CA1244579A - Radiation-sensitive coating agent and its use - Google Patents
Radiation-sensitive coating agent and its useInfo
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- CA1244579A CA1244579A CA000426131A CA426131A CA1244579A CA 1244579 A CA1244579 A CA 1244579A CA 000426131 A CA000426131 A CA 000426131A CA 426131 A CA426131 A CA 426131A CA 1244579 A CA1244579 A CA 1244579A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
- H01B3/306—Polyimides or polyesterimides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/308—Wires with resins
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- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A radiation-sensitive coating agent and its use Abstract Polyimides which contain aliphatic groups can be radiation-crosslinked with chromophoric aromatic poly-azides. Solutions in organic solvents can be used as radiation-sensitive coating agents for preparing insulating or protective coatings and as photoresists having high thermal, mechanical and chemical stability.
Description
5~
_-13~88/7F~/~
A radiat _ -sensitive coating agent and its use The present invent;on relates to a radiation~sen-sitive coating agent which consists of a polyim;de d;ssol-ved ;n an organic solvent and an organic polya~ide~ to a photographic recording material, and to the use of the coating agent for apply;ng insuL3ting or protective coat-ings, in particular in the manufacture of printed circuits, discrete semiconductor components and ;ntegrated circuits~
Polyimides have good thermal stability, and they are therefore also used ;n electronics and semiconductor tech-nology as insulating or protect;ve films or for the photo-~raphic preparation of relief images. Since polyimides are generally insoluble in organic solvents, it is neces-sary to proceed froM soluble precursors which carry radia-tion-sensitive groups or are mixed w;th rad;at;on-sensitive compounds. The polyimide is formed here only after imag-;ng, namely by thermal cyclisat;on, ;n the course of wh;ch a cons;derable amount of volatile substances 1s removed~
On heating the relief structures generated ;n the imaging suffer a considerable loss ;n thickness and a marked con-traction ;n the vert;cal d;mens;ons. This is thought of as particularly unfavourable~ because it has proved remar-kably diff;cult to generate full-scale images of a given mask~ Also, the technically compl;cated preparation of the precursors ;s uneconom;calr In addition, the various additives prevent the poly;mides thus prepared from exhi-bit;ng the good electr;cal, mechan;cal and thermal proper-ties character;stic of these polymers. German Offenlegungs-~ 2~7~
schrift 2,308,830 and German Offenlegungsschrift 2,91~,619,for example, describe such precursors.
Direct crossl;nking by high~energy radiation and hence the possibility of photostructuring polyimides di-rectly is extremely desirable to prevent the d;sadvantages mentioned. It is an object of the present invention io provide a coating agent with wh;ch polyim;des can be di-rectly radiation-crosslinked.
~ e have now found that poLyimides can be directly radiation-crosslinked with chromophoric aromatic polyazides if the polyimides contain aliphatic grvups.
The present invention relates to a radiation-sen-sitive coatin0 agent which, in addition to customary addi-t;ves, contains (a) an organic solvent, ~b) a homopoly-imide or copolyimide which is soluble in this solvent and is formed from aromatic tetracarboxylic acids and aromatic d;amines or aromatic and aliphatic d;amines, where at least one aliphatic group is bonded directly or via a bridging group to at least some of the tetracarboxylic acid radicals, of the aromatic diamine radicals, or the two radicals and/or at least some of these radicals contain as an aliphatic bridging group alkylene, alkylidene, cycloalkylidene or Si(alkyl)2, and (c) at least 0.1% by weight, based on component (b), of at least one organic chromophoric polyazide in which the azide groups are bonded to aromatic hydrocarbon radicals~
The radicals with aliphatic groups and/or bridging groups preferably contain at least S mol %, in particular at least ~0 mol % and especially at least 30 mol % in the polyimide or copolyimide, based on the polyimide. The aliphat;c groups are preferably bonded to aromatic radicals, and the bridging groups link aromatic radicals, in parti-cular 2 phenyl groups.
The al;phat;c group preferably has the formula alkyl-Q- where there are 1-6, in particular 1-3~ C atoms in the alkyl group and where Q is a direct bond, -0-, -S-, -S0-, -S02-, -C0-, -NH-, -N-alkyl having 1-~, preferably 1-3, C atoms, or -NHC0-. Examples of alkyl are methyl, ethyl, propyl9 isopropyl, 1-butyl, 2-butyl, tertiary-butyl, 1-, 2- or 3-pentyl and hexylr Ethyl and in particular methyl are preferred. The aliphatic group ;s particularly preferably methyl or methoxy.
The aliphatic bridging group is as alkylene pre-ferably ethylene or in particular methylene, as alkylidene ethylidene, 1,1- or 2,2-propylidene or 1,1- or 2,2-buty-lidene, as cycloalkylidene cyclopentylidene or cyclohexy-lidene and as S;talkyl)2 Sitmethyl)2 or Si(ethyl)2.
The bridging group is preferably methylene, 2,2-propyli-dene or S;(methyl)2.
The aliphatic groups and aliphatic bridging groups are preferably contained in the diamine radical. The co-polyimides can be random polymers or block copolymers.
Radicals of aliphatic diamines contained in the copoly-imides are preferably present in an amount of at most 20 mol %, in particular at most 10 mol %, based on the diam;nes~
Polyimides and copolyimides which are suitable For use in the coating agent of the invention have been des-cribed in the literature, can be obtained by similar methods or are commercially available.
U.S. Patent 3,856,752, for example, describes a group of suitable polyimides~ They essent;ally consist of recurring structural units of the formula I, O O
~\C-/ < ~
O O
in which the four carbonyl groups are bonded to differ-ent carbon atoms and any two carbonyl groups are in ortho-or peri-position relative to each other, Z is a tetravalent radical wh;ch contains at least one aromatic ring and Z' is a divalent organ;c radical selected from among aro--- 4matic, alkylaromatic, aliphatic, cycloaliphatic and hetero cyclic radicals, combinations thereof and radicals having oxy~en-, sulfur-, nitrogen-, silicon- or phosphorus-con-taining brid~in0 groups~ with the proviso that 1) of the total number of recurring polyimide units A) in 0 to 100 mol % of such units Z is a phenyl~
indane radical of the structural formula ,~./ ~,/
RV \R2 in which R1 is hydrogen or an alkyl radical having 1 to ~ carbon atoms and R2 is an alkyl radical havins 1 to 5 carbon atoms, and P) in 0 to 100 mol % of such units Z' is a phenyl-indane rad;cal of the structural formula R
4 (III) in which R1 is hydrogen or an alkyl radical having 1 to 5 carbon atoms, R2 is an aLkyl rad;cal having 1 to 5 carbon atoms, and R3, R4, R5 and R6 ;ndependently of one another are hydrogen, halogen, alkoxy or an alkyl radical having 1 to 4 carbon atoms and
_-13~88/7F~/~
A radiat _ -sensitive coating agent and its use The present invent;on relates to a radiation~sen-sitive coating agent which consists of a polyim;de d;ssol-ved ;n an organic solvent and an organic polya~ide~ to a photographic recording material, and to the use of the coating agent for apply;ng insuL3ting or protective coat-ings, in particular in the manufacture of printed circuits, discrete semiconductor components and ;ntegrated circuits~
Polyimides have good thermal stability, and they are therefore also used ;n electronics and semiconductor tech-nology as insulating or protect;ve films or for the photo-~raphic preparation of relief images. Since polyimides are generally insoluble in organic solvents, it is neces-sary to proceed froM soluble precursors which carry radia-tion-sensitive groups or are mixed w;th rad;at;on-sensitive compounds. The polyimide is formed here only after imag-;ng, namely by thermal cyclisat;on, ;n the course of wh;ch a cons;derable amount of volatile substances 1s removed~
On heating the relief structures generated ;n the imaging suffer a considerable loss ;n thickness and a marked con-traction ;n the vert;cal d;mens;ons. This is thought of as particularly unfavourable~ because it has proved remar-kably diff;cult to generate full-scale images of a given mask~ Also, the technically compl;cated preparation of the precursors ;s uneconom;calr In addition, the various additives prevent the poly;mides thus prepared from exhi-bit;ng the good electr;cal, mechan;cal and thermal proper-ties character;stic of these polymers. German Offenlegungs-~ 2~7~
schrift 2,308,830 and German Offenlegungsschrift 2,91~,619,for example, describe such precursors.
Direct crossl;nking by high~energy radiation and hence the possibility of photostructuring polyimides di-rectly is extremely desirable to prevent the d;sadvantages mentioned. It is an object of the present invention io provide a coating agent with wh;ch polyim;des can be di-rectly radiation-crosslinked.
~ e have now found that poLyimides can be directly radiation-crosslinked with chromophoric aromatic polyazides if the polyimides contain aliphatic grvups.
The present invention relates to a radiation-sen-sitive coatin0 agent which, in addition to customary addi-t;ves, contains (a) an organic solvent, ~b) a homopoly-imide or copolyimide which is soluble in this solvent and is formed from aromatic tetracarboxylic acids and aromatic d;amines or aromatic and aliphatic d;amines, where at least one aliphatic group is bonded directly or via a bridging group to at least some of the tetracarboxylic acid radicals, of the aromatic diamine radicals, or the two radicals and/or at least some of these radicals contain as an aliphatic bridging group alkylene, alkylidene, cycloalkylidene or Si(alkyl)2, and (c) at least 0.1% by weight, based on component (b), of at least one organic chromophoric polyazide in which the azide groups are bonded to aromatic hydrocarbon radicals~
The radicals with aliphatic groups and/or bridging groups preferably contain at least S mol %, in particular at least ~0 mol % and especially at least 30 mol % in the polyimide or copolyimide, based on the polyimide. The aliphat;c groups are preferably bonded to aromatic radicals, and the bridging groups link aromatic radicals, in parti-cular 2 phenyl groups.
The al;phat;c group preferably has the formula alkyl-Q- where there are 1-6, in particular 1-3~ C atoms in the alkyl group and where Q is a direct bond, -0-, -S-, -S0-, -S02-, -C0-, -NH-, -N-alkyl having 1-~, preferably 1-3, C atoms, or -NHC0-. Examples of alkyl are methyl, ethyl, propyl9 isopropyl, 1-butyl, 2-butyl, tertiary-butyl, 1-, 2- or 3-pentyl and hexylr Ethyl and in particular methyl are preferred. The aliphatic group ;s particularly preferably methyl or methoxy.
The aliphatic bridging group is as alkylene pre-ferably ethylene or in particular methylene, as alkylidene ethylidene, 1,1- or 2,2-propylidene or 1,1- or 2,2-buty-lidene, as cycloalkylidene cyclopentylidene or cyclohexy-lidene and as S;talkyl)2 Sitmethyl)2 or Si(ethyl)2.
The bridging group is preferably methylene, 2,2-propyli-dene or S;(methyl)2.
The aliphatic groups and aliphatic bridging groups are preferably contained in the diamine radical. The co-polyimides can be random polymers or block copolymers.
Radicals of aliphatic diamines contained in the copoly-imides are preferably present in an amount of at most 20 mol %, in particular at most 10 mol %, based on the diam;nes~
Polyimides and copolyimides which are suitable For use in the coating agent of the invention have been des-cribed in the literature, can be obtained by similar methods or are commercially available.
U.S. Patent 3,856,752, for example, describes a group of suitable polyimides~ They essent;ally consist of recurring structural units of the formula I, O O
~\C-/ < ~
O O
in which the four carbonyl groups are bonded to differ-ent carbon atoms and any two carbonyl groups are in ortho-or peri-position relative to each other, Z is a tetravalent radical wh;ch contains at least one aromatic ring and Z' is a divalent organ;c radical selected from among aro--- 4matic, alkylaromatic, aliphatic, cycloaliphatic and hetero cyclic radicals, combinations thereof and radicals having oxy~en-, sulfur-, nitrogen-, silicon- or phosphorus-con-taining brid~in0 groups~ with the proviso that 1) of the total number of recurring polyimide units A) in 0 to 100 mol % of such units Z is a phenyl~
indane radical of the structural formula ,~./ ~,/
RV \R2 in which R1 is hydrogen or an alkyl radical having 1 to ~ carbon atoms and R2 is an alkyl radical havins 1 to 5 carbon atoms, and P) in 0 to 100 mol % of such units Z' is a phenyl-indane rad;cal of the structural formula R
4 (III) in which R1 is hydrogen or an alkyl radical having 1 to 5 carbon atoms, R2 is an aLkyl rad;cal having 1 to 5 carbon atoms, and R3, R4, R5 and R6 ;ndependently of one another are hydrogen, halogen, alkoxy or an alkyl radical having 1 to 4 carbon atoms and
2) of the total number of radicals Z and Z' at least 10 mol ~ based on the individual components, are phenylindane radicals.
R2 in the formulae II and III is preferably methyl. The degree of polymerisation (number of recurring structural units) is preferably at least 20, and can amount to 1,00Q or more. The degree of polymerisation i-; parti-57g cularly preferably 5Q to S00~ in particular 100 to 300.
Alkyl R1 and R2 can be methyl, ethyl, propyl, isopropyl, butyl or pentyl~ ~1 iS par~icularly prefer-ably hydrogen or methyl and R2 methyl~
Halogen P~3, R~, R5 and R6 are preferably chlorine or bromine. Examples of alkoxy radicals R3, R
R5 and R6 are butoxy, propoxy, ethoxy and in particu-lar methoxy, while examples of alkyl radicals R3, R4,R5 and R6 are butyl, tertiary-butyl, propyl, iso-propyl, ethyl and in particular methyl. R3, R4, R5 and R6 are part;cularly preferably hydrogen, methyl or chlorine~
The phenylindanediamine component o~ the soluble polyimide can consist of any cornb;nation of ;someric or subst;tuted ;somer;c d;amino compounds wh;ch are represen-ted by the above formula III. For example~ the phenyl-indanediam;ne component can embrace 0 to 100 mol % of 5-am;no-1-(4'-aminophenyl)-1,3,3-trimethyl;ndane in a com-bination with 100 to 0 mol % of 6-am;no-1-(4'-aminophenyl)-1,3,3-tr;methyl;ndane. Moreover, each or both of these isomers can be substituted via the diamino isomers ~hich are represented by the form~la III. Examples of such sub-stituted diamino isomers are 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1~3,3-trimethylindane, 5-amino-1-(4'-amino-Ar',Ar'-dichLorophenyl3-Ar,Ar-dichloro-1,3,3-tri-methylindane, 6-amino-1-(4'-amino-Ar',Ar'-dichlorophenyl)-Ar,Ar-dichloro-1,3,3-trimethyLindane, 4-amino-6-methyl-1-~3'-amino-4'-methylphenyl)-1,3,3-trimethylindane and Ar-amino 1-(Ar'-amino 2',4'-dimethylphenyl)-1,3,3,4,6-penta-methylindane. hr and Ar' in the above formulae indicate the undefined pos;tion in the phenyl rings of the relevant subst;tuents. ~he amino groups are preferably in the 7-, in particular 5- or 6-, position and in the 3'- and ;n par-t;cular the 4'-pos;t;on.
