KR100525586B1 - A negatively acting photoresist composition based on polyimide precursors - Google Patents

Abstract

The negative photoresist composition of the present invention is a negative photoresist composition comprising a polyimide precursor (a) containing a repeating structural unit of formula (I-1), wherein the composition is a repeat of formula (I-1) having R ₂ residues. Since it contains many structures, it can be developed with alkaline aqueous developing solution for photoresists which does not contain an organic solvent.

Description

A negatively acting photoresist composition based on polyimide precursors

The present application relates to a negative photoresist composition containing a polyimide precursor (a) containing a repeating structural unit of formula (I) and a photoinitiator (b) for olefinic double bond polymerization.

In Formula I above,

A ₁ represents an oxygen atom or an NH group,

R represents the same or different organic moiety, at least some of which are photopolymerizable,

[X] represents the cyclic dianhydride residue of the same or different tetracarboxylic acid remaining after removal of the anhydride group,

Y represents the same or different diamine residue remaining after removing the amino group.

Photoresists of the type named at the beginning of the specification have been known for a long time and are described, for example, in US Pat. No. 3,957,512, US Pat. No. 4,040,831, US Pat. No. 4,548,891 or EP 0 624 826. (US Patent Application No. 08 / 524,648). In the named photoresist composition, residue R represents all organic moieties having photopolymerizable olefinic double bonds, such that the composition is subjected to the action of radiation having an appropriate wavelength through the photopolymerizable olefinic double bonds in the photoreactive polyimide precursor. By crosslinking. Named negative resists are very photosensitive and exhibit only very few removal [striping] portions that are unclear at development. In addition, coatings formed with their help can be converted to polyimide coatings by curing after exposure and development, which in particular has the advantage that the coatings become heat resistant. However, to date such negative photoresists have the disadvantage that they have to be treated substantially with a developer consisting entirely of organic solvents (which are of course undesirable due to the costs associated with environmentally friendly processing and its flammability).

ACS Polym. Prep. Vol. 33 (1), April 1992, Rumiko Hayase et al., Discloses 80% by weight of the polyimide precursor of formula I above, where R represents a 2-hydroxybenzyl moiety and is usually used for conventional positive photoresists. A positive photoresist composition consisting of 20% by weight of a naphthoquinone diazide compound used as a radiation-sensitive dissolution inhibitor is described. For the development of the positive type photoresist described above, in fact, a conventional alkaline aqueous developer mainly for photoresist may be used, for example a developer comprising an aqueous tetramethylammonium hydroxide solution, but these solutions may be used in a developer. It should still contain a significant amount of methanol (approximately 12% by volume) in order for the dissolution rate of the photoresist material to In addition, the positive type photoresist described above has a relatively large number of unclear stripping portions, which causes problems in process stability.

An object of the present invention is to provide a general type of negative photoresist composition based on the polyimide precursor of formula (I) as described above, in general working conditions such as conventional alkaline aqueous developer, for example commercially available alkaline aqueous developer. To make it available under

Brief summary of the invention

According to the invention, this object is achieved by the use of one or more substituents which increase the solubility of the photoresist composition in an alkaline aqueous medium and the R ₁ organic moiety wherein the radical R of the repeating structural unit of formula I has a photopolymerizable olefinic double bond. A negative photoresist containing a polyimide precursor (a) containing a repeating structural unit of formula (I-1) and an photoinitiator for olefinic double bond polymerization (b), which is an organic residue selected from R ₂ aryl residues The present invention is characterized in that the composition comprises a large number of structural units of formula (I-1) having R ₂ aryl moieties as a whole, so that the composition can be developed with an alkaline aqueous developer for photoresist that does not contain an organic solvent. Is solved by a negative photoresist composition.

delete

In Formula I-1 above,

A ₁ represents an oxygen atom or an NH group,

R is the same or different and at least a portion of the photopolymerizable organic moieties, R ₂ aryl having R ₁ organic moiety having a photopolymerizable olefinic double bond and at least one substituent which increases the solubility of the photoresist composition in an alkaline aqueous medium. Selected from residues,

[X] represents the cyclic dianhydride residue of the same or different tetracarboxylic acid remaining after removal of the anhydride group,

Y represents the same or different diamine residue remaining after removing the amino group.

Group [X] represents the same or different di-anhydride member residues remaining after, for example, eliminating anhydride groups in a photoreactive polyimide precursor of formula (I-1) suitable for the present invention or C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy derivatives: pyromellitic dianhydride (= PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4 '-Diphenyl sulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3', 4'-biphenyl tetracarboxylic dianhydride, 2, 3,3 ', 4'-benzophenone tetracarboxylic dianhydride, dianhydride of oxydiphthalic acid, especially 3,3', 4,4'-diphenyloxide tetracarboxylic dianhydride, (4,4'-oxydiphthalic acid 2 anhydride), 2,3,6,7-b Phthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dica Carboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane 3,3,4,4-tetracarboxylic dianhydride , 1,4,5,6-naphthalene tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 1,2 , 4,5-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride, 1,1-bis (2,3- Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride. These compounds are known and some are commercially available. It is also possible to use mixtures of dianhydrides as named above.

Group Y may represent residues of the same or different aliphatic, cycloaliphatic or aromatic diamines remaining after removal of the amino group: 1,2-diaminoethane, 1,2-diaminopropane, 1,3- Diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (amino Methyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone diamine; m- and p-phenylenediamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4'- and 3,3'-diaminodiphenyl ether, 4,4 ' And 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenylsulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4 '-And 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3 '-Dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis ( 3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 4,4'-diaminoparaphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy ) Phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4 '-Diaminodiphenylsulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, bis [4- (4-aminophenoxy) phenyl ether, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoro Lopropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3 ', 4,4'-tetraaminobiphenyl , 3,3 ', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, bis [4- (4-aminophenoxy) phenyl] sulfone, Bis [4- (3-aminophenoxy) phenyl] sulphone, bis [4- (2-aminophenoxy) phenyl] sulphone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9, 9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diami Diphenylsulfone, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenyl Rendiamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, dia Minobenzotrifluoride, diaminoanthraquinone, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4 -Aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2, 2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-di Butylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino- 2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoro Methylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy ) Diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3 ', 5,5'-tetramethyl-4,4 '-Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2', 5,5 ', 6,6'-hexfluorotolidene and 4,4' '' -Diaminoquaterphenyl.

In addition to the repeating structural units of formula (I-1) based on the group [X] or group Y type, the polyimide precursors of the compositions according to the invention are also of formula (I-1) based on two or more other types of these groups. It may include structural units. The polyimide precursor may also comprise structural units of formula (I-1) which are structural isomers of each other. The mode of the presence of structural isomeric pairs of units of formula (I-1) is shown by way of example of units of formula (I-1) derived from pyromellitic acid as group [X] (A ₁ is —O—):

A ₁ preferably represents an oxygen atom in formula (I-1).

In formula (I-1), R ₁ represents, for example, vinyl, allyl, metallyl or a residue of formula (III).

In Formula III above,

R ₄ represents hydrogen or methyl,

R ₅ represents —C _n H _2n —, where n is 2 to 12, —CH ₂ CH (OH) CH ₂ — or polyoxyalkylene having 4 to 30 carbon atoms.

Suitable examples of residues R ₅ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, —CH ₂ CH (OH ) CH ₂ -,-(CH ₂ CH ₂ O) _m -CH ₂ CH _2- , , (CH ₂ CH ₂ CH ₂ O) _m -CH ₂ CH ₂ CH ₂ -and-(CH ₂ CH ₂ CH ₂ CH ₂ O) _m -CH ₂ CH ₂ CH ₂ CH _2- (where m is 1 to 6). R ₅ is preferably ethylene, propylene, trimethylene or —CH ₂ CH (OH) CH ₂ and R ₄ is preferably methyl.

Especially preferably, R ₁ is a residue of formula III wherein R ₄ is methyl and R ₅ represents ethylene.

Preferably the R ₂ group is selected from aryl and aralkyl moieties, particularly preferably C ₆ -C ₂₀ aryl and C ₇ -C ₂₅ aralkyl moieties, very particularly preferably phenyl and benzyl moieties, these Each has 1, 2 or 3, preferably one acidic moiety bound to an aryl carbon atom as a substituent which increases the solubility of the photoresist composition in alkaline aqueous medium. Especially preferably this moiety comprises a HO group.

It has been found that the negative photoresist compositions according to the invention are particularly excellent, wherein R ₂ is selected among 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

In the photoresist composition according to the invention, the molar ratio between the R ₁ group and the R ₂ group is preferably 4: 1 to 1: 4, in particular 1: 1 to 1: 2.

For example, the composition according to the invention may be based on one type of polyimide precursor comprising both residues of the R ₁ and R ₂ type.

Another embodiment includes, for example, at least one polyimide precursor (a1) containing a repeating structural unit of formula (I-1) in which R represents an organic moiety R ₁ having an olefinic double bond capable of photopolymerization and R is alkaline. Polyimide precursors composed of at least one other polyimide precursor (a2) containing a repeating structural unit of formula (I-1) representing an aryl residue R ₂ having one or more substituents which increases the solubility of the photoresist composition in an aqueous medium It is formed by the composition containing the composition of as a component (a).

After developing the exposed area of the resist with a sufficiently high unit ratio of the formula (I-1) in the polymer, as long as at least 50% of the initial thickness of the resist coating is present (having 50% layer thickness in development), The polyimide precursor may include other types of repeating structural units in addition to the repeating units of formula (I-1) described above.

The weight average molecular weight (M _w ) of the photoreactive polyimide precursor is preferably 1,000 to 100,000, particularly preferably 3,000 to 50,000, most preferably 5,000 to 30,000. Particular light-average molecular weight of the reactive polyimide precursor (M _w) of, for example, can be measured by gel permeation chromatography using polystyrene calibration (calibration).

Photoreactive polyimide precursors are similar to known methods, for example in ACS Polym. Prep., Vol. 33 (1), April 1992] or European Patent Publication No. 0 624 826. In addition, the manufacturing method of a polyimide precursor can refer to an Example.

In general, as the photoinitiator component (b), any photoinitiator known to those skilled in the art may be useful, and they are very photosensitive in the wavelength region in question, thereby making the resist composition photosensitive. Examples of such photoinitiators are described in K.K.Dietliker, “Chemistry and Technology of UV and EB formulation for Coatings, Inks and Paints”, Volume 3: “Photoinitiators for Free Radical and Cationic Polymerization.”. For example, benzoin ethers such as benzoin methyl ether, ketals such as diethoxyacetophenone or benzyldimethyl ketal, hexaarylbisimidazole, quinones such as 2-3 tert-butyl Anthraquinones or thioxanthones are suitable, and they are amine initiators, for example thioxanthone, 2-isopropylthioxanthone or 2-chlorothioxanthone, azide and acylphosphine oxides, for example Preference is given to using with 2,4,6-trimethylbenzoyldiphenyl phosphine oxide.

Other examples of suitable photoinitiators include oxime esters described in particular US Pat. No. 5,019,482, which are considered part of this application, as well as ketocoumarin derivatives and activators described in detail in US Pat. No. 4,366,228, incorporated herein by reference. And photoinitiator systems containing amines as examples.

As photoinitiator (b), preference is given, for example, to titanocenes, for example known from U.S. Pat.

Another preferred photoinitiator that can be used in the process according to the invention is the oxime ester described in US Pat. No. 5,019,482. With some specific triketone oxime esters, dark coloring does not occur in the mixture even when heated to high temperatures. Such particularly preferred triketooxime esters are compounds of formula VIII

In the above formula (VIII),

R ₁₇ residues independently of one another represent p-tolyl, p-alkoxyphenyl or mesityl,

R ₁₈ represents C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl, C ₆ -C ₁₄ arylcarbonyl or C ₆ -C ₁₄ aryloxycarbonyl.

Triketone oxime esters of formula VIII are known methods, for example, converting the corresponding triketones into oximes (for example according to "Organic Synthesis", Vol. 40, Pages 21-23), It can then be prepared by reacting with an acid chloride or chlorocarbonyl acid ester. In the most preferred compounds of formula VIII, R ₁₇ represents p-tolyl and R ₁₈ represents C ₆ -C ₁₄ arylcarbonyl. Especially preferred are compounds of formula VIIIa.

Suitably the composition according to the invention contains from 0.1 to 20% by weight, in particular from 1 to 10% by weight of component (b) relative to component (a).

Triketooxime esters of formula (VIII) are preferably used with aromatic amines of formula (IX):

In Formula IX above,

The two R ₁₉ residues each independently represent C ₁ -C ₃ alkyl or C ₁ -C ₃ hydroxyalkyl or together with the N atom form a morpholine group,

R ₂₀ represents a C ₁ -C ₃ alkyl group, a C ₂ -C ₅ alkylcarbonyl group or a C ₇ -C ₁₀ arylcarbonyl group.

Examples of suitable aromatic amines of formula (IX) include 4-dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-dimethylaminobenzophenone, 4-morpholinobenzophenone, N-phenyldiethanolamine, Np-tolyldi Ethylamine and Np-tolyldiethanolamine. The aromatic amine of formula (IX) is added in an amount of approximately 0.5 to 5% by weight relative to component (a).

The named triketooxime and triketooxime / amine mixtures are particularly suitable for exposure to radiation of mercury i-rays. By the further use of photosensitizers, photosensitivity can also be obtained in other spectral regions, such as g-ray (436 nm) wavelengths. For example, coumarin of formula (X) can be added.

In Formula X above,

R ₂₁ and R ₂₂ are each independently C ₁ -C ₆ alkyl group,

R ₁₈ represents C ₁ -C ₆ -alkylcarbonyl, C ₁ -C ₆ -alkoxycarbonyl, C ₆ -C ₁₄ -arylcarbonyl or C ₆ -C ₁₄ -aryloxycarbonyl.

Preferably, the coumarins described in US Pat. No. 5,019,482 are used, in particular the coumarins mentioned as examples in this document. Particular preference is given to coumarins of formula (Xa).

Coumarins of formula (X) are generally used in amounts of 0.1 to 5% by weight, based on component (a). Another particularly preferred coumarin is a compound of formula XI:

In the above formula (XI),

R ₂₁ and R ₂₂ represent methyl or ethyl groups.

Such coumarin derivatives are also suitably used in amounts of 0.1 to 5% by weight relative to component (a).

The photosensitivity of the compositions according to the invention can be increased by adding aromatic heterocyclic compounds comprising at least one mercapto group. Examples of such compounds include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1H-tetrazole, 2-mercapto-4-phenylthiazole, 2-amino- 5-mercapto-4-phenylthiazole, 2-amino-4-mercapto-1,3,4-thiazole, 2-mercaptoimidazole, 2-mercapto-5-methyl-1,3,4 -Thiazole, 5-mercapto-1-methyl-1H-tetrazole, 2,4,6-trimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2,5-dimercapto-1,3,4-thiadiazole, 5-mercapto-1,3,4-thiadiazole, 1-ethyl-5-mercapto-1,2,3,4-tetra Sol, 2-mercapto-6-nitrothiazole, 2-mercaptobenzoxazole, 4-phenyl-2-mercaptothiazole, mercaptopyridine, 2-mercaptoquinoline, 1-methyl-2-mercaptoimida Sol and 2-mercapto-naphthothiazole. Such mercapto compounds are generally used in amounts of 0.5 to 5% by weight relative to component (a). Preferably 2-mercaptobenzothiazole is used.

Another particular type of embodiment of the invention includes coumarins of formula (XII) mixed with amino acids of formula (XIV) as a photoinitiator system:

In formula (XII) above,

R ₂₃ and R ₂₄ each independently represent hydrogen or C ₁ -C ₆ alkoxy,

R ₂₅ represents C ₆ -C ₁₄ aryl or a residue of formula XIII.

In formula (XIII) above,

R ₂₃ and R ₂₄ are the same as defined in formula (XII).

In Formula XIV above,

R ₂₆ is hydrogen, methyl, ethyl, i-propyl, t-butyl, phenyl, methoxy, ethoxy, hydroxy, hydroxymethyl, dimethylamino, diethylamino, acetyl, propionyl, acetyloxy, propionyloxy , -NHCONH ₂ or -NHCOOCH ₃ .

Coumarins of formula (XII) are known, for example, from US Pat. No. 4,278,751. Preference is given to coumarins of formula (XII) in which one of the R ₂₃ or R ₂₄ residues represents methoxy. 3-benzoyl-7-methoxycoumarin is particularly preferred. In addition, amino acids of the formula (XIV) are known and described, for example, in Japanese Patent Laid-Open No. 03 (1991) -170,551 (Chem, Abstr., Vol. 116 (1992), 31468b). It is. Preferably, N-phenylglycine is used. Corresponding compositions of the invention generally contain from 0.2 to 5% by weight of coumarin of formula XII and from 0.5 to 10% by weight of amino acid of formula XIV relative to component (a).

In particular, other suitable sensitizers that can be used in combination with coumarins of formula (XII) are described in Japanese Unexamined Patent Publication (Kokai) [1991] 03-170,552 (Chem. Abstr., Vol. 116 (1992), 48941y). The oxazolones described in, in particular the oxazolones of the formula XV.

In Formula XV above,

R ₂₇ represents a group of formula XVI or formula XVII.

In the above formulas XVI and XVII,

R ₂₈ is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, phenyl, hydroxy, methoxy, ethoxy, n-propoxy, n-butoxy, phenoxy, benzyl , 2-phenylethyl, hydroxymethyl, 2-hydroxyethyl, acetyl, propionyl, acetyloxy, propionyloxy, aminomethyl, 2-aminoethyl, methylamino, dimethylamino, diethylamino, -CONH ₂ , -CONHCH ₃ , -CON (CH ₃ ) ₂ , -CONHC ₂ H ₅ or -CON (C ₂ H ₅ ) ₂ .

Thus, the preferred oxazolone is 3-phenyl-5-isooxazolone.

Compositions of the present invention based on the preferred photoinitiator and initiator systems described above are particularly suitable for forming relief structures with mercury i-ray irradiation because of their high permeability in the i-ray region. However, since the compositions have very high photosensitivity in a broad range of approximately 200 nm to approximately 600 nm, their use area is not limited to i-ray exposure. Rather, actinic radiation of a wide variety of wavelengths can be used; In addition to irradiation of specific wavelengths (eg g-rays), broadband exposure is also possible.

Although generally unnecessary, to further enhance solubility in alkaline aqueous developer solutions, the negative photoresist compositions of the present invention may also include component (c):

Organosilicon compounds having at least one hydroxyl group (c1),

Compound (c2) of formula (IIa),

Compound of formula IIb (c3) and

at least one other component (c) selected from the group consisting of a mixture (c4) consisting of two or more components selected from components of the types (c1), (c2) and (c3).

In Formula IIa above,

A ₂ and A ₃ each independently represent an oxygen atom or an NR ₇ group, wherein R ₇ represents a hydrogen atom or a C ₁ -C ₄ alkyl group,

[G] represents a divalent aliphatic or aromatic group which is unsubstituted or has one or more hydroxyl substituents,

R ₆ represents an aryl moiety having one or more substituents which increases the solubility of the composition in an alkaline aqueous medium,

R ₃ represents a moiety having at least one photopolymerizable olefinic double bond,

y and z each independently represent 0 or 1.

In Formula IIb above,

R ₀ represents the same or different residues having olefinic double bonds that are photopolymerizable,

[M] is a cyclic dianhydride residue of tetracarboxylic acid remaining after removal of the anhydride group.

Organosilicon compounds (c1) are, for example, organosilanols and organosiloxanes having one or two hydroxyl groups, in particular triphenylsilanol, diphenylsilanediol, 1,4-bis (hydroxydimethyl Silyl) benzene and 1,3-bis (4-hydroxybutyl) tetramethyldisiloxane.

The compound of formula IIa contains, as residue R ₆ , preferably an aryl residue having 6 to 14 ring carbon atoms, which has one or more substituents, in particular suitably substituted phenyl residues, which increase the solubility of the composition in an alkaline aqueous medium. have. In principle, any acid residue can be used as a substituent on an aryl residue, such as a sulfonic acid residue, a HOOC 'residue or a HO residue. When [G] represents a divalent aliphatic group in the compound of formula IIa, it is suitably a C ₁ -C ₁₀ alkylene group, preferably a C ₂ -C ₆ alkylene group, particularly preferably a straight chain C _2- C ₆ alkylene group, for example ethylene, trimethylene or tetramethylene group, which is unsubstituted or has one or more hydroxyl substituents. If [G] represents a divalent aromatic group in the compound of formula (IIa), it preferably contains 6 to 20 ring carbons and, if possible, for example C ₁ -C ₄ alkylene group, in particular formula -CH _2- Or bridge members such as> C (CH ₃ ) ₂ , or> C═O or an oxygen atom to bridge two or more aromatic rings in the above groups. Particular preference is given to vinyl and isopropenyl groups, as the residues R ₃ in formula (IIa) comprise especially C ₂ -C ₆ alkenyl groups.

Examples of preferred compounds of formula IIa include, among others

As well as compounds of formula (IIa) in which both A ₂ and A ₃ both represent an oxygen atom and both y and z represent 1. For example,

to be.

Group [M] represents, for example, the residue of one of the dianhydrides remaining after removal of the anhydride group in the case of the compound of formula (IIb), which is described in the description above for group [X]. Group R ₀ in formula (IIb) represents, for example, vinyl, allyl, metallyl or a residue of formula (III).

Formula III

In Formula III above,

R ₄ represents a hydrogen atom or methyl,

R ₅ represents —C _n H _2n —, —CH ₂ CH (OH) CH ₂ — or n of 2 to 12 polyoxyalkylene having 4 to 30 carbon atoms.

Suitable examples of R ₅ residues include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, -CH ₂ CH (OH ) CH ₂ -,-(CH ₂ CH ₂ O) _m -CH ₂ CH _2- , ,-(CH ₂ CH ₂ CH ₂ O) _m -CH ₂ CH ₂ CH ₂ -and-(CH ₂ CH ₂ CH ₂ CH ₂ O) _m -CH ₂ CH ₂ CH ₂ CH _2- (where m is 1 To 6). R ₅ is preferably ethylene, propylene, trimethylene or —CH ₂ CH (OH) CH ₂ — and R ₄ is preferably methyl. As for the residue of general formula (III), it is especially preferable that R <_4> represents methyl and R <_5> represents ethylene. Specific examples of the compound of formula IIb include There is this.

delete

If present, component (c) is preferably

Triphenylsilanol, diphenylsilanediol, 1,4-bis (hydroxydimethylsilyl) benzene and 1,3-bis (4-hydroxybutyl) tetramethyldisiloxane (c1) and

A C ₂ -C ₆ alkylene group in which [G] is unsubstituted or has at least one hydroxyl substituent, in particular of the formula -C ₂ H ₄ -and Represents a group of

R ₃ represents a vinyl group or isopropenyl group,

R ₆ is selected from the group of substances consisting of compound (c2) of formula (IIa) which represents a phenyl moiety having 1, 2 or 3 substituents selected from HO and HOOC substituents.

Component (c2) is particularly preferably R ₆

And a compound of formula (IIa) representing a group selected from the group consisting of:

As component (c2), compounds of formula (IIa) in which A ₂ and A ₃ both represent an oxygen atom and both y and z represent 1 are preferred.

Component (c) may be included in an amount of from 10 to 40% by weight, based on the total amount of component (a) + component (c) in the photoresist composition according to the invention, for example. A mixture of type (c4) consisting of at least one component of type (c2) and at least one component of type (c1), wherein the weight ratio of component (c1) to component (c2) is preferably approximately 1: 1. It is suitable as this component (c1). Therefore, component (c1) is preferably a silanediol such as diphenylsilanediol.

Another particular type of embodiment of the negative photoresist according to the invention is a component selected from methacrylic esters of aliphatic and aromatic polyols and acrylic esters, allyl ethers of aliphatic and aromatic polyols and allyl esters of aliphatic and aromatic polycarboxylic acids ( d).

Component (d) can be present alone as well as in combination with component (c).

As component (d), for example, esters and partial esters of ethers and in particular of acrylic or methacrylic acids with aromatic polyols and especially aliphatic polyols having 2 to 30 carbon atoms or preferably alicyclic polyols having 5 or 6 ring carbon atoms, Is considered. These polyols can also be modified using epoxides such as ethylene oxide or propylene oxide. In addition, esters and partial esters of polyoxyalkylene glycols are also preferred. Examples of suitable component (d) include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate , Tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and polyethylene glycol di (meth) acrylates having an average molecular weight of 200 to 2000. Trimethylolpropane ethoxylate tri (meth) acrylate, trimethylolpropane polyethoxylate tri (meth) acrylate with an average molecular weight of 500-1500, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythrate Lithol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, 1,3-butanediol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta ( Meth) acrylate, sorbitol hexa (meth) acrylate, oligoester (meth) acrylate, glycerin di (meth) acrylate, Glycerin tri (meth) acrylate, 1,4-cyclohexane di (meth) acrylate, bis (meth) acrylate of polyethylene glycol having an average molecular weight of 500-1500, ethylene glycol diallyl ether, trimethylpropane triallyl ether, Pentaerythritol triallyl ether, succinic acid and adipic acid diallyl ether or mixtures of these compounds.

Preferred compositions according to the invention comprise 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the total amount of component (a), component (b), component (c) and component (d), respectively. Photoinitiator (b), if present, 25 to 45% by weight of component (c) and, if present, 3 to 50% by weight, preferably 5 to 25% by weight of component (d). Therefore, it occupies a residual amount such that component (a) adds up to 100% by weight, which is based on the total amount of components (a), (b), (c) and (d) in the composition, It is preferably contained in an amount of 20 to 95% by weight, in particular 40 to 70% by weight, very particularly 50 to 65% by weight.

The compositions according to the invention also contain other additives, for example stabilizers, in particular thermal polymerization inhibitors such as thiodiphenylamine and alkylphenols such as 4-tert-butylphenol, 2,5-di -Tert-butylhydroquinone or 2,6-di-tert-butyl-4-methylphenol. Other suitable initiators and sensitizers include, for example, aromatic ketones such as tetramethyldiaminobenzophenone, benzophenone, Michler ketones and other aromatic ketones such as US Pat. No. 3,552,973. The compounds described in, benzoin, benzoin ethers such as benzoin methyl ether, methyl benzoin, ethyl benzoin, p-maleimidobenzenesulfonic acid azide, thioxanthone derivatives, for example thioxanthone , 2-chloro thioxanthone or 2-isopropyl thioxanthone or bis azide, for example, 2,6- (4'-azidobenzylidene-4) -methylcyclohexan-1-one have. Other additives may be used alone or in combination with solvents such as N-methylpyrrolidone, butyrolactone, ethylene glycol monomethyl ether, cyclopentanone, dimethylformamide, dimethylacetamide and hexamethylphosphoric acid. Triamide; Pigments, colorants, fillers, adhesives, wetting agents and emollients, as well as dyes that may affect the spectral sensitivity of the mixture by inherent absorbance.

The photosensitive composition is prepared by mixing the components in a conventional apparatus for this purpose.

The photosensitive composition can be any type of substrate, for example metals, semimetals and silicon, such as ceramics, copper or aluminum, into which a structured protective layer or photographic image can be introduced by treatment of a coating with a developer followed by photopolymerization. It is particularly suitable as a coating for semiconductor materials such as germanium, GaAs, SiO ₂ and Si ₃ N ₄ layers.

As already explained above, the negative photoresist according to the present invention has the great advantage that it can be developed even with a pure alkaline aqueous developer as compared to conventional negative resists based on the polyimide precursor of formula (I). By "developable" is meant that the developer can completely remove a 10 μm thick layer of resist from the substrate, preferably within 5 minutes. Therefore, a preferred alkaline aqueous medium is a conventional alkaline aqueous developer for the development of conventional positive photoresists based on phenolic binders such as, for example, 1,2-diazonaphthoquinone and novolac. Such developer solutions are known in the art and include, as alkaline compounds, for example, sodium or potassium hydroxides, the corresponding carbonates, bicarbonates, silicates, metasilicates, but preferably no metals, For example, ammonia or amines such as ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamines, for example dimethylethanol Amines, triethanolamines, quaternary ammonium hydroxides such as tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide. Suitable alkaline aqueous developing solutions are generally 0.5 N or less with respect to alkali, but may also be diluted appropriately before use. For example, alkaline aqueous solutions of approximately 0.15 N to 0.4 N, preferably 0.20 N to 0.35 N are suitable.

The invention also

Coating the substrate with the negative photoresist composition described above (A),

Exposing an image area of the coated substrate (B) and

A method of forming a relief image, comprising the step (C) of removing an unexposed portion using an alkaline aqueous developer containing no organic solvent.

For example, a coated substrate can be prepared by preparing a solution or suspension of the composition. The solvent and concentration are selected mainly depending on the type of composition and the coating method. The solution is uniformly introduced onto the substrate by known coating methods such as spinning coating, immersion coating, doctor-blade coating, suspended casting, painting, spraying, in particular electrostatic spraying and reverse phase-roll coating. It is also possible to coat a final substrate, such as a printed circuit board covered with copper, by introducing a photosensitive layer onto a temporary, flexible carrier and then layer transporting through lamination.

The amount coated (layer thickness) and the type of substrate (layer carrier) depend on the desired application. It is particularly advantageous that the photosensitive composition can be used in a wide variety of layer thicknesses. This layer thickness ranges from approximately 0.5 μm to 100 μm or more.

As is known, the photopolymerization of (meth) acrylates and similar olefinically unsaturated compounds is inhibited by air, in particular oxygen in the air in the thin layer. This effect can be mitigated by known conventional methods such as, for example, introducing a temporary covering layer of polyvinyl alcohol, preexposure or preconditioning under inert gas.

After coating, the solvent is generally dried to remove leaving a layer of photosensitive composition on the carrier. Exposing the material to radiation to form an image is done in a general manner. The radiation wavelength used here typically depends on the particular composition, in particular the photoinitiator used and the sensitizer used, if present. Suitable radiation wavelengths are generally 200 to 600 nm, preferably 300 to 450 nm.

After exposure, the unexposed portions of the photoresist are treated with a developer to remove in a conventional manner, as described in more detail above.

After development, curing (D) of the exposed and developed material is preferably performed. The curing is preferably carried out at a temperature of 300 ° C. to 400 ° C., whereby the polyimide precursor is converted to a heat-stable polyimide and the volatile portion is removed, resulting in a stable relief structure at high temperatures.

The method according to the invention is characterized by providing a relief structure which is very photosensitive during exposure, resistant to heat and chemicals and has a sharp edge. For example, if the coating thickness reaches 10 μm, a structure with a minimum size of 8-10 μm can be resolved with the above procedure without further processing.

Fields in which the method of the present invention can be used include use as electronic photoresists (galvanic (electrolyte) resists, etching resists, solder top resists), production of printing plates such as offset printing plates or screen printing plates, Use in etching molded articles and in the manufacture of polyimide protective lacquers and dielectric layers, particularly in electrical engineering, in particular microelectronics.

Therefore, since the present invention relates to a method for manufacturing an electronic device, the method includes a method for forming a relief image as described above.

Example 1.1

Preparation of polyimide precursors from pyromellitic dianhydride (PMDA), 4,4'-oxydianiline (ODA) and 3-hydroxybenzyl alcohol (3-HBA)

14.06 g (64.5 mmoles) of pyromellitic dianhydride (dry for 12 hours at 140 ° C.) and 16.33 g (131.58 mmoles) of 3-hydroxybenzyl alcohol are suspended in 50 ml of N-methylpyrrolidone (NMP), followed by molecular sieve. (molecular sieve) to dry. The suspension is heated at 100 ° C. for 3 hours, giving a clear solution after a few minutes. The reaction mixture is cooled to room temperature and 21.43 g (270.9 mmoles) of pyridine and 90 ml of N-methylpyrrolidone are added. The reaction mixture is then cooled to −10 ° C. and 16.12 g (135.5 mmole) of SOCl ₂ is added over 10 minutes while maintaining the temperature at −10 ± 4 ° C. During the addition of SOCl ₂ , the viscosity increases. After dilution with 50 ml of N-methylpyrrolidone, the mixture is stirred at room temperature for 2 hours. Subsequently, 11.08 g (58.7 mmoles) of oxydianiline (ODA) dissolved in 100 ml of N-methylpyrrolidone is added dropwise to the reaction mixture at 20 to 23 ° C for 20 minutes. The mixture is then left to stir overnight at room temperature. Finally, the polyimide precursor is precipitated in 5 L of water and the water-polymer mixture is stirred for 15 minutes at a speed of 5000 rpm. The polymer is filtered off, stirred again in 4 L of water for 30 minutes and then filtered off again. Finally, the polyimide precursor thus obtained is dried at 45 ° C. for 3 days under vacuum.

Example 1.2

16.58% by weight of a photoreactive polyimide precursor (a) formed from pyromellitic dianhydride, 4,4'-oxydianiline and methacrylic acid-2-hydroxyethyl ester, having a molecular weight of approximately 13,000,

16.58 weight% of the polyimide precursor (a) formed from Example 1.1,

1.16 wt% titanocene (b) according to formula (VII),

8.29% by weight of diphenylsilanediol (c1),

8.29% by weight of 3- (o-hydroxybenzoyloxy) -2- (hydroxy) propyl methacrylate (c2),

4.97 weight% of tetraethylene glycol dimethacrylate (d),

0.07% by weight of 1,4-benzoquinone,

0.10% by weight of 3,3'-carbonylbis (7-diethylaminocoumarin) and

43.96% by weight of N-methylpyrrolidone

The negative photoresist composition prepared by mixing was poured into a container and rotated overnight to form a clear resin solution, followed by pressure filtration through a filter having a pore size of 0.8 μm. After spinning the resin solution on a silicon wafer pretreated with a binder (3500 rpm, 30 seconds), the coated wafer is dried on a hotplate at 100 ° C. for 5 minutes. As a result, a uniform polymer layer having a thickness of 10 mu m is obtained on the silicon wafer.

Subsequently, the wafer is exposed in a vacuum of an Karl-Suess MA 150 type exposure apparatus, using a chrome mask. Exposure is performed using a mercury ultrahigh pressure lamp, and the irradiation power is measured with an OAI power meter and a 405 nm probe. After exposure, the image is developed for 75 seconds with an aqueous 0.262N tetramethylammonium hydroxide (TMAH) solution, followed by washing with water. For the process described, an exposure energy of 250 mJ / cm 2 is required to form a good structure. The sharpness of the edge is good and a highly resolved relief structure is obtained, which still resolves a line of 20 μm in width.

Example 2.1

Preparation of polyimide precursors of pyromellitic dianhydride (PMDA), 4,4'-oxydianiline (ODA) and 2-hydroxybenzyl alcohol (2-HBA)

14.06 g (64.5 mmoles) pyromellitic dianhydride (dry for 12 hours at 140 ° C.) and 16.33 g (131.58 mmoles) 2-hydroxybenzyl alcohol are suspended in 50 ml of N-methylpyrrolidone (NMP), followed by molecular sieve. Dry through. The suspension is heated at 100 ° C. for 3 hours to give a clear solution after several minutes. Next, 11.75 g (58.7 mmoles) of 4,4'-oxydianiline (ODA) dissolved in 25 g of N-methylpyrrolidone is slowly added at room temperature. The reaction mixture was cooled to a temperature of 5 to 10 ° C., and 26.62 g (129 mmol) of N, N′-dicyclohexyl carbodiimide (DCC) dissolved in 75 g of N-methylpyrrolidone was 30 at a temperature of 5 to 10 ° C. It is added dropwise to the reaction mixture for a minute. The resulting mixture is then first stirred at this temperature for 1 hour and then at room temperature overnight. The reaction mixture is then filtered and the filter cake is washed with N-methylpyrrolidone. Precipitation and further workup of the polyimide precursor are carried out in accordance with Example 1.

Example 2.2

16.58% by weight of a photoreactive polyimide precursor (a) formed from pyromellitic dianhydride, 4,4'-oxydianiline and methacrylic acid-2-hydroxyethyl ester, having a molecular weight of approximately 13,000,

16.58 weight% of the polyimide precursor (a) formed from Example 2.1,

1.16 wt% titanocene (b) according to formula (VII),

8.29% by weight of diphenylsilanediol (c1),

8.29% by weight of 3- (o-hydroxybenzoyloxy) -2- (hydroxy) propyl methacrylate (c2),

4.97 weight% of tetraethylene glycol dimethacrylate (d),

0.07% by weight of 1,4-benzoquinone,

0.10% by weight of 3,3'-carbonylbis (7-diethylaminocoumarin) and

43.96% by weight of N-methylpyrrolidone

The negative photoresist composition prepared by mixing was treated according to the procedure of Example 1.2, except that the image was developed with a 0.331N aqueous solution of tetramethylammonium hydroxide (TMAH). In the description process, 250 mJ / cm 2 of exposure energy is required to form a good structure. The sharpness of the edge is good and a highly resolved relief structure is obtained, which still resolves a line of 20 μm in width.

Example 3.1

Preparation of polyimide precursors of pyromellitic dianhydride, 4,4'-oxydianiline, 3-hydroxybenzyl alcohol and 2-hydroxyethyl methacrylate (HEMA)

14.06 g (64.5 mmoles) pyromellitic dianhydride (dried for 12 hours at 140 ° C.), 18.6 g (129 mmoles) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone and 10.7 g pyridine were mixed into 140 g of diglyme, Stirred at 60 ° C. for 18 hours to form diesters of pyromellitic acid with 2-hydroxyethyl methacrylate. A diester of pyromellitic acid and 3-hydroxybenzyl alcohol is prepared as described in Example 1.1. An equimolar mixture of these two diesters is chlorinated with SOCl ₂ and converted to the final polyimide precursor using 4,4′-oxydianiline as instructed in Example 1.1.

Example 3.2

33.16 weight% of the polyimide precursor (a) formed from Example 3.1,

1.16 wt% titanocene (b) according to formula (VII),

8.29% by weight of diphenylsilanediol (c1),

8.29% by weight of 3- (o-hydroxybenzoyloxy) -2- (hydroxy) propyl methacrylate (c2),

4.97 weight% of tetraethylene glycol dimethacrylate (d),

0.07% by weight of 1,4-benzoquinone,

0.10% by weight of 3,3'-carbonylbis (7-diethylaminocoumarin) and

NMP 43.96 wt%

A negative photoresist composition prepared by mixing was prepared according to Example 2.2. For the described process, exposure energy of 500 mJ / cm 2 is required to form a good structure. The sharpness of the edge is good and a highly resolved relief structure is obtained, which still resolves a line of 20 μm in width.

Example 4

Example 3 is repeated, but 2-hydroxybenzyl alcohol is used instead of 3-hydroxybenzyl alcohol and the negative resist is developed within 25 seconds using aqueous tetramethylammonium hydroxide (TMAH) 0.331N solution. In the process described, 250 mJ / cm 2 exposure energy is required to form a good structure. The sharpness of the edge is good and a highly resolved relief structure is obtained, which still resolves a line of 20 μm in width.

Example 5.1

Except for using a polyimide precursor formed by using a molar ratio of diester of pyromellitic acid and 2-hydroxyethyl methacrylate and diester of pyromellitic acid and 2-hydroxybenzyl alcohol to 1: 2 Repeats Example 3.1.

Example 5.2

39.75% by weight of polyimide precursor (a) formed from Example 5.1,

1.39 wt% titanocene (b) according to formula (VII),

5.97 weight% of tetraethylene glycol dimethacrylate (d),

0.08% by weight of 1,4-benzoquinone,

0.12% by weight of 3,3'-carbonylbis (7-diethylaminocoumarin) and

NMP 52.69 wt%

The negative photoresist composition formed by mixing was treated according to the procedure of Example 2.2, but the negative resist was developed within 25 seconds using an aqueous solution of tetramethylammonium hydroxide (TMAH) 0.331N. In the process described, 250 mJ / cm 2 of exposure energy is required to obtain a good structure. The sharpness of the edge is good and a highly resolved relief structure is obtained, which still resolves a line of 20 μm in width.

Claims (15)

The radical R in formula I-1 is an organic moiety selected from an R ₁ organic moiety having a photopolymerizable olefinic double bond and an R ₂ aryl moiety having at least one substituent which increases the solubility of the photoresist composition in an alkaline aqueous medium. A negative photoresist composition containing a polyimide precursor (a) containing a repeating structural unit of formula (I-1) and a photoinitiator (b) for olefinic double bond polymerization, wherein the composition has a R ₂ aryl moiety. A negative photoresist composition, comprising a large number of structural units of I-1 as a whole, and capable of being developed with an alkaline aqueous developer for photoresist that does not contain an organic solvent. Formula I-1 In Formula I-1 above, A ₁ represents an oxygen atom or an NH group, R is the same or different and some or all of the organic moieties are photopolymerizable, with R ₁ organic moieties having photopolymerizable olefinic double bonds and R ₂ with one or more substituents which increase the solubility of the photoresist composition in an alkaline aqueous medium. Selected from aryl residues, [X] represents the cyclic dianhydride residue of the same or different tetracarboxylic acid remaining after removal of the anhydride group, Y represents the same or different diamine residue remaining after removing the amino group. The photoresist in an alkaline aqueous medium according to claim 1, wherein R is at least one polyimide precursor (a1) containing a repeating structural unit of formula (I-1) wherein the organic moiety R ₁ has a photopolymerizable olefinic double bond. As component (a) a polyimide precursor composition consisting of at least one other polyimide precursor (a2) containing a repeating structural unit of formula (I-1), which is an aryl residue R ₂ having one or more substituents which increases the solubility of the resist composition Negative photoresist composition. The negative photoresist composition of claim 1, wherein the molar ratio between the R ₁ and R ₂ groups in the composition is between 4: 1 and 1: 4. The negative photoresist composition of claim 1, wherein R ₂ is selected from the group consisting of aryl and aralkyl moieties, each having 1 to 3 HO substituents bonded to an aryl carbon atom. The negative photoresist composition of claim 4, wherein R ₂ is selected from the group consisting of 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl. The method of claim 1, Organosilicon compounds having at least one hydroxyl group (c1), Compound (c2) of formula (IIa), Compound of formula IIb (c3) and A negative photoresist composition containing at least one other component (c) selected from the group consisting of a mixture (c4) consisting of at least two components selected from component (c1), component (c2) and component (c3). Formula IIa In Formula IIa above, A ₂ and A ₃ each independently represent an oxygen atom or an NR ₇ group, wherein R ₇ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, [G] represents a divalent aliphatic or aromatic group which is unsubstituted or has one or more hydroxyl substituents, R ₆ represents an aryl moiety having one or more substituents which increases the solubility of the composition in an alkaline aqueous medium, R ₃ represents a moiety having at least one photopolymerizable olefinic double bond, y and z each independently represent 0 or 1. Formula IIb In Formula IIb above, R ₀ represents the same or different residues having olefinic double bonds that are photopolymerizable, [M] is a cyclic dianhydride residue of tetracarboxylic acid remaining after removal of the anhydride group. 7. The composition of claim 6 wherein component (c) Triphenylsilanol, diphenylsilanediol, 1,4-bis (hydroxydimethylsilyl) benzene and 1,3-bis (4-hydroxybutyl) tetramethyldisiloxane (c1) and 1, 2 wherein [G] is unsubstituted or represents a C ₂ -C ₆ alkylene group having at least one hydroxyl substituent, R ₃ represents a vinyl group or isopropenyl group, and R ₆ is selected from HO and HOOC substituents Or a compound of formula IIa (c2) representing a phenyl moiety having three substituents. The compound of claim 6, wherein component (c2) is a compound of Formula ₆ wherein R ₆ is A negative photoresist composition selected from compounds of formula (IIa) representing a group selected from the groups of. 7. The negative photoresist composition of claim 6, wherein component (c2) is selected from compounds of formula (IIa) in which A ₂ and A ₃ both represent an oxygen atom and y and z represent both 1. The negative photoresist composition according to claim 6, wherein component (c) is present in an amount of 10 to 40% by weight relative to the total amount of component (a) + component (c) in the composition. A mixture (c4) according to claim 10, comprising a mixture (c4) comprising at least one component (c1) and at least one component (c2) and wherein the weight ratio of components (c1) to (c2) is from 2: 1 to 1: 2. Negative photoresist composition to contain). The compound of claim 1 further comprising component (d) selected from the group consisting of acrylic and methacrylic esters of aromatic and aliphatic polyols, allyl ethers of aromatic and aliphatic polyols, and allyl esters of aromatic and aliphatic polycarboxylic acids. Negative photoresist composition. Coating the substrate with the negative photoresist composition according to claim 1 (A), Exposing an image area of the coated substrate (B) and A method of forming a relief image, comprising the step (C) of removing an unexposed portion using an alkaline aqueous developer containing no organic solvent. The method of claim 13, further comprising curing (D) the exposed and developed material. A method for manufacturing an electronic device, comprising the relief image forming method according to claim 13.