DE2623790A1 - LIGHT-SENSITIVE MEASURES FOR THE GENERATION OF PHOTORESIS LAYERS AND LIGHT-SENSITIVE RECORDING MATERIALS - Google Patents

Description

£ .Ό £ 6 I Ό U Dipl.-Chem. Dr. Brandes

Dr.-Ing. Hero y Dipl.-Phys. Wolff

8 Munich 22, Thierschstraße 8 Tel. (089) 293297
Re * - ". Wr. 124 9 71 Telex 0523325 (patwod)

^a * * Telegram address:

wolffpatent, munich

Postal check account Stuttgart 7211 (BLZ 60010070)
Deutsche Bank AG, 14/28630 (BLZ 60070070)

Office hours: 8 a.m. to 12 p.m., 1 p.m. to 4.30 p.m. except Saturdays

April 12, 1976 25/2

EASTMAN KODAK COMPANY, 343 State Street, Rochester,
New York State, United States of America

Photosensitive compound for the production of photoresist layers and photosensitive recording materials

609852/1015

262379Q I.

Photosensitive compound for the production of photoresist layers and photosensitive recording materials

The invention relates to photosensitive compositions for production of photoresist layers and light-sensitive recording materials, Containing (a) a photosensitive obtained by condensation of an acidic quinonediazide with a phenol-aldehyde resin Polymer ^ (b) an organic carboxylic acid and optionally (c) a non-photosensitive film-forming polymer. The invention further relates to a photosensitive photographic material Recording material consisting of a layer support and at least one photosensitive layer applied thereon made of a photosensitive composition of the specified features.

It is well known, e.g. from U.S. Patents 2,754,209, 3,046,110, 3 U46 112, 3 046 113, 3 046 116, 3 046 118, 3 647 443 and 3 759 and CA-PS 602 987, light-sensitive quinonediazides for the Production of photoresist layers and lithographic printing plates to use and these for the production of photocopies use. The usefulness of the photosensitive quinonediazides for the production of photoresist layers and lithographic printing plates is based on the fact that in the exposure of quinonediazides containing layers a solubility differential is created between the exposed and unexposed areas, so that after the image-appropriate exposure by means of a suitable solvent, the non-image areas can be removed, while the Image districts are retained.

The quinonediazides commonly used are monomeric compounds. They can be used in alkali-soluble polymers Binders are incorporated or are reacted with alkali-soluble polymeric substances so that they can be used as resist materials can be used and are able to withstand the abrasion of printing plates.

6 0 9 8 52/1015

There is an extensive literature on the breakdown or degradation of quinonediazides in positive-working photoresist compositions. However, the exact structure of the decay products of the quinonediazides has not yet been fully clarified. The by exposure Solubility produced by quinonediazides can be explained, for example, by the following reaction equation:

hv

or warmth

+ N.

H ₂ O

The first stage of the reaction is obviously based on the elimination of nitrogen with the production of a keto carbene. the however, further reaction of this ketocarbene cannot be predicted with any degree of certainty. One possible reaction sequence is rearrangement into a ketene with subsequent hydrolysis to the free acid. Due to the immobility of a dry film, the formation is of a ketene through an intramolecular rearrangement. However, there are also other possible information in the literature Reactions before hydrolysis.

The preparation and utility of photosensitive formaldehyde polymers with quinonediazide substituents is for example from US-PS 3,046,120, GB-PS 1,026,144 and 1,113,759, DT-PS 1,803,712 and 1,111,497 and CA-PS 903,545.

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There is some problem with the storage of photoresist compositions in that they tend to evolve nitrogen during storage. For example, it has been shown to be positive working photoresist compositions of the described Tyns are very flammable if they are kept at temperatures above 38 C for long periods of time.

It is also known, for example from U.S. Patent 2,990,281, photosensitive Hating for the purpose of improving their adhesive properties, to add certain additives to their stability or their ability to absorb printing inks. From U.S. Patent 2,990,281 it is known to use photosensitive compositions with copolymers of vinylidene compounds and dicarboxy compounds in very small amounts of stabilizing salts of organic acids to be added.

From U.S. Patents 3,046,110, 3,046,112, 3,046,113, 3,046,116 and 3,046,118 it is also known to light-sensitive comparatively small amounts of solid, non-volatile fatty acids Hate to add them to improve their ink receptivity and stability.

Although the addition of non-volatile carboxylic acids, e.g. fatty acids, it has been shown that the degree of nitrogen formation in photoresist materials is reduced due to the decomposition of quinonediazide that the presence of non-volatile acids adversely affects image degradation during development of the dry resist layer leads.

US Pat. No. 3,759,711 also discloses photosensitive vinyl polymers with quinonediazide substituents which are bonded to the polymer chain via sulfonamido or amide groups are known. These polymers have repeating units represented by the following formula on:

609852/1015

where mean:

R is a hydrogen atom or a short-chain alkyl radical 1 to 4 carbon atoms,

R, a hydrogen atom or a short-chain alkyl radical, a Aryl radical or an halogen atom,

X is a sulfonyl radical or a carbonyl radical and D is a quinonediazide group.

