JP2630488B2 - Lithographic printing plate - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an electrophotographic lithographic printing original plate made by electrophotography, and in particular, to a composition for forming a photoconductive layer of the lithographic printing original plate. Regarding improvement of things.

(Prior art and its problems) Currently, various types of lithographic printing original plates for direct plate making have been proposed and put to practical use. Among them, photoconductive particles such as zinc oxide and A photoconductor provided with a photoconductive layer containing a binder resin as a main component is subjected to a normal electrophotographic process to form a highly lipophilic toner image on the surface of the photoconductor, and then the surface is insensitive to an etchant. A technique for obtaining an offset original plate by treating with a lipophilic liquid and selectively hydrophilizing a non-image portion is widely used.

The binder resin used for forming the photoconductive layer of the lithographic printing plate precursor has, first of all, excellent film forming properties of itself and excellent dispersibility of the photoconductive powder in the binder resin, The adhesion of the formed recording layer to the substrate is good, and the photoconductive layer of the recording layer has excellent charging ability,
Various electrostatic characteristics such as low dark decay, large light decay, little pre-exposure fatigue, and it is necessary to stably maintain these characteristics due to changes in humidity during imaging, and excellent imaging It is necessary to have the property.

Second, in order to obtain good printed matter from the lithographic printing plate precursor, the surface of the photoreceptor is easily compatible with the desensitizing solution, the non-image area is sufficiently hydrophilized and has water resistance. In the above, the photoconductive layer having an image is not detached, and the affinity with the dampening solution is good, and the hydrophilicity of the non-image portion is sufficiently maintained so that no stain is generated even when the number of printed sheets is large. And the like. It is already known that the ratio of zinc oxide and binder resin in the photoconductive layer affects these performances.For example, if the ratio of binder resin to zinc oxide particles in the photoconductive layer is reduced, In addition, the desensitizing property of the surface of the photoconductive layer is improved, and the background dirt is reduced. On the other hand, the internal cohesion of the photoconductive layer itself is reduced, and the printing durability is reduced due to insufficient mechanical strength. Conversely, when the ratio of the binder resin is increased, the printing durability is improved, but the background stain is increased. In particular, it is needless to say that background contamination is a phenomenon related to the quality of the desensitizing property of the photoconductive layer surface, but the desensitizing property of the photoconductive layer surface is determined by the zinc oxide in the photoconductive layer and the binder resin. It has been clarified that the ratio is not influenced only by the ratio of the binder resin, but also greatly depends on the type of the binder resin.

For example, silicone resins (Japanese Patent Publication No. 34-6670), styrene-butadiene resins (Japanese Patent Publication No. 35-1960), alkyd resins, maleic acid resins,
Polyamide (JP-B 35-11219), vinyl acetate resin (JP-B 41-2425), vinyl acetate copolymer (JP-B 41-2426)
No., acrylic resin (JP-B-35-11216), acrylate copolymer (for example, JP-B-35-11219, JP-B-36
No. -8510, Japanese Patent Publication No. 41-13946, etc.). However, in an electrophotographic lithographic printing original plate using these resins, 1) the affinity with the photoconductive powder is insufficient, and the dispersibility of the coating liquid is poor. 2) Low chargeability of photoconductive layer 3) Image portion of copied image (particularly dot reproducibility / resolution)
4) The image quality is easily affected by the environment (for example, high temperature, high humidity, low temperature and low humidity) at the time of creating a copy image. 5) The film strength and adhesiveness of the photosensitive layer are not sufficient, and the Any of the above-mentioned problems such as detachment of the paper and the number of printed sheets cannot be increased.

In addition, as a binder resin for a photoconductive layer that achieves a balance between electrostatic properties as an electrophotographic photoreceptor and printing properties as a printing original plate, for example, in Japanese Patent Publication No. 50-31011, in the presence of fumaric acid, A copolymer composed of a resin having a wg of 1.8 × 10 ⁴ to 10 × 10 ⁴ and a Tg of 10 to 80 ° C. copolymerized with an acrylate monomer and another monomer, and a (meth) acrylate monomer and a monomer other than fumaric acid. JP-A-53-54027 discloses a terpolymer containing a (meth) acrylate having a substituent having a carboxylic acid group at least 7 atoms away from the ester bond. JP-A-54-20735 and JP-A-57-202544 disclose the use of a quaternary or pentameric copolymer containing acrylic acid and hydroxyethyl (meth) acrylate. -6
No. 8046 discloses a method using a terpolymer containing a (meth) acrylic acid ester having an alkyl group having 6 to 12 carbon atoms as a substituent and a carboxylic acid-containing vinyl monomer. Is said to be effective in improving
However, even if the resin is said to be effective in the above-mentioned electrostatic properties, moisture resistance properties and durability, it is particularly difficult to evaluate the chargeability, dark charge retention, photosensitivity electrostatic properties and light sensitivity when actually evaluated. There was a problem in the smoothness of the conductive layer and the like, which was not practically satisfactory.

As the binder resin, a resin using a resin containing a functional group that generates a hydrophilic group by decomposition has been studied. For example, a resin containing a functional group that generates a hydroxyl group by decomposition (Japanese Unexamined Patent Publication No. 195684, 62-210475,
No. 62-210476) and those containing a functional group that generates a carboxyl group by decomposition (Japanese Patent Application Laid-Open No. 62-212669).

These resins are hydrolyzed or hydrogenolyzed by a desensitizing solution or a fountain solution used for printing to produce a hydrophilic group, and when these are used as a binder resin of a lithographic printing plate precursor, they have a hydrophilic property. When a resin containing the group itself from the beginning is used, various problems (such as deterioration of smoothness or the amount of dark charge retention or the like) that are considered to be caused by strong interaction between the hydrophilic group and the surface of the photoconductive zinc oxide particle are considered. (E.g., deterioration of electrophotographic characteristics such as photosensitivity) can be avoided, and the hydrophilicity of the non-image area to be hydrophilized by the desensitizing solution is further enhanced by the above-mentioned hydrophilic group generated by decomposition in the resin. Therefore, the lipophilicity of the image area and the hydrophilicity of the non-image area become clear, preventing the ink from adhering to the non-image area during printing, and as a result, printing a large number of prints of clear image quality without background smear. This It has been described that is possible.

However, there is a demand for more efficient electrophotographic lithographic printing today. Specifically, it is necessary to improve the speed of plate making, the speed of etching processing, or the sharp image quality (particularly ground quality) from the start of printing. Despite the fact that obtaining printed matter (without dirt) (reducing waste paper) has become an important issue, offset masters using a binder resin that generates a hydrophilic group by the decomposition described above, With respect to the problem of improving the etching processing speed or reducing the waste paper, it was still difficult to say that the performance was sufficiently achieved.

Further, a technique of including hydrophilic resin particles in a photoconductive layer of a lithographic printing plate precursor is described in JP-A-1-232356 and JP-A-1-261657. By containing the hydrophilic resin as particles in the photoconductive layer, the specific surface area becomes smaller than that existing in a molecular state, and the interaction with the zinc oxide surface is reduced, so that the hydrophilic property is maintained. Nevertheless, good printing characteristics can be obtained without inhibiting the electrophotographic characteristics. However, even if such hydrophilic resin particles are used, it is still not possible to maintain sufficiently satisfactory electrophotographic characteristics, and further improvement in printability such as generation of background stain is desired.

On the other hand, as a solution to the problems of the above-described electrostatic characteristics and background contamination of printed matter, as a binder resin for an electrophotographic photosensitive member,
The copolymer component containing an acidic group in the side chain of the polymer is 0.05 to 10
Using a resin having a weight-average molecular weight of 10 ³ to 10 ⁴ containing 10% by weight (Japanese Patent Application Laid-Open No. 63-217354), a resin having a weight-average molecular weight of 10 ³ to 10 ⁴ which binds an acidic group to the terminal of the polymer main chain. Used (JP-A-64-70761), further using a resin containing a curable group-containing copolymer component (JP-A-1-100554, Japanese Patent Application No. 63-39691), and used together with a crosslinking agent (JP 1-1025
No. 73, Nos 2-874), those used in combination with a weight-average molecular weight ^of 10 ⁴ or more high molecular weight resins (JP 63-220149, the same 6
No. 3-220148, No. 64-564, JP-A No. 1-280761, 1-1166
No. 43, No. 1-169455), used in combination with heat and / or photocurable resin (JP-A-1-102573, JP-A-2-34859)
Are respectively disclosed.

However, even when these resins are used, when the photoreceptor is exposed to extremely severe conditions, it has been found that there is a problem in maintaining stable high performance and that the printability is not sufficiently satisfactory. In other words, if the charging speed is increased during the charging process, charging unevenness occurs, resulting in unevenness in a copied image, or light irradiation such as a fluorescent lamp on the surface of the photoreceptor by compensating the photoreceptor for a copying machine or the like. It has been found that when a copying operation is performed immediately after receiving the image, deterioration of a copied image (especially, reduction in image density, reduction in resolution, generation of background fog, etc.) occurs (so-called pre-exposure fatigue).

Furthermore, when used as an electrophotographic lithographic printing original plate, under the above-described conditions, the copied image becomes a deteriorated original plate, and even if it is printed as an offset master, the obtained printed matter will have reduced image quality and ground fog. This has become a serious problem that would occur.

The present invention improves the problems of the conventional electrophotographic lithographic printing plate precursor as described above.

SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrophotographic lithographic printing plate precursor having improved electrostatic characteristics, especially improved charging characteristics and pre-exposure fatigue even under severe conditions during formation of a copy image.

Another object of the present invention is to provide an excellent desensitizing property, in particular, even when the printing process is accelerated from the etching process, the hydrophilicity of the non-image portion is sufficiently maintained, no background stain is generated, and high printing durability is achieved. An object of the present invention is to provide a lithographic printing plate precursor having a strong ability.

(Means for Solving the Problems) An object of the present invention is to provide an electrophotographic method comprising providing a photoconductive layer containing at least one layer of photoconductive zinc oxide and a binder resin on a conductive support. In the lithographic printing plate precursor,
The photoconductive layer contains hydrophilic resin particles having an average particle diameter equal to or smaller than the maximum particle diameter of the photoconductive zinc oxide particles, and the binder resin is at least one of the following resins [A]. It has been found that this can be achieved by a lithographic printing plate precursor comprising at least one of a seed and a resin [B].

Resin [A]: having a weight average molecular weight of 1 × 10 ³ to 1 × 10 ⁴ , containing at least 30% by weight of a polymerization component represented by the following general formula (I), and -PO ₃
H ₂ group, -SO ₃ H group, -COOH group, R represents a hydrocarbon group or an -OR 'group (R' represents a hydrocarbon group) and a polymerization component containing at least one acidic group selected from cyclic acid anhydride-containing groups. A resin containing at least one acidic group selected from the same acidic groups as described above at one end of the polymer main chain.

General formula (I) [In the formula (I), a ₁ and a ₂ each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ₁ represents a hydrocarbon group. Binder resin [B]: represented by the following general formula (III) only at one end of a polymer main chain containing at least one of the polymer components represented by the following general formulas (IVa) and (IVb) A resin comprising a monofunctional macromonomer having a weight average molecular weight of 2 × 10 ⁴ or less formed by bonding a polymerizable double bond group and a monomer represented by the following formula (V):

General formula (III) [In the formula (III), V ₀ represents -COO-, -OCO-, -CH ₂ OCO-, -CH
_{2 COO -, - O -,} - SO 2 -, - CO -, - CONHCOO -, - CONHCONH
-, -CONHSO _2- , Or The expressed (P ₀ represents a hydrogen atom or a hydrocarbon group).

c ₁ and c ₂ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-Z ₃₁
Or -COO-Z ₃₁ via a hydrocarbon (Z ₃₁ represents a hydrogen atom or a hydrocarbon group which may be substituted). General formula (IVa) General formula (IVb) [In formula (IVa) or (IVb), V ₁ represents the same content as V ₀ in formula (III).

Q ₄₁ represents an aliphatic group or an aromatic group having 6 to 12 carbon atoms having 1 to 18 carbon atoms.

d ₁ and d ₂ may be the same or different from each other;
Represents the same contents as c ₁ and c _{2 in} I).

Q ₄₀ is -CN, -CONH ₂ or Represents

Here, T represents a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group or —COOZ ₃₂ (Z ₃₂ represents an alkyl group, an aralkyl group or an aryl group). General formula (V) [In the formula (V), V ₂ represents the same content as V ₁ in the formula (IVa).

Q ₄₂ represents e ₁ and e which represent the same contents as Q ₄₁ in formula (IVa).
₂ may be the same or different, and c ₁ in formula (III),
c Represents the same content as ₂ . That is, in the lithographic printing plate precursor of the present invention, the hydrophilic resin is dispersed as particles in the photoconductive layer, and the polymer component and the acidic group of the specific repeating unit (hereinafter, particularly referred to in the present specification) are used as the binder resin. Unless otherwise noted, the term "acidic group" shall also include a cyclic acid anhydride-containing group), and a low molecular weight resin [A] containing a polymer component containing an acidic group at one end of the polymer main chain. And the general formula (IVa) or (IVb)
A polymer containing at least one monofunctional macromonomer (M) having a polymerizable double bond group at one end of a polymer main chain containing at least one polymer component and a monomer of the general formula (V) And at least a resin [B] made of a type copolymer.

As described above, as a technique for containing hydrophilic resin particles in the photoconductive layer and as a binder resin for the electrophotographic photoreceptor, a resin containing an acidic group in a side chain or a resin binding an acidic group to a polymer main chain terminal is used. Although the techniques used are each known, as in the present invention, the specific resin according to the present invention, that is, the acidic group is a side chain of a polymer as a binder resin when the photoconductive layer contains hydrophilic resin particles. Surprisingly, the use of the resin [A] and the resin [B] composed of the above-mentioned comb-type copolymer which are simultaneously contained in the polymer and the terminal of the polymer main chain has not been solved by these known techniques alone. That the above problems are solved, that is, electrostatic characteristics (especially charging characteristics and pre-exposure fatigue)
It has been found that the printing characteristics are dramatically improved.

In the present invention, the low-molecular-weight resin [A] is used to adsorb the spectral sensitizer to the photoconductive zinc oxide in at least a dispersion system in which the photoconductive zinc oxide, the spectral sensitizer, and the hydrophilic resin particles are present. Effectively adsorbs stoichiometric defects of zinc oxide without disturbing the surface, and makes it possible to appropriately improve the coating property of the surface of zinc oxide. It was found that the sensitizing effect of the sensitizer was compensated for, the humidity characteristics were dramatically improved, the zinc oxide was sufficiently dispersed, and aggregation was suppressed. And it seems that the hydrophilic resin particles according to the present invention do not inhibit the above-mentioned interaction and exhibit good printing characteristics.

Further, the resin [B] does not impair the high performance of the electrophotographic properties due to the use of the resin [A] at all, and the resin [A] alone has insufficient mechanical strength of the photoconductive layer. It is something that makes it easy.

According to the present invention, the resin [A] and the resin [B] as the binder resin of the photoconductive zinc oxide are used to specify the weight average molecular weight of each resin, the content of the acidic group in the resin, the bonding position, and the like. By doing so, in the dispersed state where the inorganic photoconductor, the spectral sensitizer, the hydrophilic resin particles and the resin coexist, the strength of each interaction can be appropriately changed, and the state can be stably maintained. It is estimated to be. By that,
It is presumed that the charging characteristics are further improved, the charging unevenness is eliminated, and the pre-exposure fatigue property is further improved.

Further, in the present invention, the smoothness of the photoconductor surface becomes smooth. When a photoconductor having a rough surface of the photoconductive layer is used as an electrophotographic lithographic printing plate precursor, the dispersion state of the photoconductive zinc oxide particles and the above-mentioned hydrophilic resin particles and the binder resin is not appropriate, and the aggregate Since the photoconductive layer is formed in the presence of the non-image area, even if the desensitizing treatment with the desensitizing solution is performed, the non-image area is not sufficiently and sufficiently hydrophilized, causing the printing ink to adhere during printing. As a result, the background of the non-image portion of the printed matter is stained.

When the resin of the present invention is used, the interaction between the adsorption and coating of the inorganic photoconductor and the binder resin is properly performed, and the film strength of the photoconductive layer is maintained.

Furthermore, since the deterioration of image quality or the occurrence of background fogging caused by uneven charging, pre-exposure fatigue, and the like are eliminated, a very good printed image of a printed image can be obtained when used as a lithographic printing original plate.

Further, as the low molecular weight resin [A], a methacrylate component having a specific substituent and containing a benzene ring or a naphthalene ring and having an acidic group represented by the following general formulas (IIa) and (IIb): It is preferable that the resin [A] (hereinafter, this low-molecular-weight product is referred to as a resin [A ']) containing the above-mentioned components and having an acidic group bonded to the terminal.

General formula (IIa) General formula (IIb) [In the formulas (IIa) and (IIb), A ₁ and A ₂ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom,
Bromine atom, -COD ₁ or -COOD ₂ (D ₁ and D ₂ each have 1 carbon atom
~ 10 hydrocarbon groups).

B ₁ and B ₂ bind to each -COO- and the benzene ring, represents a single bond or a linking atoms 1-4 linking groups. The improvement in electrophotographic properties (especially V ₁₀ , DRR, E _1/10 ) can be achieved as compared with the case of the resin [A] using the resin [A ′].

The reason for this is unknown, but one reason is that due to the planarity effect of the benzene or naphthalene ring, which is the ester component of methacrylate, the arrangement of these polymer molecular chains at the zinc oxide interface in the film is properly performed. This is probably due to

The resin [B] further comprises -PO _{3 at} the terminal of the polymer main chain.
H ₂ group, -SO ₃ H group, -COOH group, (R ₀ represents the same content as R above) and a polymer formed by bonding at least one acidic group selected from cyclic acid anhydride-containing groups (hereinafter, this high molecular weight is referred to as resin [B ′]) ) Is preferable.

When the resin [B '] is used, the electrostatic properties, especially the DRR and
E _1/10 is better, and does not hinder the excellent properties by using resin [A] at all, and its effect is preferable because there is almost no change even in environmental changes such as high temperature / high humidity, low temperature / low humidity, etc. .

 Hereinafter, the present invention will be described in more detail.

In the present invention, the hydrophilic resin particles may form a higher-order network structure.

In the present invention, the hydrophilic resin particles have the above-mentioned average particle diameter, and a film of the resin formed by applying a solution obtained by dissolving the resin particles in any soluble solvent is distilled water. The contact angle (measured with a goniometer) is 50 ° or less, preferably 30 ° or less.

In the present invention, the hydrophilic resin is dispersed as particles in the photoconductive layer, and has an average particle size equal to or smaller than the largest particle of the photoconductive zinc oxide particles.

If the resin particles having a particle size larger than the zinc oxide particle size are present, the electrophotographic characteristics are deteriorated (particularly, uniform chargeability cannot be obtained). Fine lines are cut off, jump, or fogged in the non-image area.

Specifically, the hydrophilic resin particles of the present invention have a maximum particle size of 10 μm or less, preferably 5 μm or less. And the average particle diameter of the particles is 1.0 μm or less,
Preferably it is 0.5 μm or less.

