JPH04201387A - Direct-type original plate for lithographic printing - Google Patents

Abstract

PURPOSE:To improve an adhesion of oil ink on an image part with an image receiving layer by a method wherein at least one kind of specific nonaqueous solvent dispersion resin particle is incorporated in the image receiving layer. CONSTITUTION:At least one kind of the following nonaqueous solvent dispersion resin particle is incorporated in an image receiving layer: the nonaqueous solvent dispersion resin particle is obtained by the dispersion polymerization reaction of a monofunctional monomer with a monofunctional polymer in a nonaqueous solvent. The former is obtained by incorporating at least one kind polar group selected out of cyclic anhydride-containing group, such as carboxyl group, and nitrogen-containing heterocyclic group, which is soluble in a nonaqueous solvent but becomes insoluble when being polymerized. The latter is obtained by bonding a polymerizable double-bond group shown by a formula I only to one top end of a main chain of a polymer obtained by containing at least a repeating unit containing silicon- and/or fluorine-containing substituent. In the formula, Vo is -O-, -CONHCONH-, or the like; and a1 and a2 may be the same or different and represent hydrocarbon radical with hydrogen atom.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a lithographic printing original plate, and more particularly to a drawing-type 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,
In general, a method is adopted in which the image is drawn by hand with oil-based ink on the image-receiving layer, or by printing using a typewriter, an inkjet method, or a transfer type heat-sensitive method. others,
A method of transferring and fixing a toner image formed on a photoreceptor to an image-receiving layer through charging, exposure, and development steps using a plain paper electrophotographic copier (PPC) 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 made of a water-soluble resin such as PVA and starch, a water-dispersible resin such as a synthetic resin emulsion, and a pigment. The surface layer is made of a pigment, a water-soluble resin, and a water-resistant agent.

A typical example of such a direct drawing type lithographic printing original plate is as described in U.S. Pat.
It is composed mainly of an inorganic pigment such as calcium carbonate and a water resistance agent such as an initial condensate of melamine/formaldehyde resin.

[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, Although the printing durability is improved, the hydrophilicity is decreased and printing stains occur, and on the other hand, when the hydrophilicity is improved, the water resistance is deteriorated and the printing durability is decreased. Particularly 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 both reduced printing durability and printing stains, which is a major drawback.

Furthermore, lithographic printing plates are used to draw oil-based inks as image areas on the image-receiving layer, and if the adhesion between the image-receiving layer and the oil-based ink is not good, even if the non-image areas have sufficient hydrophilicity, Even if such printing stains do not occur, there is a problem in that oil-based ink in the image area is missing during printing, resulting in a decrease in printing durability.

The present invention is intended to improve 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 has excellent desensitization properties and does not cause not only uniform background smudge over the entire surface but also dotted background smear as an offset original plate.

The 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 the hydrophilicity of the non-image area sufficiently even when the number of prints increases, so that oil stains do not occur. An object of the present invention is to provide a direct-drawing type lithographic printing original plate having high printing durability.

[Means to solve the problem]

The present invention achieves the above-mentioned object by providing a direct-drawing lithographic printing original plate having an image-receiving layer on a support, in which the image-receiving layer contains at least one kind of non-aqueous solvent-based dispersed resin particles. This can be achieved by using a direct-printing type lithographic printing original plate that is characterized by the following.

Non-aqueous solvent-based dispersed resin particles: Carboxyl group, sulfo group, sulfino group, phosphono) l H (R, o are carbonized) that are soluble in the non-aqueous solvent but become insolubilized by polymerization. (represents a hydrogen group)], contains at least one polar group selected from a hydroxyl group, a formyl group, an amino group, a cyano group, an amino group, a cyclic acid anhydride-containing group, and a nitrogen atom-containing heterogroup. The monofunctional monomer (A) formed by the following general formula ( A monofunctional polymer formed by bonding a polymerizable double bond group represented by I) [
Copolymer resin particles obtained by polymerizing M].

General formula (1) % formula % [In general formula (I), Vo is -o-, -coo-1
-OCO-, -CH2CICD-, -C112C[][
l-, -3O2-, or -CONHCONH-, where R2 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), al+ R2 may be the same or different from each other, and may be a hydrogen atom, a halogen via an atom, a cyano group, a hydrocarbon group, -COO-R, or a hydrocarbon group (R.

represents a hydrogen atom or a hydrocarbon group which may be substituted] Furthermore, in the present invention, the non-aqueous solvent-based dispersed resin particles may have a higher-order network structure.

[Effect]

The present invention is characterized in that the image-receiving layer of a direct plate lithographic printing original plate contains the above-mentioned non-aqueous solvent-based dispersed resin particles (hereinafter simply referred to as resin particles). ) is a polymer component that contains at least one of the above specific polar groups and becomes insoluble in the non-aqueous solvent after polymerization, and a repeating unit that contains at least a fluorine atom and/or a silicon atom as a substituent. It is characterized in that it is chemically bonded to a polymer component that becomes soluble in the non-aqueous solvent even after polymerization. That is, the resin particles are composed of a portion insoluble in a non-aqueous dispersion solvent composed of a polar group-containing polymer component (A), and a monofunctional polymer CM that is soluble in the solvent. The molecular weight of the dispersion resin is 104 to 106, preferably 104 to 5X.
10'.

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

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

Therefore, in the drawing original plate of the present invention containing the resin particles in the image-receiving layer, when drawing an oil-based ink or the like on the image area and the image-receiving layer, the lipophilic group in the resin particles is This action improves the adhesion between the receiving layer and oil-based ink, improving printing durability, while in non-image areas, the resin particles quickly become hydrophilic to desensitizing liquid and soaking water. Therefore, it is clearly distinguished from the lipophilicity of the image area, and printing ink does not adhere to non-image areas during printing.

Then, it has an image-receiving layer in which such hydrophilic resin particles are dispersed in a Trix binder resin, and the non-image area is treated with a desensitizing liquid to make the surface hydrophilic, allowing direct drawing type lithographic printing. In a printing original plate used as a printing original plate, known hydrophilic resin particles exist uniformly dispersed 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 comes to be concentrated on the surface of the image-receiving layer, which is the air interface (highly lipophilic). Therefore, a smaller amount (50% compared to known lignophilic resin particle technology)
By simply dispersing the amount (up to 10% usage amount), the water retention property of the non-image area can be dramatically improved.

In addition, a hydrophobic (oleophilic) polymer component is bonded to the resin particles, and this hydrophobic portion interacts with the binder resin, which is the matrix of the image-receiving layer, resulting in the anchoring effect of this portion. Therefore, even if it exhibits hydrophilicity, it will not be eluted by soaking water during printing, and good printing characteristics can be maintained even if a large number of sheets are printed.

