JPH0794191B2 - Direct drawing type lithographic printing plate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a lithographic printing plate precursor, and more particularly to a direct drawing type lithographic printing plate precursor suitable for office printing plate precursors and the like.

(Prior Art) At present, a direct drawing type lithographic printing original plate having an image receiving layer on a support is widely used as an office printing original plate. To make a plate on such a printing original plate, that is, to form an image, generally, an oil-based ink is drawn by hand on the image receiving layer, or
Printing methods such as a typewriter, an ing jet method, or a transfer type heat-sensitive method are used. In addition, a method of transferring and fixing a toner image formed on a photoconductor through a process of charging, exposing and developing using a plain paper electrophotographic copying machine (PPC) to an image receiving layer has also started to be used in recent years. In any case, the printing plate precursor after plate making is subjected to surface treatment with a desensitizing solution (so-called etching solution) to desensitize the non-image area, and then used as a printing plate for printing the original plate.

In the conventional direct drawing type lithographic printing plate, a surface layer was provided on both sides of a support such as paper with a back layer and an intermediate layer interposed. The back surface layer or the intermediate layer is formed of a water-soluble resin such as PVA starch and a water-dispersible resin such as a synthetic resin emulsion and a pigment. The surface layer is formed of a pigment, a water-soluble resin and a waterproofing agent.

A typical example of such a direct drawing type lithographic printing plate precursor is U.S. Pat.
As described in No. 32865, the image receiving layer is mainly composed of a water-soluble resin binder such as PVA, an inorganic pigment such as silica and calcium carbonate, and a water-proofing agent such as a melamine-formaldehyde resin precondensate. It is composed.

(Problems to be Solved by the Invention) However, the conventional printing plate thus obtained is
If the hydrophobicity is increased by increasing the amount of waterproofing agent added or using a hydrophobic resin to improve printing durability, printing durability is improved, but hydrophilicity is reduced, and printing stains are reduced. On the other hand, when the hydrophilic property is improved, the water resistance is deteriorated and the printing durability is deteriorated. In particular, in a high-temperature use environment of 30 ° C. or higher, the surface layer was dissolved in the immersion water used for offset printing, and there were major drawbacks such as deterioration of printing durability and printing stains.

Further, the lithographic printing plate precursor is for drawing an oil-based ink or the like as an image portion on the image-receiving layer, and if the adhesion between the receiving layer and the oil-based ink is not good, even if the non-image portion has sufficient hydrophilicity, Even if such printing stains do not occur, there is a problem that the oil-based ink in the image portion is lost during printing, resulting in a decrease in printing durability.

The present invention solves the above-mentioned problems of the direct-drawing type lithographic printing plate precursor.

An object of the present invention is to provide, as an offset original plate, a direct drawing type lithographic printing original plate having excellent desensitizing property which does not cause spotwise background stain as well as uniform background stain.

The object of the present invention is to improve the adhesion between the oil-based ink in the image area and the image-receiving layer, and the hydrophilicity of the non-image area is sufficiently maintained even if the number of printed sheets is increased in printing, and there is no scumming. An object is to provide a lithographic printing plate precursor having high printing durability.

(Means for Solving Problems) The above-mentioned various purposes are as follows: in a direct drawing type lithographic printing plate precursor having an image receiving layer on a support, at least one part of the binder of the image receiving layer is decomposed. And a resin containing at least one functional group capable of forming at least one thiol group, phosphono group, amino group and / or sulfo group, and at least a part of which is crosslinked. As a result, the lithographic printing plate precursor according to the present invention reproduces a copy image that is faithful to the original image, and since the non-image area has good hydrophilicity, scumming does not occur, and the image receiving layer has good smoothness. And further has the advantage that the printing durability is excellent.

Further, the lithographic printing plate precursor of the invention is characterized by being unaffected by the environment at the time of plate making processing and being excellent in preservability before processing.

Below, a resin containing at least one functional group that decomposes to generate a hydrophilic group of at least one thiol group, phosphono group, sulfo group and / or amino group used in the present invention (hereinafter, simply referred to as hydrophilic The group-generating functional group-containing resin may also be referred to).

The functional group contained in the hydrophilic group-forming functional group-containing resin of the present invention produces at least one hydrophilic group by decomposition, but one or two or more hydrophilic groups may be produced from one functional group.

Hereinafter, the resin containing a functional group that generates at least one thiol group by decomposition (thiol group-forming functional group-containing resin) will be described in detail. Such a resin has, for example, at least one functional group represented by the following general formula (I) [-S-L ^A ].
It is a resin containing seeds.

General formula (I): [-S-L ^A ] In the formula, L ^A is Represents

However, R ^A ₁ , R ^A ₂ and R ^A ₃ may be the same or different and each represents a hydrocarbon group or —O—R ^A ′ (R ^A ′ represents a hydrocarbon group), and R ^A ₄ , R ^A ₅ , R ^A ₆ , R ^A ₇ , R ^A ₈ , R ^A ₉ and
R ^A ₁₀ each independently represents a hydrocarbon group.

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

In the case of representing, R ^A ₁ , R ^A ₂ and R ^A ₃ may be the same as or different from each other, and are preferably an optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms (for example, methyl). Group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, chloroethyl group, methoxyethyl group, methoxypropyl group, etc.), optionally substituted alicyclic group (eg, A cyclopentyl group, a cyclohexyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, etc.), or
An optionally substituted aromatic group (eg, phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxycarbonylphenyl group, dichlorophenyl group, etc.) or —O—R ^A ′ (R ^A ′ is a hydrocarbon Represents a group,
Specifically, the substituents described for the hydrocarbon group of R ^A ₁ , R ^A ₂ and R ^A ₃ can be mentioned as an example).

Or in the case of representing the _{^{-S-R A 8, R A}} 4, R A 5, R A 6,
R ^A ₇ and R ^A ₈ are each preferably a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (eg, 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.), even if substituted A good aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, methylbenzyl group, trimethylbenzyl group, heptamethylbenzyl group,
Methoxybenzyl group etc.), optionally substituted aryl group having 6 to 12 carbon atoms (eg phenyl group, nitrophenyl group, cyanophenyl group, methanesulfonylphenyl group, methoxyphenyl group, butoxyphenyl group, chlorophenyl group, dichlorophenyl) Group, trifluoromethylphenyl group, etc.).

In the case of representing, R ^A ₉ and R ^A ₁₀ may be the same or different, and preferred examples thereof include R ^A _{4 to} R ^A ₈
Represents the substituents described as being preferable. Another preferable thiol group-forming functional group-containing resin of the present invention is a resin containing at least one thiirane ring represented by the general formula (II) or the general formula (III).

General formula (II) General formula (III) In formula (II), R ^A ₁₁ and R ^A _{12, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group.
Preferably, it represents a substituent described as the preferable a hydrogen atom or the R ^A ₄ ~R ^A _7.

In formula (III), 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, methyl group, ethyl group, propyl group, butyl group, etc.).

Still another preferable thiol group-forming functional group-containing resin of the present invention is a resin containing at least one sulfur atom-containing heterocyclic group represented by the general formula (IV).

General formula (IV) In formula (IV), Y ^A represents an oxygen atom or -NH- group.

