JP2726333B2 - Original plate for direct drawing type lithographic printing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a lithographic printing original plate, and more particularly, to a direct drawing type printing original plate suitable for an office printing original plate or the like.

[Conventional technology]

At present, a direct-drawing lithographic printing original plate having an image receiving layer on a support is widely used as an office printing original plate. In order to perform plate making, that is, image formation on such a printing original plate, a method of drawing oil-based ink by hand on an image receiving layer, or printing by a typewriter, an ink jet system, or a transfer type thermal system is generally adopted. In addition, a method of transferring and fixing a toner image formed on a photoreceptor to an image receiving layer through a charging, exposing, and developing process using a plain paper electrophotographic copying machine (PPC) has recently started to be used.
In any case, the printing plate precursor after plate making is subjected to surface treatment with a desensitizing solution (so-called etchant) to desensitize the non-image portion, and then subjected to lithographic printing as a printing plate.

In a conventional direct-drawing lithographic printing plate precursor, a back surface layer is provided on one surface of a support such as paper, and an image receiving layer is provided on the other surface as a surface layer via an intermediate layer. The back layer or the intermediate layer is formed of a water-soluble resin such as PVA or starch, a water-dispersible resin such as a synthetic resin emulsion, and a pigment. The surface layer is formed of a pigment, a water-soluble resin, and a waterproofing agent.

As a representative example of such a direct drawing type lithographic printing plate precursor, as described in U.S. Pat.No. 2,532,865, an image receiving layer is formed of a water-soluble resin binder such as PVA, silica, calcium carbonate or the like. It is composed mainly of an inorganic pigment and a water-resistant agent such as a melamine-formaldehyde resin precondensate.

[Problems to be solved by the invention]

However, the conventional printing plate obtained in this way, when increasing the amount of a water-proofing agent to improve printing durability, or by using a hydrophobic resin to increase the hydrophobicity, Although the printing durability is improved, the hydrophilicity is reduced and the printing stain is generated. On the other hand, if the hydrophilicity is improved, the water resistance is deteriorated and the printing durability is reduced. In particular, in a high-temperature use environment of 30 ° C. or more, the surface layer (image-receiving layer) dissolves in the immersion water used for offset printing, and there are major drawbacks such as a reduction in printing durability and printing stains.

Further, the lithographic printing plate precursor draws an oil-based ink or the like as an image portion on the image receiving layer, and if the adhesiveness between the receiving layer and the oil-based ink is not good, even if the non-image portion has sufficient hydrophilicity, Even if such printing stains do not occur, there is also a problem that the oily ink in the image area is lost during printing, and as a result, the printing durability is reduced.

The present invention is directed to improving the problems of the direct drawing type lithographic printing plate precursor as described above.

SUMMARY OF THE INVENTION An object of the present invention is to provide a direct drawing type lithographic printing plate precursor which is excellent in desensitizing property and which does not generate not only a uniform background stain but also a dot-like background stain as an offset master plate.

The object of the present invention is to improve the adhesiveness between the oil-based ink and the image-receiving layer in the image area, and to maintain the hydrophilicity of the non-image area even when the number of printed sheets is increased in printing, without generating oil stains. An object of the present invention is to provide a direct drawing type lithographic printing plate precursor having high printing durability.

[Means for solving the problem]

The object of the present invention is to provide a direct-drawing lithographic printing plate precursor having an image receiving layer on a support, wherein the image receiving layer contains at least one kind of the following nonaqueous solvent-based dispersed resin particles in the image receiving layer. This can be achieved by a direct-lithographic lithographic printing plate precursor characterized in that:

Non-aqueous solvent-based dispersed resin particles: in a non-aqueous solvent, a carboxyl group, a sulfo group, a sulfino group, a phosphono group, which is soluble in the non-aqueous solvent but insolubilized by polymerization; [R ₀ is a hydrocarbon group or -OR ₁₀ (R ₁₀ represents a hydrocarbon group)
Which represents at least one polar group selected from a hydroxyl group, a formyl group, an amide group, a cyano group, an amino group, a cyclic acid anhydride-containing group and a nitrogen atom-containing heterocyclic group. Monomer (A), a silicon atom and / or
Or a monofunctional polymer having a polymerizable double bond group represented by the following general formula (I) bonded only to one end of a main chain of a polymer comprising at least a repeating unit containing a substituent containing a fluorine atom: Copolymer resin particles obtained by a polymerization reaction with the reactive polymer [M].

General formula (I) [In the general formula (I), V ₀ is -O-, -COO-, -OCO-,
_{-CH 2 OCO -, - CH 2} COO -, - SO 2 -, -CONHCOO-, or -CONHCONH- a represents (wherein, R ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), a _1,
a ₂ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—R ₂ or a hydrocarbon group (R ₂ is a hydrogen atom or In addition, in the present invention, the non-aqueous solvent-based dispersed resin particles may have a higher-order network structure.

[Action]

The present invention is characterized in that the image receiving layer of the original plate for direct drawing type lithographic printing contains the non-aqueous solvent-based dispersed resin particles, and the non-aqueous solvent-based dispersed resin particles (hereinafter simply referred to as resin particles). Is a polymer component that contains at least one specific polar group and is insoluble in the non-aqueous solvent after polymerization, and a repeating unit containing at least a fluorine atom and / or a silicon atom as a substituent. It is characterized in that a polymer component which becomes soluble in the non-aqueous solvent after the polymerization is chemically bonded. That is, the resin particles are composed of a portion insoluble in the non-aqueous dispersion solvent composed of the polar group-containing polymer component (A) and a monofunctional polymer [M] soluble in the solvent. The dispersion resin has a molecular weight of 10 ⁴ to 10 ⁶ , preferably 10 ^{4 to} 5 × 10 ⁵ .

In the present invention, the resin particles are present in the image receiving layer separately and as particles from the binder resin which is a matrix of the image receiving layer, and the resin particles are hydrophilic due to the presence of the above-mentioned specific polar group. Since the polar group does not have a protective group by a hydrophilizing treatment using a desensitizing solution and a fountain solution used for printing, the hydrophilicity can be expressed very quickly and easily.

On the other hand, the resin particles also have a polymer component containing extremely large lipophilic fluorine atoms and / or silicon atoms.

Therefore, the direct-printing original plate of the present invention containing the resin particles in the image receiving layer, when drawing the oil-based ink or the like as an image portion on the image receiving layer, by the action of the lipophilic group in the resin particles. The adhesion between the receiving layer and the oil-based ink becomes good, and the printing durability is improved. On the other hand, in the non-image area, the resin particles quickly show hydrophilicity to the desensitizing liquid and the immersion water as described above. Therefore, the printing ink is clearly distinguished from the lipophilicity of the image portion, and the printing ink does not adhere to the non-image during printing.

