JPH01288488A - Original plate for direct describing lithographic press - Google Patents

Abstract

PURPOSE:To achieve high print resistance without causing contamination of texture, by incorporating at least one type of functional group for producing at least one of thiol group, phosphono group, amino group or sulfo group through decomposition and at least one type of partially bridged resin as at least a part of binding agent in an image receiving layer. CONSTITUTION:In an original plate for direct describing lithographic press, resin is at least partially bridged. A resin previously bridged in plate making process when photo-sensitive layer forming material is applied may be employed or a resin containing a bridgeable functional group which may thermally or optically set may be employed, and bridged during manufacturing process. They may also be combinedly used. When a resin where a portion of polymer is previously bridged (A resin having bride structure in the polymer) is employed as a binding resin, it is preferable that the resin is hardly soluble or insoluble into acid or alkaline aqueous solution when the functional group contained in the resin for producing thiol group, phosphono group, amino group and/or sulfo group produces hydrophilic group through decomposition.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a lithographic printing original plate, and more particularly to a direct-drawing type lithographic printing original plate suitable for office printing original plates and the like.

(Prior Art) Currently, straight groove type lithographic printing plates having an image-receiving layer on a support are widely used as printing plates for office use. To perform plate making, that is, image formation on such a printing original plate, generally, oil-based ink is drawn by hand on the image-receiving layer, or
Printing methods such as a typewriter, an inkjet method, or a transfer type heat-sensitive method are employed. In addition, a method has recently begun to be used in which a toner image formed on a photoreceptor is transferred and fixed onto an image-receiving layer using a plain paper electrophotographic copier (PPC) through the steps of charging, exposure, and development. In any case, the printing original plate after plate making is subjected to surface treatment with a desensitizing liquid (so-called etch liquid) to make the non-image area non-greasy, and then subjected to planographic printing as a printing plate.

In conventional planographic printing plates, surface layers are provided on both sides of a support such as paper with a back layer and an intermediate layer interposed therebetween. The back layer or intermediate layer is made of a water-soluble resin such as PVA starch, a water-dispersible resin such as a synthetic resin emulsion, and a pigment. The surface layer is formed from a pigment, a water-soluble resin, and a water-resistant agent.

A typical example of such a straight groove type lithographic printing plate is U.S. Patent No. 2.
No. 532,865, the image receiving layer is PV
It is composed mainly of a water-soluble resin binder as shown in A, an inorganic pigment such as silica and calcium carbonate, and a water resistance agent such as an initial condensate of melamine/formaldehyde resin.

(Problems to be solved by the invention) However, the conventional printing plates obtained in this way are
In order to improve printing durability, increasing hydrophobicity by increasing the amount of water-resistance agent added or using hydrophobic resin will improve rigidity resistance but reduce hydrophilicity and cause printing stains. However, on the other hand, when the hydrophilicity is improved, the water resistance deteriorates and the rigidity resistance decreases. In particular, in high-temperature applications of 30° C. or higher, the surface layer dissolves in the soaking water used in offset printing, resulting in both reduced printing durability and printing stains, which is a major drawback.

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

The present invention is intended to improve the above-mentioned problems associated with direct drawing type lithographic printing original plates.

An object of the present invention is to provide a direct-drawing type lithographic printing original plate which has excellent desensitization properties and does not cause not only full-surface scumming but also spot-like scumming as an offset printing plate.

The object of the present invention is to improve the adhesion between the oil-based ink in the image area and the image-receiving layer, to maintain sufficient hydrophilicity in the non-image area even when the number of prints increases, and to prevent background smearing. An object of the present invention is to provide a lithographic printing original plate having high stiffness.

(Means for Solving the Problems) The above-mentioned aspects are such that, in a direct drawing type lithographic printing original plate having an image-receiving layer on a support, at least a part of the binder of the image-receiving layer is decomposed. The resin is characterized in that it contains at least one functional group that forms at least one thiol group, phospho group, amino group, and/or sulfo group, and is characterized in that it is at least partially crosslinked. As a result, the lithographic printing original plate according to the present invention reproduces a copy image that is faithful to the original image, has good hydrophilicity in the non-image area, does not cause scumming, and has a good smoothness of the image-receiving layer. It also has the advantage of excellent printing durability.

Furthermore, the lithographic printing original plate of the present invention is not affected by the environment during plate-making processing and has excellent storage stability before processing.

Below, the resin containing at least one kind of functional group that decomposes to produce at least one hydrophilic group of thiol group, phospho group, sulfo group and/or amino group (hereinafter simply referred to as hydrophilic group) used in the present invention will be described. (sometimes referred to as group-forming functional group-containing resin) will be explained in detail.

The functional group contained in the hydrophilic group-generating functional group-containing resin of the present invention generates at least one hydrophilic group by decomposition, and the number of hydrophilic groups generated from one functional group may be one or two or more.

Hereinafter, the resin containing a functional group that generates at least one thiol group upon decomposition (thiol group-generating functional group-containing resin) will be described in detail. Such a resin is, for example, a resin containing at least one functional group represented by the following general formula (1) (-3-L^).

General formula (1): (-3-LA) 埜"・ However, RA, RA□ and RA3 may be the same or different from each other, and each represents a hydrocarbon group or -〇-RA' (
RA' represents a hydrocarbon group), RA4, RAl
, RA6, RAff, RAa, RA9 and RAIO
each independently represents a hydrocarbon group.

The functional group of the above general formula (-3-LA) can be decomposed by
It produces a thiol group, and will be explained in more detail below.

RAl RA in the case where LA represents 13t-RA□.

RA, ,RA , propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, chloroethyl group, methoxyethyl group, methoxypropyl group, etc.), optionally substituted alicyclic groups (e.g. cyclopentyl group, cyclohexyl group) group), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, etc.), or an optionally substituted aromatic group (e.g., phenyl group, naphthyl group, etc.) group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxycarbonylphenyl group, dichlorophenyl group, etc.) or bar0-RA'(R'' represents a hydrocarbon group, specifically, the above RA, , RAz, RA
The substituents described for the hydrocarbon group can be cited as examples).

In this case, RA4, RAl, RA6, R^? , R.A.

each preferably has 1 to 12 carbon atoms and may be substituted
linear or branched alkyl groups (e.g. methyl, trichloromethyl, trifluoromethyl, methoxymethyl, ethyl, propyl, n-butyl, hexyl, 3-chloropropyl, phenoxymethyl) , 2.
2.2-trifluoroethyl group, L-butyl group, hexafluoro-1-propyl group, octyl group, decyl group, etc.)
, an 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.), optionally substituted carbon number 6 to
12 aryl groups (e.g. phenyl group, nitrophenyl group, cyanophenyl group, methanesulfonylphenyl group,
methoxyphenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group, trifluoromethylphenyl group, etc.).

RA and RAIll may each be the same or different, and preferred examples represent the substituents described as preferred for R^ and ~RAB above.

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 (If) or the general formula (■).

