JP2781090B2 - Original plate for direct drawing type lithographic printing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate precursor,
In particular, the present invention relates to a direct drawing type lithographic printing plate suitable for an office printing plate.

[0002]

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

[0003] A conventional direct drawing type lithographic printing plate precursor is provided with a back surface layer on one side of a support such as paper, and an image receiving layer as a surface layer on the other side via an intermediate layer. The back layer or the intermediate layer is formed of a water-soluble resin such as PVA or starch, a water-dispersible resin such as a synthetic resin emulsion, and a waterproofing agent. A typical example of such a lithographic printing plate precursor is U.S. Pat.
As described in JP-A-532865, a water-soluble resin binder such as PVA, an inorganic pigment such as silica, calcium carbonate and the like, and a water-proofing agent such as a melamine-formaldehyde resin precondensate are mainly used. It is configured as a component.

[0004]

However, in the conventional printing plate thus obtained, in order to improve the printing durability, a large amount of a water-proofing agent is added or a hydrophobic resin is used. When the hydrophobicity is increased to increase the printing durability, the printing durability is improved, but the hydrophilicity is reduced, and printing stains are generated. On the other hand, when the hydrophilicity is improved, the water resistance is deteriorated and the printing durability is reduced. there were. Especially in a high temperature use environment of 30 ° C or more,
The surface layer (image receiving layer) was dissolved in the immersion water used for offset printing, and there were major drawbacks such as a reduction in printing durability and the occurrence of printing stains. Further, the lithographic printing plate precursor draws an oily ink or the like as an image portion on the image receiving layer, and if the binding property between the image receiving layer and the oily ink is not good, even if the non-image portion has sufficient hydrophilicity. Even if the printing stains do not occur as described above, there is also a problem that the oily ink in the image area is lost during printing, and as a result, the printing durability is reduced.

The present invention solves the above-mentioned problems of the direct drawing type lithographic printing plate precursor. SUMMARY OF THE INVENTION An object of the present invention is to provide a direct drawing type lithographic printing plate precursor which is excellent in desensitizing property and does not generate not only a uniform background stain but also a dot-like background stain as an offset master 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, maintain the hydrophilicity of the non-image area sufficiently even when the number of printed sheets increases, and generate background stains. The object of the present invention is to provide a direct drawing type lithographic printing plate precursor having high printing durability.

[0006]

The object of the present invention is to provide a direct drawing type lithographic printing plate precursor having an image receiving layer on a support, wherein the following non-aqueous solvent-based dispersed resin particles are contained in the image receiving layer. This can be achieved by a direct-drawing lithographic printing plate precursor containing at least one kind. Non-aqueous solvent-based dispersed resin particles: In a non-aqueous solvent, it is soluble in the non-aqueous solvent, but is insolubilized by polymerization, and decomposed into a thiol group, a phosphono group, an amino group, a sulfo group or

Embedded image A monofunctional monomer (A) containing at least one functional group selected from functional groups that form a group [R ₁ represents a hydrocarbon group or an —OR ₂ group (R ₂ represents a hydrocarbon group)] )When,
A polymerizable double bond group represented by the following general formula (I) is bonded to only one terminal 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. Polymer resin particles obtained by subjecting a monofunctional polymer [M] to a dispersion polymerization reaction. General formula (I)

Embedded image [However, in the general formula (I), V ₀ is -O-, -CO
O -, - OCO -, - (CH 2) -OCO -, - (CH
_{2) -COO -, - SO 2} -,

Embedded image Represents -CONHCOO- or -CONHCONH- (R ₃ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), and a ₁ and a ₂ may be the same or different from each other;
Hydrogen atom, halogen atom, cyano group, hydrocarbon group, -C
OO-R ₄ or -COO-R ₄ via a hydrocarbon group (R
₄ represents a hydrogen atom or a hydrocarbon group which may be substituted)
Further, in the present invention, the non-aqueous solvent-based dispersed resin particles may form a higher-order network structure.

[0007]

The present invention is characterized in that the image receiving layer of the direct drawing type lithographic printing plate precursor contains the non-aqueous solvent-based dispersed resin particles, and the non-aqueous solvent-based dispersed resin particles (hereinafter simply referred to as resin particles). May be abbreviated as), but at least one thiol group, phosphono group, amino group, -PO (O
H) a polymer component containing at least one functional group that forms at least one hydrophilic group selected from R ₁ groups and the like, and which becomes insoluble in the non-aqueous solvent after polymerization, a silicon atom and / or a fluorine atom Is characterized by chemically bonding to a monofunctional polymer component which contains a repeating unit containing at least as a substituent and is soluble in the non-aqueous solvent even after polymerization.

That is, the resin particles have a portion insoluble in a non-aqueous dispersion solvent composed of a polymer component (A) containing a protected thiol group or other hydrophilic group, and a resin soluble in the solvent. It is a non-aqueous latex composed of the functional polymer [M], and the molecular weight of the dispersion resin is 10 ⁴ to 10 ⁶ , preferably 10 ^{4 to} 5 × 10 ⁵ .

In the present invention, the resin particles are present in the image receiving layer separately and as particles from the binder resin which is a matrix of the image receiving layer. The resin particles are subjected to a reaction such as a hydrolysis reaction, a redox reaction, and a photolysis reaction by a hydrophilization treatment using a desensitizing liquid and immersion water used at the time of printing, so that a protected thiol group or other hydrophilic group is protected. The portion has a property that the portion undergoes a chemical reaction to generate the hydrophilic group and is converted from hydrophobic to hydrophilic.

[0010] On the other hand, the resin particles also have a polymer component containing silicon atoms and / or fluorine atoms having extremely large lipophilicity. Therefore, the direct-lithographic lithographic printing plate precursor of the present invention containing the resin particles in the image receiving layer has a lipophilic group in the resin particles when the image receiving layer is drawn with an oil-based ink or the like as an image portion. , The adhesion between the image receiving layer and the oil-based ink is improved, and the printing durability is improved.
In the non-image area, as described above, the resin particles quickly show hydrophilicity to the desensitizing liquid and immersion water, so that they are clearly distinguished from the lipophilicity of the image area, and the printing ink adheres to the non-image area during printing. It will not be.

And an image receiving layer in which such hydrophilic resin particles are dispersed in a binder resin of a matrix.
In a printing original plate in which a non-image portion is treated with a desensitizing liquid to make the surface hydrophilic to form a direct drawing type lithographic printing original plate, known hydrophilic resin particles are uniformly dispersed throughout the surface layer. I do. On the contrary, although the non-aqueous solvent-based dispersed resin particles of the present invention are dispersed in the image receiving layer, the function of the substituent-containing polymer component having significantly large lipophilic silicon and / or fluorine atoms is exerted. As a result, it is concentrated and present on the surface of the image receiving layer which is an air interface (having a high lipophilicity). Therefore, the water retention of the non-image area is remarkably improved only by dispersing a smaller amount (the amount of use is 50 to 10% as compared with the known technique of hydrophilic resin particles).

Further, the resin particles have a hydrophobic (lipophilic) polymer component bonded thereto, and the hydrophobic portion interacts with a binder resin which is a matrix of the image receiving layer. Due to the anchor effect of this portion, even if it shows hydrophilicity, it does not elute with soaking water at the time of printing, and it is possible to maintain good printing characteristics even when printing a considerably large number of sheets.

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

It is important that the resin particles are dispersed separately and as particles from the binder resin as a matrix in the image receiving layer, and that they are concentrated near the air interface. As a result, the direct-printing original plate of the present invention forms a faithful image portion and a non-image portion, and provides a high-quality printed image free from background smear. Moreover, since the resin particles are fixed by the binder resin, they are not separated during various processing steps,
In addition, by obtaining the protective effect of the binder resin,
Excellent printing durability. In addition, due to the hydrophilicity of a hydrophilic group such as a thiol group of the resin particles, the outflow of the resin particles due to immersion water or the like at the time of printing is concerned. However, such a concern is solved by at least partially crosslinking. As described above, the original plate for direct drawing type lithographic printing according to the present invention has the advantage that the non-image portion has good hydrophilicity, so that no background smear occurs and the printing durability is excellent.

Hereinafter, the resin particles will be further described. The resin dispersion of the resin particles of the present invention comprises at least one of each of the monomer (A) and the monofunctional polymer [M]. What is important in any case is that if a resin synthesized from these monomers is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained. it can.

The hydrophilicity of the resin particles is such that a film of the resin formed by applying a solution of the resin particles in an arbitrary soluble solvent is applied and the contact angle with distilled water (measured with a goniometer) is 50 ° or less. , Preferably 30 degrees or less. In the case of network resin particles, the solubility of the resin in water is 80% by weight or less, preferably 50% by weight or less.
% By weight or less.

The resin particles of the present invention (including network resin particles)
Preferably has an average particle diameter of 0.05 to 1.0 μm. If it is larger than 1.0 μm, the smoothness of the surface layer is reduced, which causes a reduction in film strength or toner image strength. On the other hand, if it is smaller than 0.05 μm, it is similar to the case of molecular dispersion, and the effect of being particles for improving water retention is weakened. Since the resin particles of the present invention are synthesized by a dispersion polymerization method in a non-aqueous dispersion system, the average particle size of the polymer latex particles is easily reduced to 1 μm or less, and the particle size distribution is very narrow, and monodisperse particles. You can do it.

In the present invention, if the amount of the resin particles (including the network resin particles) in the image receiving layer is too small, the hydrophilicity of the non-image portion is not sufficient and the effect is lost, and the background is stained. Conversely, if the amount is too large, the hydrophilicity of the non-image area can be further improved, but the water absorption of the entire image receiving layer increases, causing a decrease in adhesion to the support and a decrease in image strength. It is preferably used in an amount of 1 to 80% by weight based on 100 parts by weight of the matrix resin of the layer.

