iiililiili^ (12) EUROPEAN PATENT SPECIFICATION

@ EuroPean Patent Office i i i l i l i i l i ^

^ - S Office europeen des brevets (fi) Publication number: 0 3 9 0 4 8 0 B 1

(12) EUROPEAN PATENT S P E C I F I C A T I O N

@ Date of publication of patent specification : @ Int. CI.5 : G03F 7 /32 01.06.94 Bulletin 94/22

@ Application number: 90303221.7

(22) Date of filing : 27.03.90

(54) Developer composition for PS plates for use in making lithographic printing plate and method of platemaking.

(§) Priority : 29.03.89 JP 77517/89

(43) Date of publication of application 03.10.90 Bulletin 90/40

(45) Publication of the grant of the patent : 01.06.94 Bulletin 94/22

@ Designated Contracting States : DE GB

(56) References cited : GB-A- 2 083 238 US-A- 4 711 836

(73) Proprietor : FUJI PHOTO FILM CO., LTD. 210 Nakanuma Minami-ashigara-shi Kanagawa-ken, 250-01 (JP)

CO o 00

o o> CO

LU

(72) Inventor : Akiyama, Keizi c/o Fuji Photo Film Co., Ltd., 4000,Kawashiri Yoshida-cho, Haibara-gun, Shizuoka-ken (JP) Inventor : Misu, Hiroshi c/o Fuji Photo Film Co., Ltd., 4000,Kawashiri Yoshida-cho, Haibara-gun, Shizuoka-ken (JP)

(74) Representative : Blake, John Henry Francis et al BROOKES AND MARTIN High Holborn House 52/54 High Holborn London WC1V 6SE (GB)

Note : Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid (Art. 99(1) European patent convention).

Jouve, 18, rue Saint-Denis, 75001 PARIS

EP 0 390 480 B1

Description

The present invention relates to a developer composition for presensitized plates for use in making lithographic printing plates (hereunder referred to as "developer composition for PS plate") and a plate-making

5 method in which such a developer composition is employed and more specifically to a developer composition for removing portions (which serving as non-image areas) of negative-working and/or positive-working PS plates and a plate-making method in which the developer composition is employed.

Japanese Patent Publication for Opposition Purpose (hereunder referred to as "J. P. KOKOKU") No. Sho 56-39464 discloses a developer composition for removing non-image areas of a light-sensitive layer which

10 comprises a weak alkaline aqueous solution-soluble organic high molecular weight polymer and a light- sensitive diazo resin. However, this developer composition does not always show ability of completely dissolving even the light-sensitive layer in non-exposed areas adjacent the surface of a substrate. For this reason, background contamination is correspondingly caused when printing operation is performed using a lithographic printing plate obtained by developing a PS plate with this developer composition.

15 It is known that a drawback of this kind can be eliminated by the addition of a sulfite such as those disclosed in J. P. KOKOKU No. Sho 56-42860 (U.S. Pat. No. 4,1 86,006) to the foregoing developercomposition. The prob- lem of such background contamination of non-image areas during printing can surely be eliminated by the addition of a reducing inorganic sulfite, but if the developer is stored for a long time period, a part of the sulfite is oxidized. This leads to the reduction in the contamination-inhibitory effect of the developer.

20 On the other hand, as a developer containing hard water is deteriorated, a binder is separated out from the developer, which possibly results in the formation of sludge. On adding a chelating agent (a hard water softener) to such a developerfor preventing the formation of sludge, the oxidation of the sulfite is accelerated.

On the other hand, a PS plate carrying a positive-working light-sensitive layer has also been widely used like PS plates provided with negative-working light-sensitive layers. However, the composition of developers

25 for the positive-working PS plate in general differs from that of developers for the negative-working ones. Therefore, a plurality of developing machines are required for treating both positive- and negative-working PS plates. This leads to an increase in the operating cost. In addition, the space for installing the developing machines is too great and the operating efficiency is also insufficient.

GB-A-2083238 discloses a one-step developer and lacquer composition, particularly for use with litho- 30 graphic printing plates sensitised with water-insoluble diazonium components. The composition is an aqueous

emulsion of a substantially water-soluble organo-lithium salt, such as lithium naphthenate, lithium benzoate or lithium ricinoleate, and an ink-receptive, film-forming, organic solvent-soluble resin.

US-A-4711836 discloses an aqueous developing solution for positive-working photoresist compositions based on novalak-type resins and a photosensitive agent. The developing solution contains a quaternary am-

35 monium hydroxide developing agent and an additive which may be 1,3,5-trihydroxybenzene. The inventors of this invention have conducted various studies in respect of developer compositions and

have found that the above-mentioned drawbacks associated with the conventional developer compositions can be eliminated by the use of an certain aromatic compounds having hydroxyl groups in the meta- configuration, typically at the 1- and 3-positions thereof, or certain salts thereof, which are free of any electron

40 attractive group. Furthermore, the inventors have also found that the developer containing such an aromatic compound

can develop not only negative-working light-sensitive materials but also positive-working light-sensitive materials provided with a light-sensitive layer which comprises an o-quinonediazide compound and an organic high molecular weight polymer if the pH value of the developer is adjusted to not less than 12. The present

45 invention has thus been completed on the basis of these findings. According to one aspect of the invention, there is provided a developer composition which comprises an

aromatic compound of general formula (I) indicated below, an alkaline agent and water. According to another aspect of the present invention, there is provided a process for developing a pre-

sensitised lithographic printing plate which comprises either 50 i) developing an imagewise light-exposed, positive working, presensitized plate having a substrate with

an imagewise light-exposed positive working light-sensitive layer containing an o-quinone diazide compound with the above developercomposition to remove light-exposed areas of the positive working light- sensitive layer, to provide a lithographic printing layer, or ii) developing an imagewise light-exposed, negative working, presensitized plate having a substrate with

55 an imagewise light-exposed negative working light-sensitive layer containing a diazo resin with the above developer composition to remove light-unexposed areas of the negative working light-sensitive layer, to provide a lithographic printing layer. The developercomposition and the plate-making process of the present invention will hereunder be de-

2

EP 0 390 480 B1

scribed in more detail. The aromatic compound used in the composition of the invention is a compound represented by the fol-

lowing general formula (I):

10

15 wherein A represents a hydrogen atom or a fused ring which may have substituents; R1 represents a hydrogen atom, a lower alkyl group or a lower alkoxy group; and M represents hydrogen, sodium, potassium or an ammonium group.

The A of formula (I) preferably represents a hydrogen atom, a phenyl ring or a naphthyl ring. The fused ring also includes those having at least one substituent. Examples of such substituents include alkyl groups

20 having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms and aralkyl groups having 7 to 12 carbon atoms.

As the lower alkyl and alkoxy groups represented by R1, preferred are those having 1 to 6 carbon atoms and a methyl group is particularly preferable as the alkyl group.

Preferred ammonium groups represented by M are those represented by the general formula: NR2R3R4R5 25 (wherein R2to R5 may be the same or different and each preferably represents hydrogen or a lower alkyl group

having 1 to 6 carbon atoms which may have substituents. Particularly preferred examples of the compounds represented by formula (I) will be listed below. The fol-

lowing compounds may of course be in the form of salts thereof and the present invention is not restricted to these specific compounds.

30

35

40

45

3

EP 0 390 480 B1

20 In the developer composition of the invention, these aromatic compounds may be used alone or in com-

bination. The amount thereof used preferably ranges from 0.001 to 10% by weight on the basis of the total weight of the developercomposition. This is because if it is used in an amount of less than 0.001% by weight, the resulting developer composition does not show sufficient ability to prevent contamination of non-image

25 areas. On the other hand, if it exceeds 10% by weight, the mechanical strength of photohardened portions of light-sensitive layers on a PS plate treated with the developer composition are deteriorated and hence the printing durability of the lithographic printing plate thus obtained is possibly impaired.

