JPH05197169A - Electrophotographic color proof original - Google Patents

Abstract

PURPOSE:To provide a high-precision, high-quality color proof facilitating the peeling of a transfer layer and a photoconducting layer and having no color drift. CONSTITUTION:An electrophotographic color proof original contains a base, a photoconducting layer, and a transfer layer, and a toner image of at least one color formed by the electrophotographic process on the transfer layer is transferred to a material to transferred together with the transfer layer to manufacture a color proof, the photoconducting layer contains the resin P and/or resin grains L including the structural unit having fluorine atom and/or silicon atom at least near the surface in contact with the transfer layer, and the adhesive strength on the surface tested by JIS Z2037-1980 (adhesive tape/sheet test method) is set to 150 gram force (g.f) or below.

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 mainly 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 film to the surface of the film, exposing the film to light, exposing it to ultraviolet rays and then developing the film to remove the photosensitive layer in the non-image area. 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, and ordering of the orderer for tone reproduction etc. After confirming that there is no difference, and if necessary correcting it, the next step is to proceed to actual printing. This step is called calibration. The former is called in-school and is intended to check each process inside the printing company, as mentioned above. On the other hand, the latter is called an outside school and is a proofreading for obtaining the printing permission from the orderer. The ink, the printing paper, etc. are the same as those in this machine printing, and the printed result is almost the same as this machine printing. here,
Proofing with printing paper used for printing on this machine is called proofing. Regarding color specification and tone reproduction of color photographs, it is necessary to confirm and correct each color,
In particular, the fact that proofreading as an outside school is repeated several times is actually the case. 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 printing durability, which is 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 a printing plate and it is difficult to maintain a certain quality because the operation requires skill.

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, such as operability and repetitive stability. 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 film), chromin (DuPont), match print (3M) and the like. These systems use color separation films, but do not use the above-mentioned proofing machine. 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 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 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, layout, suitability of color separation quality of some patterns, condition of reproducibility of tone, etc. may be performed by the conventional proofing method. Output to film, press proof or off press proof finish must be awaited, which significantly reduces the utilization efficiency of the system. Since the image data in the system can be used as digital information, some direct digital color proof systems that do not rely on conventional proofing methods have been proposed. These details are published in "Printing Information" magazine April 1991 page 2 and subsequent pages. As the method, silver salt method, electrostatic toner method (wet electrophotographic method), ink jet method,
There is 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 main paper, and some of the techniques disclosed in Japanese Patent Laid-Open No. 272469/1990, which can achieve this, have some problems. You need to take steps. Further, there is a proposal in which 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 together with the transfer layer onto a sheet of paper, as disclosed in JP-A-61-174557 (Japanese Patent Publication No. 2-43185). Kaihei 1-112264, JP-A-1-12
-281414 and Japanese Patent Laid-Open No. 11347/1993. Of these, the only one that has been put to practical use is the technique disclosed in Japanese Patent Laid-Open No. 174557/1986, which is exposed from the transparent support (polyethylene terephthalate film) side of the electrophotographic light-sensitive material, and further the conductive layer. Also has to be transparent, and is a one-time disposable, which is disadvantageous in terms of cost. Japanese Patent Application Laid-Open Nos. 1-112264 and 1-281464 describe an image forming method or a color printing method using a photosensitive paper in which a release layer and an adhesive layer are sequentially provided on the surface of a photoconductive layer, and these are developed. The feature is that the toner image together with the release layer is transferred to plain paper later. 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 applies to the method of using a recording medium having a peelable overcoat layer on the photoconductive layer of JP-A-3-11347. The present invention provides an original plate for color proofing using an electrophotographic method, in which the above problems are improved. 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 of manufacturing 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.

Means for Solving the Problems The above-mentioned problems are
An electrophotographic method for producing a color proof by including a photoconductive layer and a transfer layer, and transferring a toner image of at least one color formed on the transfer layer by an electrophotographic process to a material to be transferred together with the transfer layer. An original plate for color proofing, wherein the photoconductive layer contains a resin [P] and / or resin particles [L] containing a structural unit having a fluorine atom and / or a silicon atom at least near the surface in contact with the transfer layer. The adhesive strength of the surface tested by JIS Z0237-1980 "Adhesive tape / sheet test method" is 150 gram · f.
This has been solved by using an electrophotographic color proofing original plate characterized by being less than or equal to g (f). Preferably, the resin [P] and / or the resin particles [L] are
It also contains a structural unit having a light and / or thermosetting group. More preferably, the photoconductive layer contains a light and / or heat curing agent.

The resin [P] may be a random copolymer, but is preferably a block type copolymer, for example, a structural unit containing a fluorine atom and / or a silicon atom.
A block containing a segment (X) containing 0% by weight or more, preferably 80% by weight or more, particularly 90% by weight or more, and a segment (Y) containing no or even 20% by weight or less of the structural unit. Type copolymer (the content of the constituent unit is based on the total weight of the segment (X) or the segment (Y), respectively). In addition, the segment (Y) is preferably a structural unit having a light and / or thermosetting group, and is 1 based on the total weight of the segment (Y).
-60% by weight, more preferably 5-40% by weight. When the resin [P] is a block copolymer, the abundance ratio of the segment (X) and the segment (Y) is 5 to 9
5 / 95-5 (weight ratio), preferably 10-90
/ 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. In the present specification, the term “block-type copolymer” means a copolymer formed by linking two or more segments with a block, such as a linear block-type copolymer, a graft-type copolymer and a star-type copolymer. A polymer is shown. The photoconductive layer of the present invention may be any one as long as the photoconductive compound is dispersed in a binder resin. That is, a so-called monodispersed layer type composed only of a layer in which a photoconductive compound is dispersed, or a so-called laminated type (or function separation type) including at least a charge generation layer and a charge transport layer which are photoconductive compound dispersed layers. ) Any of
Importantly, the surface of the various photoconductive layers in contact with the transfer layer has improved surface characteristics, which allows toner to be transferred onto the transfer layer of an electrophotographic color proofing master using a conventional electrophotographic process. After the image is formed, the toner image together with the transfer layer can be easily and favorably transferred to another substrate.

In the present invention, the binder resin is a resin that forms a matrix in which the photoconductive compound is dispersed, and includes the resin [P] used in the present invention and other binder resins that are present if necessary. . Examples of block copolymers are shown below. (1) A segment (X) containing at least 50% by weight or more of a structural unit containing a fluorine atom and / or a silicon atom, and a segment (Y containing a structural unit containing at least one light and / or thermosetting group. ₁ ) a linear block copolymer (P ₁ ) The copolymer (P ₁ ) may be any conventionally known linear block copolymer, for example AB type (that is,
(X)-(Y ₁ )) block copolymer or its multiblock product, or ABA type (that is, (X)-
_{(Y 1) - (X)} , (Y 1) - (X) - (Y 1)) block copolymers. (2) A segment (X) containing at least 50% by weight or more of a structural unit containing a fluorine atom and / or a silicon atom, and a segment (Y containing a structural unit containing at least one light and / or thermosetting group. ₁₎ and AB-type block polymer chain composed of from at least three, star copolymer attached via an organic group (Z) (P ₂₎ star copolymer (P ₂₎ AB The segment (X) and the segment (Y ₁ ) in the type block polymer chain may be arranged in any order in the polymer chain. That is, the polymer is schematically shown below.

[0001]

[Chemical 1]

(Wherein Z represents an organic group, (A) represents a segment (X), and (B) represents a segment (Y ₁ )). Also, an AB type block bonded to the organic group (Z). The upper limit of the number of polymer chains is usually 15, preferably 10. The weight average molecular weight of the copolymer (P ₂ ) is 5 × 10 5.
^{It is 3} to 1 × 10 ⁶ , preferably 1 × 10 ^{4 to} 5 × 10 ⁵ . Further, the weight average molecular weight of the segment (X) in the copolymer (P ₂ ) is preferably at least 1 × 10 ³ or more. The organic group (Z) is not particularly limited as long as the molecular weight of the molecule is 1000 or less. The following trivalent hydrocarbon groups may be mentioned as examples.

[0001]

[Chemical 2]

[Here, each of r ^{1 to} r ⁶ represents a hydrogen atom or a hydrocarbon group. However, r ¹ and r ² or r ³ ~
At least one of r ⁶ is linked to the polymer chain. ]
These hydrocarbon groups are constituted alone or in any combination thereof, and in the case of a combination, -O-, -S-,-.
^{N (r 7) -, -} COO -, - CON (r 7) -, - S
_{O 2 -, - SO 2 N} (r 7) - ( wherein ^{r 7} each represents a hydrogen atom or a hydrocarbon group}, - NHCOO -, -
Heterocycles containing heteroatoms such as NHCONH-, oxygen atom, sulfur atom, nitrogen atom (eg thiophene ring, pyridine ring, pyran ring, imidazole ring, benzimidazole ring, furan ring, piperidine ring, pyrazine ring, pyrrole ring, piperazine A ring or the like) may be included. Examples of other linking groups that bond the polymer chains include those composed of a combination of a group selected from the structures below and the above-mentioned bonding unit. However, the organic group (Z) in the present invention is not limited to these.

[0085]

[Chemical 3]

(3) A segment (X) containing at least 50% by weight of a structural unit containing a fluorine atom and / or a silicon atom, and a segment containing a structural unit containing at least one type of light and / or thermosetting group. Graft type copolymer (P ₃ ) composed of (Y ₁ ); In the copolymer (P ₃ ), the order of arrangement of the segment (X) and the segment (Y ₁ ) in the polymer chain is But it's okay. That is, the polymer is schematically shown below.

[0001]

[Chemical 4]

(4) A segment (X) containing at least 50% by weight of a constituent unit having a fluorine atom and / or a silicon atom, and a segment (Y) containing a constituent unit containing a photo- and / or thermosetting functional group. ₁ ) is an AB type or ABA type block copolymer, and at least one of the segments (X) is the following graft type segment (X ′), or the segment (Y ₁ )
At least one of the following is a graft type segment (Y ′), or at least one of (X) is the following graft type segment (X ′), and at least one of the segments (Y ₁ ) is Copolymer (P ₄ ) graft type segment (X ′) which is a graft type segment (Y ′): weight average molecular weight of 1 × 10 ³ to 2 × 1.
0 is ^4, fluorine atom and / or a structural unit having a silicon atom at least 50% by weight or more, preferably 90
Monofunctional macromonomer unit which contains% by weight or more (M _A)
A segment containing at least as a copolymerization component. Graft type segment (Y ′): weight average molecular weight 1 × 10
A segment of ^{3 to} 2 × 10 ⁴ , which contains at least a monofunctional macromonomer part (M _B ) as a copolymerization component, the monofunctional macromonomer part (M _B ) including a constitutional unit containing no constitutional unit having a fluorine atom and / or a silicon atom. In the copolymer (P ₄ ), the segment (X) and the segment (Y ₁ ) may be arranged in any order. Examples of the copolymer include those schematically shown below.

[0001]

[Chemical 5]

[0001] The proportion of the segment monofunctional macromonomer unit in the (X) _{(M A),} the segment (X)
1 to 50% by weight, preferably 3 to 3 with respect to the total weight of
It is 0% by weight. Preferably, the monofunctional macromonomer part (M _B ) comprises a structural unit containing a photo- and / or thermosetting functional group, the monofunctional macromonomer part (M _B ).
1 to 50% by weight, preferably 3 to 2 with respect to the total weight of
It is contained in an amount of 0% by weight. The proportion of the segment _{(Y 1)} in the monofunctional macromonomer unit _{(M B),} based on the total weight of the segment _{(Y 1),} 1 to 50% by weight, preferably 3 to 30 wt% .

[0018]

In the original plate for color proofing of the present invention, when the photoconductive layer is a monodisperse 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 a resin [P] containing a structural unit having a fluorine atom and / or a silicon atom is made to coexist in a layer together with another binder resin to form a coating film, the resin can be formed after the coating process and before the drying step is completed. [P] migrates to the surface portion of the film, is concentrated, and exhibits peelability. The migration to the surface portion is particularly remarkable in the block copolymer. Further, when the resin [P] is a block-type copolymer, the segment (X) in the resin [P] is oriented to the surface side in contact with the transfer layer and exhibits releasability. On the other hand, since the other segment (Y) is preferably compatible with the binder resin, it is arranged in a state of being oriented inside the photoconductive layer, and as a result, the anchor effect is exerted by the interaction with the other binder resin. . Further, when the resin [P] is a block copolymer and a binder resin [Q] described later is used together, the binder resin [Q] and the segment (Y) of the resin [P] are preferably Since it 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 or the like, Since the resin [P] in the layer is cured in a state of being oriented on the surface and the binder resin [Q] is inwardly oriented, an effect that the orientation state is sufficiently fixed can be obtained. . Further, as a result, the transfer of the resin [P] to the transfer layer at the time of forming the transfer layer coating film is eliminated, and the effect that the interface between the transfer layer and the photoconductive layer is clearly formed and maintained is also obtained. . Therefore, when the color proofing master plate of the present invention is used, in the proof printing, the toner image formed by the electrophotographic process is satisfactorily transferred together with the transfer layer,
Problems such as defective peeling of the transfer layer do not occur. Also,
The solvent for coating is selected depending on the kind of the thermoplastic resin for the transfer layer. Depending on the solvent, the photoconductive layer is solvated by the solvation action with the binder resin of the photoconductive layer during the film formation of the transfer layer. In some cases, it has an adverse effect on the dispersion state of the toner and adversely affects the electrophotographic characteristics (such as easy occurrence of background fog and deterioration of image quality). Such a problem can be solved by imparting solvent resistance by crosslinking the photoconductive layer of the present invention.

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 proof 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.
It should be (g · f) or less, preferably 100 g · f or less, and more preferably 50 g · f or less. The test was performed at a peeling speed of 120 mm / min, using the electrophotographic color proofing original plate of the present invention as the “test plate” and an adhesive tape having a width of 6 mm as the “adhesive tape”. The adhesive strength is a value obtained by proportionally converting the obtained value into an adhesive tape having a width of 10 mm. [Photoconductive Layer] The photoconductive layer of the original plate for color calibration of the present invention will be described in detail below. (Resin (P)) (Segment (X)) First, the segment (X) will be described. 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 present as a substituent in the polymer side chain. Substituent having a fluorine _atom: -C _{h F 2h + 1}
(H is an integer of _{1~18), - (CF 2)} j CF
₂ H (j represents an integer of 1 to 17), -CFH ₂

[0027]

[Chemical 6]

Monovalent organic residues such as --CF _2- , --CFH
-,

[0029]

[Chemical 7]

A divalent organic residue such as Substituent having a silicon atom:

[0031]

[Chemical 8]

Monovalent or divalent organic residues and the like. In the above formula, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ may be the same or different, and may be a hydrocarbon group having 1 to 22 carbon atoms which may be substituted, and the above-mentioned fluorine atom-containing one. Monovalent organic residue, -OR 'group (R' represents an optionally substituted hydrocarbon group having 1 to 22 carbon atoms), or -OSi (R
₁ ′) (R ₂ ′) (R ₃ ′) (in the group, R ₁ ′ to R ₃ ′ represent the groups mentioned for R _{1 to} R ₅ ). R ₁ ~
Examples of R ₅ , R ′ and R ₁ ′ to R ₃ ′ are shown below: an optionally substituted alkyl group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group,
Octyl group, decyl group, dodecyl group, hexadecyl group,
2-chloroethyl group, 2-bromoethyl group, 2,2,2
-Trifluoroethyl group, 2-cyanoethyl group, 3,
3,3-trifluoropropyl group, 2-methoxyethyl group, 3-bromopropyl group, 2-methoxycarbonylethyl group, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl group, etc.), Alkenyl groups having 4 to 22 carbon atoms which may be substituted (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.), and optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-
Phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.),
An optionally substituted alicyclic group having 5 to 8 carbon atoms (eg, cyclohexyl group, 2-cyclohexyl group, 2-cyclopentylethyl group) or an optionally substituted aromatic group having 6 to 12 carbon atoms. (For example, 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.).

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 organic group, and is —O—, —S—, —NR ₁ —, —S.
_{O -, - SO 2 -,} - COO -, - OCO -, - CON
HCO -, - NHCONH -, - CONR 1 -, - SO
It may be selected from ₂ NR ₁ − and the like, and may be a divalent aliphatic group or a divalent aromatic group, or an organic group constituted by a combination of these divalent organic groups. . Here, R ₁ has the above-mentioned meaning. As the divalent aliphatic group, for example,

[0037]

[Chemical 9]

(E ₁ and e ₂ may be the same or different from each other, and each is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.) or a carbon number of 1 to 12).
Represents an alkyl group (eg, methyl group, ethyl 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 is an alkyl group having 1 to 4 carbon atoms, -CH ₂ Cl or-
Represents CH ₂ Br). Examples of the divalent aromatic group include a benzene ring group, a naphthalene ring group and a 5- or 6-membered heterocyclic group (as a hetero atom constituting the hetero ring, a hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom). Which contains at least one). 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 mentioned as examples of the substituent.

Examples of the heterocyclic group include furan ring, thiophene ring, pyridine ring, pyrazine ring, piperazine ring, tetrahydrofuran ring, pyrrole ring, tetrahydropyran ring, 1,3-oxazoline ring and the like. 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 represents a substituent shown below. _{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 (CF 2) m CFHCF 3 8) -CH (CF 3) 2

[0042]

[Chemical 10]

In the following formula, n represents an integer of 1 to 18, m represents an integer of 1 to 18, 1 represents an integer of 1 to 5, and b represents a hydrogen atom or a methyl group.