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, the resin particles exhibit water swelling property, and the water retention property becomes even better. 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 poorly soluble 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, and that they are concentrated near the air interface.

As a result, the drawing original plate of the present invention forms a faithful image area and a non-image area, and provides a high-quality printed image free from scumming.

Furthermore, since the resin particles are fixed by the binder resin, they do not peel off during various processing steps, and since the binder resin also provides a protective effect, the printing durability is excellent.

Furthermore, due to the hydrophilic nature of the specific polar groups of the resin particles, there is a concern that the resin particles may flow out due to dampening water or the like during printing, but such concerns can be resolved by crosslinking at least a portion of the resin particles.

As described above, the direct-drawing type lithographic printing original plate according to the present invention has the advantage that it does not cause background smudge because of its good hydrophilicity in the non-image area, and also has excellent printing durability.

The resin particles will be further explained below.

The dispersed resin of the resin particles of the present invention consists of at least one type each of the monomer (A) and the -functional polymer [M],
When forming a network structure, polyfunctional monomers (D) to be described later are allowed to coexist as necessary; in any case, what is important is that the resin synthesized from these monomers is If it is insoluble in the solvent, a desired dispersed resin can be obtained. More specifically, it is preferable to use the -functional polymer [M] in an amount of 1 to 50% by weight, more preferably 5 to 25% by weight, based on the monomer (A) to be insolubilized.

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 40% by weight is left undropped, when the resin particles are dispersed in the surface layer, the effect of concentrating them on the surface portion will be reduced, and as a result, the effect of improving water retention as a printing original plate will be weakened.

The wood-philicity 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 shows 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.
If it is larger than 0 μm, the smoothness of the surface layer decreases, causing a decrease in film strength or toner image strength. On the other hand, if the particle size is smaller than 0.05 μm, the particle size resembles that of molecular dispersion, and the effect of particles for improving water retention 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 particle diameter of the polymer latex particles can be easily reduced to 1 μm.
m or less, the particle size distribution is very narrow, and monodisperse particles can be obtained.

In the present invention, the resin particles (including network 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 amount of water absorbed by the entire image-receiving layer will increase and the support 0.5 parts by weight per 100 parts by weight of the matrix resin of the image-receiving layer, as this may cause a decrease in adhesion to the body.
It is preferred to use it in an amount of ~60% by weight, preferably 5-40% by weight.

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) has -CD□)l in its molecular structure.
, -3O,H, -PO,lH,, -8O2H, -OH
, -CN, -CHD, -CONH2, V containing at least one polar group selected from a hydrate-containing group and a nitrogen atom-containing heterocyclic group.

In the above polar group, Ro is an optionally substituted hydrocarbon group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-70 loethyl group, 3-chloropropyl group, 3-methoxypropyl group, 2-methoxybutyl group, benzyl group, phenyl group, propenyl group, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group) or -RIO group ( R,,l represent the same content as the hydrocarbon group of R8).

R11 and R12 may each be the same or different, and each represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 6 carbon atoms (
Specifically, it represents a hydrocarbon group with the same content as R)
represents. However, the total number of carbon atoms in R1+ and RI2 is 8
Represents something within the range.

More preferably, the total number of carbon atoms in R11 and R1□ is 4 or less.

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

Examples of aliphatic dicarboxylic anhydrides include succinic anhydride ring, glutaconic anhydride groove, maleic anhydride ring, cyclopentane-1,2-dicarboxylic anhydride ring, and cyclohexane-1,2-dicarboxylic acid ring. Examples include anhydride ring, cyclohexene-1゜2-dicarboxylic anhydride ring, 2,3-bicyclo[:2.2.2]octanedicarboxylic anhydride ring, etc. A halogen atom such as an atom, an alkyl group such as a methyl group, an ethyl group, a butyl group, a hexyl group, etc. may be substituted.

Examples of aromatic dicarboxylic anhydrides include phthalic anhydride rings, naphthalene-dicarboxylic anhydride rings, pyridine-dicarboxylic anhydride rings, thiophene-dicarboxylic anhydride rings, etc. is, for example, a halogen atom such as a chlorine atom or 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 (the alkoxy group includes, for example, (methoxy group, ethoxy group, etc.) may be substituted.

The above-mentioned complex groove containing at least one nitrogen atom preferably includes a 4- to 6-membered complex, such as a pyridine ring, a piperidine ring, a pyrrole ring,
imidazole ring, pyrazine ring, pyrrolidine ring, pyrroline ring, imidacilline ring, pyrazolidine ring, piperazine ring,
Examples include morpholine ring and pyrrolidone ring.

These heterocycles may contain substituents, such as halogen atoms (fluorine atoms, chlorine atoms,
bromine atom, etc.), an optionally substituted hydrocarbon group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 24
Droxyethyl group, 2-cyanoethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-carboxyethyl group, carboxymethyl group, 3
-Sulfopropyl group, 4-sulfobutyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-methanesulfonylethyl group, benzyl group, carboxybenzyl group, carboxymethylbenzyl group, phenyl group, carboxyphenyl group, sulfophenyl group, methanesulfonylphenyl group, ethanesulfonylphenyl group, carboxymethylphenyl group, methoxyphenyl group, chlorophenyl group, etc.), -OR,, (R, 3 may be substituted with the above carbon number 1 to 8) represents the same content as a hydrocarbon group) or -COOR,, group (R14 is R11
(representing the same content as ), etc.

In addition, the above -CD011 group, -3O21'l group, 503H
group, -P03H2 group, -P-R, group each represents an alkali metal H (e.g., lithium, sodium, potassium, etc.), an alkaline earth metal (e.g., calcium, magnesium, etc.),
Metal salts such as zinc, aluminum or organic bases (e.g.
triethylamine, pyridine, morpholine, piperazine, etc.).

The monomer (A) constituting the main component of the resin particles of the present invention may contain at least one of the above polar groups and have one polymerizable double bond group in one molecule. Either is fine.

More specifically, an example of the monomer (A) is shown by general formula (n).

General formula (n) b+ b2 (1:It=c
0CO-.

R+s R+s -o-, -3Q, -, -C-, -5O2N-, -CON
−.

R+6 -CONHCOD-,-['0NHCONH-, dimension [→
Completed.

1. Rl'? RI5 is each a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 7 carbon atoms (preferably, for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2
-Hydroxyethyl group, 3-bromo-2-hydroxypropyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 3-sulfopropyl group, benzyl group, sulfobenzyl group, methoxybenzyl group, Carboxybenzyl group, phenyl group, sulfophenyl group, carboxyphenyl group, hydroxyphenyl group, 2-methoxyethyl group, 3-methoxypropyl group, 2
-methanesulfonylethyl group, 2-cyanoethyl group, N
.

N (dichloroethyl)aminobenzyl group, N, N(
(dihydroxyethyl)aminobenzyl group, chlorobenzyl group, methylbenzyl group, N,N(dihydroxyethyl)aminophenyl group, methanesulfonylphenyl group, cyanophenyl group, dicyanophenyl group, acetylphenyl group, etc.), and RI6+Lt are the same or a hydrogen atom, a halogen atom (preferably, for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an aliphatic group having 1 to 4 carbon atoms (preferably, for example, a methyl group, an ethyl group, a propyl group, butyl group, etc.), and 1 represents an integer of 1 to 6. ] W represents the polar group of the monomer (A) described above.

1゜1□ 131゜10C=C, -COO-, -0CO-, -0-, -3
−.

-3O2-, -N-, -CON-, -3o2N-.

1] I Is Is I7 -NHCOO-, -3i-, -N) ICONH- or
- Represents a linking group selected from -1.0 or a linking group formed by a combination of these linking groups.

[Here, 1. ~1. may be the same or different,
Hydrogen atom, halogen atom (preferably, for example, fluorine atom, chlorine atom, bromine atom, etc.) or a hydrocarbon group having 1 to 7 carbon atoms (preferably, for example, methyl group, ethyl group, propyl group, butyl group, 2 -chloroethyl group, 2-methoxyethyl group, 2-methoxycarbonylethyl group, benzyl group, methoxybenzyl group, phenyl group, methoxyphenyl group, methoxycarbonylphenyl group) or the formula (I
-CL of I) represents a -W1 group, and 15 to 1. represents the same content as the above RI5. ] b+ and ba may be the same or different, and each represents a hydrogen atom, a halogen atom (preferably, for example, a fluorine atom,
chlorine atom, bromine atom, etc.), -CO[lH group, -CDO
R,, group, -CIl, C[]OR,, group (R16 represents a hydrocarbon group having 1 to 7 carbon atoms, specifically, the above-mentioned L
s) or an alkyl group having 1 to 4 carbon atoms (preferably, for example, a methyl group,
(ethyl group, propyl group, butyl group, etc.).

The above monomer (A) will be more specifically exemplified below, but the present invention is not limited thereto.

(a-1) CH2=CH-CONH2, -CONHC2H5゜CD
0II -COOCH3(a-3) C)12=c -C
1C0NI ((C measurement leaf n: integer from 1 to 12 (a-
6) a: H, CHr Kano-CONH2, -3O□NH2 DH (a-8) (a-9) L; LILI (L: 112't'1lSlhH integer (a
-13) a:
-H, -CH3I CH2=CCH3M: Ll, Na, K.

N (a-16)
a 2 -H, -C)I 3
H-N(C,H3).

C0NH(CH2),,C00M'H-N(
C, H5).

(a-18) CI(2=Ca: -H, -C)l-CONH.

C! (20CO-((:Hz)-[:OOHWiW(a
-22) Ward a: -H, CI (3 (a-23) CH, = C ■ COO (CL), OCO (C) 1.) l, C0D)
1a: -H, -CH5 Con(CH,) 20COCH=CI(-COOHa
: H, CH=, -CH2COOCH-(a-
25) ■ CH2=C CD(CH2)2N1(Co(C)12), C00Ha
: H, C)+3 n: Integer from 1 to 10 (a-26) Cl12=C [:00 (CH2)n0CO(CH,), C00Ha
: -H, -CH3, -CH2COOCHsn: 2~
Integer m of 10: Integer from 1 to 10 (however, n+m) is 10 or less) (a-27) CH2=C ■ C00CC) 1. C) I accent? ,OCO(CH,) ,C
00Ha: -H, CHs, -CI n: An integer from 1 to 4 ■ = An integer from 1 to 4 (a-28) Ctl, =Ca: -1'l, -CH.

■ C00(C)1. )2N(CH,).

(a-29) CI (2=Ca: -H, CH3 I COO (CH,) 2N (CH, C) 1208).

(a-30) (a-31) ■ (a-32) CH,=CCH,C0OH (a-33) CL=CC)12011 (a-34) ■ a: -H, CH3 CH.

(a-37) ■ CH2=C ■ C00(CH2)-N)ICO(C)I-)-COON
aa: -H, -CL, -CLCOOCL(a-
38> (a-39)(
a-40) C)12=IJ1 (a-41) a: -H, -CH5 (a-42) (a-43) (a-44) ! 0.CH,=C C'00CH,CHCH20CD(CI(2) 2CO
OII Kano (a-45) (a-46) (a-47) CH2=CH-CH20CO(CHiCOOl(n:1
An integer of ~3 (a-48) \\ Along with the above polar group-containing monomer (A), other copolymerizable monomers may be contained as a polymer component.

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 nonmetallic atoms (oxygen atoms, sulfur atoms, etc.) other than the above, and specific examples include vinylthiophene, vinyl dioxane, vinylfuran, etc. Can be mentioned. Preferred examples include vinyl or allyl alkanoates having 1 to 3 carbon atoms, acrylonitrile, methacrylonitrile, styrene and styrene derivatives such as vinyltoluene, butylstyrene, methoxystyrene,
Talolostyrene, dichlorostyrene, bromostyrene,
ethoxystyrene, etc.). However, it is not limited to these.

The proportion of monomer (A) as a polymerization component in the resin is 30% by weight or more, preferably 50% by weight or more, and particularly preferably, the resin contains monomer (A) and -functional polymers. It is composed only of merging [M].

Next, Ichinomiya functional 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 has a polymerizable double bond group represented by the general formula (I) bonded to only one end of the polymer main chain. It is important that the polymer is copolymerized with the monomer (A) and is solvated and soluble in the non-aqueous solvent. It is something that does.

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.

Moreover, the weight average molecular weight of the polymer [M] is 1×103 to 1×
105, preferably 2x103 to 5x104, particularly preferably 3x103 to 2x104.

If the weight average molecular weight of the polymer CM becomes less than 1×10 3 or more than 1×10 5 , the resulting dispersed resin particles will agglomerate, 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 (I) that is bonded only to one end of the polymer main chain will be explained below.