It is also known from US Pat. No. 3,759,711, during manufacture lithographic printing plates, based on the polymers described, the coating masses are comparatively low Add quantities of organic acids. The organic acids are supposed to enable the lithographic printing surfaces to develop properly enable and prevent deposits on the printing plates. Suitable acids are oxalic acid, malonic acid, sebacic acid, Adipic acid, succinic acid, phthalic acid, isophthalic acid, citric acid and ßutanetetracarboxylic acid.

The object of the invention was the stability of photosensitive Masses for the production of photoresist layers and photosensitive To improve recording materials based on acidic quinonediazides in storage without a reduction the image quality must be accepted.

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The invention was based on the knowledge that the thermal Stability of photosensitive compositions is essential for the production of photoresist layers and lithographic printing plates can be improved by adding at least one volatile carboxylic acid to the masses. Surprisingly it has been shown that the use of a volatile acid can not only improve the thermal stability of the masses, but rather, also the quality of the images that can be produced and the etching resistance generated from the coating compounds Layers.

The invention thus relates to a photosensitive composition for the production of photoresist layers and light-sensitive recording materials containing (a) a condensation a photosensitive polymer obtained from an acidic quinonediazide with a phenol-aldehyde resin, (b) an organic carboxylic acid and optionally (c) a non-photosensitive film-forming one Polymer which is characterized in that, as the organic carboxylic acid, it is a volatile carboxylic acid of the following formula:

- ^ jj-C - OH in which mean:

R is a hydrogen or halogen atom, a short-chain alkyl radical, a short-chain alkoxy radical, a cyano or nitro residue and

«Ι = 0, 1, 2, 3 or 4.

According to a particularly advantageous embodiment of the invention, the photosensitive mass contains a condensation one acidic quinonediazide photosensitive polymer obtained with a phenol-formaldehyde resin.

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The invention also relates to a light-sensitive photographic recording material consisting of a Layer support and at least one light-sensitive layer applied thereon Layer of photosensitive composition of the type described.

The photosensitive compositions according to the invention are suitable in Excellent way of making photoresists and lithographic printing plates, especially positive-working ones Photoresists and printing plates.

The invention thus enables the generation of photomechanical images Paths through exposure of a photosensitive recording material consisting of a layer support with at least one alkali-insoluble light-sensitive layer applied to it Layer with a photosensitive polymer produced by the condensation reaction of a quinonediazide with a Phenol-aldehyde resin, especially phenol-formaldehyde resin and a volatile carboxylic acid with actinic radiation. The exposure of the recording material causes destruction of the quinonediazide structure, the exposed areas becoming soluble in dilute alkali. When exposed to actinic radiation occurs practically no cross-linking. A positive image of the original can then be developed by removing the exposed areas the photosensitive layer can be removed with an aqueous alkaline developer.

Surprisingly, it has been found that the use of a volatile carboxylic acid in the coating compositions and recording materials not only the durability of the coating compositions and recording materials is improved, but that also in comparison to masses and recording materials that contain non-volatile acids, an improvement in the etching resistance and the exposure time is achieved and that furthermore there is no need to re-bake the recording materials after development can be. Surprisingly, it has been shown in particular that when using volatile carboxylic acids an excellent

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excellent image quality is maintained, as opposed to being used of non-volatile carboxylic acids, the use of which has been recommended.

The use of volatile carboxylic acids of the formula given, in which m = 0, 1 or 2 is.

If R in the given formula stands for an alkyl radical, then has this preferably has 1 to 3 carbon atoms and preferably consists of a methyl, ethyl or propyl radical. R stands for a short-chain alkoxy radical, this preferably also has 1 to 3 carbon atoms and consists, for example, of a methoxy, ethoxy or propoxy radical. If R stands for a halogen atom, this can consist of a bromine, chlorine, fluorine or iodine atom.

Volatile carboxylic acids in the context of the invention are preferably those with boiling points below 20O ⁰ C at atmospheric pressure. Typical volatile carboxylic acids suitable for the production of photosensitive compositions according to the invention are listed in the following table with their boiling and melting points.

Table I. Bp. ⁰ C
(760 mmHg) ge carboxylic acids 100.5 Mp ⁰ C
(760 mmHg) 118 8th 141 16.6 164 -22 187 -6 -34

Formic acid acetic acid propionic acid butyric acid valeric acid

See Morrison and Soyd, Organic Chemistry, 2nd Edition, 1966, page 579.

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It has been shown that acids with boiling points above 20O ⁰ C are not suitable. Not suitable are, for example caproic acids having a boiling point of 205 ⁰ C, Canrylsäure having a boiling point of 239 ⁰ C, benzoic acid with a boiling point of 25O ° C and cyclohexane carboxylic acid having a boiling point of 233 ⁰ C.

Fatty acids, and both saturated and unsaturated Fatty acids as previously used in the photosensitive compositions of the prior art are solids and not volatile carboxylic acids. As already explained, they lead to an improvement in the stability of the photosensitive compositions and Recording materials, however, affect the image quality in disadvantageous way.