[0044]

[Chemical 11]

[0045]

[Chemical 12]

[0046]

[Chemical 13]

[0047]

[Chemical 14]

[0048]

[Chemical 15]

[0049]

[Chemical 16]

[0050]

[Chemical 17]

[0051]

[Chemical 18]

[0052]

[Chemical 19]

[0053]

[Chemical 20]

(A-34)-(N (COR _f ) CH ₂
CH ₂₎ - will now be described monofunctional macromonomer unit _{(M A).} Monofunctional macromonomer unit _(M A)
Has a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , preferably 3 × 10 ³ to 1 × 10 ⁴ .
When the weight average molecular weight is 1 × 10 ³ or less, the length of the graft portion becomes too short, and the effect of improving the peeling property is weakened, and 2 × 10 ^{4 is obtained.}
The copolymerization reactivity decreases with monomers corresponding to the monomer and the monofunctional macromonomer unit (M _A) than the structural unit of which corresponds to the monofunctional macromonomer unit (M _A) or This is because the desired graft polymer cannot be obtained. Structural unit having a fluorine atom and / or silicon atom of the monofunctional macromonomer unit (M _A) in may be one mentioned above as a unit of the segment (X). The monofunctional macromonomer unit (M _A) are, for example, to one terminal of the polymer main chain of the structural units, having a polymerizable double bond-containing group represented by the following general formula (I) Can be one. _{CH (a 1) = C (} a 2) -V 1 - (I) wherein (I), _{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 was -COO -, - OCO -, - (CH 2)
_{m 'OCO -, - (CH} 2) m' COO- (m ' is 1
Represents an integer _{3), - O -, - SO} 2 -, - CO, -C
ON (T ¹ )-, -SO ₂ N (T ¹ )-, -CONHC
OO -, - CONHCONH- or _-C 6 _{H 4} - are presented (here, ^{T 1} represents a hydrogen atom or a hydrocarbon group).
Examples of hydrocarbon groups as T ¹ are shown below: 1 to 1 carbon atoms
18 optionally substituted alkyl groups (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-
A bromoethyl group, a 2-cyanoethyl group, a 2-methoxycarbonylethyl group, a 2-methoxyethyl group, a 3-bromopropyl group, and the like, an alkenyl group having 4 to 18 carbon atoms which may be substituted (for example, 2-methyl-1 A 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.), aralkyl group having 7 to 12 carbon atoms and optionally substituted (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.), carbon number 5-8
An optionally substituted alicyclic group (for example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (for example, a 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, dodecyl A loylamidophenyl group and the like).

When V ₁ represents —C ₆ H ₄ —, 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.), alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) and the like. a ₁ and a ₂ may be the same or different from each other, and preferably a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), a trifluoromethyl group, a cyano group, an alkyl group having 1 to 4 carbon atoms. (Eg, methyl group, 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,
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 (I),
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.

The polymerizable double bond-containing group represented by the general formula (I) may be bonded directly or may be bonded via an arbitrary linking group. Linking group is, for example, a divalent organic residue, -O -, - S -, - N (d 1) -, - SO-,
_{-SO 2 -, - COO -,} - OCO -, - CONHCO
_{-, - NHCONH -, - CON} (d 2) -SO 2 (d
₃ ), —Si (d ₄ ) (d ₅ ) —, a divalent aliphatic group or a divalent aromatic group, or an organic group composed of a combination of these divalent groups. Where d ₁ ~
d ₅ may be as listed for T ₁ in formula (I). Examples of the divalent aliphatic group include —C (k ₁ ).
(K ₂ )-, -C (k ₁ ) -C (k ₂ )-, -C≡C
_{-, - C 6 H 10 -} ,

[0001]

[Chemical 21]

[0001]. In the formula, k ₁ and k ₂ may be the same as 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 benzene ring group, a naphthalene ring group and a 5- or 6-membered heterocyclic group (as a hetero atom constituting the hetero ring, a hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom). Which contains at least one). 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 mentioned 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:

[0001]

[Chemical formula 22]

(Wherein Q is -O-, -S- or -NR
₂₀ - _{represents, R 20} is an alkyl group having 1 to 4 carbon atoms, -
A group represented by CH ₂ represents Cl or _-CH 2 Br) can be mentioned.

[0001] or more polymerizable double bond-containing group such as is preferably coupled only in the main chain one end of the monofunctional macromonomer unit (M _A). The monofunctional macromonomer unit and a polymerizable double bond-containing group represented by the general formula (I) (M _A), specific examples of the portion composed of organic residues linked thereto, each order Examples include, but are not limited to: However, in each of the following examples, P ₁ is -H, -CH ₃ , -CH ₂ COOCH ₃ ,-.
Cl, -Br or -CN is shown, and P ₂ is -H or -CH.
₃ , X is -Cl or -Br, and n is 2 to 12
Is shown, m shows the integer of 1-4.

[0001]

[Chemical formula 23]

[0001]

[Chemical formula 24]

[0001]

[Chemical 25]

[0001]

[Chemical formula 26]

[0001]

[Chemical 27]

(Segment (Y)) Next, the segment (Y) (including the segment (Y ₁ )) will be described in detail. First, the constituent unit containing a light and / or thermosetting functional group which is preferably contained in the segment (Y) will be described. The "light and / or thermosetting functional 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, 1977), Takahiro Tsunoda, “New Photosensitive Resin” (Publishing Society of Japan, 1981), G.I. E. Green
and B. P. Strak, J .; Macro. Sc
i. Reas. Macro Chem. , C21
(2), 187-273 (1981-82), C.I. G.
Rattee, “Photopolymerizati
on of Surface Coatings "
(A. WileyInter Science Pu
b. The functional groups used in conventionally known photosensitive resins and the like as the photocurable resin described in the review articles such as (1982). Further, as the thermosetting functional group, for example,
Takeshi Endo, "Precision of thermosetting polymer" (CMC
Co., Ltd., 1986, Yuji Harazaki (Latest Binder Technology Handbook) Chapter II-I (Comprehensive Technology Center, 1985), Takayuki Otsu "Synthesis and Design of Acrylic Resin and Development of New Applications" (Chubu Management Development Center Publishing) Section, published in 1985),
Eizo Omori "Functional Acrylic Resin" (Techno System,
Functional groups described in the review articles such as 1985) are listed. For example -COOH group, _-PO 3 _{H 2} group, _-SO 2 H
Group, -OH group, -SH group, -NH ₂ group, _{-NHR 103}
The group [R ₁₀₃ represents a hydrocarbon group, for example, having 1 to 1 carbon atoms.
8 alkyl group (for example, 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, The following formula:

[0059]

[Chemical 28]

A group represented by -CONHCH ₂ OR
₁₀₄ (R ₁₀₄ is a hydrogen atom or an alkyl group (for example, R _104
103 )), -N = C = O,

[0061]

[Chemical 29]

(Where

[0001]

[Chemical 30]

[0001] represents a heterocyclic ring containing nitrogen atom, the functional group is a protective group of -N = C = O group), a silane coupling group, titanate coupling group, _{- Cd} 9 = CH
d 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.)}
Etc. can be mentioned. Further, specific examples of the polymerizable double bond-containing group include CH ₂ ═CH— and CH ₂ ═CH—CH.
_{2 -, CH 2 = CH =} COO-, CH 2 = C (CH 3)
_{-COO-, CH 3 -CH = CH-} COO =, CH 2 =
_{CH-CONH-, CH 2 = C} (CH 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-} ,

[0066]

[Chemical 31]

And the like. Next, the monofunctional macromonomer part (M _B ) will be described. The monofunctional macromonomer part (M _B ) has a weight average molecular weight of 1 × 1.
0 ^{3 to} 2 × 10 ⁴ , preferably 3 × 10 ³ to 1 ×
It is in the range of 10 ⁴ . Weight average molecular weight is 1 ×
When it is 10 ³ or less, the anchor effect is weakened. Also, 2 × 10
^When it is ⁴ or more, the copolymerization reactivity between the monomer corresponding to the monofunctional macromonomer part (M _B ) and the monomer corresponding to the other structural unit constituting the segment (Y) is lowered. The constitutional unit constituting the monofunctional macromonomer part (M _B ) is
Any one containing no fluorine atom and / or silicon atom may be used. More preferably, the segment (Y) contains a structural unit containing a light and / or thermosetting functional group in an amount of 1 to 50% by weight based on the total weight of the segment (Y).
contains. 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 Unit) Further, in the other structural units in the segment (X) and the segment (Y) in the resin [P] of the present invention, the monomer thereof corresponds to the structural unit of each segment described above. Any one may be used as long as it can be copolymerized with the monomer. 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 (II). _{-CH (b 1) -C (V} 2 -R 11) (b 2) - (II) In formula (II), _{V 2} represents the contents of the same as _{V 1} in formula (I), _{b 1} and b ₂ is each a ₁ and a in the formula (I)
₂ represents the same content as that of R _1, and R ₁₁ represents the same content as T ₁ .

The content of the structural unit represented by the formula (II) in the segment (X) is usually 50% by weight or less, preferably 20% by weight or less, and more preferably none. The content of the structural unit, during the monofunctional macromonomer unit (M _A), 50 wt% or less, preferably 20 wt% or less, more preferably not contained at all. On the other hand, the content of the structural unit is
In the segment (Y), it is 0 to 95% by weight, preferably 5 to 90% by weight, based on the total weight of the segment (Y). The content of the structural unit, in the monofunctional macromonomer unit _{(M B)} in 40 to 100% by weight, preferably 50 to 95 wt%. Furthermore, the formula (I
Examples of the structural unit that can be contained together with the structural unit represented by I) include monomers copolymerizable with the monomer corresponding to the structural unit of the formula (II), such as acrylonitrile, methacrylonitrile, and heterocyclic vinyls (for example, Vinyl pyridine, vinyl imidazole, vinyl pyrrolidone, vinyl thiophene, vinyl pyrazole, vinyl dioxane, vinyl oxazine, etc.) and the like.
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]. Also,
In segment in the resin (P) (Y), with each of the structural units of the ^{_{above, -PO 3 H 2, -SO 3}} H, -COO
H, -P (= O) (OH) R ¹⁰¹ [R ¹⁰¹ represents a hydrocarbon group or -OR ¹⁰² (R ¹⁰² represents a hydrocarbon group).
And a structural unit containing at least one polar group selected from the group consisting of cyclic acid anhydride groups as a substituent can be used in an amount of less than 10% by weight based on the total weight of the segment (Y). .. Preferably R ¹⁰¹ and R ¹⁰²
Each represents a hydrocarbon group having 1 to 6 carbon atoms which may be substituted (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) and the like.

Further, examples of the cyclic acid anhydride group include residues such as aliphatic dicarboxylic acid anhydride and aromatic dicarboxylic acid anhydride. Examples of fatty acid dicarboxylic 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 can be mentioned, and these compounds include, for example, halogen atoms such as chlorine atom and bromine atom, methyl group, ethyl group, butyl group,
It may be substituted with an alkyl group such as 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 copolymerizable component containing a specific polar group as described above is, for example, a compound represented by the general formula (II)
May be any as long as it corresponds to a polar group-containing vinyl compound that can be copolymerized with a monomer corresponding to the repeating unit represented by, for example, “Polymer Data
Handbook (Basic Edition) ", Baifukan (1986), etc. Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- ( 2-amino) ethyl form, α-
Chloro compound, α-bromo compound, α-fluoro compound, α-tributylsilyl compound, α-cyano compound, β-chloro compound, β-bromo compound, α-chloro-β-methoxy compound, α, β-dichloro compound, etc. ), Methacrylic acid, itaconic acid, itaconic acid half-esters, itaconic acid half-amides, crotonic acid, 2-alkenylcarboxylic acids (for example, 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, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acids Vinyl group or allyl group half ester derivative thereof and carboxylic acid or sulfonic acid ester derivative thereof,
Examples thereof include structural units corresponding to compounds having the polar group in the substituent of the amide derivative.

(Synthesis of Resin [P]) Resin [P] of the Present Invention
And monofunctional macromonomer unit _{((M A), (M} B))
The macromonomer corresponding to can be synthesized according to a conventionally known polymerization method. For example, W. J. Burl
ant, A .; S. Hoffman “Block and
Graft polymers ”(1960, Re
nhald), R.N. J. Ceresa, Block a
nd Graft Polymers "(1962,
Butterworths), D.I. C. Allpor
t, W. H. James “Black Copolym
ers ”(1972, Applied Sci), A.S.
Noshay, J .; F. McGvath “Block
Copolymers ”(1977, Academic)
press. ), G. Huvtrez. D. J. Wi
lson, G .; Riss, NATO ASI Se
v. Sev E. 1985 , 149, V.I. Perce
a, Applied. Polymer Sci. 28
5 , 95 (1985). For example, regarding an ionic polymerization reaction using an organic metal compound (for example, alkyllithium, lithium diisopropylamide, alkali metal alcoholate, alkylmagnesium halide, alkylaluminum halide, etc.) as a polymerization initiator, see T.W. E. Hogeu-Esc
h, J. Smid, “Recent Advances
in Anionic Polymerizatio
n ”(1987, Elsevier New Yor
k) Yoshio Okamoto, Polymer, 38 , 912 (1989), Mitsuo Sawamoto, Polymer, 38 , 1018 (1989), Tadashi Narita, Polymer, 37 , 252 (1988), B.I. C. An
derson, et al, Macromolecule
es 14 , 1601 (1981), S.I. Aoshim
a, T.A. Higashimura, Macromole
Cules 22 , 1009 (1989) and the like. Regarding the ionic polymerization reaction using a hydrogen iodide / iodine system, etc., see T.W. Higashimur
a et al, Makromol. Chem. , Ma
cromol. Symp. , 13/14, 457 (19
88), Toshinobu Higashimura, Mitsuo Sawamoto, Transactions on Polymers 46 , 18
9 (1989) and the like. For the group transfer polymerization reaction, see D. Y. Sogah et a
1, Macromolecules 20 , 1473
(1987), O.I. W. Webster, D.M. Y. So
gah, Kogaku, 36 , 808 (1987), M.A. T.
Reetg, et al, Angew. Chem. In
t. Ed. Eugl. 25 , 9108 (1986) JP-A-63-97609.

The living polymerization reaction using a metalloporphyrin complex is described in T.W. Yasuda, T .; Ai
da, S.D. Inoue, Macromolecule
s, 17 , 2217 (1984), M.S. Kuroki,
T. Aida, S .; Inoue, J .; Am. Chem.
Soc. 109 , 4737 (1987), M.S. Kuro
ki et al, Macromolecules,
21 , 3115 (1988), M.S. Kuroki, I .;
Inoue, Synthetic Organic Chemistry, 47 , 1017 (198).
9) etc. Further, regarding the ring-opening polymerization reaction of a cyclic compound, S. Kobayashi, T .; Sa
egusa, "Ring Opening Polym"
“Erization” (1984, Applied)
Science Publishers, Ltd. ),
W. Seeliger et al. Angew. Ch
em. Int. Engl. 5 , 875 (1966),
S, Kobayashi et al, Poly, Bu
ll. 13 , 447 (1985), Y. Chujo e
t al, Macromolecules, 22 , 10,
74 (1989) and the like. Furthermore, regarding the photoliving polymerization reaction using a dithiocarbamate compound or a xanthate compound as an initiator, Takayuki Otsu, Kogaku, 37 , 248 (1988), Shunichi Hinomori, Ryuichi Otsu, Polym. Rep. Jap. 37 3508
(1988), JP-A 64-111, and JP-A 64-2.
6619, M.I. Niwa, Macromolecule
es, 189 , 2187 (1988) and the like. On the other hand, a polymer containing an azo group or a peroxide group is used as an initiator. By a radical polymerization reaction, a method of synthesizing a block copolymer, Ueda Akirato, polymeric Collected Papers 3
3 , 931 (1976), Akira Ueda, Osaka Municipal Industrial Research Institute Report 84 , (1989), O.I. Nuyken et a
1, Macromol. Chem. , Rapid. Co
mmun. 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 ”(1981, Tokyo Kagaku Dojin) and the like. For example, a method of grafting a polymer chain with a polymerization initiator, a chemical actinic ray (radiation, electron beam, etc.), a mechanochemical reaction in mechanical application, and the like,
A method of grafting by chemically bonding (so-called interpolymer reaction) using a polymer chain and a functional group of the polymer chain or a method of polymerizing and grafting using a macromonomer is known. ..

