JPH0439094A - Direct drawing type planographic printing base plate - Google Patents

Abstract

PURPOSE:To enhance the hydrophilicity of a non-image part and to obtain high printing durability by preventing the generation of oil contamination by adding a specific resin and, if necessary, a crosslinking agent to the binder of an image receiving layer. CONSTITUTION:The binder of the image receiving layer provided on a support contains a resin [A] having at least one kind of a functional group represented by formula (I) or (II) and a thermosetting and/or photo-setting resin (B) and also contains a crosslinking agent if necessary. When the image receiving layer is treated with a treatment solution containing a hydrophilic compound having nucleophilic reactivity, the hydrophilic compound having nucleophilic reactivity is added to and reacted with the terminal of the functional group represented by the formula (I) formed from the functional group of the resin [A] by dehydrohalogenating reaction and the image receiving layer can develop hydrophilicity and becomes insoluble or hardly soluble to water while holds hydrophilicity because a crosslinked structure is provided in the binder resin. By this method, this planographic printing base plate can reproduce a copy image faithful to the original picture and generates no background staining because the hydrophilicity of a non-image part is good.

Description

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

[Conventional technology]

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

In order to perform plate making, that is, image formation on such a printing original plate,
Generally, a method is adopted in which the image is drawn by hand with oil-based ink on the image-receiving layer, or by printing using a typewriter, an inkjet method, a transfer type heat-sensitive method, or the like.

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 through the steps of charging, exposure, and development using a plain paper electrophotographic copier (PPC). In any case, the printing original plate after plate making is subjected to surface treatment with a desensitizing treatment liquid (so-called etch liquid) to desensitize non-image areas, and then subjected to lithographic printing as a printing plate.

In the conventional direct drawing type lithographic printing original plate, 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 and starch, a water-dispersible resin such as a synthetic resin emulsion, and a pigment. The surface layer is made of a pigment, a water-soluble resin, and a water-resistant agent.

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

[Problems to be Solved by the Invention] However, conventional printing plates obtained in this manner do not require the addition of a large amount of water-resistant agent or the use of hydrophobic resin in order to improve printing durability. to increase hydrophobicity,
Printing durability improves, but hydrophilicity decreases and printing stains occur.
On the other hand, there is a problem in that improving hydrophilicity deteriorates water resistance and reduces printing durability. Particularly in a high-temperature operating environment of 30° C. or higher, the surface layer dissolves in the soaking water used in offset printing, resulting in major drawbacks such as reduced printing durability and printing stains.

Furthermore, the lithographic printing plate is used to draw oil-based ink as an image area on the image-receiving layer, and if the adhesion between this receiving layer and the oil-based ink is not good, even if the non-image area has sufficient hydrophilicity, the above-mentioned problem will occur. Even if such printing stains do not occur, there is a problem in that oil-based ink in the image area is missing during printing, resulting in a decrease in printing durability.

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

An object of the present invention is to provide a direct-drawing lithographic printing original plate which has excellent desensitization properties and does not cause spot-like stains as well as all-over stains as an offset original plate.

The object of the present invention is to improve the adhesion between the oil-based ink in the image area and the image-receiving layer, and to maintain sufficient hydrophilicity in the non-image area even when the number of prints increases, so that oil stains do not occur. An object of the present invention is to provide a direct-drawing type lithographic printing original plate having high printing durability.

[Means to solve the problem]

In the above-mentioned various aspects, in the direct drawing type lithographic printing original plate having an image-receiving layer on a support, the binder of the image-receiving layer is at least one of the following resins [A] and at least one of the following resins CB]. This can be achieved by a direct-drawing lithographic printing original plate that contains seeds and, if necessary, a crosslinking agent.

Resin [A]; Resin containing at least one polymer component having a functional group represented by the following general formula (I) and/or general formula (n) General formula (1) % Formula % General formula (n ) 1v2-←CH, →-w CH, C112-X [However, in the above formula (I) or (II), "-L-, -W
--represents -3O2-, -Co- or Ha-00[:, nl and n2 each represent 0 or 1, and X represents a halogen atom] Resin [B]; Heat and/or photocurable Resin The present invention uses a resin [A] having at least one functional group represented by the above general formula (I) or general formula (II) as a binder for the image-receiving layer of a lithographic printing original plate, and heat and/or Photocurable resin [
B], preferably a crosslinking agent, and when treated with a treatment liquid containing at least one nucleophilic hydrophilic compound, the resin [A
] or the functional group represented by the above general formula (n) by a dehydrohalogenation reaction, the terminal of the functional group represented by the formula (I) has nucleophilic reactivity. A hydrophilic compound can undergo an addition reaction, and as a result, the image-receiving layer can exhibit hydrophilicity, and at the same time, since the binder resin has a crosslinked structure, it can be hydrophilic and resistant to water. It is insoluble or poorly soluble.

As a result, the lithographic printing original plate according to the present invention reproduces a copy image that is faithful to the original image, and has good hydrophilicity in the non-image area, so it can be used as an offset original plate to prevent not only one-sided background smear but also dotted background smear. This has the advantage that the image-receiving layer has good smoothness and electrostatic properties, and has excellent printing durability.

Furthermore, the printing original plate for plate making of the present invention is not affected by the environment during plate making processing, has excellent preservability before processing, and has the characteristics that the hydrophilic treatment can be carried out quickly.

[Effect]

A typical example in which the binder resin of the image-receiving layer according to the present invention is a nucleophile is shown in the following reaction formula (1).

(2) ~ represents a resin moiety other than the functional group of formula (1) or (II).

S [], "e ■ ~ W, -CH2CH, -3o, e Hydrophilicity (1) That is, the binder resin [A] of the image-receiving layer according to the present invention
By reacting as described above with a nucleophilic compound in the processing solution only when etching the non-image area as a lithographic printing original plate.

It is characterized in that a hydrophilic group is added to the end of the product, thereby making it hydrophilic, that is, it becomes hydrophilic, and since it does not react with moisture in the atmosphere, there are no concerns regarding storage stability.

Since the vinyl sulfone group, vinyl carbonyl group, and acryloxy group represented by the general formula (I) according to the present invention are functional groups that react very quickly with nucleophilic compounds, they exhibit rapid hydrophilization. is possible.

Furthermore, the functional group represented by the general formula (II) can be expressed by the reaction formula (
As shown in 1), the dehydrohalogenation reaction easily proceeds by alkali treatment and can be converted into the corresponding functional groups of the general formula (I).
It can be used in the same way as I).

The binder resin used in the present invention will be explained in detail below. The functional group contained in the copolymer component contained in the resin [A] is represented by the general formula (I) or (n).

General formula (I) Wl-Kano CH, □CH=CH.

General formula (II) W2-←CH, -hr CH2CH, -X formula (I),
(n), -W, -, -W2- are each 5O2--C
o- or -[]OC-, n+ + n2 are each 0
or 1, and X represents a halogen atom.

In formula (I), (n), more preferably n,
n2 is O. Moreover, the halogen atom of X specifically represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

Furthermore, examples of the copolymer component having a functional group represented by the general formula (1) and/or (II) of the resin [A] of the present invention include those represented by the repeating unit of the following general formula (I). It will be done.

General formula (I) a, a2 One←CH-CH→-- 2-Y-W.

[In formula (DI), Z is -COO-1-OCO-1-0-
1C0NHCONH CH, COO -CH2DCO-, or Y represents an organic residue that directly bonds or connects -Z- and -Wo. Furthermore, Mo Z-Y1 is -E-C- Juice part and-
W. may be directly connected.

En. represents a functional group represented by general formula (I) or general formula (n).

al+a2 may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aralkyl group, or an aryl group. ] General formula (III) will be explained in more detail.

Preferably, Z is -Coo-, -0CO-, -0-.

represents.

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

Y represents a direct bond or an organic residue connecting -Z- and -Wo.

When Y represents a linked organic residue, this linking group represents a carbon-carbon bond which may be via a petero atom, and the beta atom is an oxygen atom.

(Sulfur atom, nitrogen atom)
It is composed of bonding units such as HCO[l-NIICONH-, -3i-, etc., singly or in combination. (However, r
2+ r3+r4r r, r rB are each the above rl
represents the same content as . ).

al+ az may be the same or different, and include a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, etc.), a cyano group,
Hydrocarbon groups (e.g. methyl, ethyl, propyl,
Butyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group,
an optionally substituted alkyl group having 1 to 12 carbon atoms such as hexyloxycarbonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, aralkyl group such as benzyl group, phenethyl group,
represents an aryl group such as a phenyl group, tolyl group, xylyl group, chlorophenyl group, etc.).

Furthermore, the +Z-Y bonding residue in formula (DI) is
+C10 and ~W may be directly connected.

Specific examples of polymer components having a functional group represented by the general formula (1) or (II) of resin ('Al) are shown below. However, the scope of the present invention is not limited to these. Examples ( In a-1) to (a-25), b is -H or -C
l(, R represents -C1(=C')I.

-Cl (, CH=CH, also bar CH2C')12X, and X represents -F, -C'1-Br, -4.

(a-6) 1←CH, -CH-+- (a-1) →CL-C+ 02-R COOCH, [:H, 5O2-R CH.

(a 1←CH2−CH+− Coo(CH=)2SO2 (a →CH.

C+ Con(CH2) 20[:0(CH,)2SO.

(a →CH2 C+ C0NH(CH2) 2SO.

(a-16) 1←CH2-CH-)- (a →CH, -C+ Con(CH2)20CO-R (a-18) →CH2-CL→- (a →C11, -CH÷ COR (a- 19) →C) 12-CH-+- (a-14) →CH,-CH÷ CH2C0-R CH,0CO-R (a-20) 1←CH,-C+ C00(CH,), CO-R (m: an integer of 1 to 4) [IC[+ (a-25) b →Ct1.-C+ C0NH(CH2), C0-R General formula (I) and/or (II) of the present invention as described above The resin [A] containing a polymer component containing a functional group represented by can be synthesized by a conventionally known synthesis method.

That is, a monomer containing a functional group represented by general formula (I) and/or (II) and a polymerizable double bond group (
For example, a method of polymerizing a monomer corresponding to a repeating unit of general formula (III), and a method of polymerizing a monomer corresponding to a repeating unit of general formula (III) and
n) A method of synthesis by reacting a low molecular compound containing a functional group with a polymer compound containing a polymer component containing a functional group that chemically reacts with the low molecular compound (i.e., a polymer reaction) is possible.

Furthermore, a resin having a functional group represented by the general formula (n) [A
] is synthesized, a dehydrogenation reaction is performed with an alkali treatment to obtain a functional group-containing resin [
A] can also be synthesized.

The sulfonylation, carbonylation, or carboxylic acid esterification reaction in the above monomer synthesis or polymer reaction synthesis is described, for example, in Nippon Kagaku Complete Edition, New Experimental Chemistry Course, Volume 14, [Synthesis and Reaction of Organic Compounds jp751,
plooo and p1759 (1978) published by Maruzen ■,
S., Patai, Z., Rappoport and
C. Stirling.

rThe Chemistry of 5ulfone
s and 5 ulfoxidesJP 165 (
1988), John Wiley & 5ons, etc.

When the resin [A] according to the present invention is a copolymer, the polymer component containing the functional group represented by the general formula (1) and/or (n) is a copolymer. It is preferably 1 to 95% by weight, especially 10 to 85% by weight in the polymer.

In addition, the molecular weight of the polymer of the resin is 103 to 106, especially 5.
It is preferable that it is X103-5X10'.

Furthermore, the resin [A] of the present invention preferably contains a functional group that undergoes a crosslinking reaction with the resin CB by heating, light irradiation, etc. These functional groups include the same functional groups that exhibit a crosslinking reaction (thermally and/or photocurable functional groups; sometimes abbreviated as curable functional groups) contained in the resin [B] described below. Functional groups can be mentioned. In the case of the resin [A] containing a curable functional group, the [content of the copolymer component containing the curable functional group] is preferably 1 to 20% by weight in the resin [A], More preferably 3-10
Weight%.

In the present invention, as a method for making the resin [A] contain at least one functional group selected from the group of the curable functional groups, the polymer containing the functional group of general formula (I) or (II) is A method of introducing a compound containing a curable functional group into a molecule by a polymer reaction, or a method of introducing a compound containing a curable functional group into a monomer corresponding to a copolymerization component containing one or more types of curable functional group and the above-mentioned general formula (
A method (monomer synthesis) in which a monomer corresponding to the repeating unit of II[) is copolymerized is used.

For the former polymer reaction, conventionally known methods can be used as they are; for example, Japanese Chemistry Complete Edition, New Experimental Chemistry Course,
Volume 14, “Synthesis and Reactions of Organic Compounds [I] ~ [■]”
, (1978) published by Maruhata (foundation), "Reactive Polymers" by Yoshiyu Iwakura and Keisuke Kurita, etc., and are described in detail in the well-known literature cited as a review.

The monomer corresponding to the copolymer component containing the curable functional group used in the latter monomer synthesis method is a polymer component containing a hydrophilic group-forming functional group in resin [Al (e.g. Examples include vinyl compounds containing the curable functional group that can be copolymerized with the compound corresponding to general formula (I).

Such vinyl compounds are described in, for example, Polymer Data, “Polymer Data Handbook [Basic Edition]”, Baifukan (1988).
6th edition) etc.

More specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2-amino)methyl form, α-chloro form,
α-pro-1, α-fluoro, α-tributylsilyl, α-silino, β-chloro, β-pro-1, α-chloro-β-methoxy, α, β-dichloro etc.) methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid semi-gamma mides, crotonic acid, 2-alkenylcarboxylic acids (e.g. 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid) , 4-methyl-2-hexenoic acid,
(4ethyl-2-octenoic acid, etc.) Maleic acid, maleic acid half esters, maleic acid half gamma mides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, vinyl group or allyl group of dicarboxylic acids Examples include half ester derivatives of these, ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing the polar group in a substituent of an amide derivative.

Next, resin [B] used in the present invention will be explained in detail. The resin [B] is a curable resin that undergoes a crosslinking reaction with heat and/or light, preferably one that performs a crosslinking reaction with the functional group in the resin CAl described above,
Any material may be used as long as it contains a heat- and/or photo-curable functional group (sometimes abbreviated as a curable functional group) described below.
) has already been explained.

Among the curable functional groups of the present invention, photocurable functional groups include, for example, Hideo Inui, Gentabu Nagamatsu, "Photosensitive Polymer" (Kodansha, 1977), Takahiro Tsunoda, "New Photosensitive Resin" (Printing Society of Japan). Publishing Department, 1981), G, B, Gre
en and B, P, 5trak J.

Macro, Sci, Reas, Macro, Ch
em,, C21(2), 187-273 (19
81-82), C, G, Rattey.

rPhotopolymerization of 5
surface coatings J (Aliley)
Interscience rub, published in 1982)
Examples of photocurable resins cited in the review of the above include functional groups used in conventionally known photosensitive resins.

Among the curable functional groups in the present invention, examples of "thermosetting functional groups" include Tsuyoshi Endo, "Refinement of Thermosetting Polymers J (C, M, C■, published 1986), Yuji Harasaki,""Latest Binder Technology Handbook" Chapter 1f-1 (&1 Gouging Center, published in 1985), Otsu Accompanied "Synthesis, Design and Development of New Applications of Acrylic Resins" (Chubu Business Development Center Publishing Department, published in 1985), Eizo Omori's "Function" References to functional groups can be found in reviews such as "Acrylic Resins" (published by Technosystem, 1985).

Specifically, a combination of a functional group having a dissociable hydrogen (group A functional group) and a functional group (group B) that chemically reacts and bonds with the group A, or a polymerizable double bond group, etc. Can be mentioned.

Examples of the functional group having a dissociable hydrogen atom include -D
H group, -3H group, -N112 group, -NHR, group [RI
represents a hydrocarbon group, such as an optionally substituted alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, 2-chloroethyl group, -methoxyethyl group, 2-
cyanoethyl group, etc.), an optionally substituted cycloalkyl group having 4 to 8 carbon atoms (e.g., cyclohebutyl group, cyclohexyl group, etc.), and an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group), optionally substituted aryl group (e.g. phenyl group, tolyl group, silyl group, chlorophenyl group, bromophenyl group, methoxyphenyl group) basis,
(naphthyl group, etc.)], -c 00 t+ group, -PO382 group, etc.

Examples of the functional group bonding to the functional group having dissociative hydrogen in Group B include aj a4 -C=CH group (aj r a4 is a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, etc.), or Carbon number 1
-4 alkyl groups (for example, methyl group, ethyl group, etc.).

A crosslinked structure can be formed by the chemical bond between the functional groups of Group A and Group B. For example, at least one of each of Group A and Group B shown in Table 1 below may be combined.

C0NHCH20R2CR2 is a hydrogen atom or has 1 or more carbon atoms
8 alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, etc.)], -N=C=O group and Table 1 CH.

CH2=CH-C0NH-CH,=C-C0NHCH,
0 CH=CH-CONH-CH2=C1l-0-C-CH
2=CH-NHCD-CL=CH-CH2--NHCO
-CH2=CH-3O,-,CH,=CH-CD-CH
Examples include 2=C11-0-[H2=['H-3-.

In addition, -CONHCH,OR'(R' is a hydrogen atom or carbon, or the crosslinking reaction may be a polymerizable reaction, and in this case, the polymerizable double bond group is specifically -CH2=
C1l--C)I2=CH-CH2-As an example of the monomer containing the "thermal/photocurable functional group" of the present invention, it corresponds to the "copolymer component represented by the above formula (ItT)" Any monomer that can be copolymerized with the monomer containing the curable functional group in its substituent may be used.

As specific examples of the copolymer component containing the "heat/photocurable functional group" of the present invention, repeating units (b-1) to (b-
26) is given as an example.

b b2 (b-1) →Cl. C+ COOCH=CH2 b, : H Cl, b : Same below) C00 R, b (b-2) →CH2-C+ b2 : H CD. (b2: Same below) COOCH2CI{=CH, b, b2 b (b-6) ー←[:H- C 1,000(b →CH*-C+ Con(CH.),, 0C0 R, COO(Ct{2 ),, COO-R. R,: CI{=CI{. Integer R4 (same below 2) n = integer b1 from 1 to 11 (b → CH.-C+ COD(CL) r,0['0(CI12),,R, n,n'= integer from 1 to 11 (b →Mountain C+ COD (CH2). CH Cl2-0 C0 R6 0H Mouth 0-R. CH. Cll. R5 : -CH=C}l2 CH.CII Cll. -C=CH2 R6 : CH CH2 -C=CH, R6: Same hereafter) m Integer b1 from 1 to 4 (b-8> →[:}l2-C+ b CONH (Cll.), OCO R4 (b -←CH. C+ [1:[)) IH ([: lI.) hC[1[ICH
,C}IC:}I. 00CR, k: an integer from 1 to 10 n: an integer from 1 to 1l b2 an integer from 1 to 4 (b 4-CH ÷ C0NHCH20H b.

(b-14) 1←CH-C + C0NHCII2OR.

R1: C3-C1 alkyl group (b →CH-C1l÷ C8゜ (b →CH, -C→- COD(CH2), N=C=0 CH.

b+TneyOf(Ni121: integer II3L of 2 to 1) More specifically, the monomer represented by the following general formula (TV) is contained as a copolymerization component in a total amount of 30% by weight or more (metal ) An example of the resin (B) is an acrylic copolymer.

General formula (TV) CH,=C C0D-R.

In the general formula (■), U is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom), a cyano group, or a carbon number 1
~4 alkyl group.

R6 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, tridecyl group, tetradecyl group, 2-methoxyethyl group, 2-ethoxyethyl group, etc.), carbon number 2-18
optionally substituted alkenyl group (e.g. vinyl group, allyl group, impropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.) having 7 to 12 carbon atoms
an optionally substituted aralkyl group (e.g. benzyl group, phenethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), an optionally substituted cycloalkyl group having 5 to 8 carbon atoms (e.g. cyclopentyl group) , cyclohexyl group, cyclohebutyl group) optionally substituted aryl group (e.g., phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group, chlorophenyl group,
(dichlorophenyl group, etc.).

In the resin [B], the "copolymer component containing a crosslinkable (curable) functional group" is 0.5 to
40 mol% is preferred.

The weight average molecular weight of the resin [B] is preferably 1 x 103~
1×105, more preferably 5X103 to 5X1
0'.

The ratio of resin [A] and resin [B] used in the present invention varies depending on the type, particle size, and surface condition of the inorganic photoconductive material used, but in general, the ratio of resin [A] and resin [B] used is is 5 to 80 to 95 to 20 (weight ratio), preferably 10 to 50 to 90 to 50 (weight ratio).

The proportion of the "polymer component containing a curable functional group" in the binder resin of the present invention is preferably 1 to 1 in the total amount of the binder resin.
It is 80% by weight. More preferably, it is 5 to 50% by weight.

In addition to resin [A] and resin CB], the binder resin of the present invention is
It may further contain a crosslinking agent.

As the crosslinking agent used in the present invention, compounds commonly used as crosslinking agents can be used. Specifically, "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko.
Compounds described in Taiseisha Publishing (1981), Polymer Data Handbook Basic Edition, Polymer Data Handbook, Baifukan (1986), etc., published by the Society of Polymer Science, can be used.

For example, silane coupling of organic silane compounds (e.g., vinyltrimethoxysilane, vinyltributoxysilane, T-glycidoxypropyltrimethoxysilane, T-mercaptopropyltriethoxysilane, T-aminopropyltriethoxysilane, etc.) (e.g., toluylene diisocyanate, 0-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.) isocyanate, polymeric polyisocyanate, etc.) Polyol-based compounds (e.g., 1,4-butanediol, polyoxypropylene glycol, polyJ, t-)-dialkylene glycol, 1,1.1-)limethylolpropane, etc. ) Polyurethane, polyamine compounds (e.g. ethylene diamine, T hydroxypropylated ethylene diamine, phenylene diamine hexamethylene diamine, N
-aminoethylpiperazine, modified aliphatic polyamines, etc.) Polyepoxy group-containing compounds and epoxy resins (e.g. "New Epoxy Resins" edited by Hiroshi Kakiuchi, Shokodo (1985), "Epoxy Resins" edited by Kuniyuki Hashimoto, Nikkan Kogyo Shimbunsha) (
Poly (meth) Acrylate compounds (
Examples include compounds described in Shin Okawara, Takeo Saegusa, Toshinobu Higashimura's "Oligomer" Kodansha (published in 1976), Eizo Omori "Functional Acrylic Resin" Technosystem (published in 1985), etc. Polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate,
Examples include trimethylolpropane triacrylate, pentaerythritol polyacrylate, bisphenol A-diglycidyl ether diacrylate, oligoester acrylate (methacrylates of these, etc.).

The amount of the crosslinking agent used in the present invention is preferably 0.5 to 30% by weight, particularly 1 to 10% by weight, based on the amount of resin used in the image-receiving layer.

When the crosslinking reaction is a reaction mode in which a chemical bond is formed between functional groups, examples thereof include organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.).

When the crosslinking reaction is a polymerizable reaction mode, a polymerization initiator (peroxide, azobis compound, etc.) may be used, and preferably,
azobis polymerization initiator), monomers containing polyfunctional polymerizable groups (e.g. vinyl methacrylate, allyl methacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, divinyl succinate, divinyl adipate, diallyl succinic acid) ester, 2-methylvinyl methacrylate, divinylbenzene, etc.).

When containing a photocurable functional group, the compounds cited in the above-mentioned review of photosensitive resins can be used. Examples include compounds having an allyl ester group, a cinnamoyl ester group, a dimethylmaleimide ring group, and the like.

In the present invention, a reaction accelerator may be added to the resins [A] and [B11, if necessary, in order to promote the crosslinking reaction in the photosensitive layer. For example, acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.)
, peroxides, azobis compounds, crosslinking agents, sensitizers, photopolymerizable monomers, and the like.

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. Usually, it is preferable to perform a thermosetting treatment. This heat curing treatment is performed at, for example, 60°C to 120°C for 5 minutes to 120°C.
All you have to do is process it for a minute. When a reaction accelerator is used in combination, it becomes possible to perform the treatment under milder conditions.

In addition, when a photocurable resin is used, it is crosslinked by irradiation with electron beams, The reaction is further accelerated by heating.

Also in this case, if a reaction accelerator is used in combination, the treatment can be carried out under milder conditions.

Conventionally known resins can also be used together with the resins used in the present invention. For example, silicone resin, alkyd resin, vinyl acetate resin, polyester resin, styrene-butadiene resin, acrylic resin, polybutyral resin, polyolefin resin, ethylene vinyl acetate copolymer, styrene resin, acrylate-butadiene resin, vinyl alkanoate resin, etc. Can be mentioned.

The binder resin of the present invention may be dissolved or dispersed in an organic material, 5IPj, or may even be used in an aqueous emulsion. Therefore, in addition to the resin of the present invention, any water-soluble resin can be used in combination, such as modified PVA such as PVA1 carboxyPVA, starch and its derivatives CMC, hydroxyethyl cellulose, casein, gelatin, polyvinylpyrrolidone, vinyl acetate. Crotonic acid copolymer, styrene
Water-soluble resins such as maleic acid copolymers can be used.

When these water-soluble resins are used together, it is preferable to use a water-resistant agent. Examples of the water-resistant agent include initial condensates of aminoblast such as glyoxal, melamine formaldehyde resin, and urea formaldehyde resin, and methylolated polyamide resins. Examples include modified polyamide resins such as, boamide polyamine epichlorohydrin adducts, polyamide epichlorohydrin resins, modified polyamide polyimide resins, and the like.

The resin of the present invention and known resins can be mixed in any ratio, but the functional groups that generate hydrophilic groups [formula (I) and/or (II) in the total amount of resin in the image-receiving layer] The amount of the copolymer component having a functional group] must be at least 30% by weight, preferably at least 40% by weight.

If the content of the functional group component that reacts with a nucleophilic compound to form a hydrophilic group is less than 30% by weight, the resulting direct plate printing original plate will be insensitive to desensitizing liquid and soaking water. The hydrophilicity produced by the fat treatment is not sufficient and stains occur during printing.

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, in the case of pigment, the particle size, but is generally 1/(0.1 to 5), preferably 1/(0.5) by weight. ~2.
5) The level is appropriate.

Other crosslinking agents 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, Shinzo Yamashita and Tosuke Kaneko ed. “Crosslinking Agent Handbook” published by Taiseisha (1988).
1 year) etc. can be used.

Supports used in the present invention include wood-free paper, wet reinforced paper, plastic films such as polyester films, metal plates such as aluminum plates, and the like.

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, methacrylic acid ester-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-
Emulsion-type resins such as vinyl acetate copolymers; solvent-type resins such as epoxy resins, polyvinyl butyral, polyvinyl chloride, and polyvinyl acetate; and at least one of the water-soluble resins mentioned above as a main component. , Inorganic pigments and waterproofing agents can be added as necessary.

When used as PPC plate-making, in order to further reduce scumming of the printing original plate of the present invention, an image-receiving layer, an intermediate layer and/or a backing layer are further added so that the volume resistivity of the printing original plate is 1010 to 10130 cm. A dielectric agent can be added to the coating layer. The dielectric agent may be inorganic or organic. Inorganic agents include salts of monovalent or polyvalent metals such as Na, K, Li5Mg, ZnXCo, and Ni, and organic agents include polyvinyl. Examples include polymeric cation conductive agents such as benzyltrimethylammonium chloride and acrylic resin-modified quaternary ammonium salts, and polymeric anionic conductive agents such as polymeric sulfonate salts. The amount of these conductive agents added is 3 to 40% by weight, preferably 5 to 40% by weight of the amount of binder used in each layer.
It is 20%.

In general, in order to create the direct drawing type lithographic printing original plate of the present invention,
If necessary, an aqueous solution containing an intermediate layer component is coated on one side of the support and dried to form an intermediate layer, and then an aqueous solution containing an image-receiving layer component is coated and dried to form an image-receiving layer. For example, a backcoat layer may be formed by applying an aqueous solution containing backcoat layer components to the other surface and drying it.

The adhesion amounts of the image-receiving layer, intermediate layer, and back coat layer are 1 to 30 g/m', 5 to 20 g/m', respectively.
5 to 20 g/m'' is suitable.

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

The desensitization treatment provided in the present invention is a solution ( This is achieved by treatment with an aqueous solution or a mixed solution containing a water-soluble organic solvent.

As a hydrophilic compound that causes a nucleophilic substitution reaction on the double bond of the functional group represented by general formula (I), the nucleophilicity constant n (: R, G, Pearson, Ho
Sobel, J., Songstad, J. Am.
er, [:hem, Soc,, 90°319 (19
68)] containing a substituent having a value of 5.5 or more, and which dissolves in an amount of 1 part by weight or more in 100 parts by weight of distilled water.

Specific compounds include hydrazine, hydroxylamine, sulfites (ammonium salts, sodium salts, potassium salts, zinc salts, etc.), thiosulfates, etc., and also contain hydroxyl groups, carboxyl groups, and sulfo groups in the molecule. Examples include mercapto compounds, hydrazide compounds, sulfinic acid compounds, primary amine compounds, and secondary amine compounds containing at least one polar group selected from , phosphono groups, and amino groups.

For example, mercapto compounds include 2-mercaptoethanol, 2-mercaptoethylamine, N-methyl-2-
Mercaptoethylamine, N(2-hydroxyethyl)
2-mercaptoethylamine, thioglycolic acid, thiomalic acid, thiosalicylic acid, mercaptobenzenedicarboxylic acid, 2-mercaptoethanesulpone M, 2-mercaptoethylphosponic acid, mercaptobenzenesulfonic acid, 2-mercaptopropiodilaminoacetic acid, 2-Mercapto-1-aminoacetic acid, 1-mercaptopropionyl aminoacetic acid, 1,2-dimercaptopropionyl aminoacetic acid, 2,3-dihydroxypropylmercaptan, 2-
Methyl-2-mercapto-1-aminoacetic acid, etc., and 2-hydroxyethylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxybutanesulfinic acid, carboxybenzenesulfinic acid, dicarboxybenzenesulfinic acid, etc. as sulfinic acid compounds. , 2-hydrazinoethanesulfonic acid, 4- as a hydrazide compound
hydrazinobutanesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzenedisulfonic acid, hydrazinobenzoic acid, hydrazinobenzenedicarboxylic acid, etc.
For example, N-(2
-hydroxyethyl)amine, N,N-di(2-hydroxyethyl>amine, N,N-di(2-hydroxyethyl)ethylenediamine, tri(2-hydroxyethyl)ethylenediamine, N-(2゜3-dihydroxypropyl) ) amine, N,N-di(2,3-dihydroxypropyl)amine, 2-aminopropionic acid, aminobenzoic acid, aminopyridine, aminobenzenedicarboxylic acid, 2
-hydroxyethylmorpholine, 2-carboxyethylmorpholine, 3-carboxypiperazine and the like.

These nucleophilic compounds are used by being included in the desensitizing solution described above.

The amount of the nucleophilic compound present in these treatment solutions is 0.1 mol/l-10 mol/1, preferably 0.5 mol/l-5
Mol/β.

Further, the pH of the treatment liquid is preferably 4 or more.

The conditions for the treatment are preferably a temperature of 15° C. to 60 t and an immersion time of 10 seconds to 5 minutes.

The treatment liquid may contain other compounds in addition to the above-mentioned nucleophilic compound and pl adjuster. For example, 1 to 50 parts by weight of a water-soluble organic solvent may be contained in 100 parts by weight of water. Examples of such water-soluble organic solvents include alcohols (methanol, ethanol, propatool, propargyl alcohol, benzyl alcohol, phenethyl alcohol, etc.), aromatic alcohols, and ketones (acetone, methyl ethyl ketone, acetophenone, etc.). Ethers (dioxane, trioxane, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc.) Amides (dimethylformamide, dimethylacetamide, etc.) Amino alcohols (monoethanolamine, jetanolamine, etc.) , triethanolamine, etc.), esters (methyl acetate, ethyl acetate, ethyl formate, etc.), and these may be used alone or in combination of two or more.

Further, 0.1 to 20 parts by weight of a surfactant may be contained in 100 parts by weight of water. Examples of the surfactant include conventionally known anionic, cationic, and nonionic surfactants.

For example, Hiroshi Horiguchi, “New Surfactants,” Sankyo Publishing ■, (197
Compounds described in "Synthesis of Surfactants and Their Applications" Maki Shoten (published in 1980) by Ryohei Oda and Hiroshi Teramura (published in 1980) can be used.

Furthermore, a material containing an antifoaming agent and other various additives is used as required.

The scope of the present invention is not limited to the specific compound examples described above.

The method of etching the functional group-containing binder resin of the present invention represented by the general formula (II) involves performing a dehydrohalogenation reaction as shown in the reaction formula (1) above, and then forming a double It is characterized in that the bond is made hydrophilic by a nucleophilic reaction of a nucleophilic compound.

Since the dehydrohalogenation reaction easily proceeds in a treatment solution with a p) of 16 or more, dehalogenation can be carried out by setting the pH of the etching treatment solution containing at least the above-mentioned nucleophilic compound to 6 or more. Hydrophilization is achieved by hydrogenation and nucleophilic reactions.

More preferably, the pH of the treatment liquid is 8 or higher.

Furthermore, after the dehydrohalogenation reaction has proceeded with a solution having a pH of 6 or higher, there is no problem in etching with a treatment solution containing nucleophilicity.

〔Example〕

Examples of the present invention are illustrated below, but the scope of the present invention is not limited thereto.

Example 1 A resin having the following structure [A-1
), 20 g of resin CB-1 having the following structure, 50 g of zinc oxide, and 150 g of toluene were dispersed in a ball mill for 2 hours, and then 4 g of glutaric acid was added and dispersed for 10 minutes. The obtained dispersion was applied with a wire bar so that the dry adhesion amount was 18 g/m'', dried at 100° C. for 30 seconds, and further heated at 110° C. for 2 hours to prepare a lithographic printing original plate.

Resin [A-1] -tCH2C→η=-- Coo ([:112) 2SO, CH=CH.

CH3 -suCH, -CshiJKoroku (1:H, -[:Hshir"C0
DC, H, CDDH Resin [B-1] CH.

-tcH2-C-tid CH2-CH dimension Tr1CH
2-Cll→end]-COOCI1. C00
CH, CHCH, C00N\1 Isao: 3X10' This original plate was treated with a desensitizing treatment liquid (E-
1) Dipped in water for 20 seconds and then washed with water.

Desensitizing treatment liquid (E-1) The above was dissolved.

A 2 μm droplet of distilled water was placed on this, and the contact angle with the water formed was measured with a goniometer and was found to be 10° or less. Note that the contact angle before the desensitization treatment was 98°. 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 degree of oxidation must be 20 degrees or less in terms of contact angle with water.)

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 is an offset printing machine (Oliver 52 manufactured by Sakurai Seisakusho).
(type) and printed on high-quality paper. Even after printing more than 5,000 sheets, no problems occurred in the background stains in the non-image areas and the image quality in the image areas of the printed matter.

Furthermore, using the above original plate, the environmental conditions were adjusted to 30°C and 80% RH.
When a plate was made using a 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 5000 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.

Example 2 A resin having the following structure [A-2
A mixture of 30 g of resin [:B-2] having the following structure, 50 g of zinc oxide, and 150 g of toluene was dispersed in a ball mill for 2 hours, and further, 4 g of 1,3-xylylene diisocyanate was added thereto, and the mixture was dispersed in a ball mill. Dispersed for 10 minutes. The obtained dispersion was applied with a wire bar so that the dry adhesion amount was 18 g/m', and dried at 110° C. for 1.5 hours to prepare a lithographic printing original plate.

Resin [A-2) L ~: 3. OX 1 0' Resin CB-21 C1l.

fCH2-4: Dimension r- C00CH.

Hs H ~: 2.8 X 10' This original plate was operated in the same manner as in Example 1 to perform plate making and printing.

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

This is an offset printing machine (Oliver 52 manufactured by Sakurai Seisakusho).
(type) and printed on high-quality paper. Even after printing more than 5,000 sheets, no problems occurred in the background stains in the non-image areas and the image quality in the image areas of the printed matter.

Furthermore, using the above original plate, the environmental conditions were adjusted to 30°C and 80% RH.
When a plate was made using a 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 5000 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 3 to 14 Resin CA-33 to CA-14 in Table 2 below] 25 g each
Resin [B-2] 15g, ■, 5 (N-imidazolyl)
A mixture of 5 g of carbamoylnaphthalene, 10 g of zinc oxide and 80 g of toluene was dispersed in a ball mill for 2 hours.

The obtained dispersion was applied with a wire bar so that the dry adhesion amount was 18 g/m' and dried at 120° C. for 3 hours to prepare a lithographic printing original plate. The shame of each resin [A] is 3X10
'~5X10'.

Table-2 CH5-C-X, dimension-1-r-f CH2-C-)-rrf
CH2-CHhCOO(CH,), OHCOOH This original plate was operated in the same manner as in the example process, except that a desensitizing treatment liquid (E-2) prepared according to the following formulation was used as the desensitizing treatment liquid. Performed plate making and printing.

Desensitization treatment liquid (E-2) These were dissolved in distilled water to make the total amount IA', and then hydroxylated.) The pH was adjusted to 11.0 with IJum.

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

This is an offset printing machine (Oliver 52 manufactured by Sakurai Seisakusho).
(type) and printed on high-quality paper. Even after printing more than 500 sheets, no problem occurred in the background stains in the non-image areas and the image quality in the image areas of the printed matter.

Furthermore, using the above original plate, the environmental conditions were adjusted to 30°C and 80% RH.
When a plate was made using a 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 5000 sheets.

Examples 15-25 40 g of resin [A-15'] with the following structure, 15 g each of resins [B-3] to [B-13] in Table 3 below, 5 g of silica gel
A mixture of 80 g of Sful was dispersed in a ball mill for 2 hours, and further,
5 g of the crosslinking compound shown in Table 3 below was added and dispersed for 10 minutes. The obtained dispersion was applied with a wire bar so that the dry adhesion amount was 18 g/m'' and dried at 120°C for 20 hours to prepare a lithographic printing original plate.In addition, each resin CB in Table 3] ~ was 3XIO' to 6XIO'.

Resin [A-15) 1f CH2-CH→as. 5 to CH200C-CH=CH2: 5xlO' This was made into a plate in the same manner as in Example 3, and then printed using a printing press. The density of the obtained printing original plate was 1.0 or more, and the image quality was clear. Furthermore, the image quality of the printed matter after printing 5,000 sheets was a clear image without any blurring.

Examples 26 to 37 Using each of the printing master plates prepared in Examples 2 to 25, 0.5 mol of the following nucleophilic compound, 100 g of an organic solvent, and 10 g of Nucor B4SN (manufactured by Nippon Nyukazai ■) were distilled. After adding water to bring the pH to 11, the pH of each mixture was adjusted to 11.0. Each original plate was immersed in the above treatment liquid for 30 seconds to perform a desensitization treatment, and then printed under the same printing conditions as in Example 1.

In each original plate, the contact angle of the non-image with water was 10° or less, making it sufficiently hydrophilic. Furthermore, even though the number of prints was 5,000, the print image quality of the printed matter was good with no blurring and clear images.

〔Effect of the invention〕

According to the present invention, a direct drawing type lithographic printing original plate which has excellent image receptivity and does not change over time can be obtained.

Moreover, a printing original plate with very good printing properties can be obtained.

Claims (1)

[Claims] (1) In a direct-drawing lithographic printing original plate having an image-receiving layer on a support, the binder of the image-receiving layer is the following resin [A]
A direct-drawing lithographic printing original plate comprising at least one of the following and at least one of the following resins [B] and, if necessary, a crosslinking agent. Resin [A]; General formula (I) of a resin containing at least one polymer component having a functional group represented by the following general formula (I) and/or general formula (II) ▲ Numerical formula, chemical formula, table, etc. ▼ General formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, in (I) or (II) above, -W_1
-, -W_2- are respectively -SO_2-, -CO- or -O
represents OC-, n_1 and n_2 each represent 0 or 1,
X represents a halogen atom] Resin [B]; Heat and/or photocurable resin