JPH04204536A - Original plate for direct printing type lithography - Google Patents

Abstract

PURPOSE:To provide an original plate in which even dotted greasing over the whole surface is not generated as an offset printing original plate by containing at least one kind of dispersed resin particles of nonaqueous solvent type in an image receiving layer. CONSTITUTION:At least one kind of nonaqueous solvent type dispersed resin particles is contained in an image receiving layer. The particles contains a functional group expressed by a formula I and/or a formula II, in the nonaqueous solvent. The particles are copolymer resin particles which are obtained by dispersion polymerization reaction of a unifunctional monomer (A) becoming unsoluble by polymerization while soluble to the nonaqueous solvent, to a unifunctional polymer (M) obtained by connecting a polymer double bond group expressed by formula III to one end of main chain of polymer including at least repetition unit including substituent including silicon atom and/or fluorine atom.

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 lithographic printing original plate suitable for office printing original plates and the like.

[Conventional technology]

Currently, as printing plates for office use, direct drawing type planographic printing plates having an image-receiving layer on a support are widely used.

In order to perform plate making, that is, image formation on such a printing original plate,
Generally, a method is adopted in which MIJ ink is drawn by hand on the image-receiving layer, or printing is performed using a typewriter, an ink sheet method, or a transfer type heat-sensitive method. In addition, using a plain paper electrophotographic copier (P P 'C),
A method of transferring and fixing a toner image formed on a photoreceptor to an image-receiving layer through the steps of charging, exposure, and development has also begun to be used in recent years. In any case, the printing original plate after plate making is subjected to surface treatment with a desensitizing liquid (so-called etch liquid) to desensitize non-image areas, and then subjected to lithographic printing as a printing plate.

Conventional direct-drawing lithographic printing original plates have a back layer on one side of a support such as paper, and an image-receiving layer as a surface layer on the other side with an intermediate layer interposed therebetween. The back layer or intermediate layer is formed of a water-soluble resin such as PVA and starch, a water-dispersible resin such as a synthetic resin emulsion, and a waterproofing agent.

A typical example of such a direct drawing type lithographic printing original plate is as described in U.S. Pat.
Inorganic pigments such as calcium carbonate etc. and melamine/pormaldehyde!・It is composed mainly of a waterproofing agent such as a resin initial condensate.

[Problem to be solved by the invention]

However, in conventional printing plates obtained in this way, if the hydrophobicity is increased by increasing the amount of water-resistant agent added or using a hydrophobic resin to improve printing durability, Printing durability improves, but hydrophilicity decreases and printing stains occur; on the other hand, improving hydrophilicity deteriorates water resistance.
There was a problem that printing durability decreased. In particular, in high-temperature operating environments of 30°C or higher, the surface layer (image-receiving layer) dissolves in the soaking water used in offset printing, resulting in major drawbacks such as reduced printing durability and printing stains. there were.

Furthermore, in a lithographic printing plate, images are drawn on an image-receiving layer using oil-based ink, etc. as an image area, and if the binder properties between this receiving layer and the oil-based ink are not good, even if the non-image area has sufficient hydrophilicity. Even if printing smear as described in item 1 does not occur, there is a problem in that the oil-based ink in the image area is missing during printing, resulting in a decrease in printing durability.

The present invention is intended to solve the above-mentioned problems of direct drawing type lithographic printing original plates.

An object of the present invention is to provide a direct drawing type lithographic printing original plate which is excellent in desensitization properties and does not cause not only the entire surface-like background stain but also dotted background stains as an offset original plate.

Another object of the present invention is to improve the adhesion between the oil-based ink in the image area and the image-receiving layer, and to maintain sufficient hydrophilicity in the non-image area even when the number of prints increases in conventional printing. An object of the present invention is to provide a direct drawing type lithographic printing original plate which does not cause stains and has high printing durability.

[Means to solve the problem]

The object of the present invention is to provide a support.Secondly, the present invention provides a direct-drawing lithographic printing original plate having an image-receiving layer, wherein the image-receiving layer contains at least one of the following non-aqueous solvent-based dispersed resin particles. This can be achieved by using an electrophotographic lithographic printing original plate characterized by the following.

Non-aqueous solvent-based dispersed resin particles contain a functional group represented by the following general formula (I) and/or general formula (II) in a non-aqueous solvent, and are soluble in the non-aqueous solvent but polymerize. Only at one end of the main chain of a polymer comprising at least a monofunctional monomer (A) to be insolubilized and a repeating unit containing a substituent containing a silicon atom and/or a fluorine atom, Copolymer resin particles obtained by carrying out a dispersion polymerization reaction with a monofunctional polymer [M] formed by bonding a polymerizable double bond group represented by formula (II[).

General formula (1) %Formula% General formula (TI) -W2-←CH2-→-Tr-CH2CH2X [just (
7, -1- In the formula (T) or (II), -W, -
, -W2- are each -5o2-1-co- or -00C-
, nl+ R2 each represents 0 or 1, and X represents a halogen atom] General formula (III) 1 ] CH=C Vo- [However, in the formula (Tff), Vo is 10-
1-COO-, -0CO-, -CH2CO-.

-CH2COO-, SO2.

represents -CONHCONH-), where R1 represents a hydrogen atom or a hydrocarbon having 1 to 18 carbon atoms), a l +
82 may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -Coo-
Rz or one COO-R2 (R2 represents a hydrogen atom or an optionally substituted hydrocarbon group) via a hydrocarbon group] Furthermore, in the present invention, in the non-aqueous solvent-based dispersed resin particles, General formula (1) and/or general formula (TT) above
A polymer component having a functional group represented by the above may also have a crosslinked structure.

[Effect]

The present invention provides that the non-aqueous solvent-based dispersed resin particles (hereinafter sometimes simply referred to as resin particles) contained in the image-receiving layer of a direct-drawing lithographic printing original plate have the formula (I) and/or formula
A polymer component containing at least one specific functional group represented by (n) and becoming insoluble in the non-aqueous solvent after polymerization;
It is characterized by being chemically bonded to a polymer component that contains a repeating unit containing at least a fluorine atom and/or a silicon atom as a substituent and is soluble in the non-aqueous solvent even after polymerization.

Zunawaji, the resin particles of the present invention include a portion insoluble in a non-aqueous dispersion solvent composed of a functional group-containing polymer component (A) represented by formula (T) and/or (T)); It is a non-aqueous latex composed of a monofunctional polymer CM which is soluble in the solvent, and the molecular weight of the dispersion resin is 10" to 1o'".
and preferably 104 to 10'.

In the present invention, the resin particles are present in the image-receiving layer as separate particles from the binder resin which is the 7-trix of the image-receiving layer, and the resin particles have the above general formula (T).
and/or at least one functional group represented by (II)
By containing a species, when treated with a treatment liquid containing at least one hydrophilic compound containing a nucleophilic substituent, "1 functional group of formula (T) or" 1 "formula (II)" The formula (
A nucleophilic hydrophilic compound can be added to the end of the functional group in 1), thereby allowing the resin particles to exhibit hydrophilicity.

The mechanism by which the resin particles according to the present invention are made hydrophilic by a non-nucleophilic hydrophilic compound is expressed by the following reaction formula (
11. 1) shows no resin moiety other than the functional group of formula (I) or (II).

OH- P-, -CH2CH2C]--HP~W, -CH
=CH.

HCI Only when etching a non-image area, a hydrophilic group is added to the end by reacting with a hydrophilic compound containing a nucleophilic substituent in the processing solution as shown in "-", thereby making it hydrophilic. In other words, it is characterized by being made hydrophilic, and since it does not react with moisture in the atmosphere, there are no concerns regarding storage stability. The vinyl sulfone group, vinyl carbonyl group, and acryloxy group represented by the general formula (I) according to the present invention are functional groups that react very quickly with a compound containing a nucleophilic substituent. This makes it possible to exhibit hydrophilicity.

Furthermore, the functional group represented by the general formula (In) can be expressed by the reaction formula (1).
), the dehydrohalogenation reaction proceeds easily by alkali treatment and can be converted to the corresponding functional group of general formula (1), and similar to that of formula (I). It can be used for

On the other hand, the resin particles of the present invention are characterized in that they also have a polymer component containing a significantly large fluorine atom and/or a silicon atom.

Therefore, in the direct-printing original plate of the present invention containing the resin particles in the image-receiving layer, when drawing 2h ink etc. as an image portion on the image-receiving layer, the effect of the lipophilic group in the resin particles This improves the adhesion between the receiving layer and oil-based ink, improving printing durability, while in the non-image area, the resin particles are quickly resistant to desensitizing liquid and soaking water as described in 1. Since it exhibits hydrophilicity, it is clearly distinguished from the lipophilicity of the image area, and printing ink does not adhere to the non-image area during printing.

” 1, whereas conventionally the image area was made hydrophobic by drawing oil-based ink etc. on a hydrophilic resin, the present invention
A type of direct printing type that combines the advantages of both hydrophilic and hydrophobic properties of resin particles, based on a completely different idea of making lipophilic resin particles hydrophilic in their non-image areas through surface treatment. This is an original plate for lithographic printing.

It has an image-receiving layer in which hydrophilic resin particles are dispersed in the binder resin of the matrix, and the non-image area is treated with a desensitizing liquid to make the surface hydrophilic, thereby creating an original plate for direct drawing type lithographic printing. In this type of printing original plate, known hydrophilic resin particles are uniformly present throughout the surface layer.

In contrast, although the non-aqueous solvent-based dispersed resin particles of the present invention are dispersed in the image-receiving layer, due to the action of the extremely lipophilic polymer component containing fluorine atoms and/or silicon atoms, It is present in a concentrated manner, especially in the surface area of the image-receiving layer, which is an air interface (highly 41-philic). Therefore, by dispersing a smaller amount (50 to 10% of the amount used in the known hydrophilic resin particle technology), the water retention properties of non-image areas can be dramatically improved.

In addition, in the present invention, the resin particles are made by bonding hydrophobic polymer components, and since this hydrophobic part interacts with the binder resin of the surface layer, the anchoring effect of this part makes it difficult to print during printing. It does not dissolve with soaking water and can maintain good printing characteristics even after printing a large number of sheets.

Furthermore, in the present invention, if the resin particles form a high-order network structure, the dissolution in water is further suppressed, and on the other hand, water swelling properties are exhibited, resulting in even better water retention.

That is, when it has a network structure, in the above-mentioned non-aqueous solvent insoluble part, the molecules of the polymer component (A) forming the insoluble part are bridged to form a high-order network. As a result of this, the network resin particles become releasable or insoluble in water.

It is important that the resin particles are dispersed as particles in the image-receiving layer separately from the binder resin, which is the 7-trix, and concentrated near the air interface.

As a result, the direct printing original plate of the present invention provides a high-quality printed image without scumming.

Furthermore, since the resin particles are fixed by the binder resin, they do not peel off during various processing steps, and the binder resin also provides a protective effect. Therefore, it has excellent printing durability, is unaffected by the environment during plate-making processing, and has excellent storage stability before processing.

Furthermore, there is a concern that the resin particles may flow out due to the hydrophilic nature of the specific functional groups of formulas (I) and (n) of the resin particles, but such concerns can be resolved by crosslinking at least a portion of the resin particles.

Therefore, the printing original plate for plate making according to the present invention reproduces an image faithful to the original image, has good hydrophilicity in the non-image area, does not cause scumming, and has excellent printing durability. Furthermore, it has the advantage that it is unaffected by the environment during plate-making processing and has excellent storage stability before processing.

The resin particles will be further explained below.

The dispersion resin forming the resin particles of the present invention contains a monomer (A)
and -functional polymer [M], and when forming a network structure, a polyfunctional monomer (D) described below may be co-present as necessary, and in either case, Most importantly, if the resin synthesized from these monomers is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained.

More specifically, for the monomer (A) to be insolubilized, -
It is preferable that the functional polymer [M] is used in an amount of 1 to 50% by weight, more preferably 5 to 25% by weight.

In addition, in the total number of repeating units in the -functional polymer CM), repeating units having a substituent containing a fluorine atom and/or a silicon atom must be contained in an amount of 40% or more by weight of the entire polymer [M]. is preferable, and more preferably 60 to 100% by weight. If it is less than 40% by weight, when the resin particles are dispersed in the surface layer, the concentration effect on the surface area will be reduced, and as a result, the water retention property as a printing original plate will be reduced.
The second effect will be diminished.

The hydrophilicity of the resin particles is determined by the contact angle (measured with a goniometer) with distilled water of a film of the resin formed by coating the resin particles dissolved in an arbitrary soluble solvent.
It is hydrophilic and exhibits a value of 50 degrees or less, preferably 30 degrees or less.

Further, 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.

It is preferable that the resin particles (including network resin particles) of the present invention have an average particle diameter of 0.05 to 1.0 μm. 1.0
If it is larger than .mu.m, the smoothness of the image-receiving layer decreases, causing a decrease in film strength or toner image strength. On the other hand, if the particle diameter is smaller than 0.005 μm, the particle size resembles that of molecular dispersion, and the effect of being a particle for water retention property is diminished.

Since the resin particles of the present invention are synthesized using a dispersion polymerization method in a non-aqueous solvent system, the average diameter of the polymer latex particles can easily be 1 μm or less, and the particle size distribution is very narrow, and the particles are monodisperse. It is possible to do this.

In the present invention, the resin particles (including network resin particles) are
If the amount is too small, the hydrophilicity of the non-image area will not be sufficient and the effect will be lost; if it is too large, the hydrophilicity of the non-image area will be further improved, but the etching speed of the non-image area will be reduced. In addition, the electrophotographic characteristics deteriorate under severe conditions, resulting in poor copied images.
It is preferably used in an amount of 20 to 200% by weight, preferably 80 to 150% by weight, based on 100 parts by weight of Trix resin.

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

First, we will explain the monofunctional monomer (A) which is soluble in non-aqueous solvents but becomes insolubilized by polymerization.
The monomer (A) contains a functional group represented by the general formula (I) or (TI) in its molecular structure.

General formula (I) -I'Lt-←CH2-)TT-CH=CH2General formula (
n) -W+-←CH2-)T-r-CH2CH2-x formula (I
), (TI), -W, -+ -w2- are each -5o
2-, -co- or -0OC-, nl, nl
each represents 0 or 1, and X does not represent a halogen atom.

In the above general formula (I) or (n), n, nl or O is more preferred. Moreover, the halogen atom of X specifically represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

Furthermore, the functional group of general formula (TI) can be easily converted into the corresponding functional group of formula (T) by dehydrohalogenation by alkali treatment, as shown in reaction formula (11). It can be used in the same way.

The monomer (A) constituting the main component of the resin particles of the present invention contains at least one functional group represented by the following general formula (1) and/or general formula (II). , any one containing a polymerizable double bond group in one molecule may be used.

More specifically, examples of the monomer (Δ) are represented by the following general formula (TV):
Indicated by

General formula (]■) I CH=C ■ Z　--Y-w.

In formula (IV), Z is -coo-, -oco-, -o-.

Y represents an organic residue that directly bonds or connects -2- and -W. Furthermore, ÷z-y-1- may directly connect [-C1 moiety and -Wo].

Wo represents a functional group represented by general formula (1) or general formula (II).

al, a4 may be the same or different from each other, and each
Represents a hydrogen atom, a halokene atom, a cyano group, an alkyl group, an aralkyl group, or an aryl group.

General formula (TV) will be explained in more detail.

Preferably, Z does not represent -COO-1-0CO-1-0-1.

However, r is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, 2
-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxyethyl group, 2-hydroxyethyl group, 3-bromopropyl group, etc.), optionally substituted aralkyl groups having 7 to 9 carbon atoms (e.g. benzyl group, phenethyl group, 3-phenylpropyl group, chloropenzyl group, bromobenzyl group, methylpencyl group, methoxyethyl group, chloro-methylbenzyl group, dibromobenzyl group, etc.)
, an optionally substituted aryl group (eg, phenyl group, tolyl group, xylyl group, mesityl group, methoxyphenyl group, chlorophenyl group, bromophenyl group, chloro-methyl-phenyl group, etc.).

Y represents a direct bond or an organic residue connecting -2- and -WQ.

When Y represents a linked organic residue, this linking group represents a carbon-carbon bond that may be via a heteroatom; examples of the heteroatom include an oxygen atom, a sulfur atom, or a nitrogen atom), □ - (-CH=CH→-T -0-, -5-1-N-, -
CoO-.

-CONH-, -302-, -3O2NH-, -NHC
It is composed of bonding units such as OO-1-NHCONH-, -Si-, etc., singly or in combination (with the exception of r2.
rl.

r'4. r5. r6 each represents the same content as rl above).

a3. a may be the same or different, and may be a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, etc.), a cyano group, a hydrocarbon group (e.g. methyl group, ethyl group, propyl group, butyl group, methoxycarbonyl group, Argyl groups having 1 to 12 carbon atoms, which may be substituted, such as togycylcarbonyl group, propoxycarbonyl group, butgylcarbonyl group, hexyloxycarbonyl group, methgylcarbonylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, etc. , an aralgyl group such as a Hensyl group or a phenethyl group, an aryl group such as a phenyl group, a tolyl group, a xylyl group, a chlorophenyl group, etc.).

Furthermore, -(-Z-Y-3- bond □ The remainder h( may connect C=C1 part and -wo.

More specifically, the monomer (A) in -1- is illustrated below, but the scope of the present invention is not limited thereto.

In examples (a-1) to (a-25), a is -H or -
Represents CH, R3 is -CH-CH2, -CH=CH
Two prongs! ;): Represents CH2CH2X, where X is -F+-
C (1, -Br, -I is not represented.

(Left below) (al) CH2= C C00CH2CH2SO2-R) □ (a-3) CH2= CC00(CH2
)20CO(CH2)2SO2-R3□ (a 'I) CL =C□ C0NH(CHI)2SO2-R3 C00(CH2)2SO2R3□ (a+2) CH2= C C00(CH2) 20CO~R1 (a-Ill) CH )=CH1l! H2OC
0-R3 Ushi U-bar 3 (a-20) CH2=C C00(CH2)□Co-R.

(m: an integer of 1 to 4) □ (a-25) CH2= C□ C0NH(CH2)2CO-R3 A monofunctional monofunctional unit containing a functional group of general formula (I) and/or (II) as described above Other copolymerizable monomers may be contained as a polymer component together with the polymer (Δ). Examples of other monomers include α-olefins, vinyl alkanoates or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, heterocyclic vinyls [e.g. nitrogen atom It is a 5- to 7-membered heterocyclic ring containing 1 to 3 non-metallic atoms (oxygen atoms, sulfur atoms, etc.) other than that, and specific examples include hinyl diophene, vinyl sioki → none, vinyl furan, etc. Can be mentioned. Preferred examples include vinyl or allyl alkanoates having 1 to 3 carbon atoms, methacrylonitrile, styrene and styrene derivatives (e.g., hinyltoluene, butylstyrene, methoxystyrene, chlorostyrene, cyclostyrene, promostyrene, ethoxystyrene, etc.). It will be done. However, it is not limited to these.

As a polymer component in the resin, the monomer (A) is present in an amount of 30% by weight or more, preferably 50% by weight or more, and particularly preferably, the monomer (A) is present in the resin as a polymer component. and -functional polymer [M].

Next, the monofunctional polymer [M] will be explained.

It contains at least a repeating unit containing a substituent containing a silicon atom and/or a fluorine atom, and a polymerizable double bond group represented by general formula (III) is bonded only to one end of the polymer main chain. It is important that the polymer is copolymerized with the monomer (A) and solvated and soluble in the non-aqueous solvent, and is useful for dispersion stabilization in so-called non-aqueous dispersion polymerization. It acts as a resin.

The monofunctional polymer [M] of the present invention is soluble in the nonaqueous solvent, and specifically, the monofunctional polymer [M] is soluble in the non-aqueous solvent, and specifically, it is
Any material that dissolves at least 5% by weight at 5°C may be used.

In addition, the weight average molecular weight of the polymer [M] is 1 x 103 to 1
x 10°, preferably 2 x 101 to 5 x 10'',
Particularly preferred is 3x10'' to 2XIO'.

When the weight average molecular weight of the polymer [M] becomes less than 1X10' or more than 1X10', agglomeration of the produced dispersed resin particles occurs, making it impossible to obtain fine particles with a uniform average particle size.

- In the functional polymer [M], the polymerizable double bond group component represented by the general formula (II) bonded only to one end of the polymer main chain will be explained below.

General formula (I [) II H-C O- General formula (II [) Nioite, Voi; tnie 0-, -c
oo-.

-0CO-, -CH20CO-, -CH2COO-, -
3O2-Here, R1 is not only a hydrogen atom but also a preferable hydrocarbon group such as an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group). , octyl group, decyl group, dodecyl group, hexenyl group, octadecyl group, 2-chloroethyl group, 2-promoedyl group, 2-cyanoethyl group, 2-methoxyethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.) , an optionally substituted alkenyl group having 4 to 18 carbon atoms (e.g. 2-methyl-1
-propenyl group, 2-butenyl group, 2-pentenyl group,
3-methyl-2-pentenyl group, ■-pentenyl group, 1
-hexenyl group, 2-hexenyl group, 4-methyl-2-
hexenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., hensyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphdylethyl group, chloropentyl group, promhenyl group, methylbenzyl group, edylbenzyl group, methylbenzyl group, dimethylbenzyl group, dimethylginpencyl group, etc.), optionally substituted alicyclic groups having 5 to 8 carbon atoms (for example, cyclohexyl group, 2- cyclohexylethyl group, 2-cyclopendylethyl group, etc.), or an optionally substituted aromatic group having 6 to 12 carbon atoms (for example, phenyl group, naphthyl group, I-lyl group, quinryl group, propyl group, Phenyl group, butylphenyl group, ocdylphenyl group, dodecylphenyl group, quinphenyl group, engineering I
・Xyphenyl group, quinphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acedelphenyl group, me-1-xycarbonylphenyl group, etquincarbonylphenyl group, i・4-carbonylphenyl group, acetamidophenyldophenyl group, todene [1-ylamitophenylno^, etc.]
etc.

It may have a substituent. Examples of substituents include halogen atoms (e.g., chlorine atom, bromine atom, etc.), alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, chloromethyl group, metquinemethyl group, etc.), alkoxy groups (e.g., methoxymethyl group, etc.). group, ethoxy group, propioxy group, butquine group, etc.).

al and a2 may be the same or different from each other,
Preferably a hydrogen atom, a halogen atom (for example, a chlorine atom,
bromine atom, etc.), cyan group, argyl group having 1 to 4 carbon atoms (
(for example, methyl group, ethyl group, propyl group, butyl group, etc.), -COO-R2 or C00R via a hydrocarbon group
2 (R2 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group, or an aryl group, which may be substituted; specifically, for the above R1) (represents the same content as described)
represents.

Examples of the hydrocarbons that reach one COOR2 group via the hydrocarbons listed above include a methylene group, an ethylene group, a propylene group, and the like.

More preferably, in the general formula (■[), Vn is -
COO-, -0CO-, -CH20CO-, -CH2C
OO-.

, al and a2 may be the same or different from each other, and represent a hydrogen atom, a methyl group, -COOR2 or -CH2CO
represents OR2, [R2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group,
represents a butyl group, hexyl group, etc.). Even more preferably, one of al and a2 always represents a hydrogen atom.

Specifically, the polymerizable double bond group represented by the general formula (III) is o CH) O II Ill CH2=CHl-C-0-, CH2=C-C-0-.

CHz　　　OCHzCOOCH3 ]11j CH=CH-CH-0-, CH2=C H 0=C-O- CH, C0OH □ CH2=C,, CH2=CH-C0NH-.

talent 0=C-O- CH,CH3 CH7=C-CONH-, CH=CH-CONH-.

1] 11 C1+2-CH-0-C-, CH2"CH-CH2-〇-C-.

C0OHO 1)] CH2''CH-0-, CH2=C-CH2-C-0-.

etc. can be mentioned.

Next, fluorine atoms and/or
Or, a repeating unit having a substituent containing a gay element atom will be explained.

Examples of the chemical structure of the repeating unit include those obtained from a polymerizable monomer, those consisting of a polyester structure, and those consisting of a polyneedle structure. on the chain,
Any material may be used as long as it contains a fluorine atom and/or a silicon atom.

Examples of fluorine atom-containing substituents include -ChF2h
z (11 represents an integer from 1 to 12), (CF2),
CF2H (j represents an integer of 1 to 11).

Examples of silicon atom-containing substituents include RI
R7-3i-R5,-←-5tOi-y Rs (k is 1~
20 R2H.

(represents an integer), borinoxan structure, etc.

However, Ra, Rs, and R6 may be the same or different, and are optionally substituted hydrocarbon groups or -OR. group (Rlo represents the same content as the hydrocarbon group of R1).

R1 is an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group,
Hexyl group, octyl group, denyl group, dodecyl group, hexenyl group, 2-chloro111ethyl group, 2-promoedyl group, 2,2゜2-1~lifluoroedyl group, 2-cyanoethyl group, 3.3.3-tri Fluoropropyl group, 2-methoxyfer group, 3-bromopropyl group, 2-methquine carbonyl edyl group, 2,2,2.2'.

2',2'-hexafluoroisopropyl group, etc.), substituted monoalkenyl group having 4 to 18 carbon atoms (e.g., 2
-Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, I-hexenyl group, 2-hexenyl group, 4-
methyl-2-hexenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., Hensyl group,
Phenethyl group, 3-phenylzo-U-pyl group, naphdylmethyl group, 2-naphdylezyl group, chlorophenyl group, bromopencyl group, methylbenzyl group, edylhenzyl group,
MeI xybenzyl group, dimethylbenzyl group, Tsume1-
quinbenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexyl group, 2-cyclopendylezyl group, etc.), or 6 to 8 carbon atoms]2 an optionally substituted aromatic group (e.g.
Phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, ocdylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromo Phenyl group, cyanophenyl group, acedelphenyl group, methoxycarbonylphenyl group, hydroxycarbonylphenyl group, butkin sulfonylphenyl group, acetylphenyl group
- amidophenyl group, propioamidophenyl group, todecoylamitophenyl group, etc.).

In the -OR,0 group, R10 represents the same content as the hydrocarbon group of R1 in "1.

R7, R@, Rs may be the same or different, J:<,
R1°R5, represents the same content as RG.

Next, specific examples of repeating monomers having a substituent containing a hydrogen atom and/or a silicon atom as described above are shown below. ).

(b-1) (b-2) CH2=C C00CH2CH)C, F2h I+-(b-3) ■ CH2=C C00C82CH2(CF, ), ICFJj: 1-1
Integer of 1 (b-11) " (b-5) (b-6) (b-7) b " (ba-a) □ C1(2=C □ Coo(CH2)+NH3ChRf Rf: CH2ChFzh, -T( -CH2h(℃F
2) +CF2H(a-9) 02Rf (b-To) CH2=C □ C0NHCOORf (b-I+) ■ CH2=C ■ C00CH2CF 2 CF 2 H (b-12) CH2=C ■ Coo(CH2)O-Rf (b-13) CH2=COCH3 Coo(CH2)-3i-OCH3 CH3 (b-sodium) □ CH2=CCH) ] I C0O(CH2)20-3i-CH.

Hz (b-+5) CH2=CCgHs COO3i-C,H9 6H5 (b-16) □ CH2=CR1' 1] Coo(CH2)20si-R2' ■ R1'R,',R2',R,': Carbon Alkyl group of numbers 1 to 12 (b-+7) ■ CH2=CCHff C00(CH2hO-3i-CH2CH2CF3□ CH3 (b-18) CH2=CCH3CHy l 1 ] C00(CH2)20-3i壬O3i→, CH3C1b
cHiq: an integer from 1 to 20 (b-19) CH7=CCH.

COO(CH2ho-3i-←CH2→,C0OR,'
■ CHl (b-20) (b-21) b CH2=CR1'R3' (b-22) CH2=CR1'COOCH25i-R2'R+' (b-23) (b-211) CH2=CORI' OR 'COOCH2-3j-0-3i-OR"0R" OR
'CH3R": -3i-CH3CH.

(b-25) 噸CH2=C0RI'COO(CH2h-3i-OR2'OR3' (b-26) 1l CHxCH3CH3 r: 0 or an integer from 1 to 20 (b-27) CH2=C CH20COChF+hv+ (b-28) □ CH2=C C00CH2CF2HCF 3 (b-29) The monofunctional polymer CM) of the present invention has the general formula (■) described above.
The polymerizable double bond group represented by is directly bonded to one end of the main chain of a polymer containing at least a repeating unit having a substituent containing a fluorine atom and/or a silicon atom, or an arbitrary linking group It is combined with . Specifically, the connecting group is a divalent organic residue, such as (1) 10-, -3-, -N-, -3O-, -3O, and the like.

COO-1-OCO-, -CONHCO-, -NIIC
ONH-.

d2d,, d.

Consisting of a divalent aliphatic group, a divalent aromatic group, or a combination of these divalent residues, which may have a bonding group selected from -CON-, -3O2N-, and -Si- represents an organic residue.

Here, d1 to d5 represent the same content as R1 in formula (III).

As the divalent aliphatic group, for example, −+ c −)−, −(−c=c−, −←CyoC−
→-2□ [eI and C2 may be the same or different, and each is a hydrogen atom, a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.) or an alkyl group having 1 to 12 carbon atoms (e.g. methyl group, ethyl group, propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, denyl group, etc.). Q is-
Represents O-, -S= or -NR,, -, where NR, is an alkyl group having 1 to 4 carbon atoms, -CI'hCff or -C1h
Br].

Examples of divalent aromatic groups include benzene ring groups, naphthalene ring groups, and 5- or 6-membered heterocyclic groups (hetero atoms constituting the heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom). containing at least one).

These aromatic groups may have a substituent, such as a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (e.g. methyl group, ethyl group, propyl group). , butyl group, hexyl group, octyl group, etc.), and alkoxy groups having 1 to 6 carbon atoms (eg, methquine group, ethoxy group, propioquine group, butoxy group, etc.).

Examples of the heterocyclic group include furan ring, diophene ring, pyridine ring, pyracine ring, piperazine ring, tetrahydrofuran ring, pyrrole ring, tetrahydropyran ring, 1.3-
Examples include oxazoline rings.

General formula (1) of the -functional polymer [M] as described above
Specific examples of the moiety composed of the polymerizable double bond group represented by and the organic residue linked to the polymerizable double bond group include, but are not limited to, the following. However, on each side below, Pl is -H, -CH3, -CH2C
OOCH+.

-CI, -Br or -CN, P2 is -H or -C
I(.

, X represents -c6 or -Br, n represents an integer of 2 to 12, and m represents an integer of 1 to 4.

(C-1) eI CHH= C-COO(CH2→T〇-CH=CH-0
(CH7)7-0- (C-5) C1h = C-COO, (CH2→, NH-(C-6
) Naw CH2=C-C00CHICHCH20-Day CH (C-7) eI ■ CH2=C-C0NH(CH2→□ CH (C-9) P.

CH2=C-C00CH2C1(CH70-CH (C-10) (c-13) Pl □ C1(2: c-coo (CH2e-r-(c-Il
l) H CH2=C-CONH (CI'h).

(c15) CH2= C-C0NHCOO(CH2)-T-(c-
16) CH2= C-C0NHC:ONH(CH2→□(C-
20) CI(2=C-COOCHO CH2CH2X (C-21) ■ CH3=C COO(CH2) 3 NHCOO(C)H2→7(C
-22) ■ CH2=C-Coo(CH7CH7OhiCo(CH2U.

CH.

CI(,=C)I
CL) I C0OCH2CHCH200C(CH2)-r-C-0
HCN (C-23) P2, ■ (C-25) CH2=CH-CH20CO(CH2), S
-(C-26)
CH3I CH2=CH-CH2COO(CH2=CH■ CN (C-27)
CH3CH, diCH-CH2CHCH200C(C
)+2→, -C-OHCN (C-28) □ (C-29) (C-30) In the sum total of repeating units of the monofunctional polymer [M] of the present invention, fluorine atoms and/or silicon atoms are The content of repeating units having substituents is preferably 40% by weight or more, more preferably 60 to 1% by weight of the total content.
00% by weight.

When the component 1 of the present invention is less than 40% by weight of the total,
When the resin particles are dispersed in the photoconductive layer, the effect of concentrating them on the surface area is reduced, and as a result, the effect of water retention as a printing original plate is weakened.

The monofunctional polymer [M] of the present invention can be produced by a conventionally known synthesis method. For example, (1) monofunctional polymers are produced by reacting various reagents at the ends of living polymers obtained by anionic or cationic polymerization.
A method using an ionic polymerization method to obtain M]; A radical polymerization method in which a monofunctional polymer [M] is obtained by reacting a polymer with a terminal reactive group bonded with various reagents, and a polymer obtained by a 0-fold (=1 addition or polycondensation reaction) Examples include a method using a polycondensation method in which a polymerizable double bond group is introduced in the same manner as the Rancal polymerization method described in 1.

Specifically, P. Dreyruss & R.P.
Quirk.

Encycle, Polym, Sci, Eng,...
7.551 (1987), P. F. Rempp.
, E., Franta, Adv, Pol. y
m, Sci.

58, + (+9811), V, Percec
, Appl, Poly, Sci.

285 + 95 (19811), R, Asami
, M., Takari.

Makromol, Chem, 5upp1. , 12
, 163 (1985), P. Rempp, et.
al, Makromol, Chem, 5up
p1. .

3 (+9811), Yuji Kawa, Chemical Industry, Principal.

56 (1,987), Yuya Yamashita, Polymer, Lord 988
(1982), Shibe Kobayashi, Polymers, 30°625 (1
9B+), Toshinobu Higashimura 9 Japan Adhesive Association Journal, 18,536
(1982), Hiroshi Ito-2 Polymer Processing, 35, 262
(+986), Takashi Azuma, Takashi Tsuda 2 functional materials + 19
It can be synthesized according to the methods described in reviews such as 87+ No., IO+ 5, and the literature/patents cited therein.

Furthermore, when the dispersed resin particles of the present invention have a network structure, a monofunctional monomer (Δ) containing a functional group of formula (I) and/or (1) described in "1" is added as a polymer component. The polymers of the polymer [abbreviated as polymer component (Δ)] are bridged to form a high-order network structure.

That is, the dispersed resin particles of the present invention have a polymer component (Δ)
A non-aqueous latex consisting of a portion insoluble in a non-aqueous dispersion solvent and a monofunctional polymer CM) that is soluble in the solvent, and when it has a network structure, the solvent The molecules of the polymer component (A) forming unnecessary portions are bridged.

As a result, the network resin particles become poorly soluble or insoluble in water. Specifically, the solubility of the resin in water is 80% by weight or less, preferably 50% by weight or less.

The crosslinking of the present invention can be carried out by conventionally known crosslinking methods. That is, (1) a method of crosslinking a polymer containing the polymer component (A) with various crosslinking agents or curing agents; (2) a method of carrying out a polymerization reaction by containing at least a monomer corresponding to the polymer component (A); A method of forming a network structure between molecules by coexisting a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups, and This can be carried out by a method such as a method in which a polymer containing a component containing a reactive group is crosslinked by a polymerization reaction or a polymer reaction.

Examples of the crosslinking agent used in the method (2) above include compounds commonly used as crosslinking agents.

Specifically, the compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), "Polymer Data Handbook Basic Edition" edited by The Society of Polymer Science and Technology, Baifukan (1986), etc. Can be used.

For example, organic silane compounds (e.g., hinyltrimethine silane, hinyltributoxysilane, γ-glycidoxypropyltrimethoxine lanrananate-based compounds (e.g., toluylene diisocyanate, diphenylmethane cyisocyanate-1-, l. Phenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate-1.
isopho, rhondiisonanate, polymeric polyisocyanate, etc.), polyol compounds (e.g., 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-1-limethylolpropane, etc.) , polyamine compounds (e.g., ethylenecyamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine,
N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds and epoxy resins (for example, Hiroshi Kakiuchi (ed.) [New Epoxy Resin J Shokodo (1985)
), compounds described in "Epoxy Resin" edited by Kuniyuki Hashimoto, Nikkan Kogyo Shinbunsha (published in 1969), melamine resin (for example, "Uria Melamine Resin J Nikkan Kogyo Shinbunsha", edited by Miwa Be, Hideo Matsunaga), etc. (published in 1969), poly(meth)acrylate compounds (
Examples include compounds described in Shin Okawara, Takeo Saegusa, and Toshinobu Higashimura, "Oligomers," Kodansha (published in 1976), Eizo Omori, "Functional Acrylic Resins", Technosystem (published in 1985), etc. Polyethylene glycol diacrylate-1, neopendyl glycol diacrylate-1, 1,6-hexylene diol diacrylate-1, trimedylolpropane triacrylate],
, pentaerythritol polyacrylate, hisphenol A-nglycidyl ether diacrylate, oligoester acrylate, and methacrylate-I forms thereof.

In addition, a polyfunctional monomer containing two or more polymerizable functional groups (also referred to as polyfunctional monomer (D)) or a polymerizable functional group of a polyfunctional oligomer that is made to coexist by the method (2) above may be used. Specifically, CH2= CH-CH2-, CH2= CH-C-
0 −, CH2= CH −, CH3 CH3
0 CH2=C-C-0-, CH=CH-C-0-, C
H,,, =CH-CONH-, CH3CH
) CH2=C-CONH-, CH=CH-CONH-
, o CH) O II I II CH2=CH-0-C- , CH2=C-0-C-
, CH,=CH-CH2-0-C-, CH2-C
H-NHCCI-, CH2= CH-CH2-NHCO
-, CH2= CH-SO2-, CH2,=CH-CO
-, CH2=CH-0-, CH2=CH-S-
etc. can be mentioned. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

Specific examples of monomers having two or more polymerizable functional groups include, for example, monomers or oligomers having the same polymerizable functional groups, such as styrene derivative polyhydric alcohols such as divinylbenzene and l-divinylbenzene. (For example, ethylene glycol, diethlene glycol, triethylene glycol, polyethylene glycol #200, $110
0, #600, 1,3-butanediol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.), or polyhydroxyphenols (e.g. hydroquinone, resorcinol, catechol and their esters of methacrylic acid, acrylic acid or crotonic acid (derivatives), vinyl ethers or allyl ethers, dibasic acids (e.g. malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid) etc.) vinyl esters,
Allyl esters, vinylamides or allylamides: polyamines (e.g. ethylenecyamine, 1°3-propylene diamine, 1,4-butylene diamine, etc.) and carboxylic acids containing vinyl groups (e.g. methacrylic acid, acrylic acid, crotonic acid, Examples include condensates with allyl acetic acid, etc.).

In addition, 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, methacryloylpropionic acid, acryloylpropionic acid, itaconyloyl acetic acid, itaconyloylpropionic acid, carboxylic acid anhydride, etc.) and a reactant of alcohol or amine (such as allyloxycarbonylpropionic acid) , allyloxinecarponylacetic acid, 2-allyloxycarboni6furbenzoic acid, allylaminocarbonylpropionic acid, etc.)
Ester derivatives or amyl derivatives containing vinyl groups such as vinyl methacrylate, vinyl acrylate, etc.
Vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate,
Vinyl methacryloylpropionate, allyl methacryloylpropionate, vinyloxycarbonyl methyl methacrylate, hinyloxycarbonyl acrylate oxycarbonyl ethylene ester, N-allylacrylamide, N-allylmethacrylamide, N-allylitaconamide, Allylamide methacryloylpropionate (1-aminoalcohol, etc.) or amino alcohols (e.g., aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminoethanol, 2-aminobutanol, etc.) and a vinyl group-containing carboxylic acid. Examples include condensates.

The monomer or oligomer having two or more polymerizable functional groups used in the present invention is 10 mol% or less based on the total amount of monomer (A) and other monomers coexisting with (A). ,
Preferably, it is used in an amount of 5 mol % or less to polymerize and form a resin.

Furthermore, when forming chemical bonds and bridging between polymers by the reaction of reactive groups between polymers in method ① above, it can be carried out in the same manner as the reaction of ordinary organic low-molecular compounds. can. Specifically, it is described in detail in books by Yoshiyu Iwakura, Keisuke Kurita, "Reactive Polymers," Kodansha (published in 1977), Ryohei Oda, "Polymer Fine Chemicals," Kodansha (published in 1976), and others. For example, a polymer reaction using a combination of a functional group of the Δ group (hydrophilic group polymer component) and a functional group of the B group (polymer containing a component containing a reactive group) in Table 1 below is usually well conducted. This is a known method.

In addition, R and R' in Table 1 are hydrogen atoms or hydrocarbon groups,
It represents the same content as r5+rg in the above formula (IV).

Table 1 As described above, the network-dispersed resin particles of the present invention contain a polymer component containing a polar group, a polymer component containing a repeating unit having a fluorine atom and/or a silicon atom-containing substituent, and These are polymer particles that have a structure in which molecular chains are highly cross-linked.

In dispersion polymerization, monodisperse particles with a uniform particle size can be obtained, and microparticles of 0.5 μm or less can be easily obtained, so polyfunctional monomers are used as a method for forming a network structure. Method ① using .

As the non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles, any organic solvent with an Sli point of 200°C or less may be used, and it may be used alone or in a mixture of two or more. Good too.

Specific examples of this organic solvent include alcohols such as methanol, ethanol, propatool, butanol, fluorinated alcohol, and pencil alcohol; ketones such as acetone, methyl edyl ketone, cyclohexanone, and diethyl ether; , tetrahydrofuran, ethers such as dioxane, carbonic acid esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, carbon number of hexadi, octane, decane, dodecane, tridecane, cyclohexane, cyclooctane, etc. 6～j4
aliphatic hydrocarbons, benzene, toluene, xylene,
Aromatic hydrocarbons such as chlorohenzene,
Examples include halogenated hydrocarbons such as lido, dichloroethane, tetrachloroethane, chloroporum, methylchloroporum, dichloropropane, and trichloroethane.

However, the present invention is not limited to the examples of compounds described below.

By synthesizing dispersed resin particles using a dispersion polymerization method in these non-aqueous solvent systems, the average particle diameter of the resin particles can easily be 1 μm.
In addition, the particle size distribution is very narrow and monodisperse particles can be obtained.

Specifically, K, E, J, Barrett r Di
spersi, on Polymerizat, ion
in Organic Media J John W
Hey (1975), Koichi Murata, Polymer Processing.

-Otsu J□, 20 (]974), Tsunetaka Matsumoto, Toyokichi Tange 2
Japan Adhesive Association Journal, 183 (1973), Toyokichi Tange 4
Japan Adhesive Association Journal 1↓, 26 (1987), D, J.
Wal, bridge, NATO, Adv, 5tu
rdy, ]: nst, Ser.

E, No. 67, 40 (1,983),
British Patent No. 893429, Do934038 specifications,
U.S. Patent No. 1122397, U.S. Patent No. 39004+2, U.S. Patent No. 46
The method is disclosed in the specifications of JP-A No. 06989, JP-A Nos. 60-179751 and JP-A No. 60-185963, and the like.

The dispersion resin of the present invention comprises a monomer (Δ) and a -functional polymer [
consisting of at least one or more each of M) and, if necessary, a polyfunctional monomer (r)) to form a network structure.
In any case, what is important is that if the resin synthesized from these monomers is insoluble in the non-aqueous solvent, the desired dispersed resin can be obtained. More specifically, for the monomer (A) to be insolubilized, -functional polymer [
M] is preferably used in an amount of 1 to 50% by weight, more preferably 5 to 25% by weight. Further, the molecular weight of the dispersion resin of the present invention is 10'' to 10', preferably 10
″~5X]0′.

In order to produce the dispersed resin particles used in the present invention as described above, the monomer (A), the -functional polymer [M], and the polyfunctional monomer (I)) are generally mixed. The polymerization may be carried out by heating in an aqueous solvent in the presence of a polymerization initiator such as hendyl peroxide, azobisisobutyronitrile, butylridium, or the like.

Specifically, ■monomer (Δ) and -functional polymer [M]
, multisensual! There are two methods: a method of adding a polymerization initiator to a mixed solution of lt-mer (I); It can be manufactured using any method without being limited to.

The total amount of polymerizable compounds is 5 parts by weight per 100 parts by weight of the nonaqueous solvent.
The amount is about 80 parts by weight, preferably 10 to 50 parts by weight.

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

The non-aqueous solvent-based dispersion resin produced according to the present invention as described above becomes fine particles with a uniform particle size distribution.

As the 7-trix resin used in the image-receiving layer of the present invention, any of the various binder resins conventionally known can be used. Typical examples include hinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate-1 copolymer, methacrylate-1 copolymer, acrylate copolymer, and acetic acid. Vinyl copolymers, polyvinyl butyral, alkyd resins, silicone resins, epoxy resins, epoxy ester resins, polyester resins, etc., and water-soluble polymer compounds such as polyvinyl alcohol, modified polyvinyl alcohol, starch, oxidized starch, carboxyl methylcellulose, and - Examples include lokiedyl cellulose, casein, gelatin, polyacrylate, polyvinylpyrrolidone, polyvinyl ether-maleic anhydride copolymer, polyamide, polyacrylamide, and the like.

The molecular weight of the matrix resin provided in the image-receiving layer of the present invention is preferably 103 to 106, more preferably,
5X1. The glass transition point of this resin is preferably -10°C-120°C1, more preferably 0°C to 85°C.

Inorganic pigments are used as other components of the image-receiving layer of the present invention, such as kaolin clay,
Examples include calcium carbonate, silica, titane oxide, zinc oxide, barium sulfate, and alumina.

The ratio of binder resin/pigment in the image-receiving layer varies depending on the type of material and particle size in the case of pigment, but is generally 1/(0.5 to 5), preferably 1/(0.8) by weight. ~2.
5) The level is appropriate.

A crosslinking agent may be added to the fine image-receiving layer in order to further improve the film strength. As a crosslinking agent, commonly used ammonium chloride, organic peroxide, metal soap,
Organic silanes, polyurethane crosslinking agents, epoxy resin hardening agents, etc. can be used. Specifically, Shinzo Yamashita,
Edited by Tosuke Kaneko [Crosslinking Agent Han I Book] Published by Taiseisha (1988)
1 year) etc.

Examples of the support used in the present invention include duplex paper, wet reinforced paper, Prolasdec film such as polyester film, and metal plate such as aluminum plate.

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 barafcoat is provided on the surface of the support opposite to the image-receiving layer for the purpose of preventing curling.
1. A layer (back layer) can be provided.

Here, the intermediate layer is made of acrylic resin, emulsion type resin such as ethylene-butadiene copolymer, methacrylate ester-butadiene copolymer, acrylonitrile-butadiene copolymer, edylene-vinyl acetate copolymer, epoxy resin, polyvinyl butyral, Solvent type resin such as polyvinyl chloride, polyvinyl acetate, etc.: Mainly composed of at least one of the water-soluble resins mentioned above, but an inorganic pigment or a waterproofing agent can be added as necessary.

The structure of the Barafco-1 layer is also almost the same as that of the intermediate layer.

When used as PPC plate-making, in order to further reduce background staining of the printing original plate of the present invention, the volume resistivity of the printing original plate is 1010 to ■011Ω mark.
Furthermore, dielectric agents can be added to the image-receiving layer, the intermediate layer and/or the Barafco-1 layer. The dielectric agent may be inorganic or organic.
a. Salts of monovalent or polyvalent metals such as Li, Mg, Zn, Co, and Ni; organic ones include polymer cations such as polyvinylbenzyltrimethylammonium chlorite and acrylic resin-modified quaternary ammonium salts; Examples include conductive agents and polymeric anionic dielectric agents such as polymeric sulponates. The amount of these conductive agents added is 3 to 40% by weight, preferably 5 to 40% by weight of the amount of binder used in each layer.
It is 20% by weight.

In general, to make the direct drawing type lithographic printing original plate of the present invention, an aqueous solution containing an intermediate layer component, if necessary, is coated on one side of the support and dried to form an intermediate layer, and then an image-receiving layer component is applied. An image-receiving layer is formed by applying and drying an aqueous solution containing Barafco-1, and if necessary, a back coat layer is formed by coating and drying an aqueous solution containing Barafco-1 and surrounding components on the other side. The appropriate amount of each of the image-receiving layer, intermediate layer, and back coat layer is 1 to 30 g/l and 5 to 20 g/l, respectively.

In order to create a printing plate using the direct plate lithographic printing original plate of the present invention, after forming and fixing an image on the direct plate lithographic printing plate having the above-mentioned structure using a known technique, a desensitizing solution is applied. After surface treatment to desensitize the non-image areas, the plate is used as a printing plate for lithographic printing.

The desensitization treatment provided in the present invention is performed by adding a hydrophilic compound containing a substituent that easily reacts nucleophilically to the double bond in the resin particles of the present invention containing a functional group represented by the general formula (1). This can be achieved by treatment with a solution (an aqueous solution or a mixed solution containing a water-soluble organic solvent).

As a hydrophilic compound that causes a nucleophilic substitution reaction on the double bond of the functional group represented by the general formula (I), the nucleophilic constant n [: R, G, Pearson, H.

Sobel, J., Songstad, J.
Amer, Chem, Sac.

A, 319 (1,968)) contains a substituent having a value of 5.5 or more, and in 100 parts by weight of distilled water, 1
Examples include hydrophilic compounds that dissolve in parts by weight or more.

Specific compounds include, for example, hydrazine, hydroxylamine, sulfites (ammonium salts, sodium salts, potassium salts, zinc salts, etc.), diosulfates, etc.
In addition, at least one group selected from a hydroxyl group, a carboxyl group, a sulfo group, a posboxyl group, and an amino group is present in the molecule.
Examples include mercapto compounds, hydrazide compounds, sulfinic acid compounds, primary amine compounds, and secondary amine compounds containing two polar groups.

For example, mercapto compounds include 2-mercaptoethanol, 2-mercaptoedylamine, N-methyl-2-
Mercap I ethylamine, N-(2-hydroxydiyl)2-mercaptoethalamine, thioglycolic acid,
Diolic acid, diozalidylic acid, mercaptohenzenedicarboxylic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethylphosponic acid, mercap1-pensene sulfonic acid, 2-mercaptopropionylaminoacetic acid, 2-
Mercapto-1-aminoacetic acid, 1-mercaptopropionylaminoacetic acid, 1゜2-dimercaptopropionylaminoacetic acid, 2゜3-one hydroxypropylmercaptane, 2-methyl-2-mercapl--]-aminoacetic acid, etc. and 2-hydroxydiylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxypropanesulfinic acid as sulfinic acid compounds.
Hydroxybutanesulfinic acid, calfoquinbenzenesulfinic acid, carfoquinbenzenesulfinic acid, etc.
2-hydrazinoethanesulfonic acid as a humanlant,
4-hydrazinobutanesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzene sulfonic acid, hydranobenzoic acid, hydrazinobenzenedicarboxylic acid, etc.
As a primary or secondary amine compound, for example, N-
(2-hydroxyethyl)amine, N,N-di(2-hydroxyethyl)amine, N,N-di(2-hydroxyethyl)ethylenecyamine, tos(2-hydroxyethyl)ethylenenamine, N-(2.

3-dihydroxypropyl)amine, N. N-shi (2,
3-Shihi I/Roxyprovir) amine, 2-aminopropionic acid, aminebenzoic acid, aminopyrine, aminobenzenedicarboxylic acid, 2-hytroquinedylmorpholine, 2-carboxyethylmorpholine, 3-carpogycypiperane, etc. can be mentioned.

These nucleophilic compounds are used by being included in a desensitizing treatment solution, or are used by being included in a treatment solution for separately treating resin particles.

The amount of the nucleophilic compound present in these treatment solutions is 01 mol/
fl~10 mol/l, preferably 05 mol/fl~5
It is mole/1.

Further, r) I-1 of the treatment liquid is preferably 4 or more.

The treatment conditions were a temperature of 15°C to 60°C and an immersion time of 10°C.
The time period is preferably from seconds to 5 minutes.

The treatment liquid may contain other compounds in addition to the above-mentioned nucleophilic compound and pH adjuster.

For example, add 1 part by weight of a water-soluble organic solvent to 100 parts by weight of water.
It may contain up to 50 parts by weight. Examples of such water-soluble organic solvents include alcohols (methanol,
ethanol, propatool, propargyl alcohol, hemyl alcohol, phenedyl alcohol, etc.), aromatic alcohols, ketones (acetone, methyl ethyl ketone, acetophenone, etc.), ethers (nioxane, etc.)
・Rioxane, tetrahydrofuran, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, butoshi tropyran, etc.), amides (dimethylformamide I, dimethylacetamide, etc.), amino alcohols (monoethanolamine, ethanol, etc.) amine, triethanolamine, etc.), esters (methyl acetate, ethyl acetate, ethyl formate, etc.), and these may be used alone or in combination.

Further, 01 to 20 parts by weight of a surfactant may be contained in 100 parts by weight of water. Examples of the surfactant include conventionally known anionic, cationic, and nonionic surfactants.

For example, Fu Horiguchi "New Surfactants" Sankyo Publishing), (19
Compounds described in "Synthesis of Surfactants and Their Applications" by Ryohei Oda and Hiroshi Teramura (published in 1975), Shin Shoten (published in 1980) can be used.

In addition, antifoaming agents and other various general formulas (
The method for desensitizing the resin particles of the present invention containing functional groups represented by If) is as shown in reaction formula +11 above, after dehydrohalogenation reaction, a nucleophilic The compound is characterized by being made hydrophilic through a nucleophilic reaction.

Since the dehalogenation reaction easily proceeds in a treatment solution with I) H 6 or more, by setting the pII of the etching treatment solution containing at least the above-mentioned nucleophilic compound to 6 or more, Hydrophilization by dehydrohalokenation and nucleophilic reactions is achieved.

More preferably, the pII of the treatment liquid is 8 or more.

Furthermore, after the dehydrohalogenation reaction has proceeded with a solution of pI-(6 or more), there is no problem in desensitizing it with a treatment solution of a hydrophilic group-containing compound that undergoes a nucleophilic reaction. .

〔Example〕

Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto. In addition, below, the monofunctional polymer [M] will be referred to as a macromonomer.

Macromonomer production example 1: [:M-1]2, 2, 2.
A mixed solution of 95 g of 2',2',2'-hexafluoroisopropyl methacrylate l-, 5 g of thioglycolic acid, and 200 g of toluene was heated to 70°C while stirring under a nitrogen stream. Azobisisobutyronitrile (abbreviation A.1.B).

N. )1. Og was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate-h, N+N was added to this reaction solution.
-dimethyldodecylamine1. O g and t-butylhydroquinone 0. Add 5 g and raise the temperature to 1. O 0
The mixture was stirred at ℃ for 12 hours. After cooling, add 2 ml of methanol to this reaction solution. 82 g of white powder was obtained. Polymer CM-1] had a weight average molecular weight (abbreviation Mw) of 4,000.

(M-]] Production example 2 of zo-macromonomer: (M-23 96 g of monomer (Δ-1) with the following structure, 4 g of β-mercaptopropionic acid
1. A mixed solution of 200 g of toluene was heated to a temperature of 7.
Warmed to 0°C. A. 1. B. N. 1,Qg were added and reacted for 8 hours.

The reaction solution was then cooled in a water bath to a temperature of 25°C, and 10g of 2-hydroxyethyl methacrylyl was added to it.
added. cyclohexylcarbonamide (abbreviation)
A mixed solution of 15 g of C,C,), 02 g of 4-(N,N-dimethylamino)pyridine, and 50 g of methylone chloride was added dropwise to the mixture under 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 matter was filtered off, and the filtrate was reprecipitated into n-hegirin 11.

The precipitated viscous material was collected by decantation, dissolved in 100 ml of tetrahydrofuran, and after filtering off insoluble matter again, it was reprecipitated in r)-he4.→non-Il. The polymer obtained by drying the precipitated viscous material had a yield of 160 g and a Mw of 5.
,2X]O''.

(Δ-1) C)h CH2=CCH:1 COO(CH2),03i-CH2C61(s,!H3 (M-2:I CH3) ■ CH2=C C00(CH7)20co(CH2)2S -Kon macromonomer Production Example 3: (M-33 95 g of monomer (Δ-2) having the following structure, 150 g of benzotrifluori I"
A mixed solution of 50 g of ethanol was heated to 75° C. with stirring under a nitrogen stream. 2 g of 4,4'-azohis(4-cyanovaleric acid) (abbreviated as A, C, V) was added and reacted for 8 hours. 1 methanol after cooling! The resulting polymer was dried. Next, 50 g of this polymer and 1.11 g of 2-hydroxyethyl methacrylate were heated to a temperature of 25°C. Add D. to this mixture under stirring. C. C.

15 g, 4-(N,N-dimethylamino)pyricine 0. A mixed solution of 1 g and 30 g of methylene chloride was added to 30
After stirring for 4 hours, add 3 formic acid.
g and stirred for 1 hour. Then, the precipitated insoluble matter was filtered off, and the filtrate was reprecipitated into methanol 800 ml. The precipitate was collected, dissolved in 150 g of penzotrifluori F', and the reprecipitation operation was performed again to obtain 30 g of a viscous substance. The MW of polymer [M-3] is 3. It was 3×10”.

(A-2) HI ■ CH2 =C ■ COOCR2CH2(CF2)2cF2HCM-3) CH3 ■ CH2=C CH3COOCH2C
Production examples 4 to 22 of H20CO(CH2)2C-N macromonomer: CM-4E to CM-
22:1 In Production Example 2, monomer (Δ-1) was replaced with other monomers (monomers corresponding to the polymer component numbers listed in Table-2)
Each macromonomer CMI was produced in the same manner as in Production Example 2, except that CMI was used.

Volume weight is 4X l O' ~ 6X]. O' De Atsulko.

Production examples 23 to 30 of Mac[1 monomer: [M-23] to
[M-3[]] In Macromonomer Production Example 2, 11fr1 body (
Δ-1) and 2-human [1 ginedyl methacrylate
Each macromonomer [M] was replaced with a compound corresponding to each of the polymers in Table 3 below, but in the same manner as above.
was manufactured. Each MWi;l:5XI(]' ~6XIO
” There it was.

Production example of resin particles], :[L-1] 111. of the following structure. A mixed solution of 20 g of the polymer (Δ-1), 5 g of the polymer [M-1] of Production Example 1 of Monomer 1, and 110 g of methyl ethyl chloride was heated in a nitrogen stream.
2,2'-Azohis(isovaleronitrile) (abbreviation A, B).

V, N, ) 0.2 g Processed and reacted for 2 hours.
Sara J: A, B, V.

1 g of N and O were added and reacted for 2 hours. Resin particles C obtained by filtering the obtained dispersion through a 200 metsoko nylon cloth
L-1] is the polymerization rate, O0% and average particle size (measured with Horiba, Ltd. (Japanese made CA PΔ500) 0.257 No T
It was I.

Monomer (Δ-1) C) h □ CH2=C □ C00CHzSOzCH= C) Iz Production example 2 of resin particles: l:L-2:1 -20 g of monomer (A-2) having the structure shown in F, macromonomer
Δ to 1':+ (Commercial product as a macromonomer with a polysilane structure made by Toagosei Co., Ltd.) 5 g 1 A mixed solution of 2 g of methyl ethyl gene and 120 g of methyl ethyl gene. It reacted in the same way. The polymerization rate of the obtained dispersion (1---2) was 100%
The average grain size (Y0) was 30 μm.

Monomer (Δ-2) Production examples 3 to 1.1 of resin particles: CL-3:l to Cl--
11] 20 g of each monomer (Δ) listed in Table 4 below.

A mixed solution of 4 g of macromonomer 1:M) and 150 g of an organic solvent was prepared, and other dispersed resin particles were produced in the same manner as in Production Example 1 of Resin Particles. The polymerization rate for each dispersion is 95-1
00% and the average particle size is 0.1.5~0.30μin
It was within the range of

Production examples 12 to 1.8 of resin particles:' [L-1,2]
~CL-1, 8] As shown in Table 5 below, resin particles were produced in the same manner as in Resin Particle Production Example 1 using each of the monomer (A), the crosslinking monomer, and the macromonomer. . The polymerization rate of each particle is 95
~100%, and the average particle size was 025-0.35 μm.

Example 1 Resin particles CL-[ ] 4g (as solid content) and resin (
T3-1] Methyl methacrylate-1/acrylic acid-
99/1. (ffl amount ratio) Weight average molecule M 4500
A mixture of 30 g of copolymer No. 0, long zinc oxide, and 300 g of toluene was dispersed in a homogenizer (manufactured by Nippon Seiki) for 10 minutes at a rotational speed of 6X]0" r, p, m. This dispersion is then applied to the intermediate layer of a support having a back layer on one side of double-sided paper and an intermediate layer on the other side.
-, drying:] It was coated with a wire bar so that the adhesion was 18 g/m2, and dried at 100°C for 1 minute to prepare a lithographic printing original plate.

Next, a plate is made using a commercially available PPC, and the obtained original plate is used as an ELP
- Using Fuji Photo Film (zinc oxide desensitizing solution for legs), desensitize it by passing it through an edging machine once, then apply the processing solution prepared with the following recipe (
E-1) was immersed in this solution for 3 minutes and then washed with water.

Treatment liquid (E-1,) This was dissolved in distilled water to bring the total amount to 10β, and then adjusted to pH 1.5 with potassium hydroxide.

The density of the image area of the obtained original plate was 10 or higher, there was no blurring in the non-image area, and the image area (11) was clear. The prints were printed on high-quality paper.Even after 3,000 copies were printed, there were no problems with background stains in the non-image areas of the prints or in the image quality of the image areas.

Examples 2 to 9 Each lithographic plate was prepared in the same manner as in Example 1 except that the resin particles shown in Table 6 below were used instead of the resin particles CI, -1 of the present invention. An original printing plate was prepared.

An original plate was prepared by operating the front plate in the same manner as in Example 1. The density of the obtained offset printing master plate 1 was 12.
Above all, the image quality was clear.

Furthermore, when I applied the edging process and printed it on a printing machine,
After printing 3,000 sheets, there is no fog in the non-image area of the printed matter.
The images were also clear.

Example 10 Resin particles (1, -12: 14 g (as solid content), binder resin with the following structure [:B-2] 29 g, zinc oxide 50
A mixture of 200 g of toluene and 200 g of toluene was dispersed in a homogenizer for 10 minutes at a rotation speed of 6
Dispersion was carried out for 1 minute at rotational speeds of ``r, p, m.'' The dispersion thus obtained was coated on a support under the same conditions as in Example 1, and then dried at 100 ° C. for 30 seconds. Another 1" 0°C
The mixture was heated for 1 hour to prepare a lithographic printing original plate.

Binder resin CB-2) CH3CH.

(-CH2-C)-rr(CH2CH)7-v+CH2
-Ci]--HCH2-C+T]11 COOCII, C00CH3COOCI++CHC
H2C0OH\1Hen 5xlO'' (weight ratio) This was made into a plate using the same device as in Example 1, then subjected to an edging treatment and printed on a printing press.The density of the master plate for offset printing obtained after making the plate was 10. Above all, the image quality was clear.

Furthermore, the image quality of the printed matter after printing 4000 sheets was a clear image without blurring.

Example 11 Resin particles (L-8) 4g (as solid content), resin with the following structure [:B-3'l 30g, zinc oxide 80g and 1
- A mixture of 50 g of toluene was dispersed in a ball mill for 15 hours. Next, 4 g of hekizamide diisocyanate was added to this dispersion, and the mixture was further dispersed in a ball mill for 10 minutes to form a back layer on one side of the double-sided paper and an intermediate layer on the other side. Dry on the intermediate layer of the support (71 coat weight is 2)
, 5 g/m 2 using a wire bar, and dried at 100° C. for 90 minutes to prepare a lithographic printing original plate.

Resin CB-3:] This original plate was treated with a desensitizing treatment solution [E manufactured by Fuji Photo Film ■].
Process it by passing it through the edging processor once with L P-E
After soaking for a minute, it was washed with water.

Treatment liquid (E-2) This was dissolved in distilled water, and the total amount was added to 1. After the OR, the pH was adjusted to 10.5 with potassium hydroxide.

The contact angle of the non-image area of the obtained printing plate with distilled water is 1
It was sufficiently hydrophilized at temperatures below 0°.

Next, after making a plate in the same manner as in Example I, the plate was subjected to the desensitizing treatment described in Section 2 and printed. Even after 3,000 copies were printed, there were no problems with scumming in the non-image areas or image quality in the image areas of the printed matter.

Examples 12 to 16 The following compounds were used in place of hex->nomedylene soocyanate used in Example II, and
A lithographic printing original plate was prepared in the same manner as in Example 1.

Table 7 This plate was made using the same device as in Example 1, then subjected to an edging process and printed using a printing press. The density of the master plate for offset printing obtained after plate making was 10 or more, and the image quality was clear.

Furthermore, the image quality of the printed matter after printing 3000 sheets was a clear image without blurring.

Examples 16 to 25 The same procedure as in Example 10 was used except that 4 g (as solid content) of the resin particles [L] shown in Table 8 below was used instead of 4 g of resin particles 1: L-12 in Example 10. , each lithographic printing original plate was prepared.

Table 8 When printing original plates were prepared and printed in the same manner as in Example 10, no problem occurred in the background smudges in the non-image areas of the printed matter and the image quality in the image areas even after 3000 copies were printed.

Examples 26 to 37 Using each of the photosensitive materials prepared in Examples 1 to 25, the edging process was performed as described below to prepare a master plate 1 for offset printing.

05 mol of nucleophilic compound shown in Table 9 below, 100 g of organic solvent
Distilled water was added to IOg and Newcoal 84NS (manufactured by Nippon Nyukazai ■) to adjust the pH to 11, and the pH of each mixture was adjusted to 10.5.
Adjusted to. Each photosensitive material was placed in the processing solution described above at 30℃ for 2 hours.
Soaked for minutes.

The resulting plate was printed under the same printing conditions as Example I.

(Hereinafter, blank spaces) Each of the materials thus obtained was sufficiently hydrophilic, with a contact angle with water in the non-image area of 10° or less. Furthermore, when printing was performed in the same manner as in Example 1, the number of printed sheets was 3000.
The print quality of the printed matter was clear and good, with no blurring.

〔Effect of the invention〕

According to the present invention, it is possible to obtain a direct-drawing lithographic printing original plate in which the occurrence of scumming is well suppressed and also has good printing durability.

Claims (2)

[Claims] (1) A direct-printing lithographic printing original plate having an image-receiving layer on a support, characterized in that the image-receiving layer contains at least one of the following non-aqueous solvent-based dispersed resin particles. Original plate for lithographic printing. Non-aqueous solvent-based dispersed resin particles: particles containing a functional group represented by the following general formula (I) and/or general formula (II) in a non-aqueous solvent, and which are soluble in the non-aqueous solvent but do not polymerize. The monofunctional monomer (A) that is rendered insolubilized by the above-mentioned method, and the following general compounds are added only to one end of the main chain of a polymer comprising at least a repeating unit containing a substituent containing a silicon atom and/or a fluorine atom. Copolymer resin particles obtained by carrying out a dispersion polymerization reaction with a monofunctional polymer [M] formed by bonding a polymerizable double bond group represented by formula (III). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in the above formula (I) or (II), -W_1-, -W_2 - is respectively -SO_2-, -C
Represents O- or -OOC-, n_1 and n_2 each represent 0 or 1, and X represents a halogen atom] General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, the above formula (III) , V_0 is -O-,
-COO-, -OCO-, -CH_2OCO--CH_
2COO-, -SO_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), a_1 and a_2 may be the same or different from each other. , hydrogen atom, halogen atom, cyano group, hydrocarbon group, -COO-R_2 or -COO via a hydrocarbon group
-R_2 (R_2 represents a hydrogen atom or an optionally substituted hydrocarbon group)] (2) In the non-aqueous solvent-based dispersed resin particles, the polymer component having a functional group represented by the general formula (I) and/or the general formula (II) has a crosslinked structure ( 1) The original plate for direct drawing type lithographic printing described above.