Examples of the phenylindaned;anhydr;de component hav;ng a rad;cal of the formula II are 1-~(3',4'-d;carboxy-phenyl)-1,3,3-trimethyl;ndane-5,6-d;carboxyl;c dianhydride, 1-(3'~4'-dicarboxyphenyl)-1,3,3-trimethylindane-6,7-d;car-7~
boxylic dianhydride, 1-(3',4'-dicarboxyphenyl) 3-methyl-indane-5,6-d;carboxylic dianhydride and 1-(3',4'-dicarboxy phenyl)-3-methylindane-6,7~dicarboxylic dianhydride.
A non-phenyl;ndane radical Z in the formula I can be selected from among the following groups: aromatic, aliphatic, cycloaliphatic and he~erocyclic groups, and combinations of aromat;c and aliphatic groups~ The groups can also be substituted. The groups Z can be characterised by the following structures:
i1 i 11 1 111 1 11 L ~ ~ ~ ~ O ~ ~
--\-/ \.-/
_>~
\; / ~ 1l 1 12l1 in which R12 is selected from the group consisting of ll ~10 ~~ 110 -O-, -S-, -S02-, -C - N -, -C-, -C-O-, -N-, -Si-, Rlo R
-O-Si-O-, -P-, -O-P-O-, -N=N-, -N=N-, Rll O H Rl 10 110 -C N- -CH - -CH CH -, CH-, -C- and phenylene 57~
where R10 and R11 are alkyl having preferably 1 to 6 C atoms or aryl, in particular phenyl.
Examples of sui-table tetracarboxylic anhydrides having a tetravalent radical Z are 2,3,Y,10-perylenetetra-carboxylic dianhydr;de, 1,4,5,~-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3~6,7-tetrachloronaphthaLene-1,4,5,8-tetra-carboxyl;c d;anhydr;de, phenanthrene-1,8,9,1Q-tetracarboxy-l;c dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dian-hydride, pyromellitic dianhydride, 3,3',4,4'-benzophenone-tetracarboxylic dianhydride, 2~2',3,3'-benzophenon~tetra-carboxylic d;anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydr;de, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 4,4l-isopropylidenediphthalic anhydride, 3,3'-isopropyli-denediphthalic anhydride, 4,4'-hydroxydiphthalic anhydride, 4,4'-sulfonyldiphthal;c anhydride, 3,3'-hydroxydiphthalic anhydride, 4,4'-methylenediphthalic anhydride, 4,4'-thio-diphthalic anhydride, 4,4'-ethylidenediphthalic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,2,5,6 naphtha-lenetetracarboxylic dianhydride, benzole-1,2,3,4-tetracar-bo~ylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic di-anhydride, thiophene-2,3,~,5-tetracarboxylic dianhydride and dianhydrides of the general formula Yl O / ~ O
`~r~ -Y2~ `o o C o ~4 in which each of Y1, Y2, Y3 and Y4 is selected from among hydrogen and alkyl, in particular methyl The most preferred non-phenylindane aromatic di-anhydrides are pyromell;tic dianhydride and aromatic dian-hydrides, characterised by the general formula 57~
R ~o\ jR15\~S:-\ Q
O I i1 i i1 ~0 B ~' ~' o in which R15 is methylene, oxygen, sulfonyl or in parti-cular carbonyl.
The group Z' def;ned above can be selected from among alkylene groups having 2 to 12 carbon atoms, cyclo-alkylene groups having 4 to 6 r;ng carbon atoms, a xylylene group~ arylene groups selected from among ortho-, meta-or para phenylene, tolylene~ biphenylene, naphthylene and anthrylene, a subs~ituted arylene group of the formula W
in which W is a covalent bond, sulfur, carbonyl, -NH, -N-alkyl, 0, S, SS, -N-phenyl, sulfonyl, a linear or branched alkylene group hav;ng 1 to 3 carbon atoms, alkylidene having 2 to 12 C atoms, cycloalkylidene having 5 or 6 ring carbon atoms, arylene, in particular the phenylene group, or a dialkylsilyl or diarylsilyl group, and R7 and R8 independently of each other are hydrogen, halogen, in par-ticular chlorine or bromine, alkyl having 1 to 5 carbon atoms, in particular methyl~ alkoxy having 1 to 5 carbon atoms, in particular methoxy, or aryl, in particular phenyl.
The group Z' can also have the formula ~ R10 \ R10 Rl ~ SiO ~ Si-R16_ J
in which R1U and R11 are as defined above and R16 jS
a divalent hydrocarbon radical, for example alkylene having 1 to 12, preferably 1 to 6 C atoms~ cycloalkylene having preferably 5 or 6 ring carbon atoms or phenylene. U.S. Pa-tent 4,030,948 describes diamines which have this group Z'.
It is more preferable for Z' to be groups which are derived from those aromatic diamines described in the imme-diateLy preceding paragraph. Z' is most preferably a group of the formula R7\ ~8 . 0 ~ a-- W ~
in wh;ch W is a covalent bond~ methylene, sulfur, oxygen or sulfone, and R7 and R8 independently of eacn other are hydrogen, halogen~ or alkyl having 1 to 5 carbon atoms, in particular methyl3 or a group of the formula / ~ /
Rg .~
in which R9 is hydrogen~ halo~en, or alkyl having 1 to 5 carbon atoms, ;n particular methyl.
Z' ;s particularly preferably meta- or para-pheny-lene or a radical of the formula ~-\ /r~ W ~~
=-- . =.
in which ~J is a covalent bond, methylene, alkylidene~ 2~2-propylidene, cyclohexylidene, sulfur, oxygen or sulfone~
Examples of diamines having a divalent radical Z' are 4,4'-methylenebis-(o-chloroaniline3, 3,3'-dichloroben-zidine~ 3,3'-sulfonyldianiline, 4,4'-diaminobenzophenone, 1,5-diaminonaphthalene, bis-(4-aminophenyl)-dimethylsilane~
bis-(4-aminophenyl)-diethylsilane, bis-(4-aminophenyl)-diphenylsilane, bis (4-aminophenyloxy)-dimethylsilane, bis-~4-aminophenyl)-ethylphosphine oxide, N-Cbis-~4-amino-phenyl)]-N-methylamine, N-Cbis-(4-aminophenyl)~-N-phenyl-amine, 4~4'-methylenebis-(3-methylaniline), 4,4'-methylene-bis-(2-ethylan;l1ne), 4,4'-methylenebis-(2-methoxyaniline), 5,5'-methylenebis-(2-aminophenol), 4,4'-methylenebis-(Z-methylaniline), 4,4'-hydroxybis-(2~methoxyanil;ne), 4,4'-hydroxybis-(2-chloroaniline), 5,5'-hydroxyb;s-~2~am;no-phenol), ~t,~'~thiobis-(2-methylaniline), 4~4'-thiobis-(2-methoxyaniline), 4,4'-thiobis-(2-chloroaniline), 4,4'-sul-fonylbis-(2-methylaniline), 4,4'-sulfonylb;s-(2-ethoxy~
aniline), 4,4'-sulfonylbis-(2-chloroaniline), 5~5'-sul-fonylbis-(2-aminophenol~, 3,3'-dimethyl-4,4'-diaminobenzo-phenone, 3,3'-dimethoxy-4~4'-d;aminobenzophenone, 3,3'-dichloro-4,4'-diamino~enzophenone, 4,4'-d;aminobiphenyl, m-phenylened;amine, p-phenylenediam;ne, 4,4' methylene-d;an;line, 4,4'-hydroxydianiline, 4,4'-thiodian;line, 4,4'-sulfonyld;aniline, 4,4'-isopropylidened;anil;ne, 3,3'-dimethylbenzid;ne, 3,3'-d;methoxybenzidine, 3,3'-dicarboxy-benzidine and diaminotoluene.
A preferred sub-group of soluble polyimides in-cludes those in which 0 to 100 mol % of the radicals Z have the formula t il~ C ~il t or the formula L
wh;le 100 to 0 mol % of the rad;cals Z are a mixture of ~ 3~ CH3 . = ./ and ll ~! i `.=.~
C~13 Cll3 C~ \CI~
and 100 to 1n mol % of the radicals za are a radical of the formula III ;n which R1, R3, ~4, R~ and R6 inde-pendently of one another are hydrogen or methyl and R2 is methyl, while 0 to 90 mol % of the radicals Z' have the formula R
or Rg-*- i ~=0 =~
in which ~l ;s a covalent bond, methylene, ethyl;dene, 2,2-propylidene, cyclohexyl;dene, sulfur, oxygen or sulfone, R7 and R8 independently of each other are hydrogen, halogen, alkoxy or alkyl groups hav;ng 1 to 5 carb~n atoms, and R9 is hydrogen, halogen, alkoxy or an alkyl group 3L2~i7~
having 1 to 5 carbon atoms.
Those polyimides are particularly preferred in which Z' ;s X3~ CH3 or .a mixture thereof and Z is o ., l I or ll /
or a mixture thereof.
Other polyim;des and copolyimides of the formula I
ha~;ng non-phenylindane radicals are also su;table. They can be composed of the abovement;oned, other tetracarboxylic acids and d;amines, at least some of the diamines contain-ing al;phatic groups or bridging groups. The choice of components and of the;r mix;ng rat;os can have a marked influence on the solubility. Various methods have been d;sclosed of obtain;ng soluble polyimides and copolyimides.
Such poly;m;des, wh;ch contain aliphatic groups in the dia-m;ne radicals have been described, for example, in J. of Applied Polymer Sc;ence~ Vo~. 26, 3837-3343 (1981) and in F~W. Harr;s and LnH~ ~arn;er~ Structure-Solubility 2elation-ships in Polymers, ~cadem;c Press, New York, pages 183-198 (1977)~ Homopolyimides and copolyimides preferred for the coat;ng agent of the invent;on are descr;bed in U.S. Patents
R2 in the formulae II and III is preferably methyl. The degree of polymerisation (number of recurring structural units) is preferably at least 20, and can amount to 1,00Q or more. The degree of polymerisation i-; parti-57g cularly preferably 5Q to S00~ in particular 100 to 300.
Alkyl R1 and R2 can be methyl, ethyl, propyl, isopropyl, butyl or pentyl~ ~1 iS par~icularly prefer-ably hydrogen or methyl and R2 methyl~
Halogen P~3, R~, R5 and R6 are preferably chlorine or bromine. Examples of alkoxy radicals R3, R
R5 and R6 are butoxy, propoxy, ethoxy and in particu-lar methoxy, while examples of alkyl radicals R3, R4,R5 and R6 are butyl, tertiary-butyl, propyl, iso-propyl, ethyl and in particular methyl. R3, R4, R5 and R6 are part;cularly preferably hydrogen, methyl or chlorine~
The phenylindanediamine component o~ the soluble polyimide can consist of any cornb;nation of ;someric or subst;tuted ;somer;c d;amino compounds wh;ch are represen-ted by the above formula III. For example~ the phenyl-indanediam;ne component can embrace 0 to 100 mol % of 5-am;no-1-(4'-aminophenyl)-1,3,3-trimethyl;ndane in a com-bination with 100 to 0 mol % of 6-am;no-1-(4'-aminophenyl)-1,3,3-tr;methyl;ndane. Moreover, each or both of these isomers can be substituted via the diamino isomers ~hich are represented by the form~la III. Examples of such sub-stituted diamino isomers are 5-amino-6-methyl-1-(3'-amino-4'-methylphenyl)-1~3,3-trimethylindane, 5-amino-1-(4'-amino-Ar',Ar'-dichLorophenyl3-Ar,Ar-dichloro-1,3,3-tri-methylindane, 6-amino-1-(4'-amino-Ar',Ar'-dichlorophenyl)-Ar,Ar-dichloro-1,3,3-trimethyLindane, 4-amino-6-methyl-1-~3'-amino-4'-methylphenyl)-1,3,3-trimethylindane and Ar-amino 1-(Ar'-amino 2',4'-dimethylphenyl)-1,3,3,4,6-penta-methylindane. hr and Ar' in the above formulae indicate the undefined pos;tion in the phenyl rings of the relevant subst;tuents. ~he amino groups are preferably in the 7-, in particular 5- or 6-, position and in the 3'- and ;n par-t;cular the 4'-pos;t;on.
Examples of the phenylindaned;anhydr;de component hav;ng a rad;cal of the formula II are 1-~(3',4'-d;carboxy-phenyl)-1,3,3-trimethyl;ndane-5,6-d;carboxyl;c dianhydride, 1-(3'~4'-dicarboxyphenyl)-1,3,3-trimethylindane-6,7-d;car-7~
boxylic dianhydride, 1-(3',4'-dicarboxyphenyl) 3-methyl-indane-5,6-d;carboxylic dianhydride and 1-(3',4'-dicarboxy phenyl)-3-methylindane-6,7~dicarboxylic dianhydride.
A non-phenyl;ndane radical Z in the formula I can be selected from among the following groups: aromatic, aliphatic, cycloaliphatic and he~erocyclic groups, and combinations of aromat;c and aliphatic groups~ The groups can also be substituted. The groups Z can be characterised by the following structures:
i1 i 11 1 111 1 11 L ~ ~ ~ ~ O ~ ~
--\-/ \.-/
_>~
\; / ~ 1l 1 12l1 in which R12 is selected from the group consisting of ll ~10 ~~ 110 -O-, -S-, -S02-, -C - N -, -C-, -C-O-, -N-, -Si-, Rlo R
-O-Si-O-, -P-, -O-P-O-, -N=N-, -N=N-, Rll O H Rl 10 110 -C N- -CH - -CH CH -, CH-, -C- and phenylene 57~
where R10 and R11 are alkyl having preferably 1 to 6 C atoms or aryl, in particular phenyl.
Examples of sui-table tetracarboxylic anhydrides having a tetravalent radical Z are 2,3,Y,10-perylenetetra-carboxylic dianhydr;de, 1,4,5,~-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3~6,7-tetrachloronaphthaLene-1,4,5,8-tetra-carboxyl;c d;anhydr;de, phenanthrene-1,8,9,1Q-tetracarboxy-l;c dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dian-hydride, pyromellitic dianhydride, 3,3',4,4'-benzophenone-tetracarboxylic dianhydride, 2~2',3,3'-benzophenon~tetra-carboxylic d;anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydr;de, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 4,4l-isopropylidenediphthalic anhydride, 3,3'-isopropyli-denediphthalic anhydride, 4,4'-hydroxydiphthalic anhydride, 4,4'-sulfonyldiphthal;c anhydride, 3,3'-hydroxydiphthalic anhydride, 4,4'-methylenediphthalic anhydride, 4,4'-thio-diphthalic anhydride, 4,4'-ethylidenediphthalic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,2,5,6 naphtha-lenetetracarboxylic dianhydride, benzole-1,2,3,4-tetracar-bo~ylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic di-anhydride, thiophene-2,3,~,5-tetracarboxylic dianhydride and dianhydrides of the general formula Yl O / ~ O
`~r~ -Y2~ `o o C o ~4 in which each of Y1, Y2, Y3 and Y4 is selected from among hydrogen and alkyl, in particular methyl The most preferred non-phenylindane aromatic di-anhydrides are pyromell;tic dianhydride and aromatic dian-hydrides, characterised by the general formula 57~
R ~o\ jR15\~S:-\ Q
O I i1 i i1 ~0 B ~' ~' o in which R15 is methylene, oxygen, sulfonyl or in parti-cular carbonyl.