General formula (If) AI 1 General formula (III) X In formula (II), RAII and RA□ may be the same or different from each other and each represents a hydrogen atom or a hydrocarbon group. Preferably, a hydrogen atom or the above RA, ~RA,
represents the substituents described as preferred.

In formula (I[[), XA represents a hydrogen atom or an aliphatic group. The aliphatic group is preferably a C1-C6 noalkyl group (for example, a methyl group, an ethyl group, a propyl group,
butyl group, etc.).

Still another preferred 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 general formula (IV).

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

RA13, RA14 and RAIS may be the same or different and each represents a hydrogen atom or a hydrocarbon group. Preferably, a hydrogen atom or RA4 to RA above represents a substituent described as preferred.

R'16 and R'l'l may be the same or different, and represent a hydrogen atom, a hydrocarbon group, or -〇-RA"(RA"
represents a hydrocarbon group). Preferably, the R
A , , , RA represents a substituent described as preferred.

According to yet another preferred embodiment of the present invention, the thiol group-generating functional group-containing resin has a functional group having at least two thiol groups that are sterically close to each other and simultaneously protected with one protecting group. It is a resin containing at least one kind of.

Examples of functional groups having at least two thiol groups that are sterically close to each other protected simultaneously with one protecting group include the following general formulas (V), (VI) and (
■) can be mentioned.

General formula (V) General formula (Vl) General formula (■) In formula (V) and formula (VI), Z^ directly connects carbon-carbon bonds or C-3 bonds, which may be via a heteroatom. (However, the number of atoms between sulfur atoms is 4 or less). Furthermore, one side +ZA-・-C-
)-bond may represent only a simple bond, for example as shown below.

In 2 (Vl), RAlls RAII may be the same or different, and may be a hydrogen atom, a hydrocarbon group, or -
0-RA" (R represents a hydrocarbon group).

In formula (Vl), RA18 and R^1. are preferably the same or different and include a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms (e.g., 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 (e.g. benzyl group, phenethyl group, methylbenzyl group, methoxybenzyl group, chlorobenzyl group, etc.), 5 to 7 carbon atoms an alicyclic group (e.g., cyclopentyl group, cyclohexyl group, etc.) or an optionally substituted aryl group (e.g., phenyl group, chlorophenyl group, methoxyphenyl group, methylphenyl group, cyanophenyl group, etc.) or -〇-R ”
(R” is RAI II, RAI.

(synonymous with hydrocarbon group).

In formula (■), RA2G, RA21% RA22,
RA22 may be the same or different and each represents a hydrogen atom or a hydrocarbon group. Preferably, it represents a hydrogen atom or the same meaning as the hydrocarbon group described as preferred in RAll1%RAll.

The resin containing at least one functional group represented by the general formulas (1) to (■) used in the present invention is obtained by protecting the thiol group contained in the polymer with a protective group through a polymer reaction. Polymerization by a method or a polymerization reaction of a monomer containing one or more thiol groups in a form previously protected by a protecting group or of said monomer and other monomers copolymerizable therewith. manufactured by the method.

Polymers containing thiol groups inhibit radical polymerization, so it is difficult to directly polymerize thiol group-containing monomers. It is produced by polymerizing monomers with protected thiol groups in the form of the functional groups used in the present invention, such as isothiuronium salts and Punte salts, followed by a decomposition reaction to form 1,000-ol groups.

Therefore, it is possible to arbitrarily adjust the functional group protecting the thiol group in the polymer, and it is possible to avoid mixing impurities.
For reasons such as the fact that polymerization will not occur unless the monomer ultimately has a protected thiol group, a method in which the polymer is produced by a polymerization reaction in advance from a monomer containing a functional group of the general formula (2) is preferred.

As a production method for converting one or at least two thiol groups into a functional group protected by a protecting group, for example,
“Reactive Polymers” by Yoshiyu Iwakura and Keisuke Kurita, pages 230-23
7 pages (Kodansha: published in 1977), Nippon Kagaku Venue “New Experimental Chemistry Course Volume 14, Synthesis and Reactions of Organic Compounds [■], Chapter 8, pp. 1700-1713, (Maruzen Co., Ltd. 1)
(published in 1978), J. F. W. McOmie,
rProtective Groupsin Org
anic Chemistry” Chapter 7 (Plenum
Press.

(1973), S. Patai, 'The
Chemistry of the thiol gro
up Part2 J Chapters 12 and 14 (John
It is possible to apply methods described in known literature cited in reviews such as Wiley & 5ons, published in 1974.

Monomers in which one or more thiol groups are protected with a protecting group, such as monomers containing functional groups represented by formulas (I) to (■), are specifically A compound containing a bond and at least one 1,000-ol group, for example, according to the method described in the above-mentioned known literature, etc.
Converting a thiol group to a functional group of general formulas (1) to (■), or reacting a compound containing a functional group of general formulas (1) to (■) with a compound containing a polymerizable double bond. It can be manufactured by a method.

More specifically, the following compounds can be mentioned as monomers containing functional groups of general formulas (1) to (■), but the scope of the present invention is not limited thereto. .

(1) -(-CH2-CH-)-■ C0CH5 (2) -+CH,-CH-)-SCOC,H5 (3) -+CHz-CH-)-! 5COC,H9 (4) -+CH2-CH')-■ 5COCH2(1! (5) -(-CHI-CH-)-3COOC,
H.

(9) -(-CH, -CH-)-CHzSCO
OC,I7 5COCR,CI2 IS C00CzHs 5-C3OC2H1 CH2S-COOCH.

CH25C3OC2H5 Cheers S-3-C,H.

SS! (OCR3)* (20) -(-CH, -CH-)-COO(CH
2) ZS-COCH2Cp! .

CH.

(21) -+cH2-c+ C00(CH2)zS -COOC,H5H3 (22) -(-CF(2-C-)-C00(
CH2)2S-C3OC2H5CH.

113 CH3 (24) -(-CH2-C-+-(25)
-+CHz CH+GoodCoo(CHz)zs S i (CH3)IH3 (26) -fCH2-C-+- Direct C00CHzCHCH2CH2S-C3OC2L5-C
3OCzHs (27) -(cH2-CH+- Book C00(CH□), 5COOC,H.

CH3 (28) -(-CH2--C-±-C0NH(CH
2), 5COOC, H9(30)−+c H−=c H
-)- 3〉-3 tl, u utico S□S S□S S□S S□S I S□5 (40) CH.

■ S□S lI S□5 (42)　　　　cH.

■ -(-CH, -C-÷- " C,H.

(43) −+CH, −CH→− day of the week OCH, CHCH, 5COCH.

5 COCH.

(44) -(-CH, -CH-)-■ 0-CH, CHCH.

S \/ CH.

■ (45) -+cHz C+ (47) CH.

-(-CH, -C-±- COO(CH2) 2 S S C4Hq(49)
CH.

(50) CH.

■ 1+CHt-C+ C00CCH2)2SCOCH12 (51) →CH, -CH→- CHz N HCOCHCH2 (52) CH.

-(CH2-C-Chi ■ (53) CH.

-(CH, -C+ Coo(CH2)2 3 C0NH(CH2)2Nl
lCH3 Also, in the present invention, a resin containing a functional group that decomposes to produce a phospho group, such as a group of the following general formula (■) or (IX), will be explained in detail.

General formula (■) Q[lI 1] P-RB Z", -H General formula (IX) 1-P-Z", -H 113-H In formula (■), R'' is a hydrocarbon group or - 72-R
+'' (where R@l represents a hydrocarbon, ZB□ represents an oxygen atom or a sulfur atom). Qllll represents an oxygen atom or a sulfur atom. Z'' (represents an oxygen atom or a sulfur atom .In formula (IX), Q”z, Z
S and ZI'4 each independently represent an oxygen atom or a sulfur atom.

Preferably, R' has 1 to 1 carbon atoms, which may be substituted.
2. Straight chain or branched alkyl group (e.g. 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.),
An optionally substituted alicyclic group (e.g., cyclopentyl group, cyclohexyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, methylbenzyl group, methoxybenzyl group) basis,
chlorobenzyl group, etc.) or an optionally substituted aromatic group (e.g., phenyl group, chlorophenyl group, tolyl group, xylyl group, methoxyphenyl group, methoxycarbonylphenyl group, dichlorophenyl group, etc.), or -Zll
□-R11' (Here, Zl'□ represents an oxygen atom or a sulfur atom. RB' represents a hydrocarbon group. Specifically, using the substituents mentioned above for the hydrocarbon group of R'' as an example, ).

Q", , Q"□, Zl3, Zl'3, and Z- each independently represent an oxygen atom or a sulfur atom.

Examples of the functional group that generates the phospho group represented by the formula (■) or (IX) upon decomposition include the functional groups represented by the general formula (X) and/or (XI).

General formula (X) Ql′+ -P-R irises z++, Lll.

General formula (XI) -P-Z--L- Z", -L"□ In formulas (X) and (XI), Q"+, Q@t, Z
"r % Z": +, Z! 4 and R11 represent the contents as defined in formulas (■) and (XI), respectively.

LH,, L11□ and Lll, each independently, RB□ may be the same or different from each other, and are hydrogen atoms,
Represents a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.) or a methyl group. X a and Xl'□ represent an electron-withdrawing substituent, preferably a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), -C
N, -CONH2, -NOx or -SO□RI'#(R
I'# represents a hydrocarbon group such as methyl group, ethyl group, propyl group, butyl group, hexyl group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group, etc.

n represents 1 or 2. Furthermore, when X l is a methyl group, RB and R11□ are methyl groups, and n=1.

When R11゜L", -L- represents -3i-RB4, "3", R"4 and R11, in R"S, may be the same or different, preferably a hydrogen atom, a substituted A linear or branched alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group,
Hexyl group, octyl group.

decyl group, dodecyl group, octadecyl group, chloroethyl group, methoxyethyl group, methoxypropyl group, etc.), optionally substituted alicyclic groups (e.g. cyclopentyl group,
cyclohexyl group, etc.), optionally substituted carbon number 7-
12 aralkyl groups (e.g. benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, etc.) or optionally substituted aromatic groups (e.g. phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxy carbonylphenyl group, dichlorophenyl group, etc.) or -0~RB'I/ (Rl l'' is
Represents a hydrocarbon group, specifically, the above R"3.RR4
, the substituents mentioned for the hydrocarbon group of R- can be mentioned as examples).

L-~LB:l is -C-R",, -(,-R",,
-C-0-R", -C-0-11", or -8
In the case of representing S −R”l., R115, R1'7
, R-1R''9 and R''IO each independently represent a hydrocarbon group. Preferably, the number of carbon atoms is 1 or more, which may be substituted.
6 linear or branched alkyl groups (e.g. methyl group, trichloromethyl group, trifluoromethyl group, methoxymethyl group, phenoxymethyl L 2,2.2-1 Rifle A
ethyl group, ethyl group, propyl group, hexyl group, L
-butyl group, hexafluoro-1-propyl group, etc.), optionally substituted alkyl groups having 7 to 9 carbon atoms (e.g., benzyl group, phenethyl group, methyl, Izbenzyl group, trimethylbenzyl group,・Butamethyl--nzyl group, methoxybenzyl group, etc.), optionally substituted carbon number 6
~12 aryl groups (e.g. phenyl group, l.lyl group,
(xylyl group, nitrophenyl group, cyanophenyl group, methanesulfonylphenyl group, methoxyphenyl group, butoxyphenyl group, chlorophenyl group, dichlorophenyl group, trifluoromethylphenyl group, etc.).

In the cases shown, 'yg and YB□ 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 (phospho group) of the above formula (VII[) or (IX) contained in the polymer that is protected by a protective group through a polymer reaction. A method of forming a protected form, or a functional group previously protected with a protecting group (for example, formula (X) or (X
It is produced by a method of polymerizing a monomer containing the functional group I) or a polymerization reaction between the monomer and another monomer that can be copolymerized with the monomer.

In either method, a similar synthetic reaction can be used to introduce the protective RIM. Specifically, J., F., W., McOmie, rProte.
activegroups in Organic Ch
emistry J Chapter 6 (PlenumPress,
(published in 1973), the method described in the known literature cited in the review,
Alternatively, the protection of hydroxyl groups as described in the known literature cited in the review such as Nippon Kagakujou [New Experimental Chemistry Course Volume 14, Synthesis and Reactions of Organic Compounds [■]], page 2497 (published by Maruzen Co., Ltd., 1978) Synthesis reaction similar to the method of group introduction,
Or S.

Patai, rThe Chemistry of
the Trtol GroupPart2J Chapters 13 and 14 (Wiley-1interscience1
974), T., W., Greene, rP.
protective groups in Organi
c 5ynthesis” Chapter 6 (Wi Iey-I
It can be produced by a synthetic reaction similar to the method for introducing a protecting group into a thiol group as described in the known literature cited in the review such as ``Interscience,'' published in 1981.

The following examples can be given as specific examples of compounds that can serve as repeating units of polymeric components containing functional groups of general formulas (X) and/or (XI) used as protecting groups. However, the present invention is not limited thereto.

TS i (CH:l)3 0 5i(CHJ* (5B) -(-CH2-CH-)-OHl P
OS i (CzHs)s' 0-3 t (C2H4)3 0 S i (OCHa)3 CH.

Australia 0COC,H.

Ru 0-3　i　(CH3)z Hz ■ 0-COCH.

Hz 0-3　i　(CH3)3 CH3 O-S i (CH3) tc, lI.

CH3 O5i(CHz)s CH.

Cabinet 5-COCH.

CH.

■ 0COOC,H5 CH.

S-COOC2H3 C.I.

1 1t CONHCCHJbOP OS i (CH3)+0
5i (CHz)i OCOC= Hs CH.

(73) →CH, -C-+- day of the week 5-C3OCH.

0-3　i　(C2H5)3 CH3 (75) −(−CH, −C+ ■ CH.

0-COoC,H.

CH.