Next, the non-aqueous solvent-based dispersed resin particles used in the present invention will be described in more detail. The resin particles of the present invention are produced by so-called non-aqueous dispersion polymerization. First, the non-aqueous solvent contains a monofunctional monomer (A) that is soluble but insoluble by polymerization.
Decomposes at least one thiol group, phosphono group, amino group, sulfo group or

Embedded image A functional group that forms a hydrophilic group such as a group [R ₁ represents a hydrocarbon group or an —OR ₂ group] (hereinafter, may be simply referred to as a hydrophilic group-forming functional group) will be described. The above R
₁ is specifically an aliphatic group having 1 to 22 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group,
Octyl, decyl, dodecyl, octadecyl,
2-chloroethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, allyl group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3
A phenylpropyl group, a methylbenzyl group, a chlorobenzyl group, a fluorobenzyl group, a methoxybenzyl group or the like; or an optionally substituted aryl group (for example, a phenyl group, a tolyl group, an ethylphenyl group, a propylphenyl group, a chlorophenyl group, Fluorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.), and R ₂ has the same contents as R ₁ . The hydrophilic group-forming functional group of the present invention generates at least one hydrophilic group by decomposition, but one or two or more hydrophilic groups may be generated from one functional group.

In the following, at least one thio-
The functional group generating a thiol group (thiol group-forming functional group) will be described in detail. According to one preferred embodiment of the present invention, the thiol group-forming functional group-containing monomer is a compound represented by general formula (II) - the [S-L ^A] functional group represented by at least
It contains species. Formula (II): [- S-L ^A] wherein, L ^A is

Embedded image However, R ^A _1, R ^A ₂ and R ^A ₃ may be the same or different, each represents a hydrocarbon group or -O-R ^AI (R ^AI is a hydrocarbon group), R ^A _4, R ^A ₅ , ^RA ₆ ,
_{^{R A 7, R A 8,}} R A 9 and _{^{R A 10, R A 11,}} R A 12,
R ^A ₁₃ each independently represents a hydrocarbon group.

The functional group of the general formula [-S-L ^A] is degraded by, it is intended to generate a thiol group, is described below in more detail. L ^A is

Embedded image In case of representing a, R ^A _1, R ^A ₂ and R ^A ₃ may be the same as or different from each other, preferably a hydrogen atom, an unsubstituted or good C1-18 linear or branched alkyl group ( For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group,
Octadecyl group, chloroethyl group, methoxyethyl group,
A methoxypropyl group, etc.), an optionally substituted alicyclic group (eg, cyclopentyl group, cyclohexyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group, chlorobenzyl group, A methoxybenzyl group) or an optionally substituted aromatic group (eg, phenyl, naphthyl, chlorophenyl, tolyl, methoxyphenyl, methoxycarbonylphenyl, dichlorophenyl, etc.) or —O—R ^AI (R ^AI represents a hydrocarbon group. Specifically, R ^A ₁ , R ^A ₂ , R
Substituents of the hydrocarbon group for ^A ₃ may be mentioned as examples).

L ^A

Embedded image Or in the case of representing the _{^{-S-R A 8, R A}} 4,
_{^{R A 5, R A 6,}} R A 7, R A 8 are each preferably having 1 to 12 carbon atoms which may be substituted linear or branched alkyl group (e.g. methyl group, trichloromethyl group, trifluoromethyl Group, methoxymethyl group, ethyl group, propyl group, n-butyl group, hexyl group, 3-chloropropyl group, phenoxymethyl group, 2,2,2-trifluoroethyl group, t-butyl group, hexafluoro-i -Propyl group, octyl group, decyl group, etc., and optionally substituted aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, methylbenzyl group, trimethylbenzyl group, heptamethylbenzyl group, methoxybenzyl group, etc.) ), An optionally substituted aryl group having 6 to 12 carbon atoms (eg, phenyl, nitrophenyl, cyanophenyl, methanesulfonylphenyl, Toxiphenyl, butoxyphenyl, chlorophenyl, dichlorophenyl, trifluoromethylphenyl, etc.).

L ^A is

Embedded image In case of representing a, R ^A ₉ and R ^A ₁₀ may be the same or different from each other, the preferred examples R ^A ₄ ~
Represent preferred and the substituents R ^A _8.

L ^A

Embedded image In the formula, Y ₁ represents an oxygen atom or a sulfur atom. ^{_{R A 11, R A 12,}} R A 13 may be the same or different, each preferably represents a hydrogen atom, an unsubstituted or a good 1-12 carbon linear or branched alkyl group.
Preferred examples are the same contents as the R ^A ₄ ~R ^A _8. P ₁ represents an integer of 5 or 6.

Another preferred thiol group-forming functional group-containing monomer of the present invention contains at least one thiirane ring represented by the general formula (III) or (IV). General formula (III)

Embedded image General formula (IV)

Embedded image In formula (III), R ^A ₁₄ and R ^A ₁₅ may be the same or different, each represents a hydrogen atom or a hydrocarbon group.
Preferably represents a hydrogen atom or a substituent and preferred R ^A ₄ ~R ^A _7. In the formula (IV), X ^A represents a hydrogen atom or an aliphatic group. The aliphatic group preferably represents an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, etc.).

Still another preferred thiol group-forming functional group-containing monomer of the present invention is a monomer containing at least one sulfur atom-containing heterocyclic group represented by the general formula (V). General formula (V)

Embedded image In formula (V), Y ^A represents an oxygen atom or -NH- group. ^RA ₁₆ , ^RA ₁₇ and ^RA ₁₈ may be the same or different and each represent a hydrogen atom or a hydrocarbon group. Preferably represents a hydrogen atom or a substituent and preferred R ^A ₄ ~R ^A _7. R ^A ₁₉ and R ^A ₂₀ may be the same or different, a hydrogen atom, a hydrocarbon group or -O-R
^AII (R ^AII represents a hydrocarbon group). Preferably represents a substituent and preferred by the R ^A ₁ ~R ^A _3.

According to still another preferred embodiment of the present invention, the thiol group-forming functional group-containing monomer has a form in which at least two thiol groups located at positions sterically close to each other are simultaneously protected by one protecting group. Is a monomer containing at least one functional group having Examples of the functional group having at least two thiol groups at positions close to each other sterically close to each other with one protecting group simultaneously include, for example, those represented by the following general formulas (VI), (VII) and (VIII). Can be mentioned. General formula (VI)

Embedded image General formula (VII)

Embedded image General formula (VIII)

Embedded image In the formulas (VI) and (VII), Z ^A represents a carbon-carbon bond or a chemical bond directly connecting C—S bonds which may be via a hetero atom (provided that the number of atoms between sulfur atoms is 4 ). Further, one-(Z ^A ... C) -bond represents only a mere bond, and may be, for example, as follows.

Embedded imageIn the formula (VII), R^A _{twenty one}, R^A _{twenty two}Are the same but different
A hydrogen atom, a hydrocarbon group or -OR
^AII(R^AIIRepresents a hydrocarbon group). Expression (VI
In I), R^A _{twenty one}And R^A _{twenty two}Are preferably the same as each other
Or may be different, a hydrogen atom, having 1 to 12 carbon atoms
An alkyl group which may be substituted (eg, a methyl group, an ethyl group
Group, propyl group, butyl group, hexyl group, 2-methoxy
Ethyl group, octyl group, etc.)
Aralkyl groups such as benzyl, phenethyl
Group, methylbenzyl group, methoxybenzyl group, chloroform
An alicyclic group having 5 to 7 carbon atoms (for example, cyclo
Pentyl group, cyclohexyl group, etc.) or substituted
Aryl groups (eg phenyl, chlorophenyl,
Methoxyphenyl group, methylphenyl group, cyanophenyl
Group) or -OR ^AII(R^AIIIs R^A _{twenty one}, R^A _{twenty two}To
Synonymous with a hydrocarbon group in the formula). In equation (VIII)
Where R^A _{twenty three}, R^A _{twenty four}, R^A _{twenty five}, R^A ₂₆Are the same as each other
Or may be different, each being a hydrogen atom or a hydrocarbon group
Represents Preferably, a hydrogen atom or the above R^A _{twenty one}, R^A
_{twenty two}Tables containing the same meanings as the hydrocarbon groups that are preferred in
I forgot.

The monomer (A) containing at least one of the functional groups represented by the above general formulas (II) to (VIII) used in the present invention is described, for example, in "Reactivity" by Yoshio Iwakura and Keisuke Kurita. Polymers, pp. 230-237 (Kodansha: 197)
7), edited by The Chemical Society of Japan, "New Experimental Chemistry Course Vol. 14, Synthesis and Reaction of Organic Compounds [III]", Chapter 8, pages 1700-1713 (Maruzen Co., Ltd., 1978), JFW
McOmie `` Protective Groups in Organic Chemistry ''
Chapter 7 (Plenum Press. 1973), S. Patai "The
Chemistry of the thiol group Part 2 ", Chapter 12,
The method described in Chapter 14 (John Wiley & Sons, 1974) or the like can be applied.

More specifically, the general formulas (II) to (VIII)
Examples of the monomer (A) having a functional group of the following include the following compounds.

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Next, regarding a functional group that forms at least one phosphono group and / or —PO (OH) R ₁ group by decomposition, for example, a functional group that forms a group represented by the following general formula (IX) or (X) explain in detail. General formula (IX)

Embedded image General formula (X)

Embedded image In formula (IX), R ^B is a hydrocarbon group or -Z ^B ₂ -R
^BI (where R ^BI represents a hydrocarbon, and Z ^B ₂ represents an oxygen atom or a sulfur atom). Q ^B ₁ represents an oxygen atom or a sulfur atom. Z ^B ₁ represents an oxygen atom or a sulfur atom. In the formula (XII), Q ^B ₂ , Z ^B ₃ and Z ^B
₄ each independently represents an oxygen atom or a sulfur atom. Preferably, R ^B is an optionally substituted alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group) or —Z ^B ₂ —R ^BI (where Z ^B ₂ is oxygen .R ^BI representing the atom or sulfur atom represents R ^B. represents the same content _{^{as) Q B 1, Q B 2}} , Z B 1, Z B 3, Z B 4 each independently represent an oxygen atom or a sulfur atom .