The group Z' def;ned above can be selected from among alkylene groups having 2 to 12 carbon atoms, cyclo-alkylene groups having 4 to 6 r;ng carbon atoms, a xylylene group~ arylene groups selected from among ortho-, meta-or para phenylene, tolylene~ biphenylene, naphthylene and anthrylene, a subs~ituted arylene group of the formula W
in which W is a covalent bond, sulfur, carbonyl, -NH, -N-alkyl, 0, S, SS, -N-phenyl, sulfonyl, a linear or branched alkylene group hav;ng 1 to 3 carbon atoms, alkylidene having 2 to 12 C atoms, cycloalkylidene having 5 or 6 ring carbon atoms, arylene, in particular the phenylene group, or a dialkylsilyl or diarylsilyl group, and R7 and R8 independently of each other are hydrogen, halogen, in par-ticular chlorine or bromine, alkyl having 1 to 5 carbon atoms, in particular methyl~ alkoxy having 1 to 5 carbon atoms, in particular methoxy, or aryl, in particular phenyl.
The group Z' can also have the formula ~ R10 \ R10 Rl ~ SiO ~ Si-R16_ J
in which R1U and R11 are as defined above and R16 jS
a divalent hydrocarbon radical, for example alkylene having 1 to 12, preferably 1 to 6 C atoms~ cycloalkylene having preferably 5 or 6 ring carbon atoms or phenylene. U.S. Pa-tent 4,030,948 describes diamines which have this group Z'.
It is more preferable for Z' to be groups which are derived from those aromatic diamines described in the imme-diateLy preceding paragraph. Z' is most preferably a group of the formula R7\ ~8 . 0 ~ a-- W ~
in wh;ch W is a covalent bond~ methylene, sulfur, oxygen or sulfone, and R7 and R8 independently of eacn other are hydrogen, halogen~ or alkyl having 1 to 5 carbon atoms, in particular methyl3 or a group of the formula / ~ /
Rg .~
in which R9 is hydrogen~ halo~en, or alkyl having 1 to 5 carbon atoms, ;n particular methyl.
Z' ;s particularly preferably meta- or para-pheny-lene or a radical of the formula ~-\ /r~ W ~~
=-- . =.
in which ~J is a covalent bond, methylene, alkylidene~ 2~2-propylidene, cyclohexylidene, sulfur, oxygen or sulfone~
Examples of diamines having a divalent radical Z' are 4,4'-methylenebis-(o-chloroaniline3, 3,3'-dichloroben-zidine~ 3,3'-sulfonyldianiline, 4,4'-diaminobenzophenone, 1,5-diaminonaphthalene, bis-(4-aminophenyl)-dimethylsilane~
bis-(4-aminophenyl)-diethylsilane, bis-(4-aminophenyl)-diphenylsilane, bis (4-aminophenyloxy)-dimethylsilane, bis-~4-aminophenyl)-ethylphosphine oxide, N-Cbis-~4-amino-phenyl)]-N-methylamine, N-Cbis-(4-aminophenyl)~-N-phenyl-amine, 4~4'-methylenebis-(3-methylaniline), 4,4'-methylene-bis-(2-ethylan;l1ne), 4,4'-methylenebis-(2-methoxyaniline), 5,5'-methylenebis-(2-aminophenol), 4,4'-methylenebis-(Z-methylaniline), 4,4'-hydroxybis-(2~methoxyanil;ne), 4,4'-hydroxybis-(2-chloroaniline), 5,5'-hydroxyb;s-~2~am;no-phenol), ~t,~'~thiobis-(2-methylaniline), 4~4'-thiobis-(2-methoxyaniline), 4,4'-thiobis-(2-chloroaniline), 4,4'-sul-fonylbis-(2-methylaniline), 4,4'-sulfonylb;s-(2-ethoxy~
aniline), 4,4'-sulfonylbis-(2-chloroaniline), 5~5'-sul-fonylbis-(2-aminophenol~, 3,3'-dimethyl-4,4'-diaminobenzo-phenone, 3,3'-dimethoxy-4~4'-d;aminobenzophenone, 3,3'-dichloro-4,4'-diamino~enzophenone, 4,4'-d;aminobiphenyl, m-phenylened;amine, p-phenylenediam;ne, 4,4' methylene-d;an;line, 4,4'-hydroxydianiline, 4,4'-thiodian;line, 4,4'-sulfonyld;aniline, 4,4'-isopropylidened;anil;ne, 3,3'-dimethylbenzid;ne, 3,3'-d;methoxybenzidine, 3,3'-dicarboxy-benzidine and diaminotoluene.
A preferred sub-group of soluble polyimides in-cludes those in which 0 to 100 mol % of the radicals Z have the formula t il~ C ~il t or the formula L
wh;le 100 to 0 mol % of the rad;cals Z are a mixture of ~ 3~ CH3 . = ./ and ll ~! i `.=.~
C~13 Cll3 C~ \CI~
and 100 to 1n mol % of the radicals za are a radical of the formula III ;n which R1, R3, ~4, R~ and R6 inde-pendently of one another are hydrogen or methyl and R2 is methyl, while 0 to 90 mol % of the radicals Z' have the formula R
or Rg-*- i ~=0 =~
in which ~l ;s a covalent bond, methylene, ethyl;dene, 2,2-propylidene, cyclohexyl;dene, sulfur, oxygen or sulfone, R7 and R8 independently of each other are hydrogen, halogen, alkoxy or alkyl groups hav;ng 1 to 5 carb~n atoms, and R9 is hydrogen, halogen, alkoxy or an alkyl group 3L2~i7~
having 1 to 5 carbon atoms.
Those polyimides are particularly preferred in which Z' ;s X3~ CH3 or .a mixture thereof and Z is o ., l I or ll /
or a mixture thereof.
Other polyim;des and copolyimides of the formula I
ha~;ng non-phenylindane radicals are also su;table. They can be composed of the abovement;oned, other tetracarboxylic acids and d;amines, at least some of the diamines contain-ing al;phatic groups or bridging groups. The choice of components and of the;r mix;ng rat;os can have a marked influence on the solubility. Various methods have been d;sclosed of obtain;ng soluble polyimides and copolyimides.
Such poly;m;des, wh;ch contain aliphatic groups in the dia-m;ne radicals have been described, for example, in J. of Applied Polymer Sc;ence~ Vo~. 26, 3837-3343 (1981) and in F~W. Harr;s and LnH~ ~arn;er~ Structure-Solubility 2elation-ships in Polymers, ~cadem;c Press, New York, pages 183-198 (1977)~ Homopolyimides and copolyimides preferred for the coat;ng agent of the invent;on are descr;bed in U.S. Patents
3,708,458, 3,787,367 and 3,870,677 and in German Auslege-schrift 1,962,588. Of these particularly those are prefer red which consist of radicals of benzophenonetetracarboxy-lic anhydride and/or pyromellitic dianhydr;de and, based on the diamine radicals, of 65-90 mol ~ of radicals of toluenediamine in a mixture with 35 to 10 mol X of $,4'-diam;nod;phenylmethane~ or of radicals of 2,2'- or 3,3'-di-methyl-, d;ethyl-, or dimethoxy-4,4'~d;am;nod;phenylme~hane.
, ~ -,"
~J~57~
Another preferrecl group of homopolyi~ides and co-polyimides comprises those which essent;ally cons;st of recurring structural units of the formula I in ~h;ch the four carbonyl groups are bonded to different carbon atoms and any two carbonyl groups are ;n ortho or peri-position relative to each other, Z is a tetravalent radical which contains at least one aromatic ring and Z' is a divalent organic radical selected from among aromat;c, alkylaromatic al;phatic, cycloaliphatic and heterocyclic radicals, com-binations thereof and radicals having oxygen-, sulfur-, nitrogen-, silicon-, or phosphorus-contain;ng bridging groups, with the proviso that of the total number of recur-ring poly;mide units, based on the tetracarboxylic anhy-dride radicals or diam;ne rad;cals, A) 30-100 mol % of such units Z are benzophenonetetracar-boxylic radicals and B~ 30-100 mol % of such un;ts Z' are radicals of the formulae ~8 ~18 w~
=. . =.
,Rl9 ~ ~W~-a~ ~o_ or . ll in which ~11 ;5 CH2, O, S, S02, CO or H3C-C-CH3, w2 is CH2, S, S02, CO or ~!3C-C-CH3, R18 is alkyl or alkoxy having 1 to 6 C atoms~ halogen, in particular Cl, COzH, OH, S03H or NHCOCH3 and R19 is alkyl having 1 to 6 C atoms, at least 10 mol % of these radicals being those ~hich have CH2, H3C-C-CH3, alkyl, alkoxy or NHCOCH3 groups.
Preferably R18 and R19 are methyl and W1 and ~2 C~l2.
A further suitable group of homopolyimides and co-5~
poly;mides are those wh;ch consist of recurring structural un;ts of the formula I ;n which, based on the tetracar-boxyl;c anhydr;de rad;cals or d;am;ne radicals, A) 75 to 10Q mol ~ of the un;ts Z are a pyromell;tic anhy-dr;de rad;cal and ~) 25 to 0 mol % of the units have the formula A~ r/
;n wh;ch x2 is , 52 or, in par~;cular C0, and C) 10 to 35 mol % of the un;ts Z' have the formula CH2-~
and 9Q to 65 mol ~ of the un;ts Z' have the formulae ~-\ ~ or ~ \-/
or m;xtures thereof.
Likew;se particularly su;table copoly;mides are those wh;ch cons;st of recurr;ng structural units of the formula I ;n wh;ch A) Z is a benzophenonetetracarboxyl;c d;anhydr;de rad;cal and ~) base~ on the d;amine rad;cals, 10-30 mol % of the units Z' have the formula ~ -CH2~ D_ and C) 90-70 mol X of the units Z' have the formulae fH3 l a3 '! ! or ll or m;xtures thereof.
Those polyimides are preferred which have a hi~h thermostability~ Those polyimides are particularly prefer-red which do not decompose at a temperature ~ 350C in air. It is also known that for polymeric mater;als to ~ive good photostructuring they should have a very narrow molecular weight distribution. It has been found to be very advantageous to pretreat the soluble polyimides by means of known separating methods, such as fractional pre-cipitation, to obtain coating agents which have a narrow molecular weight distr;bution. It is also known that the radiation sens;tivity increases with the average molecular weight Mw~ An average molecular weight of 1n,000 to 500,000, preferably 30~000 to 300,000, in particular 30,000 to 200,000, has been found to be favourable.
Suitable organic solvents are polar, in part;cular polar aprotic solvents which can be used alone or in mix-tures of at least two solvents~ Examples of suitable sol-vents are ethers, such as d;butyl ether, tetrahydrofuran, d;oxane, methylethylene ~lycol, d;methylethylene glycol, dimethyldiethylene glycol, diethyldiethylene glycol, and di-methyltriethylene glycol, halogenated hydrocarbons, such as methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, and 1,1,2,2-tetrachloroethane, car-boxylates and lactones, such as ethyl acetate, methyl pro-pionate~ ethyl benzoate, 2-methoxyethyl acetate, ~-butyro-lactone, r~-valerolactene and mevalolactone, carboxamides and lactams, such as formamide, acetamide, ~-methylform-amide, N,N-dimethylformamide, N,N-d;ethylformamide, N,N~
dimethylacetamide, N,N-d;ethylacetam;de, ~-butyrolactam~
-caprolactam, N-methylpyrrolidone, N-acetylpyrrolidone, N~methylcaprolactam, tetramethyl urea and hexamethylphos-phoramide, sulfoxides such as dimethyl sulfoxide, sulfones, such as dimethyl sulfone~ d;ethyl sulfone, tr;methylene sulfone, tetramethylene sulfone, pr;mary, secondary and tertiary amines, such as me~hylamine, ethylam;ne, propyl-amine, pyrrolidine, piper;dine, morpholine, dimethylam;ne, diethylamine, methylethylamine, trimethylamine, triethyl-i7~
amine, N-methyLpyrrolidine~ N-methylpiperidine, and N~
methylmorpholine, and substituted benzenes such as chloro-benzene, n;troben~ene and cresol.
The polyaz;des tb) are known, and have been descr;-bed, ~or example in European Paten~ Appl;cat;on 0,0~5,352.
They can be used alone or in any desired m;xtures.
The aromatic hydrocarbon rad;cals of the chromo-phor;c polyazides (c) can be subs~ituted by 1 or 2 halogen groups, in particular chlor;ne, and alkoxy or alkyl groups having 1 to 5 C atoms. Organic chromophoric diazides, ;n particular those without ;mide groups, are prefera~le.
These can be diazides o~ the formula ~3- D N3 in which D is arylene, such as phenylene, naphthylene, toluylene or perylene.
More preferable ;s a group of organic diazides of the formula N3 - E (Y)~ E N3 in which E is an aromat;c hydrocarbon rad;cal, ;n part;cu-lar phenylene, q ;s O or 1~ and Y ;s an ;nor~anic or orga-n;c group which forms a mesomeric system together ~ith the aromat;c hydrocarbon rad;cals E. Y is preferably 00 CO, S, SO, S02, NR' ;n wh;ch R' ;s hydroyen, alkyl, cycloalkyl O
~ 1 li aryl or aralkyl, -~HC=CH)p-C-(CH=CH)p-, -C-(CH=CH)p- or -~CH=CH)p- with p = 1-3, -CH~N-, -C=CH-~ -Cn=N-N=CH~~ -CX=CH-~ -CH=CX-, CN
-C-CH=Ca~ -CX=CH C~, -CH=N--~ f--N=CH-, , = o O
-CH=N-~ f~~o~ N=CH~ CH=CX) -CX=C-C-C-CH-~CH=CH~- , 3f ~ or N~C~Y
L~CH2 ~; ~
s~
;n wh;ch R" and R"' ;ndependently of each other are alkyl having 1 to 5 C atoms or R" and'R''I together are unsubst;-tuted or alkyl-, hydroxyalkyl-, alkoxy-, tr;alkylsilyl-, hydroxyl-, carboxyl-, alko~ycarbonyl-, amino-, alkylamino-, or dialkylamino-substituted ethylene or ~rimethylene, q is O or 1, X1 is O, S or NH, y1 is independently defined in the same way as Y and free bonds on N and X
form a fused heterocyclic ring together w;th the group E~
r1 ;s preferably a d;rect bond or -CH=CH-.
R' as alkyl preferably contains 1 to 6 C atoms, as cycloalkyl preferably 5 or 6 ring carbon atoms, as aryl preferably 6 to 12 S atoms and as aralkyL preferably 7 to 14 C atoms. Su;table subst;tuents for the ethylene or trimethylene ~roup are preferably alkyl having 1-6 C atoms~
in part;cular methyl or ethyl, hydroxyalkyl having 1 to 6 C atoms, in part;cular hydroxymethyl, alkoxy hav;ng 1 to 6 C atoms, ;n part;cular methoxy or ethoxy, alkoxycarbonyl having 1 to 12, ;n particular 1 to 6, C atoms, such as methoxycarbonyl or ethoxycarbonyl, alkylamino and d;alkyl-am;no hav;ng 1 to 6 C atoms in the alkyl group, su~h as d;-methylam;no, and trialkyls;lyl having 1 to 6 C atoms in the alkyl group, such as trimethyls;lyl.
A preferred sub-group are diaz;des of the formula CH C~H= ~ ~=CH--~CH=CH) ~CH 2 in which the a2ido groups are preferably bonded in the p-pos;tion, q is ~ or 1, and R17 is OH~ COOH, NH2, alkyl, hydroxyalkyl, alkoxycarbonyl, trialkylsilyl, alkylam;no, or d;alkylam;no. The preferred def;n;t;ons for R17 are listed above.
