DE2718130B1 - Photosensitive recording material - Google Patents

Description

R,

NH

contains, in which Ri and R2 are equal to an alkyl, aryl or substituted aryl group or equal to a heterocyclic ring, R ₃ and R ₄ equal to a CN, COOR 'or COR' group, where R 'is an alkyl, is substituted alkyl or aryl group, and in which Ri and Rj and / or R 2 and R4 are the same as the atoms required to complete a 5- or 6-membered carbocyclic or heterocyclic ring.

2. Photosensitive recording material according to claim 1, characterized in that the light-sensitive layer as a dihydropyridine compound

1,4-dihydro-2,6-dimethyl-4- (5'-nitro-

2'-furyl) -3,5-diacetopyridine or
1,4-dihydro-2,6-dimethyl-4- (5'-nitro-

2'-furyl) pyridine-3,5-dicarboxylic acid

di-tert-butyl ester or
1,4-dihydro-2,6-dimethyl-4- (5'-nitro-2'-furyl) -

pyridine-3,5-dicarboxylic acid diethyl ester
contains.

3. Photosensitive recording material according to Claims 1 and 2, characterized in that that the photosensitive layer as a dihydropyridine compound

1,4-dihydro-2,6-dimethyl-4- (5'-nitro-2'-furyl) -pyridine-3,5-dicarboxylic acid-
di-tert-butyl ester

and contains a styrene-maleic anhydride copolymer as a binder.

The invention relates to a photosensitive material for producing positive relief images, consisting of composed of a support and a photosensitive layer which is a derivative of a dihydropyridine compound and contains at least one binder.

It is known to use light-sensitive materials for image recording in reproduction technology, which change their solubility when exposed to light. Depending on whether the As solubility is increased or decreased, the image will be negative or positive.

Most of the known processes for the production of relief images produce negative image records,

while positive working systems are rarer.

A well-known positive working system is based on the light decomposition of o-quinonediazides. The one with it occurring light decomposition products are more soluble in aqueous alkaline solutions than that Output connections.

From DE-OS 23 38 223 a positive working system has become known, which consists essentially of Hexaaryldiimidazolylene, a hydrogen donor, an ethylenically unsaturated compound and consists of a binder.

Another positive working material is known from DE-OS 22 42 106. This material contains as photosensitive compound a 4- (2'-nitrophenyl) -1,4-dihydropyridine and is characterized above all by a comparatively high sensitivity to light as well a simple way of processing. The disadvantage, however, is that the solubility difference between exposed and unexposed parts of the image are present but not for many practical purposes is big enough. As a result of this small difference in solubility, the unexposed areas already loosened before the structure of the relief image is completed, which leads to a poorly formed relief, thin layers and a reduced sharpness of the image. These Defects can have very detrimental effects in a wide variety of applications. Should that Material e.g. B. are used for the production of printed circuits, it is after the washout process The light-sensitive layer remaining on the surface is already partially dissolved during the wash-out process, and so on thin that it no longer fully fulfills its purpose as a masking template during the etching process, so that Incorrect etchings occur, which affect the quality of the printed circuit. Shall the layers go to Production of offset plates are used, so the mechanical strength and thus the lack Efficiency.

A big difference in the solubility of exposed and unexposed areas; H. a broad one Processing latitude, thus, is an essential requirement that a photosensitive material has is processed after the washout process, must meet.

The object of the present invention is therefore to provide a photosensitive material for the production of positive Indicate relief images, which has an improved processing latitude.

This object can be achieved according to the invention by a photosensitive recording material for production positive relief images are solved, which is characterized in that the light-sensitive layer a dihydropyridine compound of the general formula

R ₄ R ₂

contains, in which Ri and R2 are an alkyl, aryl or substituted aryl group or equal to a heterocyclic

ORIGINAL / NSPECTED

clic ring, R ₃ and R _{4 are} equal to a CN, COOR 'or COR' group, in which R 'denotes an alkyl, substituted alkyl or aryl group, and in which Ri and R3 and / or R2 and R4 is the same as the one to complete

Tabel

a 5- or 6-membered carbocyclic or heterocyclic Ringes are required atoms.

Suitable dihydropyridine compounds are listed in the table.

K,

K ₁

CH,
CH,
CH,

CU,

NO ₂

C ₄ H.,
CH,

-CH,

CH,

CH,

CH, C | CH,) ₂ CH ₂ CO

CH ₁ -CH ₁ CH, CO

COOCH, CH, COCH, -CH, COOClCH,), CW, COOC _{2 ms} -CH, COOC _{2 ms} C ₁ -H ₁₅ COOC ₂ H ₅ "\ / COOC ₂ IIs _. · ■ '\
\ COOC _{2 ms} C ₄ H, CN CH, COOC ₂ H, / "" \
\ ^/ COOC _{2 ms} S. COOC, Hs CH, C

-OH,

V-NO ₁

- COOCH,

-COCH,

-COOC (CH,),

COOC ₂ H ₅
"COOC ₂ H ₅

COC) C ₇ H ₅

COOC ₂ H ₅

COOC ₂ H ₅
CN

CO

The 1,4-dihydro-4- (5'-nitro-2'-furyl) pyridines according to the invention can be synthesized by Hantz's pyridine of 5-nitrofurfural, a ^ -Ketocarbonsäureester or a ß-Ketocarbonsäurenitril or a 0-diketone and ammonia or a jI-aminocrotonic acid ester (Elderfield, Heterocycl. Compounds, Vol. 1.1950, p. 462 ff.).

The synthesis of 1,4-dihydro-2,6-dimethyl-4- (5'-ni-

Tro-2'-furyl) pyridine-3,5-dicarboxylic acid di-tert-butyl ester (compound 3 in the table) is shown below described, other connections can be made in the same way:

A solution from

24.4 g of 5-nitrofurfural diacetate

33.2 g of tert-butyl acetoacetate, 5.0 g of ammonium acetate

5.0 ml ammonia solution (25%)

in 40 ml of pyridine was heated on a steam bath for 6 hours. After cooling, the solution was poured into 1 liter of ice water and left to stand at ⁰ ° C. over Nachi. The deposited precipitate was recrystallized 4 times from hot ethanol. 12 g of yellow needles with a melting point of 195 ° C. are obtained.

To produce the light-sensitive recording material, the 4- (5'-nitro-2'-furyl) -l, 4-di- CW, CO

CW ₂ C (CH,), -CH ₂ -CO

CH, CH, CH, C ■■ - ()

hydropyridines with at least one known, suitably alkali-soluble binder according to the usual Coating process applied to a substrate. Suitable for the stated purpose A large number of alkali-soluble binders are known. These binders often contain alkali-solubilizing agents Groups such as acid anhydride, carboxyl, sulfonic acid groups and the like may be mentioned as examples: acrylic acid or methacrylic acid, polymers or their copolymers with other suitable monomers, such as. B. Acrylic acid esters or other acrylic derivatives, vinyl compounds, such as vinyl ether, vinyl acetate or its saponification product, Styrene, vinyl pyrrolidone, butadiene and related monomers. Polyacrylic anhydrides, copolymers of maleic anhydride, maleic acid, maleic acid half-esters, half-amides or anhydrides and Derivatives of related compounds such as B. itaconic acid, with suitable comonomers, such as. B. styrene, Ethylene, vinyl ethers, vinyl acetates, etc., polystyrene sulfonic acid or its copolymers, cellulose derivatives, such as B. carboxymethyl cellulose, cellulose phthalate or succinate, alginic acid and its derivatives. Suitable are also phenol-formaldehyde resins, known as novolaks.

Particularly advantageous binders for the production of materials according to the invention have proven to be

Styrene-maleic anhydride copolymers proved. The concentration of the 1,4-dihydro-4- (5'-nitro-2'-furyl) pyridines is about 20 to 80% by weight, based on the total weight of the photosensitive composition. The dihydropyridine compounds can stand alone or used in admixture with one another.

The sensitivity of the layer can be increased considerably by adding sensitizers. Suitable sensitizers are known from the literature, e.g. B. benzophenone, Michler's ketone, hexaarylbisimidazole. Michlers in particular have proven themselves Ketone, p-dimethylamino-benzaldehyde, 5-nitroindazolone, nitroaniline and others. The photosensitive layer can also suitable dyes and pigments and other additives such as plasticizers, adhesion promoters and the like. contain.

The conventional, known layer supports can be used as the support, their use is common in the manufacture of photographic materials of the type described herein. Paper is suitable, coated papers, foils and plates made of metal, e.g. B. aluminum and copper, furthermore layer substrates synthetic polymeric materials such as polyethylene, polypropylene, polyesters such as polyethylene terephthalate, Polyamides and substrates made of cellulose acetate, cellulose butyrate or cellulose acetate butyrate. The photosensitive layer can be applied directly to one of these Layer carrier applied and used with this to produce the relief image. However, the light-sensitive layer can also initially be applied to one so-called temporary layer carrier, preferably a transparent plastic film, applied and only immediately prior to exposure by lamination to the support with which the layer is to be used.

The recording material can also contain customary intermediate layers in order to make the light-sensitive Anchoring the layer on the substrate. Dyes, Pigments or the like. Be present.

The photosensitive to produce the images Material with light sources emitting radiation rich in ultraviolet light, e.g. B. mercury vapor lamps, xenon lamps and the like behind a template exposed The exposed material is then developed by washing out the exposed parts of the image For washing out, aqueous alkaline solutions are preferably used, which can be used as suitable alkalis e.g. Alkali carbonates, borates and alkali hydroxides as well as the known carbonate, borate and phosphate buffer systems can contain. The washout solutions can also contain surface-active substances. Depending on the type of binder used, the Of course, organic solvents can also be used for washing out.

The photosensitive recording material described is extremely suitable for the production of Printing forms, in particular offset printing forms and for the production of printed circuits. Further can be transparent or opaque copies of line, halftone or halftone originals that are positive for presentation getting produced.

That the 4- (5'-nitro-2'-furyl) -l, 4-dihydropyridines described light-sensitive compounds with so good properties were completely surprising and not obvious to the person skilled in the art. From literature (J. Am. Chem. Soc, 77/1955, p. 447, lines 1 -3 right column and Note 3) it is known that the Sensitivity to light from the position of the nitro group in the molecule is dependent So the 4- {2'-nitrophenyl) -1 / »- dihydropyridines of DE-OS 22 42 106 are described as light-sensitive substances, while the corresponding 3'- or 4'-nitro derivatives, in which the Nitro group not in o-position to the point of attachment are insensitive to light.

It could therefore not be expected by the person skilled in the art that the 4- {5'-nitro-2'-furyl) -1, 4-dihydropyridi ne, due to the position of the nitro group in the molecule are photosensitive at all, and it could be expected even less that these compounds could be used to produce photosensitive layers which compared to those of DE-OS 2242 106 by characterized by improved properties.

The following examples are intended to illustrate the invention in more detail.

B e i s ρ i e I 1

A casting solution with the following composition:

10 g phenol formaldehyde resin,

5 ml glycol monomethyl ether,

0.1 g of a blue triarylmethane dye ^

2.5 g compound 1 of the table,

0.25 g p-dimethylaminobenzaldehyde,

90 ml acetone,

is applied to an aluminum plate such as is used for the production of offset printing plates. The thickness of the dried layer is 20 μm.

The plate is then placed behind a template for 120 s with a mercury vapor lamp (1000 watt) at a distance exposed from 60 cm The exposed parts of the image are then exposed to an aqueous solution as follows Composition washed out:

30 g Na ₂ CO ₃ SiCC, 30 g Na ₃ PO ₄ 12H ₂ O, 25 ml NaOH (10% igX

Water to 1 liter.

A positive offset printing form is obtained long service life.

Example 2

A photosensitive mixture of the following composition is applied to a polyester support applied, dried and provided with a transparent, removable cover sheet:

10 g methacrylic acid methyl ester acrylic acid ethyl

ester-acrylic acid copolymer 5 g compound 14 of the table, 0.1 g of a mixture

Triethylene glycol di-n-hexanoic acid ester and

Triethylene glycol di-n-octanoic acid ester, 0.1 g of a blue triarylmethane dye, dissolved in

100 ml of methylene chloride

The layer thickness of the light-sensitive layer after drying is 50 (im.

After removing the cover sheet, the

photosensitive layer on a copper conductor plate, like used to make printed circuit boards is, laminated and behind a template 240 s with a mercury vapor lamp (1000 watt) at a distance

exposed from 60 cm. The development takes place with a Solution of the following composition:

20 g Na ₃ PO ₄ -12H ₂ O, 20 ml methyl glycol, 1 l water.

The plate is then etched in the usual way with a ferric chloride solution. After removing the mask gives a high quality printed circuit

Example 3

It is a casting solution A of the following composition:

9 g phenol formaldehyde resin, 4.5 g of compound 4 of the table, 0.1 g of a mixture

Triethylene glycol di-n-hexanoic acid ester and Triethylene glycol di-n-octanoic acid ester, 0.1 g of a blue triarylmethane dye, 150 g acetone, 20 g ethylene glycol monoethyl ether,

manufactured.

A second casting solution B is then prepared, which differs from solution A only in that it contains 4.5 g of compound 2) of DE-OS 22 42 106 as a light-sensitive substance.

Both casting solutions are made on aluminum plates, such as those used for the production of offset printing forms are used, applied so that the layer thickness after drying is 20 μ. Then according to the Details of Example 1 exposed and the exposed portions with a solution of the following composition washed out:

20 g Na ₂ CO ₃ , 20 g Na ₃ PO ₄ 12 HA 33 g NaOH,

20 ml glycol monoethyl ether, Water to 1 liter.

The following results are obtained:

Beginning

of

Composition

Diploma

of

Composition

Detachment of the layer

Plate A Plate B.

20 s 50 s

50 s 120 s

150 s 150 s

As can be clearly seen from the table, panel A is characterized by a considerably greater processing latitude.

Example 4 A casting solution of the following composition:

5 g styrene-maleic anhydride copolymer, 2.5 g compound 3 of the table, 100 ml ethyl acetate,

is applied to an aluminum plate such as is used for the production of offset printing forms. The layer thickness of the dried layer is

20 μνη. The exposure is carried out as described in Example 2. The exposed parts of the image are then dissolved out with a solution of the following composition:

20 g Na ₂ CO ₃ , 20 g Na ₃ PO ₄ -12H ₂ O, 3.3 g NaOH,

20 ml glycol monoethyl ether, Water to 1 liter.

Start of image recording: 20 s Completion of the image recording: 50 s Separation of the layer: 200 s

Example 5 A casting solution of the following composition:

5 g styrene-maleic acid half-ester copolymer, 3 g compound 2 of the table, 0.5 g of a red diazo dye (CERESROT), 100 ml of methylene chloride,

is cast on a polyester layer support so that the layer thickness of the cast layer is 10 μΐη The material is exposed for 120 s with a UV lamp (1000 watt) at a distance of 60 cm. The exposed Parts of the layer are then removed with a solution of the following composition:

20 g Na ₃ PO ₄ -UH ₂ O, 20 ml methylglycol,

Water to 1 liter.

A red duplicate of the original is obtained on a transparent base.

Example 6

A casting solution of the following composition is applied to a polyester layer support and dried:

10 g of methyl methacrylate and ethyl acrylate ester-acrylic acid copolymer and carbon black im Ratio 1: 1,

0.5 ml of a mixture

Triethylene glycol di-n-hexanoic acid ester and Triethylene glycol di-n-octanoic acid ester,

90 ml acetone.

Another layer of the following composition is then applied to this layer:

10 g styrene-maleic anhydride copolymer, 2.5 g of compound 3 of the table, 2.5 g of triethylene glycol di-n-hexanoic acid ester and

Triethylene glycol di-n-octanoic acid ester, 100 ml of acetic acid ester.

After drying, the material is used for 2 minutes a UV lamp (1000 watts) through a grid template exposed

After washing out the exposed areas with a solution of the following composition:

20 g Na ₃ PO ₄ -12H ₂ O, 20 ml methylglycol,

Water to 1 liter,

a positive raster image is obtained.

809537/445

Claims (1)

Patent claims: 1. Photosensitive recording material for the production of positive relief images from a Support and a photosensitive layer containing a dihydropyridine compound with a through contains a nitro group substituted radical and at least one binder, characterized in that that the photosensitive layer is a dihydropyridine compound of the formula