The hydrophilic resin particles have a larger specific surface area as the particle diameter is smaller, and have a good effect on the above-mentioned electrophotographic properties. Although colloidal particles (0.01 μm or less) are sufficient, they are too small. If it is too long, the same harmful effects as in the case of molecular dispersion may occur, so that it is preferable to use it at 0.001 μm or more.

Further, in the present invention, as long as the hydrophilic resin particles form a higher-order network structure, they do not elute with a fountain solution at the time of printing, and have good printing characteristics even when printing a considerably large number of sheets. Can be maintained.

In the present invention, hydrophilic resin particles not forming a higher-order network structure as described above (hereinafter, simply referred to as hydrophilic resin particles) or hydrophilic resin particles forming a higher-order network structure (hereinafter, simply referred to as It is preferable to use the network hydrophilic resin particles) in an amount of 0.1 to 5% by weight based on 100 parts by weight of the photoconductive zinc oxide. When the amount of the hydrophilic resin particles or the network hydrophilic resin particles is less than 0.1% by weight, the hydrophilicity of the non-image portion is not sufficient, and when the amount is more than 5% by weight, the hydrophilicity of the non-image portion is further improved. As a result, the electrophotographic characteristics deteriorate, and the copied image deteriorates.

The hydrophilic resin particles of the present invention include synthetic hydrophilic resins and natural hydrophilic resins, and any of them can be preferably used in the present invention.

As the network hydrophilic resin particles, those obtained by modifying these are preferably used.

For example, p.Molyneax “Water-Soluble Synthetic Pol
ymers: Properties and Behavior '' Vol.I and Vol.II CRC
Press. Inc. (1982), CAFinch "Chemistry and Te
chnology of Water-Soluble Polymers '' Plenam Press
(1973), Nakamura Y. "Water-soluble polymer" Chemical Industry Co. (19
1968), Research Group for Surface Chemistry, “Latest Processing and Modification Technology and Application Development of Water-Soluble Polymer Water-dispersible Resins”, Management Development Center Publishing Division (1981), Davidson “Water Soluble Resin” Reinh
Old reference materials such as 1968

Among them, synthetic hydrophilic resin, in the molecular structure,
Ether group, ethylene oxide group, -OH group, -SH group,
-COOH group, -SO ₂ H group, -SO ₃ H group, -PO ₃ H ₂ group, -CN group, -CON
H ₂ group, -CHO group, -SO ₂ Q ₁ group, Examples thereof include those containing at least one hydrophilic group selected from a 4- to 6-membered heterocyclic ring containing at least one nitrogen atom or an organosilane group.

In the hydrophilic group, Q ₁ may be a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, 2-chloroethyl, 2-bromoethyl, 2-bromoethyl). Fluoroethyl group, 3-chloropropyl group,
3-methoxypropyl group, 2-methoxybutyl group, benzyl group, phenyl group, propenyl group, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, etc.).

Q ₂ represents an optionally substituted aliphatic group having 1 to 6 carbon atoms (specifically, the same substituent as Q ₁ ) or —OE ₁ (E ₁ represents
Q represents a ₂ represent the same contents as).

Q ₃ and Q ₄ may be the same or different and each represents a hydrogen atom or a hydrocarbon group which may be substituted and has 1 to 6 carbon atoms (specifically, the same contents as those of Q ₁ ). However, the sum of the carbon numbers of Q ₃ and Q ₄ represents those having a total number of 8 or less.

Q ₅ , Q ₆ and Q ₇ may each be the same or different;
Represents the same content as Q ₃ and Q ₄ .

 X Represents an anion, for example, a halogen ion
(For example, chloride ion, bromine ion, iodine ion
Etc.), perchlorate ion, tetrafluoroborate ion
ON, hydroxy ion, carboxylate ion
(For example, acetonate ion, propionate ion
Etc.), sulfonate ions (for example, methanesulfone
Toion, benzenesulfonate ion, p-toluene
Sulfonate ion).

r represents 1 or 2, in the case of r = 1, at least one acidic group (-SO ₃ H in _{-Q 5 ~ 7, -PO 3 H} 2, -COO
H) is contained as a substituent.

In particular, And the like.

Further, the -COOH group, -SO ₂ H group, -SO ₃ H group, -PO ₃ H ₂ group, Are each a metal salt such as an alkali metal (eg, lithium, sodium, potassium, etc.), an alkaline earth metal (eg, calcium, magnesium, etc.), zinc, aluminum or the like, or an organic base (eg, triethylamine, pyridine,
Morpholine, piperazine, etc.).

Also, a 4-member containing at least one nitrogen atom as described above
Examples of the 6-membered heterocyclic ring include a pyridine ring, a peperidine ring, a pyrrole ring, an imidazole ring, a pyrazine ring, a pyrrolidine ring, a pyrroline ring, an imidazoline ring, a pyrazolidine ring, a piperazine ring, a morpholine ring, and a pyrrolidone ring. Can be These heterocycles may contain a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and the like) and a C1-C8 optionally substituted hydrocarbon group ( For example, methyl, ethyl, propyl, butyl, 2-chloroethyl, 2-
Bromoethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-carboxyethyl group,
Carboxymethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-methanesulfonylethyl group, benzyl group, carboxybenzyl group, carboxymethylbenzyl group, phenyl Group, carboxyphenyl group,
Sulfophenyl group, methanesulfonylphenyl group, ethanesulfonylphenyl group, carboxymethylphenyl group, methoxyphenyl group, chlorophenyl group, etc.), -OE ₂
A group (E ₂ represents the same content as the above-mentioned optionally substituted hydrocarbon group having 1 to 8 carbon atoms) or a —COOE ₃ group (E ₃ represents the same content as E ₂ ); .

Examples of the organosilane group include a repeating unit represented by the following general formula (VII).

In the formula (VII), A ⁰ represents an alkyl group having 1 to 4 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group, a 2-methoxyethyl group, -Cyanoethyl group or the like), -OE ₄ (E ₄ represents the same content as the optionally substituted alkyl group having 1 to 4 carbon atoms in A ⁰ ), or a “Z” group [Z is trimethylsiloxy, Pentamethyldisiloxanyl, heptamethyltrisiloxanyl, nonamethyltetrasiloxanyl, bis (trimethylsiloxy) methylsiloxanyl, tris (trimethylsiloxy) siloxanyl, etc.].

W ₁ is an alkyl group having 1 to 6 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, 2-methoxyethyl group, 2-ethoxypropyl group, 2-cyanoethyl Group, 2-hydroxyethyl group, 2-hydroxy-3-chloro-propyl group, 2-
Chloroethyl group), —OE ₅ (E ₅ represents the same content as E ₄ ) or a divalent hydrocarbon group having 1 to 6 carbon atoms, vinyl, methacryloxy, acryloxy, methacrylamide, acrylamide, It represents a group in which an unsaturated bond selected from the group consisting of styryl, allyl and the like is polymerized and binds to another repeating unit.

k is 0 or an integer of 1 to 10, indicating that the sum of the values of k is at least 2.

The hydrophilic resin of the present invention is a homopolymer or a copolymer containing a polymer component containing at least one hydrophilic group as described above in a polymer side chain, and the polymer component is used as a polymer component in the resin. 20% to 100% by weight, preferably 30% to 100% by weight.

More specifically, examples of the hydrophilic group-containing polymerization component are represented by general formula (VIII).

In the formula (VIII), X represents -COO-, -COC-, -O-, -SO
_2- , Or Represents [Where Z ₁ and Z ₂ each represent a hydrogen atom or a carbon atom 1
To 7 hydrocarbon groups (preferably, for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group,
2-hydroxyethyl group, 3-bromo-2-hydroxypropyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 3-sulfopropyl group, benzyl group, sulfobenzyl group, methoxybenzyl group , Carboxybenzyl group, phenyl group, sulfophenyl group, carboxyphenyl group, hydroxyphenyl group, 2-methoxyethyl group, 3-methoxypropyl group,
2-methanesulfonylethyl group, 2-cyanoethyl group,
N, N (dichloroethyl) aminobenzyl group, N, N (dihydroxyethyl) aminobenzyl group, chlorobenzyl group,
Methylbenzyl group, N, N (dihydroxyethyl) aminophenyl group, methanesulfonylphenyl group, cyanophenyl group, dicyanophenyl group, acetylphenyl group, etc.)
Wherein Z ₃ and Z ₄ may be the same or different, and represent a hydrogen atom, a halogen atom (preferably, for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an aliphatic group having 1 to 4 carbon atoms (preferably,
For example, methyl group, ethyl group, propyl group, butyl group, etc.)
And n ₁ represents an integer of ₁ to 6. ].

W is -COO -, - OCO -, - O -, - S -, - SO 2, -NHCOO-, -NHCONH-, or Or a linking group formed by a combination of these linking groups.

[Wherein, l _{1 to} l ₄ may be the same or different, and each represents a hydrogen atom, a halogen atom (preferably, for example, a fluorine atom, a chlorine atom, a bromine atom, or the like) or a hydrocarbon group having 1 to 7 carbon atoms ( Preferably, for example, methyl, ethyl, propyl, butyl, 2-chloroethyl, 2-methoxyethyl, 2-methoxycarbonylethyl, benzyl, methoxybenzyl, phenyl, methoxyphenyl, methoxy Carbonylphenyl group) or the formula (VII
It represents W-Y] group I), l ₅ ~l ₇ represents the same as the contents of the above Z _1, Z _2. Y represents the above-mentioned hydrophilic group, -OH group, -SH group,
-CHO group, -CN group, -COOH group, -SO ₂ H group, -PO ₃ H ₂ group, -SO ₂
Q ₁ unit, Represents a 4- to 6-membered heterocyclic ring or organosilano group containing at least one nitrogen atom.

[Wherein, Q ₁ to Q ₇ represents the same as the contents of the Q ₁ to Q _7. In the formula (VIII), Y may be directly bonded to the polymer main chain, or X may be -O-, In this case, -Y may be directly connected to X.

e ₁ and e ₂ may be the same or different, and each represents a hydrogen atom,
Halogen atom (preferably, for example, fluorine atom, chlorine atom, bromine atom, etc.), -COOH group, -COOQ ₅ group, -CH ₂ COOQ ₅
A group (Q ₅ represents a hydrocarbon group having 1 to 7 carbon atoms, specifically, the same contents as those described above for the hydrocarbon groups of Z ₁ and Z ₂ ) or an alkyl group having 1 to 4 carbon atoms ( Preferably, it represents, for example, a methyl group, an ethyl group, a propyl group, a butyl group and the like.

Hereinafter, the above-mentioned hydrophilic group-containing polymerization component will be exemplified more specifically, but the present invention is not limited thereto.

In each of the following examples, q ₁ represents -H, -CH ₃ , -Cl, -C
H ₂ COOH or indicates -CH ₂ COOCH _3, q ₂ is -CH _3, -COOH, -C
ONH _2, indicates -CONHC3H6N ₂ H ₅ or -COOCH _3, q ₃ represents a -CH ₃ or -H, q ₄ represents -H, a -CH ₃ or -Cl, q ₅ is -
H, -CH _3, shows a -CH ₂ COOH or -CH ₂ COOCH _3,, q ₆ are -
H, indicates -CH ₃ or -CH ₂ COOCH _3, r ₁ represents -H, a -CH ₃ or -C ₂ H _5, r ₂ is And y ₁ is -SO ₃ H, -COOH, -CH ₂ OH or -SO ₂ H, shows a -CONH ₂ or -SO ₂ NH _2, y ₂ is -OH or -N
Indicates H _2, J ₁ is Li, Na, K or HN (C ₂ H _{5) 3} or And J ₂ represents Li, Na, K or HN (C ₂ H ₅ ) ₃ . Also, v ₁ represents an integer of ₁ to 12, v ₂ represents an integer of 1 to 4, v ₃ represents an integer of 2 to 12, v ₄ represents an integer of 1 to 11, and v ₅ represents 1
An integer of ~ 10, v ₆ is an integer of 2-10, and v ₇ is 1-4
Are respectively shown.

Examples of other polymer components that can be copolymerized with the above-mentioned hydrophilic group-containing polymer component include those represented by the general formula (IX), and one or more of these are copolymerized. It can be polymerized.

General formula (IX) In formula (IX), P represents the same content as X in formula (VIII).

Q represents an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, octyl group, decyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, 2 -Chloroethyl group, 3-bromopropyl group, 2-methoxycarbonylethyl group, 4-methoxycarbonylbutyl group, 4-methoxybutyl group, 3-chloro-2-methoxypropyl group,
3-chloro-2-ethoxycarbonylpropyl group, 2-
A glycidylpropyl group, a 3-bromo-2-acetyloxy-propyl group, an alkenyl group having 2 to 20 carbon atoms which may be substituted (for example, a vinyl group or an allyl group), or a substituted alkenyl group having 5 to 12 carbon atoms. Alicyclic groups (eg, cyclopentyl, cyclohexyl, cyclooctyl, chlorocyclohexyl, bromocyclohexyl, 2-cyclohexylethyl, cyclohexylmethyl, etc.)
An optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, ethyl-2-phenylethyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, Dichlorobenzyl group, bromobenzyl group, methylbenzyl group,
A dimethylbenzyl group, a trimethylbenzyl group, a methoxybenzyl group, a dimethoxybenzyl group, a trimethoxybenzyl group, a methoxycarbonylbenzyl group, an acetamidobenzyl group, and the like; an optionally substituted aryl group having 6 to 12 carbon atoms (for example, a phenyl group) , Tolyl group, xylyl group,
Mesitylene, naphthyl, chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, fluorophenyl, methoxyphenyl, chloro-
A methyl-phenyl group, a methyl-methoxy-phenyl group,
Nitrophenyl group, methoxycarbonylphenyl group, acetamidophenyl group, ethoxyphenyl group, chloronaphthyl group, ethoxycarbonylnaphthyl group, propylphenyl group, butylphenyl group, chloromethylphenyl group, methoxymethylphenyl group, N-methylaminosulfenyl Group, etc.) or a 4- to 7-membered heterocyclic ring (a heterocyclic ring other than the nitrogen-containing heterocyclic ring exhibiting hydrophilicity as described above, such as a thiophene ring, a furan ring, a pyran ring, or a benzopyran ring). , A pyrrole ring, an indole ring,
Examples include a quinoline ring, a thiazole ring, an oxazole ring, a benzothiazole ring, and the like, and these rings may contain a substituent. The substituent has the same contents as Q in the formula (IX)).

The natural hydrophilic resin is described in detail in the comprehensive technical data collection of the above-mentioned water-soluble polymer water-dispersible resin (management development center publishing department). For example, lignin, starch, burlan, cellulose, alginic acid, dextran Dextrin, guar gum, gum arabic, glycogen, laminaran, lichenin, nigellan, and derivatives thereof.

As the derivative, sulfonated, carboxylated, phosphorylated, sulfoalkylated, or carboxyalkylated, alkylphosphorylated, and salts thereof are particularly preferable.

In the present invention, two or more natural hydrophilic resins may be used in combination.

In addition, among natural hydrophilic resins, glucose polymers,
And its derivatives are preferred, glucose polymers, and derivatives thereof, starch, glycogen, cellulose,
Likenin, dextran, nigeran and the like are preferred, and dextran and its derivatives are particularly preferred.

In order to make the above synthetic / natural hydrophilic resin into fine particles having the above-mentioned specific particle diameter, conventionally known dry and wet methods can be adopted. That is, the hydrophilic resin powder,
A method of directly pulverizing with a conventionally known pulverizer to obtain fine particles (for example, a method using a ball mill, a paint shaker, a jet mill, a hammer mill, or the like) and a method of forming polymer latex particles can be used. As the latter method for producing polymer latex particles, a conventionally known method for producing latex particles of a paint or a liquid developer for electrostatic photography can be used. That is, in a method of dispersing the hydrophilic resin in combination with a dispersing polymer, the hydrophilic resin and a dispersion assisting polymer (or coating polymer) are kneaded in advance to form a kneaded product, and then pulverized. It is a method of coexisting and dispersing.

Specifically, for example, Kenji Ueki's translation of paint flow and pigment dispersion, Kyoritsu Shuppan (1971), Solomon, Chemistry of Paint, Paint and Surface Coating theory and pract
ice ”, Yuji Harasaki“ Coating Engineering ”Asakura Shoten (1971
Yuji Harasaki, “Basic Science of Coatings” Maki Shoten (19
77), JP-A Nos. 62-96954, 62-115171, 62-7565
It is described in books such as No. 1 gazette.

Further, a method of easily obtaining latex particles of the hydrophilic resin by a conventionally known polymerization reaction such as a suspension polymerization method and a dispersion polymerization method can also be used.

Specifically, Souichi Muroi "Chemistry of Polymer Latex" Polymer Publishing Association (1970), Taira Okuda, Hiroshi Inagaki "Synthetic Resin Emulsion" Polymer Publication Association (1978), Soichi Muroi "Polymer Latex" It is described in books such as "Introduction" Kobunsha (1983).

In the present invention, a method of using polymer latex particles is preferable, and the average particle diameter is easily 1.0 μm by this method.
The following resin particles can be used.

By the way, in the electrophotographic lithographic printing plate precursor of the present invention, when the photoconductive layer is formed, a method of dispersing the photoconductive zinc oxide in an aqueous system (for example, Japanese Patent Publication No. 51-450 and 47-185)
No. 99, No. 46-41350, etc.) and a method of dispersing in a non-aqueous solvent system (for example, the above-mentioned JP-B-50-31011, JP-A-53-54027)
Nos. 54-20735, 57-202544, 58-68046, etc.)
Either method may be used, but if water remains in the photoconductive layer, the electrophotographic properties will be impaired. Therefore, a method of dispersing in a non-aqueous solvent system is preferable. Accordingly, in order to sufficiently disperse the latex particles of the hydrophilic resin of the present invention in the non-aqueous photoconductive layer, the latex particles are also preferably non-aqueous latex.

The non-aqueous solvent used in the non-aqueous latex may be any organic solvent having a boiling point of 200 ° C. or lower, and may be used alone or as a mixture of two or more.

Specific examples of this organic solvent include methanol, ethanol,
Alcohols such as 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; methyl acetate, ethyl acetate, butyl acetate and propionic acid Carboxylic esters such as methyl,
Hexane, octane, decane, dodecane, tridecane,
C6 to C14 aliphatic hydrocarbons such as cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; methylene chloride;
Dichloroethane, tetrachloroethane, chloroform,
Halogenated hydrocarbons such as methyl chloroform, dichloropropane and trichloroethane are exemplified.

If a polymer latex is synthesized by a dispersion polymerization method in these non-aqueous solvent systems, the average particle size of the latex particles can be easily adjusted to 1
μm or less, and the particle size distribution can be very narrow and monodispersed.

Specifically, KEJ Barrett “Despersion Polymeriza
John Wiley (1975), Koichiro Murata, Polymer Processing, 23 , 20 (1974), Tsunetaka Matsumoto and Tokichi Tange, Journal of the Adhesion Society of Japan, 9 , 183 (1973), Toyokichi Tange, Japan Adhesion Association Magazine 23 , 26 (1987), DJ Walbridege, NATO.A
dv.Study.Inst.Ser.E.No.67,40 (1983), BP893429
No., BP934038, USP 1122397, USP 3900412, US
P 4606989, JP-A-60-179751, and JP-A-60-185963 disclose the method.