Specific examples of the method of grafting with a polymer include T.I. Shiota et al. A
ppl. Polym. Sci. 13 , 2447 (196
9), W. H. Buck, Rubber Chemis
try and Technology, 50 , 109
(1976), Takeshi Endo, Tsutomu Yokozawa, Journal of Japan Adhesion Society, 2
4 , 323 (1988), Takeshi Endo, ibid, 25 , 4
09 (1989) and the like. Further, as a method of carrying out a polymerization reaction and grafting using a macromonomer, specifically, P. Dreyfuss & R. P. Qu
irk, Encycl. Polym. Sci. En
g. , 7 , 551 (1987), p. F. Rempp,
E. Franta, Adv. Polym. Sci. , 5
8 , 1 (1984), V.I. Percec, Appl. P
oly. Sci. , 285 , 95 (1984), R.A. A
sami, M .; Takari, Macromol. Ch
em. Suppl. , 12 , 163 (1985), p.
Rempp. , Et al, Macromol. che
m. Suppl, 8, 3 (1984), Yusuke Kawakami, Chemical Industry, 38 , 56 (1987), Yuya Yamashita, Polymer, 3
1 , 988 (1982), Shiro Kobayashi, High Polymer, 30 , 6.
25 (1981), Toshinobu Higashimura, Journal of Japan Adhesion Society, 18 ,
536 (1982), Koichi Ito, Polymer Processing, 35 , 2
62 (1986), Kishiro Higashi, Takashi Tsuda, Functional Materials, 19
87 , No. 10, 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 (1991). , CMC, YY
amashita et al. Polym. Bul
l. 5 , 361 (1981) and the like. The synthesis method of the star block copolymer is described in, for example, M. T. R
eetz, Angew. Chem. lst. Ed. En
gl 27 , 1373 (1988), M.G. Sgwar
c, “Carbanions, Living Poly
mers and Electron Transfer
r Processes "(1968, Wiley.
New York) B. Gordon et al, P
olym. bull. 11 , 349 (1984), R.I.
B. Bates et al. J. Org. Chem.
44 , 3800 (1979), Y. Sogah, A .;
C. S. Polym. Repr. 1988 , No. 2,
3, J. W. Mays. Polym. Bull. 23 ,
247 (1990), I.I. M. Khan. et al.
Macromolecules, 21 , 2684 (19)
88), A. Morikawa, Macromecul
es, 24 , 3469 (1991), Akira Ueda, Susumu Nagai,
Polymer, 39 , 202 (1990), T.H. Otsu, P
olym. Bull. 11 , 135 (1984) and the like.

Further, for example, W, J. Burrant.
A. S. Hoffman “Block and Gra
ft Polymers "(1960, Renhol
d), R.D. J. Ceresa, “Block and
Graft Copolymers "(1962, B
Uterwords) L.A. C. Allport, W.C.
H. Jame "Block copolymers"
(1972 Applied Sci), A.S. Nos
hay, J. et al. E. McGrath “BlockCopo
lymers ”(1977, Academic Pr
ess. ) Etc. More specifically, the star-type copolymer of the present invention can be synthesized using a conventionally known method for synthesizing a star-type polymer of a monomer having a polar group-containing and a polymerizable double bond-containing group. it can. For example, one of them is a polymerization reaction using carbanion as an initiator. Specifically, M. Morton, T .; E. He
lminiak et al. J. Polym. Sc
i. 57, 471 (1962), B.I. Gordon I
II, M.I. Blumethal, J .; E. Loftu
s. et al, Polym. Bull, 11, 349
(1984), R.S. B. Bates, W.C. A. Beav
ers, et al. Org, Chem. , 44, 3
It can be synthesized according to the method described in 800 (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 aforementioned —COOH group, it corresponds to a structural unit containing the specific polar group. In the monomer to be used, the polar group is preliminarily protected as a functional group, and an organic metal compound (eg, alkyllithium, lithium diisopropylamide, alkylmagnesium halide, etc.) or an ionic polymerization reaction with hydrogen iodide / iodine system, porphyrin After synthesizing a block copolymer by a so-called living polymerization reaction such as a photopolymerization reaction or a group transfer polymerization reaction using a metal complex as a catalyst, a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction to a functional group protected with a polar group. Alternatively, a deprotection reaction such as a photolysis reaction is performed to form a polar group. One example thereof is shown in the following reaction formula (I).

[0147]

[Chemical 32]

[0147] Also, monofunctional macromonomer unit _(M A)
And macromonomers corresponding to (M _B ), P. Lut
z, P. Masson et al. , Polym. B
all. 12 , 79 (1984) B. C. Ander
Son, G.M. D. Andrews et al. , Ma
cromolecules, 14 , 1601 (198)
1) K. Hatada, K .; Ute. et al, Po
lym. J. 17 , 977 (1985), 18 , 103
7 (1986), Koichi Right Hand, Koichi Hatada, Polymer Processing, 3
6 , 366 (1987), M.S. Kuroki, T .; Ai
da, T .; Am. Chem. Soc. 109 . 4737
(1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 4.
3 , 300 (1985) D.I. Y. Sogah, W .; R.
Hertler et al. , Macromolec
ules, 20 , 1473 (1987), JP-A-64-
111, the synthesis method described in JP-A No. 64-26619, Y. Yamashita, J. et al. Appl. Poly
m. Sci, Appl. Polym. Symp, 36 ,
193 (1981), K.S. K. Roy et al. ，
Makromol. Chem. 153 , 71 (197
2), Y. Yamashita et al. , Pol
ym. J. , 14 , 255 (1982), Akira Ueda, Susumu Nagai, Kagaku to Kogyo , 60, 57 (1986) and the like. The introduction of polymerizable double bond-containing group into the backbone of the end of the monofunctional macromonomer unit (M _A) and (M _B) is that in accordance with synthetic methods known macromonomer, easily performed it can. Further, when the monofunctional macromonomer part of the present invention contains a structural unit containing the specific polar group described above, the macromonomer corresponding thereto protects the polar group in advance,
After the polymerization reaction and the introduction reaction of the polymerizable double bond-containing group, the protective group is removed to facilitate the synthesis. Protecting group and elimination of the protecting group (deprotection reaction)
The above can be easily performed by utilizing the conventionally known knowledge. For example, various references are given in the above cited references, and further, Yoshio Iwakura, Keisuke Kurita, “Reactive Polymer”
Published by Kodansha Ltd. (1977), T.K. W. Greene
"Protective Groups in Orga
Nick Synthesis, "John Wiley
& Sons (1981), J. F. W. McOm
ie, “Protective Groups in O
"organic Chemistry", PlenumP
The method described in detail in the review article of Less, (1973) and the like can be appropriately selected and performed. Further, the resin [P] of the present invention can be subjected to an ionic polymerization reaction, as in the polymer synthesizing method in the macromonomer synthesizing method described above.
It can be easily produced by a known so-called living polymerization reaction such as a group transfer polymerization reaction, a metalloporphyrin polymerization reaction, and a photoiniferter method polymerization reaction. Furthermore,
Aeda Ueda, Susumu Nagai et al., Polymers, 33 131 (197)
6). It can also be produced by a radical copolymerization reaction using a high molecular weight azo initiator described in Science and Industry, 64 , 446 (1990), and the like. Resin (P) and the monofunctional macromonomer unit (M _A) and synthesis of the corresponding macromonomer (M _B) is not limited to these methods. The adjustment of the weight average molecular weight of the resin [P] of the present invention can be easily adjusted by the ratio of the total amount of all monomers used in the polymerization and the amount of various polymerization initiators, the polymerization temperature, etc., as conventionally known in the polymerization reaction. be able to. Next, a preferred embodiment of the resin particles [L] of the present invention will be described. The average particle size of the resin particles [L] is preferably 0.001 to 1 μm, more preferably 0.05 to 1 μm.
It is 0.5 μm. The shape of the resin particles [L] is spherical when produced by the non-aqueous dispersion polymerization method. As described above, the resin particles [L] include the non-aqueous solvent-insoluble segment (Xo) containing a structural unit containing 50% by weight or more of a fluorine atom and / or a silicon atom, and a fluorine atom soluble in the non-aqueous solvent. And / or containing 20% by weight or less of a constituent unit containing a silicon atom (Y
o) and.

Further, the segment (X ₀ ) constituting the insoluble portion of the resin particles may form a crosslinked structure. As a preferable method for specifically synthesizing the resin particles [L] as described above, K. E. J. Barrett "D
ispersion Polymerization
in Organic Media "John Wi
ley (1975), Koichiro Murata, Polymer processing, 2
3, 20 (1974), Tsunetaka-Toyokichi Tange Matsumoto, Japan Journal of the Adhesion Society of 9, 183 (1973), Toyokichi Tange, Journal of the Adhesion Society of Japan 23, 26 (1987), D . J. walbrid
ge, NATO. Adv. study. Inst. Se
r. E. No. 67, 40 (1983), British Patent No. 8
No. 93429, No. 934038, US Pat. No. 1
122397, 394012, and 4606989, JP-A-60-179751, and 60-185.
The "non-aqueous dispersion polymerization method" described in JP-A-2-13965 and the like is cited. The non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles has a boiling point of 20.
Any organic solvent having a temperature of 0 ° C. or lower may be used, and may be used alone or in combination of two or more kinds. Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol and benzyl alcohol, ketones such as acetone, methyl ethyl ketone, cyclohexanone and diethyl ketone, ethers such as diethyl ether, tetrahydrofuran and dioxane. , Carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate, aliphatic hydrocarbons having 6 to 14 carbon atoms such as hexane, octane, decane, dodecane, tridecane, cyclohexane and cyclooctane, benzene , Toluene, xylene, chlorobenzene and other aromatic hydrocarbons, methylene chloride,
Dichloroethane, tetrachloroethane, chloroform,
Examples thereof include halogenated hydrocarbons such as methyl chloroform, dichloropropane and trichloroethane. However, it is not limited to these.

By synthesizing dispersed resin particles in these non-aqueous solvent systems by the dispersion polymerization method, the average particle size of the resin particles easily becomes 1 μm or less, and the particle size distribution is very narrow and monodisperse particles. Can be More specifically, the monomer (x) corresponding to the structural unit forming the segment (X) and the monomer (y) corresponding to the structural unit forming the segment (Y) x) dissolves, but does not dissolve the polymerized product thereof. Using a non-aqueous solvent, a peroxide (eg, benzoyl peroxide, lauroyl peroxide, etc.), an azobis compound (eg, azobisisobutyronitrile, azobisisonitrile) is used. The polymerization may be carried out by heating in the presence of a polymerization initiator such as valeronitrile) or an organic metal compound (eg butyllithium). Alternatively, the above-mentioned monomer (x) and a polymer (py) composed of structural units corresponding to the monomer (y) may be polymerized in the same manner as above.
Furthermore, the inside of the resin particles [L] of the present invention may have a crosslinked structure. Any conventionally known method can be used to form these crosslinked structures.

That is, (a) a method of cross-linking a polymer containing a structural unit constituting the segment (X) with various crosslinking agents or curing agents, and (b) a structural unit constituting the segment (X). A method of forming a network structure between molecules by allowing a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups to coexist when polymerizing a material containing at least a monomer, And (c) a method of forming a crosslinked structure by polymerizing a monomer corresponding to a structural unit constituting the segment (X) and a monomer containing a crosslinkable group, or containing a structural unit of the segment (X) and a crosslinkable group It can be carried out by a method such as a method in which a polymer containing the constituent unit is crosslinked by a polymer reaction.

Examples of the cross-linking agent in the above method (a) include compounds that are usually used as cross-linking agents.
Specifically, compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taisei (1981), "Polymer Data Handbook Basic Edition", Baifukan (1986), edited by The Society of Polymer Science, Japan, etc. Can be used. For example,
Organic silane compounds (for example, silane coupling agents such as vinyltrimethoxysilane, vinyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane) , Polyisocyanate compounds (for example, toluylene diisocyanate, o-
Toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate,
Polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
High molecular weight polyisocyanate, etc.), polyol compound (for example, 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol,
1,1,1-trimethylolpropane, etc.), polyamine compounds (for example, ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine,
Modified aliphatic polyamines, polyepoxy group-containing compounds and epoxy resins (for example, Hiroshi Kakiuchi's "New Epoxy Resins" Shokoido (1985), Kuniyuki Hashimoto's "Epoxy Resins" Nikkan Kogyo Shimbun (1969)) Etc.), melamine resin (eg, Ichiro Miwa, Hideo Matsunaga, “Uria Melamine Resin”, Nikkan Kogyo Shimbun (1
969) compounds, etc.), poly (meth)
Acrylate-based compounds (for example, Shin Okawara, Takeo Saegusa,
Toshinobu Higashimura "Oligomer" Kodansha (Published in 1976), Eizo Omori "Functional Acrylic Resin" Techno System (19
1985) and the like.

The polymerizable functional group of the polyfunctional monomer or the polyfunctional oligomer containing two or more polymerizable functional groups coexisting in the above method (b) is specifically,
_{CH 2 = CH-CH 2 -} , CH 2 = CH-CO-O-,
_{CH 2 = CH-, CH 2 =} C (CH 3) -CO-O-,
_{CH 3 CH 2 -CO-O-,} CH 2 = CH-CONH
_{-, CH 2 = C (CH} 3) -CONH-, CH (C
_{H 3) = CH-CONH-,} CH 2 = CH-O-CO
_{-, CH 2 = C (CH} 3) -O-CO-, CH 2 = CH
_{-CH 2 -O-CO-, CH 2} = CH-NCO-, CH
_{2 = CH-CH 2 -NHCO-,} CH 2 = CH-SO 2
_{-, CH 2 = CH-CO-} , CH 2 = CH-O-, CH
₂ = CH-S- and the like can be mentioned, and a monomer or oligomer having two or more of these polymerizable functional groups having the same or different polymerizable functional groups is used.

Specific examples of the monomer having two or more polymerizable functional groups are shown below: As a monomer or oligomer having the same polymerizable functional group, a styrene derivative such as divinylbenzene or trivinylbenzene: Polyhydric alcohol (eg ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 20
0, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc., or polyhydroxyphenols (eg hydroquinone, resorcin, catechol) And their derivatives)
Methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers: dibasic acids (eg malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) Vinyl esters, allyl esters, vinyl amides or allyl amides: polyamines (eg ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) and carboxylic acids containing vinyl groups (eg methacrylic acid, acryl) Condensate with acid, crotonic acid, allyl acetic acid, etc .; Examples of monomers or oligomers having different polymerizable functional groups include vinyl group-containing carboxylic acids (eg, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl). Acetic acid, methacryloyl propionic acid, Acryloylpropionic acid, itaconiloylacetic acid, itaconiloylpropionic acid, carboxylic acid anhydride, etc.) and a reaction product of an alcohol or an amine (for example, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allyl) Ester derivatives or amide derivatives containing vinyl groups such as aminocarbonylpropionic acid (eg vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, methacryloyl propion) Vinyl acid, methacryloyl allyl propionate, methacrylic acid vinyloxycarbonylmethyl ester, acrylic acid vinyloxycarbonylmethyloxycarbonyl ethylene ester, N-a Le acrylamide, N- allyl methacrylamide, N- Ariruitakon acid amides, methacryloyl propionic acid allylamide, etc.) or amino alcohols (e.g. aminoethanol, 1-aminopropanol, 1-aminobutanol,
1-aminohexanol, 2-aminobutanol, etc.) and a vinyl group-containing carboxylic acid condensate.

The monomer or oligomer having two or more polymerizable functional groups used in the present invention is the monomer or oligomer, the monomers (x) and (y), and other coexisting monomers. It is used in an amount of 10 mol% or less, preferably 5 mol% or less, based on the total amount of the body. Further, in the case of the above method (c), when a chemical bond is formed by the reaction of the reactive groups between the polymers to form a bridge between the polymers, it is carried out in the same manner as the reaction of a normal organic low molecular compound. be able to.
In dispersion polymerization, a method for forming a network structure is to obtain monodisperse particles having a uniform particle size, and
The method (b) using a polyfunctional monomer is preferable because it is easy to obtain fine particles of 5 μm or less. That is, the above-mentioned monomer (x), monomer (y) and / or polymer (p
In y), a polyfunctional monomer is allowed to coexist, and a polymerization granulation reaction is performed to synthesize it. Furthermore, when the above polymer (py) is used, a side chain in the polymer main chain of the polymer (py) or one end of the main chain is a polymerizable polymer capable of being copolymerized with the monomer (x). A heavy bond-containing group is contained. The polymerizable double bond-containing group may be any as long as it can be copolymerized with the monomer (x), and specific examples thereof include

[0001]

[Chemical 33]

And the like (a represents H or --CH ₃ ). Specific embodiments of these polymers are described in, for example, JP-A No. 61-43757 and JP-A No. 1-257969.
No. 2-74956, No. 1-282566.
JP-A-2-173667 and JP-A-3-15862
It can be carried out in the same manner as the method described in the specification of Japanese Patent Application No. Hei 2-177449. The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the non-aqueous solvent. The amount of the polymerization initiator is 0.1 to 5% by weight based on the total weight of the polymerizable compound. The polymerization temperature is about 30 to 180 ° C, preferably 40 to 120 ° C. The reaction time is preferably 1 to 15 hours. The above resin [P] and / or resin particles [L]
Is the total binder resin (resin [P] and / or resin particles [in the case of a monodisperse layer type photoconductive layer or a layer adjacent to the transfer layer of a laminated type photoconductive layer. L] and 100 parts by weight of other binder resin as described below), preferably 0.01 to 40 parts by weight. From this range, resin [P] and / or resin particles [L]
If the ratio is small, the peeling and transfer of the transfer layer will not proceed smoothly, and if the ratio is large, the faithful reproducibility of the copied image with respect to the original will be deteriorated. Of the above range, 0.1 to 30 parts by weight is particularly preferable.

The photoconductive layer may contain other binder resin in addition to the resin (P) and / or the resin particles (L), if necessary. For example, a conventionally known binder resin for an electrophotographic photoreceptor is used. Examples of these conventionally known binder resins for electrophotographic photoreceptors include Ryuji Shibata and Jiro Ishiwatari, Kogaku, Vol. 17, p. 278 (1968) Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 ( No. 8), Koichi Nakamura, "Practical Technology of Binders for Recording Materials," Chapter 10,
C. H. C. Published (1985) edited by The Electrophotographic Society, "Present Symposium on Organic Photoreceptors for Electrophotography" Proceedings (19
1985), 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", Part 5 Chapter Corona Co., Ltd. (1988), D.I. Tatt, S.M. C. H
eidecker, Tappi, 49 (No, 10),
439 (1966), E.I. S. Baltazzi, R.A.
G. Blanclotte et al, Photo. S
ci. Eng. 16 (No. 5), 354 (197)
2), Nguyen Chan Kay, Isamu Shimizu, Eiichi Inoue, Electrophotographic Society Journal 18 (No. 2), 22 (1980) and the like.

Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and Polymers and copolymers of the derivatives, butadiene-styrene copolymers, isoprene-styrene copolymers, butadiene-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile copolymers, alkyl vinyl ether copolymers. Polymers, acrylic acid 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 copolymer, acrylamide copolymer, methacrylamide Polymer, hydroxyl-modified silicone resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl- and carboxyl-modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylic acid ester copolymer, ring Rubber-acrylic acid ester copolymer, copolymer containing nitrogen atom-free heterocycle (heterocycle is, 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.

A binder resin [Q] containing a photo- and / or thermosetting functional group is particularly preferable. The light and / or thermosetting functional group contained in the binder resin [Q] may be any, but specifically, the photo and / or thermosetting functional group contained in the resin [P] described above may be used. The same contents can be cited. The binder resin [Q] may be any as long as the above-mentioned light and / or thermosetting functional group is contained in the resin used in the conventionally known electrophotographic photoreceptor. In the binder resin [Q], 0.1 to 100 parts by weight of the binder resin [Q], a structural unit containing a light and / or thermosetting functional group is contained.
It is present in a proportion of 40 parts by weight, preferably 1 to 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 layer. May adversely affect the releasability of. If it exceeds 40 parts by weight, electrophotographic characteristics of the photoconductive layer as a binder resin may be deteriorated, the original reproducibility of a copied image may be deteriorated, and background fog may be generated in a non-image part. .. The binder resin [Q] containing a light and / or thermosetting functional 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. (Light and / or heat curing agent) As described above, in the present invention, the photoconductive layer (a layer adjacent to the transfer layer in the case of a laminated type) is further provided with a light and / or heat in order to improve curing of the film. It is preferable to contain a thermosetting agent. The term "light / and heat curing agent" includes light and / or heat setting compounds, light and / or heat setting oligomers, light and / or heat setting resins, and cross-linking agents. The amount of its use is 0. 0 based on 100 parts by weight of the total amount of the binder resin [Q] and the resin [P].
The amount is 01 to 20 parts by weight, preferably 0.1 to 15 parts by weight. When the amount used is less than 0.01 part by weight, the effect of improving the hardening of the film is weakened. Further, if it exceeds 20 parts by weight, electrophotographic characteristics are adversely affected. Light and / or thermosetting resin,
Any of the conventionally known light and / or thermosetting resins may be used. For example, the light and / or thermosetting resins mentioned above for the resin [P] of the present invention
Alternatively, a resin containing a functional group similar to the thermosetting functional group can be given as an example.

Concretely, Takeshi Endo "Refinement of thermosetting polymer" (CMC Co., Ltd., published in 1986), Yuji Harazaki "Latest binder technology handbook" Chapter II-I (Comprehensive technology) Center, 1985), Takayuki Otsu "Synthesis and design of acrylic resin and development of new applications" (Chubu Business Development Center Publishing Department 1985), Eizo Omori "Functional acrylic resin"
A conventionally known resin cited in a review article such as (Techno System, 1985) is used. As the cross-linking agent, those mentioned in the method of synthesizing the resin particles [L] can be used. As described above, in the present invention, the uppermost layer of the photoconductive layer (the layer adjacent to the transfer layer) is cured after the film formation, but the binder resin [Q], the resin [P], and the light and / or heat are used. The curing agent is preferably used in a combination of functional groups in which the polymers are easily chemically bonded. Such combinations are well known in polymer reactions, for example, A as shown in the table below.
A combination of the functional group of group B and the functional group of group B is exemplified.
(However, it is not limited to this)

[0001]

[Table 1]

R ₁₇ and R ₁₈ represent an alkyl group. R
_{19 to} R ₂₁ represent an alkyl group or an alkoxy group.
However, at least one of the substituents of R _{19 to} R ₂₁ represents an alkoxy group. 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), dithiocarbamic acid compound ( Diethyldithiocarbamate, etc.) Thiuram disulfide compound (tetramethylthiuram disulfide, etc.), Carboxylic anhydride (phthalic anhydride, maleic anhydride, succinic anhydride, butyl succinic anhydride, etc., 3,
3 ', 4,4'-tetracarboxylic acid benzophenone dianhydride, trimellitic acid anhydride, etc.) and the like. When the crosslinking reaction is in 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. To perform heat curing, for example,
Make the drying conditions more strict than the conventional drying conditions for preparing the original plate for electrophotographic color proofing. For example, the drying conditions may be high temperature and / or
Or it is a long time. Alternatively, it is preferable to further heat-treat after drying the coating solvent. For example, the treatment is performed at 60 ° C. to 150 ° C. 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 of curing a 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 active light ray" used in the present invention may be any of visible light 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 a low-pressure, high-pressure or ultra-high-pressure mercury lamp, a halogen lamp or the like is generally used. The light irradiation process is usually 10 seconds to 1 from a distance of 5 cm to 50 cm.
Irradiation for 0 minutes is sufficient. (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. 37-1
7162, 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
-254142, 62-54266, etc., and those used in the photoconductive layer containing a charge generating agent, a charge transporting agent, and a binder resin as main components.
Furthermore, JP-A-60-230147 and 60-23011
No. 48, No. 60-238853, etc., and those used in a two-layered photoconductive layer containing a charge generating agent and a charge transporting agent in separate layers.

Examples of the organic photoconductive compound used in the case of the second example are: (a) triazole derivatives described in US Pat. No. 3,121,197, etc., and (b) described in US Pat. No. 3,189,447. Oxadiazole derivative, (c) imidazole derivative described in JP-B-37-16096, (d) US Pat. No. 3,615,402;
Nos. 3,820,989 and 3,542,544, JP-B-45-555 and 51-10983, JP-A-51-93224, 55-108667, and 55-1.
56953, 56-36656, and the like, polyarylalkane derivatives described in (e) US Pat. No. 3180.
Nos. 729 and 4278746, JP-A-55-8
8064, 55-88065, 49-10553
7, ibid 55-51086, ibid 56-80051, ibid 56
-88141, 57-45545, 54-1126
37, 55-74546, etc., pyrazoline derivatives and pyrazolone derivatives, (f) US Pat. No. 36.
No. 15404, Japanese Patent Publication Nos. 51-10105, 46
-3712, 47-28336, JP-A-54.
-83435, 54-110836, 54-119.
925 phenylenediamine derivatives described in each publication,
(G) U.S. Pat. Nos. 3,567,450 and 3,180,703;
Same 3240597, same 3658520, same 423210.
3, the same No. 41795961, the same No. 4012376 each specification,
Japanese Patent Publication No. 49-35702, West German Patent (DAS)
No. 1110518, Japanese Examined Patent Publication No. 39-27577,
Arylamine derivatives described in JP-A Nos. 55-144250, 56-119132 and 56-22437, and (h) amino-substituted chalcone derivatives (i) described in US Pat. No. 3,526,501. N, N-bicarbazyl derivatives described in U.S. Pat. No. 3,542,546, etc., (j) Oxazole derivatives described in U.S. Pat. No. 3,257,203, etc.
6-46234 and the like, styrylanthracene derivatives, (l) the fluorenone derivatives and the like, which are described in JP-A-54-110837 and (m) US Pat. No. 37174.
62, JP-A-54-59143 (corresponding to US Pat. No. 4,150,987), JP-A-55-5.
2063, 55-52064, 55-46760,
55-85495, 57-11350, 57-1
48749, 57-104144 and other hydrazone derivatives, (n) US Pat. No. 40479.
48, 40407949, 4265990, 427
3846, 4299897, 4306008 and other benzidine derivatives, and (o) JP-A-58.
-190953, 59-95540, 59-971
48, 59-195658, 62-36674 and the like, stilbene derivatives described in (p) Japanese Patent Publication No. 34-10966 and (q) Japanese Patent Publication No. 43-1867.
4, polyvinylpyrene, polyvinylanthracene, and poly-2-vinyl-4- described in each of the same 43-19192 publications.
Vinyl polymers such as (4 ′, dimethylaminophenyl) -5-phenyl-oxazole and poly-3-vinyl-N-ethylcarbazole; and (r) polyacenatylene, polyindene, acenaphthylene and styrene described in JP-B-43-19193. Polymers such as copolymers, (s) Japanese Patent Publication No. 5
Condensed resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin described in JP-A-6-13940, (t) JP-A-56-90833, 56-1615.
50, various triphenylmethane polymers described in each publication.

In the present invention, the organic photoconductive compound is not limited to the compounds listed in (a) to (t),
All conventionally known organic photoconductive compounds can be used. These organic photoconductive compounds may optionally be 2
It is also possible to use more than one type. As the charge generating agent contained in the photoconductive layer, various organic and inorganic charge generating agents that are conventionally known in 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) US Pat. No. 443
6800 and 4439506, JP-A-47-
37543, 58-123541, 58-1920.
42, 58-219263, 59-78356, 60-179746, 61-148453, 61-.
238063 gazettes, Japanese Examined Patent Publications 60-5941, 60
-45664, azo pigments such as monoazo, bisazo, and trisazo pigments; (2) U.S. Pat. Nos. 3,339,086 and 4,666,802; Japanese Patent Laid-Open Nos. 51-90827 and 52-55643. Phthalocyanine pigments such as metal-free or metal phthalocyanine described in (3) U.S. Pat. No. 3,371,884;
(4) British Patent No. 2237680, indigo and thioindigo derivatives described in JP-A 47-30331, and (5) British Patent No. No. 2237679, Japanese Patent Application Laid-Open No. 47-30332, and the like, quinacridone-based pigment (6) British Patent No. 223767989, Japanese Patent Application Laid-Open Nos. 59-184348 and 62-28738,
Polycyclic quinone pigments described in JP-A-47-18544 and (7) JP-A-47-30331 and JP-A-47-1854.
3 Bisbenzimidazole-based pigments described in each publication,
(8) Squalium salt-based pigments described in U.S. Pat. Nos. 4,396,610 and 4,644082, and (9) azurenium salt-based pigments described in JP-A-59-53850 and 61-212542. is there. 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 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 binding 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 type of light source such as visible light exposure or semiconductor laser light exposure. For example, Harumi Miyamoto, Hidehiko Takei: Imaging 1973 (N
o. 8) Page 12, C.I. J. Young et al., RCA R
view 15 , p. 469 (1954), Kouhei Kiyota et al .: The Institute of Electrical Communication, J63-C (No. 2), 97.
Page (1980), Yuji Harasaki et al., Journal of Industrial Chemistry, 66 ,
78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan, 35 , 208 (1972), etc., for reference, carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine. Dyes (eg, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (may contain metal)
Etc.

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, polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include F.I. M. Harmmer "The C
yanine Dyes and Related C
The dyes described in “Ompounds” and the like can be used, and more specifically, US Pat.
110591, 3121008, 3125447,
3128179, 3132942, and 362231
7 Specifications, British Patent Nos. 12268892, 1309
Nos. 274, 14045898, Japanese Patent Publication No. 48-
7814, 55-18892, etc. are mentioned. Further, as polymethine dyes for spectrally sensitizing near-infrared to infrared light region having a long wavelength of 700 nm or more, JP-A-47-840, JP-A-47-44180 and JP-B-51-4.
1061, the same 49-5034, the same 49-45122, the same 57-46245, the same 56-35141, the same 57-15.
7254, 61-26044, 61-27551, U.S. Pat. Nos. 3,619,154 and 4,175,956.
Each issue, "Research Disclosure
e ", 1982, 216, pages 117 to 118, and the like.

The original plate for color proofing of the present invention is also 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 Applications of Photoconductive Materials and Photoreceptors", Chapters 4 to 6 Examples include polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, and the like, which are cited as references in the publication of Nippon Scientific Information Co., Ltd. (1986). Further, JP-A-58-65439, JP-A-58-102239, and JP-A-58-1.
The compounds and the like described in JP-A No. 29439 and 62-71965 can also be mentioned. Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, triphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalyl ethyl glycolate, dimethyl glycol phthalate and the like. Can be added to improve the flexibility of the photoconductive layer. These plasticizers can be contained in a range that does not deteriorate the electrostatic properties of the photoconductive layer.

The addition amount of these various additives is not particularly limited, but usually 0.0 to 100 parts by weight of the photoconductor.
It is from 01 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 each additive coexist, for example, a ball mill, a kedy mill, a sand mill, a dyno mill, a paint shaker, a roll mill, as shown in "Chemistry of paints" by Solomon et al. It is common to use a sonic disperser or the like. After that, this is applied with a bar coater, a reverse coater, a Flogmouth Geeseer, and the like at an optimum application amount, and dried to form a photoconductive layer. The resin [P] may be used together with another binder resin, and it is not particularly necessary to incorporate a complicated operation.
Any solvent may be used to disperse the photoconductive substance,
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 μ, particularly 10 to 50 μ.
When forming a photoconductive layer of a laminated type including a charge generation layer and a charge transport layer, the thickness of the charge generation layer is 0.01.
.About.5 .mu., Particularly 0.05 to 2.mu. The thickness of the charge transport layer is preferably 0.99 to 99.9 μ, and particularly preferably 9 to 90 μ. 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. [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 such as metal, paper or 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 a conductive plastic vapor-deposited Al on paper Etc. can be used.

Specifically, as an example of the conductive substrate or the conductive material, Yukio Sakamoto, Electrophotography, 14, (No.
1), pp. 2 to 11 (published in 1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry", Polymer Publishing (1975), M.S.
F. Hoover, J .; Macromol. Sci. C
hem. A-4 (6), pp. 1273-1417 (197).
The ones described in "0 years" etc. are used. [Transfer Layer] Next, the transfer layer will be described.

The resin forming the transfer layer is a thermoplastic resin and has a weight average molecular weight of 5 × 10 ³ to 1 × 10 ⁶ , preferably 1 × 10 ^{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 the composition of 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, etc. may be mentioned. For example, the Nikkan Kogyo Shimbun, "Plastic Materials Lecture Series," Volumes 1 to 1
Volume 8, (1961) Kinki Chemical Society, Vinyl Section, “Polyvinyl Chloride”, published by Nikkan Kogyo Shimbun (1988), Eizo Omori, “Functional Acrylic Resin”, Techno System Co., Ltd. (1985), Eiichiro Takiyama "Polyester Resin Handbook," published by Nikkan Kogyo Shimbun (1988), edited by Kazuo Yuki,
"Saturated Polyester Resin Handbook", Nikkan Kogyo Shimbun (1989) edited by The Polymer Society of Japan, "Polymer Data Handbook <Applications" Chapter 1 Baifukan (1986) Yuji Harazaki "Latest Binder Technology Handbook" Chapter 2 ( Compounds specifically exemplified in General Technology Center Co., Ltd. (1985) are listed. These thermoplastic resins may be used alone or in two
They can be used 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,
A plasticizer and the like can be mentioned as well as those used in the above-mentioned photoconductive layer. The film thickness of the transfer layer is 0.1 to 10 μm, preferably 0.5 to 5 μm. The transfer layer can be formed by an ordinary coating film forming method. For example, a coating solution containing an arbitrary compound as described above is used, and the same means is used for coating the photoconductive layer. Can be done. 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] The following is a method for producing a color proof by using the electrophotographic original plate for color proof of the present invention. 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, Moto Machida, "Recording Materials and Photosensitive Resins" P107-127 (1983), Academic Society Publishing Center, Electrophotographic Society, "Imaging No. 2-5 Development, fixing and charging of electrophotography" Specific embodiments are shown in “Transfer” and the like.

A combination of a scanning exposure method using a laser beam which is exposed based on digital information and a developing method using a liquid developer is preferable because a high-definition image can be formed. An example is shown below. First, the electrophotographic original plate for color proofing (hereinafter abbreviated as original plate for color proofing) of the present invention is placed on a flat bed, and after positioning by a register pin method, it is fixed by suction from the back surface by air suction. . Then, for example, "Basics and Applications of Electrophotographic Technology" (edited by The Institute of Electrophotography, Corona Publishing Co., Ltd., June 1, 1988)
Issued on the 5th) The original plate for color calibration is charged by the charging device described on page 212 and thereafter. 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 original plate for color calibration to control the charging conditions so that the surface potential is always within a predetermined range. After that, scanning exposure is performed with a laser light source, for example, 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. Then
Toner development is performed using a liquid developer. For example, remove the charged and exposed original plate for color proof from the flat bed,
Development is carried out by the direct wet development method shown on page 275 and after of the above cited material. The exposure mode at this time is determined corresponding to the toner development mode. For example, in the case of reversal development, negative exposure is performed, that is, laser light is applied to the image area, and toner having the same charge polarity as the charge polarity when charged is used. Is electrodeposited. For details of the principle, refer to 1 of the above cited material.
It is described starting on page 57. After the development, in order to remove the excess developer, squeeze as shown on page 283 of the above cited document 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 0.2~20kgf / cm ^2, more preferably 0
5-10 kgf / cm ² , transport speed is 0.1-10
The range is 0 mm / sec, and more preferably -30 mm / sec. These conditions are appropriately set depending on the physical properties of the materials of the transfer layer, the photoconductive layer, and the support of the original plate for color proof to be used so that optimum results can be obtained. The roller surface temperature is preferably kept within a predetermined range by a known means. Further, it is possible to provide a preheating means for the color proof 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 the inter-roller pressurizing means at both ends of the shaft of at least one roller. 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. By this,
The transfer layer provided on the layer is peeled off very well, and as a result, it is possible to obtain a high-quality color proof print without toner color shift and 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 of Resin [P] 1: [P-1] 80 g of methyl methacrylate, dimethylsiloxane macromonomer FM0
A mixed solution of 20 g of 725 (manufactured by Chisso Corporation, Mw1 × 10 ⁴ ) and 200 g of toluene was heated at a temperature of 75 ° C. under a nitrogen stream.
Warmed to. To this, 1.0 g of azobisisobutyronitrile (abbreviation: AIBN) was added and reacted for 4 hours. I. B. N. 0.7 g was added and reacted for 4 hours. Weight average molecular weight of the obtained copolymer (abbreviation: M
w) was 5.8 × 10 ⁴ (measured by GPC method).

[0114]

[Chemical 34]

Synthesis Examples 2 to 9 of Resin [P]: [P-2] to
[P-9] Synthesis Example 1 except that each monomer corresponding to the structural unit shown in Table 2 below was used in place of methyl methacrylate and FM-0725 in the synthesis example of the resin [P-1] Each polymer was synthesized in the same manner as in. The MW of the obtained polymer was in the range of 4.5 × 10 ^{4 to} 6 × 10 ⁴ .

[0116]

[Table 2]

[0119]

[Table 3]

[0119]

[Table 4]

Synthesis Example 10 of Resin [P]: [P-10]
60 g of 2,2,3,4,4,4-hexafluorobutylmethacrylate, macromonomer AA-6 of methylmethacrylate (manufactured by Toagosei Kagaku Co., Ltd., Mw1 × 10 ⁴ ).
A mixed solution of 40 g and 200 g of benzotrifluoride,
It heated at 75 degreeC under nitrogen stream. A. I. B.
N. 1.0 g was added and reacted for 4 hours. I.
B. N. 0.5g was added and it was made to react for 4 hours. The Mw of the obtained copolymer was 6.5 × 10 ⁴ .

[0120]

[Chemical 35]

Synthesis Examples 11 to 22 of Resin [P]: [P-1
1] to [P-22] In place of the monomer and macromonomer used in the synthesis example of the resin [P-10], the following Table 3 is used.
In the same manner as in Synthesis Example 10 except that each monomer and each macromonomer corresponding to the constitutional unit described in 1) were used, the resin [P
-11] to [P-22] were synthesized. M of the obtained resin
The w was in the range of 4.5 × 10 ^{4 to} 6.5 × 10 ⁴ .

[0122]

[Table 5]

[0119]

[Table 6]

[0119]

[Table 7]

[0119]

[Table 8]

Synthesis Example 23 of resin [P]: [P-23] methyl methacrylate 67 g, methyl acrylate 22
A mixed solution of g, methacrylic acid / g 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 [PI-1] having the following structure was added and reacted for 8 hours. After completion of the reaction, the precipitate obtained by reflowing in 1.5 liter of methanol was collected and dried to obtain a resin [P-23] of Mw 3 × 10 ⁴ with a yield of 75 g.

[0127]

[Chemical 36]

Synthesis Example 24 of Resin [P]: 70 g of [P-24] methyl methacrylate and 20 tetrahydrofuran
0 g of the mixed solution was thoroughly degassed under a nitrogen stream, and the temperature was -20 ° C.
Cooled to. 1,1-diphenylbutyllithium 0.8
g was added and reacted for 12 hours. Furthermore, in this mixed solution,
30 g of the following monomer (M-1) and tetrahydrofuran 6
0 g of the mixed solution was thoroughly degassed under a nitrogen stream and then added, and the mixture was further reacted for 8 hours. After this mixture was heated to 0 ° C., 10 ml of methanol was added and reacted for 30 minutes to terminate the polymerization. The resulting polymer solution was stirred at a temperature of 3
Set the temperature to 0 ° C and add 3 ml of 30% 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 was 6.8 × 10 ⁴ , and the yield was 76 g.
Met.

[0130]

[Chemical 37]

Synthesis Example 25 of Resin [P]: 52.5 g of [P-25] methyl methacrylate, 2 methyl acrylate
A mixed solution of 2.5 g (tetraphenylporphinate), 0.5 g of aluminum methyl and 200 g of methylene chloride was heated to 30 ° C. under a nitrogen stream. 300W for this
-Xenon lamp light through glass filter 25c
It was irradiated with light from a distance of m and reacted for 20 hours. 25 g of the following monomer (M-2) was further added to this mixture, and the mixture was similarly irradiated with light for 12 hours. Then, 3 g of methanol was added to this reaction mixture and stirred for 30 minutes to stop the reaction. next,
The reaction mixture was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried. The yield of the obtained polymer is 7
The Mw was 7 × 10 ⁴ at 8 g.

[0132]

[Chemical 38]

Synthesis Example 26 of Resin [P]: [P-26] A mixture of 60 g of ethyl methacrylate and 4.8 g of benzyl N, N-diethyldithiocarbamate was sealed in a container under a nitrogen stream and heated to 50 ° C. Warmed. For this, 40
Photopolymerization was performed by irradiating with a 0 W high pressure mercury lamp from a distance of 10 cm through a glass filter for 6 hours. This is dissolved in 100 g of tetrahydrofuran, and the following monomer (M
-3) After adding 40 g, the atmosphere was replaced with nitrogen, and light was again irradiated for 10 hours. The obtained reaction product was reprecipitated in 1 liter of methanol, collected, and dried. The obtained polymer had a Mw of 4.8 × 10 ⁴ with a yield of 73 g.

[0135]

[Chemical Formula 39]

Synthesis Example 27 of Resin [P]: [P-27] Methyl Methacrylate 50 g, Ethyl Methacrylate 25
g, a mixture of 1.0 g of benzylisopurzantate,
The container was sealed 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 polymer was made into a solution having a concentration of 40% with tetrahydrofuran, 25 g of the above monomer (M-1) was added thereto, and the atmosphere was replaced with nitrogen, followed by irradiation with light again for 10 hours. The obtained reaction product was reprecipitated in 2 liters of methanol, collected and dried. The obtained resin [P-27] had a yield of 63 g and Mw of 6 × 10 ⁴ .

[0138]

[Chemical 40]

Synthesis Examples 28 to 34 of Resin [P]: [P-2
8] to [P-34] Each resin shown in Table 4 below was synthesized in the same manner as in the synthesis example of the resin [P-26]. M of the obtained resin
The w was in the range of 3.5 × 10 ^{4 to} 6 × 10 ⁴ .

[0140]

[Table 9]

[0143]

[Table 10]

[0143]

[Table 11]

Synthesis Example 35 of Resin [P]: [P-35] In the synthesis example of Resin [P-26], instead of benzyl N, N-diethyldithiocarbamate, Compound [I-1] 18 g The reaction was performed in the same manner as in Synthesis Example 26 except that the above was used to obtain a resin [P-35] having Mw of 4.5 × 10 ⁴ .

[0144]

[Chemical 41]

Synthesis Example 36 of Resin [P]: [P-36] Synthesis Example of Resin [P-27] except that 2.5 g of the compound having the following structure was used in place of benzyl isopropyl xanthate. Mw was reacted in the same manner as in [P-27].
7.2 × 10 ⁴ of resin [P-36] was obtained.

[0146]

[Chemical 42]

Synthesis Example 37 of Resin [P]: 67 g of [P-37] methyl methacrylate, 32 methyl acrylate
g, acrylic acid 1 g, and an initiator [I-2] 1 having the following structure
A mixed solution of 7.5 g and tetrahydrofuran 150 g was heated to a temperature of 50 ° C. under a nitrogen stream. 400 in this solution
Photopolymerization was performed by irradiating with a W 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 of Mw 4.0 × 10 ⁴ with a yield of 72 g. 70 g of this polymer, 30 of the above-mentioned monomer (M-2)
A mixed solution of 100 g of tetrahydrofuran and 100 g of tetrahydrofuran was heated to 50 ° C. under a nitrogen stream and irradiated with light under the same conditions as above for 13 hours. Next, this reaction product was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried to obtain a yield of 78 g and a Mw of
A resin [P-37] of × 10 ⁴ was obtained.

[0149]

[Chemical 43]

Synthesis Examples 38 to 48 of Resin [P]: [P-3
8] to [P-48] Initiator [I-2] Resin was prepared in the same manner as in Synthesis Example 37 except that 0.031 mol of the initiator [I] shown in Table 5 below was used. [P-38]
~ [P-48] were produced. The yield of each resin obtained is 7
Mw was 4 × 10 ^{4 to} 6 × 10 ⁴ at 0 to 80 g.

[0151]

[Table 12]

[0156]

[Table 13]

[0156]

[Table 14]

[0156]

[Table 15]

[0156]

[Table 16]

Synthesis Example of Resin Particle L 1: [L-1] 40 g of monomer (LM-1) having the following structure, 2 g of ethylene glycol dimethacrylate, dispersion stabilizing resin [LP
-1] A mixed solution of 4.0 g and 180 g of methyl ethyl ketone was heated to a temperature of 60 ° C while stirring under a nitrogen stream. 0.3 g of 2,2'-azobis (isovaleronitrile) (abbreviation AIVN) was added and reacted for 3 hours.
Furthermore, A. I. VN. 0.1g was added and it was made to react for 4 hours. After cooling, a white mesh was obtained through a 200-mesh nylon cloth, which was a latex having an average particle size of 0.25 μm. (The particle size is CAPA-500 (Horiba Ltd.)
Manufactured)).

[0158]

[Chemical 44]

Synthesis Example 2 of Resin Particles L: [L-2] AB-6 as a dispersion stabilizing resin (manufactured by Toa Gosei Co., Ltd .: monofunctional macromonomer consisting of butyl acrylate unit) 5
A mixed solution of g and 140 g of methyl ethyl ketone was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. To this, a monomer LM-2 having the following structure: 40 g, ethylene glycol diacrylate 1.5 gA. I. VN. 0.2 g
And a mixed solution of 40 g of methyl ethyl ketone was added dropwise over 1 hour. After reacting for 2 hours as it is, A. I. V
N. 0.1 g was added and reacted for 3 hours to obtain a white dispersion. After cooling, the average particle size of the dispersion obtained through a 200-mesh nylon cloth was 0.35 μm. _{CH 2 = CHCONHC 6 F 13 (} LM-2) Synthesis Example of Resin Particle L 3 to 11: [L-3] - [L-1
1] In Synthesis Example 1 of resin particles L, monomer LM-1,
Resin particles were produced in the same manner as in Production Example 1 except that the compounds shown in Table 6 below were used instead of ethylene glycol dimethacrylate and methyl ethyl ketone. The average particle size of the obtained resin particles was in the range of 0.15 to 0.30 μm.

[0163]

[Table 17]

[0163]

[Table 18]

[0163]

[Table 19]

Synthesis Examples 12 to 17 of Resin Particle L: [L-1
2] to [L-17] Each resin particle was prepared in the same manner as in Synthesis Example 2 of resin particle L except that the resin [LP] shown in Table 7 below was used in place of 5 g of the dispersion stabilizing resin AB-6. Synthesized. The obtained resin particles have an average particle diameter of 0.10 to 025.
It was in the range of μm.

[0001]

[Table 20]

[0163]

[Table 21]

[0163]

[Table 22]

Synthesis Examples of Resin Particles [L] 18 to 23: [L
-18] to [L-23] Monomer LM-2 Instead of 40 g, each monomer shown in Table 8 below was used, and a dispersion stabilizing resin AB-
Each resin particle was synthesized in the same manner as in Synthesis Example 2 of resin particle L except that 6 g of a resin [LP-8] having the following structure was used instead of 6, 5 g. The average particle size of the obtained resin particles was in the range of 0.05 to 0.20 μm.

[0171]

[Chemical 45]

[0001]

[Table 23]

[0163]

[Table 24]

Synthesis Example 101 of Resin [P]: [P-10
1] A mixed solution of 70 g of methyl methacrylate, 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 the same polymeric azobis initiator [PI-1] as used in Example 23 was added and reacted for 8 hours. After completion of the reaction, the obtained reaction product was converted into methanol 1.
The precipitate obtained by re-precipitation in 5 liters was collected and dried to give a resin with a _{Mw of} 3 × 10 ⁴ [P-101] in a yield of 75 g.
Got

[0001]

[Chemical 46]

Synthesis example 102 of resin [P]: [P-10
2] 63 g of methyl methacrylate, tri (dipropyl)
A mixed solution of 12.8 g of silyl methacrylate and 200 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream,
Cooled to 20 ° C. 0.8 g of 1,1-diphenylbutyllithium was added and reacted for 12 hours. Further, to this mixed solution, a mixed solution of 30 g of the same monomer (M-1) used in Example 24 and 60 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream and added, and The reaction was carried out for 8 hours. The mixture was brought to 0 ° C. and then methanol 1
0 ml was added and reacted for 30 minutes to terminate the polymerization and deprotect the silyl ester. The temperature of the obtained polymer solution was raised to 30 ° C. with stirring, 3 ml of a 30% hydrogen chloride ethanol solution was added thereto, and the mixture was 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 was 6.8 × 10 ⁴ , and the yield was 76 g.

[0128]

[Chemical 47]

Synthesis Example 103 of Resin [P]: [P-10
3] Methyl methacrylate 63.8 g, 2- (trifluoroacetyloxy) ethyl methacrylate 19.7
A mixed solution of g, 0.5 g of (tetraphenylpolyfinato) aluminum methyl and 200 g of methylene chloride was heated to 30 ° C. under a nitrogen stream. This was irradiated with light of 300 W-xenon lamp through a glass filter from a distance of 25 cm and reacted for 20 hours. 25 g of the following monomer [M-102] was further added to this mixture, and 1
After irradiation with light for 2 hours, 3 g of methanol was added to the reaction mixture.
Was added 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 this reaction mixture for hydrolysis. Next, it was re-precipitated in 2 liters of methanol to collect the precipitate and dried. The obtained resin had a yield of 70 g and had a Mw of 7 × 10 ⁴ .

[0130]

[Chemical 48]

Synthesis Example 104 of Resin [P]: [P-10
4] A mixture of 48 g of ethyl methacrylate, 12 g of glycidyl methacrylate and 2.4 g of benzyl N, N-diethyldithiocarbamate was sealed in a container under a nitrogen stream and heated to 50 ° C. This was irradiated with light from a high-pressure water 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, and the monomer (M-2) 4
After adding 0 g, the atmosphere was replaced with nitrogen, and light was irradiated again for 10 hours.
The obtained reaction product was reprecipitated in 1 liter of methanol, collected, and dried. The obtained polymer had a yield of 73 g and an Mw of 8 × 1.
0 was ^4.

[0133]

[Chemical 49]

Synthesis Example of Resin [P] 105: [P-10
5] A mixture of 55 g of methyl methacrylate, 20 g of 3- (trimethoxysilyl) ethyl methacrylate, and 1.0 g of benzylisopropyl xanthate was sealed in a container under a nitrogen stream and heated to a temperature of 50 ° C. 400 to this
Photopolymerization was performed by irradiating with a W high pressure mercury lamp from a distance of 10 cm through a glass filter for 6 hours. The obtained reaction product was made into a solution having a concentration of 40% with tetrahydrofuran, 25 g of the following monomer [M-104] was added thereto, and the atmosphere was replaced with nitrogen, followed by irradiation with light again for 10 hours. The obtained reaction product was reprecipitated in 2 liters of methanol, collected, and dried. The obtained resin had a yield of 63 g and an Mw of 6 × 10 ⁴ .

[0136]

[Chemical 50]

Synthesis Examples 106 to 114 of Resin [P]: [P
-106] to [P-114] In the same manner as in Synthesis Example 105, the following copolymers were synthesized. Mw of the obtained resin
Was in the range of 6 × 10 ⁴ to 8 × 10 ⁴ .

[0138]

[Chemical 51]

[0139]

[Chemical 52]

[0140]

[Chemical 53]

[0141]

[Chemical 54]

[0142]

[Chemical 55]

Synthesis Example 115 of Resin [P]: [P-11
5] Mw 8.3 by the same method as in Synthesis Example 104 except that 10 g of the initiator [I-1] of Synthesis Example 35 was used instead of benzyl N, N-diethyldithiocarbamate.
A resin [P-115] of × 10 ⁴ was obtained.

[0143]

[Chemical 56]

Synthesis Example of Resin [P] 116: [P-11
6] Synthetic Example 105 except that 12 g of the initiator of Synthetic Example 36 was used instead of benzylisopropylxanthate.
In the same manner as in the above, a resin of Mw 9.3 × 10 ⁴ [P-
116] was obtained.

[0145]

[Chemical 57]

Synthesis Examples 117 to 125 of Resin [P]: [P
-117] to [P-125] benzyl-N, N-diethyldithiocarbamate, an initiator [I-104] 14g having the following structure was used, and each unit corresponding to the constitutional unit shown in Table 103 below was used. Synthetic Example 104, except that a polymer was used.
A resin having Mw of 7 × 10 ^{4 to} 9 × 10 ⁴ was obtained by the same method as described above.

[0147]

[Chemical 58]

[0148]

[Table 25]

[0149]

[Table 26]

[0150]

[Table 27]

Synthesis Examples 126 to 134 of Resin [P]: [P
-126] to [P-134] 9.6 g of the compound [1-105] having the structure shown below was used in place of the initiator of Example 36, and each monomer corresponding to the constitutional unit shown in Table 104 below was used. Mw8 was prepared in the same manner as in Synthesis Example 116 except that it was used.
A copolymer of × 10 ⁴ to 10 × 10 ⁴ was obtained.

[0152]

[Chemical 59]

[0153]

[Table 28]

[0154]

[Table 29]

[0155]

[Table 30]

[0155]

[Table 31]

Synthesis Examples 135-138 of Resin [P]: [P
-135] to [P-138] 40 g of a monomer corresponding to the structural unit shown in Table 105 below, and a compound [I-10 having the following structure:
6] A mixture of 11 g and tetrahydrofuran 40 g was sealed in a container under a nitrogen stream and heated to a temperature of 50 g. This was photo-polymerized by irradiating it with a 400 W high-pressure mercury lamp from a distance of 10 cm through a glass filter for 12 hours. To this was added 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, the atmosphere was replaced with nitrogen, and light irradiation was carried out again for 10 hours. The obtained reaction product is methanol 1
Reprecipitated to liter, collected and dried. The obtained resin is
The Mw was 6 × 10 ⁴ to 8 × 10 ⁴ .

[0155]

[Chemical 60]

[0157]

[Table 32] Synthesis Example 201 of resin [P]: [P-201] 57 g of methyl methacrylate, 28 g of methyl acrylate, 15 g of glycidyl methacrylate, initiator [I- of Synthesis Example 37]
2] A mixed solution of 17.5 g and tetrahydrofuran 150 g was heated to a temperature of 50 ° C. under a nitrogen stream. This solution 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. 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. A mixed solution of 40 g of this polymer, 60 g of the monomer (M-2) of Synthesis Example 25, and 100 g of tetrahydrofuran was heated to 50 ° C. under a nitrogen stream and irradiated with light under the same conditions as above for 15 hours. Next, this reaction product was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried to obtain a resin [P-201] having a Mw of 6 × 10 ⁴ with a yield of 78 g.

[0138]

[Chemical formula 61]

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

[0140]

[Table 33]

[0141]

[Table 34]

[0142]

[Table 35]

[0143]

[Table 36]

[0144]

[Table 37]

Synthesis Examples 215 to 233 of Resin [P]: [P
-215] to [P-233] Monomer [M-2] 60 g, instead of 60 g of each monomer [M] corresponding to the constitutional unit of the following Table-203, the same as Synthesis Example 201. Then, each resin [P-215] to [P-233] was obtained.
The Mw of each resin was in the range of 6 × 10 ^{4 to} 7 × 10 ⁴ .

[0146]

[Table 38]

[0147]

[Table 39]

[0148]

[Table 40]

[0147]

[Table 41]

[0148]

[Table 42]

Synthesis Examples 234 to 240 of Resin [P]: [P
-234] to [P-240] 70 g of a methacrylate monomer corresponding to the constitutional unit shown in Table 204 below, and Table 20 below.
Mw 6 × 10 ^{4 to} 7 by the same method as in Synthesis Example 201 except that a mixed solution of 30 g of each monomer corresponding to the structural unit Y of 4 and 15 g of the initiator [I′-7] and 100 g of tetrahydrofuran was used. 80 g of × 10 ⁴ polymer was obtained. Next, 50 g of this polymer, the monomer of Synthesis Example 25 [M
-2] A mixed solution of 50 g and 100 g of tetrahydrofuran 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. The Mw of the obtained resin is 8 × 10 ^4.
It was in the range of 10 × 10 ⁴ .

[0150]

[Table 43]

[0151]

[Table 44]

Synthesis Examples of Resin [P] 241-254: [P
-241] to [P-254] initiator [I-2] 17.5
In the same manner as in Synthesis Example 201 except that 10 g of the initiator [I′-2] was used instead of g and diethyl ether was used instead of the reprecipitation solvent methanol, each resin represented by the following formula [P -241] to [P-254] were synthesized. The Mw of the obtained resin was in the range of 7 × 10 ^{4 to} 9 × 10 ⁴ .

[0001]

[Chemical formula 62]

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

[0001]

[Chemical 63]

[0001]

[Chemical 64]

[0001]

[Chemical 65]

[0001]

[Chemical 66]

[0001]

[Chemical 67]

Synthesis example 301 of resin [P]: [P-30
1] A mixed solution of 60 g of methyl methacrylate, 30 g of macromonomer [M-301] having the following structure, 10 g of glycidyl methacrylate, and 150 g of toluene was heated to 70 ° C. under a nitrogen stream. 1.0 g of 2,2'-azobisisobutyronitrile (abbreviation: AIBN) was added and reacted for 4 hours. I. B. N. 0.5 g was added and reacted for 4 hours. Mw of the obtained resin [P-301]
(Weight average molecular weight) was 6.5 × 10 ⁴ .

[0131]

[Chemical 68]

Synthesis Examples 302-314 of Resin [P]: [P
-302] to [P-314] In Synthesis Example 1 of resin [P-301], except that 30 g of macromonomer [M-301] was replaced with 30 g of macromonomer corresponding to the structural unit of Table -302 below. The resins [P-302] to [P-314] were synthesized in the same manner as in Synthesis Example 301. The Mw of the obtained resin was in the range of 5 × 10 ⁴ to 8 × 10 ⁴ . The Mw of the macromonomer used is shown in the table below.
302.

[0133]

[Table 45]

[0134]

[Table 46]

[0135]

[Table 47]

[0136]

[Table 48]

Synthesis Examples 315 to 325 of Resin [P]: [P
-315] to [P-325] Monomers corresponding to the constitutional units shown in Table -303 below, macromonomer FM-0721 having a polysiloxane structure (manufactured by Chisso Corporation, Mw1 × 10 ⁴ ).
A mixed solution of 25 g and 200 g of toluene was heated to a temperature of 80 ° C. under a nitrogen stream.

[0138]

[Table 49]

[0139]

[Table 50]

[0140]

[Table 51]

[0141]

[Table 52]

Synthesis Examples 326 to 337 of Resin [P]: [P
-326] to [P-337] the following monomers [M-30
2], a resin [P-32 shown in the table was prepared by the same method as in Synthesis Example 301 except that a mixed solution of macromonomer corresponding to the structure in Table 304 below and 200 g of toluene was used.
6] to [P-337] were obtained. Mw of each resin is 6 × 10
It was in the range of ⁴ to 8 × 10 ⁴ .

[0143]

[Chemical 69]

[0144]

[Table 53]

[0140]

[Table 54]

[0141]

[Table 55]

[0142]

[Table 56]

Synthesis Example 401 of Resin [P]: [P-40
1] A mixed solution of 50 g of a monomer (A-401) having the following structure, 0.5 g of an initiator [1-401] having the following structure, and 50 g of tetrahydrofuran was sealed in a container under a nitrogen stream and heated to 60 ° C. Warmed. 1 with a 400W high pressure mercury lamp
Photopolymerization was carried out by irradiating light from a distance of 0 cm through a glass filter for 10 hours. To this reaction solution, a mixed solution of 25 g of methyl methacrylate, 15 g of glycidyl methacrylate, 10 g of macromonomer [MB-401] having the following structure and 50 g of tetrahydrofuran was added, and then the atmosphere was replaced with nitrogen, and light was irradiated again for 16 hours. The resulting reaction mixture was reprecipitated in 1.0 liter of methanol, collected and dried. The obtained resin [P-401] has a Mw of 6 × 10 ⁴ at 68 g.
Met.

[0147]

[Chemical 70]

[0147]

[Chemical 71]

Synthesis Example of Resin [P] 402: [P-40
2] 36 g of a monomer (A-402) having the following structure, 4 g of siloxane macromonomer Praxel-FM-725 (Mw1 × 10 ⁴ manufactured by Nitrogen KK), and an initiator [I
-402] A mixed solution of 1.0 g and tetrahydrofuran 50 g was sealed in a container under a nitrogen stream and heated to a temperature of 50 ° C. Under the same light irradiation conditions as in Synthesis Example 401, 12
It was irradiated with light for an hour and photopolymerized. 24 g of methyl methacrylate, 18 g of methyl acrylate, 18 g of glycidyl methacrylate and 6 g of tetrahydrofuran were added to this polymer solution.
After adding 0 g of the mixed solution, the atmosphere was replaced with nitrogen, and light irradiation was again performed for 10 hours. The resulting reaction mixture was reprecipitated in 1 liter of methanol, collected and dried. Obtained resin [P-
402] had a yield of 70 g and an Mw of 8 × 10 ⁴ .

[0147]

[Chemical 72]

[0147]

[Chemical formula 73]

Synthesis Example 403 of Resin [P]: [P-40
3] 25 g of methyl methacrylate, 15 g of glycidyl methacrylate, a macromonomer having the following structure (MB-40
2) 10 g, 2.5 g of an initiator [I-403] having the following structure
After degassing a mixed solution of 50 g of tetrahydrofuran and tetrahydrofuran under a nitrogen stream, photopolymerization was performed for 12 hours under the same conditions as in Synthesis Example 401. 50 g of the monomer (A-403) having the following structure and 60 g of tetrahydrofuran were added to the polymerization solution.
After adding the mixed solution of, the mixture was replaced with nitrogen, and irradiated again with light for 12 hours to polymerize. The obtained reaction product was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. Mw5.
72 g of 3 × 10 ⁴ resin [P-403] was obtained.

[0147]

[Chemical 74]

[0147]

[Chemical 75]

Synthesis Examples of Resin [P] 404 to 416: [P
-404] to [P-416] macromonomer [M-40
Resins [P-404] to [P-416] were synthesized in the same manner as in Synthesis Example 402 except that macromonomers corresponding to the constitutional units shown in Table 402 below were used instead of [1]. The Mw of the obtained resin was in the range of 5 × 10 ⁴ to 8 × 10 ⁴ . The Mw of the macromonomer used is shown in Table 402 below.

[0147]

[Table 57]

[0147]

[Table 58]

[0001]

[Chemical 76]

[0001]

[Chemical 77]

[0001]

[Chemical 78]

[0001]

[Chemical 79]

[0001]

[Chemical 80]

[0001]

[Chemical 81]

[0001]

[Chemical formula 82]

[0001]

[Chemical 83]

[0001]

[Chemical 84]

[0001]

[Chemical 85]

Synthesis Examples of Resin [P] 417 to 429: [P
-417] to [P-429] Synthesis Example 401 of Resin [P]
The polymers shown in Table 403 below were synthesized in the same manner as in. The Mw of the obtained polymer was 4 × 10 ⁴ to 8 × 10 ^4.
Was in the range. Further, the Mw of the monofunctional macromonomer used was 6 × 10 ^{3 to} 9 × 10 ⁴ .

[0147]

[Table 59]

[0147]

[Table 60]

[0147]

[Table 61]

[0147]

[Table 62]

(Examples and Comparative Examples) Example 1 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 1
g, 10 g of the binder resin [B-1] having the following structure, 0.3 g of the resin [P-2] of the present invention, and 0.1 g of the compound [A] having the following structure.
A mixture of 5 g and 80 g of tetrahydrofuran was added to 500
It was put together with glass beads in a glass container of ml, dispersed for 60 minutes with a paint shaker (manufactured by Toyo Seiki Seisakusho), and the glass beads were filtered to obtain a coating liquid for the photoconductive layer.
Then, this dispersion is applied with a wire bar on a 0.2 mm thick base paper for a master for a printing plate that has been subjected to a conductive treatment and a solvent resistance treatment, and after being dried by touch with a finger, it is heated in a circulating oven at 110 ° C. for 5 minutes. Heated for minutes. The thickness of the photoconductive layer was 8 μm.

[0001]

[Chemical formula 86]

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 ) ... 3 g ammonia (28% aqueous solution) ... 1 g ethanol ... 97 g This solution is 1.3 μm with a wire bar. And was dried in an oven at 120 ° C. for 20 seconds. Comparative Example A An electrophotographic method was performed in the same manner as in Example 1 except that 0.3 g of the resin [P-2] was not added and the same amount of the binder resin [B-1] was added instead. An original plate for color proofing was prepared. Test Example The image-capturing property and transfer property of the electrophotographic type color proofing original plates produced in Example 1 and Comparative Example A were examined. I] Imaging property: +45 in the dark on an electrophotographic original plate for color proofing
After the corona charging with V, the original was read by a color scanner in advance, the color was separated, and some corrections related to the color reproduction unique to the system were added, and then stored in the hard disk in the system as digital image data. 5 in negative mirror image mode based on the information about yellow among yellow, magenta, cyan and black.
Using a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength: 780 nm) with an output of mW, exposure was performed on the surface of the original plate for color calibration at an irradiation amount of 30 erg / cm ² at a pitch of 25 μm and a scan speed of 300 cm / sec. Subsequently, the yellow liquid developer for the signature system (Eastman Kodak (manufactured)) was added 75 times (weight ratio).
Is diluted with Isopar H (manufactured by Esso Standard Petroleum), and a bias voltage of +400 V is applied to the electrode on the side of the original plate for color proofing with a developing device having a pair of flat plate developing electrodes.
Reversal development was performed so that the toner was electrodeposited on the exposed area, and then rinsed in a bath of Isopar H alone to remove stains on the non-image area.

The above processing was repeated for each color of magenta, cyan and black. The image on the original plate for color proof obtained as described above was fixed by a heat roll fixing method. Next, the coated paper, which is the actual printing paper, and the original plate for color proofing after four-color development are superposed and contacted with each other at a pressure of 15 kgf / cm ² , between the pair of rubber rollers whose surface temperature is constantly controlled at 120 ° C. Was passed at a speed of 10 mm / sec. Then, the coated paper was cooled to room temperature while being piled up, and the coated paper was peeled off from the original plate for color proof, and the image (fog, image quality of the image) formed on the obtained coated paper was visually evaluated. In the case of the sample of Example 1, the toner on the original plate for color proofing is thermally transferred to the code paper side together with the transfer layer, and a proper mat is applied to the surface of the transfer layer to obtain a clear image without background fog. Almost no deterioration of the image quality was observed as compared with the original. Further, since the toner is completely covered with the thermoplastic resin which is the transfer layer on the coated paper, it does not rub off and the image strength is sufficient. On the other hand, in the sample of Comparative Example A, the coated paper could not be peeled from the color proofing original plate, and the photoconductive layers on the coated paper side and the color proofing original plate side were damaged, resulting in the performance as the color proofing original plate. Did not meet at all. The difference between the performances of the color proofing master of Example 1 and Comparative Example A is that in the color proofing master of Example 1, the fluorine atom-containing resin [P] coexisting in the photoconductive layer was the photoconductive layer. Due to the concentration and migration to the surface portion during formation, and because the binder resin [Q] and the resin [P] were sufficiently chemically bonded between the polymers by the crosslinking agent to form a cured film, good releasability was obtained. It is considered that this is because the interface was clearly formed. As described above, only the original plate for color proof of the present invention showed good performance as the original plate for color proof. Further, in order to investigate the peeling property of the photoconductive layer formed in Example 1 and Comparative Example A, the adhesive force on the surface of the photoconductive layer was measured before forming the transfer layer. Adhesiveness is based on JIS
Z0237-1980 "Adhesive tape / sheet test method"
It was measured by. The adhesive force of the photoconductive layer formed in Example 1 was 0 g · f, and the adhesive force of the photoconductive layer formed in Comparative Example A was 370 g · f.

Example 2 200 g of photoconductive zinc oxide, a binder resin [B-
2] 80 g, resin [P-25] 8 g of the present invention, dye [D-1] 0.018 g having the following structure, phthalic anhydride 0.20
g and 300 g of toluene into a ball mill 2
It was dispersed for a time to obtain a coating liquid for the photoconductive layer. Then, this coating solution was applied onto a 0.2 mm thick base paper for a master for a printing plate, which had been subjected to a conductive treatment and a solvent resistance treatment, with a wire bar, and was dried by touch with a finger, and then heated in a circulating oven at 110 ° C. for 10 minutes. .. The film thickness was 10 μm.

[0001]

[Chemical 87]

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. Comparative Example B Electrophotographic color proofing was performed in the same manner as in Example 2 except that 8 g of the resin [P-25] was not added and the same amount of the binder resin [B-2] was added instead. A master plate was prepared. Test Example In the color proofing masters of Example 2 and Comparative Example B, when an adhesive tape was attached to the surface of the transfer layer and peeled off, the transfer layer of the color proofing master of Example 2 was easily peeled off without feeling resistance. However, peeling failure occurred in the transfer layer of the color proofing original plate of Comparative Example B. Next, this color calibration original plate was corona-charged at -600 V in a dark place, and then, using the same digital image data as in Example 1, first, based on the information about yellow, in the positive mirror image mode, the semiconductor laser was used. Exposure of 25 erg / cm ² with light of 780 nm using
Was exposed. The residual potential of the exposed part is -120v
Met. Then, the yellow toner for Versatec 3000 (Xerox color electrostatic plotter) was diluted 50 times with Isopar H (Esso Standard Petroleum) and used, and the original surface for color proofing was developed with a developing device having a pair of flat plate developing electrodes. A bias voltage of -200 V was applied to the side electrode to perform positive development in which 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 processing is magenta, cyan,
Repeated for each color of ink. Next, the coated paper, which is the actual printing paper, and the original plate for color proof after four-color development are overlaid, and
The surface temperature is 12 in contact with each other at a pressure of 0 kgf / cm ^2.
It was passed at a speed of 6 mm / sec between a pair of rubber rollers which were constantly controlled at 0 ° C. After that, the coated paper was peeled off from the color proofing original plate after being cooled to room temperature while being piled up. In the color proofing original plate of Example 2, the toner was thermally transferred to the coated paper side together with the transfer layer,
In addition, the surface of the transfer layer was appropriately matted, and the difference from the image quality obtained by printing was small. In Comparative Example B,
Peeling failure occurred. Further, in the color proofing original plate of Example 2, since the toner was completely covered on the coated paper by the thermoplastic resin as the transfer layer, it was not scraped off. Further, in order to investigate the peeling property of the photoconductive layer formed in Example 2 and Comparative Example B, the adhesive force on the surface of the photoconductive layer was measured before forming the transfer layer. Adhesiveness is the same as JI
SZ0237-1980 "Adhesive tape / sheet test method" was used for measurement. The adhesive force of the photoconductive layer formed in Example 2 was 5 g · f, and the adhesive force of the photoconductive layer formed in Comparative Example A was 380 g · f.

Example 3 4,4'-bis (diethylamino) -2,2'-dimethyltriphenylmethane 5 as an organic photoconductive compound
g, 4 g of the binder resin [B-3] having the following structure, 0.8 g of the resin [P-15] of the present invention, and the dye [D-2] 4 having the following structural formula.
0 mg and 0.2 g of the anilide compound (B) having the following structural formula as a chemical sensitizer, and 30 ml of methylene chloride
And 30 ml of ethylene chloride were dissolved to obtain a coating liquid for the photoconductive layer. This photoconductive layer coating liquid was applied to a conductive transparent support (100) using a wire round rod.
It has a vapor deposited film of indium oxide on a μm polyethylene terephthalate support. A surface resistance of 10 ³ Ω) was applied to obtain an organic thin film having a photoconductive layer of about 4 μm.

[0192]

[Chemical 88]

In order to confirm the uneven distribution of the resin [P-15] on the surface of the photoconductive layer, the adhesive force on the surface of the photoconductive layer obtained in this example was measured by the same method as in Example 1. The adhesive force of the photoconductive layer according to this example was the same as that of this example except that the resin [P-15] was not added and the same amount of the binder resin [B-3] was added instead. The adhesive strength of the produced comparative sample was reduced to 1/50, and it was confirmed that the resin was unevenly distributed on the surface of the photoconductive layer. Furthermore, in order to form a transfer layer on this photoconductive layer, Example 1
A thermoplastic resin solution similar to the above 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, helium-neon laser light having an oscillation wavelength of 630 nm was used instead of the semiconductor laser light having an oscillation wavelength of 780 nm used in Example 1. The color copied image of the obtained coated paper after transfer was clear without background fog and showed sufficient image strength.

Example 4 5 g of bisazo pigment having the following structure, tetrahydrofuran 95
g, polyester resin Byron 200 (Toyobo Co., Ltd.)
5 g) and a tetrahydrofuran solution (30 g) were thoroughly pulverized in a ball mill. Then, this mixture was taken out, and 520 g of tetrahydrofuran was added with stirring. This dispersion was coated on the conductive transparent support used in Example 3 using a wire round rod to give about 0.7 μm.
m charge generating layer was formed.

[0001]

[Chemical 89]

Next, the hydrazone compound 20 of the following structural formula
g, polycarbonate resin (manufactured by GE, trade name Lexan 121) 20 g, resin of the present invention having the following structure [P-49]
A mixed solution of 3 g and tetrahydrofuran (160 g) was applied on the charge generation layer using a wire round rod to form a charge transport layer of about 18 μm, and a color proofing master plate having a photoconductive layer composed of two layers was obtained. ..

[0001]

[Chemical 90]

Next, this color proofing original plate was operated in a dark place in the same manner as in Example 3 to examine the image pick-up property and the transfer property. The color copied image of the obtained coated paper after transfer was clear without background fog and showed sufficient image strength. Examples 5 to 34 Resins 10 shown in Table 9 below were used instead of 8 g of the resin [P-25].
An original plate for each color proof was prepared in the same manner as in Example 2 except that g was used.

[0200]

[Table 63]

Next, these color proofing original plates were operated in a dark place in the same manner as in Example 2 to examine the image pick-up property and transfer property.
The obtained color copied images of the coated paper after transfer were all clear with no background fog and showed sufficient image strength. Example 35 8 g of resin [P-25] and 0.018 g of dye [D-1]
In the same manner as in Example 2 except that 10 g of resin particles [L-1] (as solid content) and 0.020 g of a dye [D-3] having the following structure were used instead of It was made.

[0001]

[Chemical Formula 91]

A color proof was prepared by operating this color proofing original plate in the same manner as in Example 2. The color copied image obtained was clear and free of background fog. Examples 36 to 51 In the same manner as in Example 35 except that 11 g of resin particles [L] (as solid content) shown in Table 10 below was used instead of 10 g of resin particles [L-1], each color proof plate was prepared. Was produced.

[0204]

[Table 64]

Next, these color proofing original plates were operated in the dark in the same manner as in Example 2 to examine the image pick-up property and transfer property.
All the color copied images obtained were clear without background fog and showed sufficient image strength. Examples 52 to 56 The same as Example 2 except that the resin and the coating solvent shown in Table 11 below were used instead of the thermoplastic resin: poly (vinyl acetate / crotonic acid) (95/5 molar ratio) of the transfer layer. The original plate for each color proof was prepared by the method described above.

[0206]

[Table 65]

The obtained color proof plate was examined for image pickup and transfer properties in the same manner as in Example 2.
It also showed good performance. Example 101 For the production of the coating liquid for the photoconductive layer, 1 g of X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.), 10 g of the binder resin [B-1] shown in the above Example 1, and the resin [P- 105] 0.3
g, a color proofing original plate was produced in the same manner as in Example 1 except that a mixed solution of 0.15 g of the compound [A] shown in Example 1 above and 80 g of tetrahydrofuran was used. In addition, when the image pick-up property and the transfer property were examined by the same method as in Example 1, the color proofing original plate produced in this Example had the same good performance as the color proofing original plate obtained in Example 1. showed that. Example 102 Photoconductive zinc oxide 200 was used for producing a coating liquid for photoconductive layer.
g, 80 g of the binder resin [B-102] having the following structure, 8 g of the resin [P-103], and the dye [D-
1] 0.018 g, N-hydroxysuccinimide 0.
An original plate for color proofing was produced in the same manner as in Example 2 except that a mixture of 20 g and 300 g of toluene was used.

[0001]

[Chemical Formula 92]

The same test as in Example 2 was carried out on the obtained color proofing original plate, and it was revealed that it had good performance as a color proofing original plate. Further, regarding the adhesive strength of the surface of the photoconductive layer of the original plate for color proof obtained in this example, the resin [P-103] was not added, but the same amount of the binder resin [B-102] was added. It was found that the adhesive strength was reduced to 1/60 of that of the comparative sample produced by the same method as in this example except that the above was performed. Example 103 The coating liquid for the photoconductive layer was mixed with 5 g of 4,4′-bis (diethylamino) -2,2′-dimethyltriphenylmethane, 4 g of a binder resin [B-103] having the following structure, and the above resin [P-
119] 0.8 g, the dye [D-2] 4 shown in Example 3
0 mg, and the anilide compound (B) shown in Example 3
An original plate for color proofing was produced in the same manner as in Example 3 except that 0.2 g was dissolved in a mixture of 30 ml of methylene chloride and 30 ml of ethylene chloride.

[0001]

[Chemical formula 93]

When the same test as in Example 3 was carried out on the obtained color proofing original plate, the obtained color copied image was clear with no background fog and was excellent in durability. Further, regarding the adhesive strength of the surface of the photoconductive layer of the original plate for color proof obtained in this example, the resin [P-119] was not added, but the same amount of the binder resin [B-103] was added instead. It was found that the adhesive strength was reduced to 1/70 of that of the comparative sample manufactured by the same method as that of this example except that the above was performed. Example 104 To form the charge transport layer, 20 g of the hydrazone compound shown in Example 4, 20 g of a polycarbonate resin (manufactured by GE, trade name Lexane 121), 2 g of resin [P-102], 0.04 g of isophorone diisocyanate, 0.001 g of tetrabutoxy titanate and 160 g of tetrahydrofuran
An original plate for color proofing was manufactured by the same method as in Example 4 except that the mixed solution of 1 was used. When the same test as in Example 3 was performed on the obtained color proofing original plate, the obtained color copied image was clear without background fog and was excellent in durability. Examples 105 to 110 A color proof plate was prepared in the same manner as in Example 1 except that 0.2 g of each resin shown in Table 106 below was used instead of 0.3 g of the resin [P-2].

[0001]

[Table 66]

Next, using these color proofing original plates, the image pickup property and the transfer property were examined by the same method as in Example 1. The color copied image of the obtained coated paper after transfer was clear with no background fog, and was excellent in durability and transferability. Examples 111 to 116 For the production of the coating liquid for the photoconductive layer, the photoconductive zinc oxide 200 was used.
g, 80 g of a binder resin [B-102] having the following structure, 8 g of a resin [P] shown in Table 107 below, 0.020 g of the dye [D-3] shown in Example 35, and N-hydroxysuccinimide. A color proofing original plate was produced in the same manner as in Example 2 except that a mixture of 0.20 g and toluene 300 g was used.

[0001]

[Table 67]

When these color proofing master plates were operated in the same manner as in Example 2 to produce a color proof, the color copied image obtained was clear and free from scumming. Examples 117 to 127 200 g of photoconductive zinc oxide, a binder resin [B-
104] 70 g, dye of the following structure [D-104] 0.0
A mixture of 19 g, N-hydroxymaleimide 0.018 g, and toluene 300 g was put into a homogenizer, and the rotation speed was 7 × 10 ³ r. p. m. Dispersed for 10 minutes. To this dispersion, 6 g of each resin [P] shown in the following Table-108 and a predetermined amount of the crosslinking compound shown in the following Table-108 were added, and further the rotation speed was 1 × 10 ³ r. p. m. Dispersed for 1 minute. Then, the dispersion was subjected to a conductivity treatment and a solvent resistance treatment to 0.2.
It was coated with a wire bar on a paper master sheet having a thickness of mm, dried by touch with a finger, and then heated at 140 ° C. in a circulating oven for 2 hours. The film thickness was 10 μm. Further, in order to form a transfer layer on the photoconductive layer, the same thermoplastic resin solution as in Example 1 was prepared, applied and dried.

[0193]

[Chemical 94]

[0194]

[Table 68]

Next, these color proof plates were operated in the dark in the same manner as in Example 2 to examine the image pick-up property and transfer property.
The obtained color copied images of the coated paper after transfer were clear without background fog and showed sufficient image strength. Examples 128 to 134 Binder resin [B] 60 g and resin [P] 7 shown in Table 109 below.
g and a predetermined amount of the crosslinking compound, respectively,
In the same manner as in 17, an electrophotographic color proofing original plate was prepared.

[0001]

[Table 69]

[0001]

[Table 70]

[0001]

[Table 71]

[0001]

[Table 72]

Next, these color proofing original plates were operated in a dark place in the same manner as in Example 2 to examine the image pick-up property and transfer property.
The obtained color copied images of the coated paper after transfer were all clear with no background fog and showed sufficient image strength. Examples 135 to 139 In place of the thermoplastic resin: poly (vinyl acetate / crotonic acid) (95/5 molar ratio) of the uppermost transfer layer used in Example 102, the resins and coating solvents shown in Table 110 below are used. Except that, the same procedure as in Example 102 was performed to prepare each color proofing original plate.

[0201]

[Table 73]

When the image-capturing / transferring properties of the obtained master plates for proofing each color were examined in the same manner as in Example 2, all of them showed the same level of performance as in Example 2 and were good. Example 201 For the production of a coating liquid for a photoconductive layer, 1 g of X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.), 10 g of binder resin [Q-1] having the following structure, resin [P-241] 0. An original plate for color proofing was manufactured in the same manner as in Example 1 except that a mixed solution of 3 g, 0.15 g of the compound [A] shown in Example 1 and 80 g of tetrahydrofuran was used. In addition, Example 1
When the image pick-up property and the transfer property were examined by the same method as described in 1., the color proofing master plate manufactured in this example showed good performance. Example 202 Photoconductive zinc oxide 200 was used in the production of the coating liquid for the photoconductive layer.
g, 80 g of a binder resin [Q-2] having the following structure, 8 g of the above resin [P-201], and the dye [D-1] shown in Example 2.
0.018 g, N-hydroxysuccinimide 0.20
An original plate for color proofing was manufactured in the same manner as in Example 2 except that a mixture of g and 300 g of toluene was used.

[0001]

[Chemical 95]

The same test as in Example 2 was carried out on the obtained color proofing original plate, and it was revealed that it had good performance as a color proofing original plate. Further, the adhesive strength of the surface of the photoconductive layer of the color proofing original plate obtained in this Example was the same as that of the binder resin [Q-2, without adding the block copolymer [P-201]. It was found that the adhesive strength was reduced to 1/60 of the adhesive strength of the comparative sample manufactured by the same method as in this example except that the addition of Example 203 The coating liquid for the photoconductive layer was mixed with 5 g of 4,4′-bis (diethylamino) -2,2′-dimethyltriphenylmethane, 4 g of a binder resin [Q-3] having the following structure, and the above resin [P- 21
9] 0.8 g, the dye [D-2] 40 m shown in Example 3
g, 0.2 g of the anilide compound (B) shown in Example 3
Was prepared by dissolving it in a mixture of 30 ml of methylene chloride and 30 ml of ethylene chloride, and an original plate for color proofing was produced in the same manner as in Example 3.

[0001]

[Chemical 96]

When the same test as in Example 3 was carried out on the obtained color proofing original plate, the obtained color copied image was clear with no background fog and was excellent in durability. Further, the adhesive strength of the surface of the photoconductive layer of the color proofing original plate obtained in this Example was the same as that of the binder resin [Q-3] without adding the block copolymer [P-219]. It was found that the adhesive strength was reduced to 1/90 of the adhesive strength of the comparative sample manufactured by the same method as in this example except that the addition of Example 204 To form the charge transport layer, 20 g of the hydrazone compound shown in Example 4, 20 g of a polycarbonate resin (manufactured by GE, trade name Lexane 121), 2 g of resin [P-235], 0.04 g of isophorone diisocyanate, 0.001 g of tetrabutoxy titanate and 160 g of tetrahydrofuran
An original plate for color proofing was manufactured by the same method as in Example 4 except that the mixed solution of 1 was used. When the same test as in Example 3 was performed on the obtained color proofing original plate, the obtained color copied image was clear without background fog and was excellent in durability. Examples 205 to 210 Photoconductive zinc oxide 200 was used for the production of the coating liquid for the photoconductive layer.
g, the binder resin [Q-2] of Example 202, and the following Table-20.
No. 6 resin [P] 8 g, dye [D-3] shown in Example 35
0.020 g, N-hydroxysuccinimide 0.20
g and toluene 300 g was used, and the same procedure as in Example 2 was carried out to prepare a color proofing original plate.

[0001]

[Table 74]

When these color proofing original plates were tested in the same manner as in Example 2, the color copied image obtained had clear image quality without scumming. Examples 211 to 221 200 g of photoconductive zinc oxide, a binder resin [Q-
4] 70 g, the dye [D-shown in Examples 117 to 127]
4] 0.019 g, N-hydroxymaleimide 0.
A mixture of 018 g and 300 g of toluene was placed in a homogenizer and the rotation speed was 7 × 10 ³ r. p. m. Dispersed for 10 minutes. To this dispersion, 6 g of each resin [P] shown in Table 207 below and a predetermined amount of the crosslinking compound shown in Table 207 below were added, and the rotation speed was 1 × 10 ³ r. p. m. Dispersed for 1 minute. Then, this dispersion was applied onto a 0.2 mm-thick base paper for a master for a printing plate with a wire bar, which had been subjected to a conductive treatment and a solvent resistance treatment, and was dried by touch with a finger.
was μm. Further, in order to form a transfer layer on the photoconductive layer, the same thermoplastic resin solution as in Example 1 was prepared,
An original plate for electrophotographic color proofing was obtained by coating and drying.

[0001]

[Chemical 97]

[0001]

[Table 75]

Next, these electrophotographic color proofing original plates were operated in the dark in the same manner as in Example 2 to examine the image pick-up property and transfer property. The obtained color copied images of the coated paper after transfer were all clear with no background fog and showed sufficient image strength. Examples 222 to 228 Binder resin [Q] 60 g and resin [P] 7 shown in Table 208 below.
g, and a predetermined amount of the crosslinking compound, respectively,
In the same manner as in 11, an electrophotographic type color proofing original plate was prepared.

[0188]

[Table 76]

[0001]

[Chemical 98]

[0001]

[Chemical 99]

[0001]

[Chemical 100]

[0001]

[Chemical 101]

Next, these electrophotographic color proofing original plates were operated in the dark in the same manner as in Example 2 to examine the image pick-up property and transfer property. The obtained color copied images of the coated paper after transfer were all clear with no background fog and showed sufficient image strength. Examples 229 to 233 In the production of the coating liquid for the photoconductive layer, 1 g of X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.), 10 g of binder resin [Q-1] having the following structure, and resin [P-241]. 0.3 g, a mixed solution of 0.15 g of the compound [A] shown in Example 1 and 80 g of tetrahydrofuran was used, and instead of the thermoplastic resin: poly (vinyl acetate / crotonic acid) (95/5 molar ratio) in the transfer layer. In the same manner as in Example 1 except that the resins and coating solvents shown in Table 209 below were used, each electrophotographic color proofing original plate was prepared.

[0190]

[Table 77]

The respective electrophotographic color proofing plates obtained were examined for image pick-up and transferability in the same manner as in Example 1. All of them showed the same level of performance as in Example 1 and were good. .. Examples 234 to 247 1 g of X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) and the binder resin [Q-
1] 10 g, 0.2 g of each resin shown in Table 210 below, 0.15 g of the compound [A] shown in Example 1 and 80 g of tetrahydrofuran were used, and the same operation as in Example 1 was repeated. An original plate for electrophotographic color proofing was prepared.

[0191]

[Table 78]

Next, these electrophotographic color proof masters were operated in the dark in the same manner as in Example 1 to examine the image pick-up property and transfer property. The obtained color copied images of the coated paper after transfer were all clear with no background fog and showed sufficient image strength. Example 301 For the production of the coating liquid for the photoconductive layer, 1 g of X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.), 10 g of the binder resin [B-1] shown in Example 1 above, and the resin [P- 315] 0.3
g, a color proofing original plate was produced in the same manner as in Example 1 except that a mixed solution of 0.15 g of the compound [A] shown in Example 1 above and 80 g of tetrahydrofuran was used. Further, when the image pick-up property and the transfer property were examined by the same method as in Example 1, the color proofing original plate produced in this example showed good performance. Example 302 Photoconductive zinc oxide 200 was used in the production of the coating liquid for the photoconductive layer.
g, 80 g of a binder resin [B-302] having the following structure, 8 g of the above resin [P-301], and the dye [D-
1] 0.018 g, N-hydroxysuccinimide 0.
An original plate for color proofing was produced in the same manner as in Example 2 except that a mixture of 20 g and 300 g of toluene was used.

[0001]

[Chemical 102]

The same test as in Example 2 was carried out on the obtained color proofing original plate, and it was revealed that it had good performance as a color proofing original plate. Further, the adhesive strength of the surface of the photoconductive layer of the color proofing original plate obtained in this example was the same as that of the binder resin [B-302] without adding the block copolymer [P-301]. It was found that the adhesive strength was reduced to 1/60 of the adhesive strength of the comparative sample produced by the same method as in this example except that the addition of Example 303 The coating liquid for the photoconductive layer was mixed with 5 g of 4,4′-bis (diethylamino) -2,2′-dimethyltriphenylmethane, 4 g of a binder resin [B-303] having the following structure, and the above resin [P-
324] 0.8 g, the dye [D-2] 4 shown in Example 3
0 mg, 0.2 of the anilide compound (B) shown in Example 3
g was dissolved in a mixture of 30 ml of methylene chloride and 30 ml of ethylene chloride.
A color proofing original plate was manufactured in the same manner as in Example 3.

[0001]

[Chemical 103]

When the same test as in Example 3 was carried out on the obtained color proofing original plate, the obtained color copied image was clear with no background fog and was excellent in durability. Further, the adhesive strength of the surface of the photoconductive layer of the color proof plate obtained in this example was the same as that of the binder resin [B-303] without adding the block copolymer [P-324]. It was found that the adhesive strength was reduced to 1/90 of the adhesive strength of the comparative sample manufactured by the same method as in this example except that the addition of Example 304 To form the charge transport layer, 20 g of the hydrazone compound shown in Example 4, 20 g of a polycarbonate resin (manufactured by GE, trade name Lexan 121), 2 g of resin [P-331], 0.04 g of isophorone diisocyanate, 0.001 g of tetrabutoxy titanate and 160 g of tetrahydrofuran
An original plate for color proofing was manufactured by the same method as in Example 4 except that the mixed solution of 1 was used. When the same test as in Example 3 was performed on the obtained color proofing original plate, the obtained color copied image was clear without background fog and was excellent in durability. Examples 305 to 310 0.2 g of each resin shown in Table 305 below was used instead of 8 g of the resin [P-25], and Table 305 below was used as a compound for crosslinking.
An original plate for color proofing was prepared in the same manner as in Example 2 except that the above compound was used.

[0001]

[Table 79]

A color proof was prepared by operating these electrophotographic original plates for color proofing in the same manner as in Example 2. The color copied image obtained had clear image quality without background stains. .. Examples 311 to 321 200 g of photoconductive zinc oxide, a binder resin having the following structure [B-
304] 70 g, a mixture of the dye [D-104] 0.019 g shown in Examples 117 to 127, N-hydroxymaleinimide 0.018 g and toluene 300 g,
Put in homogenizer and rotate at 7 × 10 ³ r. p. m. Dispersed for 10 minutes. To this dispersion, 6 g of each resin [P] shown in the following Table-306 and a predetermined amount of the crosslinking compound shown in the following Table-306 were added, and further the rotation speed was 1 × 10 ³ r. p. m. In 1
Dispersed for minutes. Then, this dispersion is applied with a wire bar onto a 0.2 mm-thick base paper for a master for a printing plate that has been subjected to a conductive treatment and a solvent resistance treatment, and is dried by touching with a finger.
Heated in a circulating oven for 2 hours. The film thickness was 10 μm. 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 to obtain an electrophotographic color proofing original plate.

[0001]

[Chemical 104]

[0001]

[Table 80]

Next, these electrophotographic color proofing original plates were operated in the dark in the same manner as in Example 2 to examine the image pick-up property and transfer property. The obtained color copied images of the coated paper after transfer were all clear with no background fog and showed sufficient image strength. Examples 322 to 328 Binder resin [Q] 60 g and resin [P] 7 shown in Table 307 below.
g and a predetermined amount of the crosslinking compound, respectively,
In the same manner as in 11, an electrophotographic type color proofing original plate was prepared.

[0181]

[Table 81]

In the table, B-5 to B-11 are the above-mentioned table-208.
Is a compound represented by the formula shown in. Next, these electrophotographic color proofing original plates were operated in the dark in the same manner as in Example 2 to examine the image pick-up property and the transfer property. The obtained color copied images of the coated paper after transfer were clear without background fog and showed sufficient image strength. Examples 329 to 333 In the production of the coating liquid for the photoconductive layer, 1 g of X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.), 10 g of the binder resin [B-1] shown in Example 1 above, and a resin [ P-315] 0.3
g, a mixed solution of 0.15 g of the compound [A] shown in Example 1 and 80 g of tetrahydrofuran was used, and the thermoplastic resin of the transfer layer: poly (vinyl acetate / crotonic acid) (95
Each of the electrophotographic color proofing master plates was prepared in the same manner as in Example 1 except that the resins and coating solvents shown in Table 308 below were used instead of the (5/5 molar ratio).

[0184]

[Table 82]

The respective electrophotographic color proofing plates obtained were examined for image pick-up and transferability in the same manner as in Example 1. All of them showed the same level of performance as in Example 1 and were good. .. Examples 334 to 347 Electrophotographic color proofing master plates were operated in the same manner as in Example 1 except that 0.2 g of each resin shown in Table 309 below was used instead of 0.3 g of the resin [P-2]. Was produced.

[0185]

[Table 83]

Next, these electrophotographic color proof plates were operated in the dark in the same manner as in Example 1 to examine the image pick-up property and transfer property. The obtained color copied images of the coated paper after transfer were all clear with no background fog and showed sufficient image strength. Example 401 1 g of X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.), 10 g of binder resin [B-401] represented by the following structural formula, and resin [P- 402]
0.3 g, compound [A] 0.15 shown in Example 1 above
A master plate for color proofing was manufactured by the same method as in Example 1 except that a mixed solution of 80 g of tetrahydrofuran and 80 g of tetrahydrofuran was used. Further, when the image pick-up property and the transfer property were examined by the same method as in Example 1, the color proofing original plate produced in this example showed good performance.

[0001]

[Chemical 105] Example 402 Photoconductive zinc oxide 200 was used in the production of the coating liquid for the photoconductive layer.
g, binder resin [B-302] 80 g, the above resin [P-4
01] 8 g, the dye [D-1] 0.01 shown in Example 2
An original plate for color proofing was manufactured in the same manner as in Example 2 except that a mixture of 8 g, 0.20 g of N-hydroxysuccinimide and 300 g of toluene was used. The same test as in Example 2 was carried out on the obtained color proof plate,
It has become clear that it has good performance as a color proofing original plate. Further, the adhesive strength of the surface of the photoconductive layer of the color proofing original plate obtained in this example was determined by the block copolymer [P-40
1] was not added, but instead the same amount of binder resin [B-40
It was found that the adhesive strength was reduced to 1/60 of the adhesive strength of the comparative sample manufactured by the same method as that of this example except that 2) was added. Example 403 A coating solution for a photoconductive layer was prepared by adding 5 g of 4,4′-bis (diethylamino) -2,2′-dimethyltriphenylmethane, 4 g of a binder resin [B-403] having the following structure, and the above resin [P-
417] 0.8 g, the dye [D-2] 4 shown in Example 3
0 mg, 0.2 of the anilide compound (B) shown in Example 3
g was dissolved in a mixture of 30 ml of methylene chloride and 30 ml of ethylene chloride.
A color proofing original plate was manufactured in the same manner as in Example 3.

[0001]

[Chemical formula 106]

When the same test as in Example 3 was carried out on the obtained color proofing original plate, the obtained color copied image was clear with no background fog and was excellent in durability. Further, the adhesive strength of the surface of the photoconductive layer of the color proofing original plate obtained in this example was the same as that of the binder resin [B-403] without adding the block copolymer [P-417]. It was found that the adhesive strength was reduced to 1/90 of the adhesive strength of the comparative sample manufactured by the same method as that of this example except that the adhesive strength was replenished. Example 404 For formation of the charge transport layer, 20 g of the hydrazone compound shown in Example 4, 20 g of a polycarbonate resin (manufactured by GE, trade name Lexan 121), resin [P-427] 2 g, 1,
4-Xylylenediamine 0.04 g, tetrabutoxy titanate 0.001 g and tetrahydrofuran 160 g
An original plate for color proofing was manufactured by the same method as in Example 4 except that the mixed solution of 1 was used. When the same test as in Example 3 was performed on the obtained color proofing original plate, the obtained color copied image was clear without background fog and was excellent in durability. Examples 405 to 410 8 g of resin [P-401] and dye [D-1] 0.018
g, and 8 g of each resin [P] in the following Table-405 instead of 0.20 g of N-hydroxysuccinimide, a predetermined amount of the crosslinking compound and the dye [D-3] 0.0 shown in Example 35.
A color proofing original plate was prepared in the same manner as in Example 402 except that 20 g was used.

[0001]

[Table 84]

A color proof was prepared by operating these electrophotographic original plates for color proofing in the same manner as in Example 2. The color copied image obtained was clear and free of image stains. .. Examples 411 to 420 Photoconductive zinc oxide 200 g, binder resin [B-304] 7
0 g, the dyes described in Examples 117 to 127 [D-10
4] 0.019 g, N-hydroxymaleimide 0.
A mixture of 018 g and 300 g of toluene was placed in a homogenizer and the rotation speed was 7 × 10 ³ r. p. m. Dispersed for 10 minutes. To this dispersion, 6 g of each resin [P] shown in Table 406 below and a predetermined amount of the crosslinking compound shown in Table 306 below were added, and the rotation speed was 1 × 10 ³ r. p. m. Dispersed for 1 minute. Then, this dispersion was applied on a 0.2 mm thick base paper for a master for a printing plate, which had been subjected to a conductive treatment and a solvent resistance treatment, with a wire bar, and was dried by touch with a finger, and then heated in a circulating oven at 140 ° C. for 2 hours. .. The film thickness was 10 μm. 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 to obtain an electrophotographic color proofing original plate.

[0001]

[Table 85]

Next, these electrophotographic color proofing original plates were operated in the dark in the same manner as in Example 2 to examine the image pick-up property and transfer property. The obtained color copied images of the coated paper after transfer were clear without background fog and showed sufficient image strength. Examples 421 to 427 Binder resin [B] 60 g and resin [P] 7 shown in Table 407 below.
g, and a predetermined amount of the crosslinking compound, respectively,
In the same manner as in 11, an electrophotographic type color proofing original plate was prepared.

[0181]

[Table 86]

Next, these electrophotographic color proofing original plates were operated in the dark in the same manner as in Example 2 to examine the image pick-up property and transfer property. The obtained color copied images of the coated paper after transfer were clear without background fog and showed sufficient image strength. Examples 428 to 432 In place of the thermoplastic resin: poly (vinyl acetate / crotonic acid) (95/5 molar ratio) of the uppermost transfer layer used in Example 401, the resins and coating solvents shown in Table 408 below were used. Other than that, the same operation as in Example 401 was performed to prepare each electrophotographic color proofing original plate.

[0184]

[Table 87]

The respective electrophotographic color proofing plates obtained were examined for image pick-up and transferability in the same manner as in Example 1. All of them showed the same level of performance as in Example 1 and were good. .. Examples 433 to 447 In Example 402, each electrophotographic color was prepared in the same manner as in Example 1 except that 0.2 g of each resin shown in Table 309 below was used instead of 8 g of the resin [P-401]. An original plate for calibration was prepared.

[0185]

[Table 88]

Next, these electrophotographic color proof plates were operated in the dark in the same manner as in Example 1 to examine the image pick-up property and transfer property. The obtained color copied images of the coated paper after transfer were all clear without background fog and showed sufficient image strength. Example 501 100 g of photoconductive zinc oxide, 40 g of random copolymer [P-501] having the following structure, and bromphenol blue 60
A mixture of mg, 0.2 g of phthalic anhydride and 150 g of toluene was placed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at a rotation speed of 1 × 10 ⁴ r. p. m. Dispersed for 5 minutes. Furthermore, 0.1 g of phthalic anhydride and 0.02 g of o-chlorophenol were added to this dispersion, and the rotation speed was 1 × 10 ³ r. p. m.
Dispersed for 1 minute. Then, this dispersion liquid was applied onto a 0.2 mm thick base paper for a master for a printing plate, which had been subjected to a conductive treatment and a solvent resistance treatment, by a wire bar so that the coating amount was 25 g / m ^2, and the temperature was 110 ° C. for 30 seconds. 120 more after drying
Heated at ° C for 1 hour.

[0001]

[Chemical formula 107]

Further, the same thermoplastic resin solution as in Example 1 was prepared to form a transfer layer on the photoconductive layer,
It was applied and dried. The obtained color proof plate was exposed at 633 nm using a He-Ne laser in a positive mirror image mode.
The test was performed by the same method as in Example 2 except that the plate surface exposure amount was 30 erg / cm ² with the above light.
It was clarified that the color proofing original plate of this example had good image pick-up property and transfer property. Examples 502 to 504 Instead of the random copolymer [P-501], the following random copolymers [P-502], [P-503] and [P-503] are used.
-504] was used to manufacture and test a color proofing original plate by the same method as in Example 501. When the same test as in Example 2 was performed on the obtained color proof plate,
It has been revealed that the original plate for color proof has good image pickup property and transfer property.

[0001]

[Chemical 108]

[0001]

[Chemical 109]

[Chemical 110]

[Chemical 111]

[Table 89]

[Table 90]

[Table 91]

[Table 92]

[Brief description of drawings]

FIG. 1 shows a thermal transfer device.

FIG. 2 is a schematic diagram showing a process of forming a final color proof by thermally transferring an electrophotographic color proofing original plate to a printing main paper after toner development.

[Explanation of symbols]

 1 Rubber-Coated Metal Roller 2 Heater for Built-in Heating 3 Surface Temperature Detection Unit 4 Temperature Controller 5 Electrophotographic Color Calibration Master 6 6 Composite Toner Image Consisting of 4 Color Separation Image 7 Printing Main Paper 8 Transfer Layer 9 Photoconductive Layer 10 Conductivity Support 11 Resin [P] and / or resin particles [L]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location G03G 15/01 Z 7818-2H (31) Priority claim number Japanese Patent Application No. 3-289649 (32) Priority Hihei 3 (1991) November 6 (33) Priority claiming country Japan (JP)

Claims (6)

[Claims] 1. A color proof, comprising a support, a photoconductive layer and a transfer layer, and transferring a toner image of at least one color formed on the transfer layer by an electrophotographic process onto a material to be transferred together with the transfer layer. An electrophotographic color proofing original plate for producing a print, wherein the photoconductive layer contains a resin [P] containing a structural unit having a fluorine atom and / or a silicon atom, and / or
Alternatively, the resin particles [L] are contained at least in the vicinity of the surface in contact with the transfer layer, and the surface of JIS Z0237-198 is included.
0 An electrophotographic original plate for color proofing, which has an adhesive strength of 150 gram · force (g · f) or less as tested by “adhesive tape / sheet test method”. 2. The electrophotographic original plate for color proofing according to claim 1, wherein the resin [P] contains a constituent unit having a light and / or thermosetting group. 3. The electrophotographic color proofing original plate according to claim 1, wherein the resin particles [L] contain a constitutional unit having a light and / or thermosetting group. 4. The segment (X), wherein the resin [P] contains a structural unit having a fluorine atom and / or a silicon atom in an amount of 50% by weight or more based on the total weight of the segment (X),
A block-type copolymer which does not contain a structural unit having a fluorine atom and / or a silicon atom or contains a segment (Y) in an amount of 20% by weight or less based on the total weight of the segment (Y). The original plate for electrophotographic color proofing according to Item 1. 5. The electrophotographic original plate for color proofing according to claim 4, wherein the resin [P] contains a structural unit having a light and / or thermosetting group. 6. A support, a photoconductive layer, and a transfer layer, wherein the photoconductive layer contains at least a resin [P] and / or resin particles [L] containing a structural unit having a fluorine atom and / or a silicon atom. It is included in the vicinity of the surface in contact with the transfer layer, and the adhesive strength of the surface tested by JIS Z0237-1980 "Adhesive tape / sheet test method" is 150 gram.
A color proof print comprising forming a toner image of at least one color by an electrophotographic process on a transfer layer of a master plate for color proof having a force (g · f) or less, and transferring the toner image together with the transfer layer onto a material to be transferred. Manufacturing method.