R ^A ₁₃ , 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 substituent described as the preferable a hydrogen atom or the R ^A ₄ ~R ^A _7.

R ^A ₁₆ and R ^A _{17, which} may be the same or different, each represents a hydrogen atom, a hydrocarbon group or —O—R ^A ″ (R ^A ″ represents a hydrocarbon group). Preferably, it represents the substituents described as preferable in R ^A _{1 to} R ^A ₃ .

According to still another preferred embodiment of the present invention, the thiol group-forming functional group-containing resin has a functional group having at least two thiol groups sterically close to each other in the form of being simultaneously protected with one protecting group. Is a resin containing at least one.

Examples of the functional group having at least two thiol groups sterically close to each other simultaneously protected by one protecting group include, for example, the following general formulas (V), (VI) and (VI)
Examples include those represented by I).

General formula (V) General formula (VI) General formula (VII) In the formulas (V) and (VI), Z ^A represents a carbon-carbon bond which may have a heteroatom or a chemical bond which directly connects the C—S bonds with each other (provided that the number of atoms between sulfur atoms is 4). It is within the number). Further, one Z ^A ... C bond represents only a bond, and may be, for example, as shown below.

In the formula (VI), R ^A ₁₈ and R ^A ₁₉ may be the same or different and each represents a hydrogen atom, a hydrocarbon group or —O—R ^A ″ (R ^A ″).
Represents a hydrocarbon group).

In formula (VI), R ^A ₁₈ and R ^A ₁₉ may preferably be the same or different from each other, a hydrogen atom, a carbon number of 1 to 12
An optionally substituted alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, 2
-Methoxyethyl group, octyl group, etc.), optionally substituted aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenether group, methylbenzyl group, methoxybenzyl group, chlorobenzyl group, etc.), 5 carbon atoms 7 alicyclic group (eg, cyclopentyl group, cyclohexyl group, etc.) or optionally substituted aryl group (eg, phenyl group, chlorophenyl group, methoxyphenyl group, methylphenyl group, cyanophenyl group, etc.) or —O— R ^A ″ (R ^A ″
Has the same meaning as the hydrocarbon group in R ^A ₁₈ and R ^A ₁₉ .

In formula (VII), R ^A ₂₀ , R ^A ₂₁ , R ^A ₂₂ , and R ^A _{23, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group. Preferably, a hydrogen atom or R ^A ₁₈ , R ^A
_It has the same meaning as the hydrocarbon group described as preferred in ₁₉ .

The resin containing at least one functional group represented by the general formulas (I) to (VII) used in the present invention has a thiol group contained in a polymer protected by a polymer group by a polymer reaction. Polymerization by a method or a polymerization reaction of a monomer containing one or more thiol groups previously protected by a protecting group, or of the monomer and another monomer copolymerizable therewith Manufactured by the method.

A polymer containing a thiol group, because the thiol group inhibits radical polymerization, it is difficult to polymerize a thiol group-containing monomer as it is. A thiol group is produced by polymerizing a monomer having a protected thiol group in the form of a functional group, isothiuronium salt, butene salt or the like used in the present invention, and then performing a decomposition reaction to form a thiol group.

Therefore, it is possible to arbitrarily adjust the functional group that protected the thiol group in the polymer, not to mix impurities, or
A method of producing by a polymerization reaction from a monomer containing a functional group of the general formulas (I) to (VII) in advance is preferable because it will not polymerize unless it is a monomer having a thiol group protected finally. .

Examples of the production method for converting one or at least two thiol groups into a functional group protected by a protecting group include, for example,
Yoshio Iwakura, Keisuke Kurita, "Reactive Polymers", pages 230-237 (Kodansha: 1977), edited by The Chemical Society of Japan, "New Experimental Chemistry Lecture Volume 14, Organic Compound Synthesis and Reactions [III]", 8 chapter,
Pages 1700 to 1713 (Maruzen Co., Ltd., 1978), JFW
McOmie, “Protective Groups in Organic Chemistry” Chapter 7 (Plenum Press. 1973), S. Patai, “The Chemi
stry of the thiol group part 2 "Chapters 12 and 14 (Joh
n Wiley & Sons, published in 1974, etc., the methods described in publicly known documents in the review reference can be applied.

A monomer in which one or more thiol groups are protected by a protecting group, for example, a monomer containing a functional group represented by formula (I) to (VII) is specifically a polymerizable double bond. A compound containing a bond and containing at least one thiol group,
For example, the thiol group is converted into the functional group of the general formulas (I) to (VII) or the functional group of the general formulas (I) to (VII) is contained according to the method described in the above-mentioned publicly known documents. It can be produced by a method of reacting a compound with a compound containing a polymerizable double bond.

More specifically, examples of the monomer having a functional group of the general formulas (I) to (VII) include the following compounds, but the scope of the present invention is not limited thereto. .

Further, in the present invention, a resin containing a functional group which decomposes to form a phosphono group, for example, a group represented by the following general formula (VIII) or (IX) will be described in detail. General formula (VIII) General formula (IX) In formula (VIII), R ^B is a hydrocarbon group or —Z ^B ₂ —R ^B ′.
(Wherein R ^B ′ 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 formula (IX), Q ^B ₂ , Z ^B ₃ and Z ^B ₄ each independently represent an oxygen atom or a sulfur atom.

Preferably, R ^B has 1 to 12 carbon atoms which may be substituted,
Linear or branched alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, 2-methoxyethyl group, 3
-Methoxypropyl group, 2-ethoxyethyl group, etc.), optionally substituted alicyclic group (eg, cyclopentyl group, cyclohexyl group, etc.), optionally substituted C7-12 aralkyl group (eg, , A benzyl group, a phenethyl group, a methylbenzyl group, a methoxybenzyl group, a chlorobenzyl group, etc.) or an aromatic group which may be substituted (eg, a phenyl group, a chlorophenyl group, a tolyl group,
Xylyl group, a methoxyphenyl group, a methoxycarbonylphenyl group, dichlorophenyl group), or -Z ^B ₂ -
R ^B ′ (wherein Z ^B ₂ represents an oxygen atom or a sulfur atom. R ^B ′ represents a hydrocarbon group, and specifically, the substituents described above for the hydrocarbon group of R ^B are exemplified. Can be listed).

Q ^B ₁ , Q ^B ₂ , Z ^B ₁ , Z ^B ₃ , and Z ^B ₄ each independently represent an oxygen atom or a sulfur atom.

As the functional group which produces the phosphono group represented by the formula (VIII) or (IX) by the decomposition as described above, the general formula (X)
And / or a functional group represented by (XI).

General formula (X) General formula (XI) In formulas (X) and (XI), Q ^B ₁ , Q ^B ₂ , Z ^B ₁ , Z ^B ₃ , and Z ^B
₄ and R ^B have the same meanings as defined in formulas (VIII) and (IX), respectively.

L ^B ₁ , L ^B ₂ and L ^B ₃ are independent of each other. Represents L ^B _{1 to} L ^B ₃ In the case of, R ^B ₁ and R ^B _{2, which} may be the same or different, each represents a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.) or a methyl group.
X ^B ₁ and X ^B ₂ represent an electron-withdrawing substituent, preferably a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), —CN, —CONH ₂ , —NO ₂ or —SO ₂ R ^B ″ (R ^B ″ is
Methyl group, ethyl group, propyl group, butyl group, hexyl group, benzyl group, phenyl group, tolyl group, xylyl group,
Represents a hydrocarbon group such as a mesityl group). n
Represents 1 or 2. Further, when X ^B ₁ is a methyl group, R ^B ₁ and R ^B ₂ are methyl groups and n = 1.

