DE3009928A1 - METHOD FOR PRODUCING LIGHT-SENSITIVE PRINTING PLATES - Google Patents

Description

Munich dr. e. wiegand dr. m. köhler dipl.-ing. c gernhardt

HAMBURG DIPL-ING. J. GLAESER

DIPL.-ING. W. NIEiAANN OF COUNSEL

WIEGAND NIEMANN KÖHLER GERNHARDT GLAESER

PATE NTAKWXLTE

Admitted to the European Patent Office

30091

TELEPHONE: 0S9-S554 76/7
TELEGRAMS: KARPATENT TELEX: 529068 KARP D

D-8000 MDNCHEN 2 HERZOG-WILHELM-STR. 16

W. 43651/80 - Eo / He

. March 1980

Fuji Photo Film Co., Ltd. MLnami Ashigara-Shi, Kena £ awa CJapan)

Process for the manufacture of photosensitive

Printing plates

The invention relates to a method of manufacture of photosensitive printing plates. The term "printing plates" as used herein refers to unexposed materials, which can also be referred to as printing plate precursors.

TJm a complete contact of the outermost surface of a photosensitive printing plate, whereby this Surface of the photosensitive coating or a

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'ORIGINAL INSPECTHO

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resinous topcoat layer above the photosensitive Coating can consist of receiving an original to expose the photosensitive coating, the two elements are usually placed one on top of the other! Engaging between an elastomeric sheet and a pressure glass plate attached and the gap between the elastomer sheet and the glass plate is evacuated. This process is called vacuum contact process known. An exceptionally long evacuation time is sometimes required before full contact over the entire surface of photosensitive printing plates of the usual type. Because of the smooth surfaces of the plate and the original and because of the Contact extensively; the surface is initiated and gradually progresses to the center, becomes the middle Area closed and the evacuation of the central area is seriously inhibited. When a picture exposure is carried out in the case of incomplete contact, the missing Image the sharpness, which results in the production of unacceptable print material. Because this time-consuming contacting operation Decreased the effectiveness of plate-making has been a reduction in the evacuation period since long desired.

Photosensitive printing plates and manufacturing process, eliminating the period of vacuum contact process can be shortened are given in British Patents 1,495,361, 1,512,080 and 1,542,131. In these Patent specifications is stated that by forming on the surface of the photosensitive printing plate a Matting layer that can be removed during development,

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ORIGINAL INSPECTED

the time required for vacuum contact can be markedly reduced. However, for the production of such a photosensitive printing plate, additional production steps for coating and for drying the matting layer are required, which are carried out in a specially designed coating device. As a result, the plates obtained show increased production costs.

Furthermore, another type of photosensitive printing plate is described in Japanese Patent Publication 12905/79, which consists of a photosensitive coating having a matted surface which has been obtained by incorporating a matting agent in the coating. This type of plate, which can also reduce the vacuum contact time, is shown in the accompanying Pig. Λ , the carrier 10 being provided with a photosensitive coating 20, the surface of which is matted with a finely divided material 50. Although this type of photosensitive printing plate is free from the disadvantage of the former type of plate, the plate suffers from (1) poor printing durability and (2) poor tone reproduction.

A printing plate made from a photosensitive lithographic plate having such a construction could only withstand a few prints. Presumably this is called in the photosensitive coating Matting agent incorporated finely-divided material, that remains in the image area (area where the ink is accepted due to water repellency) after Worn out after a few prints during development, so that areas remain that still do not have any printing ink

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accept more. As a result, the printing plate is quite a poor durability.

Like in Pig. 2, shown in cross section, results in the presence of particles 50A and 50B of the matting agent, which shows the exposed area 20A and the unexposed area 20B of a photosensitive lithographic Bridge plate as original M of the negative type, at active irradiation (indicated by the arrows) an image, as in Pig. 3 shown after development, where the unexposed area 20B is removed together with the particle 5OB, leaving the bare surface of the support is exposed. Occasionally, some particles such as 50A also remain. It follows that the image area the finished plate does not exactly match the original or faithfully reproduces it.

It is an object of the invention to provide a method for producing photosensitive printing plates with matted Surface without additional coating and drying processes .

Another object of the invention is a method of making photosensitive printing plates with a matted surface without any special coating device.

Another object of the invention is a method of making photosensitive printing plates with a matte surface, making lithographic printing plates of high durability and not deteriorated sound reproduction can be produced.

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The present invention provides a method of making photosensitive printing plates which comprise a photosensitive coating in which the outermost layer is drawn up and dried in a mixture with the content of a solution in a solvent the other ingredients dispersed finely-divided Material was obtained with the formation of the outermost layer and this results in a matt surface. The process is characterized by a stable dispersion of the finely divided material in the coating mixture characterized in such a way that during evaporation of the solvent individual particles of the finely-divided material on the surface as very small projections in the outermost layer remain.

Put in the drawings

Fig. 1 is a cross section of a conventional photosensitive pianographic printing plate;

FIG. 2 shows the imagewise exposure of that shown in FIG Plate,

Fig. 3 shows the same plate (Fig. 1) after development and transfer to a pianographic record,

Fig. 4 schematically and in cross section according to the plate manufactured according to the present invention at each stage of manufacture between the spread of the photosensitive Coating liquid over the carrier and drying, namely (a) immediately after spreading, (b) in the course of drying and (c) after complete removal of the volatile solvent,

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original

-X-

FIG. 5 shows the imagewise exposure of the photosensitive pianoographic plate according to the invention, as in FIG
Fig. 4 x (c) shown,

FIG. 6 shows a cross section of the plate according to FIG. 5 after development,

7 shows a further embodiment according to the invention, wherein a non-sensitive coating is applied to the light-sensitive coating and FIGS. 7 (a) and (b) each show cross-sections of the applied product, initially shortly after being coated with the coating solution (FIG 7 (a)) and after drying (Fig. 7 (b)),
and

Fig. 8 is a cross-section of the diagram shown in Fig. 7 (b)
The pianographic printing plate obtained after imagewise exposure and shown in the photosensitive plate
development
represent.

In the context of describing the invention in detail, the term "stably dispersed" means that the
Particles of the finely-divided material do not aggregate, precipitate or flow during the period between the preparation of the coating mixture and the drawing up. The period of time during which the dispersion remains unchanged preferably exceeds 2 minutes and more preferably 5 minutes. According to the preferred embodiments of the invention, however, the time periods are far longer
stability possible.

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ORIGINAL INSPECTED

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Making a photosensitive lithographic Negative type plate using photosensitive Diazonium resins are explained below with reference to the accompanying drawings.

4 (a) shows in cross section an aluminum carrier 10 immediately after being coated with a coating mixture of a diazonium resin and a suitable one Solvent dissolved binder and a finely divided material dispersed in the solution, d. H. the Coating is not yet dry. At this stage, the particles 50 are stable in the thin layer of the coating mixture 2OC dispersed.

Figure 4- (c) shows the same coated product as in Fig. 4- (a) after the coating mixture has been dried, with the particles 50 of the finely divided material protruding from the surface 2OS of the photosensitive coating and tangential to the entire surface 2OS of the coating 20 are held. It should be noted that the particles 50 are practically not within the effective Thickness of the coating 20 are present. Accordingly, the photosensitive body made according to the present invention lithographic printing plate has a microstructure which is markedly different from that of the conventional plates, with the particles 50 being practically embedded in the effective thickness of the coating 20. One such a structure is believed to be obtained when the drawn product shown in Fig. 4- (a) is dried and the solvent evaporates in the coating. This reduction in solvent destroys the dispersion of the finely divided material in the coating mixture 2OC. If

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ORIGINAL INSPECTED

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then the affinity or wettability of the finely-divided one Material to the dissolved constituents of the coating liquid, d. H. the diazonium resin, the binder and the remaining solvent, is weak, the particles become driven to the surface by the bulk of the coating liquid.

Hg. 4- (b) shows such a transition, the fine particles 50 being driven to the upper surface of the layer 20C ^{1 of} the coating liquid, which is due to the decrease in the solvent content by half to complete drying. Thus, as drying proceeds, a photosensitive lithographic printing plate having the type described in E ¹ Xg. 4- (c) shown cross-section saufbau received. This explanation results from a comparison of the following.! and only changing the chemical types of the matting agent. If the affinity of the matting agent for the other constituents of the coating mixture (corresponding to the solvent) is poor, the plate obtained assumes the cross-sectional structure shown in Fig. 4 (c), while if the matting agent has a strong affinity for the other constituents, Printing plates of the type shown in Fig. 1 can be obtained.

The photosensitive printing plates prepared in this manner can remarkably achieve those for attaining reduce the time required to fully contact the original by the vacuum contact method. Furthermore, since none of the finely divided particles is practically embedded in the photosensitive coating,

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the Oberflächenaufrauhu ^ _B · is very effective achieved. Accordingly, compared to the conventional photosensitive lithographic plates shown in FIG. 1, much smaller particles can form the surface of the photosensitive coating with an equivalent degree of construction.

Fig. 5 shows the contact exposure of the photosensitive Overlay 20 of a photosensitive lithographic plate having the cross-sectional structure shown in Fig. 4 (c) by an original M (exposure is shown by arrows), the exposed areas of the photosensitive Coating with 20A and the unexposed areas with 20B.

FIG. 6 shows a cross section of the exposed plate according to FIG. 5 after development, the unexposed area of the photosensitive coating being removed
and the bare surface of the support 10, which forms the photographic image area of the lithographic plate, is exposed. On the other hand, the exposed area remains on the support and forms a printing ink-receiving area 20A of the lithographic plate. As can be seen from the figure, no matting agent remains in the image area 20A.
The particles were removed by the development. the
Removal of the particles is complete as the particles
are only held superficially on the surface and they are practically not embedded in the interior of the coating. As a result, even after the exposed area of the photosensitive coating is crosslinked
the particles were not held firmly to the surface to prevent the development process.

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stand. In any case one can see the absence of the particulate Confirm material in the image area using a microscope.

The absence of the matting agent in the image area of the finished lithographic plate advantageously avoids those common in Pig. The lithographic plates shown in Fig. 1 (c) have their own disadvantages, namely poor printing durability and poor tone reproduction. The plate according to the invention is also free from a further defect, which is inherent in the usual photosensitive printing plates according to the structure shown in FIG. 1, namely an incomplete removal of the non-image areas when it is treated with a developer with damaged development activity , a so-called exhausted developer. Darübe rb I η from are not necessary according to the present invention, additional manufacturing processes to the surface of the photosensitive coating to roughen.

The photosensitive printing plate produced by the method according to the invention basically comprises a Support having a photosensitive layer thereon and comprising photosensitive printing plates as used in the manufacture of lithographic printing plates, letter printing plates, intaglio printing plates and other printing plates can be used. For the production of lithographic printing plates and intaglio printing plates photographic printing plates used are preferred in the context of the invention.

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The carrier consists of a dimensionally stable sheet-like Material as it is usually used for the embossing of printing plates. Examples of such carriers include paper, with plastics, e.g. B. polyethylene, polypropylene and polystyrene-coated paper, ffetal sheets, for example made of aluminum with inclusion of aluminum alloys, zinc, iron and copper, plastic films, e.g. made of cellulose diacetate, cellulose triacetate, Cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyalkylene terephthalate, Polyethylene, polystyrene, polypropylene, polycarbonate and polyvinyl acetal and papers and plastic films made with the metals specified above are coated or metallized. The appropriate vehicle will depend chosen by the type of printing plate to be produced. Used for photosensitive lithographic printing plates Aluminum sheets and composite sheets of those described in Japanese Patent Publication 18327/73 Kinds consisting of a polyethylene terephthalate film in combination with an aluminum sheet are particularly preferred. For a photosensitive letter printing plate, polyethylene terephthalate sheets, aluminum sheets are used and iron sheets preferred.

If necessary, the support is subjected to a surface treatment. For example, the surface of the support used for making photosensitive lithographic printing plates is made hydrophilic by various methods. A carrier with a plastic surface surface treatments such as chemical treatment, discharge treatment, flame treatment, etc.

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Treatment, high frequency wave treatment, glow discharge treatment, active plasma treatment and laser treatment, including US Patents 2,764,520, 3,497,407, 3 145 242, 3 376 208, 3 072 433, 3 475 '»93 and 3 360 443 and UK patent specification 788 365 is referenced, subjected or the plastic surface treated in this way is coated with a primer layer.

There are two methods of applying the primer coat. One consists of the double layer process, whereby first a layer of a hydrophobic resin, which strongly adheres to plastics and which is highly soluble, applies and then applies one layer of a hydrophilic resin and the other consists of the Single light process, with a resin layer, which contains both hydrophobic and hydrophilic layers in the same polymer.

Carriers with a surface made of a metal, in particular aluminum, are preferably such surface treatments, such as graining, immersion in an aqueous solution of sodium silicate, potassium fluorozirconate or phosphate, or subject to anodization. On the other hand, the aluminum sheet can be grained and then in a aqueous sodium silicate solution can be immersed as in US Pat. No. 2,714,066, or it can be anodized and then converted into an aqueous alkali metal silicate as described in (Japanese Patent Publication 5125/72. Each of these two aluminum sheets can advantageously be used according to the invention will. The above anodization is carried out in one of one or more aqueous or non-

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aqueous solutions of inorganic acids such as phosphoric acid, chromic acid, sulfuric acid or boric acid or organic acids such as oxalic acid and sulfamic acid or salts thereof carried out electrolyte, the
electric current is applied through an aluminum anode.

Another effective surface treatment is the electrodeposition of a silicate, as in FIG U.S. Patent 3,658,662.

The purpose of these surface treatments is not limited to making the surface of the support hydrophilic close; they are also used to prevent harmful reaction with the photosensitive to be mounted on the support Hasse as well as for the formation of an intimate contact with the light-sensitive layer.

Any of the materials can be used as the photosensitive component of the photosensitive components of the present invention Hate to be used, provided they are their solubility in the developer or the property of swelling in the Change developer after imagewise exposure. Typical examples of such materials are as follows.

(1) Composition. the diazo resins

Diazo compounds of the condensate type of p-diazodiphenylamine and paraformaldehyde can be used to advantage whether they are water-soluble or are insoluble, those that are insoluble in water and soluble in common organic solvents are preferred. Particularly preferred diazo

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compounds are condensates of p-diazodiphenylamine and Formaldehyde or acetaldehyde, and those compounds that contain at least two diazo groups in the molecule, such as salts of p-diazodiphenylamine and phenol, fluorocapric acid and triisopropylnaphthalenesulfonic acid, 4-, 4-biphenyldisul hair dryer acid, 5-nitroorthotoluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-chloro-5-nitrobenzenesulfonic acid, 2-fluorocaprylnaphthalene sulf onic acid, 1-lfaphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid and paratoluenesulfonic acid. Other suitable diazo resins are condensates of 2,5-dimethoxy-4-p-tolyl mercaptobenzene diazonium and formaldehyde and condensates of 2,5-dimethoxy-4-morpholinobenzene diazonium and formaldehyde or acetaldehyde containing the above-mentioned salts.

Also that in British Patent 1,312,925 diazo resin described is preferred.

These diazo resins can be used individually as a photosensitive material, but are preferred together used with a binder. Various polymeric compounds can be used as such binders, and the preferred polymeric compounds are those which are hydroxy, amino, carboxylic acid, amide, sulfonamide, active Contain methylene, thioalcohol or epoxy groups. from These preferred binders are also given in British Patent 1,350,521 Shellak, Polymers, which is a hydroxyethyl acrylate or hydroxyethyl methacrylate included as the main recurring unit, as in British Patent 1,460,078 and US

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-yf.

US Pat. No. 4,123,276, the polyamide resins, phenolic resins and polyvinyl acetal resins described in US Pat. No. 3,751,257, such as polyvinyl formal resins or polyvinyl butyral resins as described in British Pat. No. 1,074,392, the linear polyurethane resins described in US Pat. No. 3,660,097, polyvinyl alcohol resins esterified with phthalic acid, epoxy resins condensed from bisphenol k and epichlorohydrin, polymers containing an amino group such as polyaminostyrene or polyalkylamino (meth) acrylate, and celluloses such as cellulose acetate, cellulose alkyl ether, cellulose acetate phthalate.

The binder is conveniently contained in the photosensitive Hasse in an amount of 40 to 95 wt.%, Based on the dried state. A high binder content (less diazo resin) naturally results in a higher sensitivity, however, the stability of the Hasse degrades more rapidly with the passage of time than when the binder content is low. The optimal binder content is around 70 up to 90% by weight.

The hats made from the diazo resins can also be those described in U.S. Patent 3,236,646 Contain phosphoric acid and other additives such as dyes and pigments.

(2) Composition of o-quinonediazide compounds

Preferred o-quinonediazide compounds are o-naphthoquinonediazide compounds, as described in U.S. Patents 2,766,118, 2,767,092, 2,772,972, 2,859,112, 2,907,665,

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3 046 110, 3 046 111, 3 046 115, 3 046 118, 3 046 119, 3 046 120, 3 046 121, 3 046 122, 3 046 123, 3 061 430, 3 102 809, 3 106 465, 3 635 709 and 3 647 443 and numerous further literature references are described. According to the invention, these compounds can be used with particular advantage be used. Preferred examples are o-naphthoquinonediazide sulfonate esters or o-naphthoquinonediazide carboxylate esters of aromatic hydroxy compounds and o-ifaphthoquinonediazide sulfonic acid amide or o-naphthoquinonediazide carboxamides of aromatic amino compounds. Pyrogallol / acetone flatensates are particularly preferred, which esterifies with an o-naphthoquinonediazide sulfonic acid are, as described in U.S. Patent 3,635,709, hydroxyl terminated polyesters, the with an o-kaphthoquinonediazide sulfonic acid or o-naphthoquinonediazide carboxylic acid is esterified, as described in US Pat. No. 4,028,111, homopolymer β of p-hydroxystyrene or copolymers thereof with a further copolymerizable monomer, which with an o-naphthoquinonediazide sulfonic acid or o-kaphthoquinonediazidecarboxylic acid are esterified, as in US Pat. No. 4,139,384. described.

These o-ghinonediazide compounds can be used singly but are preferably mixed with an alkali-soluble resin. Advantageous alkali-soluble Resins include phenolic novolak resins, for example Phenol-I-Ormaldehydharze, o-Cresol-Formaldehydharze und m-cresol formaldehyde resins. These can be more preferred phenolic resins in combination with a condensate of an alkyl (C,.. Cg) -substituted phenol or cresol and aldehyde, for example tert-butylphenol-IOrmaldehyd-

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resins, as described in U.S. Patent 4,123,279. These are alkali-soluble resins in the compositions forming the photosensitive resistor in an amount of from about 50 to about 85% by weight, preferably From 50 to 80% by weight, based on the total weight of the Mass, incorporated.

The photosensitive composition composed of an o-quinonediazide compound can also contain pigments, dyes, Contains plasticizers and other additives.

(3) Compositions of photosensitive azide compounds

Suitable photosensitive azide compounds are aromatic azide compounds in which an azide group is attached to an aromatic ring either directly or through a carbonyl or sulfonyl group. Upon exposure to light, the azide group is decomposed to form a hitrin, which undergoes various reactions and renders the compounds insoluble. Preferred aromatic azide compounds are those containing at least one such group as azidophenyl, azidostyryl, azidobenzal, azidobenzpyl and azidocinnamoyl groups; Examples are ^, ^ '- DiaZidochalcon, 4-Azido-4 ^l - (4-azidobenzoylethoxy) -chalcone, υ, Ιϊ-bis-p-azidobenzal-p-phenylenediamine, 1,2,6-tri- (4 ^l - azidobenzoxy) -hexane, 2-azido-3-chlorobenzoquinone, 2,4-diazido-4 ^l -ethoxyazobenzene, 2,6-di- (4 ^l -aziaobenzal) -4-methylcyclohexanone, 4,4 ^f -diazidobenzophenone, 2, 5-diazido-3,6-dichlorobenzoquinone, 2,5-bis (4-azidostyryl) -1,3,4-oxadiazole, 2 - (- ⁴ I-Azidocinnamoyl) thiophene, 2,5-di (4 ^f -azidobenzal) cyclohexanone, 4,4'-diazido diphenylmethane, 1- (4-azidophenyl) -5-furyl- 2-penta-2,4-dien-1-one, 1- (4-azidophenyl) - 5- (4-methoxyphenyl) -

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ORIGINAL INSPECTEB

penta-1, 4-dien-3-one, 1- (4-azidophenyl) -3- (1-naphthyl) -propen-1-one, 1- (4-azidophenyl) -3- (4-dimethylaminophenyl) - propan-1-one, 1- (4-azidophenyl) -5-phenyl-1,4-pentadien-3-one, 1- (4-azidophenyl) -3- (4-nitrophenyl) -2-propen-1- one, 1- (4-azidophenyl) -3- (2-furyl) -2-propen-1-one, 1,2,5-tri- (4'-azidobenzoxy) -liexane, 2,6-bis- ( 4-azidobenzylidene-ptert-butyl) -cyclohexanone, 4,4'-diazidobenz.alacetone, 4,4'-diazidostilbene-2,2 ¹ -disulfonic acid, ^ '- azidobenzalacetophenone-2-sulfonic acid, ^ -j ^ -' -Diazidostilbene-cc-carboxylic acid, Dx- (4-azido-2 ^! -Liydroxybenzal) -acetone-2-sulionic acid, 4-azidobenzalacetophenone-2-sulfonic acid, 2-azido-1,4-dibenzenesulfonylaminonaphthalene, 4,4'-diazidostilbene -2.2 ^L disulfoanilide.

In addition to these aromatic azide compounds of low molecular weight, the azide-containing polymers are also of low molecular weight suitable as described in Japanese Patent Publications 9047/69, 31837/69, 9613/70, 24915/70, 25713/70 and Japanese Patent Applications 5102/75, 84302/75, 84303/75 and 12984/78 are described.

These photosensitive azide compounds are preferably used in combination with one as a binder polymeric compound used. The preferred binders are alkali-soluble resins, for example natural resins such as shellak and rosin, phenolic novolak resins such as phenol-formaldehyde resins and m-cresol formaldehyde resins, homopolymers of unsaturated carboxylic acids or copolymers thereof with other copolymerizable monomers, such as polyacrylic acid, Polymethacrylic acid, methacrylic acid / styrene copolymers, Methacrylic acid / methyl acrylate copolymers and styrene / maleic anhydride copolymers, resins with acetal

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IA

groups, which by reacting partially or completely saponified polyvinyl acetate with aldehydes, such as Acetaldehyde, benzaldehyde, hydroxybenzaldehyde and carboxybenzaldehyde as well as polyhydroxystyrene. Other suitable binders are in organic solvents soluble resins, e.g. B. cellulose alkyl ethers, such as cellulose methyl ether and cellulose ethyl ether.

The composition composed of the photosensitive azide compound preferably contains such a binder In an amount of about 10 to about 90% by weight, based on the total weight of the mass.

The composition composed of a photosensitive azide compound can also contain additives such as dyes, Pigments, plasticizers, wis phthalate esters, phosphate esters, aliphatic carboxylate esters, glycols and sulfonamides and sensitizers such as Michler's ketone, 9-fluorenone, i-nitropyrene, 1,8-dinitropyrene, 2-chloro-1,2-benzanthraquinone, 2-bromo-1,2-benz anthraquinone, pyrene-1,6-quinone, Contain 2-chloro-1,8-phthaloylnaphthalene and cyanacridine.

(4) masses of polymeric compounds containing a

Il

Group -CH = CH-C- in the main chain or side chain of the polymer

These masses include those that are mainly composed photosensitive polymers such as polyesters, polyamides, and polycarbonates, which have a photosensitive group -CH = CH-C- in the main chain or side chain of the polymer

Il

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contain, for example, the compounds described in U.S. Patents 3,030,208, 3,707,373 and 3,453,237, consist mainly of photosensitive polyesters that are derived from a (2-propylidene) malonic acid compound, such as cinnamylidene melonic acid and bifunctional glycols, for example those described in U.S. Patents 2,956,878 and 3,173,787 photosensitive polymers, and cinnamate esters of hydroxyl-containing polymers such as polyvinyl alcohol, Starch, cellulose and the like, such as those described in U.S. Patents 2,690,966, 2,752,372 and 2,732,30-I photosensitive polymers. These compounds can also contain sensitizers, stabilizers, plasticizers, Contain pigments and dyes.

(5) Photosensitive compositions made from addition-polymerizable unsaturated compounds

These compositions are preferably composed of (a) a vinyl monomer with at least two terminal vinyl groups, (b) a photopolymerization initiator; and (c) a polymeric compound as a binder.

Illustrative vinyl monomers which can be used as component (a) include acrylate or methacrylate esters of polyols, such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate or bis (meth) acrylamides such as methylenebis (meth) acrylamide and ethylene bis (meth) acrylamide or urethane-containing unsaturated monomers, ζ. Β. a reaction product of a diol mono (meth) acrylate and diisocyanate, such as B. Di- (2'-methacryloxyethyl) -2,4-tolylene-

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diuretliau and di- (2 ^l -acryloxyethyl) »trimeth.ylendiurethaii as described in Japanese Patent Publications 5093/60, 14719/60 and 28727/69.

Examples of photopolymerization initiators or component (b) are those in Chapter 5 of J, Kosar, Light-Sensitive Systems, listed carbonyl compounds, organic sulfur compounds, peroxides, redox compounds, azo and diazo compounds, halogen compounds and light reducible pigments. More specific examples sine given in British Patent $ 1,459,56. Other initiators known in the art can also be used.

Various known polymers can be used as the binder or component (c). Details for specific Binders are disclosed in U.S. Patent 4,072,527. That stated in British Patent 1,459,563 chlorinated polyolefin is a particularly preferred binder.

Components (a) and (c) are used in combination in a weight ratio ranging from 1: 9 to 6: 4 applied. The component (b) is in an amount of 0.5 to 10 wt.%, Based on the weight of the component (a), contain.

The photopolymerizable haters can still use thermal polymerization inhibitors, plasticizers, Contain dyes and pigments.

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The one produced by the process according to the invention photosensitive printing plate basically comprises one Support having thereon a photosensitive layer consisting of the photosensitive layer discussed above Material is built up and it may further contain a plurality of resin layers, which are on the photosensitive Layer are attached. A specific example of this is in U.S. Patent 3,136,637 described, wherein a carrier has applied to it a photosensitive layer which is coated with layers of lipophilic, hydrophobic, water-insoluble and solvent-softenable Resins are covered in this order. Other examples of photosensitive printing plates with the like Structures are described in British Patents 1 4-78 333 and 1 478 334 and they are described herein within the scope of includes photosensitive printing plates which can be produced by the process of the invention.

A variety of solvents can be used to apply the photosensitive layer, such as. B. 2-methoxyethanol, 2-ethoxyethanol, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, dimethylformamide, methanol / dichloroethylene and geraische about it. The methanol can be used starting from the above methanol / dichloroethylene mixture Replace with ethanol, n-propanol, isopropanol or mixtures thereof, and dichloroethylene can still be used with methylene chloride, trichloroethane, monochlorobenzene or with Replace mixtures thereof. Types of auxiliary solvents can continue to the systems within an area, which practically does not change the basic structure of the original mixture. To such auxiliary solvents include, for example, ketones such as acetone, methyl

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ethyl ketone, methyl isobutyl ketone and the like, esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, methylamyl acetate and the like, water and the like.

The practical range of concentration of the coating liquid with the content of the photosensitive composition dissolved in such a solvent is usually within about 0.1 to about 20 weight percent, and more preferably between 1 and 10 weight percent.

As mentioned above, the finely divided, im dispersed state to be incorporated into the coating liquid Material during the subsequent drying process be driven out. At the same time, the material must advantageously have a stable dispersion during the production of the coating liquid up to the coating work.

Illustrative and preferred fine particulate materials for use in the invention include Polyethylene particles, polypropylene particles, ethylene-propylene copolymer particles, Ethylene-vinyl acetate copolymer particles, polyethylene terephthalate particles and crosslinked vinyl polymer particles. Of these, polyethylene, polypropylene and ethylene-propylene copolymers are preferred.

The crosslinked vinyl polymer particles are produced by known methods of suspension polymerization According to one example, a mixture of a hydrophobic vinyl monomer having a vinyl group, e.g. B. Acrylate ester, Methacrylate esters, styrene, styrene derivatives and acrylonitrile, and 1 to 30 parts by weight of a polyfunctional monomer,

030039/0811

based on the yinyl monomer, ζ. Β. Divinylbenzene, polyethylene glycol diacrylate, where the number of ethylene units is 1 to 14, polyethylene glycol dimethacrylate, where the number of ethylene units is 1 to 14, irimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Pentaerythritol ti-iacrylate, pentaerythritol trimethacrylate and pentaerythritol tetramethacrylate to the aqueous medium with one usually dissolved therein Suspension polymerization used dispersants, for example inorganic powders such as zinc oxide, calcium carbonate and talc, and water-soluble polymers such as gelatin and polyvinyl alcohol, added, the polymerization system evacuated and flushed with nitrogen and under Increase the temperature to about 50 to 80 ° C with stirring a common oil-soluble polymerization initiator, e.g. B. benzoyl peroxide or azobisisobutyronitrile, to start added to the polymerization, which proceeds over a period of about 2 to 20 hours, until a dispersion of the crosslinked vinyl polymer particles is obtained. The dispersion then undergoes a solid-liquid separation operation and subjected to drying so that the particles of the crosslinked yinyl polymer are obtained.

The fine particulate used in the present invention Material has an average particle size (diameter) that conveniently ranges from about 5 to about 40 / µm, preferably 5 to 20 / µm.

The amount of fine particulate matter present on the surface of the photosensitive printing plate can be chosen within a wide range and

is generally from about 50 to about 500,000 particles per cm,

030039/0811

preferably about 1,000 to 100,000 particles per cm. Usually, the optimal range is determined empirically by repeating trials based on trial and error. The amount of fine particulate material in the coating is adjusted by taking into account the coating weight of the top layer to form the desired coverage. If the top layer of the photosensitive printing plate consists of a photosensitive layer, the fine particulate material is typically in an amount of about 0.01 to about 20% by weight, preferably about 0.1 to 10% by weight. _y based on the solids content of the coating liquid, ie the amount of the applied layer minus the solvent.

According to a preferred embodiment of the present invention, it was found that the stability the coating dispersion can be increased significantly if the dispersion is also an aqueous polymer latex with an average particle size of about 0.001 to 0.1 times the average particle size of the fine particulate material which the roughened Surface forms, contains.

Aqueous polymer latexes useful in the present invention are well known in the polymer art and are they contain fine particles of a polymer, also called latex particles, dispersed in one aqueous medium. According to the invention, a stable dispersion of the fine particulate material in the organic solvent received, case »? the latex particles from the aqueous polymer latex had an average Have particle size (diameter) within the

030039/0811

Range from a thousandth to a tenth of that average particle size of the fine particulate material. Such aqueous polymer latexes may include those having an average particle size in the range of about 0.01 to about 2 µm, preferably 0.0'i to 1 / µm and more preferably 0.02 to 0.5 / µm, to get voted.

These aqueous polymer latexes can be prepared by the vinyl monomer of emulsion polymerization is subjected in water. In one embodiment of such emulsion polymerization, the vinyl monomer becomes to an aqueous medium with a content of about 0.1 up to 20% by weight of a dispersant for emulsion polymerization, based on yinyl monomer, generally one surfactant, and about 2 to 50% by weight of water are added, with the polymerization system under vacuum is set and flushed with nitrogen. The additives used in the usual emulsion polymerization, e.g. B. Molecular weight modifiers and antioxidants, are added if necessary during the emulsification and finally an emulsion polymerization initiator, for example hydrogen peroxide, potassium persulfate, added and emulsion polymerization is carried out in the usual manner so that an aqueous polymer latex of the vinyl polymer is formed. All vinyl monomers can can be used in emulsion polymerization without any particular limitation, and details for those in production The monomers which can be used in the aqueous polymer latex are given below. For simplicity are the monomers in oil group A (hydrophobic monomers, group B (hydrophilic Monomers) and group C (crosslinkable monomers).

03003S / 081 1

Group A monomers:

Hydrophobic unsaturated vinyl monomers with a vinyl group, such as acrylate esters, methacrylate esters, vinyl esters, Styrenes and olefins.

Group B monomers:

Hydrophilic unsaturated vinyl monomers with a vinyl group, such as monomers with such functional groups as amino groups, carboxyl groups, sulfonic acid groups, Amide groups and hydroxyl groups.

Group C monomers:

Monomers with reactive crosslinkable groups, for example epoxy groups, hydroxymethylamide groups, Alkoxymethylamide groups, acyloxymethylamide groups and Isocyanate groups, as well as polyfunctional monomers with two or more vinyl groups.

Suitable combinations of these monomers for the production of aqueous polymer lateces are homopolymers from a monomer of group A or a copolymer of a combination of at least two monomers of group A, a copolymer of at least one monomer from group A and at least one monomer from group B, a copolymer at least one monomer of group A, at least one monomer of group C and at least one monomer of Group B, as well as a copolymer of at least one monomer of group A and at least one monomer of Group C. Details of applicable monomers are given below given.

030039/0811

ORIGINAL INSPECTED

The group A monomers are hydrophobic vinyl monomers with a vinyl group such as acrylate esters, methacrylates ster, vinyl ester, styrene and α-olefins, where The term “hydrophobic” means that not more than 8% by weight of the monomer is soluble in water at 20 ° C are.

Illustrative acrylate esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, Isobutyl acrylate, sec-butyl acrylate, amyl acrylate, Hexyl acrylate, 2-ethylhexyl acrylate, octyl aorylate, 2-phenoxyethyl acrylate, 2-chloroethyl acrylate, benzyl acrylate, cyclohexyl acrylate, Tetrahydrofurfuryl acrylate, phenyl acrylate, 2-methoxyethyl acrylate and 2-ethoxyethyl acrylate.

Illustrative examples of methacrylate esters include Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, Isopropyl methacrylate, n-butyl methacrylate, Iaobutyl methacrylate, sec-butyl methacrylate, amyl methacrylate, hexyl methacrylate, Cyclohexyl methacrylate benzyl methacrylate, Acetoacetoxyethyl methacrylate, chlorobenzyl methacrylate, Octyl methacrylate, lurfuryl methacrylate, tetrahydrofurfuryl methacrylate, Phenyl methacrylate, trimethylolpropane monomethacrylate, 2-methoxyethyl methacrylate and 2-xthoxyethyl methacrylate.

_{Illustrative examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl chloroacetate t} vinyl dichloroacetate, vinyl methoxyacetate, vinyl acetoacetate, vinyl benzoate, vinyl salicylate and vinyl chlorobenzoate.

030039/081 1

GRiGiWAL INSPECTED

Illustrative examples of styrenes include styrene, methylstyrene, chloromethylstyrene, trifluoromethylstyrene, Acetoxymethylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, Trichlorostyrene and bromostyrene.

Illustrative examples of olefins include butadiene, isoprene, chloroprene, propylene, vinyl chloride, vinyl bromide, Vinylidene chloride, vinylidene bromide and vinylidene fluoride.

Another example of a Group A monomer represents acrylonitrile.

The group B monomers are hydrophilic vinyl monomers with a vinyl group and a functional group such as an amino group, carboxyl group, sulfonic acid group, Amide group or hydroxyl group. The term "hydrophilic monomers" includes those monomers which are so highly soluble in water that they are difficult to emulsion polymerize when they can be used alone.

Illustrative examples of group B monomers having an amino group include dimethylaminomethyl acrylate, Dimethylaminomethyl methacrylate, diethylaminomethyl acrylate, Diethylaminomethyl methacrylate, diethylaminoethyl acrylate, Diethylaminoethyl methacrylate, tert-butylaminoethyl acrylate and tert-butylaminoethyl methacrylate.

Illustrative examples of group B monomers having a carboxyl group include acrylic acid, methacrylic acid, Itaconic acid, maleic acid, crotonic acid, fumaric acid, methylenemalonic acid, Monoalkyl itaconate, e.g. B. monomethyl itaconate,

030039/081 1

3009S28

Monoethyl itaconate and monobutyl itaconate, monoalkyl maleate, ζ. B. monomethyl maleate, monoethyl maleate, monobutyl maleate, Monopropyl maleate and monooctyl maleate, citraconic acid, sodium acrylate, Ammonium acrylate and ammonium methacrylate.

Illustrative examples of group B monomers having a sulfonic acid group include styrene sulfonic acid, Vinylbenzylsulfonic acid, vinylsulfonic acid, acryloyloxyalkylsulfonic acid, z. B. Acryloyloxymethylsulfonic acid, Acryloyloxyäthylsulfonsäure, Acryloyloxypropylsulphonic acid and acryloyloxybutylsulphonic acids, methacryloxyalkylsulphonic acids, z. B. Methacryloyloxymethylsulfonic acid, Metnacryloyloxyäthylsulfönäure, Methacryloyloxypropylsulfonic acid and methac.ryloyloxybutylsulphonic acid, acrylamide alkylsulphonic acid, z. B. S-acrylamide-S-methylethanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid and 2-acrylamide-2-methylbutanesulfonic acid as well as methacrylamide alkyl sulfonic acids, z. B. 2-Methacrylamid-2-Methy: i_ätnansulfonsäure, 2-methacrylamide-2-methylpropanesulphonic acid and 2-methacrylamide-2-metliy3.butanesulph on acid.

Illustrative examples of monomers having an amide group include acrylamide, methyl acrylamide and propyl acrylamide.

Illustrative examples of monomers with a hydroxyl group include allyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and allyl ethers of polyhydric alcohols.

Further examples of group B monomers are IT-acryloalpiperidine, Vinylpyridine, vinylpyrrolidone and maleic acid anhydri d.

030 03 9/0 8 11

3009923

The group C monomers are those monomers having a reactive crosslinkable group, for example an epoxy group, a hydroxymethylamide group, a Alkoxymethylamido group, an acyloxymethylamide group and an isocyanate group and polyfunctional monomers with two or more vinyl groups. The group C monomers are not used individually, but they become the monomers of group A or mixtures of the monomers Group A and Group B added for the purpose of producing crosslinked polymer latices.

Illustrative examples of Group C monomers with epoxy groups include glycidyl acrylate, glycidyl methacrylate, Glycidyl p-vinyl benzoate, glycidyl crotonate, diglycidyl itaconate, Diglycidyl maleate, diglycidyl methylene malonate, glycidyl vinyl ether, Allyl glycidyl ether and glycidyl-oc-chloroacrylate.

Illustrative examples of group C monomers having a hydroxymethylamide group include hydroxymethylacrylamide and hydroxymethyl methacrylamide.

Illustrative examples of group C monomers having an alkoxymethylamide group include methoxymethylacrylamide, Methoxymethyl methacrylamide, ithoxy methyl acrylamide ,. Ethoxymethyl methacrylamide, butoxymethyl acrylamide, butoxymethyl methacrylamide and hexyloxymethyl acrylamide.

Illustrative examples of Group V monomers having an acyloxymethylamide group include acetoxymethylacrylamide, Acetoxymethyl methacrylamide and propionyloxymethyl acrylamide.

030039/081 1

ORIGINAL

Illustrative examples of group C monomers with of an isocyanate group include yinyl isocyanate and allyl isocyanate.

Illustrative examples of polyfunctional monomers of group C include divinylbenzene, polyethylene glycol diacrylate, where the number of ethylene units is 1 to 14, polyethylene glycol dimethacrylate, where the number of the ethylene units is 1 to 14, trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, pentaerythritol triacrylate, Pentaerythritol trimethacrylate and pentaerythritol tetramethacrylate. The polymer latex having an epoxy group can partially under acidic or alkaline conditions be hydrolyzed so that it may contain a dihydroxyl group.

Suitable combinations of monomers which make up the aqueous polymer latex are an eomopolymer of a monomer of group A or a copolymer of at least two monomers of group A, a copolymer of at least 50% by weight, preferably at least 80% by weight, of at least one monomer of group A and at least of a monomer of group B, a terpolymer of at least 50% by weight, preferably at least 80% by weight, of one Mixture of at least one monomer from group A and at least one monomer from group C and one Group B monomers and a copolymer of a group A monomer and a group C monomer. General the hydrophilic monomers of group B are used to provide improved stability for emulsion polymerization and to give an aqueous polymer latex stable during storage.

030039/081 1

It is essential that the particles from the aqueous Polymer latex, if dispersed in an organic solvent, are insoluble in the solvent and that they do not flocculate in the solvent. Because the latex particles may be soluble or insoluble, or may or may not flocculate, depending on the composition of the Depending on the organic solvent used, there is no definition of a general composition for the monomers from which the latex particles are built. However, it can be safely said that networked Latex polymers are preferred. The preferred latices are therefore terpolymers of at least 50% by weight, preferably at least 80% by weight, of a mixture of at least a group A monomer and at least one group C monomer and a group B monomer and copolymers of at least one monomer from group A and at least one monomer from group C. There are no general rule defining the ratio of the group A monomer to the group C monomer.

A dispersant for emulsion polymerization can be generally selected from anionic, cationic, nonionic and aromatic surfactants. These surfactants can be used independently or in admixture. The dispersants for emulsion polymerization are familiar to those skilled in the art. To give some examples, the anionic surfactants include sulfate esters of higher alkanols of the formula: E-OSO ₅ M or E- (OCH ₂ CH ₂ ^ ₁ OSO ₅ M, where E is an alkyl group having 8 to 30 carbon atoms, M is an alkali or an ammonium group and 1 a number from 0 to 30, as well as alkylbenzenesulfonic acid of the formulas:

030039/081 1

ORIGINAL INSPECTTEÖ

3Q09928

where E ^{1 is} a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, R "is an alkyl group having 1 to 18 carbon atoms, M is an alkali or an ammonium group, m is a number from 0 to 30 and η is a number from 0, 3 or 4- Illustrative examples of nonionic surfactants include polyoxyethylene derivatives and higher aliphatic acid esters of saceharides * Illustrative examples of amphoteric surfactants are sulfobetaines and amino acids.

The particle size of the aqueous polymer latex can vary depending on such factors as the amounts of Emulsion polymerization dispersants, monomers and polymerization initiator, the speed of rotation during stirring and the polymerization temperature can be adjusted.

Various solvents can be used to draw up the solution from which the top layer of the photosensitive printing plate precursor is applied

030039/08 11

INSPECTED

and one or more organic solvents are generally used. In the case of using a polymer latex it is favorable that at least 10% by weight of water are dissolved in the mass at 20 ° C. In particular it is favorable if a single organic solvent is used, that the organic solvent is used to dissolve at least 10% by weight of water at 20 ° C is capable. If two or more organic solvents are used in admixture it is favorable that the solvent mixture is capable of dissolving at least 10% by weight of water at 20 ° C ice.

Illustrative examples of solvents or solvent systems are those discussed earlier.

According to the preferred embodiment of the invention, the coating liquid contains the topmost one for drawing up Layer of the photosensitive printing plate precursor in the aqueous polymer latex discussed above in an amount in the range from about 0.0001% by weight to about 10% by weight, given as the solid content, based on the organic solvents discussed above. The further below 0.0001% by weight the content, the more The stability of the dispersion of the hydrophobic polymer particles is lower and the faster the dispersion has to be are consumed during manufacture. On the other hand, ever The higher the content is above 10% by weight, the greater the tendency of the latex particles to agglomerate, as a result of which no improvement in the stability of the dispersion of the fine particulate material is obtained. That's why the content of the aqueous polymer latex is preferably about 0.005 to 5% by weight, more preferably about 0.01 to 2% by weight, given as the solid content, based on the organic solvents.

030039/081 1

The amount of in the dispersion according to the invention contained water due to the incorporation of the aqueous polymer latex is not more than about 10 wt.%, Preferably not more than 3% by weight, based on the organic solvent.

The fine particulate material and optionally The coating liquid containing the aqueous polymer latex can be applied to the carrier by various measures, such as coating by knife coating, roller coating, gravure coating, bead coating and dip coating be applied.

The layer of coating liquid can be dried in the usual way by adding the solvent at room temperature or an elevated temperature is left to evaporate. The drying temperature is preferably about 20 ° C to about 150 ° C, more preferably about 50 up to 120 ° C. Drying can also be carried out using hot air. The air temperature is about 30 ° C to 200 ° C, especially 40 to 140 ° C. The Drying temperature is not necessarily kept at a value during drying, but can be gradual increase. In some cases, beneficial results are obtained when the moisture is removed from the drying air. The heated air becomes the coated Surface at a speed of about 0.1 m / sec to 30 m / sec, in particular about 0.5 m / sec to 20 m / sec, fed "

The dry coating amount of the photosensitive coating thus prepared is preferably about 0.1 to about 7 g / m and more preferably 0.5 to

030039/0811

-X-

J9 3009028

4- g / m for the size of a planographic printing plate.

The previous explanations were used for the layer structure of a light-sensitive pianographic plate, which was produced according to the invention, the photosensitive coating being the top layer, d. H. the surface furthest from the wearer. However, the method according to the invention is also based on that in the TJS patent 3 136 637 applicable layer structure, which comprises a support, a diazo resin layer and a uppermost resin layer, which is oleophilic, hydrophobic, insoluble in water and swellable with organic solvents, wherein the surface is roughened by the presence of a matting agent. A cross section of a such structure is shown in Figs. 7 (&) and (b), in which the cross-section of the substrate 10 and the diazo resin layer 20 on the substrate are shown to be straight have been provided with a coating liquid which is oleophilic, hydrophobic, water-insoluble and in solvent swellable8 resin, such as poly (vinyl formal), dissolved in a suitable solvent, and the finely divided material 50 dispersed in this solution. The finely divided material 50 is stable in the solution dispersed and this stability is also maintained in the coating liquid layer 3OC spread over the support. The polymer latex is not shown, but is present according to a preferred embodiment of the invention.

Fig. 7 (b) shows a cross section through the same material as in Fig. 7 (a) after the evaporation of the volatile constituents in the liquid, whereby the fine

030039/081 1

ORIGINAL INSPECTED

to 30099 /

divided material 50 is retained on the surface of the outermost resin layer 30, practically all of it Volume of the matting agent is forced out or excluded from the dried layer. Venn the in photosensitive pianographic produced in this way Plate is subjected to imagewise exposure, the exposed area of the photosensitive coating in the Developer insoluble and at the same time is firmly bound to the resin layer on top. On the other hand remains the unexposed area of the photosensitive coating unchanged and soluble in the developing liquid. Therefore, when the exposed plate is subjected to development, the developing liquid can easily pass through penetrate the superficial resin layer, leaving the unexposed area of the photosensitive coating reaches and dissolves. If you rub the surface of the plate lightly with, for example, a piece of cotton wool, will the unexposed area together with the one above it Resin layer removed while in the exposed area of the photosensitive coating the photosensitive coating remains on the support together with the overlying resin layer without it being affected by the Developer liquid is attacked. In this development process, it becomes on the surface of the resin layer adhering finely divided material completely removed, as can be seen from FIG. 8, with the exposed Areas of the photosensitive coating 20A and the overlying resin layer 30A on the support 10 remain.

According to the invention, there is thus an improved method proposed for the production of a photosensitive printing plate, in which the photosensitive coating with

030039/0811

ORiGiNAL INSPECTED

a roughened surface through stable dispersion of particles of a finely divided matting agent in the coating solution for the outermost layer of the plate, which is advantageously a photosensitive layer is, and after spreading the solution on the substrate and removing the solvent is equipped, wherein the dispersion is destroyed and a dried coating is obtained in which the finely divided matting agent is distributed over the outer surface of the coating in the form of very small projections.

The preparation of the coating liquid for the surface resin layer of the photosensitive pianoographic Plate can be carried out by the same process as has been used previously for the production of coating liquids for photosensitive coatings have been applied and dealt with.

The development or treatment of the according to the invention produced photosensitive printing plate can be carried out by any conventionally known method, which do not require any special modifications.

The invention is explained in detail below with reference to the following examples, in which all parts are by weight unless otherwise specified.

example 1

An aluminum plate with a thickness of 0.24 mm was made by immersion in a 7% aqueous solution of Trisodium phosphate degreased at 60 ° C and after rinsing

030039/0811

ORIGINAL INSPECTED

the surface was grained with water by rubbing with a nylon brush under a stream of water with pumice suspended therein. After thoroughly rinsing with water, the plate was immersed in a 5 / <age aqueous sodium silicate solution (molar ratio SiO ₃ : Na ₃ O = 3.1 to 3.3: 1) of JIS-3 quality and kept at 70 ° C. for 30 to 60 years Held for seconds.

After thorough rinsing with water and drying, each of the coating compositions listed in the table below was used on a piece of the produced in this way Aluminum carrier applied.

Table I Details of the coating mass

Compare mass

2-hydroxyethyl methacrylate at 0.87 g

the content of a tetramer

2-hydroxyethyl methacrylate /

Acrylonitrile / O ethyl methacrylate /

Methacrylic acid accordingly

Example 1 of U.S. Patent

4 123 276 as copolymer (I)

2-methoxy-4-hydroxy-5-benzoyl-0.1 g

benzenesulfonic acid salt of a p-Diazo diphenylamine / paraformaldehyde condensate s

oil blue No. 603 (CI. 74-350, 0.03 g product of Orient Chemical Ind., Ltd.)

Methanol 6 g

2-methoxyethanol 6 g

030039/0811

το 3009 828 Table I. (Continuation) specification Coating compound comparison Mass C ₂ Coating Compound C ₁ 10 g Glass beads (avg
diameter 10 / in) 0.03 g comparison Mass C ^ Coating Compound Cj 10 g Siloyd (silica gel with a
average diameter
from 10 / um of the Fuji-Davidson Co.) 0.03 g comparison m
Mass C ^ Coating compound C-, 10 g Pumice (average diameter
10 / µm; 0.03 g comparison Coating Compound C, -

example 1

Mass C ₁

Finely-divided urea / formaldehyde resin (average Diameter 10 / um)

Mass C ₁ -

10 g
0.03 g

Coating Compound C-

Particulate polyethylene (average diameter 10 / µm)

10 g
0.03 g

The coating amount on a dry basis was 1.0 g / m 2 in each example. The from the coating compounds Cp C ^,

Cc and

obtained photosensitive lithographic

Plates are called Plates C ^,

Designated Cc and Cg.

030 0 39/081 1

Each of the plates C ₂ to Cg required a vacuum contact time 1/2 to 1/3 shorter than the plate Cp. Each plate was exposed to light from a metal halide lamp at a distance of 1 m for 40 seconds through a vacuum-contacted original and then by immersion developed into the subsequent developing liquid for 1 minute at room temperature, after which it was gently rubbed with cotton wool so that the unexposed part of the photosensitive coating was removed.

Developer fluid

Benzyl alcohol 3 »O g

Sodium isopropylnaphthalene sulfate 1.0 g

Sodium silicate (40% aqueous solution) 1.0 g

Water 95 g

Each of the treated plates thus prepared was used for printing. The ones from the plates C ,. and Cg printing plates held 50,000 prints while those obtained from plates Cg, C ^, C ^ and Cc gave only 20,000 to 30,000 prints.

The printing plates from plates C _x . and Cg gave printed matter with good tone reproduction, while the printed matter made from plates C ₂ to Cc showed poor tone reproduction. Microscopic examination of the surface of each printing plate immediately after development showed the presence of finely divided particles in the image area of the printing plates from the plates Cp » ^C 3» ^C 4 ^ ** ^ 5 »but no fine particles in the image area the pressure plate from the plate Cg *

030039/0811 "

ORIGINAL

As for the photosensitive lithographic plates before development, their surfaces were carefully examined under a microscope. The investigation showed that for plates C ₂ to Cc the particulate materials were more or less embedded in the photosensitive coating, while for plate Cg the matting agent practically protruded from the coating. From these observations it can be seen that the particles of glass beads, silica gel, pumice, urea / formaldehyde resin, which were used in the coating mixtures Cp to Cc, e.vae strong affinity for the coating solvent, the mixture of methanol and 2-methoxyethanol , so that they are not driven out to the surface of the coating, while the polyethylene particles, which show poor affinity for the above mixed solvent, are almost completely driven out of the outer surface of the dried coating.

Further, each plate was subjected to development with a spent developer of the same composition as above subjected, with only the plate manufactured according to the invention being successfully developed, and the other plates prepared as comparative examples show incomplete dissolution of the non-image areas showed.

Although the manufacturing method of a negative type photosensitive lithographic plate based on a diazonium resin as a photosensitive material is described in Example Λ, it goes without saying that the present invention is also applicable to the manufacture of various other types of photosensitive plates.

030039/081 1

Examples 2 to 4-

According to the procedure of Example 1, photosensitive pianoographic plates Cr ₇ to C ^ _{0 were} prepared by using coating liquids Cn to C ^ ₀ having the following compositions.

030039/081 1 ORIGINAL

Table II

Coating liquid

Solvent composition

2-methoxyethanol

Nethanoi

6.0 g

6.0 g

^C 8 2-methoxyethanol 6.0 g ο Methyl ethyl ketone 6.0 g to O
O C ₉ 2-methoxyethanol 6.0 g OJ
CD Acetonitrile 6.0 g O ^C 10 2-methoxyethanol 6.0 g OO Methyl ethyl ketone 3.0 g Methanol 3.0 g

Festo components (non-volatile) (common for the four liquids)

2-hydroxyethyl ethacrylate copolymer (I) as used in Example 1

2-Methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid salζ of a p-diazodiphenylamine / paraformaldehyde condensate

oil blue No. 603 (CI. 74-350, product of Opient Chemical Ind., Ltd.)

Powdered polyethylene with an average particle size of 10 / um

0.87 g

0.1 g

0.03 g 0.03 g

The microscopic examination of the plate surfaces found that the polyethylene parts are very small in shape Projections were present, practically the entire volume of which was exposed after drying. The vacuum contact period for each plate was determined and all plates showed a factor of 1/2 to 1/3 shorter Values as the plate made in Example 1 C ^.

Each plate was exposed and developed imagewise and then subjected to printing as in Example 1, the durability of all panels was found to be equivalent to that of panel C of Example 1; H. 5,000 prints. Furthermore, the sound reproduction properties were also equivalent and the polyethylene particles became in the image area of all plates after development not observed.

Examples 5 and 6

The procedures described in Example 1 were repeated using the coating liquids C ^ and C ₁₂ ^m ^ of the following composition.

Example 5 mass C ^

Coating liquid C ₁ prepared

according to example 1 10 g

Powdered polypropylene (mean particle size 10 µm) 0.03 S

Example 5 mass

Coating liquid C ₁ prepared

according to example 1 10 g

Powdered ethylene / propylene copolymer (mean particle size

¹⁰ / ^µm) 0.03 g

030039/081 1

ORIGINAL INSPECTED

Microscopic observation revealed that each of the light-sensitive pianoographic plates manufactured in this way use the finely-divided material used on the coating surface of the photosensitive coating in I (? form of very small protrusions protruding from the coating had bound. The vacuum contact period for each of panels C * ^ and C ^. ^ Was determined and all panels showed values shorter by a factor of 1/2 to 1/3 than the plate C ^ produced in Example 1.

Each plate was imagewise exposed and developed, followed by printing as in Example 1, the durability of all plates being proven to be equivalent to plate G, ₍ ie 50,000 impressions not observed after development.

Example 7

A 0.3 mm thick, grained aluminum plate was anodized in a sulfuric acid bath, so that an oxide surface

sheet film was obtained in an amount of about 2 g / m 2. After rinsing and drying, it became a coating liquid made of the following components on their surface

pulled so that a coating amount of about 2.5 g / m 2 obtained became.

Naphthoquinone-1,2-diazide-5-sulfonic acid

ester of polyhydroxyphenyl (compound

according to Example 1 of the TJS patent

3 635 709) 1 g

030039/0811

ORIGINAL INSPECTED

Powdered polyethylene (mean particle diameter 10 µm) 0.03 g

2-methoxyethanol 6 g

Methanol 6 g

Microscopic examination of the surface of the photosensitive coating produced in this way found that the polyethylene particles on the surface in the form of very small protrusions that protrude from the surface stretched, bound.

Determining the vacuum contact time "of this photosensitive pianographic plate gave a value 1/2 to 1/3 shorter compared to that a plate obtained by using a coating liquid containing no matting agent had been. After imagewise exposure was carried out as in Example 1, the plate became transferred to a pianographic printing plate by development with an aqueous 7% sodium silicate solution. The obtained plate withstood 60,000 prints and showed the same durability as that using one Coating liquid obtained without matting agent. The sound reproduction properties were also the same Comparison plate. When the image area surface was observed with a microscope, the presence of polyethylene particles not determined.

Aqueous polymer latices

The aqueous polymer latex I used in the following examples, as is also given in Table III, was prepared in the following manner.

030039/081 1

5ή 300992S

A sealed 10 liter glass reactor equipped with a temperature controller, stirrer, reflux condenser, heater and gas inlet was purged with nitrogen gas and charged with 7 »2 liters of distilled water and 90 g of a surfactant A, as indicated below, for emulsion polymerization. The mixture was heated to 60 ° C where it was then stirred to form a solution. Ethylenically unsaturated vinyl monomers (1.1 kg butyl methacrylate and 0.7 kg glycidyl methacrylate) were added to the solution, which was stirred at 50 to 200 rpm for 30 minutes at 60 ° G until the emulsion was formed. Polymerization initiators (1.3 g of aluminum persulfate and 0.4 g of sodium bisulfite) were added to the emulsion to start the polymerization, which proceeded over a period of 3 hours. The temperature of the reaction mixture increased from 69 ° C to about 75 ° C due to the heat of polymerization. After a 5 hour polymerization, the raw reaction product was cooled to 40 ° C. The aqueous polymer latex I obtained had a particle size of 0.03 to 0.07 μm and a solids content of 20% by weight.

The same procedure was used to prepare the aqueous polymer latex II listed in Table III. For the production of the aqueous Polyraerlatices III and IV, 0.36 kg of 1.8 kg of the vinyl monomers were first introduced into the reactor and emulsified with stirring and concurrently with the addition of the polymerization initiators, the remaining 1.44 kg of the monomers became dropwise added to the emulsion at the start of the polymerization.

030039/0811

ORIGINAL INSPECTED

Sl

OO

Dispersants A to E for emulsion polymerization

A:

^: 9 ^H 19 \ yO (CH ₂ CH ₂ O) ₃ (CH ₂ ) ₄ SO ₃ Na

B:

(CH ₂ ), SO ₃ Na

// XVo (CH ₂ CH ₂ O) ₃ H

D: C ₁

SO ₃ Na SO ₃ Na

030039/081

Table III

Aqueous polymer latex

Vinyl monomers

II

IV

Butyl methacrylate Gl y ei dyl methacrylate

Ethyl acrylate

Styrene

Butyl acrylate

Acrylic acid

N-methylol acrylamide

Diethylaminoethyl methacrylate

Ethylene glycol dimethacrylate

1.1
0.7

0.72

0.72 0.09 0.27

1.71 0.09

Surface active content of
Agent for the emul surfaces
sion polymerization active with
tel (g)

Average particle size

B / G
(95/5)

D / E
(70/30)

90

B: 128
C: 7

D: 21
E: 9

0.03-0.07 0.03-0.07

0.05-0.10

0.06-0.10

co

CD

CO

co

CQ

Examples 8 to 11 and Comparative Example 1

An aluminum plate with a thickness of 0.24 mm was through. Immersion in an aqueous 7% solution of tertiary sodium phosphate degreased at 60 ° C, washed with water and granulated with a nylon brush, with which the surface of the plate was rubbed with an aqueous suspension of pumice powder flowing over the plate. After washing with water, the granular plate was immersed in a 5% strength aqueous solution of sodium silicate JIS No. 3 (SiO ₂ / Na ₂ O = 3.1 to 3.3 as molar ratio) at 70 ° C. for 30 to 60 seconds .

After thoroughly washing with water and drying, the plate was coated with the coating liquids (C ^^) to (CLn) shown in Table IV below and dried to obtain the photosensitive lithographic printing plates CL ^ to C- η became.

030039 / 0.8 H ORHIHAL .NSPl = CIH,

as

3009 ^f 328

Attempt-

Comp. Ex. 1

Table IV Composition of the coating composition

Coating compound ''

2-hydroxyethyl / methacrylate Copolymer (as described in Example 1 of U.S. Patent 4,123,276)

2-Methoxy— ⁱ } —hydroxy-5-benzoylbenzenesulfonic acid sal of a p-mazophenylamine / paraformaldehyde-cyclic condensate

oil blue Ur. 603

(CI. 7435O, product of the rient

Chemical Industry Co., Ltd.) 2-methoxyethanol

Powdered polyethylene (average particle size 10 / um)

Example 8 Coating Compound

Example 9

coating compound (C ^^) Vässrigex * polymer latex I coating compound (C ^ c)

Coating compound (C ^) Aqueous polymer latex II Example 10 Coating mass (C ^ g)

Coating Compound (C ^ ₅ ) Aqueous Polymer Latex III Example 11 Coating Compound (C ^ r ₇ )

Coating compound (C ^,) Aqueous polymer latex IY

0.87 g 0.1 g

0.03 g

12.0 g 0.03 S

10 g
0.02 g

Ί0 g
0.02 g

10 g
0.02 g

10 g
0.02 g

030039/081 1

ii-; U

Each coating liquid was allowed to stand for 1 hour before being applied to the plate. The dry weight of the coating layer was 1.0 g / m 2. Examination of the surfaces of the photosensitive lithographic printing plate precursors C ₁ * to C ^ r ₇ revealed that the plate G ^ had fine particles exposed on the surface and that the particles were adhered to the surface. However, the individual particles were not uniformly dispersed but adhered to each other. On the other hand, each of the photosensitive lithographic printing plate precursors C ^ to C ^ n had fine particles exposed on the surface, and these particles adhered to the surface and were uniformly dispersed.

Each of these photosensitive lithographic printing plates was in intimate contact with a negative one transparent original image brought by the vacuum contact method. The time required to achieve the desired Contact was one-half to one-third that for a photosensitive lithographic printing plate required time produced without the fine particles. Each of the plates was in intimate contact with the original, image-wise, for 40 seconds, attached to an image at a distance of 1 m from the plate precursor Exposed to metal halide lamp. Then the plate was added to a developer of the following composition Tree temperature immersed for 1 minute. The surface of the plate was then lightly rubbed with cotton wool, to remove the unexposed area. A lithographic printing plate was thereby prepared.

030 0 39/0811

ORiGfNAL INSPECTED

S?

Benzyl alcohol 3.0 g

sodium isopropyl naphthalene sulfonate 1.0 g Sodium silicate (40% aqueous

Solution) 1.0 g

Water 95 g

The printing plates made from the photosensitive lithographic printing plates CL to CLr ₇ could print 50,000 reproductions.

Microscopic observation revealed that the fine particles were absent from the surfaces of the image areas of the newly developed lithographic printing plates made from the photosensitive lithographic printing plate precursors CL-to Gy, n .

Examples 12 to 14 and Comparative Examples 2 to 4

The procedure of Example 8 was followed to prepare lithographic photosensitive printing plate precursors CLg to Cp ^ using six coating fluids (Cvjg) to (C03) with those in columns I. and II of the following compositions given in Table V are repeated.

030039/081 1

coating Table V I. 6.0 g
6.0 g Attempt-
No. (O ₁₈ ) 2-methoxyethanol
Methanol 6.0 g
6.0 g
0.02 g Compare «-
example 2 (O ₁₉ ) 2-methoxyethanol
Methanol
Aqueous polymer latex I. 6.0 g
6.0 g Example 12 (O ₂₀ ) 2-methoxyethanol
Methyl ethyl ketone 6.0 g
6.0 g
. 0.02 g Comp.-
example 3 (O ₂₁ ) 2-methoxyethanol
Methyl ethyl ketone
Aqueous polymer latex I. 6.0 g
5.0 g
5.0 β "> Example 13
CD
O
CJ (O ₂₂ ) 2-methoxyethanol
Methyl ethyl ketone
Methanol 6.0 g
5.0 g
5.0 g
0.02 g <° Comp.
_o example 4
OO (C ₂₃ ) 2-methoxyethanol
Methyl ethyl ketone
Methanol
Aqueous polymer latex I. ^ Example 14

II *

2-Hydroxyethyl / methacrylate copolyraeres (like i ^ L used in example 8)

2-methoxy-4-hydroxy-5-benzoylbenzenesul hair dryer acid sal r. of a p-diazodiphenylamine / paraformaldehyde condensate

oil blue Wr. 603 (0.1. 74350, Product of Orient Chemical Industry Oo., Ltd.)

Powdered polyethylene (average particle

size 10 / um)

Composition II is common to both Examples 12 to Comparative Examples 2 to 4.

and

0.87 g 0.1 g

0.03 g 0.03 g

fc *

OO O

CD

CD

CO

ro

CDO

.3.

3009S28

Each coating was allowed to stand for 1 hour before being applied to the aluminum plate. The dry weight of the coated photosensitive layer was 1.0 g / m ₂ · Observation of the surfaces of the photosensitive lithographic printing plates revealed that each plate had fine particles exposed on the surface of the photosensitive layer and that the particles were adhered to the surface. The fine particles were exposed on the surfaces of the photosensitive lithographic printing plate precursors C ^ g, Cp ₀ and C ₂₂ , but adhered together and. were not uniformly dispersed. On the other hand, the photosensitive lithographic printing plate precursors CLq, C ₂ ^ and C ₂ ^ showed uniform dispersion of the fine particles on the surfaces.

The time required to each of the photosensitive Bringing printing plate precursors into intimate contact with a negative original image using the vacuum contact method, was one-half to one-third that required with a photosensitive lithographic printing plate Time produced with no fine particles.

Each of the plates was made in close contact with the original image imagewise in the same manner as in Example 1 exposed. The exposed plate was developed in the same manner as in Example 1 to give the lithographic one Printing plate. Each plate could print 50,000 reproductions. The examination showed the absence of fine particles from the surface of the image area of each printing plate.

030039/0811

ORIGINAL INSPECTED

Examples 15 and 16

The procedure of Example 8 was used to prepare the light-sensitive lithographic printing plate precursors C ₂ ^ and C ₂ C. under application of the two Überüugsflüssigkeiten C ₂ ^ and C ₂ c with the one indicated in columns I and II of the following Table VI compositions repeated.

030039/081 1

ORIGINA INSPECTED

Table VI

O O CO CD

Try-Mr.

Example 15 Example 16

Coating compound

(C ₂₅ )

Polypropylene particles 0.03 g (average particle size 10 / um)

Crosslinked Styrene Diviny] - 0.03 g benzene particles (average particle size 25 / um)

Composition II is common to Examples 15 and 15.

II ¹

2-hydroxyethyl / methacrylate Copolymer (as used in Example 8-)

2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid salt of a p-diazodiphenyl amine / paraformaldehyde condensate

oil blue No. 603
2-methoxyethanol
Aqueous polymer latex I.

0.87 g

0.1 g

0.03 S 12.0 g 0.02 g

CD

CD

(D

CX)

Each coating liquid was allowed to stand for 1 hour, before it was applied to the aluminum plate. The dry weight of the photosensitive layer applied

was 1.0 g / m. Any of the obtained photosensitive The lithographic printing plate precursor had fine exposed on the surface of the photosensitive layer Particles; the particles adhered to the surface and they were uniformly dispersed without sticking together.

Examples 17 and 18 and comparative examples 5 and 6

A grained aluminum plate 0.3 mm thick was immersed in sulfuric acid to form an oxide film

anodized in an amount of about 2 g / m 2. The plate was thoroughly washed with water and dried. Then they were coated with the coating liquids (C ₂₆ ) to (C ₂ ^) having the compositions listed in columns I and II of the following table "VTI. After drying, photosensitive lithographic printing ink precursors Cpg to C ₂ Q were obtained each had a photosensitive layer with a dry weight of about 2.5 g / m 2.

£ 30039/081 1

ORIGINAL INSPECTED

Attempt-
No. Coating
Dimensions Table VII I. 6.0 g
6.0 g Comp.-
example 5 <° 26> 2-methoxyethanol
Methanol 6.0 g
6.0 g
0.02 g Beep. 17th (C ₂₇ ) 2-methoxyethanol
Methanol
Aqueous polymer
latex I 6.0 g
6.0 g Comp.-
example 6 (C ₂₈ ) Methylcellosolve
acetate
Methyl ethyl ketone 6.0 g
6.0 g
0.02 g O Example 18 (C ₂₉ ) Methylcellosolve
acetate
Methyl ethyl ketone
Aqueous polymer
latex I 30039/0 OO
I.
1

II '

Naphthoquinone-1,? .- diazido-5-sulfonate ester of polyhydroxyphenyl (as described in Example 1 of U.S. Patent 3,635,709)

Phenolic uovolak formaldehyde resin

Polyethylene particles
(average particle size 10 / um)

* Composition II is common to Examples 17 and 18 and Comparative Examples 5 and 6.

1

2 g 0.03 g

CD

CD

CO

OO

Each coating liquid was allowed to stand for 1 hour before being applied to the aluminum plate. Examination of the surface of each photosensitive printing plate precursor revealed that the fine particles on the plates Cpg and Cpo adhered together and were not uniformly dispersed. On the other hand, the fine particles were uniformly dispersed on the surfaces of the plates G 1 and C _{2 Q.} In each of the photosensitive lithographic printing plate precursors, the fine particles were exposed and adhered to the surface.

The time required for each photosensitive printing plate precursor to be in intimate contact with a positive Bringing a transparent original image by the vacuum contact method was one half to one third the time required for a photosensitive lithographic printing plate precursor, that in the absence was made of fine particles.

Each of the precursor was then bildwsise exposed in the same manner as in Example 8, and developed with a 7% aqueous sodium silicate solution iS ^s, to produce the lithographic printing plate. 60,000 reproductions could be printed, and this number is equal to that obtained with a conventional printing plate made from a precursor coated with a liquid containing no matting agent. The disks made from the precursor according to the invention also had the same sound reproduction properties as the conventional disk. Examination of the developed precursors showed that polyethylene particles were absent in the image area of the plates obtained in each case.

030039/0811

jp> [

The invention has been described above on the basis of a preferred embodiment s forms are described without being limited to them.

^030039/0811

e e r s e

it

Claims (8)

Claims (1. Process for the production of a loan-sensitive Printing plate, the outermost surface of which with a finely divided Material is matted, whereby the outermost layer matted on the surface was obtained by applying a mass, which disperses a finely divided material in a solvent solution of the constituents forming the outermost layer contains, characterized in that the finely divided material is stably dispersed in the coating composition for the outermost layer and upon evaporation of the solvent from the Mass the dispersion is destroyed and the single ceilchen of the finely divided material driven out of the mass of the layer and as particles bound to the surface of the outermost layer in the form of very small protrusions the evaporation of the volatile constituents remain behind. 2. The method according to claim 1, characterized in that that a coating compound is used for the outermost layer, which additionally contains an aqueous polymer latex. 3. Method according to claim 1 or 2, characterized in that that a finely divided material with an average particle diameter of about 5 to 40 / To is used. 4. The method according to claim 1 to 3, characterized in that that as a finely divided material polyethylene 03Cf39 / 0811 30099-8 particles, polypropylene particles, ethylene-propylene copolymer particles, Ethylene-vinyl acetate copolymer particles, polyethylene terephthalate particles and / or crosslinked vinyl polymer particles be used. 5 · The method according to claim 2 to 4-, characterized in that an aqueous polymer latex is used which does not flocculate and in the solvent for the
Coating composition for the outermost layer is insoluble. 6. The method according to claim 2 to 5i, characterized in that that an aqueous polymer latex with an average particle size of about 0.001 bit * about 0.1 times the average particle size of the finely-divided Material is used. 7- method according to claim 1 to 6, characterized in that that a light-sensitive layer is used as the outermost layer. 8. The method according to claim 1 to 6, characterized in that the outermost layer is a non-photosensitive Resin layer is applied. 9 · Photosensitive printing plate, made according to
the method of claims 1 to 8. 0 3 Γ ■ .-: 3/081 1