DE2437413B2 - PROCESS FOR THE PRODUCTION OF RELIEF STRUCTURES - Google Patents

Description

—O — CH ₁ -C = CH,

RO ^

-O-

COR ₁

COR ₁

R,

3 s

40

- RO — CO-

- (CH = CHL- <O>

45

- RO - <^ O V-CH = CH-R ₃

- Ο- / θ / "CH = CH-R ₃

R = oxyalkyl
R ₁ = alkyl, phenyl. Alkoxyphenyl, halogen

phenyl

R ₂ = H. Cl, alkyl. Alkoxy
R, = carbocycl. or heterocyclic aromatic. Rest.

bound via ring-C

included, and where

b) the diamines, diisocyanates, bis-acid chlorides or dicarboxylic acids to be reacted with these compounds contain at least one cyclic structural element, according to patent 23 08 830, thereby characterized in that polycondensation products are used as soluble polymeric precursors polyfunctional carbocyclic or heterocyclic, radiation-sensitive radicals bearing Compounds with diamines can be used, with

a) the radiation-sensitive radicals R * bearing compounds two carboxylic acid chloride groups and partly in the ortho- or peri-position to it in ester-like manner on carboxyl groups contain bonded radiation-reactive groups and

b) the diamines contain at least one heterocyclic hydantoin structural element.

2. The method according to claim 1, characterized in that diamines with 1,3-bis-aryIhydantoin structural elements be used.

3. The method according to claim 2, characterized in that that as diamine 1,3-bis (p-aminopheny!) - 5,5-dimethylhydantoin is used.

4. The method according to any one of claims 1 to 3, characterized in that as polyfunctional c carbocyclic, radiation-sensitive radicals carrying compounds pyromellitic acid derivatives are used will.

5. The method according to claim 1, characterized in that the radiation-reactive group R * comes from an easily vaporizable alcohol R * H.

6. The method according to claim 5, characterized in that that the radiation-reactive group R * is derived from allyl alcohol.

7. The method according to any one of claims 1 to 6, characterized in that the soluble polymers Precursors together with radiation-sensitive, copolymerizable compounds be used.

8. The method according to claim 1, 5 or 7, characterized in that soluble polymeric precursors with allyl groups as radiation-reactive groups R * and copolymerizable compounds with one or more N-substituted malcinimide groups can be used.

9. The method according to any one of claims 1 to 8, characterized in that the soluble polymers Precursors or their mixtures with radiation-sensitive copolymerizable Compounds used together with common photoinitiators and / or photosensitizers will.

10. The method according to claim 9, characterized in that as photoinitiators and / or -Sensitizers 4,4 '- bis (diethylamino) - benzophenone, Michler's ketone and or benzoin ether be used.

The invention relates to an improvement and further development of the method according to the Patent 23 08 830 for the production of relief structures from highly heat-resistant polymers by application radiation-sensitive, soluble polymeric precursors in the form of a layer or film on a

Substrate, irradiation of the radiation-sensitive layer or film through negative originals, removal or peeling off the non-irradiated layer or film parts and then optionally Annealing of the relief structures obtained using polyaddition and polycondensation products polyfunctional carbocyclic or heterocyclic, radiation-sensitive radicals bearing Compounds with diamines, diisocyanates ^ bis-acid chlorides or dicarboxylic acids as soluble polymers Preliminary stages, where

a) the compounds carrying radiation-sensitive radicals R * have two carboxyl, carboxylic acid chloride, amino, _S isocyanate or hydroxyl groups which are suitable for addition or condensation reactions and, in some cases, in ortho or peri-position to this, radiation-reactive groups of the following structure bonded to carboxyl groups in ester-like fashion

-Q-CH ₁ -C = CH ₁

COR ₁

-RO

-RO-CO- (CH = CH) _n

I «= 1.2)

CH = CH-R ₃

CH = CH-R ₃

R = oxyalkyl
R ₁ == alkyl, phenyl, alkoxyphenyl, halogen

phenyl

R ₂ = H, Cl, alkyl, alkoxy
R ₃ = carbocyclic or heterocyclic aromatic. Rest,

bound via ring-C

included, and where

b) the diamines, diisocyanates, bis-acid chlorides or dicarboxylic acids to be reacted with these compounds contain at least one cyclic structural element.

It has now been found that soluble polymeric precursors which are even more sensitive to radiation are obtained that require significantly shorter exposure times and with which a very high resolution can be achieved if, in the production of relief structures according to Patent 23 08 830, as soluble olvmere precursors polycondensation products of polyfunctional carbocyclic or heterocyclic, Radiation-sensitive radicals carrying compounds with diamines used, wherein

a) the radiation-sensitive radicals R * bearing compounds two carboxylic acid chloride groups and partly in the ortho- or peri-position to it bonded in ester-like manner to carboxyl groups the radiation-reactive groups, and where

b) the diamines have at least one heterocyclic hydantoin structural element contain.

Diamines with 1,3-bis-arylhydantoin structural elements are particularly suitable. 1,3-bis (p-aminophenyl) -5,5-dimethylhydantoin is preferably used.

Radiation-reactive groups R *, which differ from easily evaporable alcohols R * H, such as. B. Croton and Allyl alcohol, derived, are particularly suitable. In the case of radiation crosslinking, unconverted proportions R * can be easily volatilized as R * H when the relief structures are tempered. Are particularly suitable Oxyallyl groups.

Customary photoinitiators and or photo-sensitizers can be used to increase the crosslinking rate can be used, see Industrie Chimique Beige 24, 739-64 (1959) or Light-Sensitive Systems by J. Kosar, John Wiley & Sons Inc., New York 1965, 143-46, 160-88. Well suited Sensitizers and / or initiators are e.g. B. Michlers Ketone and / or benzoin ether, 2-tert-butyl-4,4-bis (diethylamino) benzophenone.

In many cases it has proven to be beneficial to combine the soluble polymeric precursors with other radiation-sensitive, to put copolymerizable compounds. Well suited are z. B. Compounds that contain one or more N-substituted maleimide groups.

When the solvent hexamethylphosphoric triamide is used, the soluble polymeric precursors can be prepared in a particularly simple and economical manner in a one-pot reaction.
According to the method of the present invention

4j can create sharp-edged relief structures made of highly heat-resistant polymers, especially miniaturized Embodiments can be made from polymeric precursors with increased photosensitivity. It is preferably suitable for producing protective layers for semiconductor components, in particular of insulating and passivating layers. It is also used in the production of Solder protection layers on multilayer circuits, from miniaturized insulating layers to electrically conductive and / or semiconducting and / or insulating base materials, of layer circuits, of insulating layers for printed circuits with galvanically generated conductor tracks, of optically queryable Image storage and high quality print

(So shape.

The following example illustrates the invention.

example
Manufacture of the soluble, polymeric precursor

21.8 parts by weight of pyromellitic dianhydride were dissolved in 150 parts by volume of hexamethylphosphoric acid triamide, dropwise with ice cooling and stirring.

wise mixed with 11.6 parts by weight of allyl alcohol and then stirred for 4 days at room temperature. The solution was then at - 10 ⁰ C are added dropwise 24 Gewichtstei'en thionyl chloride and further stirred for one hour - 5 to. A solution of 31.4 parts by weight of 1,3-bis (p-aminophenyl) -5,5-dimethylhydantoin in 150 parts by weight of hexamethylphosphoric acid triamide was then added dropwise, and finally stirring was continued for one hour without cooling.

The soluble polymeric precursor was precipitated by adding the solution dropwise to 400 parts by volume of water and washed with water and methanol.

Production of relief structures

5 parts by weight of the polymeric precursor, 0.5 part by weight of maleic anil and 0.05 part by weight of M ichler's ketone were dissolved in 26 parts by volume of dimethylformamide. Then the solution was filtered and spun onto aluminum foil to form uniform films which were strong after evaporation of the solvent U μπ. The films were pre-screened with an MX) -W super-high pressure mercury lamp at a distance. 23 cm irradiated through a contact copy for 90 seconds and developed for 30 seconds in a mixture of tetrahydrofuran / 1-butyrolactone 5-1. A resolution of <"> μm with good edge definition was achieved. The samples obtained were tempered for 20 minutes at 300 ° C. The resolution and edge definition remained unchanged, and the relief structures then exhibited the excellent thermal, mechanical, electrical and chemical properties of polyimides. The IR spectrum of the tempered samples showed the typical band for the imide structure at 5.6 μΙΤΙ.

Claims (1)

Patent claims: 1 Process for the production of relief structures by applying radiation-sensitive structures soluble polymeric precursors in the form of a layer or film on a substrate, irradiating the radiation-sensitive layer or film through negative originals, detaching or peeling off the non-irradiated layer or film parts and optionally subsequent tempering of the resulting Relief structures, with polyaddition or polycondensation products, more polyfunctional carbocyclic or heterocyclic, radiation-sensitive radicals carrying compounds with Diamines, diisocyanates, bis-acid chlorides or dicarboxylic acids as soluble polymeric precursors, whereby a) the radiation-sensitive residues R * hit connections two door addition or Carboxyl, carboxylic acid chloride, amino, isocyanate or hydroxyl groups suitable for condensation reactions and partly in the ortho- or peri-position to this, bonded to carboxyl groups in an ester-like manner radiation-reactive groups of the following structure