General formula (I) a, a2 CII=C Vo- In general formula (I), Vo is -0-, -COO-1-
OCD-1-CH,0['0-, -CH2COO-1
-SO2-1 Here, in addition to a hydrogen atom, R1 is preferably a hydrocarbon layer including an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, heptyl group). , hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromo propyl group, etc.), carbon number 4
~18 optionally substituted alkenyl groups (e.g. 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group) , 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthyl group, Methyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), even if substituted with 5 to 8 carbon atoms A good alicyclic group (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl group, naphthyl group) , tolyl group, xylyl group,
propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group,
bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobusoylamidophenyl group, 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, methoxymethyl group, etc.), alkoxy groups (e.g., methoxymethyl group, etc.). group, ethoxy group, propioxy group, butoxy group, etc.).

al and R2 may be the same or different from each other,
Preferably hydrogen atoms, halogen atoms (e.g. chlorine atoms,
bromine atom, etc.), cyano group, alkyl group having 1 to 4 carbon atoms (
For example, methyl group, ethyl group, propyl group, butyl group) -COD-R2 or CD0R2 (R
2 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 alicyclic group, which may be substituted, and specifically, the above R + represents the same content as that described for ).

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

More preferably, in general 2N), v.

is -COO-, -0CO-, -[:R20[:0-l
-CH2COO-1 represents a, + R2 may be the same or different, and represents a hydrogen atom, a methyl group, -COO
R2 or -CH, CDOR, (R2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.). Preferably, one of aI+a2 always represents a hydrogen atom.

That is, the polymerizable double bond group represented by the general formula (I) is specifically 0 CH30 CH2=CH-C-0-, CH2=C-C-[1-, C
H2CDOCH3 CH,C0OH C[lOHO CH,=CH-0-1CH2=C-CH2-C-0-,
etc.

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

Examples of the chemical structure of the repeating unit include those obtained from radical addition polymerizable monomers, those consisting of a polyester structure, or those consisting of a polyether structure, and the side chains in the repeating units of these polymer structures, Any material may be used as long as it contains a fluorine atom and/or a silicon atom.

Examples of the fluorine atom-containing substituent include ChF2h+
+ (h represents an integer from 1 to 12), - (CF2)
, CF2)1 (j represents an integer from 1 to 11).

Examples of the silicon atom-containing substituent include R2H.

(representing a number), a polysiloxane structure, etc.

However, R,, R,, R,, may be the same or different, and may be a substituted hydrocarbon group or -0R9 group (R
9 represents the same content as the hydrocarbon group of R8).

R3 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, decyl group, dodecyl group, hexadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2゜2-trifluoroethyl group, 2-cyanoethyl group, 3.3.3-) refluoro Propyl group, 2-methoxyethyl group, 3-bromopropyl group, 2-methoxycarbonylethyl group, 2.2.2.2'.

2',2'-hexafluoroisopropyl group, etc.), an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example,
2-methyl-1-propenyl group, 2-butenyl group, 2-
Pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4
-methyl-2-hexenyl group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chloro benzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic groups having 5 to 8 carbon atoms (for example, cyclohexyl group) , 2-cyclohexyl group, 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group) group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group,
Examples include methoxycarbonylphenyl group, ethoxyluponylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc.

In the -0R3 group, R9 represents the same content as the hydrocarbon group of R3 above.

Rs, R7, Re may be the same or different, and represent the same symbol content as R3, R,,R.

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 thereto.

(b-1) (b-2> 1+CH2-C± COOCIl, CH, ChF2h,.

(b-3) +CH, -C± C00Ij12CH2 (CF2) JCFJj: 1 to 1
Integer of 1 (b-4) p: Integer of 1 to 3 (b-5) 1: Integer of 1 to 6 (b-6) (b-7> +cl(2-c± ■ Coo(C)12) 2NH3O2Rf Rf : -CHzChH*h++ (b-9) 02Rf (b-10) (C)I2-C) -Cff1COORf ■ (b-11) 1+CL-C)l ± C)1. Ct]0-Rf (b-12) ■ +CH,-[:± COO(C)I2) 0-Rf (b-13) -tCHi-Cshi locps COO(CH2)Sl-OCH3 CH1 (b-14 ) -(-C)1. -C0C'H.

COD(C12)2esI CL CH3 (b-15> C00Si-C-)1- ■ C, R5 (b-16) +CI(2-CI R,' CI(CL) JSi-R2' R,/ R+' +R2 ' + Alkyl group of R3"CI""ljl (b-17) +CH3-C+CH5 I C0D(CH2), 03tCH*CH2ChCH3 (b-18) + CL-CIC)I3CH3 Con(C'11.), O3r+[] 5i-)-1CH
3CH3CH3 q: An integer from 1 to 20 (b-19) -f-CH2-C0FH.

■ Coo(CH2)20Si-+C1(2-)-, C0O
R,'(b-20) b-23>(b-24>+CH2-C±OR,'OR' COOCH2Sl O5l-OR' ■ OR'OR'("LR': Si CH3 CH3 (b-25) 6CH-CH-1 OR4' COD (CH=) 3S+-0R2' ■ OR3' (b-26) 1 ll CH3CH, C1l.

r: 30-150 (b-27) 1 + Cl (, -C12 CH,0COC,F,h,.

(b-28) (b-29) (b-30) The monofunctional polymer [M] of the present invention has the general formula (I>
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, -0-,
-3-1-N-1-so-, -so, -, -coo-1
2ds -OCO-1-CONHCO-1-NIICON)I-
a divalent aliphatic group or a divalent aromatic group, or a divalent residue thereof, which may have a bonding group selected from 1-[:ON-, -3O2N- and -5i-; Represents organic residues formed by combinations. Here, d1 to d5
represents the same content as R in formula (I).

Examples of divalent aliphatic groups include 1 II fC±, -+C=C±, →CMMC± (e+ and C2 may be the same or different,
Each hydrogen atom, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.) or an alkyl group having 1 to 12 carbon atoms (
For example, it represents a methyl group, an ethyl group, a propyl group, a chloromethyl group, a bromomethyl group, a butyl group, a hesyl group, an octyl group, a nonyl group, a decyl group, etc. Q is 10-,-
3- or -NR2,-, R20 has 1 to 4 carbon atoms
represents an alkyl group, -CH2C1 or -CHJr)
.

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

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 an alkoxy group having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) as examples of the substituent.

Examples of the heterocyclic group include furan ring, thiophene ring, pyridine ring, pyrazine ring, piperazine ring, tetrahydrofuran groove, pyrrole ring, tetrahydropyran ring, 1.3-
Examples include oxacillin ring.

General formula (I) 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, -CH,, -CH2C
OOCH, -CI, -Or or -CM, P2 represents -H or -CHs, X represents -C1 or -Br, n represents an integer of 2 to 12, m represents 1 to 4 Indicates an integer.

(C-1) P.

CH2= C-COO(CHHO2 (C-2) CH3 CH= C11-0(CH270- (C-3) CH2=CH- (C-4) CH,=['H-CH2-(C-5
) P.

CH2= C'-['[I[l(,[')12h NH
-(C-6)P.