Further, as the network hydrophilic resin particles, specifically, at least one structure of the repeating unit of the polymer has -O
_{H, -SH, -COOH, -SO 2} H, -SO 3 H, -CN, -CONH 2, -CH
O, -SO ₂ Q ₁ , Examples include those containing at least one hydrophilic group selected from an ether group, an ethylene oxide group, a heterocyclic ring forming a 4- to 6-membered ring, and an organosilane group.

In the hydrophilic group, Q ₁ is an alkyl group having 1 to 4 carbon atoms which may be substituted, (for example, a methyl group, an ethyl group,
Propyl, butyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 3-chloropropyl, 3-methoxypropyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, etc.) .

Q ₂ is an alkyl group having 1 to 4 carbon atoms which may be substituted (specifically, it represents the same substituent as Q ₁ ) or —OE
₁ (E ₁ represents the same content as Q ₁ ).

Q ₃ and Q ₄ may be the same or different, and each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted (specifically, the same contents as those of Q ₁ ). However, Q ₃
And the sum of the carbon numbers of Q ₄ represents those having a total number of 6 or less.

Q ₅ , Q ₆ and Q ₇ may each be the same or different;
Represents the same content as Q ₃ and Q ₄ .

 X , r is X of the aforementioned hydrophilic resin particles. same as r
You.

Examples of the heterocyclic ring forming a 4- to 6-membered ring include, for example, a furan ring, a pyran ring, a tetrahydrofuran ring, a pyridine ring, a piperidine ring, a pyrrole ring, an imidazole ring,
Pyrazine ring, pyrrolidine ring, pyrroline ring, imidazolidine ring, imidazoline ring, pyrazolidine ring, piperazine ring, morpholine ring, pyrrolidone ring, dioxane ring, dioxolane ring, oxazoline ring, 1,3-oxazine-2-one ring, morpholinedione ring And a morpholinone ring.

These heterocycles may contain a substituent, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 3 carbon atoms which may be substituted (for example, , Methyl group, ethyl group, propyl group,
2-chloroethyl group, 2-cyanoethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, etc.), -OE ₂
Group (E ₂ represents the same content as optionally substituted alkyl groups of 1 to 3 carbon atoms) and the like.

Examples of the organosilane group include the same as those described above for the omeganosilane group of the hydrophilic resin particles.

The network hydrophilic resin of the present invention is a homopolymer or a copolymer containing a polymer component containing at least one of the above hydrophilic groups in a polymer side chain, and is the same as in the case of the above-described hydrophilic resin. Wherein the polymerization component is a polymerization component in the resin.
20% to 100% by weight, preferably 30% to 100% by weight
Included.

Specific general formulas and specific component examples of the network hydrophilic resin are the same as the above-described general formula (VII) and component examples (1) to (57) of the hydrophilic resin.

Also, as a natural network hydrophilic resin, specifically,
Interfacial Chemistry Study Group, “Latest Processing / Modification Technology and Application Development of Water-Soluble Polymers / Water-Dispersible Resins”, Business Development Center Publishing Division (1981), Nakamura Yasuo, “Water-Soluble Polymers” 1973), RL Davidson, "Handbook of Water-So
luble Gumsand Resins ”McGraw-Hill BOOK Company (19
1980), "Encyclopedia of Polymer Science and En
gineering "Vol.3, p69-270, John Wileyand Sons (19
1985).

Specifically, the same derivatives as the above-mentioned natural hydrophilic resins, and the same derivatives as the above-mentioned derivatives of the natural hydrophilic resins can be used.

The network hydrophilic resin particles of the present invention have a high-order network structure in which the polymer molecular chains of the polymer comprising the above-mentioned hydrophilic polymer component are bridged.

Thereby, the network hydrophilic resin particles become hardly soluble or insoluble in water. Specifically, the solubility of the resin in water is 80% by weight or less, preferably 50% by weight.
It is as follows.

The crosslinking of the present invention can be performed by a conventionally known crosslinking method. That is, (1) a method of crosslinking a polymer containing the hydrophilic polymerization component with various crosslinking agents or curing agents, and (2) a polymerization reaction by containing at least a monomer corresponding to the hydrophilic polymerization component. When performing the process, two polymerizable functional groups
A method of forming a network structure between molecules by coexisting a polyfunctional monomer or a polyfunctional oligomer containing at least one polymer, and (3) a method including a component containing the hydrophilic polymer component and a component containing a reactive group. It can be carried out by a method such as a method of cross-linking with the union by a polymerization reaction or a polymer reaction.

Examples of the cross-linking agent in the method (I) include compounds that are usually used as a cross-linking agent. Specifically, compounds described in Shinzo Yamashita and Tosuke Kaneko, “Handbook of Crosslinking Agents” Taiseisha (1981), edited by the Society of Polymer Science, “Basic Edition of Polymer Data Handbook”, Baifukan (1986), etc. Can be used.

For example, silane coupling agents for organic silane compounds (for example, vinyltrimethoxysilane, vinylolibutoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilanela Etc.), polyisocyanate compounds (e.g., toluylene diisocyanate, o-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate, polymer polyisocyanate, etc.), polyol compounds (for example, 1,4-butanediol, polyoxypropylene glycol, polyoxylenalkylene glycol, 1,1,1-trimethylol) Propane, etc.), polyamine-based compounds (for example, ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds and epoxy resins (for example, "New epoxy resin" edited by Hiroshi Kakiuchi Shokodo (1985), "Epoxy resin" edited by Noriyuki Hashimoto, compounds described in Nikkan Kogyo Shimbun (1969), etc., melamine resin (for example, Ichiro Miwa, Hideo Matsunaga) Edited by "Urea Melamine Resin" Compounds described in Shogaku Kogyo Shimbun (published in 1969), poly (meth) acrylate compounds (for example, Shin Ogawara, Takeo Saegusa, Toshinobu Higashimura "Oligomers" Kodansha (1976), Eizo Omori " Functional Acrylic Resins "Techno Systems (published in 1985) and the like. Specific examples include polyethylene glycol diacrylate, neopentyl glycol diacrylate, and 1,6-hexanediol diacrylate. , Trimethylolpropane triacrylate, pentaerythritol polyacrylate, bisphenol A-
Diglycidyl ether diacrylate, oligoester acrylate: these methacrylates and the like.

Among the curing agents of the above method (1), examples of the curing agent for a natural hydrophilic resin such as gelatin include, for example, US Pat.
057,723, 3,671,256, 3,396,029, 4,161,4
07, 4,207,109, UK Patent No. 1,322,971
No. 42-17112, JP-A-51-94817, JP-A-56-66841, JP-A-57-2
07243, 59-121327, `` The Theory of the
Photographic Processes, 4th edition (TH James et al.), Page 94, and Polymeric amine and ammonium salts (EJ Gaetals et al.), Page 321 can be used.

The polymerizable functional group of the polyfunctional monomer or oligomer having two or more polymerizable functional groups in the method (2) is specifically CH ₂ = CH—CH ₂ − , CH ₂ = CH-, CH ₂ = CH-CONH-, _{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 -, Etc. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, as a monomer or oligomer having the same polymerizable functional group, a slurry derivative such as divinylbenzene or trivinylbenzene: a polyhydric alcohol (for example, , Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 200, # 400, # 60
0,1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane,
Pentaerythritol, etc.) or polyhydroxyphenols (eg, hydroquinone, resorcin, catechol and derivatives thereof), 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, vinylamides or allylamides:
Condensates of polyamines (eg, ethylenediamine, 1,3-propylenedimine, 1,4-butylenediamine, etc.) with carboxylic acids containing vinyl groups (eg, methacrylic acid, acrylic acid, crotonic acid, allylic acid, etc.) Is mentioned.

Examples of monomers or oligomers having different polymerizable functional groups include, for example, carboxylic acids containing vinyl groups (for example, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, acryloyl propionic acid, Itaconiloyl acetic acid, itaconiloyl propionic acid, carboxylic anhydride)
And ester derivatives or amide derivatives containing a vinyl group such as a reactant of an alcohol or an amine (e.g., allyloxycarbonylpropionic acid, allyloxycarboquinylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.) For example, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloyl propionate, allyl methacryloyl propionate, vinyl methacrylate oxycarbonyl methyl ester, acrylic acid Vinyloxycarbonylmethyloxycarbonyl ethylene ester, N-allylacrylamide, N-
Allyl methacrylamide, N-allylitaconamide, methacryloylpropionic allylamide, etc.) or amino alcohols (for example, aminoethanol, 1-
Condensates of aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) with a carboxylic acid having a vinyl group. The monomer or oligomer having two or more polymerizable functional groups used in the present invention is polymerized using 10 mol% or less, preferably 5 mol% or less of all monomers to form a resin.

In the present invention, a polymer containing a polymerizable double bond group can also be used. Examples of the double bond group in this polymer include the same groups as described above. And
In the polymerization reaction between the polymers, it is a generally known method to carry out the reaction using the above-mentioned polymerizable polyfunctional monomer in combination.

Further, when a chemical bond is formed by the reaction of reactive groups between polymers in the above method (3) to form a bridge between the polymers, the reaction is performed in the same manner as the reaction of a general organic low-molecular compound. be able to. Specifically, it is described in detail in books such as Yoshio Iwakura, Keisuke Kurita, "Reactive Polymers" Kodansha (1977), Ryohei Oda, "Polymer Fine Chemicals" Kodansha (1976), and the like. For example, a macromolecular reaction is usually performed by a combination of a harmful group of a group A (a hydrophilic group polymer component) and a functional group of a group B (a polymer containing a component containing a reactive group) in Table A below. This is a well-known method.

As described above, the network hydrophilic resin particles of the present invention are polymer particles containing a polymer component containing a hydrophilic group, and having a structure in which the molecular chains are bridged to a higher order, for example, , LHSperling, `` Intrepenetrating Polymer Netwar
ks and Engineering ”vol.8, p279-340 (1985), J.
D. Anclrade, `` Hydrogels for medical and Related Me
terials "Plenum Press (1981)," Encyclopedia
of Polymer Sience and Engineering '' vol.8, p279-340
(1985), JDAnclrade, "Hydrogels for medical
andRelated Applicatio '', ACS.Symposium Series No.3
1, American Chemical Society, Washington DC (1976
), Eizo Omori, "Development Trends of Super Absorbent Resins and Their Applications" Techno Forum Co., Ltd. Publishing Division (1987), Masahiro Irie, "Manufacture and Application of Functional Polymer Gels" CM
C Co., Ltd. (1987), Kenji Tanaka, Petrotech., 10 25
(1987), Nikkei New Materials June 1, 1987,
p57, Taguchi Jun, Ishii Kunio, “Chemistry and Industry” 59 , 188 (198
5), Fushiyoshi Masuda, Functional Materials, April 1982, p36, Yoshinori Kadoma, Chemical Industry 38 , 602 (1987), etc. can be used as the hydrogel or superabsorbent resin. Examples of commercially available superabsorbent resins include Arasorp (Arakawa Chemical Industries), Wonder Gel (Kao Corporation), KI Gel (Kuraray Isoprene), Sunwet (Sanyo Kasei Kogyo), Sumika Gel (Sumitomo) Aquakeep (manufactured by Iron and Steel Chemical Co., Ltd.), Lanseal (manufactured by Nippon Xlan Industry Co., Ltd.), Lion Polymer (manufactured by Lion Corporation),
GP (manufactured by Nippon Synthetic Chemical Industry), Arialic (manufactured by Nippon Shokubai Chemical Industry), Aquaprene (manufactured by Meisei Chemical Industry),
CLD (Buckeye Cellulose), DWAL (Dow Chemica)
l), GPC (Graim Processing), Aqualon
(Hercules), Magic Water Gel (Super Absorbent)
), Cecagum (CECA), Spon Cygnus (Kanebo Synthetic Chemical), Super Lab (Asahi Kasei)
And the like.

Further, the granulation of the network hydrophilic resin in the present invention is the same as the granulation of the hydrophilic resin described above.

Next, the binder resin used in combination with the hydrophilic resin particles or the network hydrophilic resin particles will be described.

The weight average molecular weight of the resin [A] is 1 × 10 ³ to 1 × 1.
0 ^4, preferably ^{3 × 10 3 ~8 × 10 3} , the presence proportion of the copolymerizable component corresponding to a repeating unit of formula (I) is 30 wt% or more,
It is preferably from 50 to 97% by weight, and the proportion of the total amount of the acidic group-containing copolymer component and the acidic group bonded to the terminal of the main chain is as follows:
1-20% by weight is preferred. Further, the proportion of the acidic group-containing copolymer component is preferably 0.1 to 10% by weight, more preferably 0.5 to 8% by weight, and the proportion of the acidic group bonded to the main chain terminal is preferably 0.5 to 15% by weight. , More preferably 1
~ 10% by weight.

Formula (IIa) and / or Formula (IIb) in the resin [A ′]
The proportion of the methacrylate copolymer component corresponding to the repeating unit of the above is 30% by weight or more, preferably 50 to 97% by weight, and the proportion of the acidic group-containing copolymer component is preferably
It is 0.1 to 10% by weight, more preferably 0.5 to 8% by weight.
The existing ratio of the acidic group bonded to the terminal of the polymer main chain is preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight.

The glass transition point of the resin [A] is preferably -20 ° C to 110 ° C.
° C, more preferably -10 ° C to 90 ° C.

When the molecular weight of the binder resin [A] is smaller than 1 × 10 ³ , the film-forming ability is reduced and sufficient film strength cannot be maintained. On the other hand, when the molecular weight is larger than 1 × 10 ⁴ , even if the resin of the present invention is used. The fluctuation of electrophotographic characteristics (charging property, pre-exposure fatigue property) under severe conditions as described above is slightly increased, and the effect of the present invention that a stable copied image can be obtained is weakened.

If the total content of the acidic group in the binder resin [A] is less than 1% by weight, the initial potential is too low to obtain a sufficient image density. On the other hand, when the content of the acidic group is more than 20% by weight, the dispersibility of even a low molecular weight substance is reduced, the film smoothness and the high humidity property of electrophotographic properties are reduced, and furthermore, when used as an offset master. Background dirt increases.

The resin [A] of the present invention contains at least one kind of a repeating unit represented by the formula (I) as a polymerization component.

In the general formula (I), a ₁ and a ₂ represent a hydrogen atom, a halogen atom (eg, a chlorine atom or a bromine atom), a cyano group or an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, Butyl group). R ₁ is an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, 2-chloroethyl, 2-
A bromoethyl group, a 2-cyanoethyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 3-hydroxypropyl group, and the like, and an optionally substituted alkenyl group having 2 to 18 carbon atoms. A vinyl group, an allyl group, an isopropenyl group, a butenyl group, a hexenyl group, a heptenyl group, an octenyl group, etc., an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, a benzyl group, a phenethyl group, a naphthylmethyl group, 2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc., optionally substituted cycloalkyl group having 5-8 carbon atoms (eg, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.), substitution Optionally substituted aryl groups (eg phenyl, tolyl, xyl, mesityl, naph Tyl group, methoxyphenyl group,
Ethoxyphenyl, fluorophenyl, difluorophenyl, bromophenyl, chlorophenyl, dichlorophenyl, iodophenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, cyanophenyl, nitrophenyl, etc.) .

Further, preferably, the copolymer component corresponding to the repeating unit of the general formula (I) includes the above-mentioned general formula (IIa) and / or (I
It is represented by a methacrylate component containing a specific aryl group represented by Ib) (resin [A ']).

In the formula (IIa), as preferred A ₁ and A ₂ , in addition to a hydrogen atom, a chlorine atom and a bromine atom, respectively, as a preferred hydrocarbon group, an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, Propyl, butyl, etc.),
C7-C9 aralkyl group (for example, benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-methyl-benzyl group, etc.) and aryl groups (e.g. phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and the preferred hydrocarbon as -COD ₁ or -COOD ₂ (preferably D ₁ and D ₂ And those described as hydrogen groups).

In the formula (IIa), B ₁ is a single bond connecting —COO— and a benzene ring or (N ₁ represents an integer of ₁ to 3), -CH ₂ OCO-, -CH ₂ CH ₂ OCO
-, (N ₂ represents an integer of 1 or 2), a connecting group having 1 to 4 connecting atoms such as —CH ₂ CH ₂ O— and the like.

B ₂ in formula (IIb) is the same meaning as B _1.

Specific examples of the copolymer component corresponding to the repeating unit represented by the formula (IIa) or (IIb) used in the resin [A '] of the present invention are shown below. However, the scope of the present invention is not limited to these.

In each of the following examples, T ₁ and T ₂ each represent Cl, Br or I, and R ₁₁ is C _a H _{2a + 1} or A represents an integer of 1 to 4, b represents an integer of 0 or 3, and c represents an integer of 1 to 3.

The copolymerization component containing an acidic group to be copolymerized in the resin [A] of the present invention is, for example, a compound represented by the general formula (I) (the general formula (II)
a) and (IIb)) as long as it is a vinyl compound containing the acidic group which can be copolymerized as a monomer corresponding to the repeating unit represented by (IIb). 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)
Methyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α-chloro-β-methoxy form,
α, β-dichloro form), methacrylic acid, itaconic acid,
Itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (eg, 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid), maleic acid, maleic acid half esters,
Maleic acid half amides, vinylbenzene carboxylic acid, vinylbenzene sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, half ester derivatives of vinyl or allyl groups of dicarboxylic acids, and ester derivatives of these carboxylic acids or sulfonic acids, amides Compounds containing the acidic group in the substituent of the derivative are exemplified.

In the acidic group In the above, R represents a hydrocarbon group or an OR 'group (R' represents a hydrocarbon group), and R and R 'are preferably an aliphatic group having 1 to 22 carbon atoms (for example, a methyl group, an ethyl group, a propyl group). Group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 2-chloroethyl group, 2-methoxyethyl group, 3-ethoxypropyl group,
Allyl group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group, etc.), or an optionally substituted aryl group (For example, phenyl, tolyl, ethylphenyl, propylphenyl, chlorophenyl,
Fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.).

Further, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride contained include aliphatic dicarboxylic anhydride and aromatic dicarboxylic anhydride. Can be

Examples of the aliphatic dicarboxylic anhydride include a succinic anhydride ring, a glutaconic anhydride ring, a maleic anhydride ring,
Cyclopentane-1,2-dicarboxylic anhydride ring, cyclohexane-1,2-dicarboxylic anhydride ring, cyclohexene-1,2-dicarboxylic anhydride ring, 2,3-bicyclo [2.
2.2] octanedicarboxylic anhydride rings and the like, and these rings are substituted with a halogen atom such as a chlorine atom and a bromine atom, and an alkyl group such as a methyl group, an ethyl group, a butyl group and a hexyl group. Is also good.

Examples of the aromatic dicarboxylic anhydride include a phthalic anhydride ring, a naphthalene-dicarboxylic anhydride ring, a pyridine-dicarboxylic anhydride ring, a thiophene-dicarboxylic anhydride ring, and the like. Is, for example, a chlorine atom, a halogen atom such as a bromine atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (for the alkoxy group, for example, Methoxy group, ethoxy group, etc.) may be substituted.

The copolymer component containing an acidic group will be exemplified. here,
P ₁ represents H or CH ₃ , P ₂ represents H, CH ₃ or CH ₂ COOCH ₃ , R ₁₂ represents an alkyl group having 1 to 4 carbon atoms, and R ₁₃ represents an alkyl group having 1 to 6 carbon atoms. , A benzyl group or a phenyl group, c represents an integer of 1-3, d represents an integer of 2-11, e represents an integer of 1-11, f represents an integer of 2-4, g Represents an integer of 2 to 10.

In the resin [A] of the present invention, at least one acidic group selected from the same acidic groups as the above-mentioned acidic groups is bonded to the terminal of the polymer main chain.

In the resin [A], the acidic group contained in the copolymer component of the polymer and the acidic group bonded to the terminal of the polymer main chain may be the same or different. In the acidic group bonded to one end of the polymer main chain in the resin [A], preferred acidic groups include -PO ₃ H ₂ group, -SO ₃ H group, -COOH group, A cyclic acid anhydride containing group can be mentioned.

These acidic groups may be directly bonded to the terminal of the polymer main chain, or may be bonded via a linking group. The linking group may be any bonding group, but for example, if specifically mentioned, (D ₁ and d ₂ may be the same or different and each represents a hydrogen atom, a halogen atom (a chlorine atom, a bromine atom, etc.), an —OH group, a cyano group, an alkyl group (a methyl group, an ethyl group, a 2-chloroethyl group, 2-hydroxyethyl group, propyl group, butyl group, hexyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), phenyl group, etc.), (D ₃ and d ₄ represent the same contents as d ₁ and d ₂ ), -O-, -S-, ｛D ₅ represents a hydrogen atom or a hydrocarbon group (specifically, a hydrocarbon group having 1 to 12 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group) Group, decyl group, dodecyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-cyanoethyl group,
Benzyl group, methylbenzyl group, chlorobenzyl group, methoxybenzyl group, phenethyl group, phenyl group, tolyl group, chlorophenyl group, methoxyphenyl group, butylphenyl group, etc.)), -CO-, -COO-, -OCO
-, _{-SO 2 -, - NHCONH -,} - NHCOO -, - NHSO 2 -, - CONHCOO-,
-CONHCONH-, a heterocyclic ring (O, S, N
Any of 5- to 6-membered rings containing at least one or the like or a condensed ring thereof may be used: for example, a thiophene ring,
Pyridine ring, furan ring, imidazole ring, piperidine ring, morpholine ring, etc.) or ｛D ₆ and d ₇ may be the same or different and represent a hydrocarbon group or -O
d ₈ (d ₈ is a hydrocarbon group). These hydrocarbon groups, d ₅ can be cited the same as those listed) alone linking group or the like, linking group constituted by a combination thereof.

Further, in the binder resin [A], in addition to the copolymer component represented by the above general formula (I) (including those represented by the general formula (IIa) or (IIb)) and the copolymer component containing an acidic group, Further, it is preferable to further contain 1 to 20% by weight of a copolymer component containing a heat and / or photocurable functional group from the viewpoint of obtaining higher mechanical strength.

“Thermal and / or photocurable functional group” refers to a functional group that causes a curing reaction of a resin by at least one of heat and light.

Specific examples of photocurable functional groups include Hideo Inui, Mototaro Nagamatsu, "Photosensitive Polymers" (Kodansha, published in 1977), Takahiro Kakuda, "New Photosensitive Resins" (publishing department of the Printing Society of Japan, published in 1981),
GEGreen and BPStrak, J.Macro.Sci.Reas.Macro Che
m., C21 (2), 187-273 (1981-82), CGRattey, "Ph
otopolymirization of Surface Cootings "(A. Wiley I
nterScience Pub. 1982), and the like, as the photocurable resin, functional groups used in conventionally known photosensitive resins and the like are used.

Further, the “thermosetting functional group” in the present invention is a functional group other than the above-mentioned acidic group, and includes, for example, Tsuyoshi Endo, “Refinement of thermosetting polymer” (CMC Corporation, 1986), Yuji Harazaki, "Handbook of Latest Binder Technologies", Chapter II-I (Comprehensive Technology Center, published in 1985), Takayuki Otsu, "Synthesis and Design of Acrylic Resins and Development of New Applications" (Chubu Business Development Center Publishing Division,
1985), Emori Omori "Functional Acrylic Resin" (Techno System, 1985), and the like can use the functional groups of the references.

For example, -OH group, -SH group, -NH ₂ group, -NHR ₃ group [R ₃ represents a hydrocarbon group, for example, an alkyl group having 1 to 10 carbon atoms which may be substituted (for example, a methyl group, an ethyl group , Propyl, butyl, hexyl, octyl, decyl, 2
-Chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, etc.), C4-8 optionally substituted cycloalkyl group (e.g., cycloheptyl group, cyclohexyl group, etc.), C7-12 substituted group. Aralkyl groups (eg, benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, etc.), and optionally substituted aryl groups (eg, phenyl group, tolyl group, xylyl group) Chlorophenyl group, bromophenyl group, methoxyphenyl group, naphthyl group, etc.), -CONHCH ₂ OR ₄ [R ₄ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, etc.)], -N =
C = O group and {D ₉ and d ₁₀ each represent a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, etc.)} and the like. . As the polymerizable double bond group, specifically, CH ₂ CHCH—, CH ₂ CHCH—CH ₂ —, CH ₂ = CH-CONH-, _{CH 2 = CH-NHCO-, CH} 2 = CH-CH 2 -, NHCO-, CH 2 = CH-SO 2 -,
_{CH 2 = CH-CO-, CH} 2 = CH-O-, may be mentioned CH ₂ = CH-S-, and the like.

In the present invention, as a method for causing the binder resin to contain at least one functional group selected from the group of the curable functional groups, a method of introducing a polymer into a polymer by a polymer reaction, or one or a group of such functional groups. One or more monomers contained above and a monomer corresponding to the repeating unit of the above-mentioned general formula (I) (including the general formula (IIa) or (IIb)) and a copolymer containing an acidic group It can be obtained by, for example, a method of performing a copolymerization reaction with a monomer corresponding to the “coalescing component”.

For the high-molecular reaction, a conventionally known low-molecular-weight synthesis reaction method can be used as it is. For example, "The New Experimental Chemistry Course Vol. 14, edited by The Chemical Society of Japan, Synthesis and Reaction of Organic Compounds [1]-
[V] "(published by Maruzen Co., Ltd.)," Reactive Polymers "by Yoshio Iwakura and Keisuke Kurita, and the like, and are described in detail in publicly known literature and the like.

On the other hand, the "functional group which performs light and / or heat curing reaction"
Examples of the monomer containing a functional group include a vinyl compound containing the functional group, which can be copolymerized with a monomer corresponding to the repeating unit of the general formula (I). Specific examples include compounds containing the functional group in the substituents of the same compounds as the “acidic group-containing compound” described above. An example of a repeating unit containing a “heat / photocurable functional group” will be described. Here, R ₁₁ , a, d, and e represent the same contents as described above, P ₁ and P ₃ each represent H or CH ₃ , and R ₁₄ represents —CH ＝ CH ₂ or —CH ₂ CH ＝ CH ₂ R ₁₅ is -CH = CH ₂ , Or -CH = CHCH ₃ , and R ₁₆ is -CH = CH ₂ , -CH ₂ CH = C
H ₂ , Or Z represents S or O, T ₃ represents OH or NH ₂ ,
h represents an integer of 1 to 11, and i represents an integer of 1 to 10.

Further, the resin [A] of the present invention is a compound represented by the above general formula (I)
In addition to the monomer corresponding to the copolymer component of the general formulas (IIa) and (IIb) and the monomer containing an acidic group, other monomers other than these are contained as a copolymer component. Is also good.

For example, methacrylates, acrylates containing substituents other than those described in the general formula (I),
In addition to crotonic esters, α-olefins, vinyl alkanoates or allyl esters (for example, alkanoic acids such as propionic acid acetate, butyric acid, and valeric acid), acrylonitrile, methacrylonitrile, vinyl ethers,
Itaconic esters (eg, dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrenes (eg, styrene, vinyltoluene,
Chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene,
Methanesulfonyloxystyrene, vinylnaphthalene, etc.), heterocyclic vinyls (eg, vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene,
Vinylimidazoline, vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.).

In the resin [A], as a method for bonding the acidic group to one terminal of the polymer main chain, various reagents are reacted with the terminal of a living polymer obtained by conventionally known anionic polymerization or cationic polymerization (ionic polymerization method). ), A method of radical polymerization using a polymerization initiator and / or a chain transfer agent containing a specific acidic group in the molecule (a method by a radical polymerization method), or an ionic polymerization method or a radical polymerization method as described above. Easily by a synthesis method such as a method of converting a polymer containing a reactive group (for example, an amino group, a halogen atom, an epoxy group, an acid halide group, etc.) into a specific acidic group of the present invention by a polymer reaction. Can be manufactured.

Specifically, P. Dreyfuss, RPQuirk, Encycl, Polym. Sc
Review articles such as i.Eng., 7 , 551 (1987), Yoshiki Chujo, Yuya Yamashita, "Dyes and Drugs", 30 , 232 (1985), Akira Ueda, Susumu Nagai, "Science and Industry" 60 , 57 (1986) In addition, it can be produced by the method described in the cited document or the like.

Specifically, as the chain transfer agent to be used, for example, a mercapto compound (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid) containing the acidic group or the above-mentioned reactive group (that is, a group derivable to the acidic group) 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptopropionic acid
Mercaptobutyric acid, N- (2-mercaptopropionyl)
Glycine, 2-mercaptonicotinic acid, 3- [N (2-
Mercaptoethyl) carbamoyl] propionic acid, 3-
[N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2
-Mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-
Mercaptoethanol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol-2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol,
4- (2-mercaptoethyloxycarbonyl) phthalic anhydride, 2-mercaptoethylphosphonoic acid, 2-mercaptoethylphosphonoic acid monomethyl ester, and the like, or an iodized alkyl compound containing the above polar group or substituent ( For example, iodoacetic acid, iodopropionic acid, 2-
Iodoethanol, 2-iodoethanesulfonic acid, 3-
Iodopropanesulfonic acid). Preferably, a mercapto compound is used.

Specific examples of the polymerization initiator containing the acidic group or the specific reactive group include 4,4′-azobis (4-cyanovaleric acid) and 4,4′-azobis (4-cyanovaleric acid). Chloride), 2,2'-azobis (2-cyanopropanol), 2,2'-azobis (2-cyanopentanol),
2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propioamide], 2,2'-azobis {2-
Methyl-N- [1,1-bis (hydroxymethyl) -2-
Hydroxyethyl] propioamide {, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl) propane}, 2,2'-azobis [2
-(2-imidazolin-2-yl) propane], 2,2'-
Azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazopin-2-yl) propane] and the like.

The amount of these chain transfer agents or polymerization initiators is 0.5 to 10 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the total monomers.

Next, the resin [B] used in the present invention will be described.

The resin [B] satisfies the above-mentioned physical properties and is a resin comprising a graft copolymer containing at least a monofunctional macromonomer (M) and a monomer represented by the general formula (V). Features.

The resin [B] preferably has a weight average molecular weight of 3 × 10 ⁴
The above is a graft copolymer resin. More preferably, the weight average molecular weight is from 5 × 10 ^{4 to} 3 × 10 ⁵ .

The glass transition point of the resin [B] is preferably 0 ° C to 120 ° C.
And more preferably from 10 ° C to 90 ° C.

The monofunctional macromonomer (M) is obtained by adding a polymerizable double bond group represented by the general formula (III) to the general formula (IVa) or (IV
It has a weight-average molecular weight of 2 × 10 ⁴ or less which is bonded to only one end of a polymer main chain containing at least one polymer component represented by b).

In the general formulas (III), (IVa) and (IVb), c ₁ , c
_The hydrocarbon groups contained in ₂ , V ₀ , d ₁ , d ₂ , V ₁ , Q ₄₁ and Q ₄₀ each have the indicated carbon number (as an unsubstituted hydrocarbon group)
However, these hydrocarbon groups may have a substituent.

Formula showing the macromonomer (M) in (III), V ₀ is, -COO -, - OCO -, - CH 2 OCO -, - CH 2 COO -, - O
-, -SO _2- , -CO-, -CONHCOO-, -CONHCONH-, -CONHSO ₂
-, Represents Here, P ₀ is a hydrogen atom, and a preferable hydrocarbon group is an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group). Group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2
-Chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group: 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group and the like, and an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, , 2-methyl-
1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), An optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group,
-Naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (E.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or C6-C6.
12 optionally substituted aromatic groups (for example, phenyl group,
Naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl Group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.).

V ₀ In the case where is represented, the benzene ring may have a substituent.
Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group, Ethoxy group, propoxy group, butoxy group, etc.).

c ₁ and c ₂ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (for example, a chlorine atom,
Bromine atom, etc.), cyano group, alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.), -COO-Z ₃₁ or -COO-Z ₃₁ via a hydrocarbon. Z ₃₁
Represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, and specifically,
Represents a represents) the same contents as those described for P _0.

Examples of the hydrocarbon in the -COO-Z ₃₁ group via the above hydrocarbon include a methylene group, an ethylene group, a propylene group and the like.

More preferably, in the general formula (III), V ₀ is -C
OO -, - OCO -, - CH 2 OCO -, - CH 2 COO -, - O -, - CONHCOO
-, -CONHCONH-, -CONH-, -SO ₂ NH- or And c ₁ and c ₂ may be the same or different from each other, and represent a hydrogen atom, a methyl group, -COO-Z ₃₁ or -CH ₂ COOZ ₃₁ (Z ₃₁ is
A hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc.)
Represents Even more preferably, one of c ₁ and c ₂ always represents a hydrogen atom.

That is, as the polymerizable double bond group represented by the general formula (III), specifically, And the like.

In the general formula (IVa), V ₁ represents the same content as V ₀ in the formula (III).

d ₁ and d ₂ may be the same or different from each other, and have the formula (III)
Represents the same content as c ₁ and c _{2 in} .

Q ₄₁ represents an aliphatic group or an aromatic group having 6 to 12 carbon atoms having 1 to 18 carbon atoms.

Specifically, an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, an octyl group, a decyl group,
Dodecyl, tridecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2
-Hydroxylethyl group, 2-methoxyethyl group, 2-
Ethoxyethyl group, 2-cyanoethyl group, 3-chloropropyl group, 2- (trimethoxysilyl) ethyl group, 2-
Tetrahydrofuryl group, 2-thienylethyl group, 2-N,
N-dimethylaminoethyl group, 2-N, N-diethylaminoethyl group, etc., C5-C8 cycloalkyl group (for example, cyclopetyl group, cyclohexyl group, cyclooctyl group, etc.), C7-C12 substituted group Aralkyl groups (e.g., benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl, chlorobenzyl, bromobenzyl, dichlorobenzyl, methylbenzyl, chloro-methyl-benzyl) Group,
Alicyclic groups such as dimethylbenzyl group, trimethylbenzyl group, and methoxybenzyl group).

Further, an optionally substituted aryl group having 6 to 12 carbon atoms (eg, phenyl, tolyl, xylyl, chlorophenyl, bromophenyl, dichlorophenyl, chloro-methyl-phenyl, methoxyphenyl, methoxycarbonylphenyl) , A naphthyl group, a chloronaphthyl group, etc.).

In the formula (IVa), V ₁ is preferably -COO-, -OCO
-, -CH ₂ COO-, -CH ₂ OCO-, -O-, -CO-, -CONHCOO-,-
CONHCONH -, - CONH -, - SO 2 NH-, or Represents

Preferred examples of d ₁ and d ₂ represent the same contents as those of c ₁ and c ₂ described above.

In the formula (IVb), Q ₄₀ represents —CN, —CONH ₂ or T represents a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom group, etc.), a hydrocarbon group (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a chloromethyl group, a phenyl group, etc.), an alkoxy group ( such as methoxy, ethoxy), or -COO-Z ₃₂ (Z ₃₂ is preferably 1 to 8 carbon atoms
Represents an alkyl group, an aralkyl group or an aryl group having 7 to 12 carbon atoms).

The macromonomer (M) may contain two or more polymer components represented by the formula (IVa) or (IVb). When Q ₄₁ in the formula (IVa) is an aliphatic group, the aliphatic group having 6 to 12 carbon atoms may be used in an amount not exceeding 20% by weight of the total polymer components in the macromonomer (M). preferable.

Further, when V ₁ in the general formula (IVa) is —COO—, at least 30% by weight or more of the polymer component represented by the formula (IVa) in all the polymer components in the macromonomer (M). It is preferable to be contained.

Further, the monofunctional macromonomer (M) has the formula (IV)
As a third copolymer component together with the copolymer component represented by (a) and / or (IVb), a specific polar group (-COOH group, -P
O ₃ H ₂ group, -SO ₃ H group, -OH group, —CHO group, acid anhydride containing group) (macromonomer (M ′)). As the polar group-containing component, any of the above-mentioned acidic group-containing vinyl compounds that can be copolymerized with the copolymer component (IVa) or (IVb) can be used. For example, "Polymer Data Handbook (Basic)" edited by The Society of Polymer Science, Baifukan (1986
Published). Specifically, acrylic acid, α
And / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α (2-aminomethyl form, α-chloro form, α-bromo form, α-fluoro form, α-form)
Tributylsilyl form, α-cyano form, β-chloro form, β
-Bromo form, α-chloro form, β-mesoxy form, α, β-
Dichloro compound), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid semiamides, crotonic acid,
2-alkenyl carboxylic acids (for example, 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid,
-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, half-ester derivatives of vinyl or allyl groups of alcohols, and esters of these carboxylic acids or sulfonic acids, and compounds containing the acidic group in the substituents of the amide derivatives.

In the above, R 'has the same contents as R, and the same applies to the acid anhydride-containing group.

Examples of the OH group include alcohols containing a vinyl group or an allyl group (e.g., ester substituents such as allyl alcohol, methacrylic acid ester and acrylamide, compounds containing an -OH group in the N-substituent), hydroxyphenol or hydroxyphenol Examples thereof include methacrylic esters or amides containing a phenyl group as a substituent.

For example, the following monomers are shown as examples, but the scope of the present invention is not limited thereto.

Here, in each of the following examples, Q ₁ is -H, -CH ₃ , -C
l, -Br, -CN, indicates -CH ₂ COOCH ₃ or -CH ₂ COOH, Q ₂ represents -H or -CH _3, j represents an integer of 2 to 18, k is 2
Represents an integer of 5 to 5, h represents an integer of 1 to 4, and m represents 1 to
Indicates an integer of 12.

_{(Iv-15) CH 2 =} CHCH 2 OCO (CH 2) m COOH (iv-16) CH 2 = CHCH 2 h COOH (Iv-49) CH ₂ = CHCH _{2 h} OH (Iv-52) CH ₂ = CHCH _{2 h} OCO (CH _{2 j} OH The amount of the polar group-containing copolymer component in the total polymer component in the macromonomer (M ') is preferably 0.5 to 50 parts by weight, more preferably 0.5 to 50 parts by weight, per 100 parts by weight of the total polymer component. It is 1 to 40 parts by weight.

When the monofunctional macromonomer (M ') composed of the random copolymer containing a polar group is contained in the resin [B] as a copolymer component, it is contained in all graft portions of the resin [B]. The total amount of the polar group-containing components is preferably 0.1 to 10 parts by weight per 100 parts by weight of all polymer components in the resin [B]. More preferably, -COOH group, -S
When the resin (B) contains a polar group selected from an O ₃ H group and a —PO ₃ H ₂ group, the total amount present in the graft portion in the resin (B) is 0.1%.
~ 5% by weight.

The macromonomer (M) may contain a copolymer component other than the above, and can be copolymerized with the repeating unit represented by the formula (IVa) and / or (IVb) and any of the above polar group-containing repeating units. As the monomer corresponding to the repeating unit, acrylonitrile, methacrylonitrile, acrylamides, methacrylamides, styrene and derivatives thereof (for example, vinyltoluene, chlorostyrene, dichlorostyrene, bromostyrene, hydroxymethylstyrene, N, N-dimethyl) And heterocyclic vinyls (eg, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.).

When these other monomers are contained, 1 to 20 parts by weight per 100 parts by weight of the total polymer components of the macromonomer (M) (including the macromonomer (M ') unless otherwise specified)
It is preferably in parts by weight.

The macromonomer (M) used in the resin [B] of the present invention may be a compound represented by the general formula (IVa) and / or (IV)
The polymerizable double bond group represented by the general formula (III) is directly bonded to only one end of the polymer main chain composed of the repeating unit represented by b) and any repeating unit containing the polar group. Or having a chemical structure linked by an arbitrary linking group. Formula (III) component and formula (IVa)
Alternatively, the group linking the component (IVb) or the polar group-containing component includes a carbon-carbon bond (single bond or double bond) and a carbon-hetero atom bond (hetero atoms include, for example, oxygen atom, sulfur atom, nitrogen Atoms, silicon atoms, etc.), and any combination of heteroatom-heteroatom bond atomic groups.

Preferred among the macromonomers (M) of the present invention are those represented by the formula (IVa) or (IVb) (however, any polar group-containing component that can be contained in the macromonomer (M) is shown. Absent).

In the formula (IVa) or (IVb), c ₁ , c ₂ , d ₁ , d ₂ , V ₀ , V ₁ ,
Q ₄₁ and Q ₄₀ are respectively represented by Formula (III), Formula (IVa) and Formula (IVb)
Represents the same contents as those described in.

W ₀ is a simple bond or [H ₁ and h ₂ represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.) ], CH = CH, -O-, -S-, -COO -, - SO ₂ -, -NHCOO-, -NHCONH-, [H ₃ and h ₄ each represent a hydrogen atom or a hydrocarbon group having the same content as Q ₁ in the formula (IVa)], or a single linking group selected from an atomic group or an arbitrary combination thereof. Represents a linking group.

When the weight average molecular weight of the macromonomer (M) exceeds 2 × 10 ⁴ , the copolymerizability with the monomer represented by the formula (V) decreases. On the other hand, if the molecular weight is too small, the effect of improving the electrophotographic properties of the photosensitive layer will be small, so that it is preferably 1 × 10 ³ or more.

In the present invention, the macromonomer (M) used for the resin [B] can be produced by a conventionally known synthesis method.

When the above-mentioned polar group-containing component is not contained in the polymer main chain of the macromonomer (M), for example, various reagents are reacted with the terminal of the living polymer obtained by anionic or cationic polymerization to form a macromer. Ion polymerization method, terminal reactive group bonding obtained by radical polymerization using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a carboxyl group, a hydroxyl group, or an amino group in the molecule. A method of reacting an oligomer with a variety of reagents to form a macromer by a radical polymerization method, and a method of introducing a polymerizable double bond group into an oligomer obtained by polyaddition or polycondensation reaction in the same manner as in the radical polymerization method described above. A method by an addition condensation method and the like can be mentioned.

Specifically, P.Dreyfuss & RPQuirk, Encycl.Poly
m.Sci.Eng., 7 , 551 (1987), PFRempp, E.Franta, Adv.Po
lym.Sci., 58 , 1 (1984), V.Perce, Appl.Polym.Sci., 285 ,
95 (1984), R. Asami, M. TakaRi, Makvamol. Chem. Suppl., 1
2 , 163 (1985), P. Rempp et al, Makvamol. Chem. Suppl.,
8 , 3 (1984), Yusuke Kawakami, Chemical Industry, 38 , 56 (1987), Yuya Yamashita, Polymer, 31 , 988 (1982), Shiro Kobayashi, Polymer,
30 , 625 (1981), Toshinobu Higashimura, Journal of the Adhesion Society of Japan 18 , 526 (19
82), Koichi Ito, Polymer Processing, 35 , 262 (1986), Higashi Kishiro, Takashi Tsuda, Functional Materials, 1987 No.10,5, etc. can do.

Specific examples of the macromonomer (M) (containing no specific polar group-containing component) of the present invention include the following compounds. However, the scope of the present invention is:
It is not limited to these.

However, in the following examples, p ₁ represents -H or -CH _3, p ₂ represents -H, a -CH ₃ or -CH ₂ COOCH _3, R ₃₁ is -C _r H
_{2r + 1} , -CH ₂ C ₆ H ₅ , -C ₆ H ₅ or Are shown, R ₃₂ is _{-C r H 2r + 1, CH} 2 S C 6 H 5 or R ₃₃ represents -C _r H _{2r + 1} , -CH ₂ C ₆ H ₅ or -C ₆ H ₅ ,
₃₄ -C _r H _{2r + 1} or indicates _{-CH 2 C 6 H 5, R} 35 is _{-C r H 2r + 1, CH} 2
C ₆ H ₅ or R ₃₆ represents -C _r H _{2r + 1} , R ₃₇ represents -C _r H _{2r + 1} , CH ₂ C
₆ H ₅ or Wherein R ₃₈ is -C _r H _{2r + 1} , CH ₂ C ₆ H ₅ or Are shown, V ₁ is -COOCH _3, shows a -C ₆ H ₅ or -CN, V ₂ is -OC _{r
H 2r + 1, -OCOC r H} 2r + 1, -COOCH 3, -C 6 H 5 or indicates -CN,
V ₃ is -COOCH ₃ , -C ₆ H ₅ , Or -CN, and V ₄ is -OCOC _r H _{2r + 1} , -CN, -CONH ₂ or -CN.
Shows the C ₆ H _5, V ₅ represents -CN, a -CONH ₂ or -C ₆ H _5, V ₆ is -
COOCH ₃ , -C ₆ H ₅ or And T ₁ represents -CH ₃ , -Cl, -Br or -OCH ₃ , and T ₂
Represents a -CH _3, -Cl or -Br, T ₃ is -H, -Cl, -B
r, -CH _3, shows a -CN or -COOCH _3, T ₄ is -CH _3, shows a -Cl or -Br, T ₅ represents -Cl, -Br, -F, and -OH or -CN, T ₆ is _{-H, -CH 3, -Cl, -Br} , -OCH 3 or -COO
CH ₃ is shown, r is an integer of 1 to 18, s is an integer of 1 to 3, and t is an integer of 2 to 4.

(P ₁ may be the same or different, the same applies hereinafter) A macromonomer (M ') containing a specific acidic group-containing component as a copolymer component that can be used in the present invention can also be produced by a conventionally known synthesis method. In particular,
A terminal obtained by radical polymerization using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a carboxyl group, a carboxy halide group, a hydroxyl group, an amino group, a halogen atom, and an epoxy group in a molecule. It is synthesized by a method such as a radical polymerization method in which an oligomer having a reactive group is reacted with various reagents to form a macromonomer.

Specifically, P. Dreyfuss & RPQuirk, Encycl.Poly
m.Sci.Eng., 7 , 551 (1987), PFRempp, E.Franta, A
du.Polym.Sci. 58 , 1 (1984), Yusuke Kawakami, Chemical Industry, 3
8 , 56 (1987), Yuya Yamashita, macromolecules, 31 , 988 (1982),
Kobayashi Shiro, Polymer, 30 , Koichi Ito, Polymer Processing, 35 , 26
2 (1986), Kishiro Higashi, Takashi Tsuda, Functional Materials, 1987 No.10,
The compound can be synthesized according to the method described in a review such as 5 and references and patents cited therein.

However, since the macromonomer (M ') of the present invention contains an acidic group as the establishment of its repeating unit,
In the synthesis, for example, it is synthesized with the following considerations.

As one of the methods, for example, as shown in the following reaction formula (I), radical polymerization and terminal reactive groups are carried out using a monomer containing a functional group in which the acidic group is protected by the above method. Is introduced.

The polar group (-SO ₃ H group, -PO ₃ H ₂ group, -COO) randomly contained in the macromonomer (M ') used in the present invention.
H group, The protecting group reaction and deprotection reaction (for example, hydrolysis reaction, hydrogenolysis reaction, oxidative decomposition reaction, etc.) of -OH group, -CHO group, acid anhydride-containing group) can be performed by a conventionally known method. . Specifically, JFWMcOmie, “Protec
tive Gvoups in Organic Chemistry ", Plenum Press (1
973), TWGreene, “Protective Gvoups in Organi
c Synthesis ", John Wiley & Sous (1981), Ryohei Oda" Polymer Fine Chemicals "Kodansha (1976), Yoshio Iwakura, Keisuke Kurita" Reactive Polymers "Kodansha (1977),
Berner etal, J. Radiation Curing, 1986, No. 10, P1
0, JP-A-62-212669, JP-A-62-286064, JP-A-62-286064
No. 210475, JP-A-62-195684, JP-A-62-258476, JP-A-63-260439, Japanese Patent Application No. 62-220510, Japanese Patent Application No. 62-22669
It can be synthesized using the method described in No. 2, etc.

As another method, for example, as shown in the following reaction formula (II), after synthesizing an oligomer as described above, a “reactive group having a characteristic property” bonded to one end of the oligomer is used.
Is a method of synthesizing by reacting with a reagent containing a polymerized double bond group that reacts only with “specific reactivity” by utilizing the difference in reactivity between the polymer and the acidic group contained in the oligomer. .

As shown in the reaction formula (II), specific examples of combinations of the specific functional groups are shown in Table B below. However, the present invention is not limited to these, and what is important is that macromonomerization can be achieved without protecting the acidic group in the oligomer by utilizing the selectivity of the reaction in a normal organic chemical reaction. That should be done.

Examples of the chain transfer agent that can be used include, for example, the polar group or a mercapto compound containing a substituent that can be later derived into the polar group (eg, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid,
3-mercaptopropionic acid, 3-mercaptobutyric acid, N
-(2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- ( 3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4
-Mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercapul Imidazole, 2-mercapto-3-pyridinol, etc.) or a disulfide compound which is an oxidized form of these mercapto compounds, or an iodized alkyl compound containing the above polar group or substituent (for example, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferably, a mercapto compound is used.

Specific reactive group-containing polymerization initiators that can be used include, for example, 2,2′-azobis (2-cyanopropanol), 2,2′-azobis (2-cyanopentanol), 4,4 ′ -Azobis (4-cyanovaleric acid), 4,4'-
Azobis (4-cyanovaleric acid chloride), 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane], 2,2'-azobis [2- (2-imidazoline-2) -Yl) propane], 2,2'-azobis [2
-(3,4,5,6-tetrahydropyrimidin-2-yl) propane], 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] and the like and derivatives thereof.

These chain transfer agents or polymerization initiators are each 0.1 to 15% by weight based on 100 parts by weight of all monomers, and are preferably
0.5 to 10% by weight.

Specific examples of the macromonomer (M ') of the present invention include the following compounds. However, the scope of the present invention is not limited to these. Also,
In each of the following examples, Q ₂ represents -H or CH ₃ and Q ₃ is-
H, indicates -CH ₃ or -CH ₂ COOCH _3, R ₄₁ is -C _n H _{2n +} 1 _(n is an integer of _{1~18), -CH 2 C 6 H} 5, (Y ₁ and Y ₂ are each -H, -Cl, -Br, -CH ₃ , -COCH ₃ or -C
OOCH ₃ ), The illustrated, W ₁ is -CN, -OCOCH _3, shows a -CONH ₂ or -C ₆ H _5, W ₂ is -C
l, -Br, shows a -CN or -OCH _3, alpha is an integer of 2 to 18, beta is an integer of 2 to 12, gamma is an integer of 2-4.

The monomer copolymerized with the macromonomer (M) is represented by the general formula (V). In the formula (V), e ₁ ,
e ₂ may be the same or different from each other;
Represents the same content as c ₁ and c ₂ . V ₂ is equal to V ₁ of the formula (IVa) and Q
₂ represents the same contents as Q ₁ in the formula (IVa).

Further, the resin [B] of the present invention may contain other monomers together with the above-mentioned macromonomer (M) (including the macromonomer (M ')) and the monomer of the general formula (V). It may be contained as a polymerization component. Specific examples include the same compounds as those exemplified as the other polymer components in the resin [A], and vinyl compounds containing an acidic group.

In the resin [B], the composition ratio of the copolymer component having a macromonomer (M) as a repeating unit and the copolymer component having a monomer represented by the general formula (V) as a repeating unit is from 1 to 80.
/ 99 to 20 (weight composition ratio), preferably 5 to 60/95 to
The composition ratio is 40% by weight.

The above-mentioned vinyl compound containing an acidic group is described, for example, in “Polymer Data Handbook [Basic Edition]” edited by The Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α-acetoxy form)
(2-amino) methyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α-chloro-, β
-Methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half-esters, itaconic acid half-amides, crotonic acid, 2-alkenylcarboxylic acids (eg, 2-pentenoic acid, 2-methyl- 2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4
-Ethyl-2-octenoic acid), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzene carboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acids, vinyl group or allyl Half ester derivatives of these groups; ester derivatives of these carboxylic acids or sulfonic acids; and compounds containing the acidic group in the substituents of the amide derivatives.

In the case where the resin [B] contains "vinyl compound containing an acidic group" as a repeating unit as another copolymer component, the copolymer component containing the acidic group accounts for 10% by weight of the copolymer [B]. It is preferable not to exceed.

If the content of the acidic group-containing component exceeds 10% by weight, the interaction with the inorganic photoconductor particles is not significant, and the smoothness of the photoreceptor surface is impaired. As a result, electrophotographic properties (particularly, chargeability, charge in the dark) (Retention) is deteriorated.

Further, the resin [B] may be contained in the resin [A] as a “copolymerizable component containing a crosslinkable (crosslinkable) functional group”.
The same components may be contained, and the content is 0.1 to 20.
% By weight is preferred.

Further, the resin [B '] which can be used as a preferred embodiment of the present invention comprises at least one repeating unit represented by the general formula (V) and a macromonomer (M) (including a macromonomer (M')). Only at one end of the polymer main chain containing at least one repeating unit shown, -PO ₃
H ₂ group, -SO ₃ H group, -COOH group, -OH group, -SH group and (R ₀ ′ has the same contents as R, that is, a hydrocarbon group or —O
It is a polymer comprising at least one acidic group selected from the group consisting of R '(R' represents a hydrocarbon group).

Here, as the hydrocarbon group represented by R ₀ ′,
An alkyl group which may be substituted and has 1 to 18 carbon atoms (e.g., methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl, 2-methoxyethyl) , 3-methoxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group and the like, and optionally substituted aralkyl groups having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group) , Dimethylbenzyl, methoxybenzyl, chlorobenzyl, etc.), having 5 to 5 carbon atoms
Alicyclic groups (e.g., cyclopentyl group, cyclohexyl group, etc.), and optionally substituted aromatic groups having 6 to 12 carbon atoms (e.g., phenyl group, tolyl group, xylyl group, naphthyl group, chlorophenyl group, bromophenyl) Groups, alkoxyphenyl groups (alkyl groups include methyl, ethyl, propyl, butyl, hexyl, octyl,
Nonyl group, decyl group, dodecyl group, etc.), acetoxyphenyl group, methyl-chloro-phenyl group, propylphenyl group, butylphenyl group, decylphenyl group, etc.).

When the acidic group is bonded to one end of the polymer main chain, the polymer main chain should not contain a copolymer component containing a carboxyl group, a sulfo group, a hydroxyl group, or a polar group such as a phosphono group. Is preferred.

In the resin [B '], the acidic group has a chemical structure in which it is directly bonded to one end of the polymer main chain or is bonded via an arbitrary linking group.

Specific examples of these bonding groups to the main chain include the same examples as those of the resin [A].

In the resin [B '], the acidic group that can be contained in the macromonomer (M') component of the polymer and the acidic group bonded to the terminal of the polymer main chain may be the same or different.

In the resin [B] used in the present invention, in order to synthesize the resin [B ′] in which the acidic group is bonded to the terminal of the polymer main chain, the resin [B ′] is used during the polymerization of each monomer described above. This can be achieved by using a polymerization initiator or a chain transfer agent containing a group or a specific reactive group derivable therein in the molecule, and specifically, it can be obtained by the same method as in the synthesis of the resin [A]. . However, the weight average molecular weight of the resin is a predetermined value by appropriately adjusting the type and amount of the polymerization initiator / chain transfer agent, the polymerization temperature, the concentration of the monomer, the polymerization solvent and the like as conventionally known in the polymerization reaction. Can be set within the range.

The ratio of the used amount of the resin [A] to the resin [B] used in the present invention is 5 to 60 to 95 to 40 (weight ratio), preferably 10 to 50.
It is 50 to 90 to 50 (weight ratio).

In the present invention, when the resin [A] and / or the resin [B] contains a light and / or thermosetting functional group, a crosslinking agent may be used in combination to promote crosslinking in the film. Good. As the crosslinking agent to be used, a compound usually used as a crosslinking agent can be used. Specifically, the same compounds as those used for producing the above-mentioned network hydrophilic resin particles having a higher-order network structure can be used.

The amount of the crosslinking agent used in the binder resin of the present invention is preferably 0.5 to 30% by weight, particularly preferably 1 to 10% by weight based on the total amount of the binder resin.

In the present invention, a reaction accelerator may be added to the binder resin, if necessary, in order to promote a crosslinking reaction in the photosensitive layer film.

In the case of a reaction mode in which a crosslinking reaction forms a chemical bond between functional groups, for example, an organic acid (acetic acid, propionic acid, butyric acid,
Benzenesulfonic acid, p-toluenesulfonic acid, etc.).

When the crosslinking reaction is a polymerization reaction mode, a polymerization initiator (a peroxide, an azobis-based compound or the like, preferably an azobis-based polymerization initiator), a polyfunctional polymerizable monomer ( For example, vinyl methacrylate, allyl methacrylate, ethylene glycol acrylate, polyethylene glycol diacrylate, divinyl succinate, divinyl adipate, diallyl succinate, 2-methylvinyl methacrylate, divinylbenzene and the like can be mentioned.

Further, in the present invention, a resin other than the resin of the present invention can be used in combination. Examples of such resins include alkyd resins, polybutyral resins, polyolefins, ethylene-vinyl acetate copolymers, styrene resins, styrene-butadiene resins, acrylate butadiene resins,
And vinyl alkanoate resins.

When the other resin exceeds 30% (weight ratio) of the total amount of the binder resin using the resin of the present invention, the effect of the present invention (especially, improvement of electrostatic characteristics) is lost.

When the binder resin of the present invention contains a light and / or thermosetting functional group in the resin [A] and / or the resin [B], the resin is crosslinked or thermoset after applying the photosensitive layer-formed product. Is done. In order to carry out crosslinking or thermal curing, for example, the drying conditions are made stricter than the drying conditions at the time of the conventional photoreceptor production. For example, the drying conditions are high temperature and / or long time. Alternatively, it is preferable to further perform a heat treatment after drying the coating solvent. For example, the treatment is performed at 60 to 120 ° C. for 5 to 12 minutes. When the above-mentioned reaction accelerator is used in combination, the treatment can be performed under milder conditions.

The inorganic photoconductive material used in the present invention is photoconductive zinc oxide, but titanium oxide as another inorganic photoconductor,
Zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, lead sulfide and the like may be used in combination.

In the present invention, the total amount of the binder resin used for the photoconductive zinc oxide is 100 parts by weight of the photoconductor, a proportion of the binder resin is 10 to 100 parts by weight, preferably a proportion of 15 to 50 parts by weight. Used in.

In the present invention, various dyes can be used as spectral sensitizers as needed. For example, Harumiya Miyamoto, Hidehiko Takei, Imaging 1973 (No.8), page 12, CJ Young et al., RC
A Review 15, 469 (1954), Kohei Kiyota, IEICE Transactions J 63-C (No.2), 97 (1980), Yuji Harasaki et al., Industrial Chemistry 66 78 and 188 (1963), Tadaaki Tani , Journal of the Japan Society of photographic Science and Technology 35, 208 (1972) carbonium-based dyes of review references such as,
Diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (eg, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain metals), etc. No.

More specifically, examples of those mainly using a carbonium dye, a triphenylmethane dye, a xanthene dye, and a phthalein dye are described in JP-B-51-452 and JP-A-50-9.
No. 0334, JP-A-50-114227, JP-A-53-39130, JP-A-53-82353, U.S. Pat.No. 3,052,540, U.S. Pat.
54,450 and JP-A-57-16456.

Oxonol dyes, merocyanine dyes, cyanine dyes, polymethine dyes such as rhodacyanine dyes, F.
M. Harmmar `` The Cyanine Dyes and Related Compound
s '' and the like can be used, and more specifically, U.S. Pat.No. 3,047,384, U.S. Pat.No.3,110,591,
U.S. Patent No.3,121,008, U.S. Patent No.3,125,447, U.S. Patent No.3,128,179, U.S. Patent No.3,132,942, U.S. Patent No.3,622,317, U.K. Patent No.1,226,892, U.K. Patent No.1,
No. 309,274, UK Patent No. 1,405,898, JP-B-48-7814
And the dyes described in JP-B-55-18892.

Further, as polymethine dyes for spectrally sensitizing the near infrared to infrared light region having a long wavelength of 700 nm or longer, JP-A-47-840, JP-A-47-44180, JP-A-51-41061, Kaisho 49-5034,
JP-A-49-45122, JP-A-57-46245, JP-A-56-35141
No., JP-A-57-157254, JP-A-61-26044, JP-A-61-26044
No. 27551, U.S. Pat.No. 3,619,154, U.S. Pat.
Issue 6, Research Disclosure, 1982, 216, 117-11
Those described on page 8 and the like can be mentioned. The photoreceptor of the present invention is excellent in that even when various sensitizing dyes are used in combination, the performance is hardly changed by the sensitizing dye. Furthermore, various conventionally known additives for an electrophotographic photosensitive layer such as a chemical sensitizer can be used in combination, if necessary. For example, the above-mentioned review: Electron accepting compounds (for example, halogen, benzoquinone, chloranil, acid anhydride, organic carboxylic acid, etc.) described in the review such as Imaging, 1973 (No. 8), page 12, etc .; Recent Developments and Practical Use of Photoconductive Materials and Photoconductors "Chapters 4 to 6: Polyarylalkane compounds, hindered phenol compounds, p-polyphenylene, as reviewed in the publication section of the Japan Science Information Publishing Company (1986) And diamine compounds.

The amounts of these various additives are not particularly limited, but are usually 0.0001 to 2.0 parts by weight based on 100 parts by weight of the photoconductor.

The thickness of the photoconductive layer is preferably from 1 to 100 μm, particularly preferably from 10 to 50 μm.

When a photoconductive layer is used as the charge generation layer of the photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is preferably 0.01 to 1 μm, particularly preferably 0.05 to 0.5 μm.

In some cases, an insulating layer is provided for the main purpose of protecting the photoreceptor, improving durability, and improving dark attenuation characteristics. At this time, the insulating layer is set relatively thin, and the insulating layer provided when the photosensitive member is used in a specific electrophotographic process is set relatively thick.

In the latter case, the thickness of the insulating layer is between 5 and 70 μm, especially 10
Set to ~ 50μ.

Examples of the charge transport material of the laminated photoreceptor include polyvinyl carbazole, oxazole dyes, pyrazoline dyes, and triphenylmethane dyes. The thickness of the charge transport layer is preferably 5 to 40 μm, particularly preferably 10 to 30 μm.

Typical examples of the resin used for forming the insulating layer or the charge transport layer include polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, A thermoplastic resin of a polyacryl resin, a polyolefin resin, a urethane resin, an epoxy resin, a melamine resin, a silicone resin, and a curable resin are appropriately used.

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally, the support of the electrophotographic photosensitive layer is preferably conductive. As the conductive support, a base material such as a metal, paper, or a plastic sheet is impregnated with a low-resistance substance in the same manner as in the related art. A substrate that has been subjected to a conductive treatment, for example, by applying a conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided), and further coated with at least one layer for the purpose of preventing curling and the like. A substrate provided with a water-resistant adhesive layer on its surface, a substrate provided with at least one or more precoat layers as necessary on the surface layer of the support, or a substrate conductive plastic on which Al or the like is deposited is laminated on paper. Can be used.

Specifically, as an example of a conductive substrate or a conductive material, Yukio Sakamoto, Electrophotography, 14, (No. 1), p2-11 (197)
5), Hiroyuki Moriga, “Introduction to Special Paper Chemistry,” Polymer Publishing Association (1
975), MF Hoover, J. Macromol. Sci. Chem. A-4 (6),
Those described in pages 1327 to 1417 (1970) and the like are used.

A known method can be applied to prepare a lithographic printing plate using the electrophotographic lithographic printing plate precursor of the invention. That is, it is charged substantially uniformly in a dark place, and forms an electrostatic latent image by image exposure. Exposure methods include semiconductor laser, He
-Scanning exposure with Ne laser or xenon lamp,
Reflection image exposure using a tungsten lamp, a fluorescent lamp or the like as a light source, contact exposure through a transparent positive film, and the like can be mentioned. Next, the electrostatic latent image is developed with toner. As a developing method, a conventionally known method, for example, a cascade phenomenon,
Various methods such as magnetic brush development, powder cloud development, and liquid development can be used. Among them, liquid development is capable of forming a fine image and is suitable for producing a printing plate. The formed toner image can be fixed by a known fixing method, for example, heat fixing, pressure fixing, solvent fixing and the like.

The printing plate having the toner image thus formed is then subjected to a hydrophilic treatment of a non-image portion by a conventional method. A so-called desensitizing solution is usually used for the hydrophilization treatment. Conventionally, as this kind of desensitizing treatment solution, a cyanide-containing treatment solution containing ferrocyanate and ferricyanate as main components, an ammine cobalt complex, phytic acid and derivatives thereof, and a cyan-free treatment containing guanidine derivatives as main components Liquids, treatment liquids containing an inorganic or organic acid which forms a chelate with zinc ions as a main component, treatment liquids containing a water-soluble polymer, and the like are known.

For example, as a cyanide-containing processing solution, Japanese Patent Publication No. Sho 44
-9045, JP-A-46-39403, JP-A-52-76101, JP-A-57-1078
Nos. 89 and 54-117201.

Phytic acid-based compound-containing treating solution is disclosed in
No. 3807, No. 53-83805, No. 53-102102, No. 53-109701
Nos. 53-127003, 54-2803, 54-44901 and the like.

JP-A-53-104301, JP-A-53-140103, JP-A-54-18304, as a treatment solution containing a metal complex compound such as a cobalt complex
And those described in JP-B-43-28404.

As a treatment liquid containing an inorganic or organic acid, JP-B-39-13070
No. 2, No. 40-10308, No. 43-28408, No. 40-26124, and JP-A-51-118501.

As a guanidine compound-containing treatment solution, JP-A-56-111
No. 695 and the like.

Examples of the processing solution containing a water-soluble polymer include JP-A-52-126.
No. 302, No. -52-134501, No. 53-49506, No. 53-59502
No. 53-104302, JP-B 38-9665, 39-22263,
Nos. 40-763 and 40-2202, and JP-A-49-36402.

In any of the above desensitizing solutions, the zinc oxide in the surface layer serving as the photoconductive layer is ionized into zinc ions, and this ion reacts with a compound forming a chelate in the desensitizing solution. Is believed to form zinc chelates, which are deposited in the surface layer and become hydrophilic.

Therefore, the printing original plate of the present invention is a printing plate that can be printed by performing a desensitization treatment using a desensitization treatment liquid.

Preferred embodiments of the present invention can be described below.

(1) A lithographic printing plate precursor, wherein the hydrophilic resin particles form a high-order network structure.

(2) In the resin [A], as a copolymerization component represented by the general formula (I), at least one of an aryl group-containing methacrylate component represented by the following general formulas (IIa) and (IIb): An original plate for lithographic printing characterized by containing.

General formula (IIa) General formula (IIb) [In the formulas (IIa) and (IIb), A ₁ and A ₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, —COD ₁ or —COOD ₂ (D ₁ And D ₂ each have 1 to 1 carbon atoms
Represents 0 hydrocarbons).

B ₁ and B ₂ each represent a single bond or a linking group having 1 to 4 linking atoms, each linking —COO— and a benzene ring. ] (3) a monofunctional macromonomer in the binder resin (B) further -COOH group, -PO ₃ H ₂ group, -SO ₃ H group, -OH group, (R ₀ represents the same content as R in claim (1))
A lithographic printing plate precursor comprising at least one component having at least one polar group selected from a group, a -CHO group and a cyclic acid anhydride-containing group.

(4) The copolymer in the resin [B] further comprises -PO ₃ H
₂ , -SO ₃ H group, -COOH group, -OH group, -SH group and ｛R ₀ 'represents the same content as R described in claim (1))
A lithographic printing plate precursor comprising at least one polar group selected from the group consisting of:

(Example) Production example 1 of hydrophilic resin particles 1: A mixed solution of 95 g of L-1 dodecyl methacrylate, 5 g of acrylic acid and 200 g of toluene was heated to 70 ° C. while stirring under a nitrogen stream. 1.5 g of 2,2-azobis (isobutyronitrile) (abbreviation: AIBN) was added thereto and reacted for 8 hours. 12 g of glycidyl methacrylate, t-
1 g of butylhydroquinone and 0.8 g of N, N-dimethyldodecylamine were added and reacted at 100 ° C. for 15 hours (dispersion resin α).

Next, the dispersion resin α7.5 g (as solid content), 2-
A mixed solution of 50 g of hydroxyethyl methacrylate and 200 g of n-heptane was heated to 65 ° C. while stirring under a nitrogen stream. To this was added 0.7 g of 2,2-azobis (isovaleronitrile) (abbreviated as AIVN) and reacted for 6 hours.

Twenty minutes after the addition of the initiator (AIVN), the homogeneous solution began to become cloudy and the reaction temperature rose to 90 ° C. After cooling, a white dispersion was obtained through a 200-mesh nylon cloth. Average particle size 0.
It was a 19 μm latex.

Production Example 2 of hydrophilic resin particles: L-2 2-phosphonoethyl methacrylate 50 g, dispersion resin α8
g (as solid content), ethyl acetate 150 g, n-hexane 1
50 g of the mixed solution was heated to 55 ° C. while stirring under a nitrogen stream. 0.5 g of AIVN was added and reacted for 4 hours to obtain a white dispersion. After cooling through a 200 mesh nylon cloth,
The resulting dispersion was a latex having an average particle size of 0.45 μm.

Production Example 3 of hydrophilic resin particles: Reaction was carried out in the same manner as in Production Example 1, except that a mixed solution of 50 g of L-3 N-vinylpyrrolidone, 10 g of dispersion resin α (as solid content), and 200 g of toluene was reacted. 0.30 μm white latex was obtained.

Production Example 4 of hydrophilic resin amount: L-4 A mixture of 31.5 g of ethylene glycol, 51.8 g of phthalic anhydride, 6.0 g of methacrylic acid, 10 g of trichloroethylene, and 0.7 g of p-toluenesulfonic acid was heated and reacted for 6 hours. The reaction temperature was started from 107 ° C. and increased to 150 ° C. in 6 hours (water by-produced by the reaction was removed by the Dean-Stark method).

Next, a mixed solution of 6 g of methacrylic acid, 76 g of chloroform, 11.6 g of ethanol, and β5.8 g (as a solid content) of the dispersion obtained in the above reaction was refluxed under a nitrogen stream.
0.8 g of AIBN was added thereto and reacted for 3 hours to obtain a white dispersion. It was a latex having an average particle size of 0.40 μm.

Production Example 5 of Hydrophilic Resin Particles: A mixed solution of 50 g of L-5 N, N-dimethylaminoethyl methacrylate, 15 g of poly (dodecyl methacrylate) and 300 g of toluene was prepared, and the following operation was carried out under the same granulation conditions as in Production Example 1. Thus, a white dispersion having an average particle diameter of 0.28 μm was obtained.

Production Example 6 of hydrophilic resin particles: L-6 (2-hydroxyethyl acrylate / methyl methacrylate) copolymer (weight composition ratio 1/1) powder 10 g, (dodecyl methacrylate / acrylic acid) copolymer (weight composition ratio) 95/5) A mixture of 2 g and 100 g of toluene was mixed with a ball mill for 48 hours.
After a time treatment, a dispersion was obtained. The latex had an average particle size of 0.38 μm.

Production Example 7 of Hydrophilic Resin Particles: L-7 (vinyl alcohol / methacrylic acid) copolymer (weight composition ratio: 7/3) 10 g, (decyl methacrylate / N, N-dimethylaminoethyl acrylate) copolymer (weight 95/5)
A mixture of 1.8 g and 100 g of toluene was treated with a ball mill for 56 hours to obtain a dispersion. The latex had an average particle size of 0.32 μm.

Production Example 8 of hydrophilic resin particles: L-8 In Production Example 1 of hydrophilic resin particles, 2 was added to the dispersion resin α.
Except for adding 1 g of ethylene glycol dimethacrylate in addition to -hydroxyethyl methacrylate and n-heptane, the same operation as in Production Example 1 of hydrophilic resin particles was carried out to obtain latex particles having an average particle diameter of 0.25 µm.

Production Example 9 of Hydrophilic Resin Particles: L-9 In Production Example 2 of hydrophilic resin particles, 2 was added to the dispersion resin α.
-Except for adding 1.2 g of divinylbenzene in addition to phosphonoethyl methacrylate, ethyl acetate and n-hexane, the same operation as in Production Example 1 of hydrophilic resin particles was performed to obtain latex particles having an average particle diameter of 0.40 µm. Was.

Production Example 10 of hydrophilic resin particles: L-10 In Production Example 3 of hydrophilic resin particles, N was added to the dispersion resin α.
-Except for adding 1.5 g of ethylene diglycol dimethacrylate in addition to vinylpyrrolidone and toluene, the same operation as in Production Example 3 of hydrophilic resin particles was carried out, and the average particle diameter was the same as in Production Example 3 of hydrophilic resin particles. Latex particles were obtained.

Production Example 11 of hydrophilic resin particles: L-11 In Production Example 4 of hydrophilic resin particles, in addition to methacrylic acid, chloroform, and ethanol, 1,6-
Except that 00.5 g of hexanediol diacrylate was added, the same operation as in Production Example 4 of hydrophilic resin particles was performed to obtain latex particles having an average particle diameter of 0.45 μm.

Production Example 12 of Hydrophilic Resin Particles: L-12 Except for adding 0.8 g of triethylene glycol dimethacrylate in Production Example 5 of hydrophilic resin particles, the same operation as in Production Example 5 of Hydrophilic Resin Particles was carried out. Particle size
0.43 μm latex particles were obtained.

Production Example 13 of hydrophilic resin particles: L-13 50 g of the following monomer (a), 30 g of methyl methacrylate, 2
A mixed solution of 17 g of hydroxyethyl methacrylate, 3 g of allyl methacrylate and 300 g of tetrahydrofuran was heated to 80 ° C. under a nitrogen stream. After adding 1.5 g of AIBN and reacting for 6 hours, the precipitate was reprecipitated in n-hexane, and the solid was collected by filtration. After drying, 84 g of a powder was obtained.

Production Example 14 of Hydrophilic Resin Particles: A mixture of 50 g of L-14 (2-hydroxypropyl methacrylate / ethyl methacrylate) copolymer (weight composition ratio 7/3) and 200 g of methylcellosolve was heated to 40 ° C. and dissolved. . 1,
1.0 g of 6-hexamethylene diisocyanate was added and stirred for 4 hours. After cooling, the mixture was reprecipitated with water, and the solid was collected by filtration.

 After drying, 35 g of a powder was obtained.

Production Example 15 of Hydrophilic Resin Particles: A mixture of 5 g of L-15 2-methyl-2-oxazoline 5 g, 1,4-tetramethylene-2,2′-bisoxazoline 1.0 g, methyl triflate 0.1 g and acetonitrile 20 g was mixed with 100. Sealing polymerization was performed at 7 ° C. for 7 hours. The obtained reaction product was reprecipitated in methanol, and the solid was collected by filtration. After drying, powder 4.1g
I got

The resin (hydrogel) obtained in this Production Example has the following structure.

Production Example 16 of hydrophilic resin particles: L-16 A mixed solution of 50 g of 2-methanesulfonylethyl methacrylate, 0.8 g of divinylsuccinic acid, and 200 g of dimethylformamide was heated to 70 ° C. under a nitrogen stream, and 1.5 g of AIBN was added thereto for 8 hours. Reacted. The obtained reaction product was reprecipitated in hexane, and the solid was collected by filtration. After drying, 38 g of a powder was obtained.

Production Example 17 of Hydrophilic Resin Particles: A mixed solution of 20 g of L-17 acrylic acid, 4 g of monofunctional macromonomer AB-6 (manufactured by Toagosei Co., Ltd.), and 109 g of methyl ethyl ketone was added to a temperature of 65 ° C. under a nitrogen stream. Warmed. 0.2 g of AIVN was added and reacted for 2 hours, and 0.1 g of AIVN was further added and reacted for 1 hour. After cooling, a white dispersion was obtained through a 200-mesh nylon cloth. The latex had an average particle size of 0.23 μm.

Production Examples 18 to 23 of hydrophilic resin particles: L-18 to L-23 Production Example 17 was the same as in Production Example 17, except that acrylic acid 20 g and AB-64 g were replaced with the compounds shown in Table-C below. Each latex was produced in the same manner.

Synthesis Example 1 of Resin [A] of the Present Invention 1: [A-1] A mixed solution of 98 g of benzyl methacrylate, 2 g of acrylic acid, 3 g of thiosalicylic acid and 200 g of toluene was heated to 70 ° C. in a nitrogen stream.

2,2'-azobisisobutyronitrile (abbreviation AIB
N.) 1.0 g and reacted for 4 hours. Further, 0.4 g of AIBN was added for 2 hours; after that, 0.2 g of AIBN was further added and stirred for 3 hours. The weight average molecular weight (abbreviation w) of the obtained copolymer was 6.5 × 10 ³ .

Synthesis Examples 2 to 16 of Resin [A] of the Present Invention: [A-2] to [A
-16] In Synthesis Example 1 of Resin [A], each resin [A] was synthesized in the same manner as in Synthesis Example 1 except that 98 g of benzyl methacrylate and 2 g of acrylic acid were used instead of the monomers shown in Table 1 below. did. The weight average molecular weight of each resin is 6.0 × 10 ³ to 8 × 10 ³
Met.

Synthesis Examples 17 to 27 of Resin [A] of the Present Invention: [A-17] to [A
-27] In Synthesis Example 1 of Resin [A], methacrylate and mercapto compound shown in Table 2 below were used instead of 98 g of benzyl methacrylate and 3 g of thiosalicylic acid, and 150 g of toluene and 50 g of isopropanol were used instead of 200 g of toluene. Reacts in the same manner as in Synthesis Example 1,
Each resin [A] was synthesized.

Synthesis Example 28 of resin (A) of the present invention: (A-28) 1-naphthyl methacrylate 97 g, methacrylic acid 3 g,
A mixed solution of 150 g of toluene and 50 g of isopropanol,
The mixture was heated to a temperature of 80 ° C. under a nitrogen stream.

4,4'-azobis (4-cyanovaleric acid) (abbreviation AC
V.) 5.0 g was added and stirred for 5 hours. Further, 1 g of ACV was added and the mixture was stirred for 2 hours, and then 1 g of ACV was added and stirred for 3 hours.
The weight average molecular weight of the obtained copolymer was 7.5 × 10 ³ .

Synthesis Example 29 of Resin (A) of the Present Invention: (A-29) A mixed solution of 97 g of benzyl methacrylate, 3 g of vinylbenzenecarboxylic acid, 1.5 g of thiosalicylic acid and 200 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream. .

After adding 3.0 g of ACV and reacting for 6 hours, AIBN
0.4 g was added and reacted for 3 hours. W of the obtained copolymer is
It was 5.8 × 10 ³ .

(Production Example of Macromonomer Used for Resin [B]) Production Example 1 of Macromonomer 1: (MM-1) A mixed solution of 95 g of methyl methacrylate, 5 g of thioglycolic acid, and 200 g of toluene was stirred under a nitrogen stream while stirring.
Heated to a temperature of 75 ° C. 1.0 g of 2,2'-azobis (cyanovaleric acid) (abbreviated as ACV) was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and t-butylhydroquinone were added to the reaction solution.
0.5 g was added, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in 2 l of methanol,
g obtained. The number average molecular weight of the polymer (MM-1) was 6,500.

Production Example 2 of Macromonomer: (MM-2) A mixed solution of 95 g of methyl methacrylate, 5 g of thioglycolic acid and 200 g of toluene was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 1.5 g of 2,2'-azobis (isobutyronitrile) (abbreviation: AIBN) was added and reacted for 8 hours.
Next, to this reaction solution, 7.5 g of glycidyl methacrylate,
1.0 g of N, N-dimethyldodecylamine and 0.8 g of t-butylhydroquinone were added, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in 2 l of methanol,
85 g of a colorless and transparent viscous substance was obtained. The number average molecular weight of the polymer (MM-2) was 2,400.

Production Example 3 of Macromonomer: (MM-3) 94 g of propyl methanol, 2-mercaptoethanol 6
g and a mixed solution of 200 g of toluene were heated to a temperature of 70 ° C. under a nitrogen stream. 1.2 g of AIBN was added and reacted for 8 hours.

Next, the reaction solution was cooled in a water bath to a temperature of 20 ° C., 10.2 g of triethylamine was added, and 14.5 g of methacrylic acid chloride was added dropwise with stirring at a temperature of 25 ° C. or lower. After the addition, the mixture was further stirred for 1 hour. Thereafter, 0.5 g of t-butylhydroquinone was added, the mixture was heated to a temperature of 60 ° C., and stirred for 4 hours. After cooling, the precipitate was reprecipitated in 2 l of methanol to obtain 79 g of a colorless and transparent viscous substance. The number average molecular weight of the polymer (MM-3) is
4,500.

Production Example 4 of Macromonomer: (MM-4) A mixed solution of 95 g of ethyl methacrylate and 200 g of toluene was heated to a temperature of 70 ° C. under a nitrogen stream. 5 g of 2,2'-azobis (cyanoheptanol) was added and reacted for 8 hours.

After cooling, the temperature of the reaction solution was adjusted to 20 ° C. in a water bath, 1.0 g of triethylamine and 21 g of methacrylic anhydride were added, and the mixture was stirred for 1 hour and then at 60 ° C. for 6 hours.

The obtained reaction product was cooled and then reprecipitated in 2 l of methanol to obtain 75 g of a colorless and transparent viscous substance. The number average molecular weight of the polymer (MM-4) was 6.200.

Production Example 5 of Macromonomer: (MM-5) A mixture of 93 g of benzyl methacrylate, 7 g of 3-mercaptopropionic acid, 170 g of toluene and 30 g of isopropanol was heated to a temperature of 70 ° C. under a nitrogen stream to obtain a homogeneous solution. 2.0 g of AIBN was added and reacted for 8 hours. After cooling, reprecipitate in 2 l of methanol and heat to 50 ° C. under reduced pressure.
The solvent was distilled off. The obtained viscous substance was dissolved in 200 g of toluene, and glycidyl methacrylate 16 g, N, N
1.0 g of -dimethyldodecyl methacrylate and 1.0 g of t-butylhydroquinone were added, and the mixture was stirred at 110 ° C for 10 hours. This reaction solution was reprecipitated again in 21 of methanol. The number average molecular weight of the obtained pale yellow viscous substance (MM-5) was 3,40.
It was 0.

Production Example 6 of Macromonomer: (MM-6) A mixed solution of 95 g of propyl methacrylate, 5 g of thioglycolic acid and 200 g of toluene was heated to 70 ° C. while stirring under a nitrogen stream. 1.0 g of AIBN was added and reacted for 8 hours. Next, glycidyl methacrylate 13 g, N, N
1.0 g of -dimethyldodecylamine and 1.0 g of t-butylhydroquinone were added, and the mixture was stirred at 110 ° C for 10 hours. After cooling, the reaction solution was reprecipitated in 2 l of methanol to obtain 86 g of a white powder. The number average molecular weight of the polymer (MM-6) is 3,500
Met.

Production Example 7 of Macromonomer: (MM-7) 40 g of methyl methacrylate, 54 of ethyl methacrylate
g, a mixture of 6 g of 2-mercaptoethylamine, 150 g of toluene and 50 g of tetrahydrofuran were heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 2.0 g of AIBN was added and reacted for 8 hours. Next, the reaction solution was heated to a temperature of 20 ° C. in a water bath, and 23 g of methacrylic anhydride was added dropwise thereto so that the temperature did not exceed 25 ° C., followed by further stirring for 1 hour.

0.5 g of 2,2'-methylenebis (6-t-butyl-p-cresol) was added, and the mixture was stirred at 40 ° C for 3 hours. After cooling, this solution was reprecipitated in 2 l of methanol to obtain 83 g of a viscous substance. The number average molecular weight of the polymer (MM-7) was 2,200.

Production Example 8 of Macromonomer: (MM-8) 95 g of 2-chlorophenyl methacrylate, 150 of toluene
g and ethanol 150 g in a nitrogen stream at a temperature of 75
Warmed to ° C. 5 g of ACV was added and reacted for 8 hours. Next, 15 g of glycidyl acrylate, 1.0 g of N, N-dimethyldodecylamine and 1.0 g of 2,2′-methylenebis- (6-t-butyl-p-cresol) were added, and the mixture was stirred at a temperature of 100 ° C. for 15 hours. After cooling, the reaction solution was reprecipitated in 2 l of methanol to obtain 83 g of a transparent viscous substance. The number average molecular weight of the polymer (MM-8) was 3,600.

Production Examples 9 to 18 of Macromonomers: (MM-9) to (MM-1
8) The same procedure as in Preparation Example 3 was carried out except that the acid halide compounds in Table 3 below were used instead of methacrylic acid chloride in Preparation Example 3 of the macromonomer, and the macromonomer (MM-9) was used. ~ (MM-18).

The weight average molecular weights (w) of the macromonomers (MM-9) to (MM-18) were 4,000 to 5,000.

Production Examples 19 to 27 of Macromonomer: (MM-19) to (MM-2
7) In Preparation Example 2 for macromonomer, except that the monomers in Table 4 below were used instead of methyl methacrylate,
By operating in the same manner as in Production Example 2, macromonomer (MM-19)
(MM-27) was produced.

Synthesis Example 101 of Macromonomer (M '): MM-101 90 g of ethyl methacrylate, 10 g of 2-hydroxyethyl methacrylate, 5 g of thioglycolic acid and 200 of toluene
g of the mixed solution was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 2,2'-azobisisobutyronitrile (abbreviation)
(AIBN) 1.0 g and reacted for 8 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to the reaction solution, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in 2 l of n-hexane to obtain 82 g of a white powder.
The weight average molecular weight of the polymer was 3.8 × 10 ³ .

Synthesis Example of Macromonomer (M ′) 102: MM-102 Butyl methacrylate 90 g, methacrylic acid 10 g, 2-
A mixed solution of 4 g of mercaptoethanol and 200 g of tetrahydrofuran was heated to a nitrogen stream temperature of 70 ° C. 1.2 g of AIBN was added and reacted for 8 hours.

Next, the reaction solution was cooled in a water bath to a temperature of 20 ° C.,
Triethylamine (10.2 g) was added, and methacrylic acid chloride (14.5 g) was added dropwise with stirring at a temperature of 25 ° C. or lower. After the addition, the mixture was further stirred for 1 hour. Thereafter, 0.5 g of t-butylhydroquinone was added, the mixture was heated to a temperature of 60 ° C, and stirred for 4 hours.
After cooling, it is dropped into water 1 with stirring (about 10 minutes)
After stirring for 1 hour as it was and standing, water was removed by decantation. After two further washings with water, it was dissolved in 100 ml of tetrahydrofuran and reprecipitated in 2 l of petroleum ether. The precipitate was collected by decantation and dried under reduced pressure. The yield of the obtained viscous material was 65 g and the weight average molecular weight
It was 5.6 × 10 ³ .

Synthesis Example 103 of Macromonomer (M ') 103: MM-103 A mixture of 95 g of benzyl methacrylate, 5 g of 2-phosphonoethyl methacrylate, 4 g of 2-aminoethyl mercaptan and 200 g of tetrahydrofuran was stirred at a temperature of 70 DEG C. under a nitrogen stream. Warmed.

Add 1.5g of AIBN and let it react for 4 hours.
5 g was added and reacted for 4 hours. Next, the reaction solution was cooled to a temperature of 20 ° C., and 10 g of acrylic acid anhydride was added thereto.
Stirred at 2525 ° C. for 1 hour. Next, 1.0 g of t-butylhydroquinone was added and the mixture was stirred at a temperature of 50 to 60 ° C for 4 hours. After cooling,
The reaction mixture was added dropwise to the water 1 over about 10 minutes while stirring, and the mixture was stirred for 1 hour and allowed to stand, and water was removed by decantation. After repeating the washing with water twice more, it was dissolved in 100 ml of tetrahydrofuran and reprecipitated in 2 l of petroleum ether. The precipitate was collected by decantation and dried under reduced pressure. The yield of the obtained viscous material was 70 g, and the weight average molecular weight was 7.4 × 10 ³ .

Synthesis Example 104 of Macromonomer (M ') 104: MM-104 2-chlorophenyl methacrylate 95 g, monomer 5 g of the following structure (I), thioglycolic acid 4 g and toluene 20
0 g of the mixed solution was heated to a temperature of 70 ° C. under a nitrogen stream. AI
1.5 g of BN was added and reacted for 5 hours, and 0.5 g of AIBN was further added and reacted for 4 hours. Next, glycidyl methacrylate 12.4
g, 1.0 g of N, N-dimethyldodecylamine and 1.5 g of t-butylhydroquinone were added and reacted at 110 ° C. for 8 hours.
After cooling, the reaction mixture was mixed with 3 g of p-toluenesulfonic acid, 90 g
The solution was added to 100 ml of a vol% aqueous tetrahydrofuran solution and stirred at a temperature of 30 to 35 ° C for 1 hour. Water / ethanol [(1 /
3) The mixture was reprecipitated in 2 liters of a mixed solution having a “volume ratio”
The precipitate was collected by decantation. This precipitate was dissolved in 200 ml of tetrahydrofuran and reprecipitated in 2 l of n-hexane to obtain 58 g of a powder. The weight average molecular weight was 7.6 × 10 ³ .

Synthesis Example 105 of Macromonomer (M ') 105: MM-105 2,6-dichlorophenyl methacrylate 95 g, 3-
A mixed solution of 5 g of (2′-nitrobenzyloxysulfonyl) propyl methacrylate, 150 g of toluene and 50 g of isopropyl alcohol was heated to a temperature of 80 ° C. under a nitrogen stream. 2,2'-azobis (2-cyanovaleric acid) (abbreviation: AC
V.) 5.0 g was added and reacted for 5 hours, and ACV 1.0 g was further added and reacted for 4 hours. After cooling, the reaction product was reprecipitated in 2 l of methanol, and the powder was collected by filtration and dried under reduced pressure.

50 g of the above powder, 14 g of glycidyl methacrylate, 0.6 g of N, N-dimethyldosylamine, 1.0 g of t-butylhydroquinone
And 100 g of toluene were stirred at 110 ° C. for 10 hours. After cooling to room temperature, the mixture was irradiated with light for 1 hour with stirring using a high-pressure mercury lamp of 80 W. Thereafter, the reaction mixture was reprecipitated in methanol 1, and the powder was collected by filtration and dried under reduced pressure. yield
The weight average molecular weight was 7.3 × 10 ³ at 34 g.

(Production Example of Resin [B]) Production Example 1 of Resin [B] 1: Resin [B-1] 70 g of ethyl methacrylate, macromonomer (MM-
1) A mixed solution of 30 g and 150 g of toluene was heated under a nitrogen stream at a temperature of 7
Warmed to 0 ° C. Next, 0.5 g of AIBN was added and reacted for 4 hours. Further, 0.3 g of AIBN was added and reacted for 6 hours.
The weight average molecular weight of the obtained copolymer [B-1] is 9.8 × 1
0 Glass transition point ⁴ was 72 ° C..

Production Examples 2 to 15 of Resin [B]: Resins [B-2] to [B-1]
5] Under the same polymerization conditions as in Production Example 1 of Resin [B], the following Table-
Resin [B] of No. 5 was produced. The w of each resin is 8 × 10 ⁴ ~
The range was 1.5 × 10 ⁵ .

Production Example 16 of Resin [B]: Resin [B-16] 70 g of ethyl methacrylate, macromonomer (MM-
2) A mixed solution of 30 g, 150 g of toluene and 50 g of isopropanol was heated to a temperature of 70 ° C. under a nitrogen stream. Next, 4,4 '
0.8 g of -azobis (4-cyanovaleric acid was added and reacted for 10 hours. The weight average molecular weight (w) of the obtained copolymer was
The glass transition point was 72 ° C. at 9.8 × 10 ⁴ .

Production Examples 17 to 24 of Resin [B]: Resins [B-17] to [B-2]
4] In Production Example 16 of Resin [B], the macromonomer (MM
Each resin [B] was produced in the same manner as in Production Example 16 except that the macromonomer shown in Table 6 below was used instead of -2). The w of each resin was 9 × 10 ^{4 to} 1.2 × 10 ⁵ .

Production Examples 25 to 31 of Resin [B]: Resins [B-25] to [B-3]
1] In Production Example 16 of Resin [B], instead of ACV,
Except for using the azobis compounds shown in Table 7 below, the production examples were as follows.
By operating in the same manner as in 16, each polymer was produced.

Production Example 32 of Resin [B]: Resin [B-32] 80 g of butyl methacrylate, macromonomer (MM-
8) A mixed solution of 20 g, 1.0 g of thioglycolic acid, 100 g of toluene and 50 g of isopropanol was heated to 80 ° C. under a nitrogen stream.
Was heated. 1,1'-azobis (cyclohexane-1
-Carbonitrile) (abbreviation: ACHN) (0.5 g) was added and stirred for 4 hours. ACHN (0.3 g) was further added and stirred for 4 hours. The w of the obtained polymer was 8.0 × 10 ⁴ and the glass transition point was 41 ° C.

Production Examples 33 to 39 of Resin [B]: Resins [B-33] to [B-3]
9] A polymer was produced in the same manner as in Production Example 32 except that the compounds shown in Table 8 below were used instead of thioglycolic acid in Production Example 32 of Resin [B].

Production Examples 40 to 48 of Resin [B]: Resins [B-40] to [B-4]
8] Under the same polymerization conditions as in Production Example 26 of Resin [B], the following Table-9 was used.
Was produced.

The w of each resin ranged from 9.5 × 10 ^{4 to} 1.2 × 10 ⁵ .

Production Examples 49 to 56 of Resin (B): (B-49) to (B-56) Under the same polymerization conditions as in Production Example 16 of Resin (B),
Each resin shown in Table 10 below was produced. W of each resin obtained
Ranged from 9.5 × 10 ^{4 to} 1.1 × 10 ⁵ .

Synthesis Example 101 of Resin [B] of the Present Invention: [B-101] A mixed solution of 80 g of benzyl methacrylate, 20 g of compound (MM-102) of Synthesis Example 102 of macromonomer (M ') and 100 g of toluene was placed in a nitrogen stream. To a temperature of 75 ° C. 0.8 g of 1,1'-azobis (cyclohexane-1-carbocyanide) (abbreviated ABCC) was added and reacted for 4 hours, and 0.5 g of AIBN was further added and reacted for 3 hours.

W of the obtained copolymer was 1.0 × 10 ⁵ .

Synthesis Example 102 of resin [B] of the present invention: [B-102] 2-chlorophenyl methacrylate 70 g, macromonomer (M ') compound (MM-101) of Synthesis Example 101 30 g, thioglycolic acid 0.7 g and toluene 150 g Was heated to a temperature of 80 ° C. under a nitrogen stream. Add 0.5g of ABCC and react for 5 hours, then add 0.3g of ABCC and 3 hours, further add ABCC
0.2 g was added and reacted for 3 hours.

W of the obtained copolymer was 9.2 × 10 ⁴ .

Synthesis Example 103 of resin [B] of the present invention: [B-103] 60 g of ethyl methacrylate, macromonomer (M ')
A mixed solution of 25 g of the compound (MM-104) of Synthesis Example 104, 15 g of methyl acrylate and 150 g of toluene was heated at a temperature of 75 under a nitrogen stream.
Warmed to ° C. Add 0.5g of ACV and react for 5 hours.
0.3 g of V. was added and reacted for 4 hours. W of the obtained copolymer
Was 1.1 × 10 ⁵ .

Synthesis Examples 104 to 111 of Resin [B] of the Present Invention: [B-104] to [B-
111] Resin [B] was synthesized in the same manner as in Synthesis Example 101 of resin [B], using methacrylate and macromonomer corresponding to Table 11 below.

Synthesis Examples 112 to 119 of Resin [B] of the Present Invention: [B-112] to [B-
119] Resin [B] shown in Table 12 below was synthesized in the same manner as in Synthesis Example 102 of resin [B], except that methacrylate, macromonomer and mercapto compound were each replaced.

The w of each resin was 9 × 10 ^{4 to} 1.1 × 10 ⁵ .

Synthesis Examples 120 to 127 of Resin [B] of the Present Invention: [B-120] to [B-
127] Resin [B] shown in Table 13 below was synthesized in the same manner as in Synthesis Example 103 of resin [B], except that methacrylate, macromonomer and azobis compound were each replaced.

The w of each resin [B] was 9.5 × 10 ^{4 to} 1.5 × 10 ⁵ .

Examples 1 and 2 and Comparative Examples A to C Resin [A-2] 6 g (as solid content), resin [B-
1] 34 g (as solid content), 200 g of photoconductive zinc oxide,
A mixture of 0.03 g of uranine, 0.06 g of rose bengal, 0.02 g of tetrabromophenol blue, 0.20 g of maleic anhydride and 300 g of toluene was mixed with a homogenizer (Nippon Seiki Co., Ltd.).
After dispersion at 6.5 × 10 ³ rpm for 15 minutes, 2 g (as solid content) of resin particles L-17 were added thereto, and further dispersed for 1 minute.
The amount of dry adhesion on the paper which has been dispersed for
As a 25 g / m ^2, was coated by a wire bar, 30 at 110 ° C.
After drying for 2 seconds, the mixture was allowed to stand in a dark place at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material.

Comparative Example A: An electrophotographic photosensitive material was prepared in the same manner as in Example 1, except that 2 g of the dispersed resin particles L-17 were not added.

Comparative Example B: Resin used as binder resin in Example 1 [A-
2] An electrophotographic photosensitive material was prepared in the same manner as in Example 1, except that 6 g of the resin [R-1] having the following structure was used instead of 6 g.

Comparative Example C: Resin used as binder resin in Example 1 [A-
An electrophotographic photosensitive material was prepared in the same manner as in Example 1, except that 6 g of the resin [R-2] having the following structure was used instead of 2).

These photosensitive materials were examined for film properties (surface smoothness), charging properties (whether or not charging unevenness occurred), and pre-exposure fatigue properties. Further, the printability (ground stain, printing durability) when these photosensitive materials were used as an offset master plate was examined.

 The following results are summarized in Table-14.

The embodiments of the evaluation items shown in Table 14 are as follows.

Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was measured for its smoothness (sec / cc) using a Beck smoothness tester (manufactured by Kumagaya Riko Co., Ltd.) under the condition of an air capacity of 1 cc. It was measured.

Note 2) Each photosensitive material was left for one day at 20 ° C and 65% RH. Next, a fully automatic plate making machine ELP-40V (manufactured by Fuji Photo Film Co., Ltd.) was used with a charging voltage of -4.5 kV and a charging speed of 20 cm / sec.
After remodeling under the forced conditions, a solid black image was used as a copy original, and a solid image (whether or not there was unevenness during charging, density of a solid portion) obtained by making a plate using ELP-T as a toner was visually evaluated.

Note 2) pre-exposure fatigue resistance V ₁₀ Recovery rate: temperature 20 ° C., in the dark of RH 65%, at -6kV using the respective photosensitive materials Paper Analyzer (Kawaguchi Denki Co., Ltd. Paper Analyzer SP-428 type) After a corona discharge for 20 seconds, the device was left for 10 seconds, and the surface potential V ₁₀ ^A at this time was measured. On the other hand, in each of the light-sensitive material was allowed to stand for 10 seconds in Ushirogura exposed 20 seconds to the position of the fluorescent lamp light source under 2m (500 1ux), the same measuring method and again V ₁₀ ^A, measuring the surface potential V ₁₀ ^B did.
The V ₁₀ recovery rate was determined by ^{_{(V 10 B / V 10 A}} ) × 100 (%).

Image sensitivity after pre-exposure Each photosensitive material was allowed to stand in a dark room at a temperature of 20 ° C. and 65% RH for 24 hours. Next, after operating under the pre-exposure conditions described in Note 3, a copy image obtained by plate-making the photosensitive material with ELP-404V using ELP-T as a toner was visually evaluated.

Note 4) Printability Raw stain on raw material: Desensitizing processing solution EPL for each photosensitive material
-EX (manufactured by Fuji Photo Film Co., Ltd.) Using a solution diluted twice with distilled water, pass once through an etching processor to desensitize the surface of the photoconductive layer, and use this as an offset master for offset printing. Machine (Sakurai Manufacturing Co., Ltd.)
(Oliver 52 type), and the printed matter is visually evaluated to the extent that soiling occurs.

Printing durability after plate making: Plates were prepared for each photosensitive material under the same conditions as described in the pre-exposure fatigue imaging property. Next, each of these original plates was passed through an etching processor twice using a desensitizing solution EPL-EX to desensitize the surface of the photoconductive layer. Using this as an offset master, the number of sheets that can be printed on an offset printing machine (identical to the above-mentioned use) without causing background stains on the non-image portion of the printed matter and the image quality of the image portion does not occur. Good performance).

As shown in Table 14, each photosensitive material of the present invention forms a photoconductive layer having good smoothness. In addition, uniform chargeability was obtained without charging unevenness during charging, and even under the condition of a photosensitive material pre-exposed before plate making, the recovery was remarkably good, almost the same as the characteristics under unexposed. Was. The actual copied image had no ground fog, and the copied image quality was clear. This is presumably due to the fact that the photoconductor, the spectral sensitizer, and the binder resin are each adsorbed in an optimal state, and that the state is stably maintained.

In addition, the unprepared photographic material itself is desensitized with a desensitizing solution, and the contact angle with water on the surface after the treatment is as small as 10 ° C. or less, and it is sufficiently hydrophilic. I understand. Even when the printed matter was actually printed and the background stain was observed, no background stain was observed.

Furthermore, even when the plate is used as an offset master plate, the chargeability, pre-exposure fatigue property are good, and there is no background fog, and it is a clear copied image. Progress was made, and the printed matter actually printed had clear image quality without background smear even after 8,000 sheets.

In Comparative Example A in which the resin particles L did not coexist, the electrostatic properties and the image-capturability were satisfactory, but the printability was insufficient.

On the other hand, in Comparative Examples A and B using the known low-molecular-weight products, uneven charging occurred under severe conditions. Also, the pre-exposure fatigue property is large, affecting the actual imaging performance, and the copied image is deteriorated (the occurrence of ground fog, scattering of fine lines and characters, a decrease in density, etc.). Also, when the desensitization by the desensitizing treatment solution was examined, the photosensitive material at the time of the unmade plate did not have background stain on the printed matter,
It was confirmed that they were sufficiently hydrophilized. However, when the original plate that was actually made was desensitized and printed as an offset master and printed, the printed matter had noticeable background stains in the non-image area and the image quality of the image area had deteriorated since printing (thin lines and characters). Omission, decrease in concentration, etc.). This indicates that the deterioration of the image quality of the original plate obtained by plate making is not compensated by the desensitizing treatment, is reflected as it is on the printed matter, and is not practical.

From the above, only the photosensitive material of the present invention was favorable in all aspects of the smoothness, electrostatic properties and printability of the photoconductive layer.

Examples 2 to 17 In Example 1, the resin [A-2] and the resin [B-
1) and resin particles [L-17], 6 g of resin [A], 34 g of each resin [B] and 1.8 g of resin particles [L] shown in Table 15 below.
Each electrophotographic light-sensitive material was produced in the same manner as in Example 1, except for changing the above.

The photosensitive materials of the present invention are all excellent in chargeability, dark charge retention, and photosensitivity.
(80 ° C., 80% RH) or a condition of fatigue due to pre-exposure gave a clear image without generation of background fog.

Further, when this was used as an offset master master, at least 7,000 or more prints of clear image quality without background fog could be printed.

Example 22 6.5 g of a resin [A-30] having the following structure,
1) 33.5 g, zinc oxide 200 g, uranine 0.03 g, methine dye of the following structure (III) 0.040 g, methine dye of the following structure (I
V] 0.035 g, 0.01 g of 4-hydroxybenzoic acid and toluene
240 g of the mixture was placed in a homogenizer at 1 × 10 ⁴ rpm for 10 minutes.
Dispersed for minutes. 2.0 g of resin particles [L-19] was added to this dispersion.
(As solid content) and 0.5 g of glutaric anhydride were added and further dispersed in a homogenizer at 5 × 10 ³ rpm for 1 minute.

This was applied to a conductive treated paper with a wire bar so as to have a dry adhesion amount of 22 g / cm ^2, and heated at 110 ° C. for 15 seconds.
Next, after further heating at 140 ° C. for 2 hours, the mixture was allowed to stand at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material.

The characteristics of each photosensitive material were examined in the same manner as in Example 1. As a result, each photosensitive material is excellent in chargeability and pre-exposure fatigue, and the actual copied image is clear even under such severe conditions without occurrence of background fogging and fine line skipping. Gave the picture. Further, when printed as an offset master original, at least 10,000 or more prints of a clear image having no background fogging in the non-image area could be printed in any case.

Examples 23 to 26 Instead of 6.5 g of the resin [A-30] and 0.5 g of glutaric anhydride as a cross-linking agent in Example 22, each of the compounds shown in Table 16 below was used instead of the resin [B-101]. Resin [B
-20] Each photosensitive material was prepared in the same manner as in Example 36 except that 33 g was used.

The characteristics of each photosensitive material were examined in the same manner as in Example 22. As a result, each photosensitive material is excellent in chargeability and pre-exposure fatigue, and the actual copied image is clear even under such severe conditions without occurrence of background fogging and fine line skipping. Gave the picture. Further, when printed as an offset master plate, more than 8,000 sheets of printed matter having clear images without background fog in the non-image area could be printed in any case.

Examples 27 to 36 In Example 1, except that 2 g (as solid content) of each of the resin particles in Table 17 below was used instead of 2 g of the binder resin particles,
Each photosensitive material was produced in the same manner as in Example 1.

The electrostatic properties and printing properties were evaluated by operating in the same manner as in Example 2.

In each photosensitive material, both the electrostatic characteristics and the imaging properties were the same as those in Example 1.
It showed almost the same characteristics as.

In addition, when the performance of the offset lithographic original plate was evaluated by desensitization treatment, the water retention of the raw plate was good, and the printing result after the actual plate making was able to print 6,000 or more sheets.

Example 37 and Comparative Examples DF Resin [A-1] 6 g, resin [B-120] 34 g, resin particles [L-19] 2 g, zinc oxide 200 g, heptamethylenecyanine dye 0.02 g represented by the following structural formula And 300 g of toluene were dispersed in a homogenizer at a rotation speed of 1 × 10 ⁴ rpm for 10 minutes.

With this in conductive treated papers, coated at a dry coating weight 20 g / m ² and made as a wire bar, after heating for 15 seconds at 100 ° C., 1
Heat at 20 ° C. for 2 hours. Then, it was left standing in a dark place at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material.

Comparative Example D An electrophotographic photosensitive material was produced in the same manner as in Example 37, except that 2 g of the resin particles [L-19] were omitted.

Comparative Example E An electrophotographic photosensitive material was prepared in the same manner as in Example 37, except that 6 g of the resin [A-1] was used instead of 6 g of the resin [A-1].

Comparative Example F An electrophotographic photosensitive material was produced in the same manner as in Example 37 except that 6 g of the resin [A-1] was used instead of 6 g of the resin [A-1].

Various characteristics of these light-sensitive materials were examined in the same manner as in Example 1. The results are summarized in Table-18.

In the evaluation items of Table 18, the imaging method and the printing durability after plate making were performed by the following method, and other items were performed by the same method as each item of Example 1.

Note 5) Image-capability after pre-exposure: Each photosensitive material was left in a dark room at a temperature of 20 ° C. and a humidity of 65% RH for 24 hours, and then operated under the pre-exposure conditions described in Note 3). Is charged at −6 kV, and a 2.8 mW gallium-aluminum-arsenic semiconductor laser (oscillation wavelength
780 nm) on a photosensitive material surface at an irradiation dose of 64 erg / cm ² at a pitch of 25 μm and a scanning speed of 300 m / sec, and under liquid development, ELP-T (Fuji Photo Film Co., Ltd.) Was developed and fixed, and the copied image (fog, image quality) obtained by fixing was visually evaluated.

Note 6) Printing durability after plate making Each plate of the photosensitive material was made under the same conditions as described in Note 5). The desensitizing treatment and printing operation are described below in Note 4).
And the printed matter was evaluated.

In the photosensitive material of the present invention, the photoconductive layer has sufficient smoothness, no unevenness during charging, and even if there is pre-exposure, the recovery is remarkably quick, and the actual copied image is stable and good. ,
A clear image without fog was obtained. Even when used as an offset master, the non-image area is sufficiently hydrophilic and no background stains are seen, and a clear image of 8000 prints is obtained.
It was obtained even after printing.

However, Comparative Example D, which does not coexist with the resin particles of the present invention,
The printability deteriorated remarkably.

On the other hand, in Comparative Examples E and F using the known low-molecular-weight compounds, the chargeability and the pre-exposure fatigue property were reduced. Worsened. In addition, when used as an offset master, a fugitive print cannot be obtained due to fogging of printed matter and deterioration of image quality.

As described above, an electrophotographic photosensitive member that satisfies electrostatic characteristics and printability only when the resin of the present invention is used is obtained.

Examples 38 to 45 In Example 37, instead of the resin [A] 6.5 g and resin [B] 33.5 g shown in Table 19 below as a binder resin, and instead of the cyanine dye [I] 0.02 g, a dye having the following structure [ II) 0.018g
An electrophotographic photosensitive material was produced under the same conditions as in Example 37 except that the above was changed to.

Each photosensitive material of the present invention is excellent in chargeability and pre-exposure fatigue property, and an actual copied image can produce a clear image without occurrence of ground fog or fine line jump even under such severe conditions. Gave. Further, when printed as an offset master original, 8,000 or more printed materials with clear images without background fog in the non-image area could be printed.

Examples 46 to 53 In Example 37, 6 g of each of the resin [A] and 2 g of each of the resin particles L were used.
Was replaced with the compound of Table 20 below, and the heptamethine cyanine dye [III] was replaced with 0.02 g of the heptamethine cytanine dye [V] having the following structure, in the same manner as in Example 33, except that Was prepared.

The characteristics of each of these photosensitive materials were measured in the same manner as in Example 33. The results are summarized in Table-20.

Each photosensitive material of the present invention was excellent in charging unevenness and pre-exposure fatigue, and an actual copy image obtained a clear image without occurrence of background fogging and fine line skipping. Further, in the case of a resin containing a specific methacrylate component, better imaging properties were exhibited.

When each photosensitive material is used as an offset master plate, the desensitizing treatment with the desensitizing solution proceeds sufficiently, and the contact angle with water of the non-image portion of each master plate is as small as 10 degrees or less, It was sufficiently hydrophilic.
At the actual printing, 8000 sheets of clear prints without fog were printed.

(Effect of the Invention) According to the present invention, it is possible to obtain an electrophotographic photosensitive member having improved charging characteristics and pre-exposure fatigue. In addition, a lithographic printing original plate capable of obtaining a printed matter having a clear print quality can be obtained as an electrophotographic lithographic printing original plate.

Further, as a copolymer component of the resin [A], the above-mentioned formula (IIa)
Alternatively, when a specific methacrylate component represented by (IIb) is contained, better imaging properties can be obtained.

 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-261657 (JP, A) JP-A-1-232356 (JP, A) JP-A-4-73654 (JP, A) JP-A-2- 103056 (JP, A) JP-A-2-53064 (JP, A) JP-A-2-135457 (JP, A) JP-A-3-17664 (JP, A) JP-A-3-13951 (JP, A)

Claims (2)

(57) [Claims] An electrophotographic lithographic printing plate precursor comprising at least one layer of a photoconductive layer containing a photoconductive zinc oxide and a binder resin on a conductive support. Contains hydrophilic resin particles having an average particle diameter equal to or smaller than the maximum particle diameter of the photoconductive zinc oxide particles, and the binder resin is at least one of the following resins [A]
A lithographic printing plate precursor comprising at least one of a seed and a resin [B]. Resin [A]: having a weight average molecular weight of 1 × 10 ³ to 1 × 10 ⁴ , containing at least 30% by weight of a polymerization component represented by the following general formula (I), and -PO ₃ H ₂
Group, -SO ₃ H group, -COOH group, R represents a hydrocarbon group or an -OR 'group (R' represents a hydrocarbon group) and a polymerization component containing at least one acidic group selected from cyclic acid anhydride-containing groups. A resin containing at least one acidic group selected from the same acidic groups as described above at one end of the polymer main chain. General formula (I) [In the formula (I), a ₁ and a ₂ each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ₁ represents a hydrocarbon group. Binder Resin [B]: Only one terminal of a polymer main chain containing at least one of the polymer components represented by the following general formulas (IVa) and (IVb) is represented by the following general formula (III) A resin which is a copolymer comprising at least a monofunctional macromonomer having a weight average molecular weight of 2 × 10 ⁴ or less formed by bonding a polymerizable double bond group and a monomer represented by the following general formula (V). General formula (III) [In the formula (III), V ₀ represents -COO-, -OCO-, -CH ₂ OCO-, -CH
_{2 COO -, - O -,} - SO 2 -, - CO -, - CONHCOO -, - CONHCONH
-, -CONHSO _2- , Or The expressed (P ₀ represents a hydrogen atom or a hydrocarbon group). c ₁ and c ₂ may be the same or different from each other, and represent a hydrogen atom,
Represents a halogen atom, a cyano group, a hydrocarbon group, -COO-Z ₃₁ via -COO-Z ₃₁ or hydrocarbon (Z ₃₁ represents a hydrogen atom or an optionally substituted hydrocarbon group). General formula (IVa) General formula (IVb) [In formula (IVa) or (IVb), V ₁ represents the same content as V ₀ in formula (III). Q ₄₁ represents an aliphatic group or an aromatic group having 6 to 12 carbon atoms having 1 to 18 carbon atoms. d ₁ and d ₂ may be the same or different from each other, and have the formula (III)
Represents the same content as c ₁ and c _{2 in} . Q ₄₀ is -CN, -CONH ₂ or Represents Here, T represents a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group or —COOZ ₃₂ (Z ₃₂ represents an alkyl group, an aralkyl group or an aryl group). General formula (V) [In the formula (V), V ₂ represents the same content as V ₁ in the formula (IVa). Q ₄₂ represents e ₁ and e ₂ representing the same contents as Q ₄₁ in the formula (IVa).
May be the same or different, and c ₁ and c in formula (III)
Represents the same content as ₂ . ] 2. The lithographic plate according to claim 1, wherein at least one of the resin [A] and the resin [B] contains a heat and / or photocurable functional group. Original plate for printing.