JPH0212254A - Developing agent composition - Google Patents

Abstract

PURPOSE:To improve the ink-forming and the ink-repulsing properties of the title composition by composing the title composition of an alkaline aqueous solution contg. 0.1-10wt.% of one or two or more kinds of an org. solvent selected from benzyl alcohol and ethylene glycol monophenyl ether, etc., and an anionic surfactant, etc. CONSTITUTION:The composition is composed of the alkaline aqueous solution contg. 0.1-10wt.% of one or two or more kinds of the org. solvents selected from benzyl alcohol, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol-alpha-monophenyl ether and propylene glycol-alpha- monobenzyl ether, an alkali agent and the anionic surfactant. Thus, a waterless planographic printing plate having the good ink-forming property and the excellent ink-repulsing property is obtd. by developing the composition with a developer composed of the alkaline aqueous solution.

Description

Detailed Description of the Invention [Industrial Application Field] A photosensitive layer in an exposed area, that is, a non-image area in a positive waterless lithographic printing plate in which a silicone rubber layer and a photosensitive layer containing an orthoquinone diazide compound are provided in this order. After making the non-image area ink-repellent and applying ink only to the image area using the difference in ink adhesion, it is applied to a printing material such as paper. In the lithographic printing method, in which ink is transferred to a surface for printing, the special purpose of printing is that the non-printing area is not made of a layer of material that has ink repellency, such as silicone rubber, and can be printed without using dampening water. It's a method.

The printing plate used for this waterless planographic printing has a silicone rubber layer as an ink repellent layer, and has excellent properties for practical use.The printing plate has a substrate, a silicone rubber layer, and a photosensitive layer laminated in this order. (Silicone rubber lower layer type)
Many proposals have been made in which a substrate, a photosensitive layer, and a silicone rubber layer are laminated in this order (silicone rubber upper layer type).

[Problem to be solved by the invention]

In the development process of waterless photosensitive lithographic printing plates with a silicone rubber upper layer, it is necessary to use a developer containing a large amount of aliphatic hydrocarbons such as pentane and hexane in order to swell the silicone rubber layer. This is a problem in terms of safety, etc.

Traditionally, ethanol has been used as the developer for waterless photosensitive lithographic printing plates with silicone rubber underlayers.

2s-tO% isopropanol aqueous solution, 30'1i
--A butyrolactone aqueous solution, an organic solvent such as toluene, an aqueous solution containing a large amount of an organic solvent, and a strong fluoric aqueous solution such as an O, C aqueous sodium hydroxide solution are used.

For example, Japanese Patent Publication No. 6/4/3/1989 discloses that a developing solution for a waterless photosensitive lithographic printing plate with a silicone rubber underlayer has a carbon number of 5 to 5. It has been proposed that smearing does not occur by using a silicone rubber containing mainly aliphatic hydrocarbons, but this method involves swelling the surface of the silicone rubber layer,
Since the photosensitive resin layer in the non-image area is removed in a tearing manner, uniform development processing is not possible and background smear occurs. Furthermore, since aliphatic hydrocarbons having 5 to 20 carbon atoms are used, there is also a problem in terms of safety.

[Failure to solve the problem]

As a result of intensive investigation into the problems associated with positive waterless photosensitive lithographic printing plates containing a silicone underlayer type orthoquinonediazide compound, the present inventors discovered that an alkaline aqueous solution containing a specific amount of a specific organic solvent and a surfactant. It has been discovered that when used as a developer, it exhibits good ink receptivity and excellent ink repulsion, and the present invention has been achieved.

That is, the gist of the present invention is a developer composition for a positive waterless photosensitive lithographic printing plate, in which a silicone rubber layer and a photosensitive layer containing an orthoquinonediazide compound are provided on a substrate, The composition contains 0) one or more selected from benzyl alcohol, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol-α-monophenyl ether, and hyfuropylene glycol-α-monobenzyl ether. organic solvent of 0. / −
/ 0% by weight The developer composition is specially designed to be an alkaline aqueous solution containing (b) an alkaline agent and (c) an anionic surfactant.

The present invention will be explained in detail below.

Benzyl alcohol, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol used in the developer composition of the present invention.
One or two selected from α-monophenyl ether, hyfuropylene glycol-α-monopene, and dyl ether
The amount of the organic solvent or more in the developer composition is determined from o, i to IO.
% by weight is preferred, and % by weight of O,S- is more preferred. As the amount of these organic solvents increases, the development speed increases, development processing ability increases, and ink repulsion tends to improve. If the time is too long, the image area may peel off from the silicone layer or the ink receptivity of the image area may deteriorate. On the other hand, if the amount is too small, the development speed will be very slow, and the ink repellency will be reduced, causing background smearing.

Examples of alkaline agents used in the present invention include sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, and dibasic ammonium phosphate. , sodium metasilicate, sodium bicarbonate,
Inorganic alkaline agents such as ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diimpropylamine, n-butylamines, monoethanolamine, jetanolamine,
Triethanolamine, N-benzylethanolamine, monoisopropanolamine, diimpropanazine, triisopropanazine, ethyleneimine,
There are organic amine compounds such as ethylenediamine and pyridine. The content of alkaline agent in the developer composition is O
A weight ratio of 0θS to 5% by weight is suitable, and a range of 0.1 to 3% by weight is even more preferable. If the amount is too small, development will be poor, which is undesirable. On the other hand, if it is in excess, ink receptivity in the image area will be poor and printing durability will be reduced, which is not preferable.

Among these alkaline agents, organic amine compounds are particularly excellent in printing durability. Organic amine compounds (t) include jetanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, N
-Benzylethanolamine is particularly preferred. The content of the organic amine compound in the developer composition is o, i~3
Particularly preferred is the weight category.

The anionic surfactants used in the present invention include (tri) sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate,
Higher alcohol (carbon number g-22) sulfate ester salts such as the ammonium salt of lauryl alcohol sulfate ester, aliphatic alcohol phosphate ester salts such as the sodium salt of 0 cetyl alcohol phosphate, 0 alkylbenzene such as sodium dodecylbenzene sulfonate. Sulfonic acid salts, alkylnaphthalene sulfonates such as sodium isopropylnaphthalene sulfonate, sodium dibutylnaphthalene sulfonate, sodium salt of phthalene sulfonic acid/formalin condensate, sodium alkyl diphenyl ether disulfonate, polyoxyethylene lauryl ether sulfate Examples include polyoxyethylene alkyl ether sulfates such as sodium, (2) sodium pholyoxyethylene alkyl phenyl ether sulfate, and the like.

The amount of anionic surfactant in the developer is 0. /~io weight % is suitable, and o, s-s* food is more suitable. If the amount is too large, color loss will occur in the image area, and if it is too small, the development speed will be slow, and the ink repellency will be reduced, making it easy to cause scumming.

The developer composition of the present invention contains the above-mentioned organic solvent, alkaline agent, and anionic surfactant, but it is also possible to contain other additives as long as they meet the purpose of the present invention.

The positive waterless photosensitive lithographic printing plate which can be processed with the developer of the present invention has a substrate, a silicone rubber layer, and a photosensitive layer provided in this order, and the photosensitive layer contains an orthoquinone diazide compound. It is something to do. Examples of orthoquinone diazide compounds include polycondensation resins of phenols and aldehydes or ketones and the following general formula (1) or general formula (II) (wherein X is a group represented by -8o, Y or -COY,
Examples include orthoquinonediazide sulfonic acid esters or carboxylic acid esters obtained by chemically condensing orthoquinonediazide sulfonic acid or carboxylic acid derivatives represented by (Y means a removable group).

Specific examples of the compound represented by the above general formula (1) include /, cobenzoquinonediazide (co)-tersulfonyl chloride, t,S-benzoquinonediazide (J)
-a-carbonyl chloride IJ)", /,!-benzoquinonediazide (a) -S-sulfonyl chloride, /,!
Examples include -benzo nondiazide (co)-5-carbonyl chloride. Specific examples of the compound represented by the above general formula (n) include nondiazide (
J)-q-sulfonyl chloride, non-naphthoquinonediazide (co)-tercarbonyl chloride, hecona-7-toquinonediazide (2)-g-sulfonyl chloride, muco-naphthoquinonediazide (J)-s-carbonyl chloride, and the like.

As the polycondensation resin of phenols and aldehydes or ketones, for example, a polycondensate of pyrogallol and 77 tons, as described in Japanese Patent Publication No. Sho IIJ-2 and 4tθJ, As described in Publication No. 76,74IA, a mixture of pyrogallol and resorcinol and a polycondensate of a7ton, as described in Publication No. , metacresol/formaldehyde/novolac resin, Tokko Sho SO-! ; As described in Publication No. 013, para-substituted phenol/formalin resin (e.g., baracresol/formalin resin,
Paraoctylphenol/formalin resin, paraethylphenol/formalin resin, parapropylphen/-
/I/・Formalin resin, para-n-propylphenol-formalin resin, para-n-butylphenol-formalin resin, para-octylphenol-formalin resin, etc.) As described in the Japanese Patent Publication No. 1986/BOEO, the number of carbon atoms is 3. A phenol mixture containing ~l alkyl or phenyl group-substituted phenol and phenol or its methyl substituted product or a mixture thereof in a molar ratio of l:de~9:l and a polycondensate of formaldehyde (for example, the above-mentioned para-substituted (phenol, phenol para-cresol, meta-cresol, or ortho-cresol, etc.).

Ortho to the hydroxyl group of the polycondensation resin of phenols and aldehydes or ketones=? The esterification rate of the nondiazide group is preferably 15 to 100 moles, and is 20-1!
:0 mole is more preferable.

Furthermore, as an orthoquinonediazide compound, orthonaphthoquinonediazide sulfonic acid ester of polyhydroxybenzophenone (side light), cornaphthoquinonediazide (
co)-5-sulfonic acid ester, hecona-7toquinonediazide (λ)-q-sulfonic acid ester, etc.).

This polyhydroxybenzophenone is a compound obtained by substituting two or more hydrogen atoms of benzophenone with hydroxyl groups, such as dihydroxybensiphenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, octahydroxybenzophenone, or a derivative thereof (for example, / S rogen atom, alkyl group, aryl group, aralkyl group, carboxyl group substituents), and the like. Preferred is trihydroxybenzophenone or dihydroxybenzophenone, and more preferred is hydroxybenzophenone 1.2.j, u, tI'-tetrahydroxybenzophenone.

The esterification rate for hydroxyl groups is preferably 30 to 100.

In addition to the orthoquinonediazide compound, it is usually preferable to contain various resins as a binder in the photosensitive layer of the positive waterless photosensitive lithographic printing plate which can be processed with the developer of the present invention.

Examples of the binder include novolak resin, epoxy resin, polyvinyl acetal resin, and acrylic resin, but it must have good adhesiveness to the silicone rubber layer. As a binder, the following general formula (1
) or i-polymer compounds having a structural unit represented by the following general formula (IV) are preferred.

-10R"R" -CR3→- (In the formula, R1 and R2 are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxyl group, and R"
is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, n' is a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and B is an aromatic group that may have a substituent 'ctJ, %A is a covalent organic group that connects the nitrogen atom and the carbon atom of the aromatic group, and m is the number of 0 or 1. ) (In the formula, R'' is a hydrogen atom or a methyl group, X is an alkylene group, n is 0 or the number of /, Y is an alkyl group or an alkoxy group, m is 0 -.1. In particular, it is preferable that X is a methylene group and Y is an alkyl group or an alkoxy group with carbon number/-&.) The structural unit represented by the above general formula [■] is a specific ,
For example, N-(p-hydroxy7enyl)methacrylamide, N-(p-hydroxyphenyl)acrylamide, N-(,7-methyl-lyhydroxyphenyl)methacrylamide, N-(,7,&-dihydroxy Structural units derived from "phenyl)methacrylamide", N-(J-hydroxycyanophenyl)methacrylamide, N-(p-hydroxyphenylethyl)methacrylamide, etc. are particularly preferred among these. , N
-(p-hydroxyphenyl)methacrylamide.

Specifically, the structural unit represented by the general formula [, IV] is, for example, N-(,?-methylphenyl)methacrylamide, N-(,7-methylphenyl)acrylamide, N-(3-methoxy phenyl) methacrylamide,
N-(,7-methodiphenyl)acrylamide, N-
(4t-ethylphenyl)methacrylamide, N-(e
-ethylphenyl)acrylamide, N-(p-ethoxyphenyl)methacrylamide, N-(g-ethoxyphenyl)acrylamide, N-(p-butylphenyl)
Methacrylamide, N-(l-butylphenyl)acrylamide, N-benzylmethacrylamide, N-benzylacrylamide, N-(4I-methylbenzyl)methacrylamide, N-(tI-methylbenzyl)acrylamide, N-(p- methoxybenzyl)methacrylamide, N-(tI-methoxybenzyl)acrylamide,
N-(J-ethylbenzyl)methacrylamide, N-(
3-ethylbenzyl)acrylamide, N-(3-ethoxybenzyl)methacrylamide, N-(,7ethoxypenzyl)acrylamide, N-(F-butylbenzyl)methacrylamide, N-(F-butylbenzyl/I/)
Structural units derived from acrylamide and the like, particularly preferred among these are N-phenylmethacrylamide, N-(,y-methoxyphenyl)methacrylamide, and N-(&-methoxyphenyl)methacrylamide. It is.

The polymer compound having a structural unit represented by the general formula [■] or (IT) is a polymer compound having a structural unit represented by the general formula [■] or (IT).
A copolymer of a monomer inducing the structural unit represented by V) and another copolymerizable monomer is preferable, and examples of the monomer to be copolymerized include acrylics such as methyl acrylate and ethyl acrylate. Acid alkyls; Methacrylic esters such as methyl methacrylate, ethyl methacrylate, and monohydroxyethyl methacrylate; Methacrylamides such as N-methyl methacrylamide; Preferably methacrylic acid, acrylic acid, acrylonitrile, methacrylonitrile, etc. , multi-component copolymers with these are preferred. Furthermore, the molecular weight is preferably about 10,000 to 1,000,000, particularly about 3
300,000 to 300,000 is preferable.

The proportion of the orthoquinone diazide compound in the photosensitive layer is preferably from S to 60% by weight, particularly preferably from 0 to 10% by weight, and the proportion of the binder in the photosensitive layer is preferably from eo to 0% by weight. Particularly preferred is SO to 0% by weight.

The photosensitive layer may further contain an exposure-visible image imparting agent, a dye, a coatability improver, a plasticizer, a sensitizing agent, and the like.

In order to form the photosensitive layer, each component to be contained is mixed with various organic solvents such as comethoxyethanol, -monoethoxyethanol, methyl cellosolve acetate, ethyl cellosolve acetate, l-methoxy-a-pronoquinol, and methyl ethyl ketone. It is dissolved or dispersed in a solvent alone or in a mixed solvent of two or more kinds, applied according to a conventional method, and usually dried at tIo'c-7so°C.

The preferred thickness of the photosensitive layer is 0. /-100μm,
More preferably θ, j −goβm1, still more preferably 1 to 304 m.

The silicone rubber layer of the positive-working waterless photosensitive lithographic printing plate that can be processed with the developer of the present invention is, for example, a silicone rubber that can be crosslinked and has an organopolysiloxane as a main component having a repeating unit represented by the following general formula. It consists of

Here n is an integer greater than or equal to. R6 and R7 are arbitrarily selected from a hydrogen atom, an unsubstituted or substituted (for example, by a rogen atom, a cyano group, an amino group) alkyl group, alkenyl group, or phenyl group having a carbon number of /-10,
In particular, it is preferable that 60 or more of R6 and R7 are methyl groups.

The molecular weight is arbitrary, but the viscosity at 5°C, /-
/ Q (7 (7 (7 Stokes is preferable.

Organopolysiloxane in which a hydroxyl group or a hydrolyzable group (for example, an acyloxy group, an alkoxy group, a ketoximate group, an amino group, an amide group, etc.) is bonded to the terminal silicon atom of the above formula is used to crosslink by a condensation reaction, and a silicone rubber is produced. shall be.

Particularly preferably used are organopolysiloxanes having hydroxyl groups bonded to both ends, specifically, for example,
α,ω-dihydroxydimethylpolysiloxane is mentioned. Typically, these organopolysiloxanes are combined with a crosslinking agent (e.g., γ-(co-aminoethyl)aminopropyltrimethoxysilane, r-glycidoxypropyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane). silane, methyltriacetoxysilane, vinyltris(methylethylketoxime)silane, methyltris(methylethylketoxime)silane, etc.).

In order to obtain a silicone rubber layer, an uncured silicone rubber layer is usually cured. For the curing, it is preferable to add a known metal catalyst such as diptyltin diacetate, tributyltin acetate, dibutyltin dilaurate, tetramethylorthotitanate, tetramethylorthotitanate, etc. as a catalyst. These catalysts are added in an amount of 0.0/~ to the total weight of silicone rubber.
It is preferable to use 5-fold polyester, especially in the range of 0.0-1% by weight.

It is also useful to add inorganic fillers such as silica and calcium carbonate for reinforcement purposes.

In order to form a silicone rubber layer, each of the above components is mixed with aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, n-hebutane, co-methylhexane, or ,
A silicone rubber solution prepared by dissolving it in a mixed solvent with a small amount of aromatic hydrocarbons such as xylene to form a solution is applied according to a conventional method, and then heat-treated for several minutes or more at a temperature of, for example, SO℃ to tSO℃. A hardened non-stick silicone rubber layer is formed.

The thickness of the silicone rubber layer is preferably o, i to -008 m, particularly preferably / to ioo μm, and more preferably 2 to 5 m.
0 μm is preferable.

The substrate of the waterless photosensitive lithographic printing plate treated with the developer of the present invention is not particularly limited as long as it has the flexibility to be attached to a lithographic printing machine and can withstand the load applied during printing.

For example, paper such as coated paper, metal plates such as aluminum, iron, and zinc; organic polymer films such as polyolefin (e.g., polyethylene, polypropylene, etc.), polyester (e.g., polyethylene terephthalate, etc.), polyamide; Further examples include a composite of aluminum foil and a material other than the above-mentioned metal plate. It is also possible to use a substrate that is further coated on these surfaces for purposes such as prevention of 7-rusion, or paper, organic polymer film, etc. impregnated with or dispersed with an ultraviolet absorber. .

Since it is difficult to coat a photosensitive layer on a silicone rubber layer with a very low surface tension using a known coating method, the method for producing the waterless lithographic printing original plate of the present invention is usually carried out as follows. Manufactured according to a method.

(1) A method in which a photosensitive layer and a silicone rubber layer are coated in this order on a polymer film, and the substrate and silicone rubber layer are pressed together so that they are in close contact with each other.

(2) A method of press-bonding a silicone rubber layer provided on a substrate and a photosensitive layer provided on a polymer film so that the silicone rubber layer and the photosensitive layer are in close contact with each other.

The polymer film has a thickness of 0. / -! ;00μ
m polyethylene film, polypropylene film,
Examples include polyethylene terephthalate films, and films whose surfaces have been subjected to discharge treatment, roughening treatment, etc. to improve wettability may also be used.

Further, for the purpose of improving the adhesion between the photosensitive layer and the silicone rubber layer, a silane coupling agent, a silicone primer, or the like may be added to the photosensitive layer or the silicone rubber layer. In addition, in order to improve the adhesion between the silicone rubber layer and the substrate, a silane coupling agent or silicone primer, etc. is applied to the substrate, or a silane coupling agent, silicone primer, etc. is added to the silicone rubber layer. You can.

The above-described waterless photosensitive lithographic printing plate is subjected to image exposure using a light source such as a high-pressure mercury lamp, a mercury lamp, a metal halide lamp, etc., and then developed using the developer composition of the present invention. The photosensitive layer in the exposed areas is dissolved or peeled off during the development process, and the surface of the ink-repellent silicone rubber layer is exposed, forming a non-image area.On the other hand, the photosensitive layer in the unexposed areas is removed by the development process. It is possible to obtain an ink-receptive image area and a waterless lithographic printing plate without any problems.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The invention is not limited to these examples. Note that all parts used in the examples indicate parts by weight.

(Example/-j and Comparative Examples 1 to 3) N-7 enyl methacrylamide u, oy, acrylonitrile 3.2 fi, methyl acrylate 3. Col.

Ethyl acrylate l/, ji, methacrylic acid l/, α
, α'-azobisisobutyronitrile 0. A mixture of II/11 and methanol 30 was subjected to a polymerization reaction at reflux temperature for S hours under a nitrogen atmosphere.

After adding -10txtt of methoxyethanol, the temperature of the oil bath was raised to 130°C, and methanol and unreacted monomers were distilled off. After cooling, comethoxyethanol was further added to make the solid content 35% by weight, and 35% of polymer compound-7 was added.
A weight-based cocoatoxyethanol solution was obtained. The molecular weight is
Weight average molecular weight calculated by gel permeation chromatography in terms of standard polystyrene! . It was 10,000.

The inner surface of a polypropylene film 5O-aO7φ20 made by Honshu Paper ■ with a thickness of about 50 μm (wet tension 3 gdyne /
cm), add the following photosensitive solution (A) to R, D, 5 pec
It was coated using a 16 g Pacoater manufactured by Ialties Inc. and dried at 60° C. for 6 minutes to form a photosensitive layer having a thickness of S μm.

Photosensitive solution (A) (a) 35% by weight comethoxy ethanol solution of polymer compound-1 - Old... 200 parts A) Tip 3. q
-8-1 naphthoquinonediazide (J) of trihydroxybenzophenone -s-sulfonic acid ester (esterification rate 95%) 30 parts (c) -1-trichloromethyl-S-(β-( 2'-
benzofuryl) vinyl]', 3s'l-oxadiazole... 1 part (d) Resident 3M Co., Ltd. Florard FC-II30 (fluorosurfactant)...0.07 part ( e
) Victoria Pure Blue BO manufactured by Odugaya Chemical ■
H...7 parts (f) -monoethoxyethanol...
Next, the following silicone solution was applied onto the photosensitive layer using a spin coater at room temperature and /00 rpm, air-dried at room temperature for S minutes, and then heat-treated at 60° C. for 72 minutes.

Silicone solution (a) Polydimethylsiloxane with hydroxyl groups at both ends (viscosity 13,000 stokes, manufactured by Tone Silicone B)
Y/4-10/) ...100 copies etc.)
Methyltris(methylethylketoxime)silane
・Hayabusa... Part 10 (C)
Diptyltin diacetate...002 parts (d) Methylcyclohexane...
300 copies On the other hand, on an aluminum plate with a thickness of 0.2 (I), apply 5H-2260 primer manufactured by Tone Silicone ■ at room temperature / 00 rpm using a spin coater, and air dry for 5 minutes at room temperature. A polypropylene film on which the photosensitive layer and the silicone rubber layer were laminated was placed on top of the photosensitive layer and the silicone rubber layer using a laminator at a temperature of 20° C. and 20° C.
It was crimped for 1 minute. This is t, o℃
was heat-treated for 5 minutes.

After peeling off the polypropylene film, the silicone rubber layer was sufficiently cured by further heat treatment at 60° C. for 1 minute to obtain a waterless photosensitive lithographic printing plate. The thickness of the completely cured silicone rubber layer is approximately 10 tons.
It was 1m. This plate was passed through a positive original film according to the usual method, using a 7KW high-pressure mercury lamp manufactured by Ushio Inc. (UM)I.
Image exposure was carried out at -3000 for 2 minutes from a distance of /rn. j；℃
After dipping for 30 seconds, development was performed by rubbing lightly, and the results shown in Tables 1 and 2 were obtained.

Regarding ink repulsion, after development, washing with water, and drying, use Toyo King Ultra TKU manufactured by Toyo Ink Manufacturing ■.
By rolling a roller coated with Aquares G black ink onto the plate surface, those with almost no ink adhering to the non-image areas were rated as "good", and those with adhesion were rated as "bad". In addition, when the photosensitive layer in the non-image area was not clearly removed by the development process, it was judged as "unable to be developed."

(Example 6-t) N-(<c-hydroxyphenyl)methacrylamide p
, IIy, acrylonitrile 3. Coll, methyl acrylate 3. Col, methyl methacrylate 8311 ethyl acrylate/0.3 g, methacrylic acid 1.1 g, α, α'
-A mixture of 0.6 J of azobisin butyronitrile, methanol/1ast and acetone ig- under a nitrogen stream,
The polymerization reaction was carried out at reflux temperature for about 6 hours, and the solid content concentration was 4c.
A methanol/acetone solution of a polymer compound containing 0% by weight was obtained.

The weight average molecular weight was j,/10,000.

Example! In the same manner as in Example /-j-, except that the following photosensitive liquid (B) was used instead of the photosensitive liquid (A) in -5,
A waterless photosensitive lithographic printing plate was obtained.

Photosensitive liquid CB) (a) eo weight ratio methanol of polymer compound-2
Acetone solution.../5 parts (b) a,
s, q-) 7, corner 7 quinone diazide of hydroxybenzophenone (J) -3-sulfonic acid ester (esterification rate: 5%)...lS part (C) metacresol Φ formaldehyde novolak resin Muco-naphthoquinonediazide (co)-5-sulfonic acid ester (esterification rate: 23, weight average molecular weight s
, ooo)...75 parts (d) Hecona 7-toquinone diazide (λ)-5-sulfonyl chloride
...7 parts (e) Florado FC-1130 made by JMVm...0.07 parts (f) Victoria vinyl blue BOH made by Osugaya Kagaku ■...8 parts @Co-ethoxyethanol...Aso portion After image exposure, this was subjected to development treatment using the following developers 1 to 3, respectively, and the results shown in Table 3 were obtained.

Developer-l Ethylene glycol monophenyl ether sodium carbonate/IO hydrate Demol N Water developer-2 Ethylene glycol monophenyl ether, diethanolamine bionin AlB Water developer-3 Penzyl alcohol triethanolamine Demol N Water/G1 part/j part 70 parts 9A/part 15 parts 70 parts lS part qbs part 15 parts lS part 10 parts? 6.5 Partial evaluation was carried out using a Davidson Dualis 'yoo type offset printing machine after development, washing with water, drying, and without using dampening water. Toyo King Ultra TK manufactured by Toyo Ink Manufacturing ■
The ink receptivity, ink repulsion, and printing durability were examined by printing with O Aqualess GM ink. Regarding ink adhesion, when the ink film thickness on the ink roller is 3.3 am, when the reflection density of the flat part of the printed matter is equal to or higher than 5S, it is considered "good", and when it is less than 5, it is considered "poor". did. Ink repulsion is considered "good" when the reflection density of the non-image area of the printed material is 10.02 or less before printing.
If it is larger than that, it is marked as "defective". The printing life was determined by the number of sheets printed at the time when damage to the image area, including the petal area, and areas where the ink receptivity was deteriorated were observed.

Table 3 (Examples 6 to g) By using the developer composition of the present invention, a waterless lithographic printing plate with excellent ink receptivity and ink repulsion properties can be obtained. Furthermore, if an organic amine compound is used as the alkali agent, a waterless lithographic printing plate having excellent printing durability can be obtained.

(Reference Example) The negative was processed into a waterless photosensitive lithographic printing plate in the same manner as in Example /-&, except that the following photosensitive liquid (C) was used instead of the photosensitive liquid (A) in Example /-, 1. Obtained.

Photosensitive liquid (C) (a) Polymer compound described in the synthesis example of Japanese Patent Application No. 1986-33-956 -/(N-(p-hydroxyphenylmethacrylamide/acrylonitrile/methyl acrylate/ethyl acrylate/ Methacrylic acid = / 0/2
'I//! r / da 3 / g molti, weight average molecular weight / /, 10,000) 20% by weight of 2-, %) -xyethanol filtrate... 00 parts of diazo resin-7 (bala diazodi 7) Engineering amine φ
Hexafluorophosphate of formaldehyde polycondensate,
Weight average molecular weight 2 goo)...20 parts (C) Jerimer AC-10L (trade name: Polyacrylic acid bath liquid made by Nippon Tsumugiku ■)...6 parts (d) Resident 3M made Florado FC-G3Q...
... o, o o s part (e) Victoria Pure Blue BOH manufactured by Udougaya Chemical ■ ... Heko part (f) 2-methoxyethanol ... -
100 parts (b) Co-ethoxyethanol...
... 700 copies After imagewise exposure, this was developed using the following developer -q and printed under the same conditions as Examples 6 to g, and it showed excellent ink repulsion.

Further, there was no problem in ink receptivity. Moreover, the printing durability was 10,000 sheets or more.

(b) In the synthesis example of Japanese Patent Application No. 1982-33G 956, developer - ethylene glycol monophenyl ether...
・・3g part jetanolamine ・・・・
... Part 13 Pionin AII! B...
...15 parts water
9jF Part [Effect of the Invention] By using the developer composition of the present invention, a waterless lithographic printing plate having good ink receptivity and excellent ink repulsion can be obtained.

In addition, while it is impossible or difficult to use ordinary positive photosensitive lithographic printing plate developer compositions for negative tone printing plates, the developer composition of the present invention can be used for negative tone waterless photosensitive printing plates. It can also be applied to the development treatment of lithographic printing plates.

Therefore, the present invention is extremely useful industrially.

Claims (1)

[Claims] (1) A developer composition for a positive waterless photosensitive lithographic printing plate, comprising a silicone rubber layer and a photosensitive layer containing an orthoquinone diazide compound provided in this order on a substrate, the composition comprising (a) One or more organic solvents selected from benzyl alcohol, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol-α-monophenyl ether, and propylene glycol-α-monobenzyl ether, 0.1 to 10 Weight % A developer composition characterized in that it is an alkaline aqueous solution containing (b) an alkaline agent and (c) an anionic surfactant.