Although the concentration of the volatile carboxylic acids in the photosensitive compositions and layers can vary, it has proven advantageous to use the volatile acids in concentrations of 1 to 50% by weight, based on the solids content of the compositions or layers. As a very particularly advantageous concentrations of 1 to 20 wt ⁰ O have been found.

Photosensitive polymers have proven to be particularly advantageous proved, in which the quinonediazide radicals via sulfonyl ",

ü 0 0

M M

Carbonyl (- C-), carbonyloxy - (- C-0-) and sulfinyloxy (-S-0) groups are bound to the phenol-aldehyde polymer, in particular phenol-formaldehyde polymer.

The use of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride has proven to be particularly advantageous of the following formula:

609852/1015

for the preparation of the quinonediazide polymers. In the formula given, R and RN can represent ₉ or 0, where

AC

holds that R and R do not have the same meaning.

Further advantageous quinonediazides which are suitable for the preparation of the photosensitive polymers are the acid esters and acid halides of the following quinonediazides: o-benzoquinonediazide; 1,2-haphthoquinone-1-diazide; 7-methoxy-1,2-naphthoquinone-2-diazide; 6-chloro-1,2-naphthoquinone-2-diazide; 7-chloro-1 _s 2-naphthoquinone-2-diazide; 6-aitro-1,2-naphthoquinone-2-diazide; 5- (carboxymethyl) -1,2-naphthoquinone-1-diazide; 3,3'-4,4'-diphenyl-bis-chloron-4,4'-diazide;2j3-phenanthrenequinone-2-diazide; 9, IO-phenanthrenequinone-10-diazide and 3,4-chrysenequinone-3-diazide; \ tfobei applies that the quinonediazides can be substituted in various ways, for example by alkyl radicals with preferably 1 to 8 carbon atoms, for example methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl or octyl radicals and / or by Alkoxy radicals with preferably 1 to 8 carbon atoms, for example methoxy, ethoxy, propoxy, butoxy, amyloxy, hexyloxy, heptyloxy or octyloxy radicals or by other substituents which do not subsequently affect the insensitive properties of the quinonediazides.

The one used to make the photosensitive polymers Phenol-aldehyde resin, for example phenol-formaldehyde resin, can be so-called novolak resins or resol resins, such as they are known, for example, from the book by H. P. Preuss "Synthetic Resins in Coatings", Noyes Development Corporation (1965), Chapter XV, Pearl River, New York, reference is also made to Römpp, Chemie-Lexikon, 6th Edition, 1966, Volume III, pages 4460 and 5425.

The novolak resins are known to be obtained by condensation of phenols with aldehydes under acidic conditions, whereas the resole resins are produced under basic conditions. For the production of permanently meltable and soluble products less than 6 moles of aldehyde for 7 moles of a phenol are used

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det. Typically, for example, novolaks are made by heating 1 mole of a phenol with 0.5 moles of an aldehyde under acidic conditions. This is usually done at temperatures worked from about 25 to about 175 ° C.

A wide variety of phenols or phenolic compounds can be used to produce the polymers, in particular those with 2 or 3 reactive aromatic ring hydrogen atoms. Instead of an aldehyde, aldehydes can also be released Compounds are used which lead to a phenol-aldehyde condensation are capable. Examples of particularly suitable phenols or phenolic compounds for the preparation of the invention Polymers that can be used are: cresol, xylene, ethylphenol, butylphenol, isopropylmethoxyphenol, Chlorophenol, resorcinol, hydroquinone, naphthol, 2,2-bis (p-hydroxyphenyl) propane and the same. Examples of suitable aldehydes, in addition to formaldehyde, are acetaldehyde, acrolein, crotonaldehyde and furfural. An example of an aldehyde-releasing compound is 1,3,5-trioxane. If necessary, ketones such as acetone can also be used Condensation can be used with the phenolic compounds.

Phenolic resins that have proven to be particularly advantageous are those which are insoluble in water and trichlorethylene, but are easily soluble in common organic solvents, e.g. Methyl ethyl ketone, acetone, methanol and ethanol. Phenolic resins with particularly advantageous properties are furthermore those which have an average molecular weight of about 350 to 40,000, in particular from 350 to 2000.

The use of phenol-aldehyde resins has proven to be particularly advantageous which consist of cresol-formaldehyde resins and phenol-formaldehyde resins.

According to a particularly advantageous embodiment of the invention, for the production of the photosensitive masses and photosensitive Recording materials used photosensitive polymers with structural units of the following formula:

609852/1015

where mean:

a hydrogen atom or a methyl radical;

R and R either N ₉ or O and

1 to 100 MoI-I.

The use of polymers of the specified structure has proven to be particularly advantageous when X is 1 to 50 mol-I, whole especially when X stands for 4 to 20 mol-I.

The photosensitive polymers used for the production of the compositions and recording materials according to the invention can, as already explained, be produced by condensation of a suitable quinonediazide with a suitable phenol-aldehyde resin. The reaction is advantageously carried out in an organic medium or solvent, for example dioxane, tetrahydrofuran or acetone, the concentration of the reactive components advantageously being about 1 to 50 l of the weight of the solution. The reaction is expediently carried out at temperatures from 0 to 78 ^° C. and can be carried out at various pressures, preferably at atmospheric pressure. The molar ratio of acidic quinonediazide to phenol-alde-

609852/1015

hydharz is from 99: 1 to 1:99, preferably from 1:25 to 1: 5. The quinonediazide-phenol-aldehyde polymer obtained can be passed through Precipitation in dilute acid, e.g. hydrochloric acid and Separate the filter.

According to a further advantageous embodiment of the invention, the photosensitive composition or the photosensitive layer of the recording material may additionally contain a non-photosensitive film-forming polymer, in which case the weight ratio of photosensitive polymer to non-light-sensitive polymer is about 1: 1 to et \\ ^r a 99: 1 can be. If the amount of quinonediazide radicals in the photosensitive polymer of the photosensitive composition is increased, the amount of non-photosensitive polymer can be increased accordingly.

The non-photosensitive polymers can be addition homopolymers or addition copolymers that are produced by addition polymerization of one or more unsaturated compounds with a radical of the formula —C = Cd3 · Such polymers advantageously have a molecular weight of from about 2,000 to about 50,000, albeit for preparation the compositions and layers on polymers with higher or lower molecular weights can be used.

To produce these non-photosensitive polymers, the A wide variety of unsaturated monomers can be used, for example vinylamines, vinylimines, substituted and unsubstituted Styrenes, acrylates and methacrylates, e.g. alkyl acrylates and alkyl methacrylates, Vinyl halide, vinyl esters, vinyl ethers, vinyl ketones, divinyl ethers, acrylonitrile, xsxxx mixed ester amides and maleic anhydride, 1,3-butadiene, isoprene, chloroprene, divinylbenzene, acrylic acid and methacrylic acid derivatives, e.g. the corresponding Nitriles and amides as well as other common known monomers.

609852/101 5

The non-photosensitive polymers and copolymers can be prepared by customary known methods, i.e., for example, the customary known addition polymerization -Tracing, in bulk, in solution or in emulsion, in Any common polymerization initiator. For example produce advantageous polymers by polymerizing / uuinostyrene and another polymerizable ethylenic unsaturated monomers in the presence of, for example, 0.1 to 10, in particular 0.2 to 2.0% by weight of a free radical yielding agent usual polymerization initiator.

Examples of suitable initiators are peroxy compounds, e.g. , enzoyl peroxide and Üi (tert-aryl) peroxide and azo initiators, for example 1,1'-azodicyclohexanecarbonitrile and azodiisobutyrojiitrile. The polymerization can take place in the presence or absence of an inert solvent, e.g. a hydrocarbon, for example benzene, white mineral oil or a lubricating or lubricating oil, acetic acid, dioxane and the like carried out v / ground, preferably in an inert atmosphere, for example under a nitrogen blanket. The mixture is brought to a temperature where the polymerization initiator quickly generates free radicals. The most favorable temperature in the individual case depends on the initiator used in the individual case. It has proven to be expedient at temperatures of room temperature or below to work up to 150 C or above. It is usually convenient to allow the polymerization to proceed practically to completion so that no unpolymerized monomer remains and so that the proportions of the individual components in the end product are practically the same as in the monomer used for the polymerization Mixture.

Further advantageous, non-photosensitive polymers for production of photosensitive compositions and photosensitive recording materials of the invention are film-forming condensation polymers, e.g. phenol-formaldehyde resins and other resins and polymers, their use for the production of photosensitive photoresist layers and lithographic printing plates is known.

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The photosensitive elements according to the invention advantageously exist Masses of solutions or dispersions that are used for the production of resist layers and lithographic printing plates used iverden.

The most varied of materials can be used to produce the photosensitive compositions customary known solvents are used, preferably organic solvents, these preferably consisting of such exist that dissolve at least 0.2% by weight of the photosensitive polymer used, but not with the photosensitive Polymers react and which do not attack or practically do not attack the substrate to which the masses are applied. Typical suitable solvents are dimethylformamide, cyclohexane, cyclohexanone, acetonitrile, 2-ethoxyethanol, acetone, 4-butyrolactone, Ethylene glycol monomethyl ether acetate, 2-methoxyethyl acetate, butyl acetate and mixtures of these solvents with one another or with one or more short-chain alcohols and / or ketones.

The most advantageous concentration of the light-sensitive in the individual case Polymers in the coating solutions or coating compositions depend on the nature of the photosensitive polymers used layers and the applied coating methods. Coating compounds have proven to be useful to be used containing about 0.05 to about 25 weight percent photosensitive polymer.

Customary known additives, for example dyes, can be incorporated into the photosensitive compositions according to the invention and / or pigments for producing colored images, as well as a wide variety of other polymers and resins, stabilizers as well Surface-active compounds, which may be used to improve the film-forming properties or coating properties can contribute and / or to improve the adhesion of the layers applied to the layer support, furthermore to an improvement mechanical strength, chemical resistance and the like.

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Photosensitive photographic recording materials according to the Ürfindung can by customary known methods by application the coating compositions are produced on suitable substrates. The layer supports can be known from the usual Layer carriers consist, for example of fibrous ones Supports, e.g. paper, made of polyethylene-coated paper, of polypropylene-coated paper, parchment Woven fabrics and the like or also made of sheets and foils made of metals such as aluminum, copper, magnesium, zinc and the like, or also from substrates made of glass or coated glass, the glass being coated with a metal can be, for example, chromium, a chromium alloy, steel, silver, gold or platinum. The support can also consist of consist of synthetic polymeric substances, e.g. poly (alkyl methacrylates), z.ß. Poly (methyl methacrylate), polyesters, e.g. polyethylene terephthalate), Poly (vinyl acetals), polyamides, e.g. nylon, also films made from cellulose esters, e.g. cellulose nitrate, cellulose acetate, Cellulose acetate propionate, cellulose acetate butyrate and the like. The supports, especially those made of synthetic polymeric substances, such as those made of polyethylene terephthalate, can optionally have adhesive layers that promote adhesion improve the layers to be applied on the substrate. In a particularly advantageous manner, such adhesive layers can consist of Polymers, copolymers and terpolymers of vinylidene chloride consist, for example, of copolymers and terpolymers with acrylic acid aonomers, e.g. acrylonitrile and rivet ethyl acrylate and / or unsaturated Dicarboxylic acids, e.g., itaconic acid.

The layer supports can optionally also have filter layers and / or antihalation layers which can be built up of a colored polymer layer which absorbs the radiation used for exposure, after which it becomes photosensitive Shift has happened. Such layers can eliminate unwanted reflections from the substrate.

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A layer of a yellow dye in a polymeric binder has proven to be a particularly advantageous antihalation layer proven, the binder from one of the listed polymers Such an antihalation layer has proven particularly effective when used for exposure of the photosensitive layers ultraviolet radiation is used.

The light-sensitive layers can be of various thicknesses can be applied to a substrate. The most advantageous layer thickness in each individual case depends on various factors from, for example, the intended use of the material to be produced, the light-sensitive polymer used in the individual case and the nature of the other components which may optionally be present in the photosensitive layer. As has been expedient As a rule, it has been found that the resist layers have a thickness of about 3.0254 ram to 0.127 mm.

The recording materials according to the invention can according to customary known methods are exposed imagewise to actinic radiation, preferably using a radiation source whose The amount of ultraviolet light is high. Suitable radiation sources are thus for example carbon arc lamps, mercury vapor lamps, Lamps that emit fluorescent light, tungsten filament lamps, lasers, and the like.

The exposed recording materials can then be stored in the usual manner known methods are developed, for example by spray development, immersion development or by floating the developing liquid, using a solvent or a solvent system whose dissolving effect on the exposed and non-exposed districts is different. The exposed areas are removed by the solvent, whereas the unexposed areas remain unaffected. The solvents used for development can be such organic or aqueous in nature, depending on the composition

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the light-sensitive layer to be developed in the additional case. Examples of suitable solvents are water, aqueous alkali, short-chain alcohols and ketones and aqueous solutions of short-chain Alcohols and ketones. The images obtained can then be further processed in a conventional manner, depending on their nature. Intended use, for example with desisibilizing etching agents, Lacquers and the like.

In an advantageous way, one proceeds, for example, as follows:

First, a photoresist solution is applied to a clean surface, which can be etched, for example by spraying on, dipping or by fluidized coating, whereupon the applied mass is dried in the air. Optionally, the material may be subsequently heated to an elevated temperature (to be pre-baked), for example the material may contain 10 to 15 minutes at 80 ⁰ C heated i \ ^r the ground in order to remove solvent still present. The photosensitive recording material obtained can then be exposed through a corresponding original. The resist is then placed in a developer solvent, for example an aqueous alkaline developer solution, with which the exposed areas are removed x \ ^r ground. The developer used can optionally also contain one or more dyes and / or pigments and / or hardeners. Subsequently, the developed image is rinsed with distilled K'asser, dried and optionally post-baked, for example in that it is heated for 15 to 30 minutes at a temperature of 80 to 120 ⁰ C,

The substrate or the support can then be etched, for example by an acidic etching solution, for example a ferric chloride solution.

In the following, the production of some according to the invention will first be described usable photosensitive polymers as well as photosensitive polymers Recording materials are described.

6 09852/1015

A) Esterification of a cresol-formaldehyde resin with 1,2-kaphthaquinone-Z-diazide-S-sulfonyl chloride

6 g (50 ilillimole) of a commercially available cresol-formaldehyde resin (Alnovol 429K, manufacturer Chemische Werke Albert, Wiesbaden-Biebrich, sold by American Hoechst Corporation, North Somerville, New Jersey) were dissolved in 50 ml of dioxane, whereupon the solution became a solution of 15 g (55 millimoles) of 1,2-is'aphthaquinone-2-diazide-5-sulfonyl chloride (hereinafter referred to as MDS-Cl for short), dissolved in 100 ml of dioxane, were added. The NDS-Cl was thus applied in a 1 oily excess. While stirring the solution, 7.5 g (75 Ilillimoles) of a 3 3 ^? ₀ igen solution of triethylamine in dioxane was added dropwise. After stirring for 3 hours, 15 ml of distilled water was added to dissolve a gummy precipitate formed during the reaction. This precipitate presumably consisted of triethylamine hydrochloride and a high molecular weight polymer.

The gummy precipitate can be kept in solution by adding a small amount of distilled water whenever the solution becomes cloudy when the amine is added. The addition of water can be repeated until all the amine has been added.

The reaction solution obtained was then poured into 4 liters of a 0.1% hydrochloric acid solution. The deposited precipitate was filtered off, washed with distilled water and ^{dried in the air at 40 °} C. for 16 hours. In this way, a fully esterified polymer was obtained.

The polymer gave an infrared spectrum with the expected absorption peaks at 2.183 and 2.119 cm (indicating the presence of the group ,,, . 2 ).

-C-C-

pointed (in conjunction with a phenolic OH group) at 3.333 cm (see Table II).

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That for the production of the photosensitive polymer with naphthachiiion-2-diazide-5-sulfonylchloride converted cr es oil-formaldehyde polymer is hereinafter referred to as "polymer 1" for short.

ß) Esterification of a phenol-formaldehyde polymer with NDS-Cl

This time a commercially available phenol-formaldehyde resin was used for the esterification used (Durite S-3937, manufacturer Borden Chemical Division, USA), hereinafter referred to as "Polymer 2" for short will.

Several samples of the phenol-formaldehyde polymers were 2-diazide-5-sulfonyl chloride aphthachinon-esterified with different amounts of 1, 2-i \ ^T. 1001, 70%, 601, 50 ° s and 301 of the available phenolic residues were esterified. The photosensitive polymers were produced in the manner described under A).

C) Esterification of cresol novolak polymers (production of Polymers with a comparatively low content of NDS-P ^ estes)

12 g (100 millimoles) of a cresol novolak resin were added in 100 ml Dissolved dioxane, whereupon the resulting solution to a solution of 2.7 g (10 millimoles) of 1 ^ -naphthaquinone ^ -diazide-S-sulfonyl chloride, dissolved in 100 ml of dioxane was added. The resulting mixture was then placed in a 500 ml 3-neck round bottom flask given with electric stirrer and dropping funnel. The reaction flask was cooled to 10 ° C. using a water bath. Under While stirring the contents of the flask, 2.0 g (20 millimoles) of triethylamine dissolved in 30 ml of dioxane were added dropwise.

The reaction time was 2 hours, a gummy precipitate separating out. The reaction solution was filtered, whereupon the filtered solution to 4 liters of 0.1% hydrochloric acid was admitted. The reaction product precipitated in this way was filtered off with suction, washed with distilled water and

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Air dried for 16 hours at 40 ° C. In this way a light yellow reaction product was obtained with an infrared spectrum similar to the infrared spectrum of the polymer containing Was produced according to A). About 1ü ° ö des> 'resol-Kovolakes were esterified (see Table II).

D) Production of a micropositive recording material with a photoresist layer with a light-sensitive polymer with a relatively high KDo content

First, a photoresist material was made from:

light-sensitive polymer FF (ver »1. Table II) 1g Polymer 1 (Alnovol 420κ) 3 g

Cyclohexanone 17 g

The coating compound produced was coated according to the Vvirbe / coating process applied to silica plates. The coating speed was 4500 revolutions per minute. The generated Resist film had a thickness of 6000 to 8000 S.

The coated panels were "pre-baked" for 20 minutes at 80 ⁰ C and then exposed for 10 seconds to a mercury vapor lamp (Exposer I) by a line original. The exposed plates were then developed for 2.5 minutes in a developer having the following composition:

2-ethoxyethanol 10 ml

Aonylphenoxypolyglycidol as a surface-active

Compound (Olin Sufactant 10G) 7 ml

Distilled water 27 ml

Lines were disbanded before, less than 2 Ilikron. After etching of the Siliciunidioxidplatten to a depth of 8000 R all original lines were ven by means of a buffered hydrochloric acid solution 3 ^'f ikron odar wider maintained.

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BATH ORIGINAL

In a similar manner, other photosensitive polymers with a high NDS content, i.e. the polymers AA to JJ (see Table II) tested. Favorable images were obtained in all cases. Certain deviations in the image quality were observed, so that Exposure times and development times that differed slightly from one another were necessary to achieve optimal results.

Has the NüS content of the novolak polymers been increased in such a way that that 5Ü to 1001 of the residues of phenol-formaldehyde polymers available for esterification were esterified, slightly longer development times were required. Optimal results were achieved with Use of polymers obtained that have an NDS content of about

5 to 10% • Table II % NDS, divides according to A-C NDS-sulfonated polymers, herges theoretically Novolak polymer Photosensitive 100 Lich polymer 50 1 AA 100 1 BB 70 2 CC öO 2 DD 50 2 EE 40 2 FF 30th 2 GG 50 2 ₊ HH 40 Cresol Novolak A ₊ II 10 Cresol Novolak A ₊ JJ 7.5 Cresol Novolak A ₊ KK 5 Cresol novolak A ₊₊ LL 10 Cresol novolak ß ₊₊ MM 6th Cresol Novolak B ₊₊ NN Cresol novolak B. 00

= low molecular weight = high molecular weight

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E) Production of a non-photosensitive copolymer from Ethyl acrylate and methacrylic acid for a photoresist composition

In a 3 liter 3-necked flask equipped with a Nitrogen feed tube and a reflux condenser with a water jacket as well as a tapered outlet to reduce the entry of air into the flask, the following components were introduced :

2-ethoxyethyl acetate 1440 g

Ethyl acrylate 144 g

Methacrylic acid 16 g

2,2'-Azobis (2-methylpropionitrile), uncrystallized

from methanol 1.6 g

The reaction mixture was purged with nitrogen for 1 hour, after which the 3-liter flask was immersed for 16 hours in a water bath at 9O ⁰ C. Nitrogen continued to be passed through the flask while the polymerization was taking place.

It was not necessary to isolate the polymer obtained. Rather, the polymer-solvent mixture could be used straight to manufacture a micropositive resist layer can be used.

The analysis of the polymer produced gave the following data:

number average molecular weight 7,600 average molecular weight 14,100

In the following examples positive photoresist compositions are used with non-volatile carboxylic acids, e.g., decanoic acid with positive Photoresist compositions according to the invention with a content of volatile carboxylic acids with regard to thermal stability, image quality and Etching resistance compared. The following examples show the new and unexpected results that the inventive use of volatile carboxylic acids in positive

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ven photoresist compositions can be obtained. Example 1 (comparative example)

This example illustrates the thermal degradation of a micropositive Photoresist layer.

First a photoresist was made from:

6-nitroveratraldehyde (G-Kitro-2,4-dimetiioxy-benz-1 » ² S

photosensitive polymer ⁺ aldehyde) 3.6 g

2-methoxyethyl acetate 6.4 g

Butyl acetate 6.4 g

= The photosensitive polymer consisted of an m-cresol novolak resin of the following structure:

X stands for about 10 Mo1- $. The molecular weight of the polymer was around 1500 to around 2500.

A one-nanometer stainless steel container was filled with the photoresist composition in such a way that 92% of the container was filled were filled. The inside of the container was pressurized to 1550 mmHg. The temperature inside the container was 44 C. The pressure increase inside the container was determined,

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caused by the release of nitrogen from the photosensitive polymer. For comparison purposes, the experiment was shown below
Repeatedly using a resist composition without volatile acid. The results obtained are shown in Table III below
compiled.

Example 2 (comparative example)

The thermal degradation of a micropositive photoresist mass was determined with two o-quinonediazide polymers.

First, a photoresist composition was made up of the following ingredients
manufactured:

Polymer 3 (not light-sensitive, commercially available 2.4 g polymer: Acryloid ΛΤ-75, manufacturer Rohm and
Haas)

photosensitive polymer according to Example 1 1.8 g

photosensitive polymer 1.8 g

2-methoxyethyl acetate 6.9 g

Butyl acetate 6.9 g

= The photosensitive polymer corresponded to the photosensitive Polymers of Example 1, but this time X for 5 mol-I was standing.

Polymer 3 was a copolymer of acrylic acid and ethyl acrylate used as a binder.

The photoresist composition was placed in a stainless steel container and stored ^{at 44 ° C. as described in Example 1.} The pressure increase as a result of the split off nitrogen was determined. The results obtained are shown in Table III below.

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Examples 5 to 6

The thermal degradation of micropositive photoresist compositions was determined with stabilizers.

The photoresist composition described in Example 2 was made by addition various stabilizers modified. The modified photoresist compositions were again placed in a stainless steel container and stored at 44 ° C as described in Example 1. The stabilizers used and the amounts by weight of the stabilizers used based on the weight of the solid constituents the resist masses and the pressures generated by released nitrogen are shown in Table III below.

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Table III

Example stabilizing pressure at 44 C, mmHg

funds

Weight-I 9 days 2 weeks 3 weeks ThermiIdsche quali-stability did

Etch Resist

standing

capability

comparison 3 without 105 360 A. 2.51 ice 13th 105 4th vinegar CD 7.5% ice 39 130 O 5 vinegar OO 2.5% ants 26th 130 cn 6th acid »V. 2.51 propion 65 155 comparison acid O B. 5.0 hexanoe (7 days) 105 CTt comparison acid (capron) O C. 5.01 benzoin O 90 comparison acid D. 7.2% Decanoe 31 105 comparison acid (lauric) E. 2.2% malon 26th 105 comparison acid F. 14.2% stearin 26th 90 comparison acid G 2.6% oxal 26th 105 acid

725
270 bad
out
draws excellent
net
excellent
net excellent
net 310 310 excellent
net excellent
net excellent
net 350 excellent
net excellent
net excellent
net 295 excellent
net excellent
net bad 270 excellent
net excellent
net bad 260 excellent
net bad bad 285 excellent
net bad bad 220 excellent
net bad bad 235 excellent
net bad bad

With regard to the thermal stability is to be noted that a pressure increase of less than 365 mniHg within a period of 3 weeks at 44 ⁰ C as an indication of an excellent stability for positive resist compositions is.