(7B) -(-CH,-C+ Coo(CH,), 0-P-0(CH,), CN〇(C
Hz)zcN Next, examples of the functional group that generates an amino group, such as a -NH2 group and/or a =N HRC group, by the decomposition include groups represented by the following general formulas (Xll) to (XIV).

General formula (XII) -N-Coo-Rc.

RCO General Formula (XII[) General Formula (XIV) In Formula (XII) and Formula (XIV), RCO represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms (
For example, methyl group, ethyl group, propyl group, butyl group,
Hexyl group, octyl group, decyl group, dodecyl group, 2-
Chloroethyl L2-7' lomoethyl 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 (e.g., cyclopentyl group, cyclohexyl group, etc.), carbon number 7 to 12 optionally substituted aralkyl groups (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, 1-phenylpropyl group, chlorobenzyl group, methoxybenzyl group, bromobenzyl group, methylbenzyl group, etc.), An optionally substituted aryl group having 6 to 12 carbon atoms (e.g. phenyl group, chlorophenyl group, dichlorophenyl group, tolyl group, xylyl group, mesityl group, chloromethyl group, chlorophenyl group,
methoxyphenyl group, ethoxyphenyl group, chloromethoxyphenyl group, etc.).

Preferably, when RC represents the hydrocarbon group, examples thereof include hydrocarbon groups having 1 to 8 carbon atoms.

In the functional group represented by formula (Xll), RC.

represents an optionally substituted aliphatic group having 2 to 12 carbon atoms, and more specifically Rc represents a group represented by the following formula (XV).

Formula (XV) + c + -y' z In formula (XV), a1ga! each has a hydrogen atom, a halogen atom (e.g. fluorine atom, chlorine atom, etc.) or a carbon number of 1 to 12
optionally substituted hydrocarbon groups (e.g. methyl group, ethyl group, propyl group, butyl group, hesyl 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 group, methoxyphenyl group, dichlorophenyl group, chloromethylphenyl group, naphthyl group, etc.), and YC represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, etc.), a cyano group, and a carbon number of 1 to 4.
Alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), aromatic groups which may contain substituents (e.g. phenyl, tolyl group, cyanophenyl group, 2.6-
dimethylphenyl group, 2. 4. 6-trimethylphenyl group, heptamethylphenyl group, 2.6-simethoxyphenyl group, 2,4.6-)rimethoxyphenyl group, 2
-propylphenyl group, 2-butylphenyl group, 2-chloro-6-methylphenyl group, furanyl group, etc.) or -S
O□-Re6 (Re6 represents the same content as the hydrocarbon group of YC), etc. n represents 1 or 2.

More preferably, when yc is a hydrogen atom or an alkyl group, al
and a2 represents a substituent other than a hydrogen atom.

When YC is not a hydrogen atom or an alkyl group, al and a2 may be any of the groups listed above.

That is, in +d-+T-Yc, when at least Z also forms a group containing one or more electron-withdrawing groups, or when the carbon adjacent to the oxygen atom of the urethane bond forms a sterically bulky group. This shows that this is a preferable example.

Or specifically, Rcl is an alicyclic group (for example, a monocyclic hydrocarbon group (cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl i, i-methyl-cyclohexyl group, l-methylcyclobutyl group, etc.) or a crosslinked Represents a cyclic hydrocarbon group (bicyclooctane group, bicyclooctene group, bicyclononane group, tricyclohebutane group, etc.).

In general formula (XI[I), RC□ and Re3 may be the same or different and each represents a hydrocarbon group having 1 to 12 carbon atoms, specifically, an aliphatic group in yc of formula (Xn) or represents the same content as an aromatic group.

In the general formula (XTV), xCI and XC2 may be the same or different and each represents an oxygen atom or a sulfur atom. Rc4 + RC5 may be the same or different and each represents a hydrocarbon group having 1 to 8 carbon atoms, specifically an aliphatic group or an aromatic group in yc of II (XII).

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

H3 (79) -N)IcOOc-C1-1°CH.

Cb Hs (81) -NHCOOCH, CF.

(82) -NHCOOCHzCCj2z (83)
-NCOOCH, CH, SO□CH.

the law of nature CH.

CH.

(85) -NHCOOC-C (1°CH3 21"l5 CH.

U ○CHx ■ 0CHICH, OCH3 CaH9 (105) -NH-P-OC,H.

I The decomposition used in the present invention results in amino groups (e.g. -N
The resin containing at least one functional group that produces a HZ group and/or -NHR group, for example, a functional group selected from the group of the above general formulas (XI[) to (XIV), is, for example,
Edited by Kasho Nihon, “New Experimental Chemistry Course Volume 14, Synthesis and Reactions of Organic Compounds [■]” p. 2555 (published by Maruzen Co., Ltd.)
, J., F., W., McOmie, 'Protecti.
ve groups in Organic Chen
+1try J Chapter 2 (Plenum Press
(published in 1973), rProtec-tive gro
ups in Organic 5inthesis”
Chapter 7 (John Wiley & 5ons, 198
It can be produced by a method described in a known literature cited in a review such as No. 1).

For reasons such as being able to arbitrarily adjust the functional groups of general formulas (XII) to (XIV) in the polymer or preventing the inclusion of impurities, the functional groups of general formulas (XII) to (XIV) are prepared in advance. A method of manufacturing by polymerization reaction from the monomers contained is preferred. Specifically, the amine group is converted into a primary or secondary amino group containing a polymerizable double bond by the general formula (XI [)
After converting into the functional groups of ~(XIV), a polymerization reaction can be performed to produce the functional group.

Furthermore, examples of the functional group that generates at least one sulfo group upon decomposition include general formula (XI) or (X
) are mentioned.

General formula (xvt) -so□-〇 RD+General formula (
X■) -3O□-3RD2 represents early ° or -NHCORI'.

In formula (X■), R0□ represents an optionally substituted aliphatic group having 1 to 1B carbon atoms, or an aryl group having 6 to 22 carbon atoms, which may have a substituent.

The functional groups of the general formulas (XVI) and (X■) above generate sulfo groups upon decomposition, and will be explained in more detail below.

R.D.

When R11, represents −+ch-Y”, R
D4 RD3 and R”4 may be the same or different and are hydrogen atoms,
It represents 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, a pentyl group, a hexyl group). Y is an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g. 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),
An optionally substituted alkenyl group having 2 to 18 carbon atoms (e.g. vinyl group, allyl group, etc.), an aryl group having 6 to 12 carbon atoms which may contain a substituent (e.g. phenyl group, naphthyl group, nitrophenyl group) group, dinitrophenyl group, cyanophenyl group, trifluoromethylphenyl group, methoxycarbonylphenyl group, butoxycarbonylphenyl group, metaisulfonylphenyl group, benzenesulfonylphenyl group, tolyl group, xylyl group, acetoxyphenyl group, nitronaphthyl group etc.), or -C-RD, (R',
represents an aliphatic group or an aromatic group, specifically, represents the same substituent as described for YD).

n represents 0.1 or 2. More preferably RD.

Substitution s knee + c) □ In YD, at least one ■ RD4 Examples include functional groups containing an electron-withdrawing group.

Specifically, when n is 0 and YD is a hydrocarbon group containing no electron-withdrawing group as a substituent, RD.

1←C)-, at least one halo RD.

Contains a gen atom. Further, n is 0.1 or 2, and YD contains at least one electron-withdrawing group. Further examples include 埜°・ and so on. The electron-withdrawing group is a substituent having a positive Hammett's substituent constant, such as a halogen atom, -COO-1-C-1-3O□-1-CN, -No
□ etc.

Another preferred substituent is ゛-3O□-0-RD
at least two hydrocarbon groups are substituted on the carbon atoms adjacent to the oxygen atom, or n=0 or 1,
When Yl' is an aryl group, the aryl group may have substituents at the 2-position and the 6-position.

where ZD represents an organic residue forming a cyclic imide group. Preferably, general formula (X■) or (X' IX )
represents an organic residue represented by

General formula (X■) General formula (XIX) In formula (X■), RIll, RD,. may be the same or different, and each represents a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, etc.), an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g. methyl group, ethyl group, propyl group). , butyl group, hexyl group, octyl group, decyl group, doditer 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.)
, an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group, chlorobenzyl group, bromobenzyl group, etc.) , an optionally substituted alkenyl group having 3 to 1 carbon atoms (
For example, allyl group, 3-methyl-2-propenyl group), where R''S and RD& are each a hydrogen atom, an aliphatic group (specifically, RD, , and R represent the same content), or aryl represents a group (specifically, RD, represents the same content as that of Ra4).

However, R1+ and R'6 do not both represent hydrogen atoms.

When RD represents -NHCOR, RD
represents an aliphatic group or an aryl group, specifically, R
D, , and R114 each represent the same content.

In formula (X■), R11□ represents an optionally substituted aliphatic group having 1 to 1 carbon atoms or an optionally substituted aryl group having 6 to 22 carbon atoms.

More specifically, YD represented by the above formula (XVI)
represents the same content as the aliphatic group or aryl group in .

General formula [-3O□-〇-RD, used in the present invention,
) or [-3O-0-R" A method of converting into a functional group of the general formula (X
Polymerization by a polymerization reaction of one or more monomers containing one or more of the functional groups VI) or (X■), or the monomer and other monomers copolymerizable with it. Manufactured by a method.

The method for converting into the functional group by polymer reaction can be carried out in the same manner as the synthesis method for monomers.

More specifically, general formula (XVI)-3Q, -0-R''.

Alternatively, the following examples can be given as the functional group of the general formula (X■)-3O□-ORDz, but the scope of the present invention is not limited thereto.

(108) -3O,OCH,CF.

(110) -3o□OCHz(CHF)z C
Hz F(111) -3O,0CH2CCffi
3(l l 3) -3O,0(CH□)2SO,
C,H.

/ CH.

CH3 OCH3 C,HS ■ (122) 5OzOCHC0CaHq(123
) 5OzO(CH=)zso□Cz Hs(1
24) -3O,SC,T(.

(125) -3o□S Cb H1s (126)
-3O,5(C1(Z)20C,H.

(12B) -3OtOCH, CHFCH2F As mentioned above, general formulas (I) to (■), (X) to (XIV
. However, the copolymer components are not limited to these examples.

General formula (A) at a, snake One÷−CH−C+ " x'-y'-w In formula (A), X' is -O-, -CO-.

Q, Q.

I -Coo-, -0CO-, -NGO-, -CON-.

Q, Q.

Sow, 5OzN, NSO□-,
CH2b.

COO-, -CHzOCO-, (-Ch-, aromatic group,
or a heterocyclic group [however, Q,,Q! ,Q.

Q4 each represents a hydrogen atom, a hydrocarbon group, or +Y'-W) in formula (VI), and b, , b may be the same or different (, a hydrogen atom, a hydrocarbon group, or +Y'-W) in formula (VI); Vl)
→N'-W), where n is an integer from 0 to 18].

Y' represents a carbon-carbon bond that connects the bonding group X' and the bonding group [W], which may be via a heteroatom; examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom); -+CH=CH:F, -0-, -3-. -N-.

-C00~, -CONH-, -3o□-2-3O□NH
-, -NHCOO-, -NHCONH-, etc., either singly or in combination (however, b3
．． b, , bs are each as described above.

It is synonymous with b. ) W is the formula (I) ~ (■), (X) ~ (XIV), (XVI
) or (X■) represents a functional group.

al and az may be the same or different, and hydrogen atoms,
Halogen atoms (e.g. chlorine atom, bromine atom, etc.), cyano group, hydrocarbon group (e.g. methyl group, ethyl group, propyl group, butyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyl group) 1 to 1 carbon atoms that may be substituted such as oxycarbonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, etc.
(2), an aralkyl group such as a benzyl group, a phenethyl group, an aryl group such as a phenyl group, tolyl group, xylyl group, chlorophenyl group, etc.), or a substituent containing a -W group in formula (A). an alkyl group having 1 to 18 carbon atoms, an alkyl group, an alkenyl group, an aralkyl group,
represents an alicyclic group or an aromatic group).

In addition, the (-X'-Y') bonding residue in formula (A) is t ■ ←C-) Part and -W part may be directly connected.

(2) Examples of other copolymer components that can be copolymerized with these copolymer components of the present invention include vinyl acetate. Aliphatic carboxylic acid vinyl or allyl esters such as vinyl propionate, vinyl butyrate, allyl acetate, allyl propionate, etc., unsaturated carboxylic acids such as acrylic acid, methacrylic acid, slotonic acid, itaconic acid, maleic acid, fumaric acid, etc. and esters or amides of these unsaturated carboxylic acids, styrene, vinyltoluene, styrene derivatives such as α-methylstyrene, α-olefins, vinyl-substituted compounds such as acrylonitrile, methachronitri, and N-vinylpyrrolidone. Examples include heterocyclic compounds.

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

As such a resin, a resin that has been crosslinked in advance during application of the photosensitive layer forming material in the plate-making process may be used, or a resin containing a crosslinkable functional group that causes a curing reaction with heat and/or light may be used. It may also be used to crosslink during the manufacturing process of the lithographic printing original plate (for example, during the drying process). Furthermore, these may be used in combination.

When using a resin in which a portion of the polymer has been crosslinked in advance (resin having a crosslinked structure in the polymer) as a binder resin, the above-mentioned thiol group, phosphor group,
Preferably, the resin is sparingly soluble or insoluble in acidic and alkaline aqueous solutions when the hydrophilic group-forming functional group of the amino group and/or sulfo group forms the hydrophilic group by decomposition.

Specifically, the solubility in distilled water is preferably 90% 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 a polymer, commonly known methods can be used.

That is, in the polymerization reaction of monomers, there are two methods: a method in which a polyfunctional monomer is coexisting, and a method in which a functional group that promotes a crosslinking reaction is contained in the polymer and crosslinked by a polymer reaction.

The resin of the present invention does not impair image-receiving properties, or the manufacturing method is simple (e.g., a long reaction is required, the reaction is not quantitative, impurities are mixed in due to the use of a reaction accelerator, etc.) ) etc., a functional group CONHCM, OR'(R" is a hydrogen atom or an alkyl group) having a self-crosslinking reaction 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 1 or more monomers together with a monomer containing a functional group that generates a hydrophilic group by decomposition according to the present invention,
Alternatively, a monomer having two or more of the polymerizable functional groups is polymerized with a monomer containing a hydrophilic group to form a copolymer, and then the hydrophilic group is protected as described above.
The resin of the present invention can be produced.

Specifically, the polymerizable functional group is CH,=CH-1CH2
=CHCHz-1CH,=CH-C-0-1CH,C
HI 0 11I CH2=C-C-0-1CH=CH-C-O-1CH3 CH,=CH-C0NH-1CH,=C-C0NH-1
CH, =CH-NHCO-1CHz = CHCH!
N HCO-CHz-CHSow-1CH,=CH-
C0-1CH, =CH-0-1CH, =CH-3-1, etc. can be mentioned, but monomers having two or more of the above polymerizable functional groups may have these polymerizable functional groups in the same Any monomer may be used as long as it has two or more different monomers, and forms a polymer that is insoluble in non-aqueous solvents by polymerization.

Specific examples of monomers having two or more polymerizable functional groups include styrene derivatives such as divinylbenzene and trivinylbenzene; polyhydric alcohols (e.g. ethylene Glycol, diethylene glycol, triethylene glycol, polyethylene glycol #200, #400, #600, l, 3
-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) or polyhydroxyphenol (
Esters, vinyl ethers or allyl ethers of methacrylic acid, acrylic acid or crotonic acid (e.g. hydroquinone, resorcinol, catechol and their derivatives); dibasic acids (e.g. malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid) , maleic acid, phthalic acid,
Itaconic acid, etc.) vinyl esters, aluminum esters, vinylamides or allylamides: Polyamines (e.g. ethylene diamine, 1,3-propylene diamine, 1,4-butylene diamine, etc.) and carboxylic acids containing vinyl groups ( Examples include condensates with methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

In addition, monomers having different polymerizable functional groups include, for example, carboxylic acids containing vinyl groups [e.g., methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpropionic acid, acryloylpropionic acid, itaconyloyl acetic acid, itaco Niloylpropionic acid, reactants of carboxylic anhydrides and alcohols or amines (e.g. allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.)
Ester derivatives or amide derivatives containing vinyl groups (e.g., vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloylpropionate, methacryloyl Allyl propionate, vinyloxycarbonyl methyl methacrylate, vinyloxycarbonyl methyloxycarbonyl ethylene ester acrylate, N-allylacrylamide, N-allylmethacrylamide, N-
allyl itaconic acid amide, methacryloyl propionic acid allyl amide, etc.) or amino alcohols (e.g. aminoethanol, 1-amitubupanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and a vinyl group. Examples include carboxylic acid condensates.

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

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

The functional group may be any functional group as long as it can cause a chemical reaction between molecules and form a chemical bond. That is, it is possible to use a reaction mode in which bonding between molecules by condensation reaction, addition reaction, etc. or crosslinking by polymerization reaction is caused by heat and/or light.

Specifically, a functional group having a dissociable hydrogen atom [(e.g. -COOH group, -PO3H group, a group with PR+'' content or an -ORτ' group (R;' is a group with the same content as R'; ) -OH group, -3H group, -NH-R'; group (
R' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, etc.
/S\ represents a group)] and] -CH2-CH1-CH, -CH
When containing at least one set of C0NH
CHt OR' s (R' x represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, hexyl group) or a polymerizable double bond group, etc. .

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

Furthermore, for example, Tsuyoshi Ono, ``Refinement of thermosetting polymers (
C1M, C■, published in 1986), Yuji Harasaki, "Latest Binder Technology Handbook" Chapter 1I-1 (General Technology Center, 1
(Published in 1985), “Synthesis, Design and Development of New Applications of Acrylic Resins” accompanied by Otsu (Chubu Management Development Center Publishing Department, 1988)
5 years), Eizo Omori, "Functional Acrylic Resins" (Technosystem, 1985 publications), Hideo Inui, Gentabe Nagamatsu, "Photosensitive Polymers" (Kodansha, 1977 publications), Takahiro Tsunoda, "
"New Photosensitive Resin" (Printing Society Publishing Department, published in 1981)
, G, E, Green and, B, P, 5ta
r R+ J, Macro, 5ciRevs Ma
cro, Chem, C21(2), 187-2
73 (19B1-B2).

C.G. Roffey, 'Photopolym
erization of SurfaceCoati
ngs” (A, Wiley Interscience
Functional groups, compounds, etc. cited in reviews such as E.Pub, 1982) can be used.

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

Specific monomers corresponding to the copolymer component containing these crosslinkable functional groups include, for example, vinyl compounds containing the functional group that can be copolymerized with the general formula (A). Either one is fine if you have it.

For example, see the Polymer Data Handbook [Polymer Data Handbook]
Basic Edition] Baifukan (published in 1986), etc.

Specifically, acrylic acid α- and/or β-substituted acrylic acid (e.g. 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 methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (e.g. 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 Examples include half-ester derivatives of vinyl or allyl groups, ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing the crosslinkable functional group in the substituent of amide derivatives.

The proportion of the "coelectric 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 such a resin in order to promote the crosslinking reaction. Examples include acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, P-toluenesulfone M, etc.), peroxides, azobis compounds, crosslinking agents, aggravating agents, photopolymerizable monomers, and the like. Specifically, as the crosslinking agent, compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), etc. can be used.

For example, commonly used organic silane, polyurethane,
A crosslinking agent such as polyisocyanate, a curing agent such as epoxy resin, melamine resin, etc. can be used.

When containing a photocrosslinking-reactive functional group, the compounds cited in the above-mentioned review of photosensitive resins can be used.

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

Conventionally known resins can also be used together with the resins used in the present invention. Examples include silicone resins, alkyd resins, vinyl acetate resins, polyester resins, styrene-butadiene resins, acrylic resins, etc., as described above.
Vol. 278 (1968), Harumi Miyamoto, Hidehiko Takei,
Examples include known materials cited in reviews such as Imaging, 1973 (Nα8), page 9.

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

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

In addition, a crosslinking agent may be added to the image-receiving layer in order to further improve the film strength. As the crosslinking agent, commonly used ammonium chloride, organic peroxide, metal soap, organic silane, polyurethane crosslinking agent, epoxy resin curing agent, etc. can be used. Specifically, they are 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 wood-free paper, wet reinforced paper, plastic film such as polyester film, and metal plate such as aluminum plate.

In the present invention, an intermediate layer is provided between the support and the image-receiving layer for the purpose of improving water resistance and interlayer adhesion, and a back coat layer is provided on the support surface opposite to the image-receiving layer for the purpose of preventing curling. I can do it.

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

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

When used as PPC plate-making, in order to further reduce background staining of the printing original plate of the present invention, the volume resistivity of the printing original plate is set to 1010 to 1013 Ωl.
Additionally, dielectric agents can be added to the image-receiving layer, interlayer and/or backcoat layer. The dielectric agent may be inorganic or organic.
, salts of monovalent or polyvalent metals such as Li, MgZn, Co, and Ni, and organic ones such as polyvinylbenzyltrimethylammonium chloride, acrylic resin-modified quaternary ammonium salts, and polymeric cationic conductive agents. Examples include polymeric anionic conductive agents such as molecular sulfonates. The amount of these conductive agents added is 3 to 40% by weight, preferably 5 to 20% by weight of the amount of binder used.

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

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

Example 1 30 g of benzyl methacrylate, the following compound example (A)
A mixed solution of 70 g of monomers, 0.2 g of acrylic acid, 1.5 g of divinylbenzene, and 300 g of toluene was heated to 75°C under a nitrogen stream, and then 2.2'-azobisisobutyronitrile (A 1.0 g of IBN) was added and reacted for 8 hours. The weight average molecular weight of the obtained copolymer [1] was 350,000.

Subsequently, a mixture of 40 g (solid content) of this copolymer, 150 g of zinc oxide, and 300 g of toluene was dispersed in a ball mill for 1 hour to prepare an image-receiving layer-forming product.
This was applied to the intermediate layer of a support with a back layer on one side of high-quality paper and an intermediate layer on the other side, with a dry adhesion amount of 18 g/
Apply with a wire bar so that it becomes rrT, and heat at 110°C.
The mixture was dried for 1 minute to prepare a planographic printing original plate.

This original plate was treated with a desensitizing treatment solution [E manufactured by Fuji Photo Film Co., Ltd.].
LP-EX) through an etching processor once, and add 2μ of distilled water to this! The contact angle with the water formed was measured with a goniometer and was found to be 10° or less. In addition, before the desensitization treatment, it was 78°. This indicates that the non-image area of the image-receiving layer of the original plate of the present invention has changed from lipophilic to hydrophilic. The contact angle with water must be 20°C or less).

Next, a plate was made using commercially available PPC, and the obtained original plate was subjected to a desensitization 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 ground blur in the non-image area, and the image quality of the image area was clear.

This was printed on high-quality paper using an offset printing machine (Hamadaster 800SX model manufactured by Hamadastar ■).2000
Even if the number of sheets exceeded, no problem occurred in the background smear in the non-image area of the printed matter and the image quality in the image area.

Furthermore, using the above original plate, the environmental conditions were adjusted to 30°C, 180% P.
As for H, when the plate was made using commercially available PPC, the image of the obtained original plate had a density of 1.0 or more in the image area, no ground blur 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 after printing 2000 sheets.

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

Examples 2 to 14 In Example 1, instead of the resin CI) of the invention, Table-
A lithographic printing original plate was prepared in the same manner as in Example 1 except that the copolymer shown in Example 1 was used.

When this was plate-made using the same apparatus as in Example 1, the density of the obtained offset printing master plate was 1.0 or more and the image quality was clear. After further etching and printing on a printing press, the printed matter after printing 10,000 sheets had clear image quality with no capri.

Further, this photosensitive material was left under conditions of (45° C., 175% RH) and then subjected to the same treatment as above, but there was no difference at all from before aging.

Example 15 12 g of benzyl methacrylate, 80 g of monomer of the following compound example (2), 8 N-methoxymethyl methacrylamide
g) 200g toluene and 50g isopropyl alcohol
After heating the mixed solution to a temperature of 75°C under a nitrogen stream,
Add 2g of 2',2'-azobisisobutyronitrile and add 8
Time reacted.

Furthermore, the temperature was raised to 100°C and the reaction was continued for 2 hours while distilling off the isopropyl alcohol azeotropic solvent.

The weight average molecular weight of the obtained copolymer [17] was 98.0
It was 00.

Monomer [2] CH.

CH.

This coelectric material [17] was replaced with the copolymer [1] in Example 1.
] was used in the same manner as in Example 1, except that
An original plate for lithographic printing was prepared.

This was operated in the same manner as in Example 1 to perform plate making and desensitization treatment to obtain a printing original plate.

The density of the obtained offset printing master plate is 1
．． The image quality was clear when it was 0 or more. When printed with a printing machine, the printed matter after printing 2000 sheets had no fog in the non-image area and the image was clear.

Example 16 A mixture of 50 g of each of the following copolymers (A) and (B) and 250 g of toluene was heated to 60° C. and uniformly dissolved. The mixture was stirred as it was for 3 hours to react.

The weight average molecular weight of the obtained copolymer [18] of the present invention was 2.2×10'.

Copolymer [A] Double quantum uniformity 143,000CL
Cl1i CH3 copolymer CB] Double weight average molecular weight 38,000 CII3
C82CHs l 1 1i+c.

Next, a lithographic original plate with an image-receiving layer formed thereon was prepared in the same manner as in Example 1, except that 40 g of the above copolymer (18) was used instead of copolymer [1] used in Example 1. did.

When this was plate-made in the same manner as in Example 1, the density of the obtained offset printing master plate was 1.0 or more and the image quality was clear. Furthermore, when etching was performed and printed on a printing press, the image quality of the printed matter after printing 2000 sheets was clear and without blurring.

Example 17 Copolymer used in Example 16 (350 g of A, 4.5 g of 1°6-hexane diisocyanate and 200 g of toluene)
The mixture was heated to a temperature of 60°C and stirred for 3 hours. The weight average molecular weight of the obtained copolymer [18] of the present invention was 1
．． It was 8x10'.

Each lithographic printing original plate was prepared in the same manner as in Example 1 except that the above copolymer [18] was used in place of the resin (I) of the present invention.

This plate was made into a plate using the same apparatus as in Example 1, and then etched and printed using a printing press. The density of the master plate for offset printing obtained after plate making was 1.0 or more, and the image quality was clear. Furthermore, the image quality of the 2000 prints was good and no background stains occurred.

Example 18 A mixture of 550 g of the copolymer CB used in Example 16, 3.8 g of diethylene glycol, and 200 g of toluene was heated to 60° C. and stirred for 4 hours.

The weight average molecular weight of the obtained copolymer [19] of the present invention was 2.4×10'.

Subsequently, a lithographic printing original plate was prepared in the same manner as in Example 1, except that the above copolymer (19340 g) was used in place of the copolymer CI) used in Example 1.

When this was plate-made in the same manner as in Example 1, the density of the obtained offset printing master plate was 1.0 or more and the image quality was clear. Further, when the image was subjected to an etching process and printed using a printing press, the printed matter after printing 2000 sheets had no capri in the non-image area and the image was clear.

Example 19 40 g of the following copolymer [20] and [butyl methacrylate/acrylic acid (99/1) weight ratio] copolymer (weight average molecular weight 45,000)! A mixture of Og, 100 g of zinc oxide, and 300 g of toluene was dispersed in a ball mill for 2 hours.

Next, 10 g of allyl methacrylate and 2 g of allyl methacrylate were added to this dispersion.
．． Add 0.5 g of 2'-azobisisobutyronitrile,
The dispersion obtained by dispersing in a ball mill for 10 minutes was prepared in Example 1.
It was coated on the same support with a wire bar to a dry coating weight of 20 g/m, heated at 80°C for 2 hours, and then coated with 100 g/m.
A lithographic printing original plate was prepared by drying at °C for 30 minutes.

Copolymer (20) C11, CH.

-+C11z CCl1z-C-hwCOO(C1l
z) ZN=CH-C6H5C00CIh-CIl=C
T! z Weight average molecular weight: 5.6 x 10' This was plate-made using the same apparatus as in Example 1, and the density of the obtained offset printing master plate was 1.0 or more and the image quality was clear. Furthermore, when the image was etched and printed using a printing press, the image quality of the printed matter after printing 2,000 sheets was clear and free of blur.

Examples 20 to 26 Each lithographic printing original plate was prepared in the same manner as in Example 19, except that the copolymer shown in Table 2 was used instead of the resin [20] of the present invention. Created.

Table-2 C4H9Coo (CHJ JOzOClliCHFC
HzF Each of these original plates was treated in the same manner as in Example 1, and each characteristic was investigated. The density of the obtained master plate for offset printing was 1.
0 or higher, and the image quality was clear.

When the plate of the present invention was further etched and printed using a printing press, the image quality was clear and no scuffing was observed even after 2,000 copies were printed.

Example 24 A lithographic printing original plate was prepared in the same manner as in Example 23, except that 15 g each of copolymers [27] and [28] of the present invention having the chemical structures shown below were used.

Copolymer (27): weight average molecular weight N43,000 Copolymer (2B): weight average molecular weight 38,000 This was plate-made using the same device as in Example 1, then etched and printed using a printing press. . The density of the master plate for offset printing obtained after plate making was 1.0 or more, and the image quality was clear. In addition, the image quality of the printed matter after printing 10,000 sheets was a clear image without any image distortion.

Example 25 and Comparative Example B 30 g of ethyl methacrylate, monomer CD with the following structure)
40g allyl methacrylate 30g and toluene 500g
After heating the mixed solution of g to 60° C. under a nitrogen stream, 1.0 g of 2.2',-azobisvaleronitrile was added and reacted for 8 hours. The weight average molecular weight of the obtained copolymer (1) was 62,000.

A monomer (D) corresponding to the copolymer component of the present invention was then added to 30 g of this copolymer (as solid content) and a [butyl methacrylate/acrylic acid (99/1) weight ratio] copolymer (
Weight average molecular weight 45000) Log, zinc oxide 200g
, and 300 g of toluene were dispersed in a ball mill for 2 hours.

Next, 10 g of allyl methacrylate and 0.5 g of 2,2'-azobisisobutyronitrile were added to this dispersion, and dispersed in a ball mill for 10 minutes. Then, it was coated with a wire bar so that the dry adhesion amount was 25 g/ryf, and dried at 100° C. for 30 minutes to prepare an original plate for lithographic printing.

Comparative Example B A mixed solution of 60 g of ethyl methacrylate, 340 g of monomer [0340 g] 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. Time reacted. The obtained copolymer (
The weight average molecular weight of A) was 45,000.

Subsequently, Example 2 was prepared, except that the above copolymer (A) was used instead of the copolymer [29] used in Example 25.
In the same manner as in Step 5, the mixture was first dispersed in a ball mill for 2 hours, applied with a wire bar so that the dry adhesion amount was 25 g/rrf, and dried at 110°C for 1 minute to prepare a lithographic printing original plate.

Furthermore, the contact angle with water of each master plate desensitized with a non-fattening liquid was as small as 15°C or less for the master plates of the present invention and Comparative Example B, indicating that they were sufficiently hydrophilized. Ta.

Furthermore, when these were printed as master plates for offset printing, only the plates of the present invention and Comparative Example B were good in that no scumming occurred in the non-image areas.

Furthermore, when 10,000 copies of both plates were printed under conditions where the printing pressure was strong, the image quality of the 10,000 copies of the plate of the present invention was good and no scumming occurred. Comparative example E is 7000
Staining occurred on the first sheet. In the plate of Comparative Example F, scumming occurred from the beginning of printing.

Based on the above facts, only the original plate of the present invention was able to produce over 10,000 prints that always formed a clear copy image and did not cause background smudge even when the plate was made under fluctuating environmental conditions.

Examples 26 to 36 In Example 25, instead of copolymer [1], Table-
In the same manner as in Example 25, except that the copolymer of No. 3 was used,
Each lithographic printing original plate was produced.

This was made into a plate using the same apparatus as in Example 1, then etched and printed using a printing press. The density of the master plate for offset printing obtained after plate making was 1.0 or more, and the image quality was clear. Moreover, the image quality of the printed matter after single-cane printing was a clear image without any blurring.

Examples 37 to 42 Each lithographic printing original plate was produced in the same manner as in Example 25, except that the copolymer shown in Table 4 was used instead of the resin CI) of the present invention. did.

Table 4 C11, C11°I This was plate-made using the same apparatus as in Example 1, and the density of the obtained offset printing master plate was 1.0 or more, and the image quality was clear. Further, when etching was performed and printed using a printing press, the printed matter after printing 10,000 sheets had clear image quality with no fogging.

Example 43 Instead of the [butyl methacrylate/acrylic acid] copolymer used in Example 25, [butyl methacrylate/allyl methacrylate/acrylic acid (79/20/1
) Weight ratio] A lithographic printing original plate was prepared in the same manner as in Example 25 except that the copolymer was used.

As in Example 1, the fully automatic plate making machine ELP404■
When plate-making was carried out, the density of the obtained offset printing master plate was 1.0 or more and the image quality was clear. Furthermore,
When etching was performed and printed using a printing press, the printed matter after cane printing had no fog in the non-image area and the image was clear.

(Effects of the Invention) According to the present invention, it is possible to obtain an original plate for direct drawing type lithographic printing in which the occurrence of scumming is satisfactorily suppressed and also has good printing durability.

Procedural amendment August 14, 1999

Claims (3)

[Claims] (1) In a direct-drawing lithographic printing original plate having an image-receiving layer on a support, at least a part of the binder of the image-receiving layer is decomposed to form thiol groups, phospho groups, amino groups, and sulfo groups. 1. A direct-drawing lithographic printing original plate, characterized in that it contains at least one functional group that forms at least one of the above groups, and at least one resin that is at least partially crosslinked. (2) The resin contains a copolymer component containing at least one functional group that generates at least one of a thiol group, a phospho group, an amino group, and a sulfo group upon decomposition, and which generates at least one functional group among a thiol group, a phospho group, an amino group, and a sulfo group upon decomposition. The original plate for direct drawing type lithographic printing according to claim (1), which is a resin that has been crosslinked in advance so that it becomes poorly soluble or insoluble in water when produced. (3) The resin contains at least one functional group that generates at least one of a thiol group, a phospho group, an amino group, and a sulfo group upon decomposition, and a functional group that causes a curing reaction with heat and/or light. The original plate for direct drawing type lithographic printing according to claim 1, which contains at least one resin.