DE2019480A1 - Photosensitive recording material - Google Patents

Description

Photosensitive recording material

The invention relates to a photosensitive recording material, which consists of a layer support and at least one light-sensitive layer made of a polyester which composed of a photosensitive dicarboxylic acid or a derivative thereof and at least one dihydroxy compound is.

It is known that certain polymers which are soluble in organic solvents, after exposure to a suitable Light source will become insoluble in the same solvents. Ufenn one of these polymers on a layer support is applied and exposed imagewise with actinic radiation, iferden the exposed areas insoluble and the non-exposed areas that remain soluble can then removed. As a result, a polymer image is obtained on the substrate, which is produced in photomechanical production processes can be used.

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The light-sensitive polymers that can be used in this way are in particular those that contain residual double bonds that are under the effect; of actinic radiation can react with crosslinking of the polymer. From USA publication 2 956 87h; and the French patent I 137 056 a special class of photosensitive polyesters is already known, which by condensation of the ester of an acid, z. 3. Cinnairylidenialonic acid, prepared with diols or phenols, can be grounded. Those described in these patent documents. iloi ^{! i} ov.olyoster are photosensitive resins and have the properties that make them suitable for photogravure and lithography. These resins are hard, transparent, insoluble in water, but in organic solvents, e.g. B. ketones, chlorinated hydrocarbons, aromatic hydrocarbons and ethers, soluble, but they v / Erdocii insoluble in these solvents when they are exposed to actinic radiation. They are also in the acid baths used in photogravure, e.g. B. ferric chloride and nitric acid, insoluble. These resins are also oleophilic and therefore have a good affinity for lithographic. Inks on.

'.'. ^R ie already stated above, after the imagewise exposure, a layer of one of the photosensitive resins described in the above-mentioned patents, an image is developed by the unexposed areas of the layer with a solvent, preferably a chlorinated solvent, such as . B. trichlorethylene removed. With this solvent development, however, the exposed areas of the layer, which represent a negative of the original, must remain intact. It was found, however, that the solvents used for development not only selectively remove the unexposed areas but also remove them into the exposed areas

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penetrate the photosensitive layer. Even if you carry out the pocket in the way that you simply allow a stream of the solvent to flow over the layer of the exposed and crosslinked ilomopolyester, the exposed areas swell under the action of the solvent, making them very brittle and their utility is reduced as a resist material. it may also be that the details in the swollen districts · not? e exactly take the form they had originally during drying again, v / o by the resolution of the final image _Λ

is affected. ™

The object of the invention was therefore to provide an improved light-sensitive Specify recording material in which the polyester making up the piiotosensitive layer is better physical properties, especially greater durability Free the swelling in organic developing solvents and thereby images with better Provide resolution.

It has now been found da3 you can improve image resolution and exposure latitude of the light sensitive materials when the Quellun ^ sbeständi ^ ness λ increases the light-sensitive polyester, le ^ enüber the developer solvents, especially Triciiloräthylen. It has been found that it is possible to produce ss & Öb ¹ improvement in the mechanical properties and the dimensional stability of the photosensitive polyester Aufzeichnunnsmaterialien contained in the photosensitive layer can be developed a organiscjie solvent in automatic ENTV / icklervorrichtunren using containing Jltzoades. It has been found that the object set can be achieved in that in the light-sensitive layer of the light-sensitive drawing material some of the polyesters described in the above-mentioned patents

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BATH ORIGINAL

replaced by an equivalent amount of polyester units, which are derived from a light-insensitive aromatic dicarboxylic acid or a derivative thereof, by the mechanical Properties of the copolymer obtained in this way are considerably improved.

The invention now relates to a photosensitive recording material, consisting of a layer support and at least one photosensitive layer made of a polyester, which is composed of a photosensitive dicarboxylic acid or a derivative thereof with at least one dihydroxy compound, which is characterized in that at least 5MoI- % of the photosensitive Dicarboxylic acid are replaced by a light-insensitive aromatic dicarboxylic acid or a derivative thereof.

In a preferred embodiment of the invention is Polyester of the photosensitive layer of at least one Dihydroxy compound and a dicarboxylic acid mixture built up, the

a) about 70 to about 95 mol from a photosensitive Dicarboxylic acid of the general formula:

COOH

I. /

R * «~ CH CU

in which R is an alkylidene, aralkylidene or divalent means heterocyclic radical, or a derivative thereof, and

BATHROOM OHIGiNAL

b) consists of about 30 to about 5 mol% of a photosensitive aromatic dicarboxylic acid or a derivative thereof. .

Another preferred embodiment of the invention is thereby characterized in that the polyester of the photosensitive layer consists of at least one dihydroxy compound and a · Dicarboxylic acid mixture is built up that

a) from about 30 to about 70 mol% of a light-sensitive Dicarboxylic acid of the general formula I given above or a derivative thereof and

b) from about 70 to about 30 mole percent of a photosensitive aromatic dicarboxylic acid or a derivative thereof.

The mixed polyesters usable in the light-sensitive material of the invention can be prepared by polycondensation of a light-sensitive dicarboxylic acid of the above type and an aromatic dicarboxylic acid with a dihydroxy compound or a mixture of dihydroxy compounds. Instead of the dicarboxylic acids themselves, derivatives of these acids, in particular the corresponding diesters, can also be used with advantage. Accordingly, derivatives of the dihydroxy compounds can also be used. Are as

Examples for dicarboxylic acids which correspond to the general formula I given above and which can be used according to the invention are those as described, for example, in US Pat. No. 2,956,878 and French Pat. No. I 137 056, e.g. B. Ginnamylidenmalonsiuire,

Private of the acids diester used, so the listrreste exist i from alkyl radicals with 1 to 4 C-Afύπΐ5 · ΐ »,

1 Π 9 ·; I ^v , / IhH

BATH

Crotonylidene rialonic acid, γ-methylcrotonylidemrialonic acid, o-M'itrocinnamylidene dialonic acid, aaphthylallylidene rcalonic acid, 2-Fur £ uryli (lGnmalonic acid, L-Uethylpyridylidene-2-ethylidenemalonic acid, N-i'-ethylquinolidene-Z-ethylidene rualonic acid,. ·, -. ■ [ethylbe2izthiazolylidene-2-ethylidene realonic acid and υ-Diiüethyl aminocinnamylidonic acid and functional derivatives thereof Acids.

üie in the light-sensitive recording materials of the Invention usable mixed polyesters are soluble compounds, the acid residues of one of the following general formulas:

CC- Il

CH

Ch.

unci

-c -

jov / ie associated diol residues of the leashed formula ent age.

where mean:

the radicals given under formula I, an alkylene radical, for example an ethylene, Propylene or NOopentylenrest, or one Cycloalkylene radical, e.g. a cycloxylene - "-

! ü υ 8 4 h / 1

BATH ORIGINAL

or Äthoxycyclohexylearest and

2
R is an arylene radical.

Examples of suitable light-insensitive aromatic dicarboxylic acids are terephthalic acid, isophthalic acid and functional derivatives of these acids.

In a preferred embodiment of the invention, a

photosensitive dicarboxylic acid cinnamylidene malonic acid or a functional derivative of this acid, for example a short chain alkyl diesters, e.g. B. Methylcinnamylidenmalonat or Äthylcinnamylidenmalonat, and as light-insensitive Dicarboxylic acid a short-chain alkyl terephthalate ζ. B. He thy1-terephthalate or ethyl terephthalate is used.

Except terephthalic acid and isophthalic acid can be considered light-insensitive Dicarboxylic acid at least partially also succinic acid, adipic acid, azelaic acid, cyclohexanedicarboxylic acid and their diesters are used.

It has already been stated that when using a light

sensitive aromatic dicarboxylic acid or a dicarboxylic acid ester, the (der) at least 5 mol-t of the total amount Dicarboxylic acids or dicarboxylic acid esters make an improvement certain physical properties of the mixed polyester produced therefrom compared to the corresponding light-sensitive homopolyester can be achieved. Included will be a slight increase in the softening temperature and receive a decrease in solubility in organic solvents, Surprising travel becomes an improvement even then the photosensitivity of the mixed polyesters used according to the invention achieved when the amount of light-insensitive aromatic Dicarboxylic acid or dicarboxylic acid ester not more than

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10 mol% of the total amount of dicarboxylic acids or dicarboxylic acid esters matters.

The dicarboxylic acid or dicarboxylic acid ester used in the present invention mixture can be condensed with the dihydroxy compounds in particular those in US Pat. No. 2,956,078 and in French Pat 1 137 056 described aliphatic and aromatic diols, for example alkylene glycols with about 2 to about 12 carbon atoms, z. B. ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, cyclohexanedimethanol, Decamethylene glycol, dodecamethylene glycol, 1,6-IIexanediol, neopentyl glycol, 1,4-bis (ß-hydroxyethoxy) cyclohexane and aromatic diols, e.g. B. hydroquinone and p-dihydroxy methylbenzene can use.

lis it has been found that when a single diol, e.g. Ethylene glycol or cyclohexanedimethanol, which is used obtained polymers in organic solvents a low Have a swelling rate η ata χ and a high melting point. Unfortunately, these polymers generally do not have a sufficiently high molecular weight and their sensitivity as well their mechanical properties are not entirely satisfactory. However, it is possible to eliminate this disadvantage by adding the dicarboxylic acid and dicarboxylic acid ester mixture for the preparation of those used according to the invention Mixed polyester adds more than one dihydroxy compound (diol).

According to a preferred embodiment of the invention, there is this mixture of dihydroxy compounds from 2 or more diols of the general formula:

¹¹ ·, no-R'-on

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in which R ¹ denotes an alkylene radical, preferably a short-chain alkylene radical having from about 2 to about 10 carbon atoms, or a cycloalkylene radical whose alkylene group contains, for example, 3 to 10 carbon atoms.

According to a preferred embodiment of the invention, a mixture of ethylene glycol and 1,4-butanediol is used as the dihydroxy compound to produce the polyester on the photosensitive layer of the recording material of the invention.

The mixed polyesters used according to the invention can be produced *

by reacting the dicarboxylic acid or dicarboxylic acid tennis compound and the dihydroxy compounds by conventional polycondensation processes, as described, for example, in US Pat. No. 2,956,878 and French Pat. No. 1,137,056. These polycondensations are carried out, for example, by heating the mixture described above first at atmospheric pressure and then in vacuo (at about 1 mm / g pressure). The case angextfendeten temperatures are generally between about 150 and about 235 ⁰ C. Within this range, the temperature has only little effect on the molecular weight of the copolyester obtained, although the molecu- λ large weight generally increases with increasing duration of heating increases.

The catalysts that can be used here are those as described in generally used for the production of macromolecular linear polyesters. Examples of suitable catalysts are titanium esters, e.g. B. butyl titanate and titanium isopropoxide, antimony oxide, strontium oxide, and zinc acetate, ΐ / enn for direct Polyester production using a dicarboxylic acid as a starting material is used, then can be used as a catalyst for example

04a

1.0984 5 / 1S55

Sulfuric acid or ρ-toluenesulfonic acid can be used.

The layering races containing the photosensitive polyesters for the production of the sensitive recording materials of the invention can be prepared by reacting the polyester in a suitable solvent or in a solvent mixture as used for production is commonly used by polymer pastes, disperses or dissolves. Examples of solvents that can be used with advantage are ketones, ζ. B. 2-butanone, 4-methyl-2-pentanone, cyclohexanone, 4-butyrolactone, 2,4-pentanedione, and 2,5-hexanedione, ester, ζ. B, 2-ethoxyethyl acetate, 2-methoxyethyl acetate and n-butyl acetate, chlorinated solvents, e.g. B. chloroform, Dichloroethane, trichloroethane and tetrachloroethane, as well as dimethylformamide and dimethyl sulfoxide and mixtures thereof Solvent. The photosensitive copolyesters used in the coating compositions preferably make about 1 to about 20% by weight. The mixed polyesters are in one the above-mentioned solvents preferably in an amount of about 2 to about 10 weight percent, based on the coating composition, contain. The coating compositions can also contain a wide variety of photographic additives customary use, for example means for modifying the flexibility of the upper cover, means for modifying its Surface properties, dyes and pigments for coloring the top coat, agents for modifying the adhesive strength of the coating on the substrate, antioxidants, protective agents and the various other known ones Additives included.

Although the mixed polyesters used according to the invention also result in resist materials without additional sensitization, it is possible to increase its photosensitivity by adding suitable sensitizers to the photosensitive layer to increase. Suitable compounds which can be used as sensitizers are, for example, from the USA patent 2,956,871, the French patent specification

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1 137 056 and 1 238 262 are known. These include 2- (benzoylmethylene) -1-methyl-ß-nai> hthothiazole, 2-benzoylcarbethoxymethylene-1 -methyl-β-naphthothiazole, -1-carbethoxy ^ -keto-S-methyl-2-azabenzantlirone and eosin. Other sensitizers are, for example, in the French patents 1,086,257 and 1,089,290, in U.S. Patents 2,610 (Nitro compounds), 2,690,966 (triphenylmethanes), 2,670,285 (anthrones), 2,670,287 (diaminobenzophenonimides, -diphenylmethanes, -diphenylketones, -diphenylcarbinols), 2,670,286 (quinones) and 2,732,301 (thiazoles, thiazolines and cyanine dyes) described. It was also found that photosensitive recording materials with especially ™

high sensitivities can be obtained when he thy1-2- (N-methylbenzothiazolylidene) dithioacetate is used as a sensitizer.

The photosensitive recording materials of the invention can be prepared by applying the photosensitive coating compositions to layers from solvents by conventional methods. Suitable substrate materials are, for example, fiber materials, such as paper, paper coated with polyethylene, paper coated with polypropylene, parchment and linen, sheets and foils made of metals, such as, for. B. aluminum, copper, magnesium and zinc, λ

Glass and with metals such as chrome, chrome alloys, steel, silver, gold and platinum, coated glass, synthetic polymers Substances, e.g. B. poly (alkyl methacrylates), e.g. poly (methyl methacrylate), polyester materials, e.g. B. polyethylene terephthalate), Poly (vinyl acetals), polyamides such as nylon, cellulose ester materials, for example Cellulose nitrate, cellulose acetate, cellulose acetate propionate and cellulose acetate butyrate, the optimal coating thickness for a particular purpose depends on various factors from, for example, the use of which the recording material is to be fed to the respective light source used

1 0 B 8 4 5/1 K F 5

sensitive mixed polyester and the nature of the other components, which can be present in the light-sensitive layer.

As already indicated above, during the imagewise exposure of a light-sensitive layer made of a mixed polyester containing photosensitive recording material of the invention by actinic radiation and then Develop the unexposed areas with a solvent to obtain a relief image. This relief can be used to manufacture lithographic plates can be used by preparing a dyeable resist material. This mixed polyester can also be used to produce typographic reliefs, cylinders for heliography, electronic micromodulators or electronic circuits or for chemical etching of metallic parts. In such products The mixed polyesters very often form very thin Layers about 1 to 10 microns thick and sometimes even less than 1 micron, the main characteristics of which are the good resolving power, the chemical Inertness and the good maintenance of sensitivity are.

The increase in the Scheelzpnktes and the decrease in permeability to certain solvents enables the autopositive Reproduction of halftone negatives with the help of a Pigment process. After exposure of the negative, the uncrosslinked polymeric image is heated to a temperature above the Softening point of the resin heated or with a swelling agent and then brought into contact with a pigment treated so that the pigment adheres to the resin in these areas. So can permanent images, for example on a substrate made of enamelled sheet steel, ceramic or glass by using a high temperature

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glazing pigment and burning the pigmented image to the Burn out the resin and vitrify the pigment.

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

The diethyl cinnamylidene malonate used in the examples was prepared as follows:

A mixture of the following composition:

Cinnamaldehyde 1.98 kg '(15 moles)

Diethyl malonate 2.4 kg (15 moles)

Methylene chloride 3 1

Piperidine 20 ml

was refluxed with stirring so that azeotropic distillation occurred. After 26 hours of distillation, no more water could be extracted from the mixture by refluxing it and then most of the methylene chloride was removed under reduced pressure. In this way, an oily residue was obtained, which was %

Removal of the low boiling point fractions was heated to 95 ° C under a pressure of 15 mm Hg. A golden yellow oil remained, which was distilled under a pressure of 0.05 mm Hg. The main fraction ended at 130 to 132 ° C / 0.014 mm Hg. In this way a product was obtained in a Augbeute of 661, whose refractive index was 1.5092 at 25 ⁰ C.

Example , 1

The following mixture was made:

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Dry and timely

distilled ethylene glycol 46.5 g (0.75 hol)

Dimethyl terephthalate. 53.4 g CO, 195 mol)

Diethyl cinnamylidene malonate 53.4 g (0.195 mol)

This mixture was in a clean and dry reactor with Brought to a capacity of 125 ml, with a stopper and a nitrogen inlet tube was provided so that the reaction medium was in a nitrogen atmosphere during the first heating stage could be held. The reactor was also equipped with a Vigreux fractionation column, which the Condensation of the starting products with a high boiling point allowed, however, allowed the alcohol vapors formed in the course of the reaction to escape. The reactor was in a to a temperature of A silicone oil bath at 235 ° C. was immersed so that the reagents melted. Care was taken that the implementation at reduced Lighting was carried out. After the mixture has melted and had a homogeneous consistency, v / urden a few drops of titanium isopropoxide were added and heating was continued for 3 hours. This was followed by the Vigreux column and the nitrogen sparge tube was removed from the reactor and this was dropped over dry ice to a vacuum pump connected. The polymer was formed during the distillation stirred with the help of a steel stirrer. The distillation lasted 45 minutes, during which time the pressure was on 0.08 mm Hg was lowered. It xi / urde a golden yellow, dark colored obtained viscous substance, which solidified to a glass-like, amorphous mass on cooling. Dissolved in a phenol / Chlorobenzene (1/1) mixture, the substance had an inherent viscosity of 0.78 and a sensitivity (as measured by the method described in U.S. Patent 2,956,878) of 2,800 on.

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Example 2

The procedure of Example 1 was repeated, but this time the following mixture was used:

1,4-butanediol 37.4 g

Ethylene glycol 181.1 g

Diethyl terephthalate 135.8 g

Diethyl cinnaniylidene malonate 356.2 g

Titanium isopropoxide 0.1 ml

The diol mixture consisted of 15 HoI-S from 1,4-butanedibl and to 85 MoI-I from ethylene glycol, the dicarboxylic acid ester mixture consisted to 35 mol-I from dimethyl terephthalate and to 65 mol-I from diethyl cinnamylidene malonate.

The first stage of heating lasted 3 hours and the second was performed under a variable vacuum of 0.07 to 0.1 mm Hg for 90 minutes. The product obtained possessed in a phenol / chlorobenzene (1/1) mixture has an inherent viscosity of 0.84.

Example 3

The procedure of Example 1 was repeated, but this time the following mixture was used:

Ethylene glycol 101.3 g (1.634 moles)

• 1,4-butanediol 7.75 g (0.086 mol)

Dimethyl terephthalate 67.9 g (0.35 mol)

Diethyl cinnamylidene malonate 173.1 g (0.65 mol)

1 09845/1 B. 5 S BAO ORIGINAL

A few drops of titanium isopropoxide were added to this mixture, The first stage of heating lasted for 3 hours and the second stage was for 2 hours under a varying Pressure from 0.07 to 0.1 mm Hg carried out. The product obtained was a golden yellow colored substance with a glass-like consistency and it had an inherent viscosity of 0.62 in solution in a chlorobenzene / phenol (1/1) mixture.

Example 4

The procedure of Example 1 was repeated, this time using the following mixture

Ethylene glycol 53.3 g (0.86 mol)

1,4-butanediol 77.4 g (0.86 mol)

Dimethyl terephthalate 67.9 g (0.35 mol)

Diethyl cinnamylidene malonate 178.1 g (0.65 mol)

A few drops of catalyst (titanium isopropoxide) were added to this mixture. admitted. The first stage of heating lasted for hours and the second stage was under one for 40 minutes pressure varying from 0.07 to 0.1 itif. Hg performed. That The product obtained in this way had an inherent viscosity of 0.77 in solution in a chlorobenzene / phenol (1/1) mixture.

Example 5

The procedure of Example 1 was repeated, this time the following mixture was used

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1,4-butanediol 154.8 g (1.7 mol)

Dimethyl terephthalate 67.9 g (0.35 mol)

Diethyl cinnamylidene malonate 178.1 g (0.65 mol)

A few drops of titanium isopropoxide were added. The first stage of heating lasted 3 hours and the second stage was Performed for 55 minutes under 0.1 mm Hg pressure. The product obtained was in solution in a phenol / Chlorobenzene (1/1) mixture has an inherent viscosity of 0.83.

Example 6

The procedure of Example 1 was repeated, but this time the following mixture was used:

1,4-butanediol 38.7 g (0.4 mol)

Ethylene glycol 80.0 g (1.3 mol)

Diethyl terephthalate 67.9 g (0.35 mol)

Diethyl cinnamylidene malonate 178.1 g (0.65 mol)

A few drops of titanium isopropoxide were added. The first stage of heating lasted 3 hours and the second stage 1 hour. A product was obtained which, in solution in a phenol / % chlorobenzene (1/1) mixture, had an inherent viscosity of 0.75.

Example 7

The procedure of Example 1 was repeated except that this time the following mixture was usedί

1,4-butanediol 45 g (0.5 mol)

Dimethyl terephthalate 14.55 g (0.075 mol)

Diethyl cinnamylidene malonate 47.95 g (0.175 mol)

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A few drops of titanium isopropoxide were added. The first The heating stage lasted 3 hours and the second stage, carried out under a pressure of 0.05 mm Hg, lasted 50 minutes. A product was obtained which, in solution in a phenol / chlorobenzene (1/1) mixture, had an inherent viscosity of 0.98.

Example 8

The procedure of Example 1xv was repeated, this time however, the following mixture uses \ iurdei

1,4-butanediol 45 g (0.5 mol)

Atnyl cinnamylidene alonate 47.95 g (0.175 mol)

Dimethyl isophthalate 14.55 g (0.075 mol)

A few drops of titanium isopropoxide were added. The first The heating stage lasted 3 hours and the second stage, the under 0.07 mm Hg pressure lasted 1 hour. A product was obtained which was in solution in a Phenol / chlorobenzene (1/1) mixture had an inherent viscosity of 0.57.

Example 9

In one with a reflux head and a cooler provided downwardly directed piston \ tfurde under nitrogen at 200 ⁰ C a mixture of the following composition heated:

Methyl cinnamylidene malonate 775 g (3.15 mol)

Methyl terephthalate 97 g (0.5 mol)

Ethylene glycol 37 2 g (6 mol)

1,4-butanediol 180 g (2 mol)

After 30 minutes of heating, 2 ml of a 20-liter solution ^Λ ^ "- ^ - 10 9845/1555

of isopropyl titanate in butanol was added. After heating for 5 hours, 300 ml of methanol had distilled off. The mass was then poured into a reactor connected to a stirrer, condenser and vacuum pump. The pressure was slowly decreased until it reached a Ivert 1-2 mm Hg and the temperature was raised to 230 ⁰ C. A mixture of excess ethylene glycol and butenediol was collected in the condenser and, after heating for 3 hours, the polymer was removed through an outlet opening in the reactor and rapidly cooled.

Example 10

A mixture of the following composition was prepared:

Methyl cinnamylidene malonate 861 g (3.5JMoI)

Methyl terephthalate 97 g (0.5 mol)

Ethylene glycol 248 g (4 mol)

1,4-butanediol 130 g (2 mol)

Cyclohexanedimethanol 288 g (2 mol)

This mixture was λ comparable to a distillation head with a

brought down flask and heated to 20O ⁰ C. After heating for 1/2 hour, 2 μl of catalyst (2O2 solution of isopropyl titanate in butanol) were added. After 6 hours of heating, 300 ml of distillate had accumulated. The reaction product was then placed in the reactor described in Example 9 and heated to 230 ° C. under vacuum for 2 hours. The resulting polyester was removed and rapidly cooled.

The mixed polyesters obtained in the examples described above were used to produce light-sensitive images

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drawing materials used, with solutions of these polyesters in solvents such as those in the French Patent specification 1,137,056 are described on suitable Supports were applied. The photosensitive recording materials thus obtained were for grazing very well suited for photomechanical processes. To the photographic exposure and development by the further above solvent received nan resist materials, which would be very suitable for chemical etching processes.

Example 11

This example explains the advantages of the mixed polyesters used according to the invention in comparison with a similar Hoeio polyester.

A "microzinc plate ¹¹ was coated with a layer of the mixed polyester described in Example 9 and another" microzinc plate ¹¹ was coated with a layer of a homopolyester (tetramethylcinnamylidene malonate). These "micro-zinc plates ¹¹ were used in a conventional lieise for machine Typographieätzung · The film thickness corresponded to the case inpedem 2.7 g per m. The two plates were ima tet under the same conditions by a line and halftone negative. After development with trichlorethylene were the two plates dried for 10 minutes at 12O ⁰ C, then their surfaces were cleaned by wiping with a cotton pad and the upper sweep of cold calcium carbonate. then, they were immersed for 30 seconds in a 3% nitric acid solution. the plates were then placed in a Etching device, for example the MARK III etching device manufactured by dfer Tasope Company, etched without applying protective powder

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Nitric acid (42 ° Be ") 8 1

surfactant 0.696 kg

"Mona Etch" from Mono Industries Co.

"Solvesso 150" solvent 2.784 kg the Esso

Water 49.7 1

The etching temperature was 27 ⁰ C. After 10 minutes of etching had the Homo polyester resin layer detached from the plate and had fallen into the bath, while the resist layer remained sticking out of the inventively used polyester blends on the support and xfeitere 10 minutes etched long could .

Example 12

To a 15ligen solution of the polymer obtained in Example 10 in 2-methoxyethyl acetate were 0.451 methyl-N-methylbenzthiazolylidenedithiojfacetat added to broaden the spectral sensitivity. This solution was through Spin coating applied at 80 rpm to the copper side of a copper coated Bakelite plate. After this Drying, the photosensitive layer was exposed through a M.B.S, test motif in a vacuum frame. On the same Way was another plate with an ilomopolyester (tetramethylene polycinnamylidene malonate) coated and then exposed under the same conditions. The two panels were developed by simultaneous spraying with trichlorethylene. The developing device contained at a distance of 30 cm nozzles mounted from the plates intended for two types of spray, one very direct spray and another Spray in the form of a fine mist. After a few seconds he switched to the mixed polyester prepared in Example 10 coated plate the image fully developed. All the details were in the right place ^ even with direct Discussion. In contrast, were on the one with the Ilomopolyester

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coated plate even when sprayed by a fine fog bestir.ir.ite details have been lost and at the direct spraying completely destroyed the image.

ORIGINAL

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Claims (8)

Claims fly light-sensitive recording material, consisting of a layer support and at least one light-sensitive layer made of a polyester, which is composed of a light-sensitive icarboxylic acid or a derivative thereof and at least one dihydroxy compound, characterized in that at least 5 mol% of the light-sensitive dicarboxylic acid by a light-insensitive aromatic dicarboxylic acid or a derivative thereof are replaced like. 2. Photosensitive recording material according to claim 1, characterized in that the polyester consists of at least a dihydroxy compound and a dicarboxylic acid mixture is built up, the a) to about 70 to about 95 MoI-I from a light-sensitive dicarboxylic acid of the general formula: .COOH ^^ KtIl Ktti ^^^ Ki ^ COOII wherein R is alleylidene, aralkylidene or divalent means heterocyclic radical, or a derivative thereof and b) zxk about 30 to about 5% mol-V consists of a light-sensitive aromatic dicarbene acid «or a derivative thereof * 109845/1555 8AD or, _ginal 3. Photosensitive recording material according to claim 1, characterized in that the polyester is composed of at least one dihydroxy compound and a dicarboxylic acid, qemisch is constructed, that a) to about 30 to about 70 hol% from one light-sensitive dicarboxylic acid of the in AnspjAruch 2 given general Formula or a derivative thereof and b) from about 70 to about 30 mole percent of one light-insensitive aromatic dicarboxylic acid or a derivative thereof consists. 4. Photosensitive recording material according to the claims 1 and 2, characterized in that the polyester consists of at least one dihydroxy compound and one Dicarboxylic acid mixture is built up, which is up to 10 mol% a light-insensitive aromatic dicarboxylic acid contains. 5. Photosensitive recording material according to the claims 1 to 4, characterized in that the polyester consists of a dicarboxylic acid mixture and. an alkylene glycol having from about 2 to about 12 carbon atoms as dihydroxy connection is established. 6. Photosensitive recording material according to claim 5, characterized in that the polyester consists of a dicarboxylic acid mixed ge and ethylene glycol, 1,4-butanediol, cyclohexanediol or mixtures thereof is constructed as a dihydroxy compound. 109 84571555 BAD OBlGlNAt 7. Photosensitive recording material according to claims 1 to 6, characterized in that the polyester is made from cinnamylidene malonic acid or a short-chain Alkyl esters thereof as light-sensitive dicarboxylic acids Terephthalic acid, isophthalic acid or short-chain alkyl esters of which as light-insensitive aromatic dicarboxylic acid and xethylene glycol, 1,4-butanediol, cyclohexanediol or mixtures thereof is constructed as a dihydroxy compound, 8. Light-sensitive recording material according to claims 1 to 7, characterized in that the shift carrier g of brass metal. 109345/1555 BATH ORIGINAL