It has an image receiving layer in which such hydrophilic resin particles are dispersed in a binder resin of a trix, and a non-image portion is treated with a desensitizing liquid to make the surface hydrophilic, thereby allowing direct drawing lithographic printing. In a printing original plate of the type used as a printing original plate, known hydrophilic resin particles are present uniformly dispersed throughout the surface layer.

In contrast to this, the non-aqueous solvent-based dispersed resin particles of the present invention are dispersed in the image receiving layer, but by the action of a polymer component containing a remarkably lipophilic large fluorine atom and / or silicon atom, It is concentrated and present on the surface of the image receiving layer at the air interface (high lipophilicity). Therefore, smaller amounts (50 times less than known hydrophilic resin particle technology)
(Up to 10% of the amount used), the water retention of the non-image area is remarkably improved.

In addition, a hydrophobic (lipophilic) polymer component is bonded to the resin particles, and since the hydrophobic portion interacts with the binder resin which is the matrix of the image receiving layer, the anchor effect of this portion is obtained. Thus, even if the printing medium shows hydrophilicity, it is not eluted by immersion water at the time of printing, and good printing characteristics can be maintained even when printing a considerably large number of sheets.

Furthermore, in the present invention, if the resin particles form a higher-order network structure, dissolution in water is further suppressed,
On the other hand, water swelling is exhibited, and water retention is further improved.
That is, in the case of having a network structure, in the portion insoluble in the non-aqueous solvent, the molecules of the polymer component (A) forming the insoluble portion are bridged to form a higher-order network. As a result, the network resin particles are hardly soluble or insoluble in water.

It is important that the resin particles are dispersed in the image receiving layer separately from the binder resin serving as the matrix and as particles, and are concentrated near the air interface.

Thus, the direct-printing original plate of the present invention forms a faithful image portion and a non-image portion, and provides a high-quality printed image free from background smear.

In addition, since the resin particles are fixed by the binder resin, they do not peel off during various processing steps, and the protective effect of the binder resin is obtained, so that the printing durability is excellent.

Further, there is a concern that the resin particles may flow out due to a fountain solution or the like during printing due to the hydrophilicity of a specific polar group of the resin particles. However, such a concern is solved by crosslinking at least a part of the resin particles.

As described above, the original plate for direct drawing type lithographic printing according to the present invention has an advantage that the non-image portion has good hydrophilicity, does not cause background smear, and additionally has excellent printing durability.

 Hereinafter, the resin particles will be further described.

The dispersion resin of the resin particles of the present invention is composed of at least one kind of each of the monomer (A) and the monofunctional polymer [M]. What is important in any case is that if a resin synthesized from these monomers is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained. it can. More specifically, the monofunctional polymer [M] is preferably used in an amount of 1 to 50% by weight, more preferably 5 to 25% by weight, based on the insoluble monomer (A).

In addition, in the total of the repeating units of the monofunctional polymer [M], the repeating unit having a substituent containing a fluorine atom and / or a silicon atom accounts for 40% by weight or more of the entire polymer [M]. It is preferably 60 to 100% by weight. If it is less than 40% by weight, the effect of concentrating on the surface portion when the resin particles are dispersed in the surface layer is reduced, and as a result, the effect of improving the water retention as a printing original plate is reduced.

The hydrophilicity of the resin particles is such that a film of the resin formed by applying a solution obtained by dissolving the resin particles in an arbitrary soluble solvent has a contact angle with distilled water (measured with a goniometer) of 50 degrees or less, It preferably shows a value of 30 degrees or less.

In the case of network resin particles, the solubility of the resin in water is 80% by weight or less, preferably 50% by weight or less.

The resin particles (including network resin particles) of the present invention preferably have an average particle size of 0.05 to 1.0 μm. If it is larger than 1.0 μm, the smoothness of the surface layer is reduced, which causes a reduction in film strength or toner image strength. On the other hand, if it is smaller than 0.05 μm, it is similar to the case of molecular dispersion, and the effect of being particles for improving water retention is weakened.

Since the resin particles of the present invention are synthesized by a dispersion polymerization method in a non-aqueous solvent system, the average particle size of the polymer latex particles is easily 1
μm or less, the particle size distribution is very narrow, and monodispersed particles can be obtained.

In the present invention, resin particles (including network structure particles)
When the amount is too small, the hydrophilicity of the non-image portion is not sufficient and the effect is lost, and when the amount is too large, the hydrophilicity of the non-image portion is further improved, but the water absorption of the entire image receiving layer increases. ,
To cause a decrease in adhesiveness to the support, 0.5 to 100 parts by weight of the matrix resin of the image receiving layer,
It is preferred to use 60% by weight, preferably 5-40% by weight.

Hereinafter, the non-aqueous solvent-based dispersed resin particles used in the present invention will be described in more detail. The resin particles of the present invention are produced by so-called non-aqueous dispersion polymerization.

First, the monofunctional monomer (A) which is soluble in a non-aqueous solvent but insolubilized by polymerization will be described. The monomer (A) has --CO ₂ H in its molecular structure. , -SO
_{3 H, -PO 3 H 2,} -SO 2 H, -OH, -CN, -CHO, -CONH 2, -SO 2
NH ₂ , It contains at least one polar group selected from a cyclic acid anhydride-containing group and a nitrogen-containing heterocyclic group.

In the above polar group, -R ₀ is a hydrocarbon group having 1 to 6 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, 2-methoxybutyl,
Benzyl group, a phenyl group, propenyl group, a methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, etc.), or -R ₁₀ group (R ₁₀ represents the same content as the hydrocarbon group of R _0).

R ₁₁ and R ₁₂ may be the same or different, and each represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted (specifically, a hydrocarbon group having the same content as R ₀ ) Represents However, the total number of carbon atoms of R ₁₁ and R ₁₂ is within eight. More preferably, the total carbon number of R ₁₁ and R ₁₂ is 4
Represents the following.

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, for example, halogen atoms such as chlorine atom and bromine atom, and alkyl groups such as methyl group, ethyl group, butyl group and hexyl group. 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.