Examples of polyaz;des are diazidobenzene, diazido-naphthalene, d;az;dotoluene, p-d;azidob;phenylene, 4,4'-diazido-2,2-dimethylb;phenylene, 4,4'-b;saz;do diphenyl ether, ,, ~ , ~' ~4' bisazidodipnenyl ketone, 4,4'-bisazidodiphenyl sulfone, 3,3'-bisazidodiphenyl sulfide, 4,4'-bisazidodiphenylarnine, 1,2-bis-(4 azidophenyl)ethylene, 1-cyano-1~2-bis-~4-azido-phenyl)ethylene, 4-azidophenyl-(4-azidophenylvinyl) ketone bis-(4-azidophenylvinyl) ketone, 1,4-bis-(4-azidophenyl)-butadiene and those of the formulae N3-~ -C-CH=CH-CH=CH~ o-N3 , N3-~ _CHaCH-~ -N3, COOH C~OH
N3--~ ~.-CII=CH-~ -CH=CH-~ ~-N3, 3 \ _ ~ \ ~ N3~ N3-~ CH=N-N=CH--~ ~.-N , N3~ CH=N~ -N=CH-'~ N3~
N3~ -CH=N--~ -N=CH-~ -N3, o = ~
N3-~ ~.-CH=i ~=CH--~ ~.-N3, N3-~ -CH=I l=CH_-~ ~--N3~ N3-~ -CH=~ ~=CH-~ -N3, \ /
R
N3--~ ~--CH=CH-CH=~ ~=CH-CH=CH~ -N3 \ /
~%~57~
~ CH=CH-~ -N3 , i il j .-CH=CH-~ N3 3\ ~ 3\.~ E~-CH=CH-~ N
!~ '! / -CH=CH-~, ,4-N3, -l~ '! . \.= / 3 O
I If ~CH-~ -N3~ N3-~ CH=~ i=CH--~ ~--N3 ./ \O \ /
OH
o .-- o ~ ~ _ ~
N3~ CH=~ ~=CH~ --N3 , ~=~o ~ ~=~
= \ /
o N3-~ CH=~ I=C~ .-N3, ,=.~ . .=.
~i(CH3)3 N3~ .-CH=CH-CH=I i=CH-CH=CH--~ ~.-N3, OH
N3-\ ~-CH=CH-CH=~ I=CH_CH=CH~ 3, ~CH3 N3-v~ ~-CH=CH-CH=~ I=CH-CH=CH-~ -N3, o N ~ .-CH=I/ \~=CH~ N3 COOH
N3-.~ ~-CH=i l=CH_~-N3, and . ~(CH3)3 N3~ .-CH=CH-CH=i i=CH-CH=CH-~ ~--N3.
57~
The coating agents of the invention are prepared by dissolv;ng the components in organic solvents. This ;s conveniently done by first completely dissolving the polyimide with heating and then admixing the bisazide, if appropriate with sl;ght heat;ng. Undissolved portions can be removed by filtration, preferably pressure filtration.
The quantitat;ve composition of the coat;ng agent of the invention essentially depends on the desired applica-tion. It can amount to 80 to 99.9, preferably &5 to 99.9 and ;n particular 50 to 97, % by we;ght of poly;m;de ~b) and 20 to 0.1~ preferably 15 to ~.1 and in particular 10 to 3, ~ by weight of b;sazide ~c), preferabLy not more than 50% by weight, in particular not more than 3û% by weight, and especially not more than 20% by weight, of polyimide (b) and b;sazide (c) being d;ssolved in the solvent (a), based on the solution.
The photostructuring or photocrossl;nk;ng can be effected ~I;th h;gh-energy radiation, for example, by l;ght with;n the 600-~00 nm reg;on, by X~rays, laser light, elec-tron beams and the Like, in particular by light w;th;n the 450-300 ~m reg;on.
The coating agents can have ;ncorporated customary additives which have no adverse e~fect on the l;ght-sensi-t;vity. Examples of such additives are sensitisers, delustrants, flow-control agents, finely divided fillers, flame-retardants, fluorescent brighteners, antioxidants, photostabilisers, stabil;sers, dyes, pigments and tackifiers.
It is also possible to add compounds which can in-crease the sensit;vity of aromatic polyazides. Preferred compounds of this type are described ;n, for example, Photograph;c Sc;ence and Eng;neering, Vol. 17, Number 4, pages 3gO et seq. (1973). Examples are anthrone, 1,9-benzanthrone, acridine, cyanoacrid;ne, nitropyrene, 1,8 din;tropyrene, Michler's ketone, 5-n;troacenaphthene, 2-n;trofluorenone, 1,2-benzanthraquinone, and 2-chloro-1,8-phthaloylnaphthalene. Such compounds can be used alone or L57~
in a mixture. The compounds added can also be dyes which can reduce the adverse influence which reflected scattered light has on the resolving power (anti-halation agents).
Such compounds have been described~ for example, in U~S.
Patent 4,349,619.
The light-sensitive coating agent of the invention is a viscous liquid which has a long shelflife but needs to be protected from light and heat. It is particularly su;table for preparing protective and passivating coatings ;n electrical engineering and electronics and for use as a photographic recording material, for example, for prepar-ing photomasks in electron;cs, textile printing and the graph;c trades.
The light-sensitive layer can be applied to su;t-able substrates or carrier materials by means of customary methods, such as dipping, brush;ng, spraying, whirler-coating, cascade-coating or curta;n-coating. Examples of suitable substrates are plastics, metals, metal alloys, semi-metals, semi-conductors, ~lass and ceramic and other inorganic materials, for example, SiOz or Si3N4.
The solvent is then re~oved by heating, if appropriate~
in vacuo. This gives tack-free, dry and even films. The films, which are up to about 15 ~m, preferably up to 5 ~m and especially up to 2 ~m, thick, are then crosslinked by exposure to li~ht and then completely hardened, if appro priate in a heat-treatment. This gives, for example for integ-rated circuits, protective films which have excellent adhe-sion and high thermal, mechanical and chemical stability.
As is known, bisazide photocrosslinking is inhibi-ted by atmospheric oxygen, in particular in thin layers.
This effect can be avoided by means of customary methods, such as the application of a temporary protective layer of, for example, polyvinyl alcohol, by working under an inert gas or by vacuum contact with the photomask.It is also possible to add compounds which suppress the influence of oxygen.
Such compounds are described in U.S. Patent 3,479,185.
The coating agent of the invention ;s also highly ~t~ 7 - 2~ -suitable for preparing a photographic record;ng material for relief images. The present invention also relates to such a recording material comprising a carrier or substrate to which a m;xture of polyim;de ~b) and of bisa~ide (c) has been applied as light-sensitive layer. The light-sen-sitive layer can be up to 15 ,um, in par-ticular up to 5 ~m and especially up to 2 ym thick.
In the photographic recording material, the light-sensitive layer can be used as, for example, an etch resist in the manufacture of printed circuits, printing plates or integrated circuits, a relay in the preparation of X-ray masks, a soldering resist, a dielectric material for multi-layer circuits or a structural element for liquid crystal displays.
The relief structure is photographically generated by imagewise exposure through a photomask followed by deve-loping to remove the unexposed parts with a solvent or a solvent m;xture, whereupon, if desired, the image generated can be stabilised by a thermal aftertreatment.
The coating agent of the invention has various fur-ther advantages. Subsequent imide formation as in the existing light-sensitive compositions is avoided. The good film-forming properties g;ve even coatings which on exposure and thermal aftertreatment suffer virtually no loss in thickness. The solutions also have a long shelf-l;fe, and the ;mages generated adhere very firmly to the substrates~
The examples which follow illustrate the invention in more detail.
) Pre aration of polyimides P .
The polyimides are prepared in a manner described in U.S~ Patent 3,~56,75Z, namely by reacting the corresponding dianhydrides and diamines in N-methyl-pyrrolidone (N~1P) and then imidating the resulting poly-amidic acids with acetic anhydride.
The corresponding higher molecular weight polymers ~L2~7~
- ~3 -are then obtained by dissolving the resul~ing polymers in a solvent (NMP, 4-butyrolactone, di~ethyl~ormam;de or CHCl3) and subject;ng the solution to fractionaI precipitation with a non-solvent (toluene, xylene or ethanol~. Such or similar methods of separating polymers have been descri-bed, for example, ;n D. 9raun et al. Praktikum der Makro-molecularen Chem;e, ~Practical Macro~olecular Chenistry), Dr. Alfred Hut;g Verlag, 1971~ pages 95 et seq.
The polymers are characterised by the inherent viscosity ((~inh)~ 5X solutions in ~IMP at 25C).
The average molecular weights (Mw) are also de-termined, depend;ng on the solubil;ty in THF either by gelpermeation chromatography and/or by means of a lighe scattering measurement~
The gelpermeation chromatograms are recorded w;th an ;nstrument supplied by Waters GmbH using a set of columns consisting of 2 x 106A~ 2 x 105A, 2 x 104A, 2 x 103A, and 1 x 500 ~, which are calibrated by means of polystyrene standards of def;ned molecular weights within the range 4û to 107~
For determining ~he average molecular weight by light-scattering a KMX-~;nstrument suppl;ed by Chromat;x is used, 633 nm laser l;ght doing the exciting and forward scat~er;ng being measured between the angles of 6 and 7.
Preparation Example 1-.
20 9 of a polyimide prepared from benzophenone-tetracarboxylic dianhydride ~BTDA) and 5(6)-amino-1-t45-am;nopheny~ 3~3-trimethyl;ndane are d;ssolved tn 1~200 9 of 4-tu~yrolactone, the solution is filtered, and toluene is slowly added at 25C to the f;ltrate.
In the toluene to 4-butyrolactone range between 2~3:1 and 801, 7 fractions for the different molecular ~eights are isolated, of which 6 are not only highly soluble but also have good filterabil;ty.
1 , .
. .
5~
Table 1 Result of a fractional precipitation ._ _ _ _ Polyim;de Amount Mw Ratio of precip;ta-(g) ~inh ting agent to solvent ~ , Starting material 20 5~,000 0.68 2.324 Fraction 1 1.60 372,000 1.29 2.474 Fraction 2 2.41 1~4,000 0.90 2.658 Fraction 3 2.48 110.400 0.72 ~.874 Fraction 4 2.4~ 72r600 0.5~ 3.124 Fraction 5 2.25 57,400 0.50 3.445 Fraction ~ 5.13 41,70~ 0.41 4.445 Fraction 7 2.69 27r800 0.3~ _ _ 7.345 Solvent: 4-butyrolactone Precipitating agent: toluene Preparation Example 2:
20 9 of a polymer prepared from benzophenonetetra-carboxylic dianhydride and a mixture of 80 mol per cent of 5(6)-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane and 20 mol per cent of toluenediamine (TDR) are dissolved in 1,100 9 of 4-butyrolactone, and toluene is slowly added at 25C. In the toluene to 4-butyrolactone range between 1.2:1 and 4.0:1, the 5 fractions isolated differ in mole-cular weight, are h;ghly soLuble and have good filter-ability.
Pre arat;on ExamDle 3:
P . _ .
20 9 of a polymer prepared from benzophenonetetra-carboxylic dianhydride (BTDA), ~0 mol per cent of toluene-d;amine and 20 mol per cent of 4,4'-d;aminodiphenylmethane and having ('~inh ~ 0.56, Mw = 35,000) are dissolved in 2,500 g of 4-butyrolactone, the solution is filtered, and toluene is slowly added to the filtrate. In the toluene to 4-butyrolactone range between C.33:1 and 1.3:1, the 3 fractions ;solated have the following properties:
Fraction 1 (4~53 9): soluble in NMP, insoluble in 4~butyro-lactone, not filterable 7~
Fraction 2 (3n979)o rapidly soluble in NMP, slowly soluble in 4-butyrolactone, readily filterable (Mw = 77~000) Fract;on 3 (10.10 g3:readily soluble in NMP and 4-butyro-lactone, readily f-ilterable Use Examples A) Preparat;on_of coating agents and coated substrates In these examples, each additive concentration is based on the mass of the dissolved polymer~ If the con-centrat;on of a solut;on is stated, it has been calculated only from the quantities of polymer and of solvent.
, ~ -,"
~J~57~
Another preferrecl group of homopolyi~ides and co-polyimides comprises those which essent;ally cons;st of recurring structural units of the formula I in ~h;ch the four carbonyl groups are bonded to different carbon atoms and any two carbonyl groups are ;n ortho or peri-position relative to each other, Z is a tetravalent radical which contains at least one aromatic ring and Z' is a divalent organic radical selected from among aromat;c, alkylaromatic al;phatic, cycloaliphatic and heterocyclic radicals, com-binations thereof and radicals having oxygen-, sulfur-, nitrogen-, silicon-, or phosphorus-contain;ng bridging groups, with the proviso that of the total number of recur-ring poly;mide units, based on the tetracarboxylic anhy-dride radicals or diam;ne rad;cals, A) 30-100 mol % of such units Z are benzophenonetetracar-boxylic radicals and B~ 30-100 mol % of such un;ts Z' are radicals of the formulae ~8 ~18 w~
=. . =.
,Rl9 ~ ~W~-a~ ~o_ or . ll in which ~11 ;5 CH2, O, S, S02, CO or H3C-C-CH3, w2 is CH2, S, S02, CO or ~!3C-C-CH3, R18 is alkyl or alkoxy having 1 to 6 C atoms~ halogen, in particular Cl, COzH, OH, S03H or NHCOCH3 and R19 is alkyl having 1 to 6 C atoms, at least 10 mol % of these radicals being those ~hich have CH2, H3C-C-CH3, alkyl, alkoxy or NHCOCH3 groups.
Preferably R18 and R19 are methyl and W1 and ~2 C~l2.
A further suitable group of homopolyimides and co-5~
poly;mides are those wh;ch consist of recurring structural un;ts of the formula I ;n which, based on the tetracar-boxyl;c anhydr;de rad;cals or d;am;ne radicals, A) 75 to 10Q mol ~ of the un;ts Z are a pyromell;tic anhy-dr;de rad;cal and ~) 25 to 0 mol % of the units have the formula A~ r/
;n wh;ch x2 is , 52 or, in par~;cular C0, and C) 10 to 35 mol % of the un;ts Z' have the formula CH2-~
and 9Q to 65 mol ~ of the un;ts Z' have the formulae ~-\ ~ or ~ \-/
or m;xtures thereof.
Likew;se particularly su;table copoly;mides are those wh;ch cons;st of recurr;ng structural units of the formula I ;n wh;ch A) Z is a benzophenonetetracarboxyl;c d;anhydr;de rad;cal and ~) base~ on the d;amine rad;cals, 10-30 mol % of the units Z' have the formula ~ -CH2~ D_ and C) 90-70 mol X of the units Z' have the formulae fH3 l a3 '! ! or ll or m;xtures thereof.
Those polyimides are preferred which have a hi~h thermostability~ Those polyimides are particularly prefer-red which do not decompose at a temperature ~ 350C in air. It is also known that for polymeric mater;als to ~ive good photostructuring they should have a very narrow molecular weight distribution. It has been found to be very advantageous to pretreat the soluble polyimides by means of known separating methods, such as fractional pre-cipitation, to obtain coating agents which have a narrow molecular weight distr;bution. It is also known that the radiation sens;tivity increases with the average molecular weight Mw~ An average molecular weight of 1n,000 to 500,000, preferably 30~000 to 300,000, in particular 30,000 to 200,000, has been found to be favourable.
Suitable organic solvents are polar, in part;cular polar aprotic solvents which can be used alone or in mix-tures of at least two solvents~ Examples of suitable sol-vents are ethers, such as d;butyl ether, tetrahydrofuran, d;oxane, methylethylene ~lycol, d;methylethylene glycol, dimethyldiethylene glycol, diethyldiethylene glycol, and di-methyltriethylene glycol, halogenated hydrocarbons, such as methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, and 1,1,2,2-tetrachloroethane, car-boxylates and lactones, such as ethyl acetate, methyl pro-pionate~ ethyl benzoate, 2-methoxyethyl acetate, ~-butyro-lactone, r~-valerolactene and mevalolactone, carboxamides and lactams, such as formamide, acetamide, ~-methylform-amide, N,N-dimethylformamide, N,N-d;ethylformamide, N,N~
dimethylacetamide, N,N-d;ethylacetam;de, ~-butyrolactam~
-caprolactam, N-methylpyrrolidone, N-acetylpyrrolidone, N~methylcaprolactam, tetramethyl urea and hexamethylphos-phoramide, sulfoxides such as dimethyl sulfoxide, sulfones, such as dimethyl sulfone~ d;ethyl sulfone, tr;methylene sulfone, tetramethylene sulfone, pr;mary, secondary and tertiary amines, such as me~hylamine, ethylam;ne, propyl-amine, pyrrolidine, piper;dine, morpholine, dimethylam;ne, diethylamine, methylethylamine, trimethylamine, triethyl-i7~
amine, N-methyLpyrrolidine~ N-methylpiperidine, and N~
methylmorpholine, and substituted benzenes such as chloro-benzene, n;troben~ene and cresol.
The polyaz;des tb) are known, and have been descr;-bed, ~or example in European Paten~ Appl;cat;on 0,0~5,352.
They can be used alone or in any desired m;xtures.
The aromatic hydrocarbon rad;cals of the chromo-phor;c polyazides (c) can be subs~ituted by 1 or 2 halogen groups, in particular chlor;ne, and alkoxy or alkyl groups having 1 to 5 C atoms. Organic chromophoric diazides, ;n particular those without ;mide groups, are prefera~le.
These can be diazides o~ the formula ~3- D N3 in which D is arylene, such as phenylene, naphthylene, toluylene or perylene.
More preferable ;s a group of organic diazides of the formula N3 - E (Y)~ E N3 in which E is an aromat;c hydrocarbon rad;cal, ;n part;cu-lar phenylene, q ;s O or 1~ and Y ;s an ;nor~anic or orga-n;c group which forms a mesomeric system together ~ith the aromat;c hydrocarbon rad;cals E. Y is preferably 00 CO, S, SO, S02, NR' ;n wh;ch R' ;s hydroyen, alkyl, cycloalkyl O
~ 1 li aryl or aralkyl, -~HC=CH)p-C-(CH=CH)p-, -C-(CH=CH)p- or -~CH=CH)p- with p = 1-3, -CH~N-, -C=CH-~ -Cn=N-N=CH~~ -CX=CH-~ -CH=CX-, CN
-C-CH=Ca~ -CX=CH C~, -CH=N--~ f--N=CH-, , = o O
-CH=N-~ f~~o~ N=CH~ CH=CX) -CX=C-C-C-CH-~CH=CH~- , 3f ~ or N~C~Y
L~CH2 ~; ~
s~
;n wh;ch R" and R"' ;ndependently of each other are alkyl having 1 to 5 C atoms or R" and'R''I together are unsubst;-tuted or alkyl-, hydroxyalkyl-, alkoxy-, tr;alkylsilyl-, hydroxyl-, carboxyl-, alko~ycarbonyl-, amino-, alkylamino-, or dialkylamino-substituted ethylene or ~rimethylene, q is O or 1, X1 is O, S or NH, y1 is independently defined in the same way as Y and free bonds on N and X
form a fused heterocyclic ring together w;th the group E~
r1 ;s preferably a d;rect bond or -CH=CH-.
R' as alkyl preferably contains 1 to 6 C atoms, as cycloalkyl preferably 5 or 6 ring carbon atoms, as aryl preferably 6 to 12 S atoms and as aralkyL preferably 7 to 14 C atoms. Su;table subst;tuents for the ethylene or trimethylene ~roup are preferably alkyl having 1-6 C atoms~
in part;cular methyl or ethyl, hydroxyalkyl having 1 to 6 C atoms, in part;cular hydroxymethyl, alkoxy hav;ng 1 to 6 C atoms, ;n part;cular methoxy or ethoxy, alkoxycarbonyl having 1 to 12, ;n particular 1 to 6, C atoms, such as methoxycarbonyl or ethoxycarbonyl, alkylamino and d;alkyl-am;no hav;ng 1 to 6 C atoms in the alkyl group, su~h as d;-methylam;no, and trialkyls;lyl having 1 to 6 C atoms in the alkyl group, such as trimethyls;lyl.
A preferred sub-group are diaz;des of the formula CH C~H= ~ ~=CH--~CH=CH) ~CH 2 in which the a2ido groups are preferably bonded in the p-pos;tion, q is ~ or 1, and R17 is OH~ COOH, NH2, alkyl, hydroxyalkyl, alkoxycarbonyl, trialkylsilyl, alkylam;no, or d;alkylam;no. The preferred def;n;t;ons for R17 are listed above.
Examples of polyaz;des are diazidobenzene, diazido-naphthalene, d;az;dotoluene, p-d;azidob;phenylene, 4,4'-diazido-2,2-dimethylb;phenylene, 4,4'-b;saz;do diphenyl ether, ,, ~ , ~' ~4' bisazidodipnenyl ketone, 4,4'-bisazidodiphenyl sulfone, 3,3'-bisazidodiphenyl sulfide, 4,4'-bisazidodiphenylarnine, 1,2-bis-(4 azidophenyl)ethylene, 1-cyano-1~2-bis-~4-azido-phenyl)ethylene, 4-azidophenyl-(4-azidophenylvinyl) ketone bis-(4-azidophenylvinyl) ketone, 1,4-bis-(4-azidophenyl)-butadiene and those of the formulae N3-~ -C-CH=CH-CH=CH~ o-N3 , N3-~ _CHaCH-~ -N3, COOH C~OH
N3--~ ~.-CII=CH-~ -CH=CH-~ ~-N3, 3 \ _ ~ \ ~ N3~ N3-~ CH=N-N=CH--~ ~.-N , N3~ CH=N~ -N=CH-'~ N3~
N3~ -CH=N--~ -N=CH-~ -N3, o = ~
N3-~ ~.-CH=i ~=CH--~ ~.-N3, N3-~ -CH=I l=CH_-~ ~--N3~ N3-~ -CH=~ ~=CH-~ -N3, \ /
R
N3--~ ~--CH=CH-CH=~ ~=CH-CH=CH~ -N3 \ /
~%~57~
~ CH=CH-~ -N3 , i il j .-CH=CH-~ N3 3\ ~ 3\.~ E~-CH=CH-~ N
!~ '! / -CH=CH-~, ,4-N3, -l~ '! . \.= / 3 O
I If ~CH-~ -N3~ N3-~ CH=~ i=CH--~ ~--N3 ./ \O \ /
OH
o .-- o ~ ~ _ ~
N3~ CH=~ ~=CH~ --N3 , ~=~o ~ ~=~
= \ /
o N3-~ CH=~ I=C~ .-N3, ,=.~ . .=.
~i(CH3)3 N3~ .-CH=CH-CH=I i=CH-CH=CH--~ ~.-N3, OH
N3-\ ~-CH=CH-CH=~ I=CH_CH=CH~ 3, ~CH3 N3-v~ ~-CH=CH-CH=~ I=CH-CH=CH-~ -N3, o N ~ .-CH=I/ \~=CH~ N3 COOH
N3-.~ ~-CH=i l=CH_~-N3, and . ~(CH3)3 N3~ .-CH=CH-CH=i i=CH-CH=CH-~ ~--N3.
57~
The coating agents of the invention are prepared by dissolv;ng the components in organic solvents. This ;s conveniently done by first completely dissolving the polyimide with heating and then admixing the bisazide, if appropriate with sl;ght heat;ng. Undissolved portions can be removed by filtration, preferably pressure filtration.
The quantitat;ve composition of the coat;ng agent of the invention essentially depends on the desired applica-tion. It can amount to 80 to 99.9, preferably &5 to 99.9 and ;n particular 50 to 97, % by we;ght of poly;m;de ~b) and 20 to 0.1~ preferably 15 to ~.1 and in particular 10 to 3, ~ by weight of b;sazide ~c), preferabLy not more than 50% by weight, in particular not more than 3û% by weight, and especially not more than 20% by weight, of polyimide (b) and b;sazide (c) being d;ssolved in the solvent (a), based on the solution.
The photostructuring or photocrossl;nk;ng can be effected ~I;th h;gh-energy radiation, for example, by l;ght with;n the 600-~00 nm reg;on, by X~rays, laser light, elec-tron beams and the Like, in particular by light w;th;n the 450-300 ~m reg;on.
The coating agents can have ;ncorporated customary additives which have no adverse e~fect on the l;ght-sensi-t;vity. Examples of such additives are sensitisers, delustrants, flow-control agents, finely divided fillers, flame-retardants, fluorescent brighteners, antioxidants, photostabilisers, stabil;sers, dyes, pigments and tackifiers.
It is also possible to add compounds which can in-crease the sensit;vity of aromatic polyazides. Preferred compounds of this type are described ;n, for example, Photograph;c Sc;ence and Eng;neering, Vol. 17, Number 4, pages 3gO et seq. (1973). Examples are anthrone, 1,9-benzanthrone, acridine, cyanoacrid;ne, nitropyrene, 1,8 din;tropyrene, Michler's ketone, 5-n;troacenaphthene, 2-n;trofluorenone, 1,2-benzanthraquinone, and 2-chloro-1,8-phthaloylnaphthalene. Such compounds can be used alone or L57~
in a mixture. The compounds added can also be dyes which can reduce the adverse influence which reflected scattered light has on the resolving power (anti-halation agents).
Such compounds have been described~ for example, in U~S.
Patent 4,349,619.
The light-sensitive coating agent of the invention is a viscous liquid which has a long shelflife but needs to be protected from light and heat. It is particularly su;table for preparing protective and passivating coatings ;n electrical engineering and electronics and for use as a photographic recording material, for example, for prepar-ing photomasks in electron;cs, textile printing and the graph;c trades.
The light-sensitive layer can be applied to su;t-able substrates or carrier materials by means of customary methods, such as dipping, brush;ng, spraying, whirler-coating, cascade-coating or curta;n-coating. Examples of suitable substrates are plastics, metals, metal alloys, semi-metals, semi-conductors, ~lass and ceramic and other inorganic materials, for example, SiOz or Si3N4.
The solvent is then re~oved by heating, if appropriate~
in vacuo. This gives tack-free, dry and even films. The films, which are up to about 15 ~m, preferably up to 5 ~m and especially up to 2 ~m, thick, are then crosslinked by exposure to li~ht and then completely hardened, if appro priate in a heat-treatment. This gives, for example for integ-rated circuits, protective films which have excellent adhe-sion and high thermal, mechanical and chemical stability.
As is known, bisazide photocrosslinking is inhibi-ted by atmospheric oxygen, in particular in thin layers.
This effect can be avoided by means of customary methods, such as the application of a temporary protective layer of, for example, polyvinyl alcohol, by working under an inert gas or by vacuum contact with the photomask.It is also possible to add compounds which suppress the influence of oxygen.
Such compounds are described in U.S. Patent 3,479,185.
The coating agent of the invention ;s also highly ~t~ 7 - 2~ -suitable for preparing a photographic record;ng material for relief images. The present invention also relates to such a recording material comprising a carrier or substrate to which a m;xture of polyim;de ~b) and of bisa~ide (c) has been applied as light-sensitive layer. The light-sen-sitive layer can be up to 15 ,um, in par-ticular up to 5 ~m and especially up to 2 ym thick.
In the photographic recording material, the light-sensitive layer can be used as, for example, an etch resist in the manufacture of printed circuits, printing plates or integrated circuits, a relay in the preparation of X-ray masks, a soldering resist, a dielectric material for multi-layer circuits or a structural element for liquid crystal displays.
The relief structure is photographically generated by imagewise exposure through a photomask followed by deve-loping to remove the unexposed parts with a solvent or a solvent m;xture, whereupon, if desired, the image generated can be stabilised by a thermal aftertreatment.
The coating agent of the invention has various fur-ther advantages. Subsequent imide formation as in the existing light-sensitive compositions is avoided. The good film-forming properties g;ve even coatings which on exposure and thermal aftertreatment suffer virtually no loss in thickness. The solutions also have a long shelf-l;fe, and the ;mages generated adhere very firmly to the substrates~
The examples which follow illustrate the invention in more detail.
) Pre aration of polyimides P .
The polyimides are prepared in a manner described in U.S~ Patent 3,~56,75Z, namely by reacting the corresponding dianhydrides and diamines in N-methyl-pyrrolidone (N~1P) and then imidating the resulting poly-amidic acids with acetic anhydride.
The corresponding higher molecular weight polymers ~L2~7~
- ~3 -are then obtained by dissolving the resul~ing polymers in a solvent (NMP, 4-butyrolactone, di~ethyl~ormam;de or CHCl3) and subject;ng the solution to fractionaI precipitation with a non-solvent (toluene, xylene or ethanol~. Such or similar methods of separating polymers have been descri-bed, for example, ;n D. 9raun et al. Praktikum der Makro-molecularen Chem;e, ~Practical Macro~olecular Chenistry), Dr. Alfred Hut;g Verlag, 1971~ pages 95 et seq.
The polymers are characterised by the inherent viscosity ((~inh)~ 5X solutions in ~IMP at 25C).
The average molecular weights (Mw) are also de-termined, depend;ng on the solubil;ty in THF either by gelpermeation chromatography and/or by means of a lighe scattering measurement~
The gelpermeation chromatograms are recorded w;th an ;nstrument supplied by Waters GmbH using a set of columns consisting of 2 x 106A~ 2 x 105A, 2 x 104A, 2 x 103A, and 1 x 500 ~, which are calibrated by means of polystyrene standards of def;ned molecular weights within the range 4û to 107~
For determining ~he average molecular weight by light-scattering a KMX-~;nstrument suppl;ed by Chromat;x is used, 633 nm laser l;ght doing the exciting and forward scat~er;ng being measured between the angles of 6 and 7.
Preparation Example 1-.
20 9 of a polyimide prepared from benzophenone-tetracarboxylic dianhydride ~BTDA) and 5(6)-amino-1-t45-am;nopheny~ 3~3-trimethyl;ndane are d;ssolved tn 1~200 9 of 4-tu~yrolactone, the solution is filtered, and toluene is slowly added at 25C to the f;ltrate.
In the toluene to 4-butyrolactone range between 2~3:1 and 801, 7 fractions for the different molecular ~eights are isolated, of which 6 are not only highly soluble but also have good filterabil;ty.
1 , .
. .
5~
Table 1 Result of a fractional precipitation ._ _ _ _ Polyim;de Amount Mw Ratio of precip;ta-(g) ~inh ting agent to solvent ~ , Starting material 20 5~,000 0.68 2.324 Fraction 1 1.60 372,000 1.29 2.474 Fraction 2 2.41 1~4,000 0.90 2.658 Fraction 3 2.48 110.400 0.72 ~.874 Fraction 4 2.4~ 72r600 0.5~ 3.124 Fraction 5 2.25 57,400 0.50 3.445 Fraction ~ 5.13 41,70~ 0.41 4.445 Fraction 7 2.69 27r800 0.3~ _ _ 7.345 Solvent: 4-butyrolactone Precipitating agent: toluene Preparation Example 2:
20 9 of a polymer prepared from benzophenonetetra-carboxylic dianhydride and a mixture of 80 mol per cent of 5(6)-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane and 20 mol per cent of toluenediamine (TDR) are dissolved in 1,100 9 of 4-butyrolactone, and toluene is slowly added at 25C. In the toluene to 4-butyrolactone range between 1.2:1 and 4.0:1, the 5 fractions isolated differ in mole-cular weight, are h;ghly soLuble and have good filter-ability.
Pre arat;on ExamDle 3:
P . _ .
20 9 of a polymer prepared from benzophenonetetra-carboxylic dianhydride (BTDA), ~0 mol per cent of toluene-d;amine and 20 mol per cent of 4,4'-d;aminodiphenylmethane and having ('~inh ~ 0.56, Mw = 35,000) are dissolved in 2,500 g of 4-butyrolactone, the solution is filtered, and toluene is slowly added to the filtrate. In the toluene to 4-butyrolactone range between C.33:1 and 1.3:1, the 3 fractions ;solated have the following properties:
Fraction 1 (4~53 9): soluble in NMP, insoluble in 4~butyro-lactone, not filterable 7~
Fraction 2 (3n979)o rapidly soluble in NMP, slowly soluble in 4-butyrolactone, readily filterable (Mw = 77~000) Fract;on 3 (10.10 g3:readily soluble in NMP and 4-butyro-lactone, readily f-ilterable Use Examples A) Preparat;on_of coating agents and coated substrates In these examples, each additive concentration is based on the mass of the dissolved polymer~ If the con-centrat;on of a solut;on is stated, it has been calculated only from the quantities of polymer and of solvent.
4.88 9 of a polymer prepared from benzophenone-tetracarboxylic dianhydride and 5(6)-amino~1-(4'-am;no-phenyl)-1,3,3-trimethylindane and having a molecular weight of 144,000 are admixed with 43.12 9 of 4-butyrolactone and dissolved overnight by shak;ng. At 23C the solution has a v;scosity of 641 mPas. It is admixed with 293 mg (6%) of 2,h-bis(4-azidobenzylidene)-4-methylcyclohexanone and further diluted with 9.41 9 of 4 butyrolactone. The solu-tion is then filtered under 3 bar of pressure through a 0.45 um filter. The solution then has a viscosity of 228 mPas.
Using the solution to whirler-coat SiO2-coated silicon wafers in the course of 20 seconds requires a speed of 1,750 r.pOm. to prepare a 1 ,um thick f;lm.
Example 2:
1.04 g of a polymer prepared from benzophenone-tetracarbo~yl;c d;anhydr;de and 5(6)-am;no-1-(4'-am;no-phenyl)-1,3,3-tr;methyl;ndane and having a molecular weight of 184,000 ;s admixed with 10.52 9 of 4-butyrolactone and dissolved overnight by shaking.
The solution has a viscosity of 351 mPas. 73 mg (7.0%) of ~,6-bis(4-az;dobenzyl;dene)-4-methylcyclohexanone are then dissolved therein, and the solution ;s then fil-tered under 3 bar of pressure through a 0.2 JU~ f;lter. A
1 ,um th;ck f;lm ;s obta;ned on s;licon wafers at a whirler speed of 2,50~ r.p.m.
7~
~ 26 -B) Photostructur;ng on coated substrates The substrates used are 3-;nch s;l;con wafers coated w;th 0.1 ~m of S;02. Each of them ;s wh;rler-coated for 20 seconds at a speed between 1,000 r.p.m. and 6,000 r.p.mO To ensure comparable measurements, the v;s-cos;t;es of the solutions and the speecl of rotation are chosen ;n such a way that ;n each case approximately 1 /um thick f;lms are formed.
The l;ght-sens;t;ve coatings are dr;ed at 40 to 80C for 5 to 3n m;nutes ;n a c;rculat;ng a;r cab;net.
They are subjected to exposure in a mask-adjusting and exposure machine suppl;ed by Karl S'uss under a l;ght output of 30 mw/cm~ as measured with an intensity meter from Optical Associates Inc. The data relate to the 365 nm probe. Use is made of a black chromium mask which contains test patterns of any geometrical shape customary in semi-conductor manufacture, namely sized 1 ~m, 2 ,um, 3 ~m ....
10 ~mr 20 ~m .... 1CO ~m. Although crisp image structures can be generated even in exposure t;mes which are much shorter than those ;nd;cated below, only those t;mes are g;ven here where there ;s an exact 1:1 reproduct;on of all geometr;cal fi~ures equal to or greater than 4 times the film thickness (equality of grooves and r;dges).
Develop;ng takes place in a spray developer under 2 bar of pressure at speeds between 500 and 2,000 r.p.m., and requ;res between 2 and 20 seconds.
A prof;lometer suppl;ed by Tencor (Alpha-Step) is used to measure the f;lm th;ckness.
Example 3.
An ~.5% solution in 4-butyrolactone is prepared of a poly;m;de prepared from benzophenonetetracarboxyl;c d;anhydr;de and 5(6~-amino~ aminophenyl)-1,3,3-tri-methylindane and having an average molecular weight ~w of 144,000. The solution ;s admixed with 6% of 2,b-b;s-(p--azidobenzylidene)-4-methylcyclohexanone (bisaz;de No. 1), and f;ltered, and the filtrate ;s wh;rler-coated onto ~iO2-coated 3-;nch wafers at 1~75D r.p.m. ;n the s~
course of 20 seconds. The wafers are predried at 60C
for 20 minutes in a circulating air cabinet. They are then subjected to vacuum-contact exposure for 65 seconds under an add;tional supply of N2 ~as. Develop;ng takes place according to the following programme:
(Spray-developing under 2 bar at 1,000 r.p~m.):
Methylene chloridettoluene (68:32) 8 seconds Methylene chlor;de/toluene (34:66~ 3 seconds Toluene 10 seconds Any structure of 5 ~m or more ;s cr;sp and repro-duced ;n a rat;o of 1:1 (r;dges and grooves~. The film thickness is 1.02 ~m.
The coated wafers are then placed in an oven, are heated in the course of one hour at 400C in an atmos-phere of n;trogen, are left at 400C for 15 minutes and are then cooled down.
On inspection with a high-resolution microscope there are no visible changes in structure. The renewed measurement of the film thickness gives a value of 0.96 ~m~
The coated wafers are exposed in an ultrasonic bath for 10 minutes to hot N~P at 80C. The structures are found to be inert to this treatment.
Example 4:
The 8.5% poLyimide solution of Example 3 is admixed with 5.77% of 2,6-bis-(p-azidobenzylidene)-cy~lohexanone (b;sazide ~!o. 2), and filtered, and the filtrate is whirler-coated, again at 1~750 r~p.m. in the course of 20 seconds, onto SiO2-coated 3-inch wafers. They are exposed and developed according to the same programme as in Example 3.
Again an exposure time of 65 seconds ;s required to give crisp structures sized 5 ~m or greater.
Example 5:
The 8.5% polymer solution of Example 3 is admixed with 6% of bis-(4-azidophenyl ketone). The ;mage struc-tures are prepared as described in Example 3. Exposure is necessary for 320 seconds to give crisp structures.
57~
- 2~ -Example 6:
A 9% solution in 4-butyrolactone is prepared of a polymer prepared from benzophenonetetracarboxylic di-anhydr;de and 5(6)-amino-1-(4'-aminophenyl)-1,3,3-tri-methylindane and having an average molecular weigh~ of 184,000, 7% of bisazide No. 1 are added to the solut;on, and the mixture is filtered.
An SiOz-coated wafer is wh;rler-coated at S,COO
r.p.m. in the course of 20 seconds, the coatings are dried at ~0C for 1n m;nutes, and the wafer ;s then subjected to vacuum-contact exposure~ Developing takes place as follows:
Methylene chlor;de/toluene 68:32 3 seconds Methylene chlor;de/toluene 34:66 3 seconds Toluene 10 seconds ~ n exposure t;me of only 16 seconds is necessary to produce crisply resolved structures. Even 2 ~m struc-tures are sharply resolved. The film th;ckness is 0.38 ~um and, after heating at 400C in an ~l2 atmosphere, is 0.35 ym.
Example 7:
An ~.7% solution in 4-butyrolactone ;s prepared of a polymer prepared from benzophenonetetracarboxylic d;anhydr;de, ~0 mol per cent of 5(6)-am;no 1-(4'-am;no-phenyl)-1,3,3-tr;methyl;ndane and 20 rnol per cent of d;-aminotoluene and having a rrlolecular weight of 95,000, and 7~ of b;sazide No. 1 are added.
The filtered solution is whirler-coated at 1,&ûO
r.p.m. onto a wafer and exposed for 120 seconds.
Developing takes place accordin~ to the programme:
~lethylene chlor;de/toluene ~0:20 8 seconds Methylene chloride/toluene 40:60 3 seconds Toluene 10 seconds Th;s g;ves cr;sp structures hav;ng a f;lm thickness of 0.97 ,um and a resolution of 4 ,um.
The film th;ckness is a.91 ~m after heat;ng at 400C.
Example 8:
A 9X solution ir, 4-butyrolactone ;s prepared of a polymer prepared from pyromellit;c dianhydr;de ~PMDA) and St6)-am;no-1-(4'~am;nophenyl)-1,3,3-tr;methylindane and hav;ng a molecular we;gh~ of 60,000 and of b;saz;de ~lo. 1, and ;s wh;rler-coated at 1,700 r.p.m~ onto 3-;nch wafers.
Vacuum-contact exposure for 200 seconds ;s followed by the follow;ng developnent programme:
Methylene chlor;de/toluene 65:35 8 seconds ~ethylene chlor;de/~oluene 32:68 3 seconds Toluene 10 seconds There are cr;sp relief structures ;n the central part of the wafer. However, the structures o' the out-lying parts of the wafer ~outer th;rd of the radius) are underexposed.
The relief structures of the central parts have a f;lm th;ckness of 0.92 ~. On heat;ng to 400C the film th;ckness ;s 0.75 ~.
Example 9:
Coated ~afers of the type described ;n Example 8 receive an add;tional, th;n polyvinyl alcohol layer which ;s spun on at 4,COO r~p.m. ;n the form of a solution of the follow;ng compos;t;on:
Polyv;nyl alcohol ~Mow;ol 488, ~oechst) SX
Alkylphenol polyethylene glycol (Tri~on (~) X-100 9 R~hm and Haas) 0.05X
~later 94 95%
The thickness of the polyvinyl alcohol film is 0.1 ~m.
The wafers are subjected to exposure for 22û sec-onds, sprayed w;th ho~ water, dr;ed and developed as ;n E~ample 8~
In contrast to the result ;n Example 8, th;s t;me the wafers are covered over the entire area w;th uniformly e~posed rel;ef structures.
.7~"~
57~
Example 10:
A S.0% solution in ~-butyrolactone ;s prepared of a polymer prepared from benzophenonetetracarboxylic di-anhydride and 5(6)-am;no-1-(43-aminophenyl)-1,3,3-tr;-methyl;ndane and hav;ng an average molecular weight of 1~4,000, is adm;xed with 7% of 2~6-bis-(4-azidobenzyl;dene)-4-methylcyclohexan-1-one and f;ltered through 0~2 ~m. The filtrate is whirler-coated at 2,500 r.p.m. in the course of 20 seconds onto SiO2-coated 3-inch wafers and dr;ed thereon at 60 for 20 minutes in a circulating a;r cabinet.
The wa~ers are subjected to vacuum~contact exposure for 52 seconds through a black chromium mask and then developed accord;ng to the following programme (spray developer, 2 bar pressure, 1,000 r.p.m.):
Methylene chloride/toluene 68:32 10 seconds nethylene chloride/toluene 34:66 3 seconds Toluene 10 seconds The resulting crisp rel;ef structures have a thick-ness of 1.05 ~m and a resolut;on of 5 ~um in which all 0rooves and r;dges are exactly reproduced in a rat;o of 1 :1 .
Heat-treating the wafers in an oven at 400C under nitro0en ~ives no structural changes and the film th;ck-ness is then 1.00 ym.
Example 11:
-A 7% filtered solution ;n 4-butyrolactone is pre-pared of a polymer prepared from benzophenonetetracarboxy-lic dianhydride, 20 mol per cent of 5(6~ amino-1 (4'-amino-phenyl)-1~3,3-trimethylindane and 20 mol per cent of toluenediamine and having a molecular weight of 174,000, and contains 7% of 2,6-bis(4-azidobenzylidene3-4-methyl-cyclohexanone. The solution ;s whirler-coated at 1,250 r.p.m. onto a 3-;nch wafer, dried at ~0C for 20 minutes in a circulat;ng air cabinet and subjected to a 70 second vacuum-contact exposure.
The develop;ng programme ;n a spray developer under 2 bar of pressure at 1,000 r.p.m. ;s as follows:
-~2'~
Methylene chlor;de/toluene 80:20 8 seconds Methylene chloride/toluene 40:60 3 seconds Toluene 10 seconds The crisply reproduced relief structures have a f;lm th;ckness of 0~98 ~m and a resolution of 4 ~m.
Even some of ~he 3 ~m structures are sharply re-solved. On heating to 400C under nitrogen the f;nal f;lm th;ckness ;s O.9Z ~m.
_e 12:
A poly;mide prepared from benzophenonetetracarboxy-lic dianhydride, ~0 mol% of toluenediamine and 20 mol% of 4,4'-diaminodiphenylmethane (Mw = 35,000) is dissolved in 4-butyrolac~one, and the solu~ion is admixed w;th 7% of bisazide No. 1 and filtered. The 10X solution has 3 Vis-cosity of 374 mPas. Whirler-coating at 3r400 r.p.m. and dry;ng for 20 m;nutes ;s followed by a 150 second vacuum-contact exposure. Th;s gives structures which have a film thickness of 0.93 ,um. On heating ~o 4C0C the film thickness is 0.73 ,um.
Example 13:
Polymer fraction 2 of Preparation Example 3 (where Mw = 77,000) is processed together with 7% of bisazide No. 1 into a 10% solution in 4-butyrolactone. The ~afers are coated at 2,200 r.p.m. After drying at 20C it needs an exposure time of only 13 seconds to give cr;sp struc-tures having a film thickness of 0.94 ,um and a resolution of 3 ~m. The images are developed with the following developing programme in a spray developer:
~IMP 14 seconds NMP/toluene 1:1 3 seconds Toluene 10 seconds On heat;ng to 400C the film th;ckness is still 0.80 Jum. A 10 minute treatment with hot NMP at 80C in an ultrason;c bath fails to produce a change in the shape or surface of the structures.
_ample 14:
A 6~0% solut;on ;s prepared of a polyimide prepared
Using the solution to whirler-coat SiO2-coated silicon wafers in the course of 20 seconds requires a speed of 1,750 r.pOm. to prepare a 1 ,um thick f;lm.
Example 2:
1.04 g of a polymer prepared from benzophenone-tetracarbo~yl;c d;anhydr;de and 5(6)-am;no-1-(4'-am;no-phenyl)-1,3,3-tr;methyl;ndane and having a molecular weight of 184,000 ;s admixed with 10.52 9 of 4-butyrolactone and dissolved overnight by shaking.
The solution has a viscosity of 351 mPas. 73 mg (7.0%) of ~,6-bis(4-az;dobenzyl;dene)-4-methylcyclohexanone are then dissolved therein, and the solution ;s then fil-tered under 3 bar of pressure through a 0.2 JU~ f;lter. A
1 ,um th;ck f;lm ;s obta;ned on s;licon wafers at a whirler speed of 2,50~ r.p.m.
7~
~ 26 -B) Photostructur;ng on coated substrates The substrates used are 3-;nch s;l;con wafers coated w;th 0.1 ~m of S;02. Each of them ;s wh;rler-coated for 20 seconds at a speed between 1,000 r.p.m. and 6,000 r.p.mO To ensure comparable measurements, the v;s-cos;t;es of the solutions and the speecl of rotation are chosen ;n such a way that ;n each case approximately 1 /um thick f;lms are formed.
The l;ght-sens;t;ve coatings are dr;ed at 40 to 80C for 5 to 3n m;nutes ;n a c;rculat;ng a;r cab;net.
They are subjected to exposure in a mask-adjusting and exposure machine suppl;ed by Karl S'uss under a l;ght output of 30 mw/cm~ as measured with an intensity meter from Optical Associates Inc. The data relate to the 365 nm probe. Use is made of a black chromium mask which contains test patterns of any geometrical shape customary in semi-conductor manufacture, namely sized 1 ~m, 2 ,um, 3 ~m ....
10 ~mr 20 ~m .... 1CO ~m. Although crisp image structures can be generated even in exposure t;mes which are much shorter than those ;nd;cated below, only those t;mes are g;ven here where there ;s an exact 1:1 reproduct;on of all geometr;cal fi~ures equal to or greater than 4 times the film thickness (equality of grooves and r;dges).
Develop;ng takes place in a spray developer under 2 bar of pressure at speeds between 500 and 2,000 r.p.m., and requ;res between 2 and 20 seconds.
A prof;lometer suppl;ed by Tencor (Alpha-Step) is used to measure the f;lm th;ckness.
Example 3.
An ~.5% solution in 4-butyrolactone is prepared of a poly;m;de prepared from benzophenonetetracarboxyl;c d;anhydr;de and 5(6~-amino~ aminophenyl)-1,3,3-tri-methylindane and having an average molecular weight ~w of 144,000. The solution ;s admixed with 6% of 2,b-b;s-(p--azidobenzylidene)-4-methylcyclohexanone (bisaz;de No. 1), and f;ltered, and the filtrate ;s wh;rler-coated onto ~iO2-coated 3-;nch wafers at 1~75D r.p.m. ;n the s~
course of 20 seconds. The wafers are predried at 60C
for 20 minutes in a circulating air cabinet. They are then subjected to vacuum-contact exposure for 65 seconds under an add;tional supply of N2 ~as. Develop;ng takes place according to the following programme:
(Spray-developing under 2 bar at 1,000 r.p~m.):
Methylene chloridettoluene (68:32) 8 seconds Methylene chlor;de/toluene (34:66~ 3 seconds Toluene 10 seconds Any structure of 5 ~m or more ;s cr;sp and repro-duced ;n a rat;o of 1:1 (r;dges and grooves~. The film thickness is 1.02 ~m.
The coated wafers are then placed in an oven, are heated in the course of one hour at 400C in an atmos-phere of n;trogen, are left at 400C for 15 minutes and are then cooled down.
On inspection with a high-resolution microscope there are no visible changes in structure. The renewed measurement of the film thickness gives a value of 0.96 ~m~
The coated wafers are exposed in an ultrasonic bath for 10 minutes to hot N~P at 80C. The structures are found to be inert to this treatment.
Example 4:
The 8.5% poLyimide solution of Example 3 is admixed with 5.77% of 2,6-bis-(p-azidobenzylidene)-cy~lohexanone (b;sazide ~!o. 2), and filtered, and the filtrate is whirler-coated, again at 1~750 r~p.m. in the course of 20 seconds, onto SiO2-coated 3-inch wafers. They are exposed and developed according to the same programme as in Example 3.
Again an exposure time of 65 seconds ;s required to give crisp structures sized 5 ~m or greater.
Example 5:
The 8.5% polymer solution of Example 3 is admixed with 6% of bis-(4-azidophenyl ketone). The ;mage struc-tures are prepared as described in Example 3. Exposure is necessary for 320 seconds to give crisp structures.
57~
- 2~ -Example 6:
A 9% solution in 4-butyrolactone is prepared of a polymer prepared from benzophenonetetracarboxylic di-anhydr;de and 5(6)-amino-1-(4'-aminophenyl)-1,3,3-tri-methylindane and having an average molecular weigh~ of 184,000, 7% of bisazide No. 1 are added to the solut;on, and the mixture is filtered.
An SiOz-coated wafer is wh;rler-coated at S,COO
r.p.m. in the course of 20 seconds, the coatings are dried at ~0C for 1n m;nutes, and the wafer ;s then subjected to vacuum-contact exposure~ Developing takes place as follows:
Methylene chlor;de/toluene 68:32 3 seconds Methylene chlor;de/toluene 34:66 3 seconds Toluene 10 seconds ~ n exposure t;me of only 16 seconds is necessary to produce crisply resolved structures. Even 2 ~m struc-tures are sharply resolved. The film th;ckness is 0.38 ~um and, after heating at 400C in an ~l2 atmosphere, is 0.35 ym.
Example 7:
An ~.7% solution in 4-butyrolactone ;s prepared of a polymer prepared from benzophenonetetracarboxylic d;anhydr;de, ~0 mol per cent of 5(6)-am;no 1-(4'-am;no-phenyl)-1,3,3-tr;methyl;ndane and 20 rnol per cent of d;-aminotoluene and having a rrlolecular weight of 95,000, and 7~ of b;sazide No. 1 are added.
The filtered solution is whirler-coated at 1,&ûO
r.p.m. onto a wafer and exposed for 120 seconds.
Developing takes place accordin~ to the programme:
~lethylene chlor;de/toluene ~0:20 8 seconds Methylene chloride/toluene 40:60 3 seconds Toluene 10 seconds Th;s g;ves cr;sp structures hav;ng a f;lm thickness of 0.97 ,um and a resolution of 4 ,um.
The film th;ckness is a.91 ~m after heat;ng at 400C.
Example 8:
A 9X solution ir, 4-butyrolactone ;s prepared of a polymer prepared from pyromellit;c dianhydr;de ~PMDA) and St6)-am;no-1-(4'~am;nophenyl)-1,3,3-tr;methylindane and hav;ng a molecular we;gh~ of 60,000 and of b;saz;de ~lo. 1, and ;s wh;rler-coated at 1,700 r.p.m~ onto 3-;nch wafers.
Vacuum-contact exposure for 200 seconds ;s followed by the follow;ng developnent programme:
Methylene chlor;de/toluene 65:35 8 seconds ~ethylene chlor;de/~oluene 32:68 3 seconds Toluene 10 seconds There are cr;sp relief structures ;n the central part of the wafer. However, the structures o' the out-lying parts of the wafer ~outer th;rd of the radius) are underexposed.
The relief structures of the central parts have a f;lm th;ckness of 0.92 ~. On heat;ng to 400C the film th;ckness ;s 0.75 ~.
Example 9:
Coated ~afers of the type described ;n Example 8 receive an add;tional, th;n polyvinyl alcohol layer which ;s spun on at 4,COO r~p.m. ;n the form of a solution of the follow;ng compos;t;on:
Polyv;nyl alcohol ~Mow;ol 488, ~oechst) SX
Alkylphenol polyethylene glycol (Tri~on (~) X-100 9 R~hm and Haas) 0.05X
~later 94 95%
The thickness of the polyvinyl alcohol film is 0.1 ~m.
The wafers are subjected to exposure for 22û sec-onds, sprayed w;th ho~ water, dr;ed and developed as ;n E~ample 8~
In contrast to the result ;n Example 8, th;s t;me the wafers are covered over the entire area w;th uniformly e~posed rel;ef structures.
.7~"~
57~
Example 10:
A S.0% solution in ~-butyrolactone ;s prepared of a polymer prepared from benzophenonetetracarboxylic di-anhydride and 5(6)-am;no-1-(43-aminophenyl)-1,3,3-tr;-methyl;ndane and hav;ng an average molecular weight of 1~4,000, is adm;xed with 7% of 2~6-bis-(4-azidobenzyl;dene)-4-methylcyclohexan-1-one and f;ltered through 0~2 ~m. The filtrate is whirler-coated at 2,500 r.p.m. in the course of 20 seconds onto SiO2-coated 3-inch wafers and dr;ed thereon at 60 for 20 minutes in a circulating a;r cabinet.
The wa~ers are subjected to vacuum~contact exposure for 52 seconds through a black chromium mask and then developed accord;ng to the following programme (spray developer, 2 bar pressure, 1,000 r.p.m.):
Methylene chloride/toluene 68:32 10 seconds nethylene chloride/toluene 34:66 3 seconds Toluene 10 seconds The resulting crisp rel;ef structures have a thick-ness of 1.05 ~m and a resolut;on of 5 ~um in which all 0rooves and r;dges are exactly reproduced in a rat;o of 1 :1 .
Heat-treating the wafers in an oven at 400C under nitro0en ~ives no structural changes and the film th;ck-ness is then 1.00 ym.
Example 11:
-A 7% filtered solution ;n 4-butyrolactone is pre-pared of a polymer prepared from benzophenonetetracarboxy-lic dianhydride, 20 mol per cent of 5(6~ amino-1 (4'-amino-phenyl)-1~3,3-trimethylindane and 20 mol per cent of toluenediamine and having a molecular weight of 174,000, and contains 7% of 2,6-bis(4-azidobenzylidene3-4-methyl-cyclohexanone. The solution ;s whirler-coated at 1,250 r.p.m. onto a 3-;nch wafer, dried at ~0C for 20 minutes in a circulat;ng air cabinet and subjected to a 70 second vacuum-contact exposure.
The develop;ng programme ;n a spray developer under 2 bar of pressure at 1,000 r.p.m. ;s as follows:
-~2'~
Methylene chlor;de/toluene 80:20 8 seconds Methylene chloride/toluene 40:60 3 seconds Toluene 10 seconds The crisply reproduced relief structures have a f;lm th;ckness of 0~98 ~m and a resolution of 4 ~m.
Even some of ~he 3 ~m structures are sharply re-solved. On heating to 400C under nitrogen the f;nal f;lm th;ckness ;s O.9Z ~m.
_e 12:
A poly;mide prepared from benzophenonetetracarboxy-lic dianhydride, ~0 mol% of toluenediamine and 20 mol% of 4,4'-diaminodiphenylmethane (Mw = 35,000) is dissolved in 4-butyrolac~one, and the solu~ion is admixed w;th 7% of bisazide No. 1 and filtered. The 10X solution has 3 Vis-cosity of 374 mPas. Whirler-coating at 3r400 r.p.m. and dry;ng for 20 m;nutes ;s followed by a 150 second vacuum-contact exposure. Th;s gives structures which have a film thickness of 0.93 ,um. On heating ~o 4C0C the film thickness is 0.73 ,um.
Example 13:
Polymer fraction 2 of Preparation Example 3 (where Mw = 77,000) is processed together with 7% of bisazide No. 1 into a 10% solution in 4-butyrolactone. The ~afers are coated at 2,200 r.p.m. After drying at 20C it needs an exposure time of only 13 seconds to give cr;sp struc-tures having a film thickness of 0.94 ,um and a resolution of 3 ~m. The images are developed with the following developing programme in a spray developer:
~IMP 14 seconds NMP/toluene 1:1 3 seconds Toluene 10 seconds On heat;ng to 400C the film th;ckness is still 0.80 Jum. A 10 minute treatment with hot NMP at 80C in an ultrason;c bath fails to produce a change in the shape or surface of the structures.
_ample 14:
A 6~0% solut;on ;s prepared of a polyimide prepared
5~
from benzophenonetetracarboxylic dianhydride and an iso-meric mixture of 4,4'-diaminophenyLmethane derivatives ethyl~substituted in the 2- or 2,2'-position (Mw = 45,COO~
;n the presence of 7% of bisazide Mo. I. The solution is filtered and the fil~rate whirler-coated a~ 1,450 r.p.m.
onto wafers. Dryin~ is -followed by a 13 second exposure and the following development programme:
~MP/toluene 80:2û 5 seconds NMP/toluene 40:60 3 seconds Toluene 10 seconds This gives very crisp structures having a resolu-tion of 2-3 ~m and a film thickness of 0.98 um.
On heat;ng to 4noc the f;lm th;ckness ;s still 0.77 ~um.
Example 15:
A poly;m;de prepared from benzophenonetetracarboxy-l;c d;anhydr;de and 3,3'-d;methyl-4,4'-d;am;nodiphenyl-methane and hav;ng an average molecular we;ght Mw ~ 44,000 ;s dissolved ;n 4-butyrolactone. The 7% solut;on ;s ad-mixed with 7% of b;saz;de ~Jo. 1 and f;ltered through a 0.45 ~m f;lter. At 23C the solut;on has a viscosity of 335 mPas. S;02-coated 3-;nch wafers are coated at 2,350 r.p~m., and are dr;ed at 60C for 17 minutes.
Develop;ng follows the follow;ng programme:
Spray developer, 2 bar, 7~000 rup.m.:
~JMP/toluene 80:20 5 seconds ~MP/toluene 40:60 3 seconds Toluene 10 seconds A l;gh~ output of 30 mW/cm2 necess;tates an expo-sure t;me of only 8 seconds ~240 mJ/cm2) to g;ve very crisp structures (2 ym resolut;on~ wh;ch have a f;lm th;ckness of 0.92 ,um.
The wafers covered w;th photostructures are placed in an oven, heated to 400C ;n the course of 1 hour, left at that temperature for 15 m;nutes, and then cooled down.
A h;gh-resolut;on m;croscope shows virtually no 57~31 changes ;n structure, and the renewed measurement of the f;lm thickness gives a value of 0.84 jum.
The heat-treatedrelief s.ructures are finally exposed in an ultrason;c bath for 10 minutes to hot NMP
at 80C, ~fter this treatment, the microscope shows no damage to the sur-face nor any geome~rical deformation.
from benzophenonetetracarboxylic dianhydride and an iso-meric mixture of 4,4'-diaminophenyLmethane derivatives ethyl~substituted in the 2- or 2,2'-position (Mw = 45,COO~
;n the presence of 7% of bisazide Mo. I. The solution is filtered and the fil~rate whirler-coated a~ 1,450 r.p.m.
onto wafers. Dryin~ is -followed by a 13 second exposure and the following development programme:
~MP/toluene 80:2û 5 seconds NMP/toluene 40:60 3 seconds Toluene 10 seconds This gives very crisp structures having a resolu-tion of 2-3 ~m and a film thickness of 0.98 um.
On heat;ng to 4noc the f;lm th;ckness ;s still 0.77 ~um.
Example 15:
A poly;m;de prepared from benzophenonetetracarboxy-l;c d;anhydr;de and 3,3'-d;methyl-4,4'-d;am;nodiphenyl-methane and hav;ng an average molecular we;ght Mw ~ 44,000 ;s dissolved ;n 4-butyrolactone. The 7% solut;on ;s ad-mixed with 7% of b;saz;de ~Jo. 1 and f;ltered through a 0.45 ~m f;lter. At 23C the solut;on has a viscosity of 335 mPas. S;02-coated 3-;nch wafers are coated at 2,350 r.p~m., and are dr;ed at 60C for 17 minutes.
Develop;ng follows the follow;ng programme:
Spray developer, 2 bar, 7~000 rup.m.:
~JMP/toluene 80:20 5 seconds ~MP/toluene 40:60 3 seconds Toluene 10 seconds A l;gh~ output of 30 mW/cm2 necess;tates an expo-sure t;me of only 8 seconds ~240 mJ/cm2) to g;ve very crisp structures (2 ym resolut;on~ wh;ch have a f;lm th;ckness of 0.92 ,um.
The wafers covered w;th photostructures are placed in an oven, heated to 400C ;n the course of 1 hour, left at that temperature for 15 m;nutes, and then cooled down.
A h;gh-resolut;on m;croscope shows virtually no 57~31 changes ;n structure, and the renewed measurement of the f;lm thickness gives a value of 0.84 jum.
The heat-treatedrelief s.ructures are finally exposed in an ultrason;c bath for 10 minutes to hot NMP
at 80C, ~fter this treatment, the microscope shows no damage to the sur-face nor any geome~rical deformation.
Claims (20)
1. A radiation-sensitive coating agent which, in addi-tion to customary additives, contains (a) an organic sol-vent, (b) a homopolyimide or copolyimicle which is soluble in this solvent and is formed from aromatic tetracarboxylic acids and aromatic diamines or aromatic and aliphatic di-amines, where at least one aliphatic group is bonded directly or via a bridging group to at least some of the tetracarboxylic acid radicals, of the aromatic diamine radicals, or the two radicals and/or at least some of these radicals contain as an aliphatic bridging group alkylene, alkylidene, cycloalkyLidene or si(alkyl)2, and (c) at least 0.1% by weight, based on component (b), of at least one organic chromophoric polyazide in which the azide groups are bonded to aromatic hydrocarbon radicals.
2. A coating agent according to claim 1, in which the polyimide or copolyimide contains at least 10 mol%, based on the polyimide, radicals having aliphatic groups and/or bridging groups.
3. A coating agent according to claim 1, in which the aliphatic group is alkyl-Q- in which there are 1 to 6 C
atoms in the alkyl group and Q is a direct bond, -O-, -S-, -SO-, -SO2-, -CO-, -NH-, -N-alkyl having 1-6 C atoms or -NHCO- and the bridging group is as alkylene, methylene or ethylene, as alkylidene, ethylidene, 1,1- or 2,2-propyl-idene or 1,1- or 2,2-butylidene, as cycloalkylidene, cyclo-pentylidene or cyclohexylidene and as Si(alkyl)2, Si(Methyl)2 or Si(ethyl)2.
atoms in the alkyl group and Q is a direct bond, -O-, -S-, -SO-, -SO2-, -CO-, -NH-, -N-alkyl having 1-6 C atoms or -NHCO- and the bridging group is as alkylene, methylene or ethylene, as alkylidene, ethylidene, 1,1- or 2,2-propyl-idene or 1,1- or 2,2-butylidene, as cycloalkylidene, cyclo-pentylidene or cyclohexylidene and as Si(alkyl)2, Si(Methyl)2 or Si(ethyl)2.
4. A coating agent according to claim 3, in which the aliphatic group is methyl or methoxy and the bridging group is methylene, 2,2-propylidene or Si(methyl)2.
5. A coating agent according to claim 1, in which homopolyimide or copolyimide (b) essentially consists of recurring structural units of the formula (I) (I) in which the four carbonyl groups are bonded to differ-ent carbon atoms and any two carbonyl groups are in ortho-or peri- position relative to each other, Z is a tetravalent radical which contains at least one aromatic ring and Z' is a divalent organic radical selected from among aro-matic, alkylaromatic, aliphatic, cycloaliphatic and hetero-cyclic radicals, combinations thereof and radicals having oxygen-, sulfur-, nitrogen-, silicon- or phosphorus-con-taining bridging groups, with the proviso that 1) of the total number of recurring polyimide units A) in 0 to 100 mol% of such units Z is a phenyl-indane radical of the structural formula (II) ; in which R1 is hydrogen or an alkyl radical having 1 to 5 carbon atoms and R2 is an alkyl radical having 1 to 5 carbon atoms, and in 0 to 100 mol % of such units Z' is a phenyl-indane radical of the structural formula (III) in which R1 is hydrogen or an alkyl radical having 1 to 5 carbon atoms, R2 is an alkyl radical having 1 to 5 carbon atoms, and R3, R4, R5 and R6 independently of one another are hydrogen, halogen, alkoxy or an alkyl radical having 1 to 4 carbon atoms and 2) of the total number of radicals Z and Z' at least 10 mol %, based on the individual components, are phenylindane radicals.
6. A coating agent according to claim 5, in which R2 in the formulae II and III is methyl.
7. A coating agent according to claim 5, in which, in the polyimide, 0 to 100 mol % of the radicals Z are of the formula or the formula while 100 to 0 mol % of the radicals Z are a mixture of and and in which 100 to 10 mol % of the radicals Z' are equal to a radical of the formula III in which R1, R3, R4, R5 and R6 independently of one another are hydrogen or methyl and R2 is methyl, while 0 to 90 mol % of the radicals Z' have the formula or in which W is a covalent bond, methylene, ethylidene, 2,2-propylidene, cyclohexylidene, sulfur, oxygen or sulfone, R7 and R8 independently of each other are hydrogen, halogen, alkoxy or alkyl groups with 1 to 5 carbon atoms and R9 is hydrogen, halogen, alkoxy or an alkyl group having 1 to 5 carbon atoms.
8. A coating agent according to claim 5, in which, in the polyimides, Z' is or or a mixture thereof and Z is or or a mixture thereof.
9. A coating agent according to claim 1, in which homopolyimide or copolyimide (b) essentially consists of recurring structural units of the formula (I) (I) in which the four carbonyl groups are bonded to different carbon atoms and any two carbonyl groups are in ortho- or peri-position relative to each other, Z is a tetravalent radical which contains at least one aromatic ring and Z' is a divalent organic radical selected from among aromatic, alkylaromatic, aliphatic, cycloaliphatic and heterocyclic radicals, combinations thereof and radicals having oxygen-, sulfur-, nitrogen-, silicon-, or phosphorus containing bridging groups, with the proviso that of the total number of recurring polyimide units, based on the tetracarboxylic anhydride radicals or diamine radicals, A) 30-100 mol % of such units Z are benzophenonetetracar-boxylic radicals and B) 30-100 mol % of such units Z' are radicals of the formulae or in which W1 is CH2, O, S, SO2, CO or H3C-C-CH3, W2 is CH2, S, SO2, CO or H3C-C-CH3, R18 is alkyl or alkoxy having 1 to 6 C atoms, halogen, CO2H, OH, SO3H or NHCOCH3 and R19 is alkyl having 1 to 6 C atoms, at least 10 mol % of these radicals being those which have CH2, H3C-C-CH3, alkyl, alkoxy or NHCOCH3 groups.
10. A coating agent according to claim 8, in which R18 and R19 are methyl.
11. A coating agent according to claim 8, in which W1 and W2 are CH2.
12. A coating agent according to claim 1, in which homopolyimide or copolyimide (b) essentially consists of recurring structural units of the formula (I) (I) in which, based on the tetracarboxylic anhydride radicals or diamine radicals, A) 75 to 100 mol % of the units Z are a pyromellitic anhy-dride radical and B) 25 to 0 mol % of the units have the formula in which x2 is O, SO2 or CO, and C) 10 to 35 mol % of the units Z' have the formula and 90 to 65 mol % of the units Z' have the formulae or mixtures thereof.
13. A coating agent according to claim 1, in which copolyimide (b) essentially cons;sts of recurring struc-tural units of the formula (I) (I) in which A) Z is benzophenonetetracarboxylic dianhydride radical and B) based on the diamine radicals, 10-30 mol % of the units Z' have the formula and C) 90-70 mol % of the units Z' or mixtures thereof.
14. A coating agent according to claim 1, which con-tains 99.9 to 80% by weight of polyimide (b) and 0.1 to 20% by weight of bisazide (c), based on the components (b) and (c).
15. A coating agent according to claim 1, in which the solvent is a polar aprotic solvent.
16. A coating agent according to claim 1, in which the chromophoric polyazide is a diazide of the formula N3-E-(Y)q-E-N3 in which E is an aromatic hydrocarbon radical, q is 0 or 1 and Y is an inorganic or organic group which forms a meso-meric system together with the aromatic hydrocarbon radicals E.
17. A coating agent according to claim 16, in which Y
is O, CO, S, SO, SO2, NR' in which R' is hydrogen, alkyl, cycloalkyl,aryl or aralkyl, -(HC=CH)p-?-(CH=CH)p -, -?-(CH=CH) - or -(CH=CH) - with p=1-3, P P
in which R" and R"' independently of each other are alkyl having 1 to 5 C atoms or R" and R"' together are unsubstituted or alkyl-, hydroxyalkyl-, alkoxy-, trialkylsilyl-, hydroxyl-, carboxyl-, alkoxycarbonyl-, amino-, alkylamino-, or dialkylamino-substituted ethylene or trimethylene, q is 0 or 1, X1 is 0, S or NH, Y1 is independently defined in the same way as Y and free bonds on N and X1 form a fused heterocyclic ring together with the group E.
is O, CO, S, SO, SO2, NR' in which R' is hydrogen, alkyl, cycloalkyl,aryl or aralkyl, -(HC=CH)p-?-(CH=CH)p -, -?-(CH=CH) - or -(CH=CH) - with p=1-3, P P
in which R" and R"' independently of each other are alkyl having 1 to 5 C atoms or R" and R"' together are unsubstituted or alkyl-, hydroxyalkyl-, alkoxy-, trialkylsilyl-, hydroxyl-, carboxyl-, alkoxycarbonyl-, amino-, alkylamino-, or dialkylamino-substituted ethylene or trimethylene, q is 0 or 1, X1 is 0, S or NH, Y1 is independently defined in the same way as Y and free bonds on N and X1 form a fused heterocyclic ring together with the group E.
18. A coating agent according to claims 5 and 7, in which the polyazide is 2,6-bis((4-p-azidophenyl) methine)-cyclohexan-1-one.
19. A photographic recording material for relief images which consists of a substrate and a radiation-sensitive layer, where the radiation-sensitive layer applied is a mixture of poly-imide (b) and polyazide (c) according to claim 1.
20. A method of providing a substrate with an insulating or protective coating, or with a light-sensitive coating, which com-prises applying thereto a coating agent according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH241482 | 1982-04-21 | ||
| CH2414/82-1 | 1982-04-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1244579A true CA1244579A (en) | 1988-11-08 |
Family
ID=4233241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000426131A Expired CA1244579A (en) | 1982-04-21 | 1983-04-19 | Radiation-sensitive coating agent and its use |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0092524B1 (en) |
| JP (1) | JPS58191747A (en) |
| CA (1) | CA1244579A (en) |
| DE (1) | DE3372983D1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3583817D1 (en) * | 1984-05-17 | 1991-09-26 | Ciba Geigy Ag | HOMO- AND COPOLYMERS, METHOD FOR THEIR NETWORKING AND USE THEREOF. |
| JPS61275352A (en) * | 1985-05-31 | 1986-12-05 | Japan Synthetic Rubber Co Ltd | Soluble polyimide solution |
| US4786569A (en) * | 1985-09-04 | 1988-11-22 | Ciba-Geigy Corporation | Adhesively bonded photostructurable polyimide film |
| US4927736A (en) * | 1987-07-21 | 1990-05-22 | Hoechst Celanese Corporation | Hydroxy polyimides and high temperature positive photoresists therefrom |
| US4925912A (en) * | 1987-12-15 | 1990-05-15 | Ciba-Geigy Corporation | Auto-photocrosslinkable copolyimides and polyimide compositions |
| US5102959A (en) * | 1987-12-15 | 1992-04-07 | Ciba-Geigy Corporation | Auto-photocrosslinkable copolyimides and polyimide compositions |
| JP2575815B2 (en) * | 1988-06-14 | 1997-01-29 | 東芝ケミカル株式会社 | Manufacturing method of printed circuit board |
| US7648815B2 (en) * | 2000-09-12 | 2010-01-19 | Pi R&D Co., Ltd. | Negative photosensitive polyimide composition and method for forming image the same |
| JP4603215B2 (en) * | 2001-09-06 | 2010-12-22 | 三井化学株式会社 | Negative photosensitive resin composition and use thereof |
| JP2009081379A (en) | 2007-09-27 | 2009-04-16 | Showa Denko Kk | Group iii nitride semiconductor light-emitting device |
| US7955782B2 (en) | 2008-09-22 | 2011-06-07 | Honeywell International Inc. | Bottom antireflective coatings exhibiting enhanced wet strip rates, bottom antireflective coating compositions for forming bottom antireflective coatings, and methods for fabricating the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3856752A (en) * | 1973-10-01 | 1974-12-24 | Ciba Geigy Corp | Soluble polyimides derived from phenylindane diamines and dianhydrides |
| JPS5946380B2 (en) * | 1977-04-13 | 1984-11-12 | 株式会社日立製作所 | How to form an image |
| IT1144060B (en) * | 1979-05-11 | 1986-10-29 | Minnesota Mining & Mfg | PROCEDURE FOR THE MATURATION OF POLYAMIC ACIDS OR THEIR SALTS THROUGH ULTRAVIOLET IRRADIATION FOR EXAMPLE FOR THE FORMATION OF IMAGES IN SUBSTRATES AND PRODUCT OBTAINED |
| JPS5624344A (en) * | 1979-08-06 | 1981-03-07 | Hitachi Ltd | Photosensitive heat-resistant polymer composition |
| JPS57168942A (en) * | 1981-04-13 | 1982-10-18 | Hitachi Ltd | Photosensitive polymer composition |
-
1983
- 1983-04-15 DE DE8383810156T patent/DE3372983D1/en not_active Expired
- 1983-04-15 EP EP19830810156 patent/EP0092524B1/en not_active Expired
- 1983-04-19 CA CA000426131A patent/CA1244579A/en not_active Expired
- 1983-04-21 JP JP7083583A patent/JPS58191747A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3372983D1 (en) | 1987-09-17 |
| JPH0553834B2 (en) | 1993-08-11 |
| EP0092524A3 (en) | 1985-05-29 |
| EP0092524A2 (en) | 1983-10-26 |
| JPS58191747A (en) | 1983-11-09 |
| EP0092524B1 (en) | 1987-08-12 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |