JPH0130861B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to radiation-sensitive or photopolymerizable polyimide precursor compositions derived from diarylfluoro compounds useful for forming relief structures on electrical or electronic devices such as semiconductors, capacitors, and printed circuits. Photopolymerizable polymeric compositions used to form relief structures on electronic devices are well known, as shown, for example, in U.S. Pat. be. The present invention relates to novel radiation-sensitive polyimide precursor compositions. The radiation sensitive polyimide precursor composition has the following formula: (where n is a positive integer sufficiently large to correspond to the number of units in the polymer and to produce a polymer having a number average molecular weight of about 1500 to 15000, as measured by vapor osmometry, and The → symbol for a particular unit in the incorporation represents isomerization, R ¹ is a divalent aromatic, aliphatic or cycloaliphatic group containing at least 2 carbon atoms, R ² and R ³ is selected from the group consisting of a hydrogen group (radical) and any organic group containing a photopolymerizable olefin double bond, and at least one of R ² and R ³ is the above-mentioned organic group,
and R ⁴ and R ⁵ are selected from the group consisting of perfluoro and perhalofluoroaliphatic hydrocarbons containing 1 to 8 carbon atoms; (wherein n corresponds to the number of units in the polymer and is a positive integer sufficiently large to produce a polymer having a number average molecular weight of 1500 to 15000 as measured by vapor pressure osmosis; The symbol → for a particular unit of represents isomerization, R ⁶ is a 6 characterized by benzenoid unsaturation.
contains at least one membered carbon atom ring and
R is a tetravalent aromatic organic group in which four carbonyl groups are directly bonded to separate carbon atoms in the ring of the R ⁶ group, and R ² and R ³ are a hydrogen group and a photopolymerizable olefinic dihydrogen group. This R ² is selected from the group consisting of any organic group containing a heavy bond.
and at least one of R ³ is an organic group as described above, R ⁴ and R ⁵ are selected from the group consisting of perfluoro and perhalofluoroaliphatic hydrocarbons containing 1 to 8 carbon atoms, and A and A' is selected from the group consisting of H, Cl, Br, and _NO2 ), 2. a radiation-sensitive polymerizable polyfunctional acrylate compound, and 3. a photopolymerization initiator consisting of a hydrogen donor initiator and an aromatic biimidazole. This includes drug systems. The radiation-sensitive polyimide precursor compositions of the present invention are useful in forming relief structures on electrical and electronic devices such as capacitors and semiconductors. A solution of the composition is applied to a substrate, such as a silicon wafer, and dried to form a film on the substrate. The film is then exposed to radiation through a mask template (pattern) and photopolymerized. The unexposed and unpolymerized portions of the film are dissolved away by a developer solution to form a relief structure. The resulting relief structure is baked to remove the photopolymerized material and produce a polyimide structure with sharp definition and good mechanical, chemical and electrical properties. The radiation-sensitive polyimide precursor composition of the present invention has the following formula: (where n corresponds to the number of units in the polymer and is a positive integer sufficiently large to produce a polymer having a number average molecular weight of 1500 to 15000 as measured by vapor osmometry; and The symbol → for a particular unit in indicates isomerization, R ¹ is a divalent aromatic, aliphatic or cycloaliphatic group containing at least 2 carbon atoms, R ² and R ³ is selected from the group consisting of a hydrogen group (radical) and any organic group containing a photopolymerizable olefin double bond, and at least one of R ² and R ³ is the above organic group, and R ⁴ and R ⁵ is selected from the group consisting of perfluoro and perhalofluoroaliphatic hydrocarbons containing from 1 to 8 carbon atoms or also of the formula (wherein n corresponds to the number of units in the polymer and is a positive integer sufficiently large to produce a polymer having a number average molecular weight of 1500 to 15000 as measured by vapor pressure osmosis; The symbol → for a particular unit of represents isomerization, R ⁶ is a 6 characterized by benzenoid unsaturation.
contains at least one membered carbon atom ring and
R is a tetravalent aromatic organic group in which four carbonyl groups are directly bonded to separate carbon atoms in the ring of the R ⁶ group, and R ² and R ³ are hydrogen groups and photopolymerizable olefinic groups. selected from the group consisting of any organic group containing a double bond;
At least one of R ² and R ³ is a group of the above organic group, and R ⁴ and R ⁵ are selected from the group consisting of perfluoro and perhalofluoro aliphatic hydrocarbons containing 1 to 8 carbon atoms. , and A and A' are selected from the group consisting of H, Cl, Br and _NO2 ), 2 a radiation-sensitive polymerizable polyfunctional acrylate compound, and 3 a hydrogen donor initiator and an aromatic biimidazole. It includes a photoinitiator system. In said polymers in which R ⁴ and R ⁵ are selected from the group consisting of perfluoro and perhalofluoroaliphatic hydrocarbons having 1 to 8 carbon atoms, perfluoro and perhalofluoro do not contain hydrogen. means substance. Instead, the hydrogens are replaced entirely by fluorine (perfluoro) or by at least one fluorine and another halogen (perhalofluoro). In preferred compositions of the invention ^R4 and ^R5 are selected from the group consisting of _-CF3 , _-CClF2 and _CBrF2 . Of particular interest is that R ⁴ and R ⁵ are CF ₃
It is something that is. formula The polymer of formula (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n are as defined above) can be produced by one of at least two methods. One way is to use the formula (wherein R ⁴ and R ⁵ are as defined above) a polycarboxylic dianhydride with the structural formula H ₂ N−R ¹ −NH ₂ (wherein R ¹ contains at least 2 carbon atoms) the two amino groups of said diamine are each bonded to separate carbon atoms of said divalent group). It includes producing a product having an olefinically unsaturated monoepoxide added onto the product. In a particularly preferred method for producing the composition of the invention, the polycarboxylic dianhydride is
R ⁴ and R ⁵ have the formula CF ₃ so that the dianhydride is 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride. 2,2- preferably used in the reaction product
Bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride can be produced by the method described in US Pat. No. 3,310,573. Suitable diamines include those described in more detail in US Pat. Nos. 3,179,614 and 3,179,634. Also, U.S. Patent No.
The diamines disclosed in US Pat. No. 3,310,573 as well as those disclosed in US Pat. No. 3,959,350 are also suitable. Suitable diamines disclosed in the above-referenced patents include those of the formula _H2N - ^R1 - _NH2 , where ^R1 is

【formula】

[expression] and

[Formula] (wherein R'' is an alkylene chain containing 1 to 3 carbon atoms, -O-, -S-, -SO ₂ -,

【formula】

【formula】 【formula】

[Formula] and Beauty

A divalent compound selected from the group consisting of [Formula] in which R and R' are groups having 1 to 6 carbon atoms selected from the group consisting of alkyl and aryl. Examples include aromatic diamines with a benzenoid group.
Further diamines disclosed in the above-referenced patents have the formula H ₂ N−R ¹ −NH ₂ , where R ¹ is

[expression] or

[Formula]) is mentioned. Examples of diamines with such structures are 4,
4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyldiethylsilane, 4,4'-Diaminodiphenyldiphenylsilane, 4,4'-Diaminodiphenylethylphosphine oxide, 4,4'-Diaminodiphenylphenylphosphine oxide, 4,4'-Diaminodiphenyl N- Methylamine, 4,4'-diaminodiphenyl N-phenylamine, 1,3-
Bis(4-aminophenoxy)benzene, 1,4
-bis(4-aminophenoxy)benzene and mixtures thereof. Suitable diamines disclosed in the above-referenced U.S. Pat. No. 3,310,573 have the structure [In the formula, R ⁴ and R ⁵ are the formula CCl _n F _3-n (in the formula, m is 0 to
1) and A and A' are selected from the group consisting of H, Cl, Br and _NO2 ]
Examples include diarylfluorodiamines having the following. Any suitable solvent can be used for the reaction of the diamine and polycarboxylic dianhydride. Such suitable solvents are organic solvents whose functional groups do not react with either the dianhydride or the diamine to the extent that they react with each other. In addition to being inert to the system and preferably being a solvent to the product, the organic solvent is a solvent for at least one of the reaction components (the dianhydride or the diamine) and preferably for the reaction components. Must be a solvent for both reaction components. A more detailed description of such suitable solvents can be found in US Pat. Nos. 3,179,614, 3,179,634 and 3,959,350. Suitable conditions for reacting dianhydrides and diamines are also described in U.S. Pat. No. 3,959,350;
It is described in detail in the specifications of No. 3179614 and No. 3179634. As previously described, the olefinically unsaturated monoepoxide is added to the reaction product prepared from the dianhydride and diamine. Such monoepoxides have the formula [In the formula, R ⁷ is preferably an olefinic unsaturated group containing a (meth)acrylic ester-containing group]. Preferred olefinically unsaturated monoepoxides are the unsaturated epoxides glycidyl acrylate and glycidyl methacrylate. As an example, the following formula shows the glycidyl The product with methacrylate addition is shown. Preferably, the composition of addition product in solvent for the dianhydride/diamine reaction is about 10-50% by weight adduct and about 50-90% by weight based on the combined weight of adduct and solvent. Contains solvent. In the production of addition products of monoepoxides to dianhydride/diamine reaction products, dianhydride/diamine
reacting a diamine reaction product (polyamic acid) with hydroxyethyl acrylate, hydroxyethyl methacrylate or a combination of the two;
A subsequent reaction with an olefinically unsaturated monoepoxide is advantageous. In this process, terminal acid anhydride groups are interrupted or attached and compounds with well-defined structures are obtained.
The solubility is also influenced by the terminating reagent, and in particular the photosensitivity of the addition product is enhanced due to the unsaturation