By the decomposition as described above, the formula (IX) or (X)
Examples of the functional group that generates a phosphono group represented by are the functional groups represented by the general formulas (XI) and / or (XII). General formula (XI)

Embedded image General formula (XII)

Embedded image In formulas (XI) and (XII), Q ^B ₁ , Q ^B ₂ ,
_{^{Z B 1, Z B 3,}} Z B 4 and R ^B represent the content as defined by the respective formulas (IX) and (X). L ^B _1, L ^B ₂
And L ^B ₃ are each independently of one another

Embedded image Represents L ^B ₁ ~L ^B ₃ is

Embedded image In case of representing a, R ^B ₁ ~R ^B ₂ may be the same or different, each represents a hydrogen atom, a halogen atom (e.g. a chlorine atom, a bromine atom, a fluorine atom) or a methyl group. X ^B ₁ and X ^B _{2 each} represent an electron-withdrawing group (here, the electron-withdrawing group is a substituent having a positive Hammett's substituent constant, such as a halogen atom,

Embedded image And the like), preferably a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), -CN, -
CONH ₂ , —NO ₂ or —SO ₂ ^RBII ( ^RBII is a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a benzyl group, a phenyl group, a tolyl group, a xylyl group,
Represents a hydrocarbon group such as a mesityl group). n is 1
Or 2 is represented. Further, when X ^B ₁ is a methyl group, R
^B ₁ and R ^B ₂ represents n = 1 with a methyl group.

[0032] L ^B ₁ ~L ^B ₃ is

Embedded image In the case of representing, R ^B ₃ , R ^B ₄ and R ^B ₅ may be the same or different from each other, and are preferably a hydrogen atom,
A linear or branched alkyl group having 1 to 18 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, chloroethyl group , A methoxyethyl group, a methoxypropyl group, etc.), an alicyclic group which may be substituted (for example, a cyclopentyl group, a cyclohexyl group, etc.),
An optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl, phenethyl, chlorobenzyl, methoxybenzyl, etc.), an optionally substituted aromatic group (e.g., phenyl, naphthyl, chlorophenyl, A toryl group, a methoxyphenyl group, a methoxycarbonylphenyl group, a dichlorophenyl group, etc.) or ^-ORBIII ( ^RBIII
Represents a hydrocarbon group, and specifically, R ^B ₃ ,
Represents a R ^B _4, substituents such R ^B ₅ can be cited as an example).

L ^B _{1 to} L ^B ₃ are

Embedded image In case of representing ^{_{a, R B 6, R B 7}} , R B 8, R B 9
And R ^B ₁₀ each independently represents a hydrocarbon group. Preferably substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms (for example, methyl group, trichloromethyl group, trifluoromethyl group, methoxymethyl group, phenoxymethyl group, 2,2,2- Trifluoroethyl group, ethyl group,
Propyl group, hexyl group, t-butyl group, hexafluoro-i-propyl group, etc.),
9 aralkyl groups (for example, benzyl group, phenethyl group,
A methylbenzyl group, a trimethylbenzyl group, a heptamethylbenzyl group, a methoxybenzyl group, etc., an aryl group having 6 to 12 carbon atoms which may be substituted (for example, a phenyl group,
Tolyl, xylyl, nitrophenyl, cyanophenyl, methanesulfonylphenyl, methoxyphenyl, butoxyphenyl, chlorophenyl, dichlorophenyl, trifluoromethylphenyl, etc.).

[0034] further L ^B ₁ ~L ^B ₃

Embedded image In the formula, Y ^B ₁ and Y ^B ₂ represent an oxygen atom or a sulfur atom.

The functional group used in the present invention has at least one functional group.
The seed-containing monomer can be synthesized by introducing a protecting group according to a conventionally known method. The same synthetic reaction can be used as a method for introducing a protecting group. Specifically, JFWMcOmie “Protective groups
in Organic Chemistry ", Chapter 6 (Plenum Press, 197
Or the hydroxyl group described in “New Experimental Chemistry Lecture Vol. 14, Synthesis and Reaction of Organic Compounds [V]” edited by The Chemical Society of Japan, page 2497 (published by Maruzen Co., Ltd., 1978). Synthetic reaction similar to the method of introducing a protecting group into S. Patai, or `` The Chemistry of the Triol
Group Part 2 ”Chapters 13 and 14 (Wiley-Intersci
ence 1974), TWGreene "Protective group
s in Organic Synthesis ", Chapter 6 (Wiley-Interscien
1981) and the like, and can be produced by the same synthetic reaction as the method for introducing a protecting group into a thiol group.

Specific examples of the compound which can be a repeating unit of a polymerization component having a functional group capable of forming a phosphono group of the general formula (XI) and / or (XII) used in the present invention are as follows. be able to.

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Next, an amino group such as —NH
Examples of the functional group that generates _two groups and / or a —NHR ^C group include groups represented by the following general formulas (XIII) to (XV). General formula (XIII)

Embedded image General formula (XIV)

Embedded image General formula (XV)

Embedded image In the formulas (XIII) and (XV), R ^C ₀ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group) Group, decyl group, dodecyl group, 2-chloroethyl group, 2-bromoethyl group, 3-chloropropyl group,
2-cyanoethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-methoxycarbonylethyl group, 3-
A methoxypropyl group, a 6-chlorohexyl group, etc.), an alicyclic group having 5 to 8 carbon atoms (eg, cyclopentyl group, cyclohexyl group, etc.), an aralkyl group which may be substituted having 7 to 12 carbon atoms (eg, benzyl group, Phenethyl group, 3-
Phenylpropyl group, 1-phenylpropyl group, chlorobenzyl group, methoxybenzyl group, bromobenzyl group,
An optionally substituted aryl group having 6 to 12 carbon atoms (e.g., phenyl, chlorophenyl, dichlorophenyl, tolyl, xylyl, mesityl, chloromethyl, chlorophenyl, methoxyphenyl); Ethoxyphenyl group, chloromethoxyphenyl group, etc.). When R ^C ₀ represents the hydrocarbon group, hydrocarbon groups having 1 to 8 carbon atoms are preferred.

In the functional group represented by the formula (XIII), R
^C ₁ represents an aliphatic group having 2 to 12 carbon atoms which may be substituted, and more specifically, R ^C ₁ represents a group represented by the following formula (XVI). Formula (XVI)

Embedded image In the formula (XVI), a ₄ and a ₅ are each a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, etc.) or a hydrocarbon group having 1 to 12 carbon atoms which may be substituted (eg, a methyl group, an ethyl group, Propyl, butyl, hexyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-
Chloroethyl, 3-bromopropyl, cyclohexyl, benzyl, chlorobenzyl, methoxybenzyl, methylbenzyl, phenethyl, 3-phenylpropyl, phenyl, tolyl, xylyl, mesityl, chlorophenyl Methoxyphenyl group, dichlorophenyl group, chloromethylphenyl group, naphthyl group, etc.), Y ^C represents a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms ( For example, a methyl group, an ethyl group, a propyl group, a butyl group and the like, and an aromatic group which may contain a substituent (for example, a phenyl group, a tolyl group, a cyanophenyl group, a 2,6-dimethylphenyl group, a 2,4, 6-trimethylphenyl group, heptamethylphenyl group, 2,6-dimethoxyphenyl group, 2,4,6 Trimethoxyphenyl group, 2-propylphenyl group, 2-butylphenyl group, 2-chloro-6-methylphenyl group, furanyl group), or -SO ₂
-R ^C ₆ (R ^C ₆ is Y represent similar content and ^C hydrocarbon group) and the like. n represents 1 or 2.

More preferably, when Y ^C is a hydrogen atom or an alkyl group, a ₄ and a ₅ on carbon adjacent to the oxygen atom of the urethane bond represent a substituent other than a hydrogen atom.
When Y ^C is not a hydrogen atom or an alkyl group, a ₄ and a ₅ may be any of the groups described above. That is,

Embedded image In the above, it is preferable to form a group containing at least one or more electron-withdrawing groups or a case where carbon adjacent to an oxygen atom of a urethane bond forms a sterically bulky group. is there.

R ^C ₁ is an alicyclic group such as a monocyclic hydrocarbon group (eg, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-methyl-cyclohexyl, 1-methylcyclobutyl). Or a bridged cyclic hydrocarbon group (bicyclooctane group, bicyclooctene group,
Bicyclononane group, tricycloheptane group, etc.).

In the general formula (XIV), R ^C ₂ and R ^C ₃
May be the same or different and each represents a hydrocarbon group having 1 to 12 carbon atoms, and specifically represents the same content as the aliphatic group or the aromatic group in Y ^C of the formula (XVI). In the general formula (XIV), X ^C ₁ and X ^C ₂ may be the same or different and each represent an oxygen atom or a sulfur atom. R
^C ₄ and R ^C ₅ may be the same or different and each represents a hydrocarbon group having 1 to 8 carbon atoms, and specifically, represented by the formula (XVI)
It represents an aliphatic group or an aromatic group in the Y ^C.

Specific examples of the functional groups of the formulas (XIII) to (XV) are shown below. As specific monomers containing these functional groups
Is a thiol group or phosphono group
In specific examples of the monomer containing a functional group, the thiol group
Unit instead of a functional group or phosphono group functional group
And the like.

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The functional group used in the present invention to generate an amino group (for example, an —NH ₂ group and / or an —NHR group) by decomposition, for example, a functional group selected from the group of the above general formulas (XIII) to (XV) Monomers containing at least one compound are described, for example, in "Nippon Kagaku Koza Koza Vol. 14, Synthesis and Reaction of Organic Compounds [V]", page 2555 (published by Maruzen Co., Ltd.), JFW McOmie, "Protective groups in Organic". C
hemistry ”Chapter 2 (PlenumPress 1973),“ P
rotective groups in Organic Sinthesis ", Chapter 7 (Joh
n Wiley & Sons, 1981) and the like.