The photoresist coatings produced were applied Silica plates applied, whereupon the layers produced exposed imagewise and then thinned by immersion in a alkaline developer with sodium phosphate and sodium silicate were developed. The image quality was determined by determining the dimensions of the smallest lines could be measured. To determine the test resistance the resist layers were etched in a buffered hydrofluoric acid solution for 10 minutes. The resistance to etching a photoresist layer is then referred to as excellent, if the etching factor does not exceed 1.

As can be seen from Table III, the comparative composition contained A no carboxylic acid. As a result, the thermal stability was very poor.

Examples 3 to 6 relate to photoresist compositions according to the invention. They each contained a volatile carboxylic acid. In these cases, the thermal stability and the image quality were excellent. The etching resistance was insufficient in the case of the test pieces containing benzoic acid and hexanoic acid. the most favorable results have been obtained in the case of Examples 3 bis, in which cases formic acid, acetic acid and propionic acid were used.

Comparing the results obtained in Examples 3 to 5 with the results obtained using non-volatile carboxylic acids, i.e. using a Fatty acid, such as stearic acid (comparative examples B, C, D, E, and F as well as G) results in the following:

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The thermal stability is improved, but the quality of the image will be improved and etching resistance decreased in all cases. Ls it can be assumed that the dild quality is adversely affected, v / eil the solid, non-volatile acids do not leave the layers can be removed before the images are generated.

Example 7

A lithographic printing plate has been made smaller in that
A photosensitive mass of the following composition was applied to an anodized aluminum layer support with a thickness of 0.15 rum:

light-sensitive NDS polymer , 'A according to Table II 130 g

non-photosensitive binder based on J "', thy lac ry la t-methacrylic acid according to E 500 g

liisessi · '6 a

Dye (Sudan IV) G, 9 g

The Kes sealant was applied to the aluminum substrate at 27 ⁰ C on a drum in a Scliiclitstärke of 200 mg / O, in OD ". The coated layer was then dried in a Luftunwälzofen at 5 7 ⁰ C.

The produced recording material was then left for 2 minutes exposed with a carbon arc lamp through a line slide and then developed by diluting it for 1 minute with a alkaline solution of tribasic sodium phosphate and sodium silicate was scraped off.

Hit the printing plate made in this way could do more
than 10,000 prints can be made.

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Claims (8)

PATENT CLAIMS 1y Photosensitive compound for the production of photoresist layers and light-sensitive recording materials containing (a) a condensation of an acidic quinonediazide photosensitive polymer obtained with a phenol-aldehyde resin, (b) an organic carboxylic acid and optionally (c) a non-photosensitive film-forming polymer, characterized in that it is used as an organic carboxylic acid a volatile carboxylic acid of the following formula: f 1 - (- CHR- ^ C - OH contains, in which mean: R is a hydrogen or halogen atom, a short-chain alkyl radical, a short-chain alkoxy radical, a cyano or nitro residue and m = 0,1,2,3 or 4. 2. Photosensitive composition according to claim 1, characterized in that that the weight ratio of photosensitive polymer to non-photosensitive polymer is 1: 1 to 99: 1. 3. Photosensitive composition according to claims 1 and 2, characterized in that that it contains, as (c) non-photosensitive film-forming polymer, a polymer obtained by Addition polymerization of one or more unsaturated compounds with a radical of the formula: c = c; 609852/1015 26237 4. Photosensitive composition according to claim 1, characterized in that that the quinonediazide radicals of the photosensitive polymer via sulfonyl, carbonyl, carbonyloxy or sulfinyloxy radicals are bound to the phenol-aldehyde resin. 5. Photosensitive composition according to claim 1, characterized in that it contains a volatile carboxylic acid with a boiling point of 200 ⁰ C or less at atmospheric pressure. 6. Photosensitive composition according to one of claims 1 to 5, characterized characterized in that they contain the volatile carboxylic acid in a concentration of 1 to 50% by weight, based on the total weight the solids of the mass contains. 7. Photosensitive hats according to claims 1 to 6, characterized in that that it contains one of the following structural units as a photosensitive polymer: 609852/1015 where mean: R a U assers toff a toi .; or an "ethyl radical; R ⁴ and U ⁵ = IN ₂ or O ₃ where it applies that R ⁴ and R ⁵ do not have the same meaning and where furthermore X stands for 1 to 99 MoI- ⁰ S. 8. Photosensitive photographic recording material consisting of from a layer support and at least one on top applied photosensitive layer which contains (a) a photosensitive polymer obtained by the condensation of an acidic quinonediazide with a phenol-aldehyde resin, (b) an organic carboxylic acid and optionally (c) a non-light-sensitive film-forming polymer, characterized in that that the light-sensitive layer, as an organic carboxylic acid, is a volatile carboxylic acid of the following formula: Ii-f-CH! H C-OM contains, in which mean: R is a hydrogen or halogen atom, a short-chain one Alkyl radical, a short-chain alkoxy radical, a cyano or mitro radical and m = 0,1,2,3 or 4. 609852/1015 BATH ORIGINAL