C)1. = C-C00CH2CHC1 (20- Kano (C-7) P.

number CH, = C-C0NH (CH leaf (C-9) P.

CHa=CcoocLcllcl(, o-goose H (C-13) P.

■ CH2=C−Coo(CH2−+τ (C-14) P.

CL=C-CONI((CH2k (C-15) P2 CH,=[knee C mouth N) ICOO(C)12h(C-1
6) P.

CH2=C-C0NHCONH(CH#-(C-17)
CH2=CH-CH,-COOboCL±1(
C-20) P2 CIl, = C-C00CHO CH,CH,X (C-21) P.

Flea CH2=C C00(CL), NHCOO(CH#-(C-22)
P.

CH,=C-COO(CH2CH20srCO(C1
l#-CH3 CH=CH 1-C00CH2CHCH200C (CH2hC-
CN (C'-23) (C-25) (1:)1. =CH-[:)12DCD(CH2),-
3-(C'-26)CH.

CH2=CH-[:H, C0D (CL), -C-CN (C-27) CI'la CH, =CH-CH, CH2H20DC (CI2), -
C-0HCN (C-28) C00(CH2), -3- (C-29) L; UUUH2UH2 (C-30) L, uULtlzL:L Sum of repeating units of the Ichinomiya functional polymer [M] of the present invention In the above, the repeating unit having a substituent containing a fluorine atom or/and a silicon atom is preferably contained in an amount of 40% by weight or more, more preferably 60 to 1% by weight of the total.
00% by weight.

If the above-mentioned components of the present invention are not swirled by 40% of the total weight, the effect of concentrating the resin particles on the surface portion when dispersed in the image-receiving layer decreases, and as a result, the effect of improving water retention as a printing original plate is reduced. fades away.

The monofunctional polymer [M] of the present invention can be produced by a conventionally known synthesis method. For example, (1) reacting various reagents with the ends of living polymers obtained by anionic polymerization or cationic polymerization to form monofunctional polymers C;
MI is obtained by ionic polymerization method: (1) Obtained by radical polymerization using a polymerization initiator and/or chain transfer agent containing a reactive group such as a carboxyl group, hydroxyl group, or amino group in the molecule. A method using a radical polymerization method to obtain a monofunctional polymer [M] by reacting a polymer with a terminal reactive group bond with various reagents; Examples include a method using a polyaddition condensation method in which a polymerizable double bond group is introduced in the same manner as described above.

Specifically, P, Dreyfuss & RoP, Qu
irk.

Bncycle, Polym, Sci, Eng,, 7
, 551 (19B?), P, F.

Rempp, B., Franta, Adv, Po.
lym, Sci., 58, 1 (1984), V.P.
ercec, Appl, Poly, Sci, 28
5.

95 (1984), R, ^sami, M, Ta
kari, Makromol.

Chem, 5upI)1. ．． 12, 163 (198
5) , P. Rempp, etal, Makro
mol, Chem, 5upp1. , 8 , 3 (19
84), Yuji Yogami, Chemical Industry, 38, 56 (19
87), Yuya Yamashita, Polymer, 31, 988 (198
2), Shibe Kobayashi, Polymers, 30, 625 (198
1), Toshinobu Higashimura, Japan Adhesive Association Journal, 18, 536
(1982), Hiroshi Ito-1 Polymer Processing, 35, 26
2 (1986), Higashi Takashibe, Tsuda Takashi, Functional Materials, 1
987. Reviews of Nα10,5, etc. and references cited therein.
It can be synthesized according to methods described in patents and the like.

Furthermore, when the dispersed resin particles of the present invention have a network structure, the above-mentioned polar group-containing functional monomer (A> as the polymer component (A)) is bridged to form a higher-order polymer. It forms a network structure.

That is, the dispersed resin particles of the present invention have a portion insoluble in a non-aqueous dispersion solvent composed of the polymer component (A) as described above, and a functional polymer [M] that is soluble in the solvent. When the non-aqueous latex has a network structure, the molecules of the polymer component (A) forming the portion insoluble in the solvent are bridged.

As a result, the network resin particles become poorly soluble or insoluble in water, and specifically, the solubility of the resin in water is 8.
It is 0% 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, they are described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), and "Polymer Data Handbook Basic Edition" published by The Society of Polymer Science and Technology, Baifukan (1986), etc. Compounds can be used.

For example, silane coupling agents such as organic silane compounds (e.g., vinyltrimethoxysilane, vinyltributoxysilane, T-glycidoxypropyltrimethoxysilane, T-mercaptopropyltriethoxysilane, T-aminopropyltriethoxysilane) etc.), polyisocyanate compounds (e.g. toluylene diisocyanate, 0-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, isocyanate, polymeric polyisocyanate, etc.), polyol compounds (for example, 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1.1-)! ] methylolpropane, etc.), polyamine compounds (e.g., ethylenediamine, T-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds, and epoxy resins (For example, "New Epoxy Resin" edited by Hiroshi Kakiuchi, published by Shokodo (1985), "New Epoxy Resin" edited by Kuniyuki Hashimoto, "
Compounds described in "Epoxy resin" Nikkan Kogyo Shimbunsha (1969 publication), etc.), melamine resins (for example, compounds described in "Uria Melamine Resin" edited by Miwabe and Hideo Matsunaga, Nikkan Kogyo Shimbunsha (1969 publication), etc.) compounds), poly
(Meth)acrylate compounds (for example, compounds described in Makoto Okawara, Takeo Saegusa, and Toshinobu Higashimura, ed., "Oligomer", Kodansha (1976), Eizo Omori, "Functional Acrylic Resin", Technosystem (1985), etc. Specific examples include polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol polyacrylate, bisphenol A-diglycidyl ether diacrylate, Examples include oligoester acrylates and methacrylates thereof.

In addition, as a polyfunctional monomer containing two or more polymerizable functional groups [also referred to as polyfunctional monomer (D)] or a polyfunctional oligomer containing two or more polymerizable functional groups that are made to coexist in the method (①) above, , specifically CH2=CH-CH2-, CH2=C
H-C-0-1CH2=CH-1CH3CH30 CH2=C-C-0-1CH=CH-C-0-, CH,
=CH-CONH-, CH3CH3 CH2=C-CONH-, CH=CH-CONH-, O
CH2O II I II CH2=CH-0-C-1CH2=C-0-C-1C)
1. =CH-CH, -0-C-1C'H, =CH-NH
CO-1CH, =CH-CH2-NHCO-, C11,
=CH-3O2-1CH, =CH-CD-, CH2=C
Examples include H-0-1CH2=CH-5-. 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 styrene derivatives such as divinylbenzene and trivinylbenzene; polyhydric alcohols (e.g. , ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol #200, #40
0, #600.1.3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.), or polyhydroxyphenols (such as hydroquinone, resorcinol, catechol and their derivatives) of methacrylic acid,
Acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers: vinyl esters of dibasic acids (e.g. malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) , allyl esters, vinylamides or allylamides: polyamines (e.g. ethylenediamine, 1°3-
Examples include condensates of propylene diamine, 1,4-butylene diamine, etc.) and carboxylic acids containing vinyl groups (for example, methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

In addition, monomers or oligomers having different polymerizable functional groups include, for example, carboxylic acids containing vinyl groups (such as methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid,
Reactants of alcohols or amines (e.g. allyloxycarbonylpropionic acid, allyloxycarbonyl acetic acid, 2-
Vinyl group-containing ester derivatives such as allyloxycarbonylbenzoic acid, allyloxycarbonylbenzoic acid, allyloxycarbonylbenzoic acid, etc. or amide derivatives containing vinyl groups (such as vinyl methacrylate,
Vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloylpropionate, allyl methacryloylpropionate, vinyloxycarbonyl methyl methacrylate, vinyloxycarbonylmethyloxycarbonyl acrylate ethylene ester, N-allylacrylamide, N-allylmethacrylamide, N-allylitaconamide, methacryloylpropionic acid allylamide, etc.) or amino alcohols (e.g. aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-amino hexanol,
2-aminobutanol, etc.) and a carboxylic acid containing a vinyl group.

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 the bottom notes of Giyu Iwakura, Keisuke Kurita, "Reactive Polymers" Kodansha (published in 1977), Ryohei Oda, "Polymer Fine Chemicals" Kodansha (published in 1976), etc. For example, polymer reactions involving combinations of functional groups in Group A (hydrophilic group polymer components) and Group B (polymers containing components containing reactive groups) in the table below are usually well known. This is one of the methods. Note that R21+R22 in Table 1 is a hydrocarbon group, and L in the above formula (II)
Represents the same content as la and Is in l.

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 .

The non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles may be any organic solvent as long as it has a boiling point of 200° C. or lower, and it may be used alone or in combination of two or more.

Specific examples of this organic solvent include alcohols such as methanol, ethanol, propatool, butanol, fluorinated alcohol, and benzyl alcohol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and diethyl ketone, and ethers such as diethyl ether, tetrahydrofuran, and dioxane. carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, aliphatic hydrocarbons having 6 to 14 carbon atoms such as hexane, octane, decane, dodecane, tridecane, cyclohexane, cyclooctane, benzene , aromatic hydrocarbons such as toluene, xylene, and chlorobenzene, methylene chloride,
dichloroethane, tetrachloroethane, chloroform,
Examples include halogenated hydrocarbons such as methylchloroform, dichloropropane, and trichloroethane. However, it is not limited to the compound examples described above.

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
spersionPoly++++erization
in Organic Media J John N
i1ey (1975), Koichi Murata, Polymer Processing, -
'-120 (1974), Tsunetaka Matsumoto and Toyokichi Tange, Journal of Japan Adhesive Association, 183 (1973), Toyokichi Tange, Journal of Japan Adhesive Association 23.26 (1987), D, J,
Walbridge, NATO, Adv, 5tud
y, In5t, Ser.

E! , N1167.40 (1983), British Patent No. 89
3429, 934038, U.S. Patent No. 11
22397, 3900412, 4606989 specifications, JP 60-179751, JP 60-1859
The method is disclosed in 63 publications and the like.

The dispersion resin of the present invention comprises a monomer (A) and a -functional polymer [
M], and when forming a network structure, a polyfunctional monomer (D) is allowed to coexist as necessary; in any case, the important thing is that these monomers If the resin synthesized from the non-aqueous solvent is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained. More specifically, for the monomer (A) to be insolubilized, -functional polymer [M]
It is preferable to use 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 104 to 106, preferably 104 to 5X.
It is 105.

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 (D) are generally mixed in a non-aqueous solution. The polymerization may be carried out by heating in a solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, or butyllithium. Specifically, (1) monomer (A) and -functional polymer [M],
Methods include adding a polymerization initiator to a mixed solution of the polyfunctional monomer (D), and (ii) adding a mixture of the above polymerizable compound and polymerization initiator dropwise or optionally into a nonaqueous solvent. It can be manufactured using any method without being limited to these.

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. Reaction time is 1-1
5 hours is preferred.

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

As the matrix resin provided for the image-receiving layer of the present invention, all conventionally known binder resins can be used. Typical examples 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.
In addition, polyvinyl alcohol, water-soluble polymer compounds,
Examples include 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 matrix resin provided in the image-receiving layer of the present invention is preferably 103 to 10''.

More preferably, it is 5X'103 to 5X10'. Also, the glass transition point of this resin is preferably -10°C to 120°C.
°C, 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, titanium 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.

In addition, a crosslinking agent may be added to the image-receiving layer in order to further improve the film strength. As the crosslinking agent, commonly used ammonium chloride, organic peroxide, metal soap, organic silane, polyurethane crosslinking agent, epoxy resin curing agent, etc. can be used. Specifically, it is described in Shinzo Yamashita and Tosuke Kaneko, "Handbook of Crosslinking Agents," published by Taiseisha (1981). For example, the same compounds as those explained in connection with the crosslinking compound for resin particles can be mentioned.

Examples of the support used in the present invention include wood-free paper, wet reinforced paper, plastic 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 backcoat layer (back layer) is provided on the support surface opposite to the image-receiving layer for the purpose of preventing curling. ) can be provided.

Here, the intermediate layer is made of acrylic resin, ethylene-butadiene copolymer, methacrylate ester-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-butadiene copolymer,
Emulsion type resin such as vinyl acetate copolymer; Solvent type resin such as epoxy resin, polyvinyl butyral, polyvinyl chloride, polyvinyl acetate: Composed mainly of at least one type of water-soluble resin as mentioned above. However, inorganic pigments and waterproofing agents can be added as necessary.

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

When used as PPC plate-making, in order to further reduce scumming of the printing original plate of the present invention, a replacement receiving layer, an intermediate layer and/or a backing layer are added so that the volume resistivity of the printing original plate is 1010 to 1013ΩCm. A dielectric agent can be added to the coating layer. The dielectric agent may be inorganic or organic.
Salts of monovalent or polyvalent metals such as a, K, Li, Mg, Zn, Co, and Ni, and organic ones such as polyvinylbenzyltrimethylammonium chloride and acrylic resin-modified quaternary ammonium salts, etc. Examples include polymeric anionic conductive agents such as agents and polymeric sulfonates. The amount of these conductive agents added is 3 to 40% by weight, preferably 5 to 20% by weight of the amount of binder used in each layer.

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 a support, dried to form an intermediate layer, and then an intermediate layer containing an image-receiving layer component is formed. An aqueous solution may be applied and dried to form an image-receiving layer, and if necessary, an aqueous solution containing backcoat layer components may be applied and dried to the other side to form a backcoat layer. The amount of each of the image-receiving layer, intermediate layer, and back coat layer is 1
-30g/m', 5-20g/m', 5-20g/m' are suitable.

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.

〔Example〕

Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto. In addition, the Ichinomiya functional polymer [M] of the following resin examples is referred to as a macromonomer.

Production example L of macromonomer: [M-1] 2.2.2.2
A mixed solution of 95 g of ',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 A, 1. B,
1.0 g of N, ) 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 this reaction solution, and the mixture was stirred at a temperature of 100° C. for 12 hours. After cooling, this reaction solution was reprecipitated into 2 liters of methanol to obtain 82 g of white powder. Polymer CM-1] had a weight average molecular weight (abbreviation ~) of 4,000.

[M-11! Production example 2 of H. macromonomer: [: A mixed solution of 96 g of monomer (A-1) with the lower structure of M-21, 4 g of β-mercaptopropionic acid, and 200 g of toluene was heated to 70° C. under a nitrogen stream. It was warm. A.1. B, N, 1.0g
was added and reacted for 8 hours.

The reaction solution was then cooled in a water bath to a temperature of 25°C, and 10 g of 2-hydroxyethyl methacrylate was added thereto. Dicyclohexylcarbonamide (abbreviation rule C,
A mixed solution of 15 g of C,), 0.2 g of 4-(N,N-dimethylamino)pyridine, and 50 g of methylene chloride was added dropwise over 30 minutes with stirring, 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 collected in n-hexane I! ! It sank back inside.

The precipitated viscous substance was collected by decantation, dissolved in 100 bottles of tetrahydrofuran, and after filtering off the insoluble matter again, n-
It was reprecipitated into hexane 1β.

The yield of the polymer obtained by drying the precipitated viscous substance was 60 g.
It was ~5.2 x 103.

(A-1) CH3 CH2=CCH3 ■ C0D(CH2) 20Si-('82CgH5CH3 CM-2:1 1H・CIl,=C゛COD (CH,) , OCO(C112)S -CH
3 Production example 3 of macromonomer: [M-31 95 g of monomer (A-2) with the following structure, 150 g of benzotrifluoride
A mixed solution of 50 g of ethanol and 50 g of ethanol was heated to 75° C. with stirring under a nitrogen stream. 4.4'~Azobis (4
~cyanovaleric acid) (abbreviation A, (:, V,) 2 g was added and reacted for 8 hours. After cooling, it was reprecipitated in methanol 11 and the resulting polymer was dried. Next, 50 g of this polymer and 2 -Hydroxyethyl methacrylate (11 g) is dissolved in 150 g of benzotrifluoride at a temperature of 25°C.To this mixture, D, C, C, 15 g, 4- (N,
A mixed solution of 0.1 g of N-dimethylaminopyridine) and 30 g of methylene chloride was added dropwise over 30 minutes, and the mixture was further stirred for 4 hours. After that, 3 g of formic acid was added and stirred for 1 hour, the precipitated insoluble matter was filtered off, and the filtrate was mixed with methanol 800 I
lji! It sank back inside. The precipitate was collected, dissolved in 150 g of benzotrifluoride, and reprecipitated again to obtain 30 g of a viscous substance. Polymer CM-3] ~ is 3,3 X
It was 10'.

(A-2) CH3 CH2=C C00CH,CH,(CF2)2[:F,H[M-3] CH3 ■ CH,=CCH3 CD0CR,CH,0CO(CH2)2C-N CH3 -+CH,-C →-- COD(CH2)2(CM, CF, H Macromonomer production examples 4-22: [M-4E-
CM-221 Production Example 2 except that monomer (A-1) in Production Example 2 was replaced with another monomer (monomer corresponding to the polymer component listed in Table-2). In the same way, each macro
[M] was produced.

Each ~ was 4X10' to 6X108.

Production examples 23 to 30 of macromonomer: [M-23]
~[:M-30) In Macromonomer Production Example 2, monomer (A-1)
Each macromonomer CM) was produced in the same manner except that 2-hydroxyethyl methacrylate and 2-hydroxyethyl methacrylate were replaced with compounds corresponding to each of the polymers in Table 3 below. Each ~ was 5X103 to 6X103.

Production example 31 of resin for dispersion stabilization: 27 g of [M-311 octyl methacrylate], 60 g of monomer (F-1) corresponding to the following structure CM-1], 3 g of glycidyl methacrylate, and 200 g of penzotrifluoride. The mixed solution was heated to a temperature of 75°C while stirring under a nitrogen stream. 2.2'-azobisisobutyronitrile (abbreviation ^,
1. B, N, ) 1.0g was added and reacted for 4 hours, and then A, 1. 0.5 g of B and N were added and reacted for 4 hours. Next, add 5 g of 5N methacrylic acid to this reaction mixture.
, N-dimethyldodecylamine 1. Add 0.5 g of OgS t-butylhydroquinone and heat at 110°C.
Stir for hours. After cooling, it was re-precipitated in methanol 21 to collect a slightly brownish oil, and then dried. The yield was 73 g, and the weight average molecular weight (~) was 3.6 x 10'.

CM-31] C00C) 12CH2C3F, C00C,H,.

IH3, CH3 Reiichi±CH2-[1 Knee)-r-C=CH2C00CH2
CHCH200C Hibiki H Resin particle production example 1: [L-1] Acrylic acid 20
g1 Polymer CM-115g of macromonomer production example 1
A mixed solution of 110 g of methyl ethyl ketone was heated to 60° C. under a nitrogen stream. 2.2'-azobis(isovaleronitrile) (abbreviations A, B, V, N,) 0.2
g was added and reacted for 2 hours, and further A, B, V, N, 0
1 g was added and reacted for 2 hours. The obtained dispersion was
Resin particles obtained by filtration with 0 mesh nylon cloth [L-1
] has a polymerization rate of 100% and an average particle size (manufactured by Horiba, Ltd.: CA
(measured with PA500) 0.20. It was um.

Production example 2 of resin particles: CL-2) Acrylic acid 20
g1 Macromonomer AK-5 (commercially available as a macromonomer with a polysiloxane structure manufactured by Toagosei ■) 5g1 A mixed solution of 2g of divinylbenzene and 120g of methyl ethyl ketone was prepared, and the reaction was carried out in the same manner as in Example 1 for the production of resin particles. The polymerization rate of the obtained dispersion CL-2 was 100% and the average particle size was 0.28 μm.

Production examples 3 to 26 of resin particles: [L-3E to [L-
26] A mixed solution of 20 g of monomer (A), 4 g of macromonomer [M], and 150 g of an organic solvent, each of which is listed in Table 4 below, was prepared in the same manner as in Production Example 1, except that each dispersed resin particle was produced. The polymerization rate of each dispersion was 95 to 100%. Further, the average particle size of the multiparticles was in the range of 0.15 to 0.30 μω, and the monodispersity was also good.

Production examples 27 to 37 of resin particles: CL-27E to C
L-37] Resin particles were produced in the same manner as in Production Example 2, except that the polyfunctional compound shown in Table 5 below was used in place of 2 g of divinylbenzene.

The polymerization rate of each particle is 100% and the average particle size is 0.25 to 0.
．． It was 35 μm.

Example 1 Resin particles [L-2333g (as solid content) and [methyl methacrylate/allylic acid (99/1) weight ratio]
Copolymer (weight average molecular weight 45 (1 (10) 30 g:
[B-1] A mixture of 100 g of zinc oxide and 300 g of toluene was heated in a homogenizer (manufactured by Nippon Seiki ■) for 6 hours.
X 10' r, p, m.

Dispersion was carried out for 10 minutes at a rotation speed of . Next, this dispersion was applied with a wire bar to the intermediate layer of a support, which had a back layer on one side of high-quality paper and an intermediate layer on the other side, so that the dry adhesion was 18 g/m'. Then, it was dried at 100° C. for 1 minute to prepare a lithographic printing original plate.

Next, a plate was made using a commercially available PPC, and the obtained original plate was used as an ELF
-EX (Zinc oxide desensitizing liquid manufactured by #photographic film■)
The sample was desensitized by passing it through an etching machine once to obtain a printing original plate.

The density of the image area of the obtained original plate was 1.0 or more, there was no ground blur in the non-image area, and the image quality of the image area was clear.

This is an offset printing machine (Oliver 52 manufactured by Sakurai Seisakusho).
(type) and printed on high-quality paper. Even after 3,000 sheets were printed, there were no problems with background stains in non-image areas or image quality in image areas of the printed matter.

Examples 2 to 9 Each lithographic printing material was prepared in the same manner as in Example 1, except that the copolymer shown in Table 6 was used instead of the resin [1] of the present invention. The original version was made.

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

The density of the obtained offset printing master plate is 1
, 2 or higher, the image quality was clear. Furthermore, when etching was performed and printed using a printing press, the printed matter after printing 3,000 sheets had no fog in the non-image area and the image was clear.

Example 10 A mixture of 4 g (solid content) of resin particles [L-1], 129 g of a binder resin [:B-2], 50 g of zinc oxide, and 200 g of toluene was mixed in a homogenizer with 6X
Dispersion was carried out for 10 minutes at a rotational speed of 103r, p6m, and then 0.5g of phthalic anhydride was added to give IX 10-3r.
Dispersion was performed for 1 minute at p and m.

The dispersion thus obtained was coated on a support under the same conditions as in Example 1, dried at 100°C for 30 seconds, and further
A lithographic printing original plate was prepared by heating at 0° C. for 1 hour.

Binder resin [B-2] CH3 -f-CH2-[knee → T "Ko C1 (, -C'H-to neck-1] C00CH3COOCH2 CH3CH3 CH2-C+-±CL-Cshir- CDOCH2CH-CII2 C0OH\1 to 5X10' (weight ratio) This was plate-made using the same apparatus as in Example 1, then etched and printed using a printing press.

The density of the master plate for offset printing obtained after plate making was 1.0 or more, and the image quality was clear.

The image quality of the printed matter after printing 4,000 sheets was clear and without blurring.

Example 11 A mixture of 314 g of resin particles CL-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 further dispersed in a ball mill for 10 minutes. 25g dry weight on layer
/m' with a wire bar and dried at 100° C. for 90 minutes to prepare a lithographic printing original plate.

Resin [B-33 ~ 5.3 x 10' This original plate was treated with a desensitizing treatment liquid [Fuji Photo Film JLZA■
Processed by passing it through an etching processor once using ELP-EXE, and adding 2μ of distilled water to this! When the contact angle with the water formed was measured with a goniometer, the result was 1.
The angle was 0" or less. The angle was 98° before the desensitization treatment.

This means that the non-image portion of the image-receiving layer of the original plate of the present invention is
Indicates that the property has changed from lipophilic to hydrophilic. (Usually, the degree of hydrophilicity that does not cause printing stains, spot stains, etc. in non-image areas during printing is determined by a contact angle with water of 20° or less. is necessary).

Next, after making a plate in the same manner as in Example 1, the above-mentioned desensitization treatment was performed and printing was performed. Even after more than 3,000 sheets 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 A lithographic printing original plate was prepared in the same manner as in Example 1, except that the compounds shown in Table 7 below were used instead of hexamethylene diisocyanate used in Example 11.

Table 7 This was plate-made using the same device as in Example 1, then etched and printed using a printing press. The density of the master plate for offset printing obtained after plate making was 1.0 or more, and the image quality was clear.

The image quality of the printed matter after printing 3,000 sheets was clear and without blurring.

Examples 16 to 25 In Example 11, each was carried out in the same manner as in Example 11, except that 4 g (as solid content) of the resin particles [L] of crosslinked Table-8 was used instead of 4 g of resin particles [L-3]. An original plate for lithographic printing was prepared.

Table 8 When each original plate was prepared and printed in the same manner as in Example 11, no problem occurred in the ground force blur in the non-image area of the printed matter or in the image quality even after 3000 copies were printed.

〔Effect of the invention〕

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

Claims (1)

[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: In a non-aqueous solvent, carboxyl groups, sulfo groups, sulfino groups, phosphono groups, ▲ mathematical formulas, chemical formulas, tables, etc. that are soluble in the non-aqueous solvent but become insolubilized by polymerization. There is ▼ [R_0 is a hydrocarbon group or -O
R_1_0 (R_1_0 represents a hydrocarbon group)]
A monofunctional monomer containing 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 ( A) and a polymerizable double bond represented by the following general formula (I) only at 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 groups. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the general formula (I), V_0 is -O-, -COO
-, -OCO-, -CH_2OCO-, -CH_2CO
O-, -SO_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents -CONHCOO- or -CONHCONH- (
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, and may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R_2 or via a hydrocarbon group (R_2 represents a hydrogen atom or a hydrocarbon group that may be substituted)] (2) The above non-aqueous solvent-based dispersed resin particles form a high-order network structure. The original plate for direct drawing type lithographic printing according to claim (1), characterized in that: