JPH0511303B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical field] The present invention relates to a material in which a radiation-sensitive polymer is coated on a base material, in which the polymer contains a structural unit of benzophenone tetracarboxylic acid imide, and to such a material. for the phototechnical formation of relief patterns and protective coatings. BACKGROUND OF THE INVENTION Photographic imaging methods using line-sensitive polymers for the formation of various relief images have become important for the production of various devices in electronics and semiconductor engineering. For such photosensitive polymers, specific properties are desired depending on the purpose of use, and various polymers have become known for these properties. The photosensitivity of such polymers is relatively low, requiring the addition of various photoinitiators or sensitizers to obtain economical exposure times. A disadvantage of such additives is that they may reduce mechanical and physical properties. Furthermore, high temperature stability of the formed pattern image and the photochemically created protective coating is desired for certain applications. Particularly suitable for this are polyimides. Because of their insolubility, it is necessary to start from soluble pre-products, which, after photopolymerization, are converted into polyimides by heat treatment only. Conventionally, it has not been known to directly photocrosslink polyimides. From German Patent Application No. 3007445, polyamides and polyesters containing benzophenonetetracarboxylic imide units are known.
The physical and mechanical properties of fibers and films made of this substance can be improved by exposure to light. However, no mention is made of the formation of protective coatings or of photographic image formation methods. [Disclosure of the Invention] The object of the present invention is a material in which a radiation-sensitive polymer is coated on a base material, wherein the polymer has a structural unit of the following formula: [In the above formula, R is a substituted or unsubstituted divalent aliphatic group, a substituted or unsubstituted cyclic aliphatic group, which may be interrupted by a heteroatom, an aromatic group, a heterocyclic group, or a cycloaliphatic group. an aliphatic or araliphatic group, an aromatic group in which two aromatic nuclei are connected via one aliphatic group, or at least one alkyl group, cycloalkyl group, alkoxy group, alkoxyalkyl group , alkylthio group, alkylthioalkyl group, hydroxyalkyl group,
An aromatic group substituted by a hydroxyalkoxy group, a hydroxyalkylthio group, or an aralkyl group, or an aromatic group in which two adjacent carbon atoms of the aromatic group are substituted by one alkylene group. , R′ independently has the same meaning as R, and q represents a number of 0 or 1, in which case when R is an aromatic group, q is 0
is not substituted by an alkylene group, or is not substituted by the above-mentioned groups at both positions ortho to the N atom in the formula]
It is characterized by being a homopolymer or copolymer containing at least 5 mol% or more of the total amount of the polymer. DETAILED DESCRIPTION OF THE INVENTION The amounts of the structural elements of the formula depend essentially on the desired photosensitivity of the homopolymer or copolymer and their structure. Its amount is 5 to 100 mol %, preferably 20 to 100 mol %, particularly preferably 40 to 100 mol %, especially 50 to 100 mol % of the total polymer. Particularly preferably the homopolymers and copolymers contain 80-100 mol % of the structural elements of the above formula. In the case of homopolymers or copolymers in which R and R' in the structural elements of the formula represent aliphatic or cycloaliphatic groups, the amount of these structural elements is preferably at least 50 mol %,
This is especially the case when the homopolymers and copolymers are polyamides and polyesters. When R and R' in the formula mean a divalent aliphatic group, they are preferably 2 to 30
, especially 6 to 30, especially 6 to 20 carbon atoms. In one preferred embodiment, R and R' each represent one or more oxygen atoms,
S, SO, SO ₂ , NH, NR ^a , NR ^a ₂ G, a straight-chain or branched alkylene group optionally interrupted by cyclohexylene, naphthylene, phenylene or hydantoin groups. R ^a is
For example, it can be an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 or 6 ring carbon atoms, a phenyl group or a benzyl group. G represents an anion of a protic acid, such as a halogen anion, sulfate or phosphate. In one preferred embodiment, R and R' are straight-chain or branched alkylene radicals having 6 to 30 carbon atoms, -(CH ₂ ) _n
-R ¹ -(CH ₂ ) _o - [wherein R ¹ represents a phenylene group, naphthylene group, cyclopentylene group or cyclohexylene group, m and n each independently represent the number 1, 2 or 3] group, −R ² −
(OR ³ ) _p −O−R ² − [However, R ² is ethylene, 1,2
-propylene, 1,3-propylene or 2-methyl-1,3-propylene, and R ³ is ethylene, 1,2-propylene, 1,2-butylene,
represents 1,3-propylene or 1,4-butylene, and p represents a number from 1 to 100]
based on or represents the group of Examples of aliphatic groups 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, hexylene, heptylene , octylene, decylene, dodecylene, tetradecylene, hexadecylene, octadecylene, eicosylene,
2,4,4-trimethylhexylene, 1,10-dialkyldecylene (in which case the alkyl preferably has 1 to 6 carbon atoms),
Substituted 1,11-undecylene as described for example in EP-B-0011559, e.g. [Here p represents a number from 1 to 100] or −(CH ₂ ) ₃ [−O(−CH ₂ ) ₄ −] _p O(−CH ₂ ) − ₃ [Here p represents a number from 1 to 100 Jeff amines, dimethylenecyclohexane,
xylylene, and diethylenebenzene.
Particularly preferably R or R' is a long-chain branched alkylene radical having, for example, 8 to 30 carbon atoms. When R or R' in the above formula is an aliphatic group, it is represented by the following formula: in which R ¹⁶ and R ¹⁷ are C ₁ -C ₆ alkyl groups, in particular methyl or phenyl groups, and R ²⁰ is a cycloalkylene group such as e.g. cyclohexylene and especially _C1 - _C12 alkylene groups, especially _C1 - _C6 alkylene groups,
For example 1,3-propylene or 1,4-butylene and x is at least one rational number, such as from 1 to 100, preferably from 1 to 10
is the number of Diamines having such groups are described in US Pat. No. 3,435,002 and US Pat. No. 4,030,948. Aliphatic groups which may be interrupted by heterocyclic groups can be, for example, those derived from N,N'-aminoalkylated hydantoins or benzimidazoles. Examples include N,N′-(γ-aminopropyl)-
5,5-dimethyl-hydantoin or the same benzimidazolone and the following formula [In the formula, R ^b is an alkylene group having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, or

[Formula], where R ^c means a hydrogen atom or a methyl group, and a is 1 to
(representing an integer of 20) can be given. Suitable substituents for aliphatic groups are, for example, hydroxyl groups, halogens such as F or Cl, or 1
an alkoxy group having 6 to 6 carbon atoms. The heterocyclic diamine group is preferably derived from N-heterocyclic diamines, such as pyrrolidine,
It is derived from indole, piperidine, pyridine, pyrrole (the N atom of which may be alkylated, for example, by methylation), and the like. One example is N-methyl-4-amino-5-
It is aminomethylpiperidine. If R or R' in the above formula denotes a divalent cycloaliphatic group, this preferably contains 5 to 8 ring carbon atoms and is especially unsubstituted or preferably 1 to 8 ring carbon atoms. A mononuclear or dinuclear cycloalkylene group having 5 to 7 ring carbon atoms substituted with an alkyl group containing 4 carbon atoms. In one preferred embodiment, when R or R' is a cycloaliphatic residue, this is represented by the formula

[expression] or

[Formula], in which q is 0 or 1, R ⁴ independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and X represents a direct bond, O ,S,
SO ₂ represents an alkylene group having 1 to 3 carbon atoms or an alkylidene group having 2 to 6 carbon atoms. R ⁴ is preferably an ethyl group and a methyl group, X is preferably a methylene group, and alkylidene groups are e.g. erythidene and 1,1-
or preferably contains 2 or 3 carbon atoms, such as 2,2-propylidene. When R or R' is cycloalkylene, examples include 1,2- or 1,3-cyclopentylene, 1,2-, 1,3- or 1,4-cyclohexylene, cycloheptylene, cyclooctylene. , methylcyclopentylene, methyl- or dimethylcyclohexylene, 3- or 4-methylcyclohex-1-yl, 5-methyl-3-methylenecyclohex-1-yl, 3,3'- or 4,4' -bis-cyclohexylene, 3,3'-dimethyl-4,4'-biscyclohexylene, 4,4'-
Biscyclohexylene ether, sulfone,
methane or 2,2-propane, bis-
Mention may be made of the groups aminomethyltricyclodecane, bis-aminomethylnorbornane and menthanediamine. Particularly preferred examples of R or R' as cycloaliphatic group are 1,4- or 1,3-cyclohexylene, 2,2,6-trimethyl-6-methylene-
cyclohex-4-yl, methylenebis(cyclohex-4-yl) or methylenebis(3-methylcyclohex-4-yl). When R or R' is an araliphatic group,
It preferably contains 7 to 30 carbon atoms. If the aromatic groups of this araliphatic group are bonded (which is preferred) to the N atom of the group of the above formula, they are treated as if R or R' represents an aromatic group. Preferably, it is substituted. This araliphatic group is preferably 7 to 30
, especially 8 to 22 carbon atoms. The aromatic group in this araliphatic group is preferably one phenyl group. If R or R' denotes an araliphatic group, these mean in particular an aralkylene group which is unsubstituted or whose aryl group is substituted by an alkyl group, the alkylene group being linear or may be branched. In one preferred example, the araliphatic group has the formula [In this formula, R ⁴ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and r represents an integer of 1 to 20]. In the above formula, the free bond is
o-, m-, and especially p- for the C _r H _2r group.
and one or both of the groups R ⁴ are preferably bonded in the o-position relative to this free bond. Examples of when R or R' is an araliphatic group include 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-phenylene-propylene, p-phenylenebutylene, 3-ethyl-p-
Phenylenepentylene and among others, e.g. EP
-A-0069062, various long-chain phenylene alkylene groups, i.e. 6-
(p-phenylene)-6-methylhept-2-yl, 6-(3'-methyl-p-phenylene)-6-methylhept-2-yl, 6-(3'-ethyl-p-
phenylene)-6-methylhept-2-yl, 6
-(3',5'-dimethyl-p-phenylene)-6-methylhept-2-yl, 11-(p-phenylene)-
2,11-dimethyl-dodec-1-yl, 13-(p
-phenylene)-2,12-dimethyltetradecy-
3-il is mentioned. R or R' may also be an aromatic group,
In this case, two aromatic nuclei, in particular phenyl nuclei, can be linked via an aliphatic group.
This group is preferably of the following formula [In this formula, both bonds are attached to the group Q in the p-position, in the m-position and especially in the o-position, and the group Q is attached to C ₁ -C ₁₂ , especially C ₁ -
C ₆ alkylene group, which may be interrupted by O or S]. Base Q
Examples include ethylene, 1,2- or 1,3-
Propylene, butylene, -CH ₂ -O-CH ₂ -, -
_CH2 -S- _CH2- and _{-CH2CH2 -} O- _CH2
Examples include CH ₂ −. Among the homopolymers and copolymers according to the invention, preference is given in particular to those in which R or R' denotes a structural element which represents a substituted aromatic group. The number of substituents on the aromatic group is preferably 1 to 20, particularly 1 to 20.
It contains 12 and especially 1 to 6 carbon atoms. This substituent is in particular a _C5 or _C6 cycloalkyl group, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, an alkoxy group, an alkoxyalkyl group, an alkylthio group, an alkylthioalkyl group, hydroxyalkyl group,
A hydroxyalkoxy or hydroxyalkylthio group, or also a benzyl, trimethylene or tetramethylene group. As the alkoxyalkyl group, alkoxymethyl is preferable,
As the alkoxy group, a methoxy group is preferable. Examples of various substituents include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, octyl, dodecyl,
Tetradecyl, eicosyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, methoxymethyl, methoxyethyl, ethoxymethyl, propoxymethyl, butoxymethyl,
Mention may be made of benzyl, methylbenzyl, phenylethyl, methylthio, ethylthio, hydroxyethyl, methylthioethyl and hydroxyethylthio. Preferred groups are methoxymethyl, ethoxymethyl, methyl, ethyl, n-propyl, i-propyl, trimethylene, tetramethylene, cyclopentyl and cyclohexyl. Particularly preferred are methyl, ethyl and i-propyl. As substituted aromatic groups, mention may be made, for example, of mononuclear or polynuclear, in particular dinuclear, groups. Mononuclear radicals can contain up to 4, preferably 2, particularly preferably 1 substituents, and dinuclear radicals can contain up to 4, preferably 1 or 2 substituents. can be contained within each nucleus. The inventors have found that the photosensitivity of their homopolymers or copolymers is particularly high when one or two substituents are attached in a position ortho to the N atom of the above formula. Ta. Therefore, substitution in the ortho position is preferred. This aromatic residue is preferably bonded in the meta or para position to the N atom. When R or R' is an aromatic group, this is 7
It can contain from 7 to 30 carbon atoms, especially from 7 to 20 carbon atoms. The aromatic group is preferably a hydrocarbon group or a pyridine group, substituted as described above. Examples of preferred groups include the following formula:

【formula】

【formula】

【formula】

【formula】

【formula】

[expression] or

[Formula] [In these formulas, R ⁴ is an alkyl group having 1 to 6 carbon atoms in the case of mono-substitution, the other R ⁴ is hydrogen, and in the case of di-, tri- or tetra-substitution is an alkyl group having 1 to 6 carbon atoms in which two R ⁴ are
R ⁴ is hydrogen or an alkyl group having 1 to 6 carbon atoms, or in the case of di-, tri- or tetra-substitution, two adjacent R ⁴ in the phenyl ring are trimethylene or tetramethylene group in which R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Y means O, S, NH, CO or CH ₂ , and R ⁵ is a hydrogen atom, or represents an alkyl group having 1 to 5 carbon atoms, R ⁶ represents an alkyl group having 1 to 5 carbon atoms,
And Z is a direct bond, O, S, SO, SO ₂ , CO,
O=CO, O= ^CNR7 , ^NR7 , CONH, NH, ^R7
SiR8 , ^{R7OSiOR8 ,} an alkylene group having 1 to 6 carbon atoms,
means an alkenylene or alkylidene group, a phenylene group or a phenyldioxy group having 2 to 6 carbon atoms, and R ⁷ and R ⁸ independently of each other represent an alkyl group having 1 to 6 carbon atoms, or a phenyl group; , and j is a number from 1 to 10, especially from 1 to 3]. Z is the formula [In this formula, G means sulfur or oxygen, f is a number of 0 or 1, g is a number of 1 to 6,
and h represents a number from 1 to 50, especially from 1 to 10, and R ¹⁶ and R ¹⁷ have the above-mentioned meanings or the following formula and K is the group of

【formula】

[Formula] Ma Taha

[Formula] wherein R ²⁵ represents hydrogen, a C ₁ -C ₆ alkyl group or a phenyl group.
R ₅ and R ₆ are preferably methyl groups, Y preferably means -CH ₂ - or -O-, and Z is preferably a single bond, -O-, -CH ₂ -, or 2 to 4 is an alkylidene group having 5 carbon atoms. R ₇ and R ₈ are especially methyl, ethyl and phenyl groups. The alkylene group preferably contains 2 to 4 carbon atoms and is especially an ethylene group. The alkenylene group is particularly preferably an ethenylene group. Preferred examples are toluylene groups, o,o'-substituted diaminodiphenylenes, diaminodiphenylmethanes and diaminodiphenyl ether groups. A particularly preferred group is the following formula:

【formula】

【formula】

【formula】

[expression] or

##STR1## where Z means a single bond, O, especially _CH.sub.2 , and _R.sub.9 represents a hydrogen atom, a methyl group, an ethyl group or an isopropyl group. Examples of substituted aromatic groups 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-isopropyl, 1,4-phenylene, 3,5-dimethyl-1,4-phenylene, 2,4-dimethyl-
1,3-phenylene, 2,3-dimethyl-1,3
-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, and also 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 divalent group, 4-methoxymethyl-
1,3-phenylene, 3-methyl-p-diphenylene, 3-ethyl-p-diphenylene, 3,3'-
Dimethyl-p-diphenylene, 3,3'-diethyl-p-diphenylene, 3-methyl-3'-ethyl-
p-diphenylene, 3,3',5,5'-tetramethyl-diphenylene, 3,3'-methyl-5-5'-ethyl-p-diphenylene, 4,4'-dimethyl-m
-diphenylene, 3,3'-diisopropyl-diphenylene, and the following groups, [In these formulas, Z′, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent a group listed in the table below].

【table】

【table】

Table The diamines from which R or R' are derived are known or can be prepared by known methods. Diamines having polysiloxane structural units are known from US Pat. No. 3,435,002 and EP-A-O, 054426. The polymers to be used according to the invention have an average molecular weight (number average molecular weight) of at least 2000, preferably at least 5000 or more. The upper limit of this molecular weight essentially depends on the properties that determine its processability, such as solubility. This upper limit is up to 500000, preferably 100000,
And particularly preferably it can be up to 60,000. Furthermore, the polymer may be a statistically distributed polymer or a block polymer. These polymers are produced according to customary methods in various equipment equipped for this purpose. These polymers preferably have a linear structure, but may also be slightly branched by at least trifunctional monomers added in small amounts. These homopolymers or copolymers are preferably polyimides, polyamides, saturated polyesters, polycarbonates, polyamideimides, polyesterimides, polyesteramides, polysiloxanes, unsaturated polyesters, epoxy resins, aromatic polyesters, etc. selected from ethers, aromatic polyetherketones, aromatic polyethersulfones, aromatic polyketones, aromatic polythioethers and mixtures of these polymers. Among these polymers, particularly preferred are polyimides having a repeating structural element of the formula (where q = 0) or a repeating structural element of the formula (where q = 0) and the following formula: (However, in this formula, A is a tetravalent organic residue, and R ¹⁰ is a divalent organic residue). In these homopolymerized polyimides and copolymerized polyimides, R and R ¹⁰ particularly represent aromatic organic groups. Among the copolymerized polyimides, those containing at least 60 mol%, particularly at least 80 mol%, of the structural elements of the formula are particularly preferred. When A in the above formula is not a benzophenone group, it may be selected from an aromatic group, an aliphatic group, a cycloaliphatic group, a heterocyclic group, and a combination of an aromatic group and an aliphatic group. These groups may also be substituted. This group A can be characterized by the following structure:

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】 【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] [However, R ₁₅ is -O-, -S-, SO ₂ -,

【formula】

【formula】 【formula】

【formula】

【formula】 【formula】

[Formula]- N=N-,

【formula】

[Formula] −CH ₂ −, CH ₂ CH ₂ −,

【formula】

[Formula] is selected from phenylene and O(-R ^d -O-) _b , where b is a number from 1 to 10, and R ^d is alkylene. cycloalkylene, arylene or aralkylene, or R ₁₆ and R ₁₇ preferably represent an alkyl group having 1 to 6 carbon atoms]. Two of the free bonds in the groups listed in each of the above formulas are always present on adjacent carbon atoms. Suitable tetracarboxylic acid anhydrides or their esters having one tetravalent residue A are, for example: 2,3,9,10-perylenetetracarboxylic dianhydride, 1,4 , 5,8-naphthalene tetracarboxylic 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-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyl Tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 4,4'-isopropylidene diphthalic anhydride, 3,3'-isopropylidene diphthalic acid Acid anhydride, 4,4'-oxydiphthalic anhydride, 4,4'-sulfonyldiphthalic anhydride, 3,3'-oxydiphthalic anhydride, 4,4'-methylenediphthalic anhydride 4,4'-thiodiphthalic anhydride, 4,4'-ethylidene diphthalic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5- Naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, Benzol-1,2,3,4-tetracarboxylic dianhydride, Thiophene-2,3,4,5 , tetracarboxylic dianhydride, 1-(3',4'-dicarboxyphenyl)-1,
3,3-trimethylindane-5,6-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-1,
3,3-trimethylindane-6,7-dicarboxylic acid dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methylindane-5,6-dicarboxylic acid dianhydride, tetrahydrofuran Tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclooctane tetracarboxylic dianhydride, and 1-(3′4′-dicarboxyphenyl)-3-methylindane-6,7-dicarboxylic acid Dianhydride, as well as general formula Dianhydrides of the formula in which Y ₁ , Y ₂ , Y ₃ and Y ₄ are each hydrogen, an alkyl group or especially a methyl group. Preferred non-benzophenone aromatic dicarboxylic acid anhydrides include pyromellitic dianhydride and general formula [However, R ₁₅ is methylene, oxygen, sulfonyl or

[Formula] or

These are various aromatic dianhydrides characterized by the following formula: The group R ¹⁰ defined above can be selected from the group below. That is, alkylene groups having 2 to 10 carbon atoms, cycloalkylene groups having 4 to 6 ring carbon atoms, xylylene groups,
or an arylene group selected from m- or p-phenylene, tolylene, biphenylene, naphthylene or anthrylene, or the following formula unsubstituted or substituted arylene group [in the above formula, W is a covalent bond, sulfur, carbonyl, -
NH-, -N-alkyl, O,S,SS, -N-phenyl, sulfonyl, straight-chain or branched alkylene radicals having 1 to 3 carbon atoms, having 2 to 12 carbon atoms alkylidene group, 5
or a cycloalkylidene group having 6 ring carbon atoms, an arylene, especially a phenylene group, or a dialkyl- or diarylsilyl group, R ₁₈ and R ₁₉ independently of each other hydrogen,
halogen, especially chlorine or bromine, alkyl having 1 to 5 carbon atoms, especially methyl, 1
alkoxy, especially methoxy, or aryl, especially phenyl, having from 5 to 5 carbon atoms. R ¹⁰ further preferably includes groups derived from the various aromatic diamines described above. Most preferably R ¹⁰ is [In the above formula, W is a covalent bond, a methylene group,
represents sulfur, oxygen or sulfone, and R ₁₈
and R ₁₉ are each independently hydrogen, halogen or 1
alkyl having 5 to 5 carbon atoms, especially methyl group] or the following formula: [In this formula, R ²¹ represents hydrogen, halogen or alkyl having 1 to 5 carbon atoms, especially methyl]. R ¹⁰ is particularly preferably an m- or p-phenylene group or a formula [In this formula, W means a covalent bond, methylene group, 2,2-propylidene group, cyclohexylidene group, sulfur, oxygen or sulfone]. Examples of diamines having a divalent group ^R10 include 4,4'-methylenebis-(o-chloroaniline), 3,3'-dichlorobenzidine, 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-[bis-(4-aminophenyl)]-N-methyl Amine, N-[bis-(4-aminophenyl)]-N-phenylamine, 4,4'-methylenebis-(3-methylaniline), 4,4'-methylenebis-(2-ethylaniline), 4,4' -methylenebis-(2-methoxyaniline), 5,5'-
methylenebis-(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-methylaniline), 4,4'-
Thiobis-(2-methoxyaniline), 4,4'-thiobis-(2-chloroaniline), 4,4'-sulfonylbis-(2-methylaniline), 4,4'-sulfonylbis-(2-ethoxy aniline), 4,4'-
Sulfonylbis-(2-chloroaniline), 5,
5'-sulfonylbis-(2-aminophenol),
3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3-dimethoxy-4,4'-diaminobenzophenone, 3,3'-dichloro-4,4'-diaminobenzophenone, 4,4'-diaminobiphenyl, m-phenylenediamine, p-phenylenediamine, 4,4'-methylene dianiline, 4,4'-
Oxydianiline, 4,4'-thiodianiline,
4,4'-sulfonyl dianiline, 4,4'-isopropylidene dianiline, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-
dicarboxybenzidine, diaminotoluol,
Examples include 4,4'-methylene-bis-(3-carboxyaniline) and esters thereof. These homopolyimides and copolyimides according to the present invention can be produced by adding benzophenonetetracarboxylic anhydride and diamines of the formula NH ₂ RNH ₂ in a conventional manner. with a further tetracarboxylic acid anhydride and/or a further diamine of the formula NH ₂ R ¹⁰ NH ₂ and then under the action of the carboxylic anhydride and/or under subsequent heating. This is done by imide cyclization. In another known method, diisocyanates are reacted with tetracarboxylic dianhydrides to form polyimides. For the preparation of other homopolymers and copolymers, the starting point is functional imide derivatives of benzophenonetetracarboxylic acid. These imide derivatives have the formula [In this formula, R and R' have the same meanings as given above, c is a number from 1 to about 500,
and Y means a functional group]. This functional group is for example
NHR ²² , OH, SH, O-acyl, COOR ²² ,
CON( ^R22 ) ₂ , COCl, COBr,

【formula】

【formula】

and halogens, among them Cl and Br. R ²² is a hydrogen atom or an optionally hydroxylated hydrocarbon group, for example 1 to 20, especially 1 to 12
an alkyl or hydroxyalkyl group having 7 to 20 carbon atoms, preferably an aralkyl group having 7 to 20 carbon atoms, especially 7 to 16 carbon atoms;
Preferably it is an aryl group having 6 to 20, especially 6 to 16, carbon atoms, or preferably a cycloalkyl group having 5 to 7 ring carbon atoms. R ²³ has the same meaning as R ²² or
or

can mean [formula]. The acyl group may contain 1 to 20, preferably 1 to 12 carbon atoms. Compounds with c=1 in the formula are known in part from DE 30 07 445 A1 or can be prepared by analogous methods. For example, introduction of other functional groups such as glycidyl groups is carried out by conventional methods. Compounds in which c is 1 or more are novel compounds and are also an object of the present invention. These are oligomers and low molecular weight polyimides with terminal functional groups. These are prepared in a manner similar to that for polyimides, the size of c being determined by the amount of monomers of the formula Y--R--NH ₂ used together. Using these oligomers and low molecular weight polymers, block polymers are obtained having respective blocks of, for example, polyimide and, for example, polyamide blocks, polyester blocks and other polyimide blocks. Another preferred group of polymers for the coating materials according to the invention are various organic diamines,
The above formula (in this formula, q=1 and R
and a polyamide or copolymerized polyamide having a structural element (in which an amino group or a carboxyl group is bonded to the group R'). In the case of a homopolymer, the molecular chain is composed of a dicarboxylic acid and a diamine having the structural element of the formula, or the molecular chain is composed of a dicarboxylic acid or diamine having the structural element of the formula. organic diamine or dicarboxylic acid, and may not contain a benzophenone residue. The copolyamide contains further diamine, dicarboxylic acid or aminocarboxylic acid groups. Suitable dicarboxylic acids are, for example, straight-chain or branched aliphatic dicarboxylic acids having preferably 2 to 20, especially 4 to 16 carbon atoms, 5
Cycloaliphatic dicarboxylic acids having from 8 to 7 ring carbon atoms, which are unsubstituted or substituted in particular by alkyl groups, and preferably from 8 to 7 ring carbon atoms;
Aromatic dicarboxylic acids having 22 carbon atoms, unsubstituted or substituted by an alkyl group, Cl or Br. Examples of these are malonic acid, adipic acid, trimethyladipic acid, pimelic acid, corkic acid, azelaic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, p-diphenyldicarboxylic acid, bis-(4 -carboxylphenyl)ether or bis-(4-carboxylphenyl)-
Sulfone can be given. Suitable diamines are, for example, straight-chain or branched aliphatic diamines having preferably 2 to 30, especially 4 to 20 carbon atoms, non-alphatic diamines preferably having 5 to 7 ring carbon atoms. Cycloaliphatic diamines substituted or substituted by alkyl, especially methyl groups, preferably 7
araliphatic diamines having from 6 to 24 carbon atoms, and aromatic diamines having from 6 to 22, especially from 6 to 18 carbon atoms, which may be unsubstituted or substituted, in particular by alkyl groups. They are diamines. Examples thereof include ethylene diamine, propylene diamine, 1,3- or 1,4-butylene diamine, pentylene diamine, 1,6-hexylene diamine, octylene diamine, decylene diamine, dodecylene diamine, e.g. , 10-dimethyl-1,10-decylendiamine or 1,10-di-n-hexyl-1,
1,10-alkyl-substituted 1,10-decylendiamines such as 10-decylendiamine, xylylenediamine, isophoronediamine, 1,3- or 1,4-cyclohexanediamine, 1,3-
or 1,4-phenylenediamine, methylphenylenediamine, tolylenediamine, p-diphenylenediamine, bis-(p-aminophenyl)
Examples include ether, bis-(p-aminophenyl) sulfone, and bis-(p-aminophenyl)-methane. Aminocarboxylic acids include aromatic, cycloaliphatic or aliphatic aminocarboxylic acids, such as aminobenzoic acid, aminocyclohexanecarboxylic acid, and e.g.
- ε-aminocarboxylic acids such as aminocaproic acid or 11-aminoundecanoic acid. Another preferred group of polymers for the materials of the invention consists of various organic diols, dicarboxylic acids, hydroxycarboxylic acids and various diols or dicarboxylic acids or mixtures of these monomers (with the formula It is a polyester or a copolymerized polyester having a structural element in which q=1 and a hydroxyl group or a carboxyl group is bonded to the R and R' groups. Homopolymer polyesters are those whose molecular chain is composed of dicarboxylic acids and diols of the above formula, or those whose molecular chain is composed of diols or dicarboxylic acids of the above formula and various organic diols that do not contain benzophenone groups. Alternatively, it may be composed of a dicarboxylic acid. The copolyesters contain additional residues of various dicarboxylic acids, diols, and/or hydroxycarboxylic acids. Suitable dicarboxylic acids are as described above. Polyesters based on aromatic dicarboxylic acids, especially terephthalic acid and/or isophthalic acid, are preferred. Examples of diols include 1,
Cycloaliphatic diols such as 4-cyclohexanediol, aromatic diols such as bisphenol-A, and especially
Optionally substituted aliphatic diols, such as branched and especially straight-chain alkylene diols having 12, preferably 2 to 6 carbon atoms, and 1,4-bis-hydroxymethylcyclohexane and Examples include hydroxypivalic acid neopentyl glycol ester. Particularly preferred are ethylene glycol, trimethylene glycol, tetramethylene glycol and hexamethylene glycol. Examples of hydroxycarboxylic acids include m- or p-hydroxybenzoic acid or aliphatic ω-hydroxycarboxylic acids such as γ-hydroxyvaleric acid, hydroxypivalic acid and ε-caprolactone. In another preferred embodiment, the polymers for the materials of the invention are polyamideimides or polyesterimides. Such polymers have the following formula tricarboxylic acids or their polymer-forming derivatives, such as esters, acid anhydrides or acid halides. The trivalent residue D of the formula is preferably a hydrocarbon residue having 6 to 16 carbon atoms, with two carboxyl groups attached to two adjacent carbon atoms. I can do it. Preferred is trimellitic acid. These polyamideimides can be composed only of the diamine of the above formula and the tricarboxylic acid of the above formula. Copolymers are obtained, for example, when dicarboxylic acids and/or diamines, as already mentioned above for polyamides, are additionally used together in the preparation of polyamide-imides and also in that of the formula. Polyesterimides are produced by first reacting an aminocarboxylic acid or aminoalcohol with a tricarboxylic acid of the above formula to give a dicarboxylic acid or hydroxycarboxylic acid, and then condensing this with diols and/or dicarboxylic acids of the above formula. It can be obtained by converting it into polyester. In this case too, additionally other dicarboxylic acids and/or diols can be used to form the copolymer. Furthermore, polyesteramides are also preferred. These polymers condensate dicarboxylic acids of the above formula and/or other additional dicarboxylic acids with diols of the above formula and/or other diols and diamines of the above formula and/or other diamines. obtained by,
The individual monomers have already been described. The N atom of the amide group in each of the aforementioned polymers is preferably an alkyl group having 1 to 6 carbon atoms, such as an aryl group such as phenyl, an aralkyl group such as benzyl, or an aralkyl group such as cyclohexyl. Optionally substituted with a cycloalkyl group. Other suitable polymers for the film coating materials of the invention are, for example: diols of the formula a and optionally other diols together with silane compounds of ( ^R24 ) ₂ - _SiB2 , R ²⁴ is preferably alkyl having 1 to 6 carbon atoms, especially methyl, or cycloalkyl, especially phenyl, and B is Br
or in particular Cl, or alkoxy or aryloxy groups preferably having 1 to 6 carbon atoms, especially methoxy or phenoxy groups). These polymers therefore have the formula

[Formula] O and possibly the following formula

It can have the structural elements of the formula: In the above formula, E corresponds to a radical of the formula, q=1 and E' is a divalent radical of a diol. The diols HOE′OH that can be used are as already described. Furthermore, these polys have the following formula Additional blocks having structural elements of 1,000,000 or more can be included, these blocks making up to 50% by weight of the total polymer. b. Unsaturated polyesters consisting of unsaturated dicarboxylic acids, in particular maleic acid, diols of the formula HOEOH and optionally other similarly dicarboxylic acids of the formula as well as other diols HOE'OH. Suitable dicarboxylic acids are as already mentioned. These polymers therefore have the formula [E″ represents a divalent residue of an ethylenically unsaturated dicarboxylic acid].Other structural elements include the following:

【formula】

[Formula] and

〔Effect of the invention〕

The polymer coating on the material of the invention has high photosensitivity, sufficient for many applications, and it can be directly photocrosslinked. The protective films and relief images produced in this way are excellent due to their high adhesive strength and high thermal, mechanical and chemical stability, and the coatings made of polyimide are especially excellent in these stability. There is. Only a slight weight loss is observed during thermal after-treatment. Moreover, the use of various additives for forming or enhancing the photosensitivity can be omitted. Although this material is stable in storage, it needs to be protected from the effects of light. The present invention will be explained in more detail below using Examples. A Preparation Example of Starting Product 1 27.28 g in nitrogen gas in a cylindrical vessel equipped with a stirrer, dropping funnel, internal thermometer and nitrogen inlet tube
(0.12 mol) of 4,4'-diamino-3,3'-dimethyldiphenylmethane is dissolved in 370 g of N-methylpyrrolidone (abbreviated as NMP) and cooled to 0-5°C. Next, 39.43g (0.1225
mol) of benzophenonetetracarboxylic dianhydride (abbreviated as BTDA) is prepared and added in portions over a period of 4 hours. Thirty minutes after the last addition, 48.48 g (0.48 mol) of triethylamine and 110.1 g (1.08 mol) of acetic anhydride are added dropwise and the resulting polyamic acid is cyclized to polyimide. After stirring for 16 hours at room temperature, the solution is poured into 6 water under vigorous stirring and the precipitated product is overseparated. The product is treated again with 6 portions of water, filtered and dried in vacuo at 80°C. The intrinsic viscosity, measured in a 0.5% strength solution in NMP at 25° C., is 0.97 dl/g. The glass transition temperature Tg measured by scanning differential thermal calorimetry DSC is 285°C. Example 2 Proceed as in Example 1, but with 66.7 mol%
of BTDA and 33.3 mol % of pyromellitic dianhydride (abbreviated as PMDA) is used. The properties of the obtained copolymerized polyimide are as follows. [η] = 0.93 dl/g Tg = 304°C Example 3 As in Example 1, 3,3'-diethyl-
A technical grade mixture of 4,4'-diaminodiphenylmethane, 3-ethyl-4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenylmethane was reacted with a stoichiometric amount of BTDA. Polyimide is obtained by cyclization. [η] = 1.00 dl/g Tg = 263°C Example 4 The procedure of Example 3 is repeated using a mixture of 50 mol% BTDA and 50 mol% PMDA. The copolymerized polyimide obtained has the following properties: [η] = 0.87 dl/g Tg = 288°C Example 5
of the same diamine mixture as in Example 3 above in NMP.
A solution containing 4.02 g of BTDA is condensed with 3.78 g of BTDA (mole ratio of diamine mixture: BTDA = 3:2) to form a polyamic acid block having terminal amino groups. Next, after cooling this solution to -15°C, 3.5717 g of isophthalic acid dichloride was added first.
Then add 2.6791 g of diamine mixture (molar ratio of isophthalic acid dichloride:diamine mixture =
3:2). By stopping the cooling, the temperature slowly rises to room temperature. After 5 hours, 3 ml of propylene oxide, and after another 30 minutes.
Add 6.51 g triethylamine and 26.6 g acetic anhydride. The block copolymerized polyamideimide is precipitated by stirring overnight and the next day by stirring the mixture in water. The properties of this are as follows: [η] = 0.82 dl/g Tg = 221°C Example 6 Similarly to Example 1, a mixture of 4,4'-diaminodiphenylmethane and 2,4-diaminotoluol (molar ratio = 19.7:80.3) with an equivalent amount of BTDA. The properties of the obtained polyimide are as follows: [η] = 0.43 dl/g Tg = 309°C Example 7 In the same manner as in Example 1, 2,4-diaminotoluol and 5,(6)-amino-1-( 4-aminophenyl)-
A mixture with 1,3,3-trimethylindan (molar ratio = 54.4:45.6) is polycondensed with an equivalent amount of BTDA. The properties of the copolymerized polyimide obtained are as follows: [η] = 0.42 dl/g Tg = 309°C Examples 8 and 9 In the same manner as in Example 1, BTDA was added to an equivalent amount of 2-amino-6-methyl-6-( 4-aminophenyl)-heptane or 2-amino-6-methyl-6-(3-
Polyimide is produced by condensation polymerization with ethyl-4-aminophenyl)-heptane. The properties of these polyimides are as follows: [η] = 0.34 and 0.23 dl/g Tg = 177°C and 170°C Example 10 In a sulfonation flask equipped with a stirrer, an internal thermometer, a nitrogen inlet and a water separation device. 13.21g
(0.038 mol) of 1,10-diamino-1,10-di-
n-hexyldecane and 13.34g BTDA
(0.038 mol) is stirred in 100 ml of o-dichlorobenzole under nitrogen gas for 30 minutes. This mixture was then gradually heated to reflux temperature (175 °C),
A clear, pale yellow solution forms. During 90 minutes, the condensed water is distilled off together with o-dichlorobenzole and separated in a water separator. A sample for analysis is taken by stirring a portion of the cooled solution into hexane, filtering and drying. The properties of the obtained polyamide are as follows: [η] = 0.36 dl/g Tg = 63°C Example 11-20 The diamines listed in the table below were prepared in the same manner as in Example 1.
Polyimide was produced by condensation polymerization with BTDA, and the properties listed in the table below were found for each of these polymers.

【table】

【table】

[Table] *Example 21 of conversion to acetate ester upon cyclization with acetic anhydride [Polyimide of isocyanate and acid anhydride] In a reaction vessel equipped with a stirrer, a reflux condenser and a gas inlet tube, at room temperature under N ₂ 0.7905g
(0.0021 mol) of N,N'-di-(3-isocyanato-4-methyl)-phenylparabanic acid and
1.4633 g (0.0084 mol) toluene-2,4-diisocyanate in DMSO (23 ml) is charged and to this is added 3.386 g (0.0105 mol) benzophenonetetracarboxylic dianhydride. The mixture is warmed to 90°C and kept at this temperature for 24 hours. After cooling, the solution is stirred and poured into water to precipitate the polymer. [η] = 0.228 dl/g Tg = 349°C Example 22 [Polyimide/Polyesteramide] In a reaction vessel, 1.5 g (7.39 mmol) of isophthalic acid dichloride was added to 38 ml of N-methylpyrrolidone.
Dissolve in DMP and cool to -15°C. Then 0.537 g (4.92 mmol) m-aminophenol and 1.4 ml triethylamine are added to this. 2.832 g (17.2 mmol) after 30 minutes
of 3,6-diaminodeurene and 0.65 ml of triethylamine are added. The temperature is raised to 0°C by removing the cooling bath, and to this
Add 4.76 g (14.78 mmol) BTDA.
After stirring for 8 hours at room temperature, during 16 hours
The polyamic acid is cyclized to polyimide by addition of 4.5 ml of triethylamine and 12.6 ml of acetic anhydride. This is post-treated according to a conventional method. [η] = 0.38 dl/g Example 23 [Polyimide/Polycarbonate] Under the same conditions as in Example 26, the following components are reacted with each other in the order listed. Phosgene 0.008 mol Bisphenol 0.0053 mol Mesitylenediamine 0.01866 mol BTDA 0.016 mol [η] = 0.16 dl/g Tg = 261°C Example 24 [Polyimide/Polyamideimide] 7.5 mmol of 4,4'-diamino-3,5,3' ，
5'-tetraethyldiphenylmethane and 2.5 mmol of 4,4'-diaminodiphenylmethane at 25
ml of NMP, cool the solution to −15° C. and react it with 2.5 mmol of anhydrous trimellitate acid chloride in the presence of 0.4 ml of triethylamine. The prepolymer thus formed is then further reacted with 7.5 mmol of BTDA and then cyclized using triethylamine and acetic anhydride. [η] = 0.58 dl/g Tg = 257°C 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 0°C. Then at -15℃
Add 0.01 mol of isophthalic acid dichloride and 6.1 ml of triethylamine. Cooling is stopped after 15 minutes and stirring is continued for a further 8 hours at room temperature. Cyclization is carried out using acetic anhydride. [η] = 0.09 dl/g Tg = 127°C Example 26 [Polyimide/polyphenylene sulfide] 1.6458 g of 3,6-diaminodeylene and
0.9333 g of polyphenylene sulfide containing terminal amino groups [Polymer Bulletin 4, 459-466 (1981)
[produced according to the method] at 0℃ to 25℃ for 24
3.4313g BTDA in 24 hours in ml NMP
and then cyclized with triethylamine and acetic anhydride. [η] = 0.576 dl/g Tg = 411°C Example 27 [Polyimide/Polyethersulfone] The terminal amino group-containing polyethersulfone used here was composed of 4,4'-dichlorodiphenyl sulfone, bisphenol A, and 4-chloronitrobenzole in the presence of potassium carbonate
It is prepared by condensation in DMF followed by reduction of its terminal nitro group. 3.018 g of 3,6-diaminodurene and
Add 1.796g of the above polyether sulfone to 44ml
React with 6.231 g of BTDA in NMP and cyclize to polyimide. [η] = 0.516dl/g Tg = 380℃ B Application example 5% on a synthetic resin plate coated with copper on one side
A thin polymer coating is formed by centrifugal spray application of a concentrated polymer solution and then removal of the solvent in an air circulating oven. As a solvent,
acetophenone (for the polymers of examples 1, 2 and 4), butyrolactone (for example 3), o-dichlorobenzole (for example 10, but without separation of the polymer), o for the polymers of other examples. - Using methylpyrrolidone. The plate thus coated is exposed at room temperature to a 1000 watt ultraviolet lamp through a photomask (Stouffer light wedge) at a distance of 18 cm.
The exposed plate is then developed in a solvent, with the unexposed parts of the polymer coating being dissolved away. Visualization of this relief image is then carried out by etching away the exposed copper layer with a FeCl ₃ solution. Exposure times, developers used and sensitivities are listed in the table below. In this table, MEK stands for methyl ethyl ketone and DMF stands for dimethyl formamide.

【table】

【table】

Claims (1)

[Claims] 1. A material in which a radiation-sensitive polymer is coated on a base material, in which the polymer has a structural unit of the formula [In the above formula, R is a heteroatom, an aromatic group,
Substituted or unsubstituted divalent aliphatic groups, substituted or unsubstituted cycloaliphatic or araliphatic groups, divalent aromatic nuclei optionally interrupted by heterocyclic or cycloaliphatic groups are linked via one aliphatic group, or at least one alkyl group, cycloalkyl group, alkoxy group, alkoxyalkyl group, alkylthio group, alkylthioalkyl group, hydroxyalkyl group,
R represents an aromatic group substituted with a hydroxyalkoxy group, a hydroxyalkylthio group, or an aralkyl group, or an aromatic group in which two adjacent carbon atoms are substituted with one alkylene group; ' independently has the same meaning as R, and q represents a number of 0 or 1, and R, which is an aromatic group, is unsubstituted by an alkylene group when q is 0, or Both ortho positions with respect to the N atom in the formula are not substituted by the above-mentioned groups], based on the total amount of the polymer, at least 5 mol% A material coated with a coating. 2 The above homopolymer or copolymer contains structural units of the above formula from 5 to 50% of the total amount of the polymer.
The material according to claim 1, containing 100 mol%. 3. The material according to claim 1, wherein the substituent of the aromatic group has 1 to 20 carbon atoms. 4. The material according to claim 3, wherein the substituent is an alkyl, alkoxy or alkoxyalkyl group having 1 to 6 carbon atoms, or a benzyl, trimethylene or tetramethylene group. 5. The material according to claim 1, wherein one or two substituents are bonded to the aromatic group at positions ortho to the N atom thereof. 6 When R is an aliphatic group, it has 2 to 30 carbon atoms, when it is a cycloaliphatic residue, it has 5 to 8 ring carbon atoms, and when it is an araliphatic residue, it has 7 to 30 ring carbon atoms.
2. A material according to claim 1, having from 7 to 30 carbon atoms in the case of substituted aromatic residues. 7 When R is an aliphatic group, one or more oxygen atoms, NH, NR ^a or NR ^a ₂ G (however,
R ^a represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 or 6 ring carbon atoms, a phenyl group or a benzyl group, and G represents an anion of a protonic acid), A linear or branched alkylene group which may be interrupted by a cyclohexylene group, a naphthylene group, a phenylene group or a hydantoin group, and when R is a cycloaliphatic group, an unsubstituted or alkyl group. substituted by a group,
A monocyclic or bicyclic cycloalkylene group having 5 to 7 ring carbon atoms, and when R is an araliphatic group, it is unsubstituted or an aryl group substituted with an alkyl group. Aralkylene group (However, even if the alkylene residue is linear,
or branched) and, when R is an aromatic group, is a pyridine residue substituted by an alkyl group, an alkoxy group, an alkoxyalkyl group, a trimethylene group or a tetramethylene group. or a hydrocarbon residue, the material according to claim 1. 8 When R is an aliphatic group, a linear or branched alkylene group having 6 to 30 carbon atoms, -(CH ₂ ) _n -R ¹ -(CH ₂ ) _o - [provided that R ¹ represents a phenylene group, a naphthylene group, a cyclopentylene group, or a cyclohexylene group, and m and n each independently represent the number 1, 2 or 3], -R ² -(OR ³ ) _p - O-R ² - [where R ² is ethylene, 1,2-propylene, 1,3-propylene or 2-methyl-1,3-propylene, and R ³ is ethylene, 1,2-propylene, 1,2 ，
-butylene, 1,3-propylene, or 1,4
- represents butylene, and p represents a number from 1 to 100], or The material according to claim 7, which is based on. 9 When R is a cycloaliphatic group, the following formula [Formula] or [Formula] [where q is 0 or 1, and R ⁴ is independently hydrogen or 1 to 6 carbon atoms] means an alkyl group having atoms, and X is a direct bond,
O, S, an alkylene group having 1 to 3 carbon atoms, or an alkylidene group having 2 to 6 carbon atoms]. 10 The aromatic aliphatic group has the following formula 8. The material according to claim 7, wherein R ⁴ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and r represents an integer from 1 to 16. 11 The aromatic group has the following formula [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] or [Formula] [In the formula, R ⁴ is 1 to 6 in the case of monosubstitution
an alkyl group having 1 to 6 carbon atoms and the other R ⁴ is hydrogen; and in case of di-, tri- or tetra-substitution, two R ⁴ are an alkyl group having 1 to 6 carbon atoms and the other R ⁴ is hydrogen or an alkyl group having 1 to 6 carbon atoms, or in the case of di-, tri- or tetra-substitution, two adjacent R ⁴ in the phenyl ring
is a trimethylene group or a tetramethylene group, other R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y is O,
S, NH, CO or _CH2 , _R5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and ^R6 represents an alkyl group having 1 to 5 carbon atoms. , and Z is a single bond, O, S, SO, SO ₂ , CO, O=CO, O=
CNR ⁷ , NR ⁷ , CONH, NH, R ⁷ SiR ⁸ , R ^7
OSiOR8 , means an alkylene group having 1 to 6 carbon atoms, an alkenylene or alkylidene group having 2 to 6 carbon atoms, a phenylene group or a phenyldioxy group, provided that in the above
R ⁷ and R ⁸ independently represent an alkyl group or phenyl group having 1 to 6 carbon atoms, and j is a number from 1 to 10. material. 12 The aromatic group has the following formula [Formula] [Formula] [Formula] [Formula] or [Formula] [In the formula, Z means a single bond, O, especially CH ₂ ,
12. The material according to claim 11, wherein R ⁹ represents a hydrogen atom, a methyl group, or an ethyl group. 13 Homopolymers or copolymers are polyimides, polyamides, saturated polyesters, polycarbonates, polyamideimides, polyesterimides, polyesteramides, polysiloxanes, unsaturated polyesters, epoxy resins, aromatic polyethers, aromatic 2. A material according to claim 1, selected from group polyetherketones, aromatic polyethersulfones, aromatic polyketones, aromatic polythioethers and mixtures of these polymers. 14 The polymer is a polyimide having a repeating structural element of the formula (where q = 0), or a repeating structural element of the formula (where q = 0) and the following formula (However, in this formula, A is a tetravalent organic residue, and R ¹⁰ is a divalent organic residue). material. 15 Polymers of the formula (where q=
14. The material according to claim 13, which is a polyamide or copolyamide having a structural element of 1 and an amino group or a carboxyl group is bonded to each R and R' group. 16 Polymers consisting of organic diols and dicarboxylic acids, hydroxycarboxylic acids and diols or dicarboxylic acids, or mixtures of these monomers (where q=1 and each R and R' have hydroxyl 14. The material according to claim 13, which is a polyester or copolyester having a structural element of 100% or 200% or 300% carboxyl groups. 17 Structural unit of the formula on the base material [In the above formula, R is a heteroatom, an aromatic group,
Substituted or unsubstituted divalent aliphatic residues, substituted or unsubstituted cycloaliphatic or araliphatic groups, optionally interrupted by heterocyclic or cycloaliphatic groups, two aromatic an aromatic group whose nucleus is linked via one aliphatic group, or at least one
alkyl groups, cycloalkyl groups, alkoxy groups, alkoxyalkyl groups, alkylthio groups, alkylthioalkyl groups, hydroxyalkyl groups,
represents an aromatic residue substituted with a hydroxyalkoxy group, a hydroxyalkylthio group or an aralkyl group, or an aromatic group in which two adjacent carbon atoms are substituted with one alkylene group, R' independently has the same meaning as R, and q represents a number of 0 or 1, and when R is an aromatic residue, when q is 0, it is substituted by an alkylene group. or both positions ortho to the N atom in the formula are not substituted by each of the aforementioned groups], based on the total amount of the polymer, at least 5 mol% or more. A method for forming a protective layer or relief image on a substrate, characterized in that a material coated with a sensitive polymer is imagewise exposed, optionally through a photomask, and optionally the exposed areas are subsequently removed using a developer. .