Further, as the heterocyclic ring containing at least one nitrogen atom, preferably a heterocyclic ring forming a 4- to 6-membered ring, for example, a pyridine ring, a piperidine ring, a pyrrole ring, an imidazole ring, a pyrazine ring, Examples include a pyrrolidine ring, a pyrroline ring, an imidazoline ring, a pyrazolidine ring, a piperazine ring, a morpholine ring, and a pyrrolidone ring. 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 group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-butoxy Ethyl 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, A sulfophenyl group, a methanesulfonylphenyl group, an ethanesulfonylphenyl group, a carboxymethylphenyl group, a methoxyphenyl group, a chlorophenyl group, etc., -OR ₁₃ (where R ₁₃ is the above-mentioned hydrocarbon having 1 to 8 carbon atoms which may be substituted) And -COOR ₁₄ group (R ₁₄ represents the same content as R ₁₃ ) and the like.

Further, the -COOH group, -SO ₂ H group, SO ₃ H group, -PO ₃ H ₂ group, Are metal salts such as alkali metals (eg, lithium, sodium, potassium, etc.), alkaline earth metals (eg, calcium, magnesium, etc.), zinc, aluminum, etc., or organic bases (eg, triethylamine, pyridine, morpholine, piperazine, etc.) ) May be formed.

Monomer (A) constituting the main component of the resin particles of the present invention
May be any as long as it contains at least one of the above polar groups and has one polymerizable double bond group in one molecule. More specifically, examples of the monomer (A) are shown by the general formula (II).

General formula (II) In the formula, X ₁ is a direct bond or -COO-, -OCO-, -O-, -SO ₂
−, -CONHCOO-,-CONHCONH-, Represents

R ₁₅ is a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms which may be substituted (preferably, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group,
-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.)
R ₁₆ and R ₁₇ 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) or an aliphatic group having 1 to 4 carbon atoms (preferably, for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), and i represents an integer of 1 to 6. W represents a polar group of the monomer (A).

L ₁ is -COO -, - OCO -, - O -, - S -, - SO 2 -, -NHCOO-, 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 formula (II)
Represents a-[L ₁ -W] group, and l _{5 to} l ₉ represent the same as those of R ₁₅ described above. B ₁ and b ₂ may be the same or different and include a hydrogen atom, a halogen atom (preferably, for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a —COOH group, a —COOR ₁₈ group, and a —CH ₂ COOR
₁₈ groups (R ₁₈ represents a hydrocarbon group having 1 to 7 carbon atoms, and specific examples thereof include the same contents as the hydrocarbon group of R ₁₅ ) or an alkyl group having 1 to 4 carbon atoms (preferably , For example, a methyl group, an ethyl group, a propyl group, and a butyl group).

Hereinafter, the above-mentioned monomer (A) will be illustrated more specifically, but the present invention is not limited thereto.

_{(A-47) CH 2 =} CH-CH 2 OCO (CH 2 n COOH n: 1~3 integer In addition to the polar group-containing monomer (A) as described above, another copolymerizable monomer may be contained as a polymer component. Examples of other monomers, for example, α-olefins,
Vinyl alkanoate or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, heterocyclic vinyls [for example, a non-metal atom other than a nitrogen atom (oxygen atom, sulfur atom, etc.) And a 5- to 7-membered heterocyclic ring containing 3 to 3, and specific compounds include vinyl thiophene, vinyl dioxane, and vinyl furan. Preferred examples include, for example, vinyl or allyl esters having 1 to 3 carbon atoms, acrylonitrile, methacrylonitrile, styrene and styrene derivatives (for example, vinyltoluene, butylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene). , Ethoxystyrene, etc.). However, it is not limited to these.

As a polymerization component in the resin, the proportion of the monomer (A) is at least 30% by weight, preferably at least 50% by weight, and particularly preferably, the resin and the monomer (A) are monofunctional polymer. It is composed of only the combination [M].

Next, the monofunctional polymer [M] will be described. A polymerizable double bond group represented by the general formula (I) is bonded to only one terminal of the polymer main chain at least containing a repeating unit containing a substituent containing a silicon atom and / or a fluorine atom. It is important that the polymer to be formed is copolymerized with the monomer (A) and solvated with the non-aqueous solvent so as to be soluble, and functions as a dispersion stabilizing resin in so-called non-aqueous dispersion polymerization. It is what you do.

The monofunctional polymer [M] of the present invention is soluble in the non-aqueous solvent, and specifically, has a temperature of 25 parts per 100 parts by weight of the solvent.
What is necessary is to dissolve at least 5% by weight at ° C.

The weight average molecular weight of the polymer [M] is 1 × 10 ³ to 1 × 1.
0 ⁵ and is preferably ^{2 × 10 3 ~5 × 10 4} , particularly preferably ^{3 × 10 3 ~2 × 10 4} .

When the weight average molecular weight of the polymer [M] is less than 1 × 10 ³ or more than 1 × 10 ⁵ , the generated dispersed resin particles are aggregated, and fine particles having a uniform average particle size cannot be obtained. .

In the monofunctional polymer [M], the polymerizable double bond group component represented by the general formula (I) which is bonded only to one terminal of the polymer main chain will be described below.

General formula (I) In the general formula (I), V ₀ is -O-, -COO-, -OCO-,
_{-CH 2 OCO -, - CH 2} COO -, - SO 2 -, Represents

Here, R ₁ 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, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group) Octyl, decyl, dodecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2
-Methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group and the like, and an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2 -Pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), and having 7 to 12 carbon atoms. Aralkyl groups (e.g., benzyl, phenethyl, 3-
Phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.),
An alicyclic group which may have 5 to 8 carbon atoms and may be substituted (for example, a cyclohexyl group, a 2-cyclohexylethyl group,
2-cyclopentylethyl group, etc.), or C6-C6
12 optionally substituted aromatic groups (for example, phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxy) Phenyl group, decyloxyphenyl group,
Chlorophenyl, dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, propioamidophenyl, dodecyloylamidophenyl, 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, a chlorine atom, a bromine atom, etc.), an alkyl group (eg, a methyl group, an ethyl group,
A propyl group, a butyl group, a chloromethyl group, a methoxymethyl group and the like; an alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group and a butoxy group).

a ₁ and a ₂ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (eg, a chlorine atom or a bromine atom), a cyano group, an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, Ethyl, propyl, butyl, etc.)
-COO-R ₂ or COOR ₂ via a hydrocarbon (R ₂ represents a hydrogen atom or an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group having 1 to 18 carbon atoms, and these are substituted even if well, specifically, represent represent) the same contents as those described above R _1.

Examples of the hydrocarbon in the —COO—R ₂ group via the above hydrocarbon include a methylene group, an ethylene group, and a propylene group.