Examples of the alkaline agents used in the developercomposition of the present invention include inorganic alkaline agents such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, li-

30 thium hydroxide, sodium tertiary phosphate, sodium secondary phosphate, ammonium tertiary phosphate, ammonium secondary phosphate, sodium metasilicate, sodium bicarbonate, sodium borate, ammonium borate and ammonia; and organic amine compounds such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine,

35 ethylenediamine and pyridine. These alkaline agents may be employed alone or in combination. Preferred examples of the alkaline agents are sodium silicate, potassium silicate, sodium hydroxide, po-

tassium hydroxide, monoethanolamine, diethanolamine, and triethanolamine which may be used alone or in combination.

The amount of these alkaline agents generally ranges from 0.05 to 10% by weight and preferably 0.1 to 40 7% by weight on the basis of the total weight of the developer composition practically used.

The developer composition of the present invention may optionally comprise at least one anionic surfactant. Moreover, it is also possible to add at least one organic solvent to the developer composition.

Examples of the anionic surfactants are sodium salt of lauryl alcohol sulfate; sodium salt of octyl alcohol sulfate; ammonium salt of lauryl alcohol sulfate; salts of higher alcohol sulfuric acid esters having 8 to 22 carbon

45 atoms such as secondary sodium alkylsulfates; salts of aliphatic alcohol phosphoric acid esters such as sodium salt of cetyl alcohol phosphoric acid ester; salts of alkylarylsulfonic acids such as sodium salt of dodecylben- zenesulfonic acid, sodium salt of isopropylnaphthalenesulfonic acid and sodium salt of metanitrobenzenesul- fonic acid; alkylaryl carboxylic acid salts such as sodium 4-n-butylbenzoate and potassium 4-t-butylbenzoate; sulfonic acid salts of alkylamides such as C17H33CON(CH3)CH2CH2S03Na; sulfonic acid salts of dibasic ali-

50 phatic acid esters such as sodium dioctyl sulfosuccinate and sodium dihexyl sulfosuccinate; and salts of aryloxyalkylene sulfuric acid esters such as dipotassium 8-(2-naphthyloxy)-3,6-dioxaoctyl disulfate.

Preferred anionic surfactants used in this invention include those represented by the following general formula (II):

A(-(CH2)m -0-(CH2CH(Ri)-0-)n -S03" -M+) p (II) 55 In formula (II), Arepresents an optionally substituted aryl group; R1 represents a hydrogen atom or a lower

alkyl group; M represents a hydrogen atom, an alkali metal or an ammonium group; m is 0 or an integer of not less than 1 , n is 0 or a positive number provided that m and n are not zero simultaneously; and p is an integer of 1 to 5.

The aryl group A is preferably a phyenyl or naphthyl group, more preferably a naphthyl group. The aryl

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EP 0 390 480 B1

10

group may have at least one substituent. Preferred examples of such substituents include alkyl groups having 1 to 18, preferably 1 to 12 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, aralkyl groups having 7 to 18 carbon atoms, alkoxy groups having 1 to 18 carbon atoms, nitro group, and halogen atoms. Examples of lower alkyl groups, R1, include those having 1 to 3 carbon atoms and preferably methyl group. Preferred examples of alkali metal M include sodium and potassium and examples of ammonium group include NH4 and NH(C2H5)3. m represents 0 or an integer of not less than 1 , preferably 0 or an integer ranging from 1 to 5 and more preferably 0. n represents 0 or a positive number, preferably 0 or a number of up to 30. n herein means an average added mole number of oxides. Therefore, the compounds represented by the foregoing formula (II) of course include mixtures of those differing in the added mole number of oxides. In addition, m and n cannot be zero simultaneously as already mentioned above, p is an integer of 1 to 5 and in particular 1 or 2.

Particularly preferred compounds represented by the general formula (II) will be listed below, but the invention is not restricted to these specific examples.

15

( D - O f C H j - C H a - O h S O a N a

20

(2 )

25

Q f C I U - C H i - O h S O a N a

30 (3 ) O f C H j - C H j - O h o S D a . N a

35

40

CH(CH3)

O f C r U - C H i - O H . sSOaNa

45 (5 ) + C H J - 0 t C H , - C H , - 0 h o S 0 , N a

50

(6 )

0 ( C H 2 - C H 2 - 0 h o S 0 3 K

55

5

EP 0 390 480 B1

(7) (CHa) ,CI ■OtCH2-CH2-0)- .oS03Na

10 (8 )

• O t C H j - C H a - O h S O a N a

15

20

R: mixture of -C6H13 and -C7H15

(9) H,sC3 - O f C H a - C H s - O h o S O a N a

25 d o ) H U t C H a - C H , - O h o . »SOaNa

The compounds of the formula (II) can be prepared by the process disclosed in J. P. KOKAI No. Sho 59- 195641 (U.S.S.N. 601,814 filed April 19, 1984, now abandoned).

30 These anionic surfactants may be used alone or in combination. Particularly preferred is a combination of the surfactant represented by formula (II) and an alkyl aryl sulfonic acid salt.

These anionic surfactants are used in the developer composition in an amount suitably ranging from 0.1 to 5% by weight with respect to the total weight of the developercomposition practically employed. This is because if it is less than 0.1% by weight, the effect thereof cannot be expected, while if it exceeds 5% by weight,

35 for instance, dyes contained in a photohardened light-sensitive layer are dissolved out in excess and the mechanical and chemical strength of the photohardened images is deteriorated.

The organic solvents which may be added to the developercomposition are preferably selected from those having a solubility in water of not more than about 10% by weight, in particular not more than 5% by weight. Examples of the organic solvent include 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol- 1, 4-phenylbu-

40 tanol-1 , 4-phenylbutanol-2, 2-phenylbutanol-1 , ,2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxy benzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 4-methylcyclohexanol and 3-methylcyclohexanol.

The amount of the organic solvents preferably ranges from 1 to 5% by weight with respect to the total weight of the developercomposition practically employed. The amount of the organic solvent is closely related

45 to that of the surfactant. More specifically, the amount of the anionic surfactant should be increased with the increase in that of the organic solvent. This is because if the amount of the anionic surfactant is low and that of the organic solvent is great, the organic solvent is not solubilized in water and as a result, good developing properties of the composition cannot be ensured.

The developercomposition of the invention may optionally comprise additives such as antifoaming agents so and/or water softeners. Examples of water softeners include polyphosphates such as Na2P207, Na5P303,

Na3P309, Na204P(Na03P)P03Na2 and Calgon (trade name of sodium polymetaphosphate, available from Cal- gon Inc. (U.S.A.)); polyaminocarboxylic acids and salts thereof such as ethylenediaminetetraacetic acid and potassium and sodium salts thereof, diethylenetriaminepentaacetic acid and potassium and sodium salts thereof, triethylenetetraminehexaacetic acid and potassium and sodium salts thereof, hydroxyethylethylene-

55 diaminetriacetic acid and potassium and sodium salts thereof, nitrilotriacetic acid and potassium and sodium salts thereof, 1,2-diaminocyclohexanetetraacetic acid and potassium and sodium salts thereof and 1,3-diamino-2-propanoltetraacetic acid and potassium and sodium salts thereof; and organophosphonic acids, potassium, sodium and ammonium salts thereof such as amino tri(methylene phosphonic acid), ethylenediamine tetra(methylene phosphonic acid), diethylenetriamine penta(methylene phosphonic acid), triethylenetetra-

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EP 0 390 480 B1

mine hexa(methylene phosphonic acid), and hydroxyethylethylenediamine tri(methylene phosphonic acid). The optimum amount of the water softener varies depending on the hardness and the amount of hard water

used, but the amount thereof in general ranges from 0.01 to 5% by weight and preferably 0.01 to 0.5% by weight 5 on the basis of the total weight of the developer composition practically used.