In the case of representing, R ^B ₃ , R ^B ₄ and R ^B ₅ may be the same or different from each other, preferably a hydrogen atom, or an optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms. 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,
Methoxypropyl group etc.), optionally substituted alicyclic group (eg cyclopentyl, cyclohexyl group etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (eg benzyl group, phenethyl group, chlorobenzyl group, Methoxybenzyl group, etc.) or an optionally substituted aromatic group (eg, phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxycarbonylphenyl group, dichlorophenyl group, etc.) or —O—R ^B (R ^B
Represents a hydrocarbon group, specifically, the above R ^B ₃ , R ^B ₄ ,
The substituents mentioned for the hydrocarbon group of R ^B ₅ can be mentioned as an example).

In the case of representing -R ^B ₁₀ , R ^B ₆ , R ^B ₇ , R ^B ₈ , R ^B ₉ and
R ^B ₁₀ each independently represents a hydrocarbon group. Preferably a linear or branched alkyl group having 1 to 6 carbon atoms which may be substituted (eg, 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.), optionally substituted 7 to 7 carbon atoms
9 aralkyl groups (eg, benzyl group, phenethyl group,
A methylbenzyl group, a trimethylbenzyl group, a heptamethylbenzyl group, a methoxybenzyl group, etc., and an optionally substituted aryl group having 6 to 12 carbon atoms (eg, phenyl group, tolyl group, xylyl group, nitrophenyl group, cyanophenyl group) , Methanesulfonylphenyl group, methoxyphenyl group, butoxyphenyl group, chlorophenyl group, dichlorophenyl group, trifluoromethylphenyl group, etc.).

When represented, Y ^B ₁ and Y ^B ₂ represent an oxygen atom or a sulfur atom.

The resin containing at least one functional group used in the present invention has a hydrophilic group (phosphono group) of the above formula (VIII) or (IX) contained in a polymer protected by a protective group by a polymer reaction. Or a functional group previously protected by a protecting group (eg, formula (X) or (XI))
Of the functional group) or a monomer and the other monomer which can be copolymerized with the monomer.

In either method, the same synthetic reaction can be used as the method for introducing the protective group. Specifically, JFWMcOmie, `` Protective groups in Organic Ch
“Emistry” Chapter 6 (Plenum Press, published in 1973), the method described in the literature cited in the reference, or “The New Experimental Chemistry Course, Volume 14, Organic Compound Synthesis and Reaction [V]” edited by the Chemical Society of Japan.
2497 (published by Maruzen Co., Ltd., 1978), a synthetic reaction similar to the method of introducing a protecting group into a hydroxyl group described in a known document of a review reference, or S. Patai, “The Chemistry of t.
he Triol Group Part 2 ”Chapters 13 and 14 (Wiley-Inter
1974), TW Greene, "Protective groups
in Organic Synthesis ”Chapter 6 (Wiley-Interscience1
It can be produced by a synthetic reaction similar to the method of introducing a protective group into a thiol group described in publicly known documents such as review references cited in 981).

The following examples can be given as specific examples of the compound that can be a repeating unit of the polymerization component containing the functional group of the general formula (X) and / or (XI) used for the protective group. However, the present invention is not limited to these.

Next, examples of the functional group that produces an amino group such as an —NH ₂ group and / or an —NHR ^C group by the decomposition include groups represented by the following general formulas (XII) to (XIV).

General formula (XII) General formula (XIII) General formula (XIV) In formulas (XII) and (XIV), R ^C ₀ is each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group). , Octyl 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-
Methoxypropyl group, 6-chlorohexyl group, etc.), alicyclic group having 5 to 8 carbon atoms (eg, cyclopentyl group, cyclohexyl group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl) Group, phenethyl group, 3-
Phenylpropyl group, 1-phenylpropyl group, chlorobenzyl group, methoxybenzyl group, bromobenzyl group,
Methylbenzyl group, etc.), an aryl group having 6 to 12 carbon atoms which may be substituted (eg, phenyl group, chlorophenyl group,
Dichlorophenyl group, tolyl group, xylyl group, mesityl group, chloromethyl group, chlorophenyl group, methoxyphenyl group, ethoxyphenyl group, chloromethoxyphenyl group and the like).

When R ^C ₀ preferably represents the hydrocarbon group, hydrocarbon groups having 1 to 8 carbon atoms can be mentioned.

In the functional group represented by the formula (XII), R ^C ₁ has 2 carbon atoms.
To ^C 12 represent an optionally substituted aliphatic group, and more specifically, R ^C ₁ represents a group represented by the following formula (XV).

Expression (XV) In formula (XV), a ₁ and a ₂ are each a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom or the like) or a hydrocarbon group having 1 to 12 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, Propyl group, butyl group, hexyl group, methoxymethyl group,
Ethoxymethyl group, 2-methoxyethyl group, 2-chloroethyl group, 3-bromopropyl group, cyclohexyl group,
Benzyl group, chlorobenzyl group, methoxybenzyl group,
(Methylbenzyl group, phenethyl group, 3-phenylpropyl group, phenyl group, tolyl group, xylyl group, mesityl group, chlorophenyl group, methoxyphenyl group, dichlorophenyl group, chloromethylphenyl group, naphthyl group, etc.)
The stands, Y ^C is a hydrogen atom, a halogen atom (e.g. fluorine atom, a chlorine atom), a cyano group, an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, etc.), substituted An aromatic group which may contain a group (for example, phenyl, tolyl group, cyanophenyl group, 2,6-dimethylphenyl group, 2,4,6-trimethylphenyl group, heptamethylphenyl group, 2,6-dimethoxyphenyl group Group, 2,4,6-trimethoxyphenyl group, 2-propylphenyl group, 2-
Butylphenyl group, 2-chloro-6-methylphenyl group, furanyl group, etc.) or —SO ₂ —R ^C ₆ (R ^C ₆ has the same meaning as the hydrocarbon group of Y ^C ) and the like. n represents 1 or 2.

More preferably, when Y ^C is a hydrogen atom or an alkyl group, a ₁ on the carbon adjacent to the oxygen atom of the urethane bond and
a ₂ represents a substituent other than a hydrogen atom.

When Y ^C is not a hydrogen atom or an alkyl group, a ₁ and a ₂ may be any of the groups described above.

That is, In the above, it is shown that the case where a group containing at least one or more electron-withdrawing groups is formed or the case where the carbon adjacent to the oxygen atom of the urethane bond forms a sterically bulky group is a preferable example. is there.

Or specifically, R ^C ₁ is an alicyclic group (for example, a monocyclic hydrocarbon group (cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 1-methyl-cyclohexyl group, 1-methylcyclobutyl group, etc.)) Or a crosslinked cyclic hydrocarbon group (bicyclooctane group, bicyclooctene group, bicyclononane group, tricycloheptane group, etc.)}.

In the general formula (XIII), 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, specifically, a fat in Y ^C of the formula (XII). It has the same meaning as the group or aromatic group.

In the general formula (XIV), X ^C ₁ and X ^C ₂ may be the same or different and each represents an oxygen atom or a sulfur atom.
R ^C ₄ and R ^C ₅ may be the same or different and each has 1 carbon atom.
~ 8 hydrocarbon groups, specifically Y ^C of formula (XII)
Represents an aliphatic group or an aromatic group.

Specific examples of the functional groups of the formulas (XII) to (XIV) are shown below, but the present invention is not limited thereto.

(81) -NHCOOCH ₂ CF ₃ (82) -NHCOOCH ₂ CCl ₃ By the decomposition used in the present invention, an amino group (for example, --NH ₂
Group and / or -NHR ^C group) -containing functional group, for example, a resin containing at least one functional group selected from the group of the above general formulas (XII) to (XIV) is, for example, edited by Nippon Kagaku,
"New Experimental Chemistry Course, Volume 14, Synthesis and Reactions of Organic Compounds [V]", page 2555 (published by Maruzen Co., Ltd.), JFWMcOmie,
"Protective groups in Organic Chemistry" Chapter 2 (Plenum Press, 1973), "Protective groups in O"
rganic Sinthesis ”Chapter 7 (John Wiley & Sons, 1981
It can be produced by a method described in a publicly known document such as a general reference.

Since the functional groups of the general formulas (XII) to (XIV) in the polymer can be arbitrarily adjusted or the impurities are not mixed, the functional groups of the general formulas (XII) to (XIV) are previously prepared. A method of producing by a polymerization reaction from the contained monomer is preferable. Specifically, a primary or secondary amino group containing a polymerizable double bond is converted into a functional group of the general formulas (XII) to (XIV) by, for example, the method described in the above-mentioned publicly known documents. After the conversion into a polymer, a polymerization reaction can be carried out to produce the product.

Further, as the functional group which forms at least one sulfo group by the decomposition, for example, a general formula (XVI) or (XVII
The functional group represented by I) may be mentioned.

Formula _{(XVI) -SO 2 -O-R} D 1 formula _{(XVIII) -SO 2 -O-R} D 2 expression in (XVI), R ^D ₁ is Or represents -NHCOR ^D ₇ .

In formula (XVIII), R ^D ₂ represents an optionally substituted aliphatic group having 1 to 18 carbon atoms or an aryl group having 6 to 22 carbon atoms and optionally having a substituent.

The functional groups represented by the general formulas (XVI) and (XVIII) generate a sulfo group by decomposition, and will be described in more detail below.

R ^D ₁ In the case of representing, R ^D ₃ and R ^D ₄ may be the same or different, and are 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, Ethyl group, propyl group, butyl group, pentyl group, hexyl group). Y is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, 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 , A dichloromethyl group, a trichloromethyl group, a 2-methoxycarbonylethyl group, a 2-propoxycarbonylethyl group, a methylthiomethyl group, an ethylthiomethyl group, etc.), an alkenyl group having 2 to 18 carbon atoms which may be substituted (for example, vinyl. Group, allyl group, etc.), carbon number 6-12
An aryl group which may contain a substituent (for example, phenyl group, naphthyl group, nitrophenyl group, dinitrophenyl group, cyanophenyl group, trifluoromethylphenyl group, methoxycarbonylphenyl group, butoxycarbonylphenyl group, methanesulfonyl group Phenyl group, benzenesulfonylphenyl group, tolyl group, xylyl group, acetoxyphenyl group, nitronaphthyl group, etc.), or (R ^D ₈ represents an aliphatic group or an aromatic group, specifically, Y
Represents the same as the content of the substituent described in ^D ). n represents 0, 1 or 2. More preferably, In, a functional group containing at least one electron-withdrawing group can be mentioned. Specifically, when n is 0 and Y ^D is a hydrocarbon group containing no electron withdrawing group as a substituent, In, at least one halogen atom is contained. Further, n is 0, 1 or 2, and Y ^D contains at least one electron-attracting group. Furthermore, n is 1 or 2 and Y ^D is Etc. The electron-withdrawing group is a substituent having a positive Hammett's substituent constant, for example, a halogen atom, -COO-, _{-SO 2 -, - CN, -NO} 2 , and the like.

As another preferred substituent, at least two hydrocarbon groups are substituted on the carbon atom adjacent to the oxygen atom in —SO ₂ —O—R ^D , or n = 0 or 1 and Y ^D is an aryl group. In this case, the case where the aryl group has a substituent at the 2-position and the 6-position is exemplified.

In the case of representing, Z ^D represents an organic residue forming a cyclic imide group. Preferably, it represents an organic residue represented by the general formula (XVIII) or (XIX).

General formula (XVIII) General formula (XIX) In formula (XVIII), R ^D ₉ and R ^D ₁₀ may be the same or different, and each is a hydrogen atom, a halogen atom (for example, a chlorine atom,
Bromine atom etc.), alkyl group having 1 to 18 carbon atoms which may be substituted (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group) , 2-chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, 3
-Chloropropyl group, 2- (methanesulfonyl) ethyl group, 2- (ethoxyoxy) ethyl group, etc.), carbon number 7
To 12 optionally substituted aralkyl groups (eg, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group, chlorobenzyl group, bromobenzyl group, etc.), carbon number 3 To 18 optionally substituted alkenyl groups (eg, allyl group, 3-methyl-2-propenyl group), R ^D ₅ and R ^D ₆ are each a hydrogen atom, an aliphatic group (specifically, R ^D ₃ and R ^D ₄ have the same meanings), or an aryl group (specifically R ^D ₅ and R ^D ₆ ). ^D _{3 has} the same content as that of R ^D ₄ . However, neither R ^D ₅ nor R ^D ₆ represents a hydrogen atom.

When R ^D ₁ represents —NHCOR ^D ₇ , R ^D ₇ represents an aliphatic group or an aryl group, and specifically, R ^D ₃ and R ^D ₄ each have the same content.

In the formula (XVII), R ^D ₂ represents an optionally substituted aliphatic group having 1 to 18 carbon atoms or an aryl group having 6 to 22 carbon atoms which may have a substituent.

More specifically, it has the same contents as the aliphatic group or aryl group in Y ^D represented by formula (XVI).

Used in the present invention, the general formula [-SO ₂ -O-R ^D _1] or resin containing at least one functional group selected from [-SO ₂ -O-R ^D _2] group, the polymer A method of converting the contained sulfo group into a functional group of the general formula (XVI) or (XVIII) by a polymer reaction, or a method of converting the functional group of the general formula (XVI) or (XVI
II) prepared by a method of polymerizing by a polymerization reaction of one or more monomers containing one or more functional groups or one or more monomers or other monomers copolymerizable therewith It

The method of converting the functional group by the polymer reaction can be performed in the polymer reaction in the same manner as the method of synthesizing the monomer.

Can further include the following as an example as specifically formula _{(XVI) -SO 2 -O-R} D 1 or the general formula _{(XVIII) -SO 2 -O-R} D 2 functional groups, the The scope of the invention is not limited to these.

(108) −SO ₂ OCH ₂ CF ₃ (110) -SO ₂ OCH ₂ (CHF) ₂ CH ₂ F (111) -SO ₂ OCH ₂ CCl ₃ (113) −SO ₂ O (CH ₂ ) ₂ SO ₂ C ₄ H _{9 (123) -SO 2 O (CH} 2) 2 SO 2 C 2 H 5 (124) -SO 2 SC 4 H 9 (125) -SO 2 SC 6 H 13 (126) -SO 2 S (CH 2) 2 OC ₂ H ₅ (128) −SO ₂ OCH ₂ CHFCH ₂ F As described above, the compounds represented by the general formulas (I) to (VII) and (X) to (X) used in the method for producing a desired resin by a polymerization reaction are used.
The copolymer component containing the functional groups IV), (XVI) and (XVIII) will be described more specifically. Examples thereof include components represented by the following general formula [A]. However, the copolymer components are not limited to these examples.

General formula (A) In the formula (A), X ′ represents —O—, —CO—, —COO—, —OCO.
-, -SO ₂ -, _{-CH 2 COO -, - CH 2} OCO-, Indicates an aromatic group or a heterocyclic group (provided that Q ₁ , Q ₂ , Q ₃ , Q ₄
Each represent a hydrogen atom, a hydrocarbon group, or Y'-W] in formula (VI), b ₁ and b ₂ may be the same or different, and a hydrogen atom, a hydrocarbon group or formula (VI) Y'- in
W), and n represents an integer of 0 to 18].

Y'represents a carbon-carbon bond which connects the bonding group X'and the bonding group [W], and which may be through a hetero atom (the hetero atom represents an oxygen atom, a sulfur atom or a nitrogen atom), For example CH = CH, -O-, -S-, -COO -, - CONH -, - SO 2 -, - SO 2 NH -, - NHCOO-,
-NHCONH-, which has the constitution alone or in combination of binding units equal (although b _3, b _4, b ₅ are each the same meaning as the b _1, b _2.) W is formula (I) To (VII), (X) to (XIV), (XVI) or (XVII).

a ₁ and a ₂ may be the same or different, and are a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group,
Hydrocarbon group (for example, methyl group, ethyl group, propyl group, butyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxy A carbonylmethyl group, an optionally substituted alkyl group having 1 to 12 carbon atoms, an aralkyl group such as a benzyl group and a phenethyl group, a phenyl group, a tolyl group, an xylyl group, an aryl group such as a chlorophenyl group) or a formula ( A) represents an alkyl group having 1 to 18 carbon atoms, an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group, or an aromatic group, which may be substituted with a substituent containing a -W group. .

In addition, the [-X'-Y '] bond residue in the formula (A) is And the -W portion may be directly connected.

Along with these copolymer components of the present invention, other copolymer components that can be copolymerized include, for example, the corresponding monomers, for example, vinyl acetate, vinyl propionate, vinyl butyrate, Aliphatic carboxylic acids such as allyl acetate and allyl propionate or allyl esters, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, stronic acid, itaconic acid, maleic acid and fumaric acid, and unsaturated carboxylic acids thereof. And styrene derivatives such as styrene, vinyltoluene and α-methylstyrene, α-olefins, vinyl group-substituted heterocyclic compounds such as acrylonitrile, methacrylonitrile and N-vinylpyrrolidone.

The resin of the present invention is further used in a direct drawing type lithographic printing plate precursor,
It is characterized in that at least a part thereof is crosslinked.

As such a resin, a resin which has been cross-linked in advance at the time of applying the photosensitive layer forming material in the plate making process may be used, or a resin containing a cross-linkable functional group which causes a curing reaction with heat and / or light. It may be used for crosslinking during the process of producing the lithographic printing plate precursor (for example, during the drying process). Further, these may be used in combination.

When a part of the polymer uses a pre-crosslinked resin (a resin having a crosslinked structure in the polymer) as a binder resin, the thiol group, phosphono group, amino group and In addition to the above, a resin that is hardly soluble or insoluble in an acidic or alkaline aqueous solution when a functional group that produces a hydrophilic group of a sulfo group produces the hydrophilic group by decomposition is preferable.

Specifically, it has a solubility in distilled water of preferably 20% by weight or less, more preferably 70% by weight or less at a temperature of 20 to 25 ° C.

As a method for introducing a crosslinked structure into the polymer, a generally known method can be used. That is, in the polymerization reaction of monomers, there are a method in which a polyfunctional monomer is allowed to coexist for polymerization, and a method in which a polymer contains a functional group that promotes a crosslinking reaction and is crosslinked by a polymer reaction.

The resin of the present invention does not impair the image receiving property, or the manufacturing method is simple (for example, a long reaction time is required, the reaction is not quantitative, impurities are mixed by using a reaction accelerating aid, etc.) ) Etc., a functional group having a self-crosslinking reaction: —CONHCH ₂ OR ′ (R ′ is a hydrogen atom or an alkyl group) or a crosslinking reaction by polymerization is effective.

In the polymerization-reactive group, preferably, the polymerizable functional group is 2
A method of polymerizing a monomer having at least one together with a monomer containing a functional group that produces a hydrophilic group by the decomposition of the present invention,
Alternatively, by polymerizing a monomer having two or more polymerizable functional groups together with a monomer containing a hydrophilic group into a copolymer, and then protecting the hydrophilic group as described above,
The resin of the present invention can be manufactured.

Specifically as the polymerizable functional group, CH ₂ = CH-, CH ₂ = CH-CH
_2- , CH ₂ = CH-CONH-, _{CH 2 = CH-NHCO-, CH} 2 = CH-CH 2 -NHCO-, CH 2 = CH-SO 2 -, CH 2 = CH-CO-, CH 2 = CH-O-, CH 2 = CH-S -, Etc. can be mentioned, but the monomer having two or more polymerizable functional groups is
Any monomer may be used as long as it has two or more of the same or different polymerizable functional groups, and a polymer insoluble in a non-aqueous solvent is formed by polymerization.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, a monomer having the same polymerizable functional group as a styrene derivative such as divinylbenzene or trivinylbenzene: a polyhydric alcohol (for example, ethylene. Glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 200, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) or , Polyhydroxyphenols (eg hydroquinone, resorcin, catechol and their derivatives)
Methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers: dibasic acids (for example, 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.) and the like.

Further, as a monomer having a different polymerizable functional group, for example, a carboxylic acid containing a vinyl group [for example, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, acryloyl propionic acid, itaconiloyl acetic acid, itaconic acid Niloylpropionic acid, a reaction product of an alcohol or an amine with a carboxylic acid anhydride (for example, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid,
Etc.] etc.] or a vinyl group-containing ester derivative or amide derivative (for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloyl propionate). , Allyl methacryloylpropionate, vinyloxycarbonylmethyl methacrylate, vinyloxycarbonylmethyloxycarbonylethylene acrylate, N-
Allyl acrylamide, N-allyl methacrylamide,
N-allylitaconic acid amide, methacryloyl propionic acid allylamide, etc., or amino alcohols (eg, amino ethanol, 1-amino propanol, 1
-Aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and a vinyl group-containing carboxylic acid condensate.

The monomer having two or more polymerizable functional groups used in the present invention is 10 mol% or less, preferably 5 mol% of the total monomers.
The following is used to polymerize to form a resin.

