CA1256759A - Coated material and its use - Google Patents

Abstract

Process for the production of protective coatings and relief structures Abstract:
Coated material of a support, onto which is applied a radiation-sensitive coating of a homopolymer or copolymer with at least 5 mol %, based on the polymer, of structural units of the formula I

Description

~l256759 K~14430/1~2/~
Process for the production of protective coatings and relief structures _ _ The present invention relates to a process for the production of protective coatings or relief structures by using a carrier coated with a radiation-sensitive polymer, the polymer containing benzophenonetetracarboxylic acid imide unitslto coated materials containing selected polymers, and to the use of this material for photographic production of relief structures and of protective films.
Photographic imaging processes with radiation-sen-sitive polymers for the production of relief images have achieved great importance in the production of components in electronics and semiconductor technology. Such photopolymers are required to have certain properties~ depending on the intended use, and various polymers have been disclosed for this purpose. The photosens;tivity of such polymers is rela-tively low, which necessitates the addition of photoinitia-tors or sensitisers in order to achieve economical exposure times. The disadvantage of such additives is that they can impair the mechanical and physical properties.
High heat stabilities of the structures produced or of photochemically produced protective coatings are further-moredesired for certain applications. Polyimides are par-ticularly suitable for this. Because of their insolubility, soluble intermediates must be used as starting materials, and these are converted into polyimides by after-treatment with heat only after the photopolymerisation has been carried out. Direct photocrosslinking of polyimides has not yet been disclosed.
German Offenlegungsschrift 3,007,445 discloses poly-amides and polyesters with benzophenonetetracarboxylic acid imide unitsO The physico-mechanical properties of fibres or films of this material can be improved by exposure~ The pro-duction of protective coatings or photographic imaging pro-cesses are not mentioned at all.
'~

~25~;7S9 The present invention relates to a process for the production of a relief structure or a protective coating on a carrier onto which is applied a coating of a radiation-sen-sitive polymer, wherein the polymer is a homopolymer or co-polymer with at least 5 mol %, based on the polymer, of struc-tural units of the formula I
O O
Il ll 11 /C\ ~-\ /C\ ~e\ /C\
~R ~N~ R- ( I ) Il 11 O O
in which R is a divalent unsubstituted or substituted ali-phatic radical which can be interrupted by hetero-atoms or aromatic, heterocyclic or cycloaliphatic groups, an unsubsti-tuted or substituted heterocyclic, cycloaliphatic or arali-phatic radical, an aromatic radical in which two aryl nuclei are linked via an aliphatic group, or an aromatic radical which is substituted by at least one alkyl, cycloalkyl, alkoxyalkyl, alkoxy, alkylthio, alkylthioalkyl, hydroxyalkyl, hydroxyalkoxy, hydroxyalkylthio or aralkyl group or in which two adjacent C atoms of the aromatic radical are substituted by an alkylene group, R' independently has the same meaning as R and q is 0 or 1, an aromatic radical R not being substi-tuted by alkylene or not being substituted by the abovemen-tioned radicals in both ortho-positions relative to the N
atoms if q ;5 r said process comprising the steps of i) imagewise or direct exposure of said coated material to high-energy radiation, and if desired, ii) removal of the unexposed portions by means of a developer.
The amount of structural elements of the formula I
essentially depends on the desired photosensitivity of the homopolymers or copolymers and their build-up. The amount can be 5 to 100 mol %, preferably 20 to 100 %, in particular 40 to 100 mol % and especially 50 to 100 mol %, based on the polymer. Homopolymers and copolymers w;th 80-100 mol % of ~25~7S9 structuralelements ofthe formulaI very particularly preferred.
In homopolymers or copolymers with structuraL ele-ments of the formula I in which R and R' are aliphatic or cycloaliphatic radicals, the amount of these structural ele-ments is preferably at Least S0 mol %, especially when the homopolymers and copolymers are polyamides and polyesters.
A divalent aliphatic radical R or R' in formula I
preferably contains 2 to 30, in particular 6 to 30 and especially 6 to 20, C atoms. In a preferred sub-group, R
and/or R' are linear or branched alkylene wh h ca be inter-rupted by oxygen atoms, S, S0, S02, NH, NRa2, ~ ~
cyclohexyleneO naphthylene, phenylene or hydantoin radicals.
Ra can be, for example, alkyl with 1 to 12 C atoms, cyclo-alkyl with 5 or 6 ring C atoms, phenyl or benzyl. ~ is an anion of a protic acid, for example halide, sulfate or phos-phate~ In a preferred embodiment, R and/or R' are linear or branched alkylene with 6 to 30 C atoms, -~CH2)m-R1-(C~l2)n-, in which R1 is phenylene, naphthylene, cyclopentylene or cyclohexylene and m and n independently of one another are the number 1, 2 or 3, -R2-(oR3)po-R2-, in which R2 is ethylene, 1,2-propylene, 1,3-propylene or 2-methyl-1,3-pro-pylene, R3 is ethylene, 1,2-propylene, 1,2-butylene, 1,3-propylene or 1,4-butylene and p is a number from 1 to 100, or \ /
- (CH2 ) 3-C~ ,C~ ~CH- (CH2 ) 3 -Examples of aliphatic radicals are: methylene, ethylene, 1,2- or 1,3-propylene, 2,2-dimethyl-1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,3- or 1,5-pentylene, the hexyl-enes, heptylenes, octylenes, decylenes, dodecylenes, tetra-decylenes, hexadecylenes, octadecylenes, e;cosylenes, 2,4,4-trimethylhexylene, 1,10-dialkyldecylene, in which the alkyl preferably contains 1 to 6 C atoms, substituted 1,11-undecyl-enes, for example those described in European Patent B-0,011,559, Jeffamines, for example -(CH2)3-(OCHCH2)pO(CH2)3~ in which p is 1 to 100, or ` ~567~;~

-tCH2 ~ (CHz)4 ~ ~CH2~ in which p is 1-100, dimethylenecyclohexane, xylylene and diethylenebenzene. R
and R' are particularly preferably longer-chain, branched alkylene with, for example, 8 to 30 C atoms.
An aliphatic radical R or R' in formula I can also be a polysiloxane radical of the formula -R --~S io~S i_n20 ~R ~ R

in which R1~ and R17 are C1-C6-alkyl, in particular methyl, or phenyl, R20 is cycloalkylene, for example cyclo-hexylene, or, in particular, Cl-cl2-alkylene~ especially C1-C6-alkylene, for example 1,3-propylene or 1,4-butylene, x is a rational number of at least 1, for example 1 to 100, preferably 1 to 10. Such diamines conta;n;ng this radical are described in U.S. Patent Specification 3,435,002 and U.SO
Patent Specificat;on 4,030,948.
Al;phat;c radicals interrupted by heterocyclic radi-cals can be, for example, those der;ved from N,N'~amino-alkylated hydantoins or benzim;dazoles. Examples are N,N'-(~-aminopropyl)-5~5-dimethyl-hydanto;n or -benzimidazolone, and those of the formula ~2~-(C~1~)3 - ~ Rb in which Rb is alkylene with 1 to 12, preferably 1 to 4, C
ms or (CH21CHcO)aCH2CH2, in which Rc is a hydrogen atom or methyl and a is an integer from 1 to 2û.
Examples of suitable substituents for the aliphatic ~L2S~S~

radicaLs are hydroxyl, halide, such as F or Cl, and alkoxy with 1 to 6 C atoms.
Heterocyclic diamine radicals are preferably derived from N-heterocycl;c diamines, for example from pyrrolidine, indole, piperidine, pyridine or pyrrole, the N atom of which can be alkylated, for example methylated. An example is N-methyl-4-amino-5-aminomethylpiperidine.
A divalent cycloaliphatic radical R or R' in formula I preferably contains 5 to 8 ring C atoms and is, in parti-cular, mononuclear or dinuclear cycloalkylene which has 5 to 7 ring C atoms and is unsubstituted or substituted by alkyl, which preferably contains 1 to 4 C atoms. In a preferred embodiment, a cycloaliphatic radical R or R' is one of the formula ~ ~~' or ~ \-- X -~

in which q is O or 1, the radicals R4 independently of one another are hydrogen or alkyl with 1 to 6 C atoms and X is a direct bond, O, S, S02, alkylene with 1 to 3 C atoms or alkylidene with 2 to 6 C atoms. R4 is preferably ethyl or methyl, X is preferably methylene and the alkylidene radical preferably contains 2 or 3 C atoms and is, for example, ethylidene or 1,1- or 2,2-propylidene.
Examples of a cycloalkylene radical R or R' are:
1,2- or 1,3-cyclopentylene, 1~2-, 1,3- or 1,4-cyclohexylene, cycloheptylene, cyclooctylene, methylcyclopentylene, methyl-or dimethyl-cyclohexylene, 3- or 4-methylcyclohex-1-yl, 5-methyl-3-methylenecyclohex-1-yl, 3,3'- or 4,4'-bis-cyclo-hexylene, 3,3'-dimethyl-4,4'-biscyclohexylene, 4,4'-biscyclo-hexylene ether, -sulfone, -methane or -2,Z-propane and the radicals of bis-aminomethyltricyclodecane, bis-aminomethyl-norbornane and menthanediamine.
Particularly preferred cycloaliphatic radicals R and/