It is preferable to store an aqueous solution (Solution A) containing a compound of formula (I) and an aqueous solution (Solution B) containing an alkaline agent and to combine Solutions Aand B when used to prepare the developer composition of the present invention. Anionic surfactants, organic solvents, water softeners and/or antifoaming agents, if they are used, may be added to Solution A, Solution B or both.

10 The PS plates which have been treated with the developer of the invention may optionally be subjected to water washing followed by a desensitization treatment; to a desensitization treatment without water washing; to a treatment with an aqueous solution containing an acid; or to a treatment with an aqueous solution containing an acid followed by a desensitization treatment.

Moreover, in the developing process of the PS plate of this kind, the working efficiency of the developer 15 is reduced due to the reduction of the alkali concentration. The reduction of the alkali concentration is caused

due to consumption thereof with the quantity of PS plates processed and oxidation by air observed after a long run of an automatic developing machine. The working efficiency of the developer may be restored by the supplementation of a replenisher for developer as disclosed in Japanese Patent Un-examined Publication (hereunder referred to as "J.P. KOKAI") No. Sho 54-62004.

20 The light-sensitive diazo resins to be incorporated into negative-working light-sensitive layers to which the developer of the invention is applied are those disclosed in U.S. Patent Nos. 2,679,498; 3,050,502; 3,163,633; and 3,406,159; and J.P. KOKOKU Nos. Sho 49-48001 and Sho 49-45322, which are made substantially water-insoluble and organic solvent-soluble according to the methods disclosed in J.P. KOKOKU No. Sho47-1167, U.S. Patent No. 3,300,309; J. P. KOKAI Nos. Sho 54-98613, Sho 56-121031, Sho 59-78340, Sho

25 59-22834 and Sho 63-262643. More specifically, the light-sensitive diazo resins are first synthesized in the form of inorganic salts such as zinc chloride complex salts and then converted into salts with organic compounds having phenolic hydroxyl groups or sulfonate groups or both of them, or into salts with hexafluorophos- phoric acid or tetraf luoroboric acid or complex salts thereof to thus make the light-sensitive diazo resins water- insoluble.

30 In the light-sensitive layer of PS plates, a hydrophobic resin is in general used in combination with the foregoing substantially water-insoluble diazo resin and various such hydrophobic resins are known and used in this field. These hydrophobic resins are substantially selected, in the present invention, depending on requirements specific to each plate-making technique. Of course, the resins must be lyophi lie to impart sufficient ink receptivity to the resulting lithographic printing plates, must further be physically and chemically compat-

35 ible with the light-sensitive diazo resins which are soluble in the usual organic solvents and hardly soluble or completely insoluble in water and must have film-forming ability. In particular, the resin is desirably those having hardness, elasticity and flexibility to some extent since the resin serves as a substrate which is excellent in compatibility with ink and on which an ink film is formed. Thus the resin on the substrate can withstand the friction during printing operation to provide several tens of thousands to several hundreds of thousands of print-

40 ed matters. Examples of the resins which satisfy the foregoing requirements include epoxy resins; polyamide resins;

halogenated vinyl resins, in particular polyvinyl chloride; polyvinylidene chloride; chlorinated polyolef ins; polyvinyl acetates; acetal resins such as formals and butyrals; soluble urethane resins such as those available from GOODRICH CO., LTD. (U.S.A.) under the trade name of ESTANE; styrene/maleic anhydride copolymers,

45 their half esters or half amides; cellulose derivatives; shellac, rosin or modified products thereof; acrylic acid/acrylate copolymers; multi component copolymers of 2-hydroxyethyl (met h)acry late, (meth)acrylonitrile, (meth)acrylic acid and optional other copolymerizable monomers as disclosed in J.P. KOKAI No. Sho 50- 118802 (U.S. Pat. No. 4,123,276); multicomponent copolymers of (meth)acrylic acid which is esterified with dicarboxylic acid ester residue and has a hydroxyl group at its end, (meth)acrylic acid and optional other co-

50 polymerizable monomers as disclosed in J.P. KOKAI No. Sho 53-120903; multicomponent copolymers of a monomer having aromatic hydroxyl groups (such as N-(4-hydroxyphenyl) methacrylamide), (meth)acrylic acid and optional other copolymerizable monomers as disclosed in J.P. KOKAI No. Sho 54-98614 and U.S. Pat. No. 4,731,316; and multicomponent copolymers of alkyl acrylates, (meth)acrylonitrile and unsaturated carboxylic acids as disclosed in J.P. KOKAI No. Sho 56-4144 (U.S. Pat. No. 4,304,832).

55 in addition, acidic polyvinyl alcohol derivatives and acidic cellulose derivatives are also useful in the invention. Other useful examples of the hydrophobic resins include high molecular weight polymers obtained by making polyvinyl acetals or polyurethanes alkali-soluble such as those disclosed in J.P. KOKOKU No. Sho 54-19773 (U.S. Pat. No. 3,732,105) and J.P. KOKAI Nos. Sho 57-94747 (U.S. Pat. No. 4,387,151), Sho 60- 182437 (U.S. Pat. No. 4,631,245), Sho 62-58242 and Sho 62-123453 (B.P. No. 2,185,120).

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EP 0 390 480 B1

Alight-sensitive solution for forming a light-sensitive layer is in general prepared by dissolving the water- insoluble diazo resin and the foregoing hydrophobic resin in a proper solvent such as lower alcohols, glycol ether, dialkylformamides, chlorinated solvents or a mixture thereof, optionally adding a dye or a pigment to

5 color the solution and optionally adding other components such as plasticizers, dyes for printing out and sta- bilizers. The light-sensitive layer of a negative-working PS plate can be obtained by applying the light-sensitive layer on a proper substrate and then drying.

On the other hand, the positive-working light-sensitive layer to which the developer of the invention is applied can be obtained from compositions which have been known as positive-working light-sensitive com-

10 positions containing o-quinonediazide compounds. Particularly preferred are those obtained from light- sensitive compositions containing o-quinonediazide compounds and phenolic resins.

The o-quinonediazide compounds are those which have at least one o-quinonediazide group and whose alkali-solubility is enhanced by irradiating with actinic rays. Such o-quinonediazide compounds which can be employed in the present invention may have a variety of structures. These o-quinonediazide compounds are

15 detailed in "Light-Sensitive Systems", J. Koser, published by John Wiley & Sons, Inc. (pp. 339 - 352). Partic- ularly preferred are sulfonic acid esters or sulfonamides of o-quinonediazide obtained through a reaction with aromatic polyhydroxyl compounds or aromatic amine compounds.

The most preferred o-quinonediazide compounds are esters of benzoquinone-(1,2)-diazidosulfonic acid chloride or naphthoquinone-(1,2)-diazidosulfonic acid chloride with pyrogallol-acetone resin as disclosed in

20 J.P. KOKOKU No. Sho 43-28403 (U.S. Pat. No. 3,635,709). Other preferred o-quinonediazide compounds are, for instance, esters of benzoquinone-(1,2)-diazidosulfonic acid chloride or naphthoquinone-(1,2)-diazidosulfonic acid chloride with phenol-formaldehyde resin as disclosed in U.S. Patent Nos. 3,046,120 and 3,188,210.

Examples of further preferred o-quinonediazide compounds include those known and disclosed in a variety of patents such as J.P. KOKAI Nos. Sho 47-5303, Sho 48-63802, Sho 48-63803, Sho 48-96575, Sho 49-

25 38701 and Sho 48-13354, J.P. KOKOKU Nos. Sho 41-11222, Sho 45-9610 and Sho 49-17481, U.S. Patent Nos. 2,797,213; 3,454,400; 3,544,323; 3,573,917; 3,674,495 and 3,785,825; U.K. Patent Nos. 1,227,602; 1,251,345; 1,267,005; 1,329,888 and 1,330,932; and German Patent No. 854,890.

The positive-working light-sensitive composition may comprise only o-quinonediazide compounds such as those listed above, but preferably the o-quinonediazide compounds are used in combination with a binder.

30 Preferred examples of such binders are aqueous alkaline solution-soluble novolak resins. Typical examples thereof include phenol-formaldehyde resins, cresol-formaldehyde resins, phenol-cresol-formaldehyde resins, p-tert-butylphenol-formaldehyde resins and phenol-modified xylene resins.

Besides, polyvinyl compounds having phenolic hydroxyl groups such as polyhydroxystyrene polymers and copolymers thereof; and halogenated polyhydroxystyrene polymers and copolymers thereof are also useful

35 as the binder. The amount of the o-quinonediazide compounds preferably ranges from 10 to 50% by weight and more

preferably 20 to 40% by weight on the basis of the total weight of the light-sensitive composition. On the other hand, that of the resins having phenolic hydroxyl groups serving as binders ranges from 45 to 80% by weight and preferably 50 to 70% by weight on the basis of the total weight of the light-sensitive composition.

40 The positive-working light-sensitive composition may further comprise fillers, dyestuff, dyes, pigments, photolyt ically decomposable acid-generators such as 1,2-naphthoquinone-(2)-4-sulfonic acid chloride and/or fluorine atom-containing surfactants for improving coating properties of the composition as well as other additives and auxiliary agents usually employed in compositions of this kind. The amount of these additives varies depending on the kinds thereof, but in general ranges from 0.01 to 20% by weight and preferably 0.05 to

45 1 0% by weight on the basis of the total weight of the light-sensitive composition. A light-sensitive solution for forming a positive-working light-sensitive layer is likewise prepared by dis-

solving the o-quinonediazide compound and the aforesaid resin as a binder in a proper solvent such as those listed above in connection with the negative-working light-sensitive layer and optionally adding other components such as those listed above. The light-sensitive layer of a positive-working PS plate can be obtained by

so applying the light-sensitive layer on a proper substrate and then drying. The aforementioned light-sensitive layer (inclusive of both positive and negative ones) is applied onto the

surface of a variety of substrates selected depending on purposes. Examples of materials for such substrates are paper; paper laminated with a plastic film of, for instance, polyethylene, polypropylene or polystyrene; a metal plate such as an aluminum (inclusive of alloys thereof), zinc or copper plate; a plastic film such as a

55 cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate or polyvinyl acetal film; and paper or a plastic film which is laminated with a foil of the foregoing metal or onto which one of the foregoing metal is deposited. Metal substrates such as aluminum plates are preferably employed in particular for manufacturing PS plates.

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EP 0 390 480 B1

In the case of using a metal support having, in particular, aluminum surface, it is preferred that the support is subjected to a surface treatment such as graining treatment, dipping treatment in an aqueous solution of, for example, sodium silicate, potassium fluorozirconate or a phosphate, or an anodic oxidation treatment.

5 Furthermore, an aluminum plate which is grained and then subjected to a dipping treatment in an aqueous solution of sodium silicate is preferably used in this invention. Also, an aluminum plate subjected to an anodic oxidation treatment and then dipping treatment in an aqueous solution of an alkali metal silicate such as that described in U.S. Patent No. 3,181,461 is suitably used. The aforesaid anodic oxidation treatment is carried out by passing electric current in an electrolyte composed an aqueous solution or non-aqueous solution of an

10 inorganic acid (such as phosphoric acid, chromic acid, sulfuric acid, or boric acid), an organic acid (such as oxalic acid, or sulfamic acid), or a salt thereof singly or as a combination of the solutions, using an aluminum plate as the anode.

Also, the application of electrodeposition of silicate such as that described in U.S. Patent No. 3,658,662 is effective in this invention.

15 Furthermore, a support electrolytically grained such as that disclosed in J.P. KOKAI No. Sho 46-27481 , J.P. KOKAI Nos. Sho 52-58602 and Sho 52-30503, which is further subjected to a combined surface treatment of the above-described anodic oxidation treatment and sodium silicate treatment, is also useful.

Also, an aluminum support subjected to mechanical graining, chemical etching, electrolytic graining, anodic oxidation treatment, and further sodium silicate treatment such as that disclosed in J.P. KOKAI No. Sho

20 56-28893 may be used in the present invention. Still further, an aluminum support which is subjected to the above-described surface treatment or treat-

ments and then under-coated with a water-soluble resin such as polyvinylphosphonic acid, a polymer or a copolymer having a sulfonic group at the side chain, polyacrylic acid, a water-soluble metal salt (e.g., zinc borate), a yellow dye, and/or an amine may be used.

25 PS plates may be prepared by dissolving the foregoing light-sensitive composition in a proper solvent, applying the solution onto the surface of the aluminum substrate thus treated in an amount ranging from 0.1 to 7 g/m2 and preferably 0.2 to 5 g/m2 (determined after drying) and then drying the coated film.

Alithographic printing plate, which is obtained by imagewise exposing a negative-working PS plate to light from a light source rich in ultraviolet rays such as a metal halide lamp and then developing the PS plate with

30 the developer composition of the present invention, can always provides printed matters free of background contamination. In addition, if the pH value of the developer of the present invention is controlled to not less than 12, a positive-working PS plate which is likewise imagewise exposed to light can also be developed with the developer of the invention and the resulting lithographic printing plate provides good printed matter.

As explained above, the developercomposition of the present invention whose pH is adjusted to not less 35 than 12 makes it possible to treat both negative-working and positive-working PS plates. For this reason, the

working efficiency is greatly improved since it is not necessary to previously provide two kinds of developer compositions and two kinds of developing machines. Besides, initial cost can be saved and the space for installing such machines are also greatly reduced.

The developer composition of the present invention will hereunder be described in more detail with refer- 40 ence to the following non-limitative working Examples and the effects practically achieved by the present in-

vention will also be discussed in detail in comparison with Comparative Examples.

Examples 1 and 2 and Comparative Example 1

45 A2S aluminum plate having a thickness of 0.15 mm was immersed in a 10% aqueous solution of sodium tertiary phosphate maintained at 8°C for 3 minutes to degrease the plate. After the plate was grained with a nylon brush and a slurry of pumice stone as an abrasive, it was desmutted with a 3% aqueous solution of sodium aluminate maintained at 60°C . Subsequently, the aluminum plate was anodized in a 20% sulfuric acid solution for 2 minutes at a current density of 2 A/dm2 and then treated with a 2.5% aqueous solution of sodium

so silicate at 70 ° C for one minute. Then there was applied, to the surface of the aluminum plate, a solution of light-sensitive composition (hereunder referred to as "light-sensitive solution") which comprised 10 g of hex- afluorophosphate of a condensate of p-diazodiphenylamine with paraformaldehyde (degree of PF6 salt- substitution = 89%), 90 g of 2-hydroxyethyl methacrylate/acrylonitrile/ethyl methacrylate/methacrylic acid (50/26/20/4 wt%; weight ratio of charged monomers), 1 g of sodium isopropylnaphthalene sulfonate, 2 g of

55 phosphorous acid, 3 g of Victoria Pure Blue BOH (available from HODOGAYA CHEMICAL CO., LTD.), 7 g of tricresyl phosphate, 600 g of ethylene glycol monomethyl ether, 600 g of methanol and 600 g of ethylene di- chloride and then the coated film of the solution was dried at 100° C for 2 minutes to give a PS plate. The coated amount (determined after drying) of the light-sensitive layer was equal to 1 .5 g/m2.

The PS plates thus prepared were exposed to light and developed with a developer having the following

9

EP 0 390 480 B1

composition with an automatic developing machine 800U (available from Fuji Photo Film Co., Ltd.). The lithographic printing plates obtained in Examples 1 and 2 never caused background contamination unlike the lithographic printing plate obtained in Comparative Example 1. The developers listed in Table I were diluted

5 1/10 (volume ratio) prior to use.

Table I

Component Amount (pa r t by w e i g h t )

Comp. Ex.1 Ex. 1 Ex. 2

1 - P h e n y l e t h a n o l 85 85 85

T r i e t h a n o l a m i n e 30 30 30

Monoethanolamine 2 2 2

Potassium n a p h t h a l e n e s u l f o n a t e 25 25 25

Water 60 60 60

Compound of formula (I) — (a) 3 (b) 3

EDTA ( e t h y l e n e d i a m i n e t e t r a a c e t i c acid) 0.05 0.05 0 . 0 5

pH 10.7 10.5 10 .5

30 Example 3 and Comparative Example 2

300 g of ethylene glycol monoethyl ether was heated to 100° C in a stream of nitrogen gas and there were dropwise added 70 g of 2-hydroxyethyl methacrylate, 80 g of acrylonitrile, 130 g of benzyl methacrylate, 20 g of methacrylicacid and 1 .2 g of benzoyl peroxide thereto over 2 hours. 15 Minute after the dropwise addition,

35 300 g of ethylene glycol monomethyl ether and 0.3 g of benzoyl peroxide were added to the reaction mixture and the reaction was continued for additional 4 hours. After the completion of the reaction, the reaction mixture was diluted with methanol, poured into water to precipitate the resulting copolymer and the copolymer was dried in vacuo at 70°C. The acid value of the resulting 2-hydroxyethyl methacrylate copolymer (A) was found to be 40.2.

40 A light-sensitive solution having the following composition was applied onto the surface of an aluminum plate which had been subjected to the same treatments used in Examples 1 and 2 and then dried at 100°C for 2 minutes to thus give a PS plate. The coated amount of the light-sensitive layer was 2.5 g/m2 (determined after drying).

10

EP 0 390 480 B1

Component Amount ( g )

2 -Hydroxye thy l m e t h a c r y l a t e copolymer (A) 87

2 -Methoxy-Zj -hydroxy-5-benzoy l benzene s u l f o n a t e 10

of the c o n d e n s a t e of p - d i a z o d i p h e n y l a m i n e and

p a r a f o r m a l d e h y d e

Oil Blue 603 ( t r i p h e n y l methane type o i l - 3

s o l u b l e dye; a v a i l a b l e from ORIENT CHEMICAL

INDUSTRIES LTD.)

2 -Methoxye thano l 60q

Methanol 600

Ethylene d i c h l o r i d e 500

An original negative transparency was closely placed on the PS plate thus obtained, the plate was imagewise exposed to light from a 30 Acarbon arc lamp at a distance of 80 cm for 50 seconds and then developed with each developer listed in Table II below with an automatic developing machine 800H (available from Fuji Photo Film Co., Ltd.). The result obtained are summarized in Table III given below.

Table I I

Component Amount (g)

Comp. Ex. 2 Ex. 3

Sodium a lky lnaphtha lene su l fona te (ava i lab le 30 30

from Kao Atlas Co . , Ltd . under the t r a d e

name of PELEX NBL)

Benzyl alcohol 3° 3°

Triethanolamine 20 20

Monoethanolamine ̂ ^

N i t r i l o t r i a c e t i c acid 0.1 0.1

Sodium s u l f i t e 3 0

2-Methylresorcin 0 3

Water to 1000 ml 1000 ml

pH 10.6 10. n

11

EP 0 390 480 B1

Table I I I

Ex. No. Storage Time Background Contamination Observed Under of Developer Forced Conditions (stored at 60° C for 3 days )

Comp. 0 no background con tamina t ion

Ex. 2 one y e a r s l i g h t l y contaminated if the amount of dampen-

ing water is reduced.

Ex. 3 0 no background con tamina t ion

one yea r no background con tamina t ion

As seen from the results listed in Table III, if the developercomposition containing 2-methylresorcin was used, the resulting lithographic printing plate caused no background contamination even when the developer was stored for a long time and when the plate was prepared from the PS plate which had been stored under the forced conditions (60°C for 3 days).

Example 4 and Comparative Example 3

An aluminum plate (1050) having a thickness of 0.24 mm was degreased by washing it with trichloroethy- lene, the surface of the plate was grained with a nylon brush and an aqueous suspension of pumice stone and then sufficiently washed with water. The plate was etched by immersing it in a 25% aqueous solution of sodium hydroxide maintained at 45°C for 10 seconds, washed with water, then immersed in a 20% aqueous solution of nitric acid for 20 seconds and washed with water. The etched quantity of the plate was about 3 g/m2. Then the plate was anodized with the use of a direct current at a current density of 15 A/dm2 in a 7% sulfuric acid solution as an electrolyte to form an anodized layer (25 g/m2), washed with water and dried. There- after, a light-sensitive solution having the following composition was applied onto the surface of the aluminum plate thus treated and dried at 100 ° C for 90 seconds to give a positive-working PS plate. The amount of the light-sensitive layer applied was 2 g/m2 (determined after drying).

12

EP 0 390 480 B1

L i g h t - s e n s i t i v e S o l u t i o n

Component Amount <6)

E s t e r i f i e d product of naph thoqu inone - 1 , 2 - d i a z i d o - 0 . 9 0

5 - s u l f o n i c acid c h l o r i d e and p y r o g a l l o l / a c e t o n e

r e s i n (Note 1)

C r e s o l / f o r m a l d e h y d e r e s in 1-70

t - B u t y l p h e n o l / f o r m a l d e h y d e r e s i n (Note 2) 0 . 0 5

Naphthoquinone- 1 , 2 - d i a z i d o - U - s u l f o n i c acid c h l o r i d e 0 . 0 3

T e t r a h y d r o p h t h a l i c acid anhydr ide ° - 2 0

Oil Blue #603 (blue dye a v a i l a b l e from ORIENT 0 . 0 5

CHEMICAL INDUSTRIES CO., LTD.)

Methyl e thyl ketone 8

Ethylene g lycol monomethyl e the r 15

Note 1: The compound de sc r i bed in Example 1 of U.S. P a t e n t

No. 3 , 6 3 5 , 7 0 9 .

Note 2: The compound de sc r i bed in U.S. Pa tent No. 4 , 1 2 3 , 2 7 9 .

This positive-working PS plate was exposed to light from a 1 .5 KW metal halide lamp at a distance of 90 cm and then developed with each of the developers listed in Table IV below with an automatic developing machine 800U (available from Fuji Photo Film Co., Ltd.).

As a result, lithographic printing plates from which the exposed portions were completely dissolved out and removed were obtained. In particular, when the developer of Example 4 was employed, the coupling be- tween the decomposed o-quinonediazide and the undecomposed one was not observed even after 2 m2/ 1 of the PS plate was processed, the substrate was not contaminated by the coupling product and the resulting lithographic printing plate provided good printed matter free of background contamination.

On the other hand, when the developer of Comparative Example 3 was employed, the foregoing coupling was observed and the removal of the film-edge portion was necessary. Moreover, no background contamination was observed on the printed matter produced by the lithographic printing plate prepared by developing a negative-working PS plate used in Example 1 with the developer of Example 4. However, the lithographic printing plate obtained by the use of the developer of Comparative Example 3 produced printed matter having background contamination.

As has been explained above in detail, the processing of both negative-working and positive-working PS plates can be performed in the same automatic developing machine with the same developer, if the developer composition of the present invention is adopted.

13

EP 0 390 480 B1

Table IV

Component . Amount (g)

Ex. U Comp. Ex. 3

Sodium naphthalene su l fona t e ̂ n

0.3 0 2 - M e t h y l r e s o r c i n

* These d e v e l o p e r s were p repared by adding the compounds l i s t e d i n

Table IV to Ml of a 2.5 wt* aqueous s o l u t i o n of potass ium s i l i c a t e

(the molar r a t i o , Si02/K20, was 1 . 1 ) .

Claims

1. A developer composition comprising an alkaline agent, water, and an aromatic compound represented by the following general formula (I):

wherein A represents a hydrogen atom or a fused ring which may have substituents; R1 represents a hydrogen atom, a lower alkyl group or a lower alkoxy group; and M represents hydrogen, sodium, potassium or an ammonium group.

2. The developercomposition of claim 1 wherein in formula (I), A represents a hydrogen atom, a phenyl ring or a naphthyl ring which may be substituted with at least one substituent selected from alkyl groups having 1 to 1 2 carbon atoms, alkenyl groups having 2 to 1 2 carbon atoms and aralkyl groups having 7 to 1 2 carbon atoms; R1 is selected from hydrogen, and alkyl and alkoxy groups having 1 to 6 carbon atoms; and M is selected from sodium and potassium atoms and ammonium groups represented by the general formula: NR2R3R4R5 wherein R2 to R5 may be the same or different and each represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms which may have substituents.

3. The developercomposition of Claim 1 wherein the amount of the aromatic compound ranges from 0.001 to 10% by weight on the basis of the total weight of the developercomposition.

4. The developer composition of Claim 1 wherein the alkaline agent is at least one of sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, sodium tertiary phosphate, sodium secondary phosphate, ammonium tertiary phosphate, ammonium secondary phosphate, sodium metasilicate, sodium bicarbonate, sodium borate, ammonium borate, ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n- butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine and pyridine.

14

EP 0 390 480 B1

10

15

5. The developercomposition of Claim 1 wherein the amount of the alkaline agent ranges from 0.05 to 10% by weight on the basis of the total weight of the developer composition practically used.

5 6. The developer composition of Claim 5 wherein the amount of the alkaline agent ranges from 0.1 to 7% by weight on the basis of the total weight of the developer composition practically used.

7. The developer composition of Claim 1 wherein the pH value of the developer composition is adjusted to not less than 12.

10 8. the developer composition of Claim 1 further comprising at least one anionic surfactant selected from sodium salt of lauryl alcohol sulfate; sodium salt of octyl alcohol sulfate; ammonium salt of lauryl alcohol sulfate; salts of higher alcohol sulfuric acid esters having 8 to 22 carbon atoms; salts of aliphatic alcohol phosphoric acid esters; salts of alkylarylsulfonic acids; alkylaryl carboxylic acid salts; sulfonic acid salts of alkylamides; sulfonic acid salts of dibasic aliphatic acid esters; and salts of aryloxyalkylene sulfuric acid esters.

9. The developer composition of Claim 8 wherein the amount of the anionic surfactant ranges from 0.1 to 5% by weight on the basis of the total weight of the developer composition practically employed.

20 10. The developercomposition of Claim 1 further comprising at least one organic solvent having a solubility in water of not more than about 10% by weight, selected from 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol-1 , 4-phenylbutanol-1 , 4-phenylbutanol-2, 2-phenylbutanol-1 , 2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 4-methylcyclohexanol and 3-methylcyclohexanol.

25 11. The developer composition of Claim 8 wherein the amount of the organic solvent ranges from 1 to 5%

by weight on the basis of the total weight of the developer composition practically employed.

12. The developercomposition of Claim 1 further comprising antifoaming agents and/or water softeners and 30 the water softener is at least one of Na2P207, Na5P303, Na3P309, Na204P(Na03P)P03Na2, Calgon, ethy-

lene-diaminetetraacetic acid and potassium and sodium salts thereof, diethylenetriaminepentaacetic acid and potassium and sodium salts thereof, triethylenetetraminehexaaceticacid and potassium and sodium salts thereof, hydroxyethylethylenediaminetriacetic acid and potassium and sodium salts thereof, nitrilotriacetic acid and potassium and sodium salts thereof, 1 ,2-diaminocyclohexanetetraacetic acid and

35 potassium and sodium salts thereof and 1,3-diamino-2-propanoltetraacetic acid and potassium and sodium salts thereof.

13. The developer composition of Claim 12 wherein the amount of the water softener ranges from 0.01 to 5% by weight on the basis of the total weight of the developer composition practically used.

40 14. A process for developing a presensitised lithographic printing plate which comprises either i) developing an imagewise light-exposed, positive working, presensitized plate having a substrate with an imagewise light-exposed positive working light-sensitive layer containing an o-quinonediazide compound with the developer composition of any one of Claims 1 to 13 to remove light-exposed areas of the positive working light-sensitive layer, to provide a lithographic printing layer, or ii) developing an imagewise light-exposed, negative working, presensitized plate having a substrate with an imagewise light-exposed negative working light-sensitive layer containing a diazo resin with the developercomposition of any one of Claims 1 to 1 3 to remove light-unexposed areas of the negative working light-sensitive layer, to provide a lithographic printing layer.

50 15. The process of Claim 14 wherein after the presensitised plate is developed, it is further subjected to water washing followed by a desensitisation treatment; directly to a desensitisation treatment without water washing; to a treatment with an aqueous solution containing an acid; or to a treatment with an aqueous solution containing an acid followed by a desensitisation treatment.

55 16. The process of claim 14 wherein a replenisher for developer is supplemented to the developer during de- velopment processing.

17. The method of claim 14, wherein the image-forming layer of the negative-working presensitised printing plate comprises a substantially water-insoluble and organic solvent-soluble light-sensitive diazo resin and

45

15

EP 0 390 480 B1

a hydrophobic resin.

Patentanspruche

1. Entwicklerzusammensetzung, umfassend ein alkalisches Mittel, Wasser und eine aromatische Verbin- dung, die durch die folgende allgemeine Formel (I) dargestellt ist:

worin A ein Wasserstoffatom odereinen kondensierten Ring bedeutet, derSubstituenten haben kann; R1 ein Wasserstoffatom, eine niedere Alkylgruppe oder eine niedere Alkoxygruppe bedeutet; und M Was- serstoff, Natrium, Kalium oder eine Ammoniumgruppe bedeutet.

2. Entwicklerzusammensetzung nach Anspruch 1, worin in Formel (I) A ein Wasserstoffatom, einen Phe- nylring oder einen Naphthylring bedeutet, welcher mit mindestens einem Substituenten, ausgewahlt aus Alkylgruppen mit 1 bis 12 Kohlenstoffatomen, Alkenylgruppen mit 2 bis 12 Kohlenstoffatomen und Aralkylgruppen mit7 bis 12 Kohlenstoffatomen, substituiertsein kann; R1 ausgewahlt ist aus Wasserstoff und Alkyl- und Alkoxygruppen mit 1 bis 6 Kohlenstoffatomen; und M ausgewahlt ist aus Natrium- und Ka- liumatomen und Ammoniumgruppen, die durch die allgemeine Formel; NR2R3R4R5 dargestellt sind, worin R2 bis R5 gleich oder verschieden sein konnen und jeweils ein Wasserstoffatom oder eine niedere Alkyl- gruppe mit 1 bis 6 Kohlenstoffatomen, welche Substituenten haben kann, bedeutet.

3. Entwicklerzusammensetzung nach Anspruch 1, worin die Menge der aromatischen Verbindung im Be- reich von 0,001 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Entwicklerzusammensetzung, liegt.

4. Entwicklerzusammensetzung nach Anspruch 1 , worin das alkalische Mittel mindestens eines von Natri- umsilicat, Kaliumsilicat, Natriumhydroxid, Kaliumhydroxid, Natriumtertiarphosphat, Natrium-sekundarphosphat, Ammoniumtertiarphosphat, Ammonium-sekundarphosphat, Natriummetasilicat, Natriumbicar- bonat, Natriumborat, Ammoniumborat, Ammoniak, Monomethylamin, Dimethylamin, Trimethylamin, Mo- noethylamin, Diethylamin, Triethylamin, Monoisopropylamin, Diisopropylamin, n-Butylamin, Monoetha- nolamin, Diethanolamin, Triethanolamin, Monoisopropanolamin, Diisopropanolamin, Ethylenimin, Ethyl- endiamin und Pyridin ist.

5. Entwicklerzusammensetzung nach Anspruch 1, worin die Menge des alkalischen Mittels im Bereich von 0,05 bis 1 0 Gew.-%, bezogen auf das Gesamtgewicht der praktisch verwendeten Entwicklerzusammen- setzung, liegt.

6. Entwicklerzusammensetzung nach Anspruch 5, worin die Menge des alkalischen Mittels im Bereich von 0,1 bis 7 Gew.-%, bezogen auf das Gesamtgewicht der praktisch verwendeten Entwicklerzusammenset-

7. Entwicklerzusammensetzung nach Anspruch 1 , worin der pH-Wertder Entwicklerzusammensetzung auf nicht weniger als 12 eingestellt ist.

8. Entwicklerzusammensetzung nach Anspruch 1 , welche ferner mindestens ein anionisches oberf lachen- aktives Mittel, ausgewahlt aus Natriumsalz von Laurylalkoholsulfat; Natriumsalz von Octylalkoholsulfat; Ammoniumsalz von Laurylalkoholsulfat; Salzen von hoheren Alkohol-Schwefelsaureestern mit 8 bis 22 Kohlenstoffatomen; Salzen von aliphatischen Alkohol-Phosphorsaureestern; Salzen von Alkylarylsulfon- sauren; Alkylarylcarbonsauresalzen; Sulfonsauresalzen von Alkylamiden; Sulfonsauresalzen von zweiba- sischen aliphatischen Saureestern; und Salzen von Aryloxyalkylen-Schwefelsaureestern, umfalit.

0"R+

( I )

zung, liegt.

16

EP 0 390 480 B1

9. Entwicklerzusammensetzung nach Anspruch 8, worin die Menge des anionischen oberflachenaktiven Mittels im Bereich von 0,1 bis 5Gew.-%, bezogen auf das Gesamtgewicht der praktisch eingesetzten Ent- wicklerzusammensetzung, liegt.

10. Entwicklerzusammensetzung nach Anspruch 1, welche ferner mindestens ein organisches Losungsmittel mit einer Loslichkeit in Wasser, die nicht mehr als etwa 10 Gew.-% betragt, ausgewahlt aus 1-Phenyl- ethanol, 2-Phenylethanol, 3-Phenylpropanol-1 , 4-Phenylbutanol-1 , 4-Phenylbutanol-2, 2-Phenylbutanol- 1, 2-Phenoxyethanol, 2-Benzyloxyethanol, o-Methoxybenzylalkohol, m-Methoxybenzylalkohol, p-Me- thoxybenzylalkohol, Benzylalkohol, Cyclohexanol, 2-Methylcyclohexanol, 4-Methylcyclohexanol und 3- Methylcyclohexanol, umfalit.

11. Entwicklerzusammensetzung nach Anspruch 8, worin die Menge des organischen Losungsmittels im Be- reich von 1 bis 5 Gew.-%, bezogen auf das Gesamtgewicht der praktisch eingesetzten Entwicklerzusam- mensetzung, liegt.

12. Entwicklerzusammensetzung nach Anspruch 1, welche ferner Antischaummittel und/oder Wasserent- hartungsmittel umfalit und wobei das Wasserenthartungsmittel mindestens eines von Na2P207, Na5P303, Na3P309, Na204P(Na03P)P03Na2, Calgon, Ethylendiamin-tetraessigsaure und Kalium- und Natriumsal- zen davon, Diethylentriamin-pentaessigsaure und Kalium- und Natriumsalzen davon, Triethylen-tetra- min-hexaessigsaure und Kalium- und Natriumsalzen davon, Hydroxyethylethylendiamin-triessigsaure und Kalium- und Natriumsalzen davon, Nitrilo-triessigsaure und Kalium- und Natriumsalzen davon, 1,2- Diaminocyclohexan-tetraessigsaure und Kalium- und Natriumsalzen davon und 1,3-Diamino-2-propanol- tetraessigsaure und Kalium- und Natriumsalzen davon ist.

13. Entwicklerzusammensetzung nach Anspruch 12, worin die Menge des Wasserenthartungsmittels im Be- reich von 0,01 bis 5 Gew.-%, bezogen auf das Gesamtgewicht der praktisch verwendeten Entwicklerzu- sammensetzung, liegt.

14. Verfahren zum Entwickeln einer vorsensibilisierten lithographischen Druckplatte, welches entweder i) das Entwickeln einer bildmaliig belichteten positiv arbeitenden vorsensibilisierten Platte mit einem Substrat mit einer bildmaliig belichteten positiv arbeitenden lichtempf indlichen Schicht, die eine o-Chi- nondiazidverbindung enthalt, mit der Entwicklerzusammensetzung nach einem der Anspruche 1 bis 13, urn belichtete Stellen der positiv arbeitenden lichtempf indlichen Schicht zu entfernen, urn eine li- thographische Druckschicht zu ergeben, oder ii) das Entwickeln einer bildmaliig belichteten negativ arbeitenden vorsensibilisierten Platte mit einem Substrat mit einer bildmaliig belichteten negativ arbeitenden lichtempfindlichen Schicht, die ein Diazoharz enthalt, mit der Entwicklerzusammensetzung nach einem der Anspruche 1 bis 13, urn un- belichtete Stellen der negativ arbeitenden lichtempfindlichen Schicht zu entfernen, urn eine lithogra- phische Druckschicht zu ergeben, umfalit.

15. Verfahren nach Anspruch 14, worin die vorsensibilisierte Platte, nachdemsieentwickeltworden ist, weiter einem Waschen mit Wasser, gefolgt von einer Desensibilisierungsbehandlung; direkt einer Desensibili- sierungsbehandlung ohne Waschen mit Wasser; einer Behandlung mit einer walirigen Losung, die eine Saure enthalt; oder einer Behandlung mit einer walirigen Losung, die eine Saure enthalt, gefolgt von einer Desensibilisierungsbehandlung, unterzogen wird.

16. Verfahren nach Anspruch 14, worin eine Nachfullosung fur den Entwickler dem Entwickler wahrend der Entwicklungsbehandlung zugesetzt wird.

17. Verfahren nach Anspruch 14, worin die bilderzeugende Schicht der negativ arbeitenden vorsensibilisierten Druckplatte ein im wesentlichen wasserunlosliches und in organischem Losungsmittel losliches lichtempf indliches Diazoharz und ein hydrophobes Harz umfalit.

Revendications

1. Composition de developpateur comprenant un agent alcalin, de I'eau et un compose aromatique represents par la formule generale (I) suivante

17

EP 0 390 480 B1

dans laquelle A represents un atome d'hydrogene ou un noyau condense qui peut comporter des substituants; R1 represents un atome d'hydrogene, un groupe alkyle inferieur ou un groupe alcoxy inferieur; et M represents un atome d'hydrogene, de sodium, de potassium ou un groupe ammonium.

Composition de developpateur selon la revendication 1, dans laquelle, dans la formule (I), A represents un atome d'hydrogene, un noyau phenyle ou un noyau naphtyle, qui peutetre substitue parau moins un substituant choisi parmi les groupes alkyle comportant 1 a 12 atomes de carbone, les groupes alcenyle comportant 2 a 12 atomes de carbone et les groupes arylalkyle comportant 7 a 12 atomes de carbone; R1 est choisi parmi un atome d'hydrogene et les groupes alkyle et alcoxy comportant 1 a 6 atomes de carbone; et M est choisi parmi les atomes de sodium et de potassium et les groupes ammonium represents par la formule generale: NR2R3R4R5 dans laquelle R2 a R5 peuvent etre identiques ou differents et represented chacun un atome d'hydrogene ou un groupe alkyle inferieur comportant 1 a 6 atomes de carbone, qui peut porter des substituants.

Composition de developpateur selon la revendication 1 , dans laquelle la quant its de compose aromatique s'echelonne de 0,001 a 10% en poids, par rapport au poids total de la composition de developpateur.

Composition de developpateur selon la revendication 1 , dans laquelle I'agent alcalin est au moins un des composes silicate de sodium, silicate de potassium, hydroxyde de sodium, hydroxyde de potassium, phosphate tertiaire de sodium, phosphate secondaire de sodium, phosphate tertiaire d'ammonium, phosphate secondaire d'ammonium, metasilicate de sodium, bicarbonate de sodium, borate de sodium, borate d'ammonium, ammoniac, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine et pyridine.

Composition de developpateur selon la revendication 1 , dans laquelle la quantite d'agent alcalin s'echelonne de 0,05 a 1 0% en poids, par rapport au poids total de la composition de developpateur pratiquement utilisee.

Composition de developpateur selon la revendication 5, dans laquelle la quantite d'agent alcalin s'echelonne de 0,1 a 7% en poids, par rapport au poids total de la composition de developpateur pratiquement utilisee.

Composition de developpateur selon la revendication 1, dans laquelle le pH de la composition de developpateur est ajuste a pas moins de pH 12.

Composition de developpateur selon la revendication 1, comprenant, en outre, au moins un tensioactif anionique choisi parmi le sel de sodium de sulfate d'alcool lauryl ique; le sel de sodium de sulfate d'alcool octylique; le sel d'ammonium de sulfate d'alcool laurylique; les sels d'esters d'acide sulfurique d'alcools superieurs comportant 8 a 22 atomes de carbone; les sels d'esters d'acide phosphorique d'alcools aliphatiques; les sels d'acides alkylarylsulfoniques; les sels d'acides alkylarylcarboxyliques; les sels d'acide sulfonique d'alkylamides; les sels d'acide sulfonique d'esters de diacides aliphatiques; et les sels d'esters d'acide sulfurique d'aryloxyalkylene.

Composition de developpateur selon la revendication 8, dans laquelle la quantite de tensioactif anionique s'echelonne de 0,1 a 5% en poids, par rapport au poids total de la composition de developpateur pratiquement employee.

Composition de developpateur selon la revendication 1, comprenant, en outre, au moins un solvant or-

18

EP 0 390 480 B1

ganique ayant une solubilite dans I'eau de pas plus d'environ 10% en poids, choisi parmi le 1-phenylethanol, le 2-phenylethanol, le 3-phenylpropanol-1, le 4-phenylbutanol-1, le 4-phenylbutanol-2, le 2-phenylbutanol-1, le 2-phenoxyethanol, le 2-benzyloxyethanol, I'alcool o-methoxybenzylique, I'alcool m-methoxybenzylique, I'alcool p-methoxybenzylique, I'alcool benzylique, le cyclohexanol, le 2-methylcyclohexanol, le 4-methylcyclohexanol et le 3-methylcyclohexanol.

Composition de developpateur selon la revendication 8, dans laquelle la quantite de solvant organique s'echelonne de 1 a 5% en poids, par rapport au poids total de la composition de developpateur pratiquement employee.

Composition de developpateur selon la revendication 1, comprenant, en outre, des agents anti-mousses et/ou des adoucisseurs d'eau, et I'adoucisseurd'eau estau moins un compose parmi Na2P207, Na5P303, Na3P309, Na204P(Na03P)P03Na2, Calgon, I'acide ethylenediaminetetraacetique et ses sels de potassium etde sodium, I'acide diet hylenetriaminepentaacetique etses selsde potassium etde sodium, I'acide triethylenetetraminehexaacetique et ses sels de potassium et de sodium, I'acide hydroxyethylethylene- diaminetriacetique et ses sels de potassium et de sodium, I'acide nitrilotriacetique et ses sels de potassium et de sodium, I'acide 1,2-diaminocyclohexanetetraacetique et ses sels de potassium et de sodium et I'acide 1,3-diamino-2-propanoltetraacetique et ses sels de potassium et de sodium.

Composition de developpateur selon la revendication 12, dans laquelle la quantite d'adoucisseur d'eau s'echelonne de 0,01 a 5% en poids, par rapport au poids total de la composition de developpateur pratiquement utilisee.

Precede de developpement d'une plaque d'impression lithographique presensibilisee, qui comprend i) soit le developpement d'une plaque presensibilisee positive exposee a la lumiere selon une image, possedant un substrat avec une couche photosensible positive exposee a la lumiere selon une image contenant un compose diazoture d'o-quinone avec la composition de developpateur selon I'une quelconque des revendications 1 a 13 poureliminer les zones exposees a la lumiere de la couche photosensible positive, afin de fournir une couche d'impression lithographique, ii) soit le developpement d'une plaque presensibilisee negative exposee a la lumiere selon une image, possedant un substrat avec une couche photosensible negative exposee a la lumiere selon une image contenant une resine diazoTque avec la composition de developpateur selon I'une quelconque des revendications 1 a 1 3 pour eliminer les zones non exposees a la lumiere de la couche photosensible negative, afin de fournir une couche d'impression lithographique.

Precede selon la revendication 14, dans lequel, apres le developpement de la plaque presensibilisee, on la soumet ensuite a un lavage a I'eau suivi d'un traitement de desensibilisation; directement a un traitement de desensibilisation sans lavage a I'eau; a un traitement avec une solution aqueuse contenant un acide; ou a un traitement avec une solution aqueuse contenant un acide, suivi d'un traitement de desensibilisation.

Precede selon la revendication 14, dans lequel on rajoute un complement de developpateur au developpateur au cours du precede de developpement.

Precede selon la revendication 14, dans lequel la couche formant une image de la plaque d'impression presensibilisee negative comprend une resine diazoTque photosensible essentiellement insoluble dans I'eau et soluble dans les solvants organiques et une resine hydrophobe.

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iiililiili^ (12) EUROPEAN PATENT SPECIFICATION