resin (Q₁) And (Q₂) From
A resin [Q] selected from the group consisting of, and light and / or heat
Including a resin [R] containing a constitutional unit having a curable group
And the resin [P] is in contact with at least the transfer layer
It exists in the vicinity of the surface and has JIS Z0237-1 of the surface.
Tested by 980 "Adhesive tape / sheet test method"
That the adhesive force is less than 150gram force (gf)
An original plate for electrophotographic color proofing. (1) Resin (P₁): Having a fluorine atom and / or a silicon atom
50 units for the weight of the segment (X)
Light and / or thermosetting with segment (X) containing more than amount%
A cell containing a structural unit containing at least one chemical group.
And a linear block type copolymer containing a pigment (Y). (2) Resin (P₂): Having a fluorine atom and / or a silicon atom
50 units for the weight of the segment (X)
Light and / or thermosetting with segment (X) containing more than amount%
A cell containing a structural unit containing at least one chemical group.
And a linear block type polymer chain containing
Star consisting of at least three bonded through an organic group (Z)
Type copolymer. (3) Resin (P₃): Having a fluorine atom and / or a silicon atom
50 units for the weight of the segment (X)
Light and / or thermosetting with segment (X) containing more than amount%
A cell containing a structural unit containing at least one chemical group.
A graft-type copolymer containing a pigment (Y). (4) Resin (P_Four): Having a fluorine atom and / or a silicon atom
50 units for the weight of the segment (X)
Light and / or thermosetting with segment (X) containing more than amount%
A cell containing a structural unit containing at least one chemical group.
And AB type or ABA type block containing cement (Y)
A polymer and at least one of the segments (X)
Is one of the following graft type segments (X '),
At least one of the
Segment (Y '), or the number of segments (X) is small.
At least one is the following graft type segment (X ')
And at least one of the segments (Y) is
A copolymer which is a graft type segment (Y '). Graft type segment (X '): Weight average molecular weight is 1 x 1
0³~ 2 x 10^FourAnd a fluorine atom and / or silicon
A structural unit having an atom is referred to as a macromonomer part (M _A) Heavy
Macromonomer part containing 50% by weight or more based on the amount
(M_A) Containing segments. Graft type segment (Y '): Weight average molecular weight is 1 x 1
0³~ 2 x 10^FourAnd a fluorine atom and / or silicon
Consisting of structural units that do not contain structural units that contain atoms
Macromonomer part (M_B) Containing segments. (5) Resin (Q₁): 1 x 10³~ 2 x 10^FourWeight average of
Having a molecular weight of formula (I): --CH (a₁) −C (a₂) (COOR₃) − (Where a is₁And a₂Are hydrogen atom, halogen atom,
Represents a cyano group or a hydrocarbon group, R₃Is a hydrocarbon group
Represents the structural unit and -PO₃H₂, -SO₃H, -COOH
 , -PO (OH) (R₁) (Where R₁Is a hydrocarbon group or -OR₂(R₂ 
Represents a hydrocarbon group)) and a cyclic acid anhydride group
Randomly constituting units having polar groups selected from the group
At least 3 polymer chains contained in the organic group (Z)
And a structural unit represented by the above formula I.
Content of resin (Q₁30% by weight or more based on the total weight of
The content of the structural unit having the polar group is the resin (Q₁)
Star type copolymerization of 1 to 20% by weight based on the total weight of
body. (6) Resin (Q₂): 1 x 10³~ 2 x 10^FourWeight average of
A segment having a molecular weight and containing a structural unit represented by the above formula (I)
(M) and -PO₃H₂, -SO₃H, -COOH, -PO (OH) (R₁) (Expression
Medium, R₁Is a hydrocarbon group or -OR₂(R₂ Represents a hydrocarbon group)
Represents a group) and a cyclic acid anhydride group.
A segment (N) containing a structural unit having a polar group, and
Containing at least three linear block-type polymer chains containing
A star-type copolymer formed by bonding via a functional group (Z). 2. The electrophotographic color proofing plate 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 plate 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 plate 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 original plate 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 plate 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 proof original plate 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 original plate 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 original plate according to claim 1, wherein the resin [P] is a resin (P ₄ ) and the resin [Q] is a resin (Q ₂ ).