DE2209749A1 - Process for the preparation of a negative photosensitive composition - Google Patents

Description

PHN.3145

Dipl.-Inn. HOPST AUER

Note: U.V.P., .... y uLC2.LAiUrEIiFABRIEKEM

Afcie: PHN-5H3
Registration dated Feb. 28, 1972

"Method of making a negative photosensitive composition".

The invention "relates to a method of manufacture a negative photosensitive mass.

Such compositions are to be understood as meaning mixtures which become insoluble on exposure or their solubility or Solution speed is at least reduced.

The known negative photosensitive materials can be divided into four groups, namely:

1. Masses made up of non-photosensitive polymers and a substance exist, which reacts with the polymer on exposure and thereby links the polymer molecules, creating an insoluble network will;

2. Compounds containing polymeric substances with light-sensitive groups which, when exposed to light, link the molecules and thus form an insoluble network;

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3. Solutions of monomers which polymerize under the action of light. This group could also use mixtures of a polymerizable substance and a polymerizing catalyst on exposure to light decomposing compound include;

4. Mixtures of a soluble or sparingly soluble polymer and a light-sensitive, soluble compound that changes when exposed to light decomposed to an insoluble substance.

The negative photosensitive composition according to the invention cannot be placed in any of these groups. The effect of this mass is based on the decomposition of a low molecular weight substance under the action of light to form a product which enters into a substitution reaction with a soluble polymer, which results in a reduction in the solubility of this polymer.

Accordingly, the invention relates to a method for producing a negative photosensitive composition, which is characterized in that one has a phenolic OH group containing resin with at least one free ortho- or I-arastelle in the phenol group and as a photosensitive substance a 1,3-diphenyltriazene the general formula

dissolves in an inert solvent,

where in the formula R and R ^{1 represent} an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a halogen atom or a benzoyl group, η and n 'have the value 0, 1, 2 or 3 and R _{1 represent} hydrogen or a methyl group.

Of those with alkyl or alkoxy groups. Aubatituted triasens are preferably those with alkyl groups with 1 to 4 carbon atoms

209846/1039 BATH ORIGINAL

- CH - CH ₂ - 0

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and triazenes substituted by alkoxy groups with 1-2 C atoms are used.

The diphenyltriazenes of the general formula mentioned are for the most part known compounds. The fabrics can get through in Houben-Weyl, Methods of Organic Chemistry, Volume 10 / 3t, p.710-720, methods described are produced.

Examples of resins that can be used in the new photosensitive composition include: Novolaks and epoxy resins such as:

- CHn ~ CH - CHn ι

^X 0 ''

the latter with phenol carboxylic acids, such as .4 »4-M ^ (p-hydroxyphenyl) -valeric acid, 4-hydroxybenzoic acid, 3> 5-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid and gallic acid, esterified dind.

There can be resins with very different mean

Molecular weights are used. Resins with too high a molecular weight However, they are not or less useful because they cannot be brought into solution or their solubilities increase are little different from those of the resins after exposure. Resins with too low a molecular weight can be unfavorable film-forming Have properties or poor adhesiveness. In general, resins with a average molecular weight of about 500 to about 1500 selected.

Pyridine, ketones,

such as acetone, cyclopentanone, cyclohexanone, methyl ethyl ketone, etc., Esters such as ethyl acetate, butyl acetate, methyl glycol acetate and the like. Or Dimethylformamide can be used. Mixtures of the solvents mentioned can of course also be used.

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22097Λ9

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Di · substitution reaction that occurred upon exposure

calibrated, works optimally in an alkaline environment. Hence can if desired, the photosensitive composition also has an organic one Base such as diazobicyclooctane can be added.

The ratio between the amount of triazene compounds

applications and the amount of resin is not particularly critical. In general 3-5 parts by weight of triazene compound per 10 parts by weight of resin applied.

The masses according to the invention are very high

thermal stability so that no noticeable dark reaction occurs.

The masses are so sensitive to light

that after attachment to the base and after drying, at which the latter process preferably temperatures of 90 to 100 ° C not exceeded, when exposed to a high pressure mercury vapor lamp of 500 W at a distance of 35 cm, an exposure time from 1 to a few tens of seconds is sufficient.

The masses also have the favorable property that the triazene compounds do not crystallize out on drying.

The latent image obtained on exposure can be obtained by immersion in aqueous alkali with a pH of about 12 to about 13 »6 or by splashing or spraying with this lye.

The image can be treated with 1 to 2n

Lye or removed with the solvents used in the masses will.

The photosensitive compositions according to the invention

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can be used, for example, in the graphics industry for the production of printing plates and used in the electronics industry to manufacture printed wiring, transistors, and integrated circuits will.

The invention is explained in more detail below with the aid of a few examples.

1. From a solution of 173 mg of 1-phenyl-3-phenyl-triazene and 530 mg Alnovol 429 K (Alnovol 429 K is a condensation product of formaldehyde and metacresol with 5 to 6 metacresol groups per mole) in 9-3 ml of pyridine, a film was poured onto glass. This was dried in 15 minutes at a temperature of 80 C, after which the film had a thickness of about 1 / µm. The film was 2 minutes long behind a template with a 500 W high pressure mercury vapor lamp exposed at a distance of 35 cm and then for 2.5 minutes Developed in a KOH solution in water with a pH of 13 »3. In this way, a satisfactory image of the original was obtained.

2. From a solution of 191 mg of 1-p-tolyl-3-p- * olyltriazene and 509 mg of Alnovol 429 K in 10 ml of pyridine became a film on glass infused. This was done in 10 minutes at a temperature of 100 ° C dried, after which the film had a thickness of about 1 / µm. To 10 seconds exposure behind an original with a 500 W high pressure citrus silver vapor lamp at a distance of 35 cm and after subsequent development of 6 minutes in a KOH solution in water with a With a pH of 13 »1, an image of the original was obtained.

3. From a solution of 210 mg of i-p-methoxyphenyl-3-pmethoxy-phenyl-triazene and 490 ag Alnovol 429 K in 9 »3 nil pyrisine a film poured onto glass. This was done in 15 minutes at a Temperature of HO C dried, after which the film has a thickness of about

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1 / um. After exposure of 75 seconds behind an original with • a 500 W high pressure mercury vapor lamp at a distance of 35 cm and after subsequent development for 2.5 minutes in a KOH solution in water with a pH of 13 »3, an image of the template became obtain.

4 From a solution of 215 mg of i-o-chlorophenyl-3-o-

chlorophenyl-triazene and 405 mg Alnovol 429 K in 9 »3 ml pyridine a film poured onto glass. This was done in 15 minutes at a Temperature of 80 C dried, after which the film has a thickness of about 1 / um. After exposure for 2 minutes behind an original with a 500 W high pressure mercury vapor lamp at a distance of 35 cm and after subsequent development for 2.5 minutes in a KOH solution in water with a pH of 13.5, an image of the template became obtain. '

5. A solution of 235 mg 1- (2,5-dichlorophenyl) -3-OTchlorophenyltriazene and 465 mg Alnovol 429 K in 9 »3 ml pyridine became a film poured onto glass. This was dried in 15 minutes at a temperature of 80 C, after which the film had a thickness of about 1 / um. After exposure for 1 minute behind an original with a 500 W high pressure mercury vapor lamp at a distance of 35 cm and after subsequent development in a KOH solution in water with a pH of 13.5, an image of the template was obtained.

6. A film was cast onto glass from a solution of 260 mg of 1-o _T p-dichlorophenyl-3-o, ρ-dichlorophenyl-triazene and 450 mg of Alnovol 429 K in 9-3 ml of pyridine. This was dried in 15 minutes at a temperature of 8O ⁰ C, after which the film to have a thickness of about 1 /. After exposure for 1 minute behind an original with a 500 W high pressure mercury vapor lamp in front of it.

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35 cm and after subsequent development of 2.5 minutes in one KOH solution in water with a pH of 13 »5 was a picture of the Received template.

7. From a solution of 260 mg of i-p-bromophenyl-3-p-bromophenyl-triazene and 440 mg of Alnovol 429 K in 10 ml of pyridine was a Film poured onto glass. This was dried in 10 minutes at a temperature of 100 ° C., after which the film had a thickness of about 1 μm exhibited. After exposure for 1 minute behind an original with a 500 W high pressure mercury vapor lamp at a distance of 35 cm and after subsequent development for 1.5 minutes in a KOH solution in water with a pH of 13 »3, an image of the template was obtained.

8. From a solution of 350 mg of 1-gehnyl-3-phenyl-3-methyl-triazene and 600 mg of Alnovol 429 K in 12 ml of pyridine was a Film poured onto glass. This was done in 15 minutes at one temperature dried at 80 C. After exposure for 10 seconds behind an original with a 500 W high pressure mercury vapor lamp in a distance of 35 cm and after subsequent development of 2.5 Minutes with a KOH solution in water with a pH of 15 »5 an image of the original was obtained.

9. From a solution of 199 mg of 1-p-tolyl-3-raethyl-3-p-tolyl-triazene and 501 mg of Alnovol 429 K in 10 ml of pyridine, a film was poured onto glass. This was done in 10 minutes at one temperature dried by 100 C, after which the film has a thickness of about 1 / ÜB exhibited. After exposure for 30 seconds behind an original with a 500 W high pressure mercury vapor lamp at a distance of 35 cm and after subsequent development of 3 minutes in a KOH solution in In water with a pH of 15 »2, an image of the original was obtained.

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10. From a solution of 218 mg of i-p-methoxyphenyl-3-pmethoxyphenyl-3-methyl-triazene and 480 mg Alnovol 429 K in 9 »3 ml Pyridine was cast as a film on glass. Lieser was in 15 minutes dried at a temperature of 80 C, after which the film has a thickness of about 1 / µm. After exposure for 1 minute behind an original with a 500 W high pressure mercury vapor lamp at a distance of 35 cm after subsequent development of 2.5 minutes in one KOH solution in water with a pH of 13 »3 was a picture of the Received template.

11. From a solution of 280 mg of i-o-chlorophenyl-3-ochlorophenyl-3-methyi-triazene and 600 mg of Alnovol 429 K in 12.6 ml of pyridine, a film was poured onto glass. This was done in 15 minutes dried at a temperature of 80 C, after which the film had a thickness of about 1 / µm. After exposure of 30 seconds behind a template with a 500 W high pressure mercury vapor lamp in a distance of 35 cm and after subsequent development of 2.5 minutes in a KOH solution in water bit a pH value of 1.2 get a picture of the original.

12. From a solution of 280 mg of i-p-chlorophenyl-3-pchlorophenyl-3-methyl-triazene and 600 mg of Alnovol 429 K in 12.6 ml of pyridine, a film was poured onto glass. This was in 15 minutes dried at a temperature of 80 C, after which the film has a thickness of about 1 / µm. After exposure for 30 seconds behind an original bit of a 500 W high pressure mercury vapor lamp in one A distance of 35 cm and after subsequent development of 2 minutes in a KOH solution in water with a pH of 15 * 2 became a Image of the original received.

13 ... From a solution of 349 mg i-Oyp-Dichlorrhenyl-3-

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o.p-dichlorophenyl ^ -methyl-triazene and 600 mg Alnovol 429 K in 13.6 ml of pyridine, a film was poured onto glass. This was in 15 Minutes dried at a temperature of 80 G, after which the film had a thickness of about 1 / µm '. After exposure of 2.5 minutes behind a template with a 500 W high pressure mercury vapor lamp in one Distance of 35 approx and after subsequent development of 2.5 minutes in a KOH solution in water with a pH of 13.5 was a Image of the original received.

14. From a solution of 267 mg of i-p-bromophenyl-3-p-bromo-

phenyl-3-methyl-triazine and 433 mg of Alnovol 429 K in 10 ml of fyridine were a PIIm poured onto glass. This was done in 10 minutes at a Temperature of 100 C dried, after which the film has a thickness of about 1 / um. After 1 minute of exposure behind a template with a 500 W high pressure mercury vapor lamp at a distance of 35 cm and after subsequent development for 2.5 minutes in a KOH solution in water with a pH of 13 »1, an image of the template became obtain,

15 · From a solution of 350 mg of i-p-Benzoylphdnyl-3-ni-

chlorophenyl-3-methyl-triazene and 600 mg Alnovol 429 K in 13 »6 ml pyridine a film was poured onto glass. This was dried in 15 minutes at a temperature of Θ0 C, after which the film had a thickness of about 1 / µm. After exposure for 30 seconds behind an original in a 500 W high pressure silver vapor lamp at a distance of 35 cm and after subsequent development of 2 minutes in a KOH solution in water with a pH of 13 »2, a Image of the original received.

16. From a solution of 470 mg 1-o, m-dichlorophenyl-3-

o, B-dichlorophenyl-3-methyl-triazene, 480 mg of a condensation product

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of 4,4-di-p-hydroxyphenylvaleric acid and Araldite F (Ciba) (Araldite F is the diglycidyl ether of 2,2-di-p-hydroxyphenylpropane) and 10 mg of diazabicyclooctane in 9 »1» 1 pyridine, a film was cast on glass . This was dried for 6 minutes at a temperature of 105 C, after which the film had a thickness of about 1 / µm. ^Fter exposure of 30 seconds behind einer'Vorlage bits of a 500 W high-pressure mercury vapor lamp at a distance of 35 cm and after subsequent development of 7 minutes in an aqueous NaOH solution hit a pH of 1314 an image of the original was obtained ,

17. 326 mg of 1,3-di-p-chlorophenyl-3-methyl <-triazene and 928 ng of a condensation product of 1 VaI DER 332 (DER 332 has the following Structuri

H ₂ C - CH-CH ₂ -O

with 1.2 VaI p-hydroxybenzoic acid were dissolved in 5 β pyxidine. A A film of this mixture was applied to oxidized Si disks by centrifugation at a speed of 25ΟΟ revolutions / min. After drying for 15 minutes at 90 ° C., after 110 seconds of exposure behind an original with a 500 W high pressure mercury vapor lamp in one Distance of 35 cm and after 15 seconds of development in a solution of KOH in water with a pH of 12.3 an image was obtained,

18. 285 mg of 1,3-di-p-chlorophenyl-3-methyl-tri »* en and 85Ο 1 mg of condensation product of 1 value of DER 332 with 1.2 parts of 2,4-dihydroxybenzoic acid and 14 mg of diazabicylooctane were dissolved in 50 g of cyclopentanone. A film of this mixture was produced on oxidized Si disks by centrifugation at a speed of 2500 Uedrthungen-min attached. After drying in 15 minutes at 90 C,

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0 - CH ₉ 'CH - CH ₀ )

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after 20 seconds of exposure behind an original with a 500 W high pressure mercury vapor laiipe at a distance of 35 cm and after 40 seconds development in a solution of KOH in water with a pH value an image of 12.5 was obtained.

19. 316 mg 1 ^ -Di-p-chlorophenyl ^ -methyl-triazene and mg of a condensation product of 1 VaI DER 332 with 1.2 VaI 3 »5-dihydroxybenzoic acid were dissolved in 5 g of cyclopentanone. A film of this mixture was made on oxidized Si disks by centrifugation a speed of 25OO revolutions / min attached. After drying in 15 minutes at 90 C, after 50 seconds of exposure behind a Template with a 500 W high pressure mercury vapor lamp at a distance of 35 cm and after 15 seconds development in a KOH solution an image was obtained in water at pH 12.2.

20. 263 mg of 1,3-M-p-tolyl-3-methyl-triazene and 865 mg of a condensation product of 1 VaI DER 332 with 1.2 VaI p-hydroxybenzoic acid and 124 mg of diazabicylooctane were dissolved in 5 g of cyclopentanone. A film of this mixture was made on oxidized Si wafers by centrifugation at a speed of 2500 revolutions / min appropriate. After drying in 15 minutes at 90 ° C., after 200 seconds Exposure behind an original with a 500 W high pressure mercury vapor lamp at a distance of 35 cn * and after 50 seconds of development an image was obtained in a KOH solution in water at pH 12.5.

21. 296 mg of 1,3-di-p-chlorophenyl-3-methyl-triazene and

839 ^m g of a condensation product of 1 DER 332 VaI VaI 1.2 p-hydroxybenzoic acid and 118 mg Diazabicylooctan were dissolved in 5 g Fyridin. A film of this mixture was attached to glass by centrifugation at a speed of 2500 revolutions / min. To

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Drying in 15 minutes at 90 ° C., after 50 seconds of exposure behind an original with a 500 W high pressure mercury vapor lamp at a distance of 35 cm and after 25 seconds of development in a solution of KOH in water, it has a pH value a " ⁰ Ud" was obtained from 12.3.

22. 326 mg of 1,3-di-p-chlorophenyl-3-methyl-triazene and mg of a condensation product of 1 VaI DER 332 with 1.2 VaI p-hydroxybenzoic acid were dissolved in 5 g of pyridine. A film of this mixture was centrifuged at a speed of 2500 revolutions / min attached to glass. After drying in 15 minutes at 90 ° C, after 70 seconds of exposure behind an original with a 500 W high pressure mercury vapor lamp and after 30 seconds of development in a solution of KOH An water with a pH of 12 ,? was a Image received.

23. 263 mg of 1,3-di-p-tolyl-3-methyl-triazeh and 865 mg of a condensation product of 1 value of DER 332 with 1.2 value of p-hydroxybenzoic acid and 124 mg of diazabicylooctane were dissolved in 5 g of cyclopentanone. A film of this mixture was attached to glass by centrifugation at a speed of 2500 revolutions / min. After drying in 15 minutes at 90 ^e C, acn 100 seconds exposure behind a template with a 500 W Höchdruck mercury vapor lamp at a distance of 35 cm and after 35 seconds development in a solution of KOH in water with a pH value of 12 , 5 an image was obtained.

24. 284 mg of 1,3-di-p-chlorophenyl-3-methyl-triazene and 850 mg of a condensation product of 1 value of DER 332 with 1.2 parts of 3 _{tons of} 5-dihydroxybenzoic acid and 115 mg of diazabicylooctane were dissolved in 5 g of dimethylformamide. A film of this mixture was centrifuged at a speed of f'SPO revolutions min to ^ i-

209846/1039 B * ⁰ O ^RIGINAL

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SiOj disks attached. "After drying in 15 minutes at 90 C, after 45 seconds exposure behind an original with a 500 W high pressure mercury vapor lamp at a distance of 35 cm and after 20 seconds of development in a solution of KOH in water with a pH of 12.0 an image was obtained.

25. 285 »g 1, 3-di-p-chlorophenyl-3-methyl-triazene and 854 mg of a condensation product of 1 VaI DER 332 with 1.2 VaI 2,4-dihydroxybenzoic acid and 121 mg of diazabicylooctane w.urden in 5 g of methyl glycol acetate solved. A film of this mixture was centrifuged at a speed of 2500 revolutions / min on Si-SiOp disks appropriate. After drying in 15 minutes at 90 C, after 50 seconds exposure behind an original with a 500 "W high pressure mercury dara lamp at a distance of 35 c »and after 80 seconds Developing in a solution of KOH in water with a pH value of 12.7, an image was obtained.

26. 313 mg of 1,3-di.p-chlorophenyl-3-methyl-triazene and 937 mg of a condensation product of 1 VaI DER 332 with 1.2 VaI 2,4-dihydroxybenzoic acid were dissolved in 5 g pyridine. A film of this mixture was applied to Si-SiOp disks by centrifugation at a speed of 2500 revolutions / min. After drying for 5 minutes at 90 ^° C., after 30 seconds of exposure behind an original with a 500 W high pressure mercury vapor lamp at a distance of 35 ° C. and after 35 seconds of development in a solution of KOH in water with a pH host an image of 12.3 was obtained.

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Claims (9)

- 14 - FHN.5143 PATENT CLAIMSi 1. Process for the preparation of a negative photosensitive composition, characterized in that one is a phenolic
Resin containing OH groups with at least one free ortho or para site in the phenyl group and a 1,3-diphenyltriazene of the general formula as the photosensitive substance 1 η ¹ in an inert solvent 15st, where in the formula R and R ^{1 represent} an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a halogen atom or a berwyl group, η and n ¹ the value 0, 1, 2 or 3 and R. represents hydrogen or a methyl group. 2. The method according to claim 1, characterized in that nan as resin is a novolak or one with a phenol carboxylic acid esterified epoxy resin used. 3. The method according to claim 1 or 2, characterized in that a resin with an average molecular weight of about 500 to about 15ΟΟ is used. 4. The method according to any one of claims 1 to 3t characterized that for 10 parts by weight of resin 3 to 5 parts by weight the triazene compound can be used. 5. Negative photosensitive mass, marked
by a content of a resin containing phenolic OH groups with at least one free ortho or para site in the phenol group, with a 1,3-diphenyltriazene of the general formula as the photosensitive substance 209846/1039 - 15 - PEK.5143 is used., in which formula R and R ^{1 represent} an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom or a benzoyl group, while η and n 'have the value 0, 1, 2 or 3 and R _{1 represents} hydrogen or a methyl group, the whole being dissolved in an inert solvent. 6. Negative photosensitive composition according to claim 5 »characterized by a content of a novolak or one with a phenol carboxylic acid esterified epoxy resin. 7. Negative photosensitive composition according to claim 5 or: 6, characterized by a content of a resin with an average molecular weight of about 500 to about 15ΟΟ. 8. Negative photosensitive composition according to one of claims 5 ^ is 7 »characterized in that to 10 parts by weight Resin 3 ^ is 5 parts by weight of triazene compound available. are. 9. A method for generating images on a base, characterized in that a negative photosensitive composition according to one of claims 5 ^ i- ³ 8 is applied to the base, the photosensitive layer is dried, exposed behind a template and with an aqueous alkali a pH of about 12 to about 13t6 is developed. 209846/1039