More preferably, in the general formula (I), V ₀ is -CO
O -, - OCO -, - CH 2 OCO -, - CH 2 COO -, - O -, - CONH
-, -SO ₂ NH-, or A ₁ and a ₂ may be the same or different from each other, and represent a hydrogen atom, a methyl group, -COOR ₂ or -CH ₂ COOR ₂ ;
₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc.). Even more preferably, one of a ₁ and a ₂ always represents a hydrogen atom.

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

Next, the repeating unit having a substituent containing a fluorine atom and / or a silicon atom in the monofunctional polymer [M] will be described.

Examples of the chemical structure of the repeating unit include those obtained from a radical addition polymerizable monomer, those formed of a polyester structure, those formed of a polyether structure, and the like. Any one containing a fluorine atom and / or a silicon atom may be used.

Examples of the fluorine atom-containing substituent include -C _h F _{2h + 1}
(H represents an integer of 1 to 12),-(CF ₂ ) _j CF ₂ H (j is 1
Represents an integer of ~ 11), (1 represents an integer of 1 to 6) and the like.

As the silicon atom-containing substituent, for example, (K represents an integer of 1 to 20), a polysiloxane structure and the like.

However, R ₃ , R ₄ and R ₅ may be the same or different and may be a substituted or unsubstituted hydrocarbon group or —OR ₉ group (R ₉ represents the same content as the hydrocarbon group of R ₃ ).

R ₃ 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,
Hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2,2-trifluoroethyl group, 2-cyanoethyl group, 3,3,3-trifluoropropyl Group, 2-methoxyethyl group, 3-bromopropyl group, 2-methoxycarbonylethyl group, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl group, etc.), having 4 to 18 carbon atoms. An alkenyl group which may be substituted (for example, a 2-methyl-1-propenyl group, 2-
Butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-
Hexenyl group, 4-methyl-2-hexenyl group, etc., and optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthyl) An ethyl group, a chlorobenzyl group, a bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms ( For example, a cyclohexyl group, a 2-cyclohexyl group, a 2-cyclopentylethyl group or the like and an optionally substituted aromatic group having 6 to 12 carbon atoms (for example, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl) Group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenylethoxyphenyl group , Butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group,
Acetamidophenyl group, propioamidophenyl group,
Dodecyloylamidophenyl group, etc.).

In the —OR ₉ group, R ₉ has the same content as the above-mentioned hydrocarbon group of R ₃ .

R ₆ , R ₇ , and R ₈ may be the same or different, and represent the same symbol content as R ₃ , R ₄ , and R ₅ .

Next, specific examples of the repeating unit having a substituent containing a fluorine atom and / or a silicon atom as described above are shown below. However, the scope of the present invention is not limited to these.

The monofunctional polymer [M] of the present invention is a polymer having at least a polymerizable double bond group represented by the general formula (I) and a repeating unit having a substituent containing a fluorine atom and / or a silicon atom. It is one that is directly bonded to one end of the main chain of the union or bonded by an arbitrary linking group. Specifically, the linking group is a divalent organic residue,
O-, -S-, _{-SO -, - SO 2 -,} - COO -, - OCO -, - CONHCO -, - NHCON
H-, as well as Represents a divalent aliphatic group or a divalent aromatic group, or an organic residue composed of a combination of these divalent residues, which may have a bonding group selected from the group consisting of: Where d ₁
To d ₅ represents the same meaning as R ₁ in formula (I).

As a divalent aliphatic group, for example, And e ₂ and e ₁ may be the same or different and each is a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 12 carbon atoms (eg, a methyl group , Ethyl, propyl, chloromethyl, bromomethyl, butyl, hexyl, octyl, nonyl, decyl, etc.). Q is -O
-, - S- or -NR ₂₀ - represents, R ₂₀ represents an alkyl group having 1 to 4 carbon atoms, a -CH ₂ Cl or -CH ₂ Br}.

Examples of the divalent aromatic group include a benzene ring group, a naphthalene ring group and a 5- or 6-membered heterocyclic group (a heteroatom selected from an oxygen atom, a sulfur atom and a nitrogen atom as a heteroatom constituting a heterocyclic ring) At least one). These aromatic groups may have a substituent, for example, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a propyl group) , A butyl group, a hexyl group, an octyl group, etc.) and a C1-C6 alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.) are mentioned as examples of the substituent.

As the heterocyclic group, for example, a furan ring, a thiophene ring,
Examples include a pyridine ring, a pyrazine ring, a piperazine ring, a tetrahydrofuran ring, a pyrrole ring, a tetrahydropyran ring, a 1,3-oxazoline ring, and the like.

As described above, specific examples of the polymerizable double bond group represented by the general formula (I) of the monofunctional polymer [M] and a portion composed of an organic residue linked thereto are as follows. But are not limited to these. However, in each of the following examples, P ₁ is -H, -CH ₃ , -CH ₂ COOC
H _3, -Cl, shows -Br or -CN, P ₂ represents -H or -CH _3, X represents a -Cl or -Br, n is an integer of 2 to 12, m is 1 Indicates an integer of 4.

_{(C-3) CH 2 =} CH- (C-4) CH 2 = CH-CH 2 - _{(C-17) CH 2 =} CH-CH 2 -COO- (CH 2 n _{(C-25) CH 2 =} CH-CH 2 OCO (CH 2) n -S- In the total of the repeating units of the monofunctional polymer [M] of the present invention, the repeating unit having a substituent containing a fluorine atom or / and a silicon atom preferably contains 40% by weight or more of the whole, More preferably 60-100
% By weight.

When the amount of the above components of the present invention is less than 40% by weight of the entirety, when the resin particles are dispersed in the image receiving layer, the effect of concentrating on the surface decreases, and as a result, the effect of improving the water retention as a printing original plate is reduced. It will fade.

The monofunctional polymer [M] of the present invention can be produced by a conventionally known synthesis method. For example, a method by an ionic polymerization method in which various reagents are reacted with the terminal of a living polymer obtained by anionic polymerization or cationic polymerization to obtain a monofunctional polymer [M].
Using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a carboxyl group, a hydroxy group, and an amino group,
A polymer obtained by a radical polymerization method in which a polymer having a terminal reactive group bond obtained by radical polymerization is reacted with various reagents to obtain a monofunctional polymer [M], a polymer obtained by a polyaddition or polycondensation reaction And a method by a polyaddition condensation method for introducing a polymerizable double bond group in the same manner as the above radical polymerization method.

Specifically, P.Dreyfuss & RPQuirk, Encycl.Poly
m.Sci.Eng., 7 , 551 (1987), PFRempp, E.Franta, Adv.P
olym.Sci., 58 , 1 (1984), V.Percec, Appl.Poly.Sci., 28
5 , 95 (1984), R. Asami, M. Takari, Makromol. Chem. Supp
l., 12 , 163 (1985), P. Rempp. et al, Makromol. Chem. Sup.
pl., 8 , 3 (1984), Yusuke Kawakami, Chemical Industry, 38 , 56 (198
7), Yuya Yamashita, Polymer, 31 , 988 (1982), Shiro Kobayashi,
Polymer, 30, 625 (1981), Higashimura Satoshinobe, Journal of the Adhesion Society of Japan,
18 , 536 (1982), Koichi Ito, Polymer Processing, 35 , 262 (198
6), can be synthesized according to the methods described in the reviews of Kishiro Higashi, Takashi Tsuda, Functional Materials, 1987 , No. 10, 5, etc. and references and patents cited therein.

Further, when the dispersed resin particles of the present invention have a network structure, the above-mentioned polymer having the polar group-containing monofunctional monomer (A) as the polymer component (A) is bridged to form a higher order polymer. A network structure is formed.

That is, the dispersed resin particles of the present invention comprise, as described above, a portion insoluble in the non-aqueous dispersion solvent composed of the polymer component (A) and a monofunctional polymer [M] soluble in the solvent. In the case of a non-aqueous latex having a network structure, the molecules of the polymer component (A) which is insoluble in the solvent are bridged.

Thereby, the network resin particles become hardly soluble or insoluble in water, and specifically, the solubility of the resin in water is
It is at most 80% by weight, preferably at most 50% by weight.

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

Examples of the cross-linking agent in the above method include compounds that are usually used as a cross-linking agent. Specifically, compounds described in Shinzo Yamashita, 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 such as organic silane compounds (for example, vinyltrimethoxysilane, vinyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, etc. 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, polyoxyalkylene glycol, 1,1,1-trimethylol) Propane, etc.), polyamine-based compounds (eg, ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine,
Modified aliphatic polyamines), polyepoxy group-containing compounds and epoxy resins (eg, "New Epoxy Resin" edited by Hiroshi Kakiuchi, Shokodo (1985), "Epoxy Resin" edited by Kuniyuki Hashimoto, Nikkan Kogyo Shimbun (1969) Etc.), melamine resins (eg, "Urea Melamine Resin", edited by Ichiro Miwa and Hideo Matsunaga, Nikkan Kogyo Shimbun (1969)
Etc.), poly (meth) acrylate compounds (for example, "Oligomers" edited by Shin Okawara, Takeo Saegusa, Toshinobu Higashimura Kodansha (1976), Eizo Omori "functional acrylic resin" Techno System (1985), and specifically, polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, and pentaerythritol polyacrylate. , Bisphenol A-
Examples include diglycidyl ether diacrylate, oligoester acrylate, and methacrylates thereof.

Further, as a polymerizable functional group of a polyfunctional monomer (also referred to as a polyfunctional monomer (D)) or a polyfunctional oligomer containing two or more polymerizable functional groups coexisting by the above method, 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-, may be mentioned CH ₂ = CH-S-, and the like. 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, as monomers or oligomers having the same polymerizable functional group, styrene derivatives such as divinylbenzene and trivinylbenzene: polyhydric alcohols (for example, , Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 200, # 400, # 60
0,1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane,
Methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers of pentaerythritol or polyhydroxyphenol (eg, hydroquinone, resorcin, catechol and derivatives thereof): dibasic acids (eg, malonic acid, succinic acid) acid,
Vinyl esters, allyl esters, vinylamides or allylamides of glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc .: polyamines (eg, ethylenediamine, 1,3-propylenediamine, 1,4-) Condensates of butylene diamine and the like and carboxylic acids having a vinyl group (for example, methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

Examples of the monomer or oligomer having a different polymerizable functional group include, for example, carboxylic acids containing a vinyl group (for example, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, allyloyl propionic acid, Itaconiloyl acetic acid,
A reactant of an itaconiloylpropionic acid, a carboxylic anhydride, etc.) with an alcohol or an amine (eg, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid,
Ester derivatives or amide derivatives containing vinyl groups such as 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc. (eg, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, itacone) Allyl acrylate, vinyl methacryloyl acetate, vinyl methacryloyl propionate, allyl methacryloyl propionate, vinyloxycarbonylmethyl methacrylate, vinyloxycarbonylmethyloxycarbonyl ethylene acrylate, N-allyl acrylamide, N-allyl methacrylamide, N-allyl Itaconic acid amide, methacryloyl propionic acid allyl amide, etc.) or amino alcohols (eg, aminoethanol, 1-aminopropanol, 1-amido) Butanol, 1-amino hexanol, 2-amino butanol) and the like condensates of carboxylic acids containing vinyl groups.

The monomers or oligomers having two or more polymerizable functional groups used in the present invention include monomers (A) and (A)
10 mol% or less based on the total amount of other monomers coexisting with
Polymerization is preferably performed using 5 mol% or less to form a resin.

Furthermore, when a chemical bond is formed by the reaction of reactive groups between polymers in the above method to form a bridge between the polymers, the reaction can be performed in the same manner as a reaction of a normal organic low-molecular compound. . 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 by a combination of a functional group of Group A (hydrophilic group polymer component) and a functional group of Group B (polymers containing a component containing a reactive group) in the table below is generally well known. Method. Note that R ₂₁ and R in Table 1
₂₂ is a hydrocarbon group, represented by l ₈ and l ₉ in L ₁ of the above formula (II)
Represents the same content as

As described above, the network-dispersed resin particles of the present invention contain a polymer component containing a polar group and a polymer component containing a repeating unit having a fluorine atom and / or a silicon atom-containing substituent, and have an intermolecular chain. Are polymer particles having a high-order bridged structure.

In dispersion polymerization, since monodisperse particles having a uniform particle diameter are obtained and microparticles having a particle size of 0.5 μm or less are easily obtained, a polyfunctional monomer is used as a method for forming a network structure. The method used is preferred.

The non-aqueous solvent used in the production of the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or less, 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. However, the present invention is not limited to the compound examples described above.

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

Specifically, KEJ Barrett "Dispersion Polymeriza
tion in Organic Media "John Wiley (1975), Koichiro Murata, Polymer Processing, 23 , 20 (1974), Tsunetaka Matsumoto / Toyoyoshi Tange, Japan Adhesion Society Journal 9 , 183 (1973), Tange Toyoyoshi, Japan Adhesion Association Journal 23 , 26 (1987), DJ Walbridge, NATO.Adv.
study.Inst.Ser.E.No.67,40 (1983), UK Patent No. 8934
29, 934038, U.S. Patent Nos. 1122397, 39004
12, 4606989 specifications, JP-A-60-179751, 60-185
The method is disclosed in 963 publications and the like.