On the other hand, in the present invention, a resin containing a crosslinkable functional group that undergoes a curing reaction with heat and / or light together with the above-mentioned hydrophilic group-forming functional group is used as a binder, and a crosslinked structure is formed in the subsequent master plate manufacturing process. May be formed.

The functional group causes a chemical reaction between molecules to form a chemical bond.
Any may be used as long as it can be obtained. That is, condensation reaction
Cross-linking between molecules due to addition reaction or polymerization reaction
The reaction mode in which a bridge is generated by heat and / or light is used.
Can be used. Specifically, dissociative hydrogen atom
Having a functional group [(eg, --COOH group, --PO₃H₂Base,(▲ R^″ ₁▼ is R₁~_ThreeWithin the same hydrocarbon group represented by
Yoji or ▲ -OR ₁▼ group (▲ R ₁▼ is ▲ R^″ ₁▼
Group)), --OH group, --SH group, --NH.
▲ R^″ _Two▼ group (▲ R^″ _Two▼ is a hydrogen atom or a methyl group,
C1-C4 alkyl groups such as ethyl, propyl and butyl groups
Represents a rukyi group)] and -NCO, -NCS, cyclic dicarphonic anhydride and each group
When containing at least one selected combination of functional groups
Alternatively, -CONHCH₂OR ″_Three(R ″_ThreeIs a hydrogen atom or
Cyl group, ethyl group, propyl group, butyl group, hexyl group
Represents an alkyl group having 1 to 6 carbon atoms) or a polymerizable group
A heavy bond group etc. are mentioned.

Specific examples of the polymerizable double bond group include those mentioned above as specific examples of the polymerizable functional group.

For example, Takeshi Endo, "Refinement of thermosetting polymers"
(CMC Corporation, published in 1986), Yuji Harazaki, "Latest Binder Technology Handbook" Chapter II-1 (General Technology Center, published in 1985), Takayuki Otsu "Synthesis and design of acrylic resin and new application development" (Chubu Management) Development Center Press, 1985), Eizo Omori "Functional Acrylic Resin" (Techno System 1985) Hideo Inui, Mototaro Nagamatsu, "Photosensitive Polymer" (Kodansha,
1977), Takahiro Tsunoda, "New Photosensitive Resin" (Publishing Society of Japan, 1981), GEGreen and, BPStar R, J.Mac
ro.Sci Revs Macro.Chem., C21 (2), 187-273 (1981-
82), CGRoffey, “Photopolymerization of SurfaceCo
The functional groups / compounds and the like cited in the review articles such as "atings" (A.Wiley Interscience Pub. 1982) can be used.

These crosslinkable functional groups may be contained in one copolymer component together with the hydrophilic group-forming functional group,
It may be contained in a copolymer component separate from the copolymer component containing the hydrophilic group-forming functional group.

Specific examples of the monomer corresponding to the copolymer component containing the crosslinkable functional group include, for example, vinyl compounds containing the functional group that can be copolymerized with the general formula (A). Any one will do.

For example, it is described in "Polymer Data Handbook [Basic Edition]", edited by Japan Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form,
α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α-chloro-β-methoxy form, α, β-dichloro form Body, etc.), methacrylic acid, itaconic acid, itaconic acid half-esters, itaconic acid half-amides, crotonic acid, 2-alkenylcarboxylic acids (for example, 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid). , 4-methyl-
2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acids And a compound having a crosslinkable functional group in the substituent of the carboxylic acid or sulfonic acid ester derivative, amide derivative, or the like.

The ratio of the "copolymer component containing a crosslinkable functional group" in the resin of the present invention is preferably 1 to 80% by weight in the resin. More preferably, it is 5 to 50% by weight.

If necessary, a reaction accelerator may be added to the resin in order to accelerate the crosslinking reaction. For example, acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, P-toluenesulfonic acid, etc.), peroxides, azobis compounds,
Examples thereof include a crosslinking agent, a sensitizer, and a photopolymerizable monomer. Specifically, as the cross-linking agent, specifically, compounds described in “Cross-linking agent handbook” edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha Co., Ltd. (1981) can be used. For example, a commonly used crosslinking agent such as organic silane, polyurethane or polyisocyanate, or a curing agent such as epoxy resin or melamine resin can be used.

In the case of containing a photocrosslinking-reactive functional group, the compounds cited in the above-mentioned review article on the photosensitive resin can be used.

When a resin containing a crosslinkable functional group is used, at least a part of the polymer can be crosslinked in the process of forming the image receiving layer or the process of heating and / or light irradiation before the etching treatment. Usually, it is preferable to carry out a heat curing treatment. This heat curing treatment can be performed by tightening the drying conditions in the conventional production of a photoreceptor. For example, the treatment may be performed at 60 ° C. to 120 ° C. for 5 minutes to 120 minutes. When the above reaction accelerator is used in combination, the treatment can be performed under more mild conditions.

Conventionally known resins can be used together with the resin used in the present invention. Examples thereof include silicone resins, alkyd resins, vinyl acetate resins, polyester resins, styrene-butadiene resins, acrylic resins, etc. as described above, and specifically, Ryuji Kurita and Jiro Ishiwatari, Polymer, No. 17
Volume, p. 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No. 8) p. 9, etc.

An inorganic pigment is used as another component of the image receiving layer of the present invention, and examples of the inorganic pigment include kaolin clay,
Examples thereof include calcium carbonate, silica, titanium oxide, zinc oxide, barium sulfate and alumina.

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

In addition, a crosslinking agent may be added to the image receiving layer in order to further improve the film strength. As the cross-linking agent, commonly used ammonium chloride, organic peroxide, metal soap, organic silane, polyurethane cross-linking agent, epoxy resin curing agent and the like can be used. Specifically, it is described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981).

Examples of the support used in the present invention include high-quality paper, wet-strength 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 side of the support opposite to the image receiving layer for curling prevention. You can

Here, the intermediate layer is an emulsion resin such as an acrylic resin, a styrene-butadiene copolymer, a methacrylic acid ester-butadiene copolymer, an acrylonitrile-butadiene copolymer, an ethylene-vinyl acetate copolymer; an epoxy resin, a polyvinyl butyral. Solvent-based resins such as polyvinyl chloride, polyvinyl acetate; at least one of the above-mentioned water-soluble resins, etc., as a main component, but if necessary, an inorganic pigment or a waterproofing agent should be added. You can

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

When used as a PPC plate making, in order to further reduce the background stain of the printing original plate of the present invention, the volume resistivity as the printing original plate is 10 ¹⁰ ~ 10 ¹³ Ωcm, further image receiving layer, an intermediate layer and A dielectric agent can be added to the backcoat layer. The dielectric agent may be inorganic or organic, and if it is inorganic, Na, K, Li, M
Salts of monovalent or polyvalent metals such as g, Zn, Co and Ni, and organic ones such as polyvinyl benzyl trimethyl ammonium chloride, acrylic resin modified quaternary ammonium salt, and other polymeric cationic conductive agents and polymeric sulfonic acids Examples include polymeric anionic conductive agents such as salts. The amount of these conductive agents added is 3 to 40% by weight, preferably 5 to 20% by weight, based on the amount of binder used in each amount.

To prepare the lithographic printing plate precursor of the invention, generally, one surface of the support is coated with an aqueous solution containing an intermediate layer component, if necessary, and dried to form an intermediate layer, and then an aqueous liquid containing an image receiving layer component is formed. An image receiving layer may be formed by coating and drying, and if necessary, an aqueous liquid containing a backcoat layer component may be coated and dried on the other surface to form a backcoat layer. The amount of each of the image receiving layer, the intermediate layer, and the back coat layer is 1 to 30 g / m ² , 5 respectively.
To 20 g / m ^2, it is appropriate 5 to 20 g / m ^2.

The resin of the present invention includes a resin that decomposes to produce a thiol group, a phosphono group, an amino group or a sulfo group when irradiated with an actinic ray. The active light used here is preferably light in the wavelength range of 200 to 900 nm, and its light source includes, for example, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp or a carbon arc lamp.

(Examples) Examples of the present invention will be shown below, but the scope of the present invention is not limited thereto.

Example 1 30 g of benzyl methacrylate, 70 g of the monomer of the following compound example (A), 0.2 g of acrylic acid, 1.5 g of divinylbenzene and 300 g of toluene were heated to a temperature of 75 ° C. under a nitrogen stream, and then 2 , 2'-Azobisisobutyronitrile (AIB
N) 1.0 g was added and reacted for 8 hours. The weight average molecular weight of the obtained copolymer [1] was 350,000.

Then, a mixture of 40 g of this copolymer [as solid content], 150 g of zinc oxide, and 300 g of toluene was mixed in a ball mill with 1
Time dispersion to adjust the image receiving layer forming material, a back layer which on one side of fine paper, dry coating weight of 18 g / m ² on the intermediate layer of the support an intermediate layer provided on the other side To obtain a lithographic printing plate precursor, which was then coated with a wire bar and dried at 110 ° C. for 1 minute.

This original plate is treated with a desensitizing solution [Fuji Photo Film Co., Ltd.
ELP-EX] was passed through an etching processor once, and a drop of distilled water (2 μm) was placed on it. The contact angle with water formed was measured by a goniometer and found to be 10 ° or less. It was 78 ° before the desensitizing treatment. This indicates that the non-image area of the image-receiving layer of the original plate of the present invention changed from lipophilicity to hydrophilicity (usually, the non-image area does not cause print background stains, dot-like stains, etc. during printing). The degree of chemical conversion is required to be less than 20 ° of contact angle with water).

Next, plate making was performed using a commercially available PPC, and the obtained original plate was subjected to a desensitizing treatment under the same conditions as above to obtain a printing original plate.

The density of the image area of the obtained original plate was 1.0 or more, there was no background fog in the non-image area, and the image quality of the image area was clear. This was printed on a high-quality paper by using an offset printing machine (Hamaduster 800SX type, manufactured by Hamada Star Co., Ltd.) Even if the number of printed sheets exceeds 2000, there is no problem with the background stain of the non-image area of the printed matter and the image quality of the image area.

Further, using the above original plate, the environmental conditions were 30 ° C. and 80% PH, and the image of the obtained original plate was obtained by making the plate with a commercially available PPC.
The density of the image area was 1.0 or more, there was no background fog in the non-image area, and the image quality of the image area was clear. When this was printed in the same manner as above, there was no problem even if 2000 sheets were printed.

As described above, this original plate did not deteriorate the image quality by PPC plate making even under the condition of high temperature and high humidity.

Examples 2-14 In Example 1, instead of the resin [1] of the present invention,
A lithographic printing plate precursor was prepared in the same manner as in Example 1 except that the copolymer shown in 1 was used.

When a plate was prepared using the same apparatus as in Example 1, the obtained master plate for offset printing had a density of 1.0 or more and the image quality was clear. When the product was further etched and printed with a printing machine, the printed matter after printing 10,000 sheets had a clear image quality without fog.

Further, this light-sensitive material was left under the conditions of (45 ° C., 75% RH) and then subjected to the same processing as above, but there was no difference from that before the passage of time.

Example 15 After heating 12 g of benzyl methacrylate, 80 g of the monomer of the following compound example (2), 8 g of N-methoxymethylmethacrylamide, 200 g of toluene and 50 g of isopropyl alcohol to a temperature of 75 ° C. under a nitrogen stream, 2 g of 2 ', 2'-azobisisobutyronitrile was added and reacted for 8 hours. Furthermore, the temperature was raised to 100 ° C. and the reaction was carried out for 2 hours while distilling off the isopropyl alcohol azeotropic solvent.

The weight average molecular weight of the obtained copolymer [15] was 98,000.

Monomer (2) A lithographic printing plate precursor was produced in the same manner as in Example 1 except that this copolymer [15] was used instead of the copolymer [1] in Example 1.

This was operated in the same manner as in Example 1 to carry out plate making / desensitizing treatment to obtain a printing original plate.

The density of the obtained master plate for offset printing is 1.
The image quality was clear at 0 or more. Place printed with a printing machine, 200
The printed matter after printing 0 sheets had no fog in the non-image area and the image was clear.

Example 16 50 g of each of the following copolymers [A] and [B] and toluene 2
50 g of the mixture was heated to a temperature of 60 ° C. and uniformly dissolved. The mixture was stirred as it was for 3 hours and reacted.

The weight average molecular weight of the obtained copolymer (16) of the present invention is 2.
It was 2 × 10 ⁵ .

Copolymer [A]: Weight average molecular weight 43,000 Copolymer [B]: Weight average molecular weight 38,000 Subsequently, Example 1 was repeated except that 40 g of the above copolymer [16] was used instead of the copolymer [1] used in Example 1.
A lithographic original plate having an image-receiving layer formed in the same manner as in (1).

As a result of plate making in the same manner as in Example 1, the obtained master plate for offset printing had a density of 1.0 or more and the image quality was clear. Furthermore, when the product was etched and printed by a printing machine, the image quality of the printed matter after printing 2000 sheets was clear without background fog.

Example 17 A mixture of 50 g of the copolymer [A] used in Example 16, 4.5 g of 1,6-hexanediisocyanate and 200 g of toluene was added at a temperature of 60.
The mixture was heated to ℃ and stirred for 3 hours. The weight average molecular weight of the obtained copolymer [17] of the present invention was 1.8 × 10 ⁵ .

Each lithographic printing plate precursor was prepared in the same manner as in Example 1, except that the above copolymer [17] was used in place of the resin [1] of the present invention.

This was made into a plate with the same apparatus as in Example 1, then subjected to etching treatment and printed with 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. Further, the image quality of the printed matter printed on 2000 sheets was good, and no background stain was generated.

Example 18 A mixture of 50 g of the copolymer [B] used in Example 16, 3.8 g of diethylene glycol and 200 g of toluene was heated to a temperature of 60 ° C. and stirred for 4 hours. The weight average molecular weight of the obtained copolymer [18] of the present invention was 2.4 × 10 ⁵ .

Subsequently, Example 1 was repeated except that 40 g of the above copolymer [18] was used in place of the copolymer [1] used in Example 1.
A lithographic printing plate precursor was prepared in the same manner as in.

As a result of plate making in the same manner as in Example 1, the obtained master plate for offset printing had a density of 1.0 or more and the image quality was clear. Further etching treatment and printing with a printing machine revealed that the printed matter after printing 2000 sheets had no fog in the non-image area and the image was clear.

Example 19 A mixture of 40 g of the following copolymer [19] and 10 g of [butyl methacrylate / acrylic acid (99/1) weight ratio] copolymer (weight average molecular weight 45,000), 100 g of zinc oxide, and 300 g of toluene in a ball mill. Dispersed for 2 hours.

Next, 10 g of allyl methacrylate and 2,2 'were added to this dispersion.
-0.5 g of azobisisobutyronitrile was added, and the dispersion obtained by dispersing in a ball mill for 10 minutes was applied to a support similar to that of Example 1 with a wire bar so that the dry adhesion amount was 20 g / m ^2. A lithographic printing plate precursor was prepared by coating and drying at 80 ° C. for 2 hours and then at 100 ° C. for 30 minutes.

Copolymer (19) Weight-average molecular weight 5.6 × 10 ^{4 When} this was made into a plate by the same apparatus as in Example 1, the density of the master plate for offset printing obtained was 1.0 or more, and the image quality was clear. Further, after etching and printing with a printing machine, the image quality of the printed matter after printing 2000 sheets was clear without background blur.

Examples 20 to 25 In Example 19, Table 2 was used instead of the resin [19] of the present invention.
Each lithographic printing plate precursor was produced in the same manner as in Example 19 except that the copolymer shown in 1 was used.

The characteristics of each of these original plates were examined in the same manner as in Example 1. The density of the obtained master plate for offset printing was 1.0 or more, and the image quality was clear. The plate of the present invention is 2000
The image quality was clear and no background stain was observed on the printed matter.

Example 26 A lithographic printing plate precursor was prepared in the same manner as in Example 1 except that 15 g of each of the copolymers [26] and [27] of the present invention having the chemical constitution shown below was used.

Copolymer [26]: Weight average molecular weight 43,000 Copolymer [27]: Weight average molecular weight 38,000 This was subjected to plate making with the same device as in Example 1, then etching treatment and printing with 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. Further, the image quality of the printed matter after printing 10,000 sheets was a clear image with no background fog.

Example 27 and Comparative Example A Ethyl methacrylate 30 g, monomer [D] 40 having the following structure
A mixed solution of g, 30 g of allyl methacrylate and 500 g of toluene was heated to a temperature of 60 ° C. under a nitrogen stream, 1.0 g of 2,2 ′,-azobisvaleronitrile was added, and the mixture was reacted for 8 hours. The weight average molecular weight of the obtained copolymer [I] was 62,000.

Monomer corresponding to the copolymer component of the present invention [D] Then, a mixture of 30 g of this copolymer (as solid content) and 10 g of [butyl methacrylate / acrylic acid (99/1) weight ratio] copolymer (weight average molecular weight 45000), 200 g of zinc oxide, and 300 g of toluene was ball-milled. Dispersed for 2 hours.

Next, 10 g of allyl methacrylate and 2,
0.5 g of 2'-azobisisobutyronitrile was added, and the resulting dispersion was dispersed in a ball mill for 10 minutes, and the resulting dispersion was applied to a support paper similar to that of Example 1 so that the dry adhesion amount was 25 g / m ^2. It was coated with a bar and dried at 100 ° C. for 30 minutes to prepare a lithographic printing plate precursor.

Comparative Example A A mixed solution of 60 g of ethyl methacrylate, 40 g of monomer [D] and 200 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream, and then 1.0 g of 2,2′-azobisisobutyronitrile was added.
Reacted for hours. The weight average molecular weight of the obtained copolymer [A] was 45,000.

Then, in the same manner as in Example 27 except that the above copolymer [A] was used in place of the copolymer [I] used in Example 27, first, the mixture was dispersed in a ball mill for 2 hours and dried. Apply with a wire bar so that the adhered amount becomes 25 g / m ^2, and 110 ℃
And dried for 1 minute to prepare a lithographic printing plate precursor.

Further, the contact angle of each of the master plates subjected to the desensitizing treatment with a desensitizing solution with water was as small as 15 ° C. or less for the master plates of the present invention and Comparative Example A, showing that they were sufficiently hydrophilized. .

Further, when printing these as a master plate for offset printing, the plates of the present invention and Comparative Example A were good in that no background stain was generated in the non-image area. Furthermore, after printing 10,000 sheets under the condition that both plates have strong printing pressure,
With the plate of the present invention, the quality of the printed matter printed on 10,000 sheets was good and no background stain was generated, but in Comparative Example A, background stain was generated at the 5500th sheet.

From the above facts, it was possible to obtain 10,000 or more prints which always form a clear copy image and have no background stain even when the original plate of the present invention is used for plate making under changing environmental conditions.

Examples 28 to 38 In Example 27, instead of the copolymer [I], Table 3
Each lithographic printing plate precursor was prepared in the same manner as in Example 27 except that the copolymer of Example 1 was used.

This was subjected to plate making with the same device as in Example 1, then etching treatment and printing with 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. Further, the image quality of the printed matter after printing 10,000 sheets was a clear image with no background fog.

Examples 39 to 44 In Example 27, Table 4 was used instead of the resin [I] of the present invention.
Each lithographic printing plate precursor was produced in the same manner as in Example 27 except that the copolymer shown in 1 was used.

When the plate was made using the same apparatus as in Example 1, the density of the master plate for offset printing obtained was 1.0 or more.
The image quality was clear. When the product was further etched and printed with a printing machine, the printed matter after printing 10,000 sheets had a clear image quality without fog.

Example 45 Instead of the [butyl methacrylate / acrylic acid] copolymer used in Example 27, [butyl methacrylate /
Allyl methacrylate / acrylic acid (79/20/1) weight ratio] A lithographic printing plate precursor was prepared in the same manner as in Example 27 except that the copolymer was used.

When this was subjected to plate making by a fully automatic plate making machine ELP404V as in Example 1, the density of the obtained master plate for offset printing was 1.0 or more and the image quality was clear. Furthermore, after etching treatment and printing with a printing machine, the printed matter after printing 10,000 sheets had no fog in the non-image area and the image was clear.

(Effect of the Invention) According to the present invention, it is possible to obtain a direct-drawing type lithographic printing plate precursor in which the occurrence of background stain is satisfactorily suppressed and the printing durability is also good.

Claims (3)

[Claims] 1. A direct-drawing lithographic printing plate precursor having an image-receiving layer on a support, wherein a thiol group, a phosphono group, an amino group and a sulfo group are formed by decomposition as at least part of the binder of the image-receiving layer. A direct-drawing lithographic printing plate precursor comprising at least one functional group which forms at least one of the groups and at least one resin which is at least partially crosslinked. 2. The resin contains a copolymerization component containing at least one functional group capable of generating at least one group selected from a thiol group, a phosphono group, an amino group and a sulfo group upon decomposition, and further comprising: The direct-drawing lithographic printing plate precursor as claimed in (1), which is a resin which has been pre-crosslinked so as to be sparingly soluble or insoluble in water when a group is formed. 3. A function of causing the resin to undergo a curing reaction with at least one kind of functional group that generates at least one group of a thiol group, a phosphono group, an amino group and a sulfo group by decomposition and with heat and / or light. A lithographic printing plate precursor for direct drawing according to claim 1, which is a resin containing at least one group.