~25~759 or R' are 1,4- or 1,3-cyclohexylene, 2,2,6-trimethyl-6-methylene-cyclohex 4-yl, methyleneb;s(cyclohex-4-yl) and methyleneb;s(3-methylcyclohex-4-yl).
An araliphatic radical R or R' preferably contains 7 to 30 C atoms. If the aromatic group of the araliphatic radical is bonded to the N-atoms in the radical of the for-mula I, wh;ch is the preferred case, these aromat;c groups are preferably subst;tuted in the same way as an aromatic rad;cal R or R', including the preferred substitutions. The araliphatic radical preferably contains 7 to 30, in particular 8 to 22, C atoms. The aromatic radical in the araliphatic radical ;s preferably a phenyl radical. An araliphatic radi-cal R or R~ is, in particular, aralkylene wh;ch ;s unsubst;-tuted or subst;tuted by alkyl on the aryl radical, the alkyl-ene radical being linear or branched. In a preferred embodi-ment, the aral;phat;c rad;cal has the formula \.ll / r 2r in which the radicals R4 independently of one another are hydrogen atoms or, in particular, alkyl with 1-6 C atoms and r is an integer from 1 to 20.
The free bond can be in the o-positionr m-position or, in part;cular, p-pos;t;on relat;ve to the CrH2r group and one or both of the radicals R4 are preferably bonded in the o-position relative to the free bond.
Examples of an araliphatic radical R or R' are: m-or p-benzylene, 3-methyl-p-benzylene, 3-ethyl-p-benzylene, 3,5-dimethyl-p-benzylene, 3,5-diethyl-p-benzylene, 3-methyl-5-ethyl-p-benzylene, p-phenylenepropylene, 3-methyl-p-phenyl-ene-propylene, p-phenylenebutylene, 3-ethyl-p-phenylenepentyl-ene and, in particular, longer~chain phenylenealkylene radi-cals, which are described, for example, in European Patent A-0,069,062: 6-(p-phenylene)-6-methylhept-2-yl, 6-(3l-~2567~i;9 methyl-p-phenylene)-6-methylhept-2-yl, 6-(3'-ethyl-p-phenyl-ene)-6-methylhept-2-yl, 6-t3',5'-dimethyl-p-phenylene)-6-methylhept-2-yl, 11-(p-phenylene)-2,11-dimethyl-dodec-1-yl and 13-tp-phenylene)-2,12-dimethyltetradec-3-yl.
R and/or R' can also be an aromatic radical in which t~o aryl nuclei, in particular phenyl, are linked via an ali-phatic group. This radical preferably has the formula ~>~.=./ \.=./

in which the free bonds are in the p-, m- or, in particular, o-posit;on relative to the Q group and Q is C1-C12-alkylene, in particular C1-C6-alkylene, which can be interrupted by 0 or S. Examples of Q are ethylene, 1,2- or 1,3-propylene, butylene, -CH2-0-CH2, -CH2-S-CH2- and -CH2CH2 0-CH2CH2 ' Particularly preferred homopolymers and copolymers are those with structural elements of the formula I in which R and/or R' are substituted aromatic radicals. The substitu-ent on the aromatic radical preferably contains 1 to 20, in particular 1-12 and especially 1-6, C atomsu The substituent is, ;n particular, C5- or C6-cYcloalkyl, linear or branched alkyl, alkoxy, alkoxyalkyl, alkylthio, alkylthioalkyl, hydroxyalkyl, hydroxyalkoxy or hydroxyalkylthio with 1 to 6 C atoms, benzyl, trimethylene or tetramethylene. Alkoxy-methyl is the preferred alkoxyalkyl radical and methoxy is the preferred alkoxy radical. Examples of the substituents are: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, octyl, dodecyl, tetradecyl, eicosyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, methoxymethyl, methoxyethyl, ethoxymethyl, propoxymethyl, butoxymethyl, benzyl, methylbenzyl, phenethyl, methylthio, ethylthio, hydroxyethyl, methylthioethyl and hydroxyethylthio. Pre-ferred radicals are methoxymethyl~ ethoxymethyl, methyl, ethyl, n-propyl, i-propyl, trimethylene, tetramethylene, cyclopentyl and cyclohexyl. Methyl, ethyl and i-propyl are ~25~ 9 particularly preferred. The substituted aromatic radical can be a mononuclear or polynuclear, in particular a dinuclear, radical. Mononuclear radicals can contain up to 4, prefer-ably 2 and in particular 1, substituents and dinuclear radi-cals can contain up to 4, preferably 1 or 2, substituents in each nucleus. It has been found that the photosensitivity of homopolymers or copolymers is particularly high if one or two substituents are bonded in the ortho-position relative to the N atom~ Substitution in the ortho-pos;tion is thus preferred. The aromatic radical is preferably bonded in the meta- or para-position relative to the N atom.
An aromatic radical R or R' can contain 7 to 3û, in particular 7 to 20~ C atoms~ The aromatic radical is prefer-ably a hydrocarbon radical or a pyridine radical, which is substituted as defined above~
A preferred sub-group are those aromatic radicals of the formulae \ ~ \ / 4 \ ~ \~/ R4~ /R' R~

R4~

R4 R5 1 or t i! ! '.=.>~
~o/ \.' R5/ \R6 3L2567~9 ~ R4 +

R ~4 4~ + ~ 4 in which, in the case of monosubst;tution, one radical R~
;s aLkyl with 1 to 6 C atoms and the other radicals R4 are hydrogen, and in the case of di-, tri- or tetra-substitution, two radicals R4 are alkyl with 1 to 6 C atoms and the other radicals R4 are hydrogen atoms or alkyl with 1 to 6 C atoms, or in the case of di-, tri- or tetra-substitution, two vicinal radicals R~ in the phenyl ring are trimethylene or tetramethylene and the other radicals R4 are hydrogen atoms or alkyl with 1 to 6 C atoms, Y is 0, S, NH, CO or CH2, R5 is a hydrogen atom or alkyl with 1 to 5 C atoms, R6 is alkyl with 1 to 5 C atoms and Z is a direct bond, O, S, SO, S02, O O
CO, CO, CNR7, NR7, CONH, NH, R7SiR8, R70SioR8, R7 ~ R7 --si---osi~
18 ~ 18 Jj alkylene with 1 to 6 C atoms, which can be interrupted by -O-or -S-, or is alkenylene or alkylidene with 2 to 6 C atoms, phenylene or phenyldioxy, in which R7 and R8 independently of one another are alkyl with 1 to 6 C atoms or phenyl and j is 1-10, in particular 1-3. Z can also have the formula f ( H2)g ~ Sio ~ Si--(CH2)g-(G)f-in which ~ is S or, in particular, O, f is O or, in particu-lar, 1, 9 is 1-6, h is 1 to 50, in particular 1 to 10, and R16 and R17 are as defined above, or can be a radical of ~5~75g the formula C

O O R25 o O R250 in which K is -hC--C-~ -CR25-C- or -C-N--C, in which R25 is H, C1-C6-alkyl or phenyl. R5 and R6 are preferably methyl, Y is pre~erably -CH2- or -0- and Z is preferably a direct bond, -0-, -CH2- or alkylidene with 2 to 4 C atoms. R7 and R8 are, ;n particular, methyl, ethyl or phenyl. The alkylene rad;cal preferably conta;ns 2 to 4 C atoms and is, ;n parti-cular, ethylene. Alkenylene is, in particular, ethenylene.
A preferred sub-group are toluylene radicals and radicals of 0,0'-substituted diaminodiphenylenes, diaminodi-phenyLmethanes and diaminodiphenyl ethers.
A particularly preferred group are those aromatic radicals of the formulae H C ~ ! ~CH3 C~13 ~ ! CH 3 ! i! ~ ! i! i i! ~ ! i!
H3C ~i CH3 C~H ~

C~3 &H3 -- ~ 7-- Z --~ ~ _ and \O=-/ \o=-/
R9/ ~9 in which Z is a direct bond, 0 or, in particular, CH2 and R9 is a hydrogen atom, methyl, ethyl or isopropyl.
Examples of substituted aromatic radicals are: 4-methyl-1,3-phenylene, 4-ethyl-1,3-phenylene, 2-methyl-1,3-phenylene~ 4-benzyl-1,3-phenylene~ 4-methoxymethyl~1,3-phenylene, tetrahydro-1,3- or -1,4-naphthylene~ 3-propyl-1,3-or -1,4-phenylene, 3-;sopropyl-1,4-phenylene, 3,5-dimethyl-~S~7$g 1,4-phenylene, 2,4-dimethyl-1,3-phenylene, 2,3-dimethyl-1,4-phenylene, 5-methyl-1,3-phenylene, 2,3,5,6-tetramethyl-1,4-or -1,3-phenylene, 3-methyl-2,6-pyridylene, 3,5-dimethyl-2,6-pyridylene, 3-ethyl-2,6-pyridylene, 1-methyl-2,7-naphthylene, 1,6-dimethyl-2,7-naphthylene, 1-methyl-2,4-naphthylene, 1,3-dimethyl-2,4-naphthylene, the divalent radicals of 5-amino-1-(3'-amino-4'-methylphenyl)-1,3,3-trimethylindane or 6-amino-5-methyl-1-(3'-amino-4'-methyl)-1,3,3-trimethylindane, 4-methoxymethyl-1,3-phenylene, 3-methyl-p-diphenylene, 3-ethyl-p-diphenylene, 3,3'-dimethyl-p-diphenylene, 3,3'-di-ethyl-p-diphenylene, 3-methyl-3'-ethyl-p-diphenylene, 3,3', 5,5'-tetramethyl-diphenylene, 3,3'-methyl-5,5'-ethyl-p-di-phenylene, 4,4'-dimethyl-m-diphenylene, 3,3'-diisopropyl-diphenylene and radicals of the formulae H3C/ ~./ \0/ ~./ \CH ~. ~ - C112 - ~ -\~ _ ./ \,~ _ ./

_o_~ -- CH2 --~
o ~ ~ o o \~ ./ \,,_. \ / \./

~ / _ CH3~ ~CH3 \ _ / 2 \ /-- ~ '-S~
O Cl O

CH

Rll R12 ~ /

æ~ R 1~ --Z~ .~Rl = D =-- ~=--R~3 ~14 and _.~ ~.-z~ -R12 ~=- =-~1 ; ~hich z~ R11 R12 R13 and R14 have the meanings given in the following table:

~2~

Z' __ Rl2 Rl3 _ . _ CH2Methyl Methyl _ CH2Methyl Ethyl _ CH? Ethyl Ethyl _ CH2 Isopropyl Isopropyl _ CH2 Methoxymethyl _ ~
CH2 Benzyl ` Benzyl _ _ CH2 Methyl Methyl H H
CH2 Ethyl Ethyl H H
CH2 Isopropyl Isopropyl H
CH2 Methoxymethyl H H
CH2Methyl ¦ Ethyl H H
CH2 Methoxymethyl Methoxym thyl CH2 Methyl Methyl Methyl Methyl CH2 EthyL Ethyl Ethyl Ethyl CH2 Methyl Methyl Ethyl Ethyl CH2 Ethyl Ethyl Isopropyl Isopropyl CH2 Isopropyl Isopropyl Isopropyl Isopropyl CH2 Isopropyl Isopropyl H H
CH2 ~lethoxy ~lethoxy H H
O Methyl Methyl _ O Ethyl Ethyl _ _ O Methyl Methyl H H
O Methyl Methyl Methyl Methyl O Methyl Methyl Ethyl Ethyl S Methyl Methyl ~ _ _ _ 9.Z~ 9 ~/ ~ + ~ hyL ~ _ S Methyl Methyl H H
S Methyl Methyl Methyl Methyl S Ethyl Ethyl Ethyl Ethyl S Methyl Methyl Ethyl Ethyl CO Methyl Methyl _ CO Methyl Methyl H H
CO Methyl Methyl Methyl Methyl .
S2 Methyl Methyl _ S2 Methyl Methyl H H
S2 Methyl Methyl Methyl ~lethyl S2 Ethyl- Ethyl Methyl Methyl SO Methyl Methyl _ SO Methyl Methyl H H
COO Methyl Methyl H H
COO Methyl Methyl Methyl Methyl CONCH3 Methyl Methyl H H
~CH3 Methyl Methyl _ ~CH3 Methyl Methyl Methyl Methyl CO~H Methyl ~Sethyl _ NH Ethyl Ethyl H H
NL ~I=thyl Methyl _ .

~Z567~;9 ~ = ,RI 1 Rl 2 ~ Rl 4 Si(~lethyl)2 ~lethyl ~lethyl _ Si(Phenyl)2 Methy1 Methyl Mcthyl Methyl Si(O`Iethyl)2 Ethyl Fthyl _ Si(OPhenyl)2 Methyl ~lethyl H H
Ethylene Methyl Methyl _ Ethylene Methyl Methy1 Methyl Methy1 Ethylene Ethyl Ethyl H H
Ethylene Methy1 Methyl _ Phenylene H H Methyl Methy1 Pheny1ene Alky1 Alky1 _ (CH3)2C< Methy1 Me,hy1 H H
(CH3)2C~ Methyl Methyl Methyl ~lethyl (CF3)2C\ Methyl Methyl Methyl Methyl The diamines from which R and R' are derived are known or they can be prepared by known processes. Diamines with polysiloxane units are known from U.S. Patent Specifica-tion 3,435,002 and from European Patent A-0,054,426.
The polymers to be used according to the invention have average molecular weights ~number-average) of at least

2,000, preferably at least 5,000. The upper limit essentially depends on properties which determine the processability, for example the solubility of the polymers. It can be up to 500,000, preferably up to 100,000 and in particular up to 60,000. The polymers can furthermore be random polymers or block polymers. They are prepared by conventional processes in equipment envisaged for this purpose. The polymers are preferably built up in a linear manner, but can also be ~2S~
~ 16 -slightly branched with at least trifunctional monomers, which are added in small amounts.
The homopolymers or copolymers are preferably chosen from the 9roup comprisin~ polyimides, polyamides, saturated polyesters, polycarbonates, polyamide-imides, polyester-imides, polyester-amides, polysiloxanes, unsaturated poly-esters, epoxy resins, the aromatic polyethers, the aromatic polyether-ketones, the aromatic polyether-sulfones, the aromatic polyketones~ the aromatic polythioethers, the aromatic polyimidazoles and the aromatic polypyrrones, and mixtures of these polymers.
Materials containing radiation-sensitive layers of these polymers are, with the exception of polyimides, novel and constitute another object of the ;nstant invention.
Very particularly preferred amongst these polymers in the process according to the invent;on is a polyimide with recurring structural elements of the formula I in which q is 0, or a copolyimide of recurring structural elements of the formula I in which q is 0 and recurring structural elements of the formula II 1l N/ \~ lO (II) Il 11 O O
in which A is a tetravalent organic radical and R10 is 3 divalent organic radical.
In the homopolyimides and copolyimides, R and R1U
are, ;n particular, aromatic organic radicals. Particularly preferred copolyimides are those which contain at least 60 mol %~ preferably 80 mol %, of structural elements of the formula I.
A radical A in formula II which is not a benzophenone radical can be selected from the following groups: aromatic, aliphatic, cycloaliphatic and heterocyclic groups, and com-binations of aromatic and aliphatic groups. The groups can also be substituted. The groups A can have the following structures:

~2~75~3 11 ll ll - ~--~ 3 /-=-\--'.=.' '.=.' ,!, ~!, ,1 ' CH \CH

11 1 15 il X X. \._./ and \.--/
X X ' / \./ \ / \0/ \

in l,~hich R15 iS chosen from the group cons;sting of ll lRl6 1l l 16 -O-, -S-, -S02-, -C-N-, -C-O-, -N-, -Si-, lRl6 l 16 lRl6 -O-S i-O-, -P-, -0-~-0-, -N=N-, -N=N-, 11 ll R17 0 0 o ~2~ S~

0 H Rll6 l16 -C-N-, 2 ' -C~2CH2-, -CH-, -C-phenylene and -O-~Rd-~b, in which b is 1-10 and Rd is alkylene, cycloalkylene, arylene or aralkylene, and in which R16 and R17 are alkyl with preferably 1 to 6 C atoms or aryl, in particular phenyl. Of the free bonds in the above formulae, two are always on vicinal C atoms.
Examples of suitable tetracarboxylic acid anhydrides or esters thereof with a tetravalent radical A are: 2,3,9~10-perylenetetracarboxylic ac;d d;anhydr;de, 1,4,5,8-naphthalene-tetracarboxyl;c ac;d dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,7-dichloronaphtha-lene-1,4,5,8-tetracarboxyl;c acid dianhydr;de, 2,3,6,7-tetra-chloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, phenanthrene-1,8,9,10-tetracarboxylic acid d;anhydr;de, pyro-mell;t;c acid dianhydr;de, 3,3',4,4'-b;phenyltetracarboxyl;c ac;d d;anhydr;de, 2,2',3,3'-biphenyltetracarboxylic acid di-anhydride, 4,4'-isopropylidenediphthalic anhydride, 3,3'-isopropylidened;phthalic anhydride, 4,4'-oxydiphthalic anhydride, 4,4l-sulfonyldiphthalic anhydride, 3,3'-oxydi-phthal;c anhydr;de, 4,4'-methylened;phthal;c anhydride~ 4,4'-th;odiphthalic anhydride, 4,4'-ethylidenediphthal;c anhydride, 2~3,6,7-naphthalenetetracarboxylic acid d;anhydr;de, 1,2,4,5-naphthalenetetracarboxyl;c acid d;anhydr;de, 1,2,5,6-naphtha-lenetetracarboxyl;c acid d;anhydridef benzene-1,2,3,4-tetra-carboxylic acid dianhydr;de, thiophene-2,3,4,5-tetracarboxy-lic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-1,3,3-tri-methylindane-5,6-d;carboxylic acid dianhydride, 1 (3',4'-dicarboxyphenyl)-1,3,3-trimethylindane-6,7-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methylindane-5,6-dicarboxylic ac;d d;anhydride, tetrahydrofurantetracarboxyl;c ac;d dianhydride, cyciopentanetetracarboxylic acid dianhydride, cyclooctanetetracarboxylic acid dianhydride and 1-(3',4'-di-carboxyphenyl)-3-methylindane-6,7-dicarboxylic acid dianhyd-~2~ 59 ride and dianhydrides of the general formula 1 o Il ~ \ 11 o/ ~C .-Y2~ \o O ~ H-o in which Y1, Y2, Y3 and Y4 are each selected from hydrogen and alkyl, in particular methyl.
The most preferred aromatic dianhydrides which do not contain benzophenone radicals are pyromellitlc dianhydride and aromatic dianhydrides which have the general formula R. ~ 5\ ~-, R
O~ i O
o in which R15 is methylene, oxygen, sulfonyl or The group R10 defined above can be selected from alkylene groups with 2 to 20 carbon atoms, cycloalkylene groups with 4 to 6 ring carbon atoms, a xylylene group, arylene groups selected from meta- or para-phenylene, tolyl-ene, biphenylene, naphthylene and anthrylene, and an unsub-stituted or substituted arylene group of the formula R18~ ~Rlg = 9 in which W is a covalent bond, sulfur, carbonyl, -NHr -N-alkyl, 0, S, SS, -N-phenyl~ sulfonyl, a linear or branched alkylene group with 1 to 3 carbon atoms, alkylidene with Z

5~

- zo -to 12 C atoms, cycloalkylidene with 5 or 6 ring carbon atoms, arylene, in particular the phenylene group, or a dialkyl- or diaryl-silyl group and R18 and R19 independently of one another are each hydrogen, halogen, in particular chlorine or bromine, alkyl with 1 to 5 carbon atoms, in particular methyl, alkoxy with 1 to 5 carbon atoms, in particular meth-oxy, or aryl, in particular phenyl.
R10 more preferably is a group derived from one of the aromatic diam;nes which have been described above. R10 is most preferably a group of the formula 18\.~ ./ l9 - W --~

;n which ~J ;s a covalent bond, methylene, sul-fur, oxygen or sulfone and R18 and R19 independently of one another are hydrogen, halogen or alkyl with 1 to 5 carbon atoms, in par-ticular methy~, or a group of the formula ~ 21/ \ ~

in which R21 is hydrogen, halogen or alkyl with 1 to 5 carbon atoms, in particular methyl.
R10 is particularly preferably meta- or para-phenylene or a radical of the formula - W -~

in which W is a covalent bond, methylene, 2,2-propylidene, cyclohexylidene, sulfur, oxygen or sulfone.
Examples of diamines with a divalent radical R10 are:
4,4'-methylenebis-~o-chloroaniline)~ 3,3'-dichlorobenzidine,

3,3'-sulfonyldianiline, 4,4'-diaminobenzophenone, 1,5-di-aminonaphthalene, bis-(4-aminophenyl~-dimethylsilane, bis-(4-~f~s~

aminophenyl)-diethylsilane, bis-(4-aminophenyl~-diphenyl-silane, bis-(4-aminophenyloxy)-dimethylsilane, bis-(4-amino-phenyl)-ethylphosphine oxide, N-~bis-(4-aminophenyl)]-N-methyLamine, N-[bis-(4-aminophenyl)]-N-phenylamine, 4,4'-methylenebis-(3-methylaniline), 4,4'-methylenebis-(2-ethyl-aniline), 4,4'-methylenebis-(2-methoxyaniline), 5,5'-methyl-enebis-(2-aminophenol), 4,4'-methylenebis-(2-methylaniline),

4,4'-oxybis-~2-methoxyaniline), 4,4'-oxybis-(2-chloroaniline),

5,5'-oxybis-(2-aminophenol), 4,4'-thiobis (2-methy!aniline), 4,4'-thiobis-(2-methoxyaniline), 4,4'-thiobis-(2-chloroanil-ine), 4,4'-sulfonylbis-(2-methylaniline), 4,4'-sulfonylbis-(2-ethoxyaniline), 4,4'-sulfonylbis-(2-chloroaniline), 5,5'-sulfonylbis-(2-aminophenol), 3,3'-dimethyl-4,4'-diaminobenzo-phenone, 3,3'-dimethoxy-4,4'-diaminobenzophenone, 3,3'-di-chloro-4,4'-diaminobenzophenone, 4,4'-diaminobiphenyl, m-phenylenediamine, p-phenylenediamine, 4,4'-methylenedianiline~
4,4'-oxydianiline, 4,4'-thiodianiline, 4,4'-sulfonyldianiline, 4,4'-isopropylidenedianiline, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-dicarboxybenzidine, diaminotoluene, 4,4'-methylene-bis-(3-carboxyaniline) and esters thereof.
The homopolyimides and copolyimides are prepared in the customary manner, by reaction of benzophenonetetracar-boxylic acid anhydride with diamines of the formula NH2RNH2r if appropriate together with other tetracarboxylic acid anhydrides of the formula O O
ll ll 0/ \~ \0 ll 11 O O

and/or othe-r diamines of the formula NH2R10NH2, and sub-sequent imide cyclisation under the action of carboxylic acid anhydrides and/or subsequent heating. In another known pro-cess, diisocyanates are reacted with tetracarboxylic acid di-anhydrides to give polyimides.

~25~i7S~

The other chosen homopolymers and copolymers are pre-pared starting from functional imide derivatives of benzo-phenonetetracarboxylic acid~ They can have the formula III

O O O\

~\C/ ~ R-Y ( 11 1 ) Il \ O ~ C

in which R and R' are as defined above, c is a number from 1 to about 500 and Y is a functional group. Examples of such funct;onal groups can be: r~HR22, OH, SH, O-acyl, COOR22, CON(R22)2, COCl, COBr, -O-CH2-CH-CH2, COO-CH2-CH-CH2, O O
r~R23-CH2-CH-CH2 and halogen, in part;cular Cl and Br.

R22 ;s a hydrogen atom or a hydrocarbon radical~ which may or may not be hydroxylated, for example alkyl or hydroxyalkyl with preferably 1-20, in particular 1-12, C atoms, aralkyl w;th preferably 7-20, in particular 7-16, C atoms, aryl with preferably 6-20, in part;cular 6-16, C atoms or cycloalkyl with preferably 5-7 ring C atoms. R23 can have the same meaning as R22 or can be -CH2CH-CH2 n The acyl group can o contain 1 to 20, preferably 1-120 C atoms~
The compounds of the formula III in wh;ch c ;s 1 are known ;n some cases from German Offenlegungsschrift 3,007,4~5 or they can be prepared by analogous processes. Further functional groups, for example the glyc;dyl group, are intro-duced by customary processes.
The compounds of the formula III in which c >1 are novel and the invention l;kewise relates to these compounds.
These are oligomeric and low-molecular polyimides with func-tional end groups. They are obtained by processes analogous to those for poly;mides, the size of c being determined by ~s~q~

the amount of monomers of the formula Y-R-NH2 also used.
Block polymers with polyimide blocks and, for example, poly-amide, polyester or other polyimide blocks are obtained, for example, with these ol;gomers and low-molecular polymers.
A further preferred group of polymers for the mater-ial according to the invention are polyamides or copolyamides of organic d;am;nes, d;carboxylic acids, ~taminocarboxylic acids and diamines or dicarboxylic acids with structural ele-ments of the formula I, in which q ;s 1 and ;n which amine groups or carboxyl groups are bonded to the R and R' groups, and mixtures of the monomers.
The homopolymers can be those in which the molecular chains are built up from d;carboxylic ac;ds and diamines with structural elements of the formula I, or those in which the molecular chains are built up from dicarboxylic acids or di-am`ines with structural elements of the formula I and organic d;amines or dicarboxylic acids, which contain no benzophenone radicals. The copolyamides contain other diamine or dicar-boxylic acid radicals or aminocarboxylic acid radicals.
Examples of suitable dicarboxylic acids are linear or branched aliphatic dicarboxylic acids with preferably 2 to 20, in particular 4 to 16, C atoms, cycloaliphatic dicarboxy-lic acids which have 5 to 7 ring C atoms and are unsubstitu-ted or, ;n particular, substituted by alkyl, and aromatic di-carboxyl;c acids which preferably have 8 to 22 C atoms and are unsubstituted or substituted, for example by alkyL, Cl or bromine. Examples are: malonic acid, ad;p;c acid, tri-methylad;pic acid, p;melic acid, suberic acid, azelaic acid, dodecanedicarboxylic acid, the cyclohexanedicarboxyl;c acids, isophthalic acid, terephthalic acid, p-diphenyldicarboxylic acid, bis-(4-carboxyphenyl) ether and bis-(4-carboxyphenyl) sulfone.
Examples of su;table diamines are linear or branched aliphatic diamines with preferably 2 to 30, in particular 4 to 20, C atoms, cycloaliphatic diamines which have preferably 5 to 7 ring C atoms and are unsubstituted or substituted by alkyl, in particular methyl, araliphatic diamines with prefer-~25~7'S9 ably 7 to 24 C atoms and aromatic diamines with 6 to 22,preferably 6 to 18, C atoms, which can be unsubstituted or, in particular, substituted by alkyl. Examples are: ethylene-diamine, propylenediamine, 1,3- or 1,4-butylenediamine, pen-tylenediamine, 1,6-hexylenediamine, octylenediamine, decylene-diamine, dodecylened;amine, 1,10-alkyl-substituted 1,10-decylenediamines, for example 1,10-dimethyl-1,10-decylenedi-amine or 1,10-di-n-hexyl-1,10-decylenediamine, xylylenedi-amine, isophoronediam;ne, 1,3- or 1,4-cyclohexanediamine, 1,3- or 1,4-phenylenediamine, methylphenylene-diamine, toluylenediamine, p-biphenylenediamine, bis-~p-aminophenyl) ether, bis-tp-aminophenyl) sulfone and bis-(p-aminophenyl)-methane.
The aminocarboxylic acids can be aromatic, cycloali-phatic or aliphatic aminocarboxylic acids, for example amino-benzoic acid, aminocyclohexanecarboxylic acid and ~-amino-carboxylic acids, such as ~-aminocaproic acid or 11-aminoun-decanoic acid.
A further preferred group of polymers for the mater-ial according to the invention are polyesters or copolyesters of organ;c diols, dicarboxylic acids, hydroxycarboxylic acids and diols or dicarboxylic acids with structural elements of the formula I ;n wh;ch q is 1 and in which hydroxyl or car-boxyl groups are bonded to the R and R' groups, and mixtures of the monomers.
The homopolyesters can be those in which the mole-cular chains are built up from diols and dicarboxylic acids of the formula III, or those in which the molecular chains are built up from dicarboxylic acids or d;ols of the formula III and organ;c diols or dicarboxylic acids containing no benzophenone radicals. The copolyesters contain other rad;-cals of dicarboxylic ac;ds~ diols and/or hydroxycarboxylic acids.
Suitable d;carboxylic acids have been mentioned above~
Polyesters based on aromatic dicarboxylic acids, in particu-lar terephthalic ac;d andtor isophthalic acid, are preferred~
Suitable diols are cycloaliohatic diols, such as 1,4-cyclo-~ .

3L2S675~

hexanediolr aromatic diols, such as bisphenol A, and, in particular, unsubstituted or substituted aliphatic diols, such as branched and, in particular, lirlear alkylenediols with, for example, 2 to 12, preferably 2 to 6, C atoms, as well as 1,4-bis-hydroxymethylcyclohexane and neopentylglycol hydroxypivalate. Ethylene glycol, trimethylene glycol, tetramethylene glycol and hexamethylene glycol are particu-larly preferred. Examples of suitable hydroxycarboxylic ac;ds are m- or p-hydroxybenzoic acid and aliphatic ~-hydroxy-carboxylic acids, for example ~-hydroxyvaleric acid, hydroxy-pivalic acid and ~-caprolactone.
In another preferred embodiment, the polymers for the material according to the invention are polyamide-imides or polyester-imides. Such polymers can be obtained by incor-poration of tricarboxylic acids of the formula IV or polymer-forming derivatives thereof, such as the ester, anhydride or acid halide:
HOOC
~D-COOH
HOOC I V

The trivalent radical can be a hydrocarbon radical which preferably has 6 to 16 C atoms and in which two car-boxyl groups are bonded to two ad~acent C atoms. Trimellitic acid is preferred.
The polyamide-imides can be built up only from di-amines of the formula III and tricarboxylic acids of the formula IV. Copolymers are obtained if dicarboxylic acids andlor diamines, for example those which have been mentioned above for the polyamides~ are additionally also used in the preparation of the polyamide~imides, including those of the formula III .
Polyester-imides can be obtained if an am;nocarboxy~
lic ac;d or an aminoalcohol is first reacted with tricarboxy-lic acids of the formula IV to give dicarboxylic acids or hydroxycarboxylic ac;ds, and these are then further subjected to a polycondensation reaction with diols and/or dicarboxylic acids of the -formula III to give polyesters. Other dicar-boxylic acids and/or diols can also additionally be used here for the preparation of copolymers.
Furthermore, polyester-am;des are also preferred.
These polymers are obtained when dicarboxylic acids of the formula III and/or other dicarboxylic acids are subjected to a polycondensation reaction with diols of the formula III
and/or other diols and diamines of the formula III and/or other diamines, the individual monomers having already been mentioned above.
The N atoms of the amide groups in the polymers men-tioned above can be substituted by alkyl with preferably 1 to 6 C atoms, aryl, for example phenyl, aralkyl, for example benzyl, or cycloalkyl, for example cyclohexyl.
Examples of other suitable polymers for the coated material according to the invention are:
a) Polysiloxanes of diols of the formula III and, if appropriate, other diols, and silanes of the formula (R24)2SiB2, in which R2~ is preferably alkyl with 1 to

6 C atoms, in particular methyl, or cycloalkyl, in particular phenyl, and B is Br or, in particular, Cl, or alkoxy or aryl-oxy with preferably 1 to 6 C atoms, in particular methoxy or phenoxy~ These polymers can thus contain structural elements of the formula R24 lR24 1 -Si-o-E-O- and, if appropriate, of the formula -Si-o-E'-o in which E is the radical of the formula I in which q is 1, and E' ;s the divalent radical of a diol. Suitable diols HOE'OH
have already been mentioned above. These polymers can also additionally contain blocks with structural elements of the formula --Sio--~L~5~;7~5~

it being possible for these blocks to amount to up to 50 mol ~, based on the polymer.
b) Unsaturated polyesters of unsaturated dicarboxylic acids, in part;cular male;c acid, and diols of the formula I
(HOEOH) and, if appropriate, other dicarboxylic acids, also of the formula I, and other diols HOE'OH. Suitable dicar-boxylic acids have already been mentioned above. These polymers can thus contain structural elements of the formula O O
-C-E"-C~OEO- in which E'l is the divalent radical of an ethylenically unsaturated dicarboxyl;c acid. Other struc-tural elements which the polyesters can contain are O o O O o Il 1I 1l 11 and 1I 1l -C-E"'-C-OEO-, -C-E"'-C-OE'O- -C-E"-C-OE'O, in wh;ch E"' is the d;valent rad;cal of a dicarboxylic acid of the formula I or of another dicarboxylic acid~
These polymers can additionally be polymerised by heat in the presence of customary polymerisation catalysts as a result of the presence of the ethylenically unsaturated groups, reactive diluents, such as styrene, also being pre-sent, if appropriate.
c) Suitable epoxy resins can be obtained in various ways. Thus, the epoxide compounds of the formula III can be reacted catalytically, for example with tertiary amines, by themselves or together with other polyepoxide compounds with more than one epoxide group in the molecule, to give poly-ethers, or they can be reacted with the customary hardeners, such as polyols, polycarboxylic acids and anhydrides thereof, or polyamines. The diamines~ diols and dicarboxylic acids of the formula III can also be used as hardeners, in which case it is then also possible to use only customary polyepoxide compounds without benzophenonetetracarboxylic acid radicalsu The epoxy res;ns can be used as prepolymers wh;ch can be hardened by heat after the irradiation.
d) Aromatic polyethers can be obtained, for example, by ~2~6~

reacting compounds of the formula III in which Y is OH or halogen, in particular Br or Cl, and R and R' are aromatic radicals, with phenyl-aromatic dichlorides or bromides or diols. Examples of suitable halides and diols are mono-nuclear or dinuclear phenyl-aromatic derivatives, such as hydroguinone, p-dichloro- or p-dibromo-phenylene, p-dihydroxy-phenylene, p-dichloro- or p-dibromo-diphenylene, bis-(p-hydroxyphenyl) ether and bis-(p-chlorophenyl) ether.
The phenyl-aromatic radicals can contain further sub-stituents, for example alkyl with preferably 1 to 4 C atoms.
If dinuclear phenyl-aromatic radicals in wh;ch the phenyl groups are bonded to a sulfone group are used, polyether-sulfones are obtained. Examples of such derivatives are bis-(p-chlorophenyl) sulfone and bis-tp-hydroxyphenyl) sulfone.
Polyethers containing only structural elements of the formula I are obtained from compounds of the formula III in which Y
is OH and compounds of the formula III ;n which Y ;s halogen.
e) Aromatic polyketones can be obtained by react;ng aromatic compounds of the formula III in which Y is H with aromat;c acid halides of the formula III in which Y is an ac;d halide group, in particular an acid chloride group, in the presence of Lew;s acids. Other aromatic, in particular phenyl-aromatic, compounds and/or aromatic, in particular phenyl-aromatic, dicarboxylic acid dihalides can additionally also be used. The aromatic compounds are preferably mono-nuclear or dinuclear phenyl-aromatics or dicarboxyl;c acid dihalide derivatives thereof. Examples are benzene, toluene, diphenyl, diphenylmethane, diphenyl ketone, diphenyl sulfone, diphenyl ether, terephthaloyl dichloride and 4,4'-chlorocar-bonyl-diphenyl, -diphenylmethane, -diphenyl ether or -diphenyl sulfone. If the ether derivatives are used, poly-ether-ketones are obtained. The aromatic hydrocarbons and dicarboxylic acid d;hal;des can be subst;tuted, for example by alkyl with 1 to 4 C atoms.
f) Aromatic polythioethers can be obtained, for example, by reacting aromatic compounds of the formula III in which Y
is halogen, such as Cl or, in particular, Br, with di-alkali ~L25~;7S~

metal sulfides, for example Na2S. Other aro~atic, in par-ticular phenyl-aromatic, dihalogen compounds, preferably chlorides or, in particular, bromides, can also additionally be used. Aromatic polysulfides can also be obtained by reacting aromatic compounds of the formula III in which Y is SH by themselves or together with other dimercaptans, in particular phenyl-aromatic dimercaptans, or, in particular, alkali metal salts thereof, for example the sodium salts, with compounds of the formula III in which Y is halogen, in particular Br, and/or other dihalides, in particular phenyl-aromatic dihalides, for example bromides~ Such halides have already been mentioned above. Examples of suitable aromatic dimercaptans are 1,4-phenylenedimercaptan and p-biphenylene-dimercaptan.
~) Examples of other suitable polymers are those which can be obtained by reacting compounds of the formula III in which Y is OH, NH2 or COOH with diisocyanates or diepoxides.
h) Another group of suitable polymers are aromatic poly-imidazoles. They can be obtained by reacting esters of the formula III, by themselves or together with other aromatic dicarboxylic acid diesters, and aromatic tetramines, for example 3,3',4,4'-tetraaminobiphenyl, to give polyamide intermediates, which are then subjec-ted to a condensation reaction by heating to give the polyimidazoles.
i) A further group of suitable polymers are aromatic polypyrrones. They can be obtained, for example, by reacting tetracarboxylic acid anhydrides of the formula V

C O O O O O
/ 11 11 11~ 11 11 11 //C\ ~-\ /C\ ;,~-\ /C\ ~C\ ~-\ /C\ ,~\ /C
R-N~ , 11 ~ 11 11 O ~d o in which R is as defined above and d is a number from 1 to 500, with aromatic tetramines, for example 3,3l,4,4'-tetra-aminodiphenyl. In this reaction, soluble intermediates are ~s~

first formed, and are subjected to a polycondensation reac-tion by heating to give polypyrrones. The compounds of the formula V can be obtained by reacting an excess of benzophen-onetetracarboxylic acid dianhydride with diamines of the formula H2NRNH2. These compounds can also be used, for example~ for the preparation of polyimides.
To produce the coated material according to the in-vention or for use in the process according to the invention, the polymer or a mixture of the polymers is advantageously dissolved in a suitable organ;c solvent, if appropriate with warming. Examples of suitable solvents are polar, aprotic solvents, which can be used by themselves or in mixtures of at least two solvents. Examples are: ethers, such as dibutyl ether, tetrahydrofuran, dioxane, methylene glycol, dimethyl-ethylene glycol, dimethyldiethylene glycol, diethyldiethylene glycol and dimethyltriethylene glycol, halogenated hydrocar-bons, such as methylene chloride, chloroform, 1,2-dichloro-ethane, 1,1,1-trichloroethane and 1,1,2,2 tetrachloroethane, carboxylic acid esters and lactones, such as ethyl acetate, methyl propionate, ethyl benzoate, 2-methoxyethyl acetate, r-butyrolactone, o-valerolactone and pivalolactone, carboxylic acid amides and lactams, such as formamide, acetamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacet-amide, ~-butyrolactam, ~-caprolactam, N-methylpyrrolidone, N-acetylpyrrolidone, N-methylcaprolactam, tetramethylurea and hexamethylphosphoric acid amide, sulfoxides, such as dimethyl-sulfoxide, sulfones, such as dimethyl sulfone, diethyl sul-fone, trimethylene sulfone and tetramethylene sulfone, tri methylamine, triethylamine, N-methylpyrrolidine, N-methyl-piperidine, N-methylmorpholine and substituted benzenes, such as chlorobenzene, nitrobenzene, phenols or cresol. In the case of insoluble polymers, it is possible to use soluble intermediates, which are then irradiated, after the coating operation, and subsequently converted into the polymers by heating.

~2~;S75~

Undissolved constituents can be removed by filtra-tion, preferably pressure filtration. The concentratjon of polymer in the coating agent thus obtained is preferably not more than 50% by weight, in particular not more than 30% by weight and especially not more than 20~ by weight, based on the solution. Coating agents containing polymers with struc-tural elements of the formula I in which R and also R' are aromatic radicals or araliphatic radicals substituted as de-fined are novel and the invention likewise relates to these coating agents.
Other` customary addit;ves which do not adversely affect the photosensitivity can be incorporated during the preparation of the solutions. Examples of these additives are delustering agents, flow control agents, fine-particled fillers, flameproofing agents, fluorescent brighteners, anti-oxidants, light stabilisers, stabilisers, dyes, pigments and adhesion promoters. Furthermore, if desired, sensitisers, for example thioxanthone derivatives or benzophenone deriva-tives, can also additionally be incorporated, in order to increase the photosensitivity still further, as well as anti-halo dyes, for example those described in U.S. Patent Speci-fication 4,349,619.
The coating agent can be applied to suitable sub-strates or carrier materials by means of customary methods, such as dipping, brushing and spraying processes and wh;rler coat;ng, cascade coating and curtain coating.
Examples of suitable substrates are plastics, metals and metal alloys, semimetals, semiconductors, glass~ ceramics and other ;norganic materials, for example SiO2 and Si3N4.
After coating, the solvent is removed~ if necessary by warm-ing and if necessary in vacuo. Non-tacky, dry, uniform films are obtained. The films applied can have coating thicknesses of up to about 500 ~m or more, preferably of 0~5 to 500 ,um and in particular of 1 to 50 lum, depending on their use.
The radiation-sensitive coating in the material according to the invention can be crosslinked by the action of radiation.

~5~7~

The photostructuring or photocrosslinking can be caused by high-energy radiation, for example by light, in particular in the UV range, by X-rays, laser light, electron beams and the like. The material according to the invention is outstandingly suitable for producing protective films and passivating lacquers and as a photographic recording material for heat-stable relief images.
The invention also relates to this use. Examples of fields of use are protective, insulating and passivating lacquers in electrotechnology and electronics, photomasks for electronics, textile printing and the graphics industry, etch resists for the production of printed circuits and printing plates and integrated circuits, relays for the production of X-ray masks, solder-stopping lacquers, dielectrics for multi-layer circuits and structural elements for liquid crystal displays.
Protective films are produced by direct exposure, the exposure times essent;ally depending on the coat~ng thick-nesses and the photosensitivity.
Photographic production of the relief structure is effected by image-wise exposure through a photomask, and subsequent development with a solvent or a solvent mixture, the non-exposed portions be;ng removed, after which the image produced can be stabilised, if appropriate, by after-treat-ment with heat.
The invention furthermore relates to such a process for the application of relief structures. Suitable developers are, for example, the abovementioned solvents.
The polymer layer of the material to be used accord-ing to the invention has a photosensitivity which is suffi-cient for many intended uses and in some cases is high, and it can be photocrosslinked directly. The protective films and relief images, especially those oF polyimide coatings, are distinguished by a good adhesion and a high heat resis-tance, mechanical strength and resistance to chemicals. Only a slight shrinkage is observed on after-treatment with heat.
Furthermore, additives to produce or increase the photosen-~25~7~

sitivity can be avoided. The material is stable on storagebut should be protected from the effect of light.
The examples which follow illustrate the invention in more detail.
A) Preparation of the starting substance_ Example 1: 27.28 9 (0.12 mol) of 4,4'-diamino-3,3'~dimethyl-diphenylmethane are dissolved in 370 g of N-methylpyrrolidone (NMP) under nitrogen in a cylindrical vessel equipped with a stirrer, dropping funnel, internal thermometer and nitrogen inlet tube, and the solut;on is cooled to 0 to 5C. 39.43 9 (0.1225 mol) of benzophenonetetracarboxylic acid dianhydride (BTDA) are now prepared, and are added in portions in the course of 4 hours. 30 minutes after the last addition, 48.48 g (0.48 mol) of triethylamine and 11û.1 g (1.08 mol) of acetic anhydride are added dropwise in order to cyclise the resulting polyamide acid to the polyimide. After the solution has been stirred at room temperature for 16 hours, it is poured onto 6 litres of water, with vigorous stirring, and the product which has precipitated out is filtered off.
The product is again treated with 6 litres of water and fil-tered off, and is dried at 8ûC in vacuo. The intrinsic viscosity, measured as a 0.5% strength solut;on in NMP at 25C, is 0.97 dl/g. The glass transition temperature (Tg), measured by differential scanning calometry (DSC) is 285C.
Example 2: The procedure followed is as in Example 1, but a mixture of 66.7 mol % of BTDA and 33~3 mol % of pyromellitic dianhydride (PMDA) is used. Properties of the resulting co-polyimide:
~ = 0.93 dl/g Tg = 304C.
Example 3_ An industrial mixture of 3,3'-diethyl-4,4'-di-aminodiphenylmethane, 3-ethyl-4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenylmethane is reacted with a stoichiometric amount of BTDA and the product is cyclised to the polyimide, as described in Example 1.
r~ = 1.ûO dl/g Tg = 263C

~LZ567~

Examp e 4: Example 3 ;s repeated with a mixture of 50 mol %
of sTDA and 50 mol X of PMDA. The result;ng copolyimide has the following properties:
hv = 0.87 dl/g Tg = 288C.
Example 5: A solution of 4.02 g of diamine mixture according to Example 3 in NMP as the solvent is subjected to a conden-sation reaction with 3.78 9 of BTDA ~molar ratio of diamine mixture to BTDA = 3:2) in a condensation apparatus as des-cribed in Example 1 to give a polyamide acid block with amino end groups. The solution is then cooled to -15C and 3.5717 9 of ;sophthaloyl dichloride are subsequently first added, followed by 2.6791 9 of diamine mixture tmolar ratio of iso-phthaloyl dichloride: diamine mixture = 3:2). By removing the cooling, the temperature gradually rises to room temperature.
After 5 hours, 3 ml of propylene oxide are added, and after another half an hour, 6.51 9 of triethylamine and 26.6 g of acetic anhydride are added. The mixture is stirred overnight and the block copolyamide is precipitated the following day by stirring the mixture into water. Properties:
= 0.82 dl/g Tg = 221C
Example 6: A mixture of 4,4'-diaminodiphenylmethane and 2,4-diaminotoluene (molar ratio 19.7:80.3) is subjected to a polycondensation reaction with the equivalent amount of BTDA
as described in Example 1. Properties of the polyimide:
= 0.43 dl/g Tg = 309C.
Example 7: A mixture of 2,4-diaminotoluene and 5(6)-amino-1-(4-aminophenyl)-1,3,3-trimethylindan`e (molar ratio 54.4:
45.6) is subjected to a polycondensation react;on w;th an equivalent amount of BTDA as described ;n Example 1. Proper-ties of the copolyimide:
~ = 0.42 dl/g Tg = 309C.
Exameles 8 and 9: Polyimides are prepared by polycondensa-tion of BTDA w;th an equ;valent amount of 2-am;no-6-methyl-.

6-(4-aminophenyl)-heptane or 2-amino-6-methyl-6-t3-ethyl~4~
aminopheny l)heptane in a manner similar to that described in Example 1. Properties of the polyimides:
~ = 0.34 and 0.23 dl/g Tg = 177C and 170C.
Example 10: A mixture of 13.21 9 (0.038 mol) of 1,10-di-amino-1,10-di-n-hexyldecane and 13.34 g of BTDA (0.038 mol) in 100 ml of o-dichlorobenzene is stirred under nitrogen for 30 minutes in a sulfonat;on flask with a stirrer, internal thermometer, nitrogen inlet tube and water separator. The m;xture is then heated slowly to the reflux temperature (175C),. a clear light yellow solution being for~ed. The water of condensation is distilled off together w;th the o-dichlorobenzene in the course of 90 minutes, and is removed in the water separator.
A sample is isolated for analytical purposes by stirring a portion of the cooled solution into hexane, filter-ing off the product and drying it. Properties of the poly-imide:
~ = 0.36 dltg Tg = 63C
Examples 11-20: The following diamines are subjected to a polycondensation reaction with BTDA to give polyimides as described in Example 1, and the stated properties of the polymers are determined.

~%~

Examp~e Diamine 72 (dl/g) Tg(C) ... ___ ~ \ ~

. 11 ~H2N~ C 2 0, 75 2 6 4 ~ CH~ . __ 12 ~ CH2 1 ~ 08 2 65 __ ~ --- -- -I
13 . _ . 0 ~ 75 251 _ __ . ..

14 (2N-(CH2)3-~o 0.239 76 (~2n-(CH2)3-~i~o 30 ~

2 0. 674 266 H N~/ \-~ -NH
__ .. _ __ , . _ _ ._ ...

1;~5~7S9 Exampl,e~ Dlanin; i'l/~ Tg(C) ¦ 16 ¦ 2 ( N ~3 ~ i l 7 ~ CN2) -NH2 0~167 ¦ 120 3 ~ U3~
0~/ ~ 0 0,248 146 ¦ 18 l ~- 5CH2cH2 . ~2 \ / ~ CH2 20 Mol%
.

0~115 197 * Conversion on cyclisation with acetic anhydride in ethyl acetate ~2S6~5~3 - 3~ -Example 21: (Polyimide from isocyanate and anhydride) 0.7905 g (0.0021 mol) of N,N'-di-(3-isocyanato-4-methyl)-phenyl-parabanic acid and 1~4633 9 (0.0084 mol) of toluene 2,4-diisocyanate in dimethylsulfoxide (23 ml) are initially introduced into a reaction vessel with a stirrer, reflux condenser and gas inlet tube at room temperature under N2, and 3.386 g (0.0105 mol) of ben~ophenonetetracarboxy-lic acid d;anhydride are added. The mixture is warmed to 90C and kept at this temperature for 24 hours. After cooling, the solution is stirred into water and the polymer ;s prec;p;tated.
h = 0.228 dl/g Tg = 349C.
Example 22: (Poly;m;de/polyester-amide) 1.5 g ~7.39 mmol) of ;sophthaloyl d;chloride are dis-solved ;n 38 ml of N-methylpyrrolidone (NMP) ;n a reaction vessel and the solution is cooled to -15C. 0.537 g (4.92 mmol) of m-aminophenol and 1.4 ml of triethylamine are then added. After 30 minutes, 2.832 g (17.2 mmol) of 3,6-diamino durene and 0.65 ml of triethylam;ne are added. By removing the cooling bath~ the temperature is allowed to rise to 0C, and 4.76 9 (14.78 mmol) of BTDA are added~ After the mixture has been stirred at room temperature for 8 hours, the poly-amide acid is cyclised to the polyimide over a period of 16 hours by addition of 4.5 ml of triethylamine and 12.6 ml of ace~ic anhydride, and the polyimide is worked up in the cus-tomary manner.
~ = n.38 dl/g.
Example 23: (Polyimide/polycarbonate) The following components are reacted with one another in the following sequence under the same conditions as in Example 26: 0.008 mol of phosgene, 0.0053 mol of bisphenol A, 0.01866 mol of mesitylenediamine and 0.016 mol of BTDA.
= 0.16 dl/g Tg ~ 261C
Example 24: (Polyimide/polyamide-imide)

7.5 mmol of 4,4'-diamino-3,5,3',5'-tetraethyldiphenyl-~2~q~9 methane and 2.5 mmol of 4,4'-diaminodiphenylmethane are dis-solved in 25 ml of NMP, and the solution is cooled to -15C
and reacted with 2.5 mmol of trimellitic anhydride chloride in the presence of 0.4 ml of triethylamine. The prepolymer thereby formed is then further reacted with 7.5 mmol of BTDA
and the product is subsequently cyclised with triethylamine and acetic anhydride.
~ = 0.58 dl/g Tg = 257C.
Example 25: (Polyimide-ester) 20 mmol of 3-amino-6-hydroxydurene are reacted with 0.01 mol of BTDA in 34.5 ml of NMP at 0C. 0.01 mol of isophthaloyl dichloride and 6.1 ml of triethylamine are then added at -15C~ After 15 minutes, the cooling is removed and stirring is continued at room temperature for 8 hours.
The cyclisation is effected with acetic anhydride.
~ = 0.09 dl/g Tg = 127C.
Example 26- (Polyimide/polyphenylene sulfide) 1.6458 9 of 3,6-diaminodurene and 0.9333 g of a poly-phenylene sulfide with amino end groups Cprepared according to Polymer Bulletin 4, 459-466 (1981)] are reacted with 3.4313 9 of BTDA in 24 ml of NMP at 0 to 25C for 24 hours and the product is then cyclised with triethylamine and acetic anhydride.
~ ~ 0.576 dl/g Tg = 411C.
Example 27 (Polyimide/polyether-sulfone) .
The polyether-sulfone with amino end groups used for this is prepared by condensation of 4,4'-dichlorodiphenyl sulfone, bisphenol A and 4-chloronitrobenzene in the presence of potassium carbonate in dimethylformamide and subsequent reduction of the terminal nitro groups. In a manner similar to that in Example 26, 3.018 9 of 3,6-diamino durene and 1.796 9 of the polyether-sulfone are reacted with 6.231 9 of BTDA in 44 ml of NMP and the product is cyclised to the polyimide.

~:~S67~9 )~, = 0.516 Tg = 380C.
s) Use Examples A thin film of polymer is produced on a sheet of plastic, which is laminated with copper on one side, by centrifuging on a 5% polymer solution and then removing the solvent in a circulating air oven. The solvents used are acetophenone (polymers from Examples 1, 2 and 4), butyro-lactone ~Example 3), o-dichlorobenzene (Example 10, without isolation of the polymer) and N-methylpyrrolidone for the polymers of the remaining examples.
The sheets thus coated are exposed through a photo-mask (Stouffer wedge) at room temperature with a 1,000 watt UV lamp from a distance of 18 cm. The exposed sheets are then developed with a solvent, the non-exposed portions being dissolved away from the polymer film. The relief image is then rendered v;sible by etching away the exposed copper layer with FeCl3 solution.
The exposure time, the developer used and the photo-sensitivity are shown in the following table. MEK is methyl ethyl ketone and D~F is dimethylformamide.

~256'7~;9 Table ~ . . . _ ~
! Polymer Exposure Sensitivity i according to time Developer (Stouffer scale i Example tseconds) l . __ _ .__ ! 1 120 ~P 6-7 2 120 ~IP 5 3 100 ~P S
4 240 ~IP 4-5 300 ~IP 8 6 360 ~P 6 7 360 ~IP 3

8 120 ~lP~lEK (1:1) 6

9 120 ~MEK (1:1) 9

- 10 15 N~P 7

11 5 DMF 5

12 600 ~IP I 4-5

13 300 DMF ¦ 5-6

14 180 NMP I 4 500 X-ylene-/CHC13 (1:2) 4 17 600 Toluene./CHC13(9:1) 18 900 N~P

600 Toluene/NMP (3:10) ~3 360 ~nP 3 300 NMP 3~4 i 26 240 NMP 5-6 . . _ 120 ~IP 7 ._ _ . _ ._ ._._ ~

Claims (19)

WHAT IS CLAIMED IS:

1. A process for the production of a relief structure or a protective coating on a carrier, onto which is applied a coating of a radiation-sensitive polymer, wherein the poly-mer is a homopolymer or copolymer with at least 5 mol %, based on the polymer, of structural units of the formula I

(I) in which R is a divalent unsubstituted or substituted ali-phatic radical which can be interrupted by hetero-atoms or aromatic, heterocyclic or cycloaliphatic groups, an unsub-stituted or substituted cycloaliphatic or araliphatic radical, an aromatic radical in which two aryl nuclei are linked via an aliphatic group, or an aromatic radical which is substitu-ted by at least one alkyl, cycloalkyl, alkoxy, alkoxyalkyl, alkylthio, alkylthioalkyl, hydroxyalkyl, hydroxyalkoxy, hydroxyalkylthio or aralkyl group or in which two adjacent C
atoms of the aromatic radical are substituted by an alkylene group, R' independently has the same meaning as R and q is 0 or 1, an aromatic radical R not being substituted by alkylene or not being substituted by the abovementioned radicals in both ortho-positions relative to the N atom if q is 0, said process comprising the steps of i) imagewise or direct exposure of said coated material to high-energy radiation, and where required ii) removal of the unexposed portions by means of a developer.

2. A process according to claim 1, in which the homo-polymer or copolymer contains 5 to ,00 mol % of structural units of the formula I, based on the polymer.

3. A process according to claim 1, in which the substi-tuent on the aromatic radical contains 1 to 20 C atoms.

4. A process according to claim 3, in which the substi-tuent is alkyl, alkoxy or alkoxyalkyl with 1 to 6 C atoms, benzyl, trimethylene or tetramethylene.

5. A process according to claim 1, in which one or two substituents on the aromatic radical are bonded in the ortho-position relative to the N atom.

6. A process according to claim 1, in which an aliphatic radical R contains 2 to 30 C atoms, a cycloaliphatic radical R contains 5 to 8 ring C atoms, an araliphatic radical R con-tains 7 to 30 C atoms or a substituted aromatic radical R
contains 7 to 30 C atoms.

7. A process according to claim 1, in which an aliphatic radical R is linear or branched alkylene which can be inter-rupted by oxygen atoms, NH, NRa or , in which Ra is alkyl with 1 to 12 C atoms, cycloalkyl with 5 or 6 ring C
atoms, phenyl or benzyl and G? is the anion of a protic acid, or by cyclohexylene, naphthylene, phenylene or hydantoins, a cycloaliphatic radical R is monocyclic or bicyclic cycloal-kylene which has 5 to 7 ring C atoms and is unsubstituted or substituted by alkyl, an araliphatic radical R is aralkylene which is unsubstituted or substituted on the aryl by alkyl, it being possible for the alkylene radical to be linear or branched, or an aromatic radical R is a hydrocarbon radical or a pyridine radical, which is substituted by alkyl, alkoxy, alkoxyalkyl, trimethylene or tetramethylene.

8. A process according to claim 7, in which an aliphatic radical R is linear or branched alkylene with 6 to 30 C atoms, -(CH2)m-R1-(CH2)n-, in which R1 is phenylene, naphthylene, cyclopentylene or cyclohexylene and m and n independently of one another are the number 1, 2 or 3, , in which R2 is ethylene, 1,2-propylene, 1,3-propylene or 2-methyl-1,3-propylene, R3 is ethylene, 1,2-propylene, 1,2-butylene, 1,3-propylene or 1,4-butylene and p is a number from 1 to 100, or

9. A process according to claim 7, in which a cycloali-phatic radical R is a radical of the formula in which q is 0 or 1, the radicals R4 independently of one another are hydrogen or alkyl with 1 to 6 C atoms and X is a direct bond, 0, S, alkylene with 1 to 3 C atoms or alkylidene with 2 to 6 C atoms.

10. A process according to claim 7, wherein the arali-phatic radical has the formula in which the radicals R4 independently of one another are hydrogen atoms or alkyl with 1 to 6 C atoms and r is an integer from 1 to 16.

11. A process according to claim 7, in which the aro-matic radical has the formula in which, in the case of monosubstitution, one radical R4 is-alkyl with 1 to 6 C atoms and the other radicals R4 are hydrogen, and in the case of di-, tri- or tetra-substitution, two radicals R4 are alkyl with 1 to 6 C atoms and the other radicals R4 are hydrogen atoms or alkyl with 1 to 6 C atoms, or in the case of di-, tri- or tetra-substitution, two vicinal radicals R4 in the phenyl ring are trimethylene or tetramethylene and the other radicals R4 are hydrogen atoms or alkyl with 1 to 6 C atoms, Y is 0, S, NH, CO or CH2, R5 is a hydrogen atom or alkyl with 1 to 5 C atoms, R6 is alkyl with 1 to 5 C atoms and Z is a direct bond, O, S, SO, SO2, , CNR7, NR7, CONH, NH, R7SiR8, R7OSiOR8, alkylene with 1 to 6 C atoms, alkenylene or alkylidene with 2 to 6 C atoms, phenylene or phenyldioxy, in which R7 and R8 independently of one another are alkyl with 1 to 6 C
atoms or phenyl and j is 1-10.

12. A process accord1ng to claim 11, in which the aromatic radical is or in which Z is a direct bond, 0 or, in particular, CH2 and R9 is a hydrogen atom, methyl or ethyl.

13. A process according to claim 1, in which the homo-polymer or copolymer is selected from the group comprising polyimides, polyamides, saturated polyesters, polycarbonates, polyamide-imides, polyester-imides, polyester-amides, poly-siloxanes, unsaturated polyesters, epoxy resins, the aromatic polyethers, the aromatic polyether-ketones, the aromatic polyether-sulfones, the aromatic polyketones, the aromatic polythioethers and mixtures of these polymers.

14. A process according to claim 13, in which the poly-mer is a polyimide with recurring structural elements of the formula I in which q is 0 or a copolyimide of recurring structural elements of the formula I in which q is 0 and recurring structural elements of the formula II

(II) in which A is a tetravalent organic radical and R10 is a divalent organic radical.

15. A process for the preparation of a relief structure according to claim 1, said process comprising as additional step iii) a thermal aftertreatment to stabilise the produced image.

16. A coated material comprising a carrier onto which is applied a radiation-sensitive polymer said polymer containing at least 5 mol %, based on the polymer, of structural units of formula I according to claim 1 in which q is 1 and where-in said polymer is selected from the group comprising the polyamides, saturated polyesters, polycarbonates, polyamide-imides, polyester-imides, polyester-amides, polysiloxanes, unsaturated polyesters, epoxy resins, the aromatic polyethers, the aromatic polyether-ketones, the aromatic polyether-sulf-fones, the aromatic polyketones, the aromatic polythioethers and mixtures of these polymers.

17. A material according to claim 16 in which R and R' are aromatic radicals of the formulae in which Z is a direct bond, 0 or, in particular, CH2 and R9 is a hydrogen atom, methyl or ehtyl.

18. A material according to claim 16, in which the poly-mer is a polyamide or copolyamide of organic diamines, di-carboxylic acids, .omega.-aminocarboxylic acids and diamines or dicarboxylic acids with structural elements of the formula I

in which q is 1 and in which amine groups or carboxyl groups are bonded to the R and R' groups, and mixtures of the monomers.

19. A material according to claim 16, wherein the polymer is a polyester or copolyester of organic diols, dicarboxylic acids, hydroxycarboxylic acids and diols or dicarboxylic acids with structural elements of the formula I in which q is 1 and in which hydroxyl or carboxyl groups are bonded to the R and R' groups, and mixtures of the monomers.