The dispersion resin of the present invention is composed of at least one kind of each of the monomer (A) and the monofunctional polymer [M]. When forming a network structure, the polyfunctional monomer ( In any case, what is important is that a resin synthesized from these monomers is insoluble in the non-aqueous solvent.
A desired dispersion resin can be obtained. More specifically,
The monofunctional polymer [M] is preferably used in an amount of 1 to 50% by weight, more preferably 5 to 25% by weight, based on the insoluble monomer (A). The molecular weight of the dispersion resin of the present invention is from 10 ⁴ to 10 ⁶ , preferably from 10 ^{4 to} 5 × 10 ⁵ .

In order to produce the dispersed resin particles used in the present invention as described above, generally, the monomer (A) and the monofunctional polymer [M] are used.
Further, the polyfunctional monomer (D) may be heated and polymerized in a non-aqueous solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, and butyllithium.
Specifically, a method of adding a polymerization initiator to a mixed solution of the monomer (A), the monofunctional polymer [M], and the polyfunctional monomer (D); There is a method of dropping or arbitrarily adding a mixture of a polymerizable compound and a polymerization initiator, and the like. The method is not limited to these, and the compound can be produced by any method.

The total amount of the polymerizable compound is 5 per 100 parts by weight of the non-aqueous solvent.
It is about 80 parts by weight, preferably 10 to 50 parts by weight.

The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the polymerizable compound. The polymerization temperature is about 50 to 180 ° C, preferably 60 to 120 ° C. The reaction time is preferably 1 to 15 hours.

As described above, the non-aqueous dispersion resin produced by the present invention is fine and has a uniform particle size distribution.

As the matrix resin provided in the image receiving layer of the present invention, all resins conventionally known as various binder resins can be used. Typical ones are vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer, methacrylate copolymer, acrylate copolymer, vinyl acetate copolymer, polyvinyl butyral, alkyd resin, Silicone resin, epoxy resin, epoxy ester resin, polyester resin, etc., and water-soluble polymer compounds such as polyvinyl alcohol, modified polyvinyl alcohol, starch, oxidized starch, carboxymethylcellulose, hydroxyethylcellulose, casein, gelatin, polyacrylate, polyvinylpyrrolidone , Polyvinyl ether-maleic anhydride copolymer, polyamide, polyacrylamide and the like.

The molecular weight of the resin of the matrix provided to the image receiving layer of the present invention is preferably 10 ³ to 10 ⁶ , more preferably 5 ×.
10 ^{3 to} 5 × 10 ⁵ . The glass transition point of the resin is preferably from -10C to 120C, more preferably from 0C to 85C.

As another component of the image receiving layer of the present invention, an inorganic pigment is used. As the inorganic pigment, for example, kaolin clay, calcium carbonate, silica, titanium oxide, zinc oxide,
Examples include barium sulfate and alumina.

The ratio of the binder resin / pigment in the image receiving layer differs depending on the kind of the material and the particle size in the case of the pigment, but is generally about 1 / (0.5 to 5), preferably about 1 / (0.8 to 2.5) by weight. Is appropriate.

In addition, a crosslinking agent may be added to the image receiving layer in order to further improve the film strength. As a crosslinking agent, commonly used ammonium chloride, organic peroxide, metal soap,
An organic silane, a crosslinking agent for polyurethane, a curing agent for epoxy resin, or the like can be used. Specifically, Shinzo Yamashita,
Tosuke Kaneko "Handbook of Crosslinking Agents" Taiseisha Publishing (1981)
And so on. For example, the same as described for the crosslinkable compound of the resin particles can be used.

Examples of the support used in the present invention include high-quality paper, wet-strengthened paper, plastic films such as polyester films, and metal plates such as aluminum plates.

In the present invention, an intermediate layer is provided between the support and the image receiving layer for the purpose of improving water resistance and interlayer adhesion, and a back coat layer (back layer) is provided on the opposite side of the support from the image receiving layer for the purpose of preventing curling. ) Can be provided.

Here, the intermediate layer is an emulsion resin such as an acrylic resin, an ethylene-butadiene copolymer, a methacrylate-butadiene copolymer, an acrylonitrile-butadiene copolymer, an ethylene-vinyl acetate copolymer; an epoxy resin, a polyvinyl butyral , Polyvinyl chloride, polyvinyl acetate, and other solvent-based resins; composed of at least one of the above-mentioned water-soluble resins as a main component, and adding an inorganic pigment or a water-proofing agent as necessary. Can be.

 The configuration of the back coat layer is almost the same as that of the intermediate layer.

When used as a PPC plate making, in order to further reduce the background contamination of the printing original plate of the present invention, the substitutional receiving layer, the intermediate layer, and the like so that the volume specific resistance as the printing original plate becomes 10 ¹⁰ to 10 ¹³ Ωcm. And / or a dielectric agent can be added to the back coat layer. The dielectric agent may be an inorganic one or an organic one. In the case of an inorganic one, Na, K, Li,
Salts of monovalent or polyvalent metals such as Mg, Zn, Co, Ni, etc., and organic cation conductive agents such as polyvinylbenzyltrimethylammonium chloride and quaternary ammonium salts modified with acrylic resin, and organic sulfonic acids Polymeric anionic conductive agents such as salts are included. The amount of these conductive agents is 3 to 40% by weight, preferably 5 to 20% by weight, based on the amount of the binder used in each layer.

In order to prepare the direct-printing type lithographic printing plate precursor according to the invention, generally, if necessary, an aqueous solution containing an intermediate layer component is applied and dried on one surface of the support to form an intermediate layer, and then the image receiving layer component is contained. An aqueous solution may be applied and dried to form an image receiving layer, and if necessary, an aqueous solution containing a backcoat layer component may be applied and dried on the other surface to form a backcoat layer. Incidentally image receiving layer, an intermediate layer, the deposition amount of the back coat layer, respectively ^{1~30g / m 2, 5~20g / m} 2, it is appropriate 5 to 20 g / m ^2.

The preparation of a printing plate using the direct-drawing lithographic printing plate precursor of the present invention is performed by forming and fixing an image on a direct-drawing lithographic printing plate precursor having the above-described configuration by a known technique, and then using a desensitizing solution. After desensitizing the non-image area by surface treatment with, a printing plate is provided for lithographic printing.

〔Example〕

Examples of the present invention will be described below, but the contents of the present invention are not limited to these. The following monofunctional polymer [M] of the resin example is referred to as a macromonomer.

Production example 1 of macromonomer: [M-1] 95 g of 2,2,2,2 ', 2', 2'-hexafluoroisopropyl 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. Azobisisobutyronitrile (abbreviation AIBN)
1.0 g was added 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 temperature was lowered.
The mixture was stirred at 100 ° C for 12 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain 82 g of a white powder.
The weight average molecular weight (abbreviation w) of the polymer [M-1] is 4000.
Met.

Production Example 2 of Macromonomer: [M-2] A mixed solution of 96 g of a monomer (A-1) having the following structure, 4 g of β-mercaptopropionic acid, and 200 g of toluene was heated to a temperature of 70 ° C. under a nitrogen stream. 1.0 g of AIBN was added and reacted for 8 hours. Next, the reaction solution was cooled in a water bath, and the temperature was 25 ° C.
And 10 g of 2-hydroxyethyl methacrylate
Was added. Dicyclohexylcarbonamide (abbreviated DC
C.) A mixed solution of 15 g, 0.2 g of 4- (N, N-dimethylamino) pyridine and 50 g of methylene chloride was added dropwise with stirring over 30 minutes, and the mixture was further stirred for 4 hours. Next, 5 g of formic acid was added, and after stirring for 1 hour, the precipitated insoluble material was separated by filtration.
Re-sinked inside. The precipitated viscous material was collected by decantation, dissolved in 100 ml of tetrahydrofuran, and the insoluble material was separated by filtration and reprecipitated in n-hexane 1. The polymer obtained by drying the precipitated viscous material was 5.2 g at 60 g in yield.
It was 10 ³ .

Production Example 3 of Macromonomer: [M-3] A mixed solution of 95 g of monomer (A-2) having the following structure, 150 g of benzotrifluoride, and 50 g of ethanol was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. did. 4,4'-azobis (4-
2 g of cyanovaleric acid (abbreviated ACV) was added and reacted for 8 hours. After cooling, the resulting polymer was reprecipitated in methanol 1 and dried. Next, the polymer was dissolved in 50 g of this polymer, 11 g of 2-hydroxyethyl methacrylate, and 150 g of benzotrifluoride, and the temperature was adjusted to 25 ° C. To this mixture, with stirring, 15 g of DCC,
A mixed solution of 0.1 g of 4- (N, N-dimethylaminopyridine) and 30 g of methylene chloride was added dropwise over 30 minutes, and the mixture was further stirred for 4 hours. Then, after adding 3 g of formic acid and stirring for 1 hour,
The precipitated insoluble material was separated by filtration, and the filtrate was reprecipitated in 800 ml of methanol. The precipitate was collected, dissolved in 150 g of benzotrifluoride, and reprecipitated again to obtain 30 g of a viscous substance. W of the polymer [M-3] was 3.3 × 10 ⁴ .

Production Examples 4 to 22 of macromonomers: [M-4] to [M-2
2] Another monomer (monomer corresponding to the polymer component shown in Table 2) in place of monomer (A-1) in Production Example 2
In the same manner as in Production Example 2, except for replacing the above, each macromonomer [M] was produced. Each w was 4 × 10 ^{3 to} 6 × 10 ⁸ .

Production Examples of Macromonomer 23 to 30: [M-23] to [M-3
0] In Production Example 2 of the macromonomer, the monomer (A-
1) and 2-hydroxyethyl methacrylate, respectively
Instead of the compound corresponding to each of the polymers in Table 3 below,
Otherwise, each macromonomer [M] was produced in the same manner. Each w was 5 × 10 ^{3 to} 6 × 10 ³ .

Production Example 31 of dispersion stabilizing resin: [M-31] A mixed solution of 27 g of octyl methacrylate, 60 g of monomer (F-1) corresponding to the following structure [M-1], 3 g of glycidyl methacrylate and 200 g of benzotrifluoride: The mixture was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 2,2'-
1.0 g of azobisisobutyronitrile (abbreviation: AIBN) was added and reacted for 4 hours, and 0.5 g of AIBN was further added and reacted for 4 hours. Next, 5 g of methacrylic acid, N, N-
1.0 g of dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added, and the mixture was stirred at 110 ° C. for 8 hours. After cooling, the precipitate was reprecipitated in 2 l of methanol, and a slightly brownish oily substance was collected and dried. Weight average molecular weight (w) with 73g yield
It was 3.6 × 10 ⁴ .

Production Example 1 of Resin Particles: [L-1] A mixed solution of 20 g of acrylic acid, 5 g of the polymer [M-1] of Production Example 1 of macromonomer, and 110 g of methyl ethyl ketone was heated to a temperature of 60 ° C. under a nitrogen stream. . 0.2 g of 2,2'-azobis (isovaleronitrile) (abbreviated ABVN) was added and reacted for 2 hours, and 0.1 g of ABVN was further added and reacted for 2 hours. The resulting dispersion was filtered through a 200-mesh nylon cloth, and the resin particles [L-1] obtained had a polymerization rate of 100% and an average particle size (measured by HORIBA, Ltd .: CAPA500) of 0.20 μm.

Production Example 2 of Resin Particles: [L-2] A mixed solution of 20 g of acrylic acid, 5 g of macromonomer AK-5 (a commercially available macromonomer having a polysiloxane structure manufactured by Toagosei Co., Ltd.), 2 g of divinylbenzene, and 120 g of methyl ethyl ketone The reaction was conducted in the same manner as in Production Example 1 of the resin particles. The polymerization rate of the obtained dispersion [L-2] is
At 100%, the average particle size was 0.28 μm. Production Examples 3 to 26 of resin particles: [L-3] to [L-26] A mixed solution of 20 g of monomer (A), 4 g of macromonomer [M] and 150 g of organic solvent described in Table 4 below. The other dispersion resin particles were produced in the same manner as in Production Example 1 except for the above. The polymerization rate of each dispersion was 95 to 100%. The monodispersibility was also good when the average particle size of each particle was in the range of 0.15 to 0.30 μm.

Production Examples 27 to 37 of Resin Particles: [L-27] to [L-37] Production Example 2 was the same as Production Example 2 except that the polyfunctional compound shown in Table 5 below was used in place of 2 g of divinylbenzene. Resin particles were produced in the same manner. 100% polymerization rate for each particle
The average particle size was 0.25 to 0.35 μm.

Example 1 3 g of resin particles [L-23] (as solid content) and 30 g of [methyl methacrylate / allylic acid (99/1) weight ratio] copolymer (weight average molecular weight 45,000): [B-1] zinc oxide 100
g and 300 g of toluene were dispersed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at a rotation speed of 6 × 10 ³ rpm for 10 minutes. Then back layer The dispersion on one side of quality paper, coated with a wire bar to a dry coating weight on the intermediate layer of the support an intermediate layer provided on the other side is 18 g / m ² Then, it was dried at 100 ° C. for 1 minute to prepare a lithographic printing plate precursor.

Next, plate making was performed using a commercially available PPC, and the obtained plate was used for ELP-EX
Using a zinc oxide desensitizing solution (manufactured by Fuji Photo Film Co., Ltd.), the film was desensitized by passing through an etching machine once to obtain a printing original plate.

The density of the image portion of the obtained original plate was 1.0 or more, there was no background fog in the non-image portion, and the image quality of the image portion was clear.
This is an offset printing machine (Oliver manufactured by Sakurai Seisakusho Co., Ltd.)
52 type) and printed on high quality paper. Even if the number of prints exceeded 3,000, no problem was caused in the background smear of the non-image portion and the image quality of the image portion of the printed matter.

Examples 2 to 9 In Example 1, instead of the resin [1] of the present invention,
Except for using the copolymers shown in Table 6, operations were performed in the same manner as in Example 1 to prepare lithographic printing original plates.

This was operated in the same manner as in Example 1 to prepare an original plate.

The density of the obtained master plate for offset printing is
The image quality was clear at 1.2 and above. Further, when the sheet was etched and printed by a printing machine, the printed matter after printing 3,000 sheets had no fog in the non-image portion and the image was clear.

Example 10 4 g (as solid content) of resin particles [L-1], 29 g of binder resin [B-2] having the following structure, 50 g of zinc oxide and toluene
200 g of the mixture was dispersed in a homogenizer at a rotation speed of 6 × 10 ³ rpm for 10 minutes. Further, 0.5 g of phthalic anhydride was added and dispersed at 1 × 10 ³ rpm for 1 minute. After applying the dispersion thus obtained on a support under the same conditions as in Example 1, 10
The resultant was dried at 0 ° C. for 30 seconds and further heated at 110 ° C. for 1 hour to prepare a lithographic printing original plate.

This was made into a plate using the same apparatus as in Example 1, then subjected to an etching treatment, and printed using a printing machine. The density of the master plate for offset printing obtained after plate making is 1.0 or more,
The image quality was clear. The image quality of the printed matter after printing 4,000 sheets was a clear image without background fog.

Example 11 A mixture of 4 g of resin particles [L-3] (as solid content), 30 g of resin [B-3] having the following structure, 80 g of zinc oxide and 150 g of toluene was dispersed in a ball mill for 1.5 hours. Next, 4 g of hexamethylene diisocyanate was added to this dispersion, and the mixture was dispersed in a ball mill for another 10 minutes.The intermediate layer of the support provided with a back layer on one side of the high-quality paper and an intermediate layer on the other side. The solution was coated on the layer with a wire bar so that the dry adhesion amount was 25 g / m ^2, and dried at 100 ° C. for 90 minutes to prepare a lithographic printing original plate.

This original plate was passed through an etching processor once with a desensitizing solution [ELP-EX manufactured by Fuji Photo Film Co., Ltd.], and treated with 2 μl of distilled water to form a contact angle with the formed water. Was measured with a goniometer,
10 ° or less. The angle was 98 ° before the desensitization treatment. This indicates that the non-image portion of the image receiving layer of the original plate of the present invention has changed from lipophilic to hydrophilic (usually, the non-image portion does not generate printing background stain, dot stain, etc. during printing). It is necessary that the degree of conversion be 20 ° or less in contact angle with water).

Next, the plate was made in the same manner as in Example 1, and then subjected to the desensitizing treatment and printing was performed. As a result, even if the number of sheets exceeded 3,000, no problem was caused in the background smear of the non-image portion of the printed matter and the image quality of the image portion.

Examples 12 to 16 Except that the compounds shown in Table 7 below were used instead of hexamethylene diisocyanate used in Example 11, a lithographic printing original plate was produced in the same manner as in Example 1.

This was made into a plate using the same apparatus as in Example 1, then subjected to an etching treatment, and printed using a printing machine. The density of the offset printing master plate obtained after plate making was 1.0 or more, and the image quality was clear. The image quality of the printed matter after printing 3000 sheets was a clear image without background fog.

Examples 16 to 25 The procedure of Example 11 was repeated, except that 4 g of the crosslinked resin particles [L] (as solid content) in Table 8 were used instead of 4 g of the resin particles [L-3]. A lithographic printing plate precursor was prepared.

When a printing original plate was prepared and printed for each original plate in the same manner as in Example 11, no problem was caused in the background fog and the image quality of the non-image portion of the printed matter even when the number of printed sheets exceeded 3,000.

〔The invention's effect〕

ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production of background fogging is suppressed well and the original plate for direct drawing type lithographic printing which has favorable printing durability can be obtained.

Claims (2)

(57) [Claims] 1. A direct drawing type lithographic printing plate precursor having an image receiving layer on a support, characterized in that the image receiving layer contains at least one kind of the following non-aqueous solvent-based dispersed resin particles. A lithographic printing original plate. Non-aqueous solvent-based dispersed resin particles: in a non-aqueous solvent, a carboxyl group, a sulfo group, a sulfino group, a phosphono group, which is soluble in the non-aqueous solvent but insolubilized by polymerization; [R ₀ is a hydrocarbon group or -OR ₁₀ (R ₁₀ represents a hydrocarbon group)
Which represents at least one polar group selected from a hydroxyl group, a formyl group, an amide group, a cyano group, an amino group, a cyclic acid anhydride-containing group and a nitrogen atom-containing heterocyclic group. Monomer (A), a silicon atom and / or
Or a monofunctional polymer having a polymerizable double bond group represented by the following general formula (I) bonded only to one end of a main chain of a polymer comprising at least a repeating unit containing a substituent containing a fluorine atom: Copolymer resin particles obtained by subjecting the reactive polymer [M] to a dispersion polymerization reaction. General formula (I) [In the general formula (I), V ₀ is -O-, -COO-, -OCO-,
_{-CH 2 OCO -, - CH 2} COO -, - SO 2 -, It represents -CONHCOO- or -CONHCONH- (where, R ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), a _1, a ₂ are,
May be the same or different from each other, via a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R ₂ or a hydrocarbon group (R ₂ represents a hydrogen atom or a hydrocarbon group which may be substituted ) 2. The lithographic printing plate precursor according to claim 1, wherein the non-aqueous solvent-based dispersed resin particles form a high-order network structure.