Further, the functional group which forms at least one sulfo group upon decomposition includes, for example, a compound represented by the following general formula (XVII):
Or a functional group represented by (XVIII). Formula _{(XVII) -SO 2 -O-R} D 1 formula _{(XVIII) -SO 2 -S-R} D 2 formula (XVII) Medium R ^D ₁ is

Embedded image Or an -NHCOR ^D _7. In the formula (XVIII), R
^D ₂ is an optionally substituted aliphatic group having 1 to 18 carbon atoms,
Or an aryl group which may have a substituent having 6 to 22 carbon atoms.

The functional groups of the general formulas (XVII) and (XVIII) generate a sulfo group by decomposition, and will be described in more detail below. R ^D ₁

Embedded image In the formula, R ^D ₃ and R ^D ₄ may be the same or different, and represent a hydrogen atom, a halogen atom (for example, a fluorine atom,
A chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group,
Pentyl group, hexyl group). Y ^D has 1 to 1 carbon atoms
18 optionally substituted alkyl groups (for example, methyl group,
Ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, trifluoromethyl group, methanesulfonylmethyl group, cyanomethyl group, 2-methoxyethyl group, ethoxymethyl group, Chloromethyl group, dichloromethyl group, trichloromethyl group, 2-methoxycarbonylethyl group, 2-
Propoxycarbonylethyl group, methylthiomethyl group,
Ethylthiomethyl group, etc.), an alkenyl group having 2 to 18 carbon atoms which may be substituted (for example, vinyl group, allyl group, etc.),
An aryl group which may have a substituent having 6 to 12 carbon atoms (for example, a phenyl group, a naphthyl group, a nitrophenyl group,
Dinitrophenyl, cyanophenyl, trifluoromethylphenyl, methoxycarbonylphenyl, butoxycarbonylphenyl, methanesulfonylphenyl, benzenesulfonylphenyl, tolyl, xylyl, acetoxyphenyl, nitronaphthyl, etc.) or

Embedded image (R ^D ₈ represents an aliphatic group or an aromatic group, and specifically represents the same as the above-mentioned substituent of Y ^D ). n
Represents 0, 1 or 2. More preferably, the substituent:

Embedded image In the above, a functional group containing at least one electron-withdrawing group is exemplified. Specifically, when n is 0 and Y ^D is a hydrocarbon group containing no electron-withdrawing group as a substituent,

Embedded image Contains at least one halogen atom. Further, n is 0, 1 or 2, and Y ^D contains at least one electron-withdrawing group. Further, when n = 1 or 2,

Embedded image And the like.

Another preferred substituent is -SO
_{In 2-} O- ^RD , the carbon atom adjacent to the oxygen atom is substituted by at least two hydrocarbon groups, or n =
When 0 or 1 and Y ^D is an aryl group, the aryl group may have a substituent at the 2-position and the 6-position.

R ^D ₁

Embedded image In the case of, Z ^D represents an organic residue forming a cyclic imide group. Preferably, the general formula (XIX) or (XX)
Represents an organic residue represented by General formula (XIX)

Embedded image General formula (XX)

Embedded image Wherein _{^{(XIX), R D 9,}} R D 10 may be the same or different and each are each a hydrogen atom, a halogen atom (e.g. a chlorine atom,
A bromine atom etc., an alkyl group which may be substituted and has 1 to 18 carbon atoms (e.g., methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, 2-chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, 3
-Chloropropyl group, 2- (methanesulfonyl) ethyl group, 2- (ethoxyoxy) ethyl group, etc.), having 7 to 7 carbon atoms.
12 aralkyl groups which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group,
Chlorobenzyl group, bromobenzyl group, etc.), having 3 to 3 carbon atoms
Represents 18 alkenyl groups which may be substituted (for example, allyl group, 3-methyl-2-propenyl group, etc.).

R ^D ₁ is

Embedded imageIn the case of representing,^D _Five, R^D ₆Is a hydrogen atom,
Aliphatic groups (specifically, R ^D _Three, R^D _FourSame as that of
) Or an aryl group (specifically, R^D _Three, R^D _Four
Represents the same content as that of. Where R^D _Fiveas well as
R^D ₆Do not both represent a hydrogen atom. R^D ₁But-
NHCOR^D ₇In the case of representing,^D ₇Is an aliphatic group
Or an aryl group, and specifically, R^D _Three, R^D _FourNoso
These represent the same contents. In the formula (XX), R^D _TwoIs carbon
An aliphatic group which may be substituted and has 6 to 18 carbon atoms;
Represents an aryl group which may have 22 substituents. More
Specifically, Y represented by the above formula (XVII)^DFat in
It represents the same content as an aliphatic group or an allyl group.

The general formula [-SO used in the present invention_Two-O
-R^D ₁] Or [-SO_Two-OR ^D _Two] Selected from the group
Monomers containing at least one functional group are
It can be synthesized based on knowledge of an organic reaction. An example
For example, J.F.W.McOmie, `` Protective Groups in Organic C
hemistry "; PlenumPress (1973), T.W.Green
e, `` Protective Groups in Organic Sinthesis '' John W
Preservation of carboxyl groups such as iley & Sons (1980)
Can be synthesized in the same manner as the protection reaction.

More specifically, the compound represented by the general formula (XVII) -SO_Two-O
-R^D ₁Or a compound of the general formula (XVIII) -SO _Two-OR^D _TwoOfficial
The following examples can be given as the functional groups.
The scope of the description is not limited to these.

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As the insoluble polymer component in the resin particles of the present invention, together with the monofunctional monomer (A), another monomer copolymerizable with the monomer (A) is present as a polymer component. You may. Examples of such a monomer include, in addition to methacrylic acid esters, acrylic acid esters, crotonic acid esters, α-olefin acid, vinyl carboxylate or acrylic acid esters (for example, acetic acid, propionic acid as carboxylic acid) , Butyric acid, valeric acid, benzoic acid,
Naphthalene carboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic esters (eg, dimethyl ester, diethyl ester, etc.),
Acrylamides, methacrylamides, styrenes (eg, styrene, vinyltoluene, chlorostyrene,
Hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinylsulfone-containing compounds, vinylketone-containing compounds, heterocyclic vinyls (for example, vinylpyrrolidone, vinylpyridine, vinylimidazole, Vinylthiophene, vinylimidazoline, vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.).

As the polymer component in the resin particles of the present invention,
The proportion of the monomer (A) is 30% by weight or more, preferably 5% by weight.
0% by weight or more, and particularly preferably, the resin particles are composed of only the monomer (A) and the monofunctional polymer [M]. When the composition contains another copolymerizable monomer, the content of the other monomer is at most 20% by weight or less. When the resin particles are copolymers, the polymer component containing a hydrophilic group-forming functional group in the resin particles of the present invention is 10 to 95% by weight, preferably 20 to 90% by weight of the total copolymer.
% By weight. What is important as the polymer component that becomes insoluble in the non-aqueous solvent is that the material after the formation of the hydrophilic group has a hydrophilicity represented by a contact angle to distilled water of 50 ° or less. .

Next, the monofunctional polymer [M] will be described. A polymerizable double-bonding group represented by the general formula (I) is bonded to only one terminal of the polymer main chain at least including a repeating unit containing a substituent containing a silicon atom and / or a fluorine atom. It is important that the polymer is characterized by copolymerizing with the monomer (A) and solvating with the non-aqueous solvent and being soluble. It works.
The monofunctional polymer [M] of the present invention is soluble in the non-aqueous solvent, and specifically, at a temperature of 25 ° C. with respect to 100 parts by weight of the solvent.
Should be at least 5% by weight. The weight average molecular weight of the monofunctional polymer [M] is from 1 × 10 ³ to 1 × 10 ⁵ , preferably 2 × 10 ^3.
5 × 10 ⁴ , particularly preferably 3 × 10 ³ to 2 × 10 ⁴
It is. The weight average molecular weight of the monofunctional polymer [M] is 1 ×
When it becomes less than 10 ³ or more than 1 × 10 ⁵ ,
Aggregation of the generated dispersed resin particles occurs, and fine particles having a uniform average particle size cannot be obtained.

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

Embedded imageIn the general formula (I), V₀Is -O-, -COO-,-
OCO-,-(CH _Two) -OCO-,-(CH_Two) -C
OO-, -SO_Two−,

Embedded image Represents -CONHCOO- or -CONHCONH-.

Here, R ₃ is a hydrogen atom, and a preferable hydrocarbon group is an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group). , 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-
A methoxyethyl group, a 3-bromopropyl 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.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group,
Phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group,
A methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) Or an optionally substituted aromatic group having 6 to 12 carbon atoms (for example, phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, 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, propionitrile amido phenyl group, such as dodecane white ylamide phenyl group).

V ₀ is

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

A₁And a_TwoAre the same but different
And preferably a hydrogen atom, a halogen atom (eg,
Chlorine atom, bromine atom, etc.), cyano group,
Alkyl group (for example, methyl group, ethyl group, propyl
Group, butyl group, etc.) -COO-R _FourOr through hydrocarbons
-COOR_Four(R_FourIs a hydrogen atom or a group having 1 to 18 carbon atoms.
Alkyl group, alkenyl group, aralkyl group, alicyclic group or
Represents an aryl group, which may be substituted
Specifically, the above R₁As described for
Represents the contents of). -C via the above hydrocarbon
OOR_FourExamples of the hydrocarbon in the group include a methylene group,
Examples include a tylene group and a propylene group.

More preferably, in the general formula (I):
V ₀ is, -COO -, - OCO -, - CH 2 OCO-,
_{-CH 2 COO -, - O -} , - CONH -, - SO 2 N
H-, -CONHCOO- or

Embedded image A ₁ and a ₂ may be the same or different from each other, and represent a hydrogen atom, a methyl group, —COOR ₄ ′ or —C
H ₂ COOR ₄ ′, wherein R ₄ ′ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc.). represents one is always a hydrogen atom in the a ₁ and a _2.

That is, as the polymerizable double bond group-containing moiety represented by the general formula (I), specifically,

Embedded image And the like.

Next, the repeating unit having a substituent containing a silicon atom and / or a fluorine atom in the monofunctional polymer [M] will be described. Examples of the chemical structure of the repeating unit include those obtained from a radical addition polymerizable monomer, those formed of a polyester structure, those formed of a polyether structure, and the like. And any one containing a silicon atom and / or a fluorine atom. As the substituent containing a fluorine atom, for example, -C _h F _{2h + 1} (h
Represents an integer of 1 to 12),-(CF ₂ ) _j CF ₂ H
(J represents an integer of 1 to 11),

Embedded image And the like.

As the substituent containing a silicon atom, for example,

Embedded image And a polysiloxane structure. Where R ₅ ,
R ₆ and R ₇ may be the same or different and represent an optionally substituted hydrocarbon group or an —OR ₁₁ group (R ₁₁ represents the same content as the hydrocarbon group of R ₅ ). R ₅ represents an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, 2
-Chloroethyl group, 2-bromoethyl group, 2,2,2-
Trifluoroethyl group, 2-cyanoethyl group, 3,3
3-trifluoropropyl group, 2-methoxyethyl group,
3-bromopropyl group, 2-methoxycarbonylethyl group, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl group and the like, and optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, , 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-
2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc., and optionally substituted aralkyl groups having 7 to 12 carbon atoms (for example, benzyl group) Phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), Carbon number 5
To 8 optionally substituted alicyclic groups (e.g., cyclohexyl group, 2-cyclohexyl group, 2-cyclopentylethyl group, etc.) or optionally substituted aromatic groups having 6 to 12 carbon atoms (e.g., Phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, didecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl Group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecylylamidophenyl group, etc.). . In the —OR ₁₁ group, R ₁₁ represents the same content as the above-mentioned hydrocarbon group of R ₅ . R ₈ , R ₉ and R ₁₀ may be the same or different and represent the same contents as R ₅ , R ₆ and R ₇ .

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

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The monofunctional polymer [M] of the present invention comprises a polymerizable double bond represented by the general formula (I) and a repeating unit having a substituent containing a silicon atom and / or a fluorine atom. At least one terminal of the main chain of the polymer is directly bonded or bonded with an arbitrary linking group. Specifically, the linking group is a divalent organic residue,

Embedded image And a bonding group selected from the following. It represents an organic residue composed of a divalent aliphatic group or a divalent aromatic group, or a combination of these divalent residues. Where g ₁
To g ₅ represent the same meaning as R ₁ in formula (I).

As the divalent aliphatic group, for example,

Embedded image {E ₁ and e ₂ which include may be the same or different, each represents a hydrogen atom, a halogen atom (e.g. fluorine atom, a chlorine atom, a bromine atom) or an alkyl group (e.g. methyl group having 1 to 12 carbon atoms , Ethyl, propyl, chloromethyl, bromomethyl, butyl, hexyl, octyl, nonyl, decyl, etc.). Q
Is -O -, - S- or -NR ₁₂ - it represents, R ₁₂ is an alkyl group having 1 to 4 carbon atoms, -CH ₂ Cl or -CH ₂ Br
｝.

The divalent aromatic group includes, for example, a benzene ring group, a naphthalene ring group and a 5- or 6-membered heterocyclic group (hetero atoms constituting a heterocyclic ring are selected from oxygen, sulfur and nitrogen atoms. Containing at least one heteroatom). These aromatic groups may have a substituent, for example, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a propyl group) , A butyl group, a hexyl group, an octyl group, etc.) and a C1-C6 alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.) are mentioned as examples of the substituent.
Examples of the heterocyclic group include a furan ring, a thiophene ring, a pyridine ring, a pyrazine ring, a piperazine ring, a tetrahydrofuran ring, a pyrrole ring, a tetrahydropyran ring, and a 1,3-
Oxazoline ring and the like.

The monofunctional polymer [M] of the general formula (I)
Specific examples of the polymerizable double bond group-containing portion represented by and the portion composed of an organic residue linked thereto include the following, but are not limited thereto.
However, in each of the following examples, P ₁ is -H, -CH ₃ ,-
CH ₂ COOCH _3, -Cl, shows -Br or -CN, P ₂ represents -H or -CH _3, X ₁ represents a -Cl or -Br, n is an integer of 2 to 12, m Is 1-4
Indicates an integer.

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In the total of the repeating units of the monofunctional polymer [M] of the present invention, the repeating units having a substituent containing a silicon atom and / or a fluorine atom account for 40 units in total.
% By weight or more, more preferably 60 to 100% by weight. When the content of the above components of the present invention is less than 40% by weight, the effect of concentrating the resin particles dispersed in the image receiving layer, particularly on the surface portion, is reduced, and as a result, the effect of improving the water retention as a printing original plate is reduced. Would.

The monofunctional polymer [M] of the present invention can be produced by a conventionally known synthesis method. For example,
A) a method by ionic polymerization, in which a terminal of a living polymer obtained by anionic or cationic polymerization is reacted with various reagents to obtain a monofunctional polymer [M];
B) a polymer having a terminal reactive group bond obtained by radical polymerization using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a carboxyl group, a hydroxyl group, or an amino group in the molecule; A radical polymerization method of reacting various reagents to obtain a monofunctional polymer [M]; c) polymerizing the polymer obtained by polyaddition or polycondensation reaction in the same manner as in the above radical polymerization method. Examples include a method by a polyaddition condensation method for introducing a heavy bond group.

Specifically, P. Dreyfuss & RP Quirk
, Encycl. Polym. Sci. Eng., 7 , 551 (198
7), PF Rempp, E. Franta, Adv. Polym. Sci., 5
8 , 1 (1984), V. Percec, Appl. Poly. Sci., 2
85 , 95 (1984), R. Asami, M. Takari, Macro
mol. Chem. Suppl., 12 , 163 (1985), P. Rem.
pp., et al, Macromol. Chem. Suppl., 8 , 3 (198
4), Yusuke Kawakami, Chemical Industry, 38 , 56 (1987),
Yuya Yamashita, High Polymer, 31 , 988 (1982), Shiro Kobayashi, High Polymer, 30 , 625 (1981), Toshinobu Higashimura, Journal of the Adhesion Society of Japan, 18 , 536 (1982), Koichi Ito,
Polymer synthesis, 35 , 262 (1986), Kishiro Higashi, Takashi Tsuda, Functional Materials, 1987 , No. 10, 5, and the like, and synthesis can be performed according to the methods described in the references and patents.

As a method for synthesizing the monofunctional polymer [M] as described above, more specifically, a polymer [M] containing a repeating unit corresponding to a radical polymerizable monomer is disclosed in
No. 67563, Japanese Patent Application No. 63-64970, Japanese Patent Application Nos. 1-206989 and 1-69011, each of which is described in the specification of the application, and contains a polyester structure or a polyether structure as a repeating unit. The polymer [M] to be obtained is disclosed in Japanese Patent Application Nos. 1-56379 and 1-58989.
It is obtained in the same manner as the method described in the specification of the application as each of the above-mentioned 1-56380.

As described above, the dispersed resin particles of the present invention are decomposed to form a monofunctional monomer (A) having a functional group which generates at least one hydrophilic group by the above-mentioned monofunctional resin [M]. Is a copolymer resin particle obtained by dispersion polymerization in the presence of a polymer.

The resin particles of the present invention may be at least partially crosslinked. Resin particles in which at least a part of the polymer has been cross-linked in advance (resin having a cross-linked structure in the polymer) are obtained by decomposing the hydrophilic group-forming functional group contained in the resin into a hydrophilic group. Particularly, resin particles that are hardly soluble or insoluble in acidic and alkaline aqueous solutions are preferable.

Further, when the dispersed resin particles of the present invention have a network structure, a polymer component having the above-mentioned hydrophilic group-forming functional group-containing monofunctional monomer (A) as a main component [polymer component ( A) is bridged between the polymers to form a higher-order network structure.

That is, the dispersed resin particles of the present invention comprise a non-aqueous resin composed of a portion insoluble in a non-aqueous dispersion solvent composed of the polymer component (A) and a polymer soluble in the solvent. When it is a latex and has a network structure, the molecules of the polymer component (A) forming a part insoluble in the solvent are bridged. As a result, the network resin particles after the generation of the hydrophilic group become hardly soluble or insoluble in water. Specifically, the solubility of the resin in water is 80% by weight or less, preferably 50% by weight or less.

The crosslinking of the present invention can be carried out by a conventionally known crosslinking method. That is, (a) a method of crosslinking a polymer containing the polymer component (A) with various crosslinking agents or curing agents, and (b) a method of 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 when performing a polymerization reaction by It can be carried out by a method such as a method of cross-linking the united component (A) with a polymer containing a component containing a reactive group by a polymerization reaction or a polymer reaction.

As the crosslinking agent in the method (a), there can be mentioned compounds which are usually used as a crosslinking agent.
Specifically, compounds described in Shinzo Yamashita and Tosuke Kaneko, "Handbook of Crosslinking Agents" Taiseisha (1981), edited by the Society of Polymer Science, "Basic Edition of Polymer Data Handbook", Baifukan (1986), etc. Can be used.

For example, organic silane compounds (for example, vinyltrimethoxysilane, vinyltributoxysilane,
silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, etc.), polyisocyanate-based compounds (eg, toluylene diisocyanate, o-toluene) Range isocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymer polyisocyanate, etc.), polyol compound (for example, 1, 4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane, etc.), polyamine-based compounds (for example, ethylenediamine, γ-hydroxyp Pill of ethylene diamine,
Phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.),
Polyepoxy group-containing compound and epoxy resin (for example,
"New epoxy resin" edited by Hiroshi Kakiuchi, Shokodo (1985), "Epoxy resin" edited by Kuniyuki Hashimoto, compounds described in Nikkan Kogyo Shimbun (1969), etc., melamine resin (for example, Ichiro Miwa, Hideo Matsunaga) Compounds described in “Uria Melamine Resin” edited by Nikkan Kogyo Shimbun (1969) and the like, and poly (meth) acrylate compounds (for example, “Oligomer” Kodansha (1976) edited by Shin Okawara, Takeo Saegusa, Toshinobu Higashimura Compounds described in Eizo Omori, “Functional Acrylic Resin” Techno System (published in 1985) and the like. Specifically, polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6- Hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol polyacryle Door, bisphenol A-
Examples include diglycidyl ether diacrylate, oligoester acrylate, and methacrylates thereof.

Polymerization of a polyfunctional monomer (also referred to as a polyfunctional monomer (D)) or a polyfunctional oligomer containing two or more polymerizable functional groups coexisting by the method (b) As the functional functional group, specifically,

Embedded image And the like. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

Specific examples of the monomer having two or more polymerizable functional groups include, as monomers or oligomers having the same polymerizable functional group, styrene derivatives such as divinylbenzene and trivinylbenzene; Alcohol (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 20)
0, $ 400, $ 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, or the like, or polyhydroxyphenol (e.g., hydroquinone, resorcin, catechol) And their derivatives)
Methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers: dibasic acids (eg, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) Vinyl esters, allyl esters, vinyl amides or allyl amides: polyamines (eg, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) and carboxylic acids containing vinyl groups (eg, methacrylic acid, acrylic Acid, crotonic acid, allyl acetic acid, etc.).

Examples of the monomer or oligomer having a different polymerizable functional group include carboxylic acids having a vinyl group (eg, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, allyloyl) Reactants of propionic acid, itaconiloyl acetic acid, itaconiloyl propionic acid, carboxylic anhydride, etc. and alcohols or amines (for example, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropion) Ester derivative or amide derivative containing a vinyl group such as an acid or the like (eg, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, methacryloy) Vinyl acetate, methacryloyl propionic acid vinyl, methacryloyl propionic acid allyl, vinyl methacrylate oxycarbonyl ester, vinyl acrylate oxycarbonyl methyloxycarbonyl ethylene ester, N- allyl acrylamide, N-
Allyl methacrylamide, N-allylitaconic acid amide, methacryloylpropionic acid allylamide, etc.) or amino alcohols (eg, aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and vinyl group And a condensate with a carboxylic acid containing the same.

The monomer or oligomer having two or more polymerizable functional groups used in the present invention may be a monomer (A)
And 10% based on the total amount of other monomers coexisting with (A).
Polymerization is carried out using not more than 5 mol%, preferably not more than 5 mol% to form a resin.

Further, when a chemical bond is formed by a reaction between reactive groups between polymers in the above method (c) to form a bridge between polymers, the reaction between the ordinary organic low-molecular compound and The same can be done. Specifically, Yoshio Iwakura, Keisuke Kurita "Reactive Polymers" Kodansha (1977), Ryohei Oda "Polymer Fine Chemicals" Kodansha (1976),
JP-A-61-43775, Japanese Patent Application No. 1-149030.
No. 5 is described in detail in the specification and the like.

For example, a polymer reaction using a combination of a functional group of Group A and a functional group of Group B shown in Table 1 below is a well-known method. Note that R ₁₃ and R _{14 in} Table 1 are used.
Is a hydrocarbon group, and has the same contents as g ₄ and g ₅ in —Si (g ₄ ) (g ₅ ) — described above.

[Table 1] In the dispersion polymerization, monodisperse particles having a uniform particle diameter are obtained, and fine particles of 0.5 μm or less are easily obtained. (B) is preferred.

As described above, the network-dispersed resin particles of the present invention contain protected thiol groups, phosphono groups, -PO (O
H) Particles of a polymer containing a repeating unit containing an R ₁ group and an amino group, and a polymer component soluble in the non-aqueous solvent, and having a structure in which the molecular chains are highly bridged. .

The non-aqueous solvent used in the production of the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or lower, and may be used alone or as a mixture of two or more. Good. Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol and benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ketones such as diethyl ketone, diethyl ether,
Ethers such as tetrahydrofuran and dioxane; carboxylic esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; and fats having 6 to 14 carbon atoms such as hexane, octane, decane, dodecane, tridecane, cyclohexane and cyclooctane. Group hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; and halogenated hydrocarbons such as methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane, and trichloroethane. However, the present invention is not limited to the compound examples described above.

By synthesizing the dispersed resin particles by a dispersion polymerization method in these non-aqueous solvent systems, the average particle diameter of the resin particles can be easily reduced to 0.8 μm or less, and the distribution of the particle diameter is very narrow and monodispersed. Particles. Specifically, KEJ Barrett "Dispersion Polymerization
in Organic Media "John Wiley (1975), Koichiro Murata, Polymer Processing, 23 , 20 (1974), Tsunetaka Matsumoto, Toyoyoshi Tange, Journal of the Adhesion Society of Japan 9 , 183 (197)
3), Tokichi Tange, Journal of the Adhesion Society of Japan 23 , 26 (198)
7), DJ Walbridge, NATO. Adv. Study. Inst. Se
rE No. 67, 40 (1983), UK Patent No. 893
429, 934038, U.S. Pat.
Nos. 2397, 3900412 and 460689, JP-A-60-179751, 60-18596
The method is disclosed in three publications.

The dispersion resin of the present invention comprises at least one kind of each of the monomer (A) and the monofunctional polymer [M],
In the case of forming a network structure, a polyfunctional monomer (D) is co-present if necessary, and in any case, it is important that the resin synthesized from these monomers is added to the non-aqueous solvent. If insoluble, desired dispersed resin particles can be obtained.
More specifically, the amount of the monomer (A) is 30% by weight or more, preferably 50% by weight or more,
The monofunctional polymer [M] is preferably used in an amount of 1 to 50% by weight, more preferably 2 to 30% by weight,
Particularly preferably, it is 5 to 25% by weight. When other copolymerizable monomers are used, the amount of other monomers is 20% by weight or less. The molecular weight of the dispersed resin particles of the present invention is 10 ⁴ to 10
⁶ , preferably 10 ^{4 to} 5 × 10 ⁵ .

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

The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably about 10 parts by weight, per 100 parts by weight of the nonaqueous solvent.
５０50 parts by weight. The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the polymerizable compound. The polymerization temperature is 30
To 180 ° C, preferably 40 to 120 ° C. The reaction time is preferably 1 to 15 hours.

As described above, the non-aqueous dispersion resin produced according to the present invention becomes fine particles having a uniform particle size distribution.

As the matrix resin (binder resin) provided in the image receiving layer of the present invention, all resins conventionally known as various binder resins can be used. Typical 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., as well as water-soluble polymer compounds, polyvinyl alcohol, modified polyvinyl alcohol, Examples include starch, oxidized starch, carboxymethylcellulose, hydroxyethylcellulose, casein, gelatin, polyacrylic acid, polyvinylpyrrolidone, polyvinylether-maleic anhydride copolymer, polyamide, and polyacrylamide.

The molecular weight of the resin of the matrix provided in the image receiving layer of the present invention is preferably 10 ³ to 10 ⁶ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁵ . The glass transition point of this resin is preferably from -10 ° C to 120 ° C.
° C, more preferably 0 ° C to 85 ° C. The content ratio of the resin particles in the image receiving layer is about 1 to 80 parts by weight of the resin particles with respect to 100 parts by weight of the matrix resin. If the amount is less than 1% by weight, background smearing occurs, and if it is more than 80% by weight, the image strength is undesirably reduced.

As other components of the image receiving layer of the present invention, an inorganic pigment is used. Examples of the inorganic pigment include kaolin clay, calcium carbonate, silica, titanium oxide, and the like.
Examples include zinc oxide, barium sulfate, and alumina. The ratio of the binder resin / pigment in the image receiving layer varies depending on the kind of the material and the particle size in the case of the pigment, but is generally 1 / (0.5 to 5) by weight ratio, preferably 1 / (0.8%). ~ 2.
5) The degree 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 cross-linking agent, ammonium chloride, an organic peroxide, ordinarily used,
Metallic soaps, organic silanes, polyurethane crosslinking agents, epoxy resin curing agents, and the like can be used. Specifically, it is described in Shinzo Yamashita and Tosuke Kaneko, "Handbook of Crosslinking Agents", Taiseisha Publishing (1981) and the like.

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

In the present invention, an intermediate layer is provided between the support and the image receiving layer for the purpose of improving water resistance and interlayer adhesion, and a back coat layer is provided on the support opposite to the image receiving layer for the purpose of preventing curling. (A back layer) can be provided. Here, the intermediate layer is an emulsion resin such as an acrylic resin, an ethylene-butadiene copolymer, a methacrylate-butadiene copolymer, an acrylonitrile-butadiene copolymer, an ethylene-vinyl acetate copolymer, an epoxy resin, a polyvinyl butyral. It is composed mainly of at least one kind of solvent-type resin such as polyvinyl chloride and polyvinyl acetate, and the above-mentioned water-soluble resin, and can add an inorganic pigment or a water-proofing agent as needed. . The configuration of the back coat layer is almost the same as that of the intermediate layer.

When used as a PPC plate, in order to further reduce the background contamination of the printing plate precursor of the present invention, the image receiving layer and the image receiving layer must have a volume resistivity of 10 ¹⁰ to 10 ¹³ Ωcm as the printing plate precursor. A dielectric agent can be added to the intermediate layer and / or the back coat layer. The dielectric agent may be an inorganic one or an organic one. Among the inorganic ones, Na, K, Li, Mg, Zn, Co, Ni, etc.
Salts of polyvalent or polyvalent metals, and, in the case of organic compounds, a polymeric cationic conductive agent such as polyvinylbenzyltrimethylammonium chloride and quaternary ammonium salt modified with an acrylic resin, and a polymeric anionic dielectric agent such as a polymeric sulfonate. No. The amount of these conductive agents to be added is 3 to 40% by weight, preferably 5 to 2% by weight of the binder used for each layer.
0% by weight.

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

A printing plate using the direct-drawing lithographic printing plate precursor of the present invention is prepared by forming and fixing an image on the direct-drawing lithographic printing plate precursor having the above-described structure by a known technique,
After desensitizing non-image areas by surface treatment with desensitizing solution,
Used as a printing plate for lithographic printing.

As a method for desensitizing resin particles used in the present invention, that is, a method for decomposing a protected hydrophilic group such as a thiol group, one of the methods is to decompose the protected hydrophilic group. And a method of hydrolysis with an aqueous solution under acidic conditions of pH 1 to 6 and alkaline conditions of pH 8 to 12 arbitrarily. Adjustment of these pH can be easily performed by a known compound. Alternatively, a method by a redox reaction with a reducing or oxidizing water-soluble compound is also possible, and as these compounds, known compounds can be used, for example, hydrous hydrazine, sulfite, lipoic acid, hydroquinones, formic acid, Thiosulfate, hydrogen peroxide, persulfate, quinones and the like.

The treatment liquid may contain another compound for accelerating the reaction or improving the storage stability of the treatment liquid. For example, 1 to 50 parts by weight of an organic solvent soluble in water may be contained in 100 parts by weight of water. Examples of such water-soluble organic solvents include alcohols (methanol, ethanol, propanol, propargyl alcohol, benzyl alcohol, phenethyl alcohol, etc.),
Ketones (acetone, methyl ethyl ketone, acetophenone, etc.), ethers (dioxane, trioxane, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc.), amides (dimethylformamide, dimethylacetamide, etc.) ), Esters (methyl acetate, ethyl acetate, ethyl formate, etc.) and the like, and these may be used alone or in combination of two or more.

Further, 0.1 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 or nonionic surfactants. For example, compounds described in Hiroshi Horiguchi “New Surfactant” Sankyo Publishing Co., Ltd. (1975), Ryohei Oda, Kazuhiro Teramura “Synthesis of Surfactant and Its Application” Maki Shoten (1980) Can be used.

The scope of the present invention is not limited to the specific compound examples described above. The condition of the treatment is a temperature of 15 ° C.
The immersion time at ６０60 ° C. is preferably 10 seconds to 5 minutes.

[0104]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to this. First, production examples of the monofunctional polymer [M] for resin particles and resin particles will be described. Production Example 1 of Monofunctional Polymer [M]: [M-1] A mixed solution of 95 g of 2,2,2,2 ', 2', 2'-hexafluoroisopropyl methacrylate, 5 g of thioglycolic acid and 200 g of toluene was prepared. The mixture was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 1.0 g of azobisisobutyronitrile (abbreviated as AIBN) 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,
Stirred at 12 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain 82 g of a white powder.
The weight average molecular weight of the polymer [M-1] was 4000. Monofunctional polymer [M-1]

Embedded image

Production Example 2 of Monofunctional Polymer [M]: [M-
2] A mixed solution of 96 g of a monomer (MA-1) having the following structure, 4 g of β-mercaptopropionic acid, and 200 g of toluene was heated to a temperature of 70 ° C under a nitrogen stream. A. I. B. N.
1.0 g was added and reacted for 8 hours. Next, the reaction solution was cooled in a water bath to a temperature of 25 ° C., and 10 g of 2-hydroxyethyl methacrylate was added thereto. 15 g of dicyclohexylcarbonamide (abbreviated as DCC), 4
A mixed solution of 0.2 g of-(N, N-dimethylamino) pyridine and 50 g of methylene chloride was added dropwise with stirring over 30 minutes, and the mixture was further stirred for 4 hours. Next, 5 g of formic acid was added, and the mixture was stirred for 1 hour. The precipitated insoluble material was separated by filtration, and the filtrate was reprecipitated in 1 liter of n-hexane. The precipitated viscous material was collected by decantation, dissolved in 100 ml of tetrahydrofuran, filtered again to remove insoluble material, and then reprecipitated in 1 liter of n-hexane. The polymer [M-2] obtained by drying the precipitated viscous material had a weight average molecular weight of 5.2 × 10 5 in a yield of 60 g.
^{Was 3} . Monomer (MA-1)

Embedded image Monofunctional polymer [M-2]

Embedded image

Production Example 3 of Monofunctional Polymer [M]: [M-
3] A mixed solution of 95 g of a monomer (MA-2) having the following structure, 150 g of benzotrifluoride, and 50 g of ethanol was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 2,4'-azobis (4-cyanovaleric acid) (abbreviation: ACV) 2 g
Was added and reacted for 8 hours. After cooling, the precipitate was reprecipitated in 1 liter of methanol, and the obtained polymer was dried. Next, 50 g of this polymer and 2-hydroxyethyl methacrylate 11
g, dissolved in 150 g of benzotrifluoride, at a temperature of 25 ° C.
And The mixture was stirred with D.I. C. C. 15g, 4
A mixed solution of 0.1 g of-(N, N-dimethylamino) pyridine and 30 g of methylene chloride was added dropwise over 30 minutes, and the mixture was further stirred for 4 hours. Thereafter, 3 g of formic acid was added and the mixture was stirred for 1 hour. Next, the precipitated insoluble matter was separated by filtration, and the filtrate was reprecipitated in 800 ml of methanol. The precipitate was collected, dissolved in 150 g of benzotrifluoride, and reprecipitated again.
30 g of a viscous material was obtained. The weight average molecular weight of the polymer [M-3] was 3.3 × 10 ⁴ . Monomer (MA-2)

Embedded image Monofunctional polymer [M-3]

Embedded image

Production Examples 4 to 22 of Monofunctional Polymer [M]:
[M-4] to [M-22] In Production Example 2, other monomers (monomers corresponding to the polymer components described in Table 2) instead of the monomer (MA-1)
The monofunctional polymer [M] was produced in the same manner as in Production Example 2 except that was used. Each weight average molecular weight is 4 × 10 ³ ~
It was 6 × 10 ³ .

[Table 2]

[Table 3]

[Table 4]

[Table 5]

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

[Table 6]

[Table 7]

[Table 8]

Production Example 31 of Monofunctional Polymer [M]: [M
-31] Octyl methacrylate 30 g, a monomer having the following structure (M
A-3) A mixed solution of 70 g, 3 g of glycidyl methacrylate and 200 g of benzotrifluoride was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. A. I. B.
N. 1.0 g was added and reacted for 4 hours. I. B.
N. 0.5 g was added and reacted for 4 hours. Next, 5 g of methacrylic acid, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to the reaction mixture, and the mixture was stirred at 110 ° C. for 8 hours. After cooling, the precipitate was reprecipitated in 2 liters of methanol, and a slightly brownish oily substance was collected and dried. Weight average molecular weight 3.6 with 73 g yield
× 10 ⁴ . Monomer (MA-3)

Embedded image Monofunctional polymer [M-31]

Embedded image

Production Example 32 of Monofunctional Polymer [M]: [M
-32] A mixed solution of 80 g of the following monomer (MA-4), 20 g of glycidyl methacrylate, 2 g of 2-mercaptoethanol and 300 g of tetrahydrofuran was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. To this, 2,2'-azobis (isovaleronitrile) (abbreviation: AIV.
N. ) 0.8 g was added and reacted for 4 hours. I.
V. N. 0.4 g was added and reacted for 4 hours. After cooling the reaction product to a temperature of 25 ° C., 4 g of methacrylic acid was added, and D.C. C. C. 6 g, 4- (N, N-dimethylamino) pyridine 0.1 g and methylene chloride 15 g
Was added dropwise over 1 hour, and the mixture was further stirred for 3 hours. Next, 10 g of water was added, and the mixture was stirred for 1 hour. The precipitated insoluble matter was separated by filtration, and the filtrate was reprecipitated in 1 liter of methanol to collect an oily substance. Furthermore, this oily substance is
After dissolving in 50 g, insolubles were separated by filtration and reprecipitated again in 1 liter of methanol to collect and dry the oil. Yield 5
The weight average molecular weight of 6 g was 8 × 10 ³ .

Monomer (MA-4)

Embedded image Monofunctional polymer [M-32]

Embedded image

Production Examples 33 to 3 of Monofunctional Polymer [M]
9: [M-33] to [M-39] Monofunctional polymers [M] in Table 4 below were synthesized by performing the reaction as shown in Production Example 32. The weight average molecular weight of each polymer [M] was in the range of 6 × 10 ^{3 to} 9 × 10 ³ .

[Table 9]

[Table 10]

Production Example 1 of Resin Particles: [L-1] A mixed solution of 10 g of monofunctional polymer [M-1] and 200 g of methyl ethyl ketone was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. Monomer (A-1) 40 having the following structure
g, ethylene glycol dimethacrylate 10 g, 2,
2'-azobis (isovaleronitrile) (abbreviated as A.I.
V. N. ) A mixed solution of 0.5 g and methyl glycol ketone 240 glycol was added dropwise over 2 hours, and the mixture was reacted for 2 hours. Further, A. I. V. N. 0.5 glycol was added and reacted for 2 hours. After cooling, a white dispersion was obtained through a 200 mesh nylon cloth. Average particle size 0.20μm
(CAPA-500, manufactured by HORIBA, Ltd., particle size measurement). Monomer (A-1)

Embedded image

Production Examples 2-12 of Resin Particles: [L-2]-
[L-12] In Production Example 1 of resin particles, the monofunctional polymer [ M-
1], and resin particles were produced in the same manner as in Production Example 1 except that each of the compounds shown in Table 5 below was used instead of the monomer (A-1). The average particle size of each particle was in the range of 0.15 to 0.30 μm.

[Table 11]

[Table 12]

Production Examples 13 to 23 of Resin Particles: [L-1
3] to [L-23] Resin particles [L-23] were prepared in the same manner as in Production Example 1 except that the polyfunctional compound shown in Table 6 below was used instead of ethylene glycol dimethacrylate in Production Example 1 of resin particles. -1
3] to [L-23]. The polymerization rate of each particle is 9
The average particle size was 0.15 to 0.25 μm at 5 to 98%.

[0116]

[Table 13]

Production Example 24 of Resin Particles: [L-24] A mixed solution of 8 g of monofunctional polymer [M-21] and 130 g of methyl ethyl ketone was stirred at 60 ° C. under a nitrogen stream.
Was heated. To this, 45 g of the following monomer (A-13),
5 g of diethylene glycol dimethacrylate, I.
V. N. A mixed solution of 0.5 g and 150 g of methyl ethyl ketone was added dropwise over 1 hour. I. V. N.
0.25 g was added and reacted for 2 hours. After cooling, the dispersion obtained through a 200 mesh nylon cloth had an average particle size of 0.25 μm. Monomer (A-13)

Embedded image

Production Example 25 of Resin Particles: [L-25] A mixed solution of 7.5 g of the monofunctional polymer [M-12] and 230 g of methyl ethyl ketone was stirred for 6 hours under a nitrogen stream.
Warmed to 0 ° C. In addition, the monomer (A-10) 25
g, acrylamide 15 g, A.I. I. V. N. 0.5
g and 200 g of methyl ethyl ketone were added dropwise over 2 hours, and the mixture was further reacted for 1 hour. Further, A. I.
V. N. After adding 0.25 g and reacting for 2 hours, the dispersion was cooled, and the average particle size of the dispersion obtained through a 200-mesh nylon cloth was 0.25 μm.

Production Example 26 of Resin Particles: [L-26] 42 g of the following monomer (A-14), 8 g of ethylene glycol diacrylate, 8 g of monofunctional polymer [M-23]
And 230 g of dipropyl ketone in a nitrogen stream at a temperature of 60 ° C.
Was heated. This was dropped into a solution of 200 g of dipropyl ketone over 2 hours with stirring. After the reaction as it was for 1 hour, A.I. I. V. N. 0.3 g was added and reacted for 2 hours. After cooling, the dispersion obtained through a 200 mesh nylon cloth had an average particle size of 0.20 μm. Monomer (A-14)

Embedded image

Production Examples 27 to 36 of Resin Particles: [L-2
7] to [L-36] In Production Example 26 of the resin particles, the monofunctional polymer [M-
Each particle was produced in the same manner as in Production Example 26 except that each monofunctional polymer [M] shown in Table 7 below was used instead of [23]. The average particle size of each particle is 0.20 μm to 0.25 μ
m.

[0121]

[Table 14]

Production Examples of Resin Particles 37 to 42: [L-3
7] to [L-42] In Production Example 25 of resin particles, a monomer (A-10),
Each particle was produced in the same manner as in Production Example 25 except that each compound shown in Table 8 below was used instead of acrylamide, the reaction solvent, and methyl ethyl ketone. The average particle size of each particle was in the range of 0.15 μm to 0.30 μm.

[Table 15]

[Table 16]

Example 1 10 g of resin particles [L-1] (as solid content) and resin [B-1]: methyl methacrylate / acrylic acid (99%)
/ 1, weight ratio) (weight average molecular weight 4500)
0): 20 g, zinc oxide 100 g and toluene 300 g
Was dispersed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at a rotation speed of 6 × 10 ³ rpm for 10 minutes. Next, this dispersion is coated with a wire bar on a middle layer of a support having a back layer on one side and a middle layer on the other side of a high-quality paper so that the dry adhesion amount is 18 g / m ^2. And 1
After drying at 00 ° C. for 1 minute, a lithographic printing original plate was prepared. Next, the plate was made using a commercially available PPC, and the resulting plate was etched once using an aqueous solution obtained by diluting a desensitizing solution ELP-EX manufactured by Fuji Photo Film Co., Ltd. 5 times with distilled water. I passed. Further, a solution obtained by diluting 0.5 mol monoethanolamine in 1 liter of distilled water [treatment solution (E
-1)] for 3 minutes. The density of the image portion of the obtained original plate was 1.0 or more, there was no background fog in the non-image portion, and the image quality of the image portion was clear. This was applied to an offset printing machine (Oliver 52, manufactured by Sakurai Seisakusho Co., Ltd.) and printed on high quality paper. Even if the number of sheets exceeds 3,000, no problem was caused in the background stain on the non-image portion and the image quality of the image portion of the printed matter.

Examples 2 to 15 The procedure of Example 1 was repeated, except that the copolymer shown in Table 9 was used instead of the resin particles [L-1] of the present invention. Thus, each lithographic printing original plate was prepared.

[Table 17] By operating this in the same manner as in Example 1, the density of the obtained master plate for offset printing in which an original plate was prepared was 1.
At two or more, the image quality was clear. Further, when the sheet was etched and printed by a printing machine, the printed matter after printing 3000 sheets had no fog in the non-image portion and the image was clear.

Example 16 A mixture of 4 g (as solid content) of resin particles [L-32], 29 g of a binder resin [B-2] having the following structure, 50 g of zinc oxide and 200 g of toluene was placed in a homogenizer at 6 × 1.
Disperse at 0 ³ rpm for 10 minutes.
g and 0.02 g of o-chlorophenol, and 1 ×
Dispersed at 10 ³ rpm for 1 minute. The dispersion thus obtained was coated on a support under the same conditions as in Example 1 and
It dried at 00 degreeC for 30 second, and also heated at 110 degreeC for 1 hour, and produced the lithographic printing original plate. Binder resin [B-2]

Embedded image This was made into a plate using the same apparatus as in Example 1, then subjected to an etching treatment, and printed using a printing machine. The density of the master plate for offset printing obtained after plate making was 1.0 or more, and the image quality was clear. The image quality of the printed matter after printing 5,000 sheets was a clear image without background fog.

Example 17 A mixture of 15 g (as solid content) of resin particles [L-34], 20 g of resin [B-3] having the following structure, 80 g of zinc oxide and 150 g of toluene was dispersed in a ball mill for 1.5 hours. . Next, 4 g of hexamethylene diisocyanate was added to this dispersion, and the mixture was dispersed in a ball mill for another 10 minutes to form a back layer on one side of the high-quality paper and an intermediate layer on the other side provided with an intermediate layer on the other side. 25 g / m ² of dry adhesion on top
Was applied with a wire bar and dried at 100 ° C. for 90 minutes to prepare a lithographic printing original plate. Resin [B-3]

Embedded image This original plate is treated with a desensitizing solution [Fuji Photo Film Co., Ltd.
ELP-EX] and passed once through an etching processor, and further added to the following desensitizing solution (E-2).
It was immersed at 5 ° C. for 3 minutes. Desensitization treatment liquid (E-2): Diethanolamine 75 g Neosoap (Matsumoto Yushi Co., Ltd.) 6 g Benzyl alcohol 100 g was dissolved in distilled water to make a total volume of 1 liter. A droplet of 2 μl of distilled water was placed on the printing plate thus obtained, and the contact angle with the formed water was measured with a goniometer and found to be 10 ° or less. In addition, it was 98 degrees before the desensitization treatment. This indicates that the non-image portion of the image receiving layer of the original plate of the present invention has changed from lipophilic to hydrophilic (normally, the non-image portion does not generate printing background stains and dot stains during printing. Is required to be 20 ° or less in contact angle with water). Next, Example 1
When the plate was made in the same manner as described above and subjected to the desensitizing treatment and printing was performed, no problem was caused in the background smear of the non-image portion and the image quality of the image portion even when the number of sheets exceeded 3,000.

Examples 18 to 22 Except that hexamethylene diisocyanate used in Example 17 was replaced by the compound shown in Table 10 below,
A lithographic printing original plate was produced in the same manner as in Example 1.

[Table 18] This was made into a plate using the same apparatus as in Example 1, then subjected to an etching treatment, and printed using a printing machine. The density of the master plate for offset printing obtained after plate making was 1.0 or more, and the image quality was clear. The image quality of the printed matter after printing 5,000 sheets was a clear image without background fog.

Examples 23 to 36 Each original plate was prepared in the same manner as in Example 17 except that 15 g of the following resin particles [L] were used instead of 15 g of the resin particles [L-34]. Was prepared.

[Table 19] Each master was made into a plate as in Example 17, and the master was passed through an etching machine once using ELP-EX, and then placed in a resin particle desensitizing solution (E-3) having the following formulation. The sample was immersed for 2 minutes to make it insensitive. Resin particle desensitized liquid (E-3): 65 g of boric acid 6 g of Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 6 g of benzyl alcohol 80 g dissolved in distilled water to make a total volume of 1 liter, and then pH 10 with potassium hydroxide. Aqueous solutions adjusted to 5 were printed in the same manner as in Example 1. As a result, each of the original plates was printed with a clear image quality with no background smearing.
Zero or more sheets were obtained.

[0129]

According to the present invention, it is possible to obtain an original plate for direct drawing type lithographic printing which is excellent in suppressing occurrence of background fogging and has good printing durability.

Claims (2)

(57) [Claims] 1. A direct drawing lithographic printing plate precursor having an image receiving layer on a support, characterized in that the image receiving layer contains at least one kind of the following nonaqueous solvent-based dispersed resin particles. A lithographic printing original plate. Non-aqueous solvent-based dispersed resin particles: in a non-aqueous solvent, soluble in the non-aqueous solvent but insolubilized by polymerization; by decomposition, thiol group, phosphono group, amino group, sulfo group or A monofunctional monomer (A) containing at least one functional group selected from functional groups that form a group [R ₁ represents a hydrocarbon group or an —OR ₂ group (R ₂ represents a hydrocarbon group)] )When,
A polymerizable double bond group represented by the following general formula (I) is bonded to only one terminal 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. Polymer resin particles obtained by subjecting a monofunctional polymer [M] to a dispersion polymerization reaction. General formula (I) [However, in the above general formula (I), V ₀ is -O-,-
COO -, - OCO -, - (CH 2) -OCO -, -
(CH ₂ ) —COO—, —SO ₂ —, Represents -CONHCOO- or -CONHCONH- (R ₃ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), and a ₁ and a ₂ may be the same or different from each other;
Hydrogen atom, halogen atom, cyano group, hydrocarbon group, -C
OO-R ₄ or -COO-R ₄ via a hydrocarbon group (R
₄ represents a hydrogen atom or a hydrocarbon group which may be substituted)
Represents 2. The direct drawing type lithographic printing plate precursor according to claim 1, wherein the non-aqueous solvent-based dispersed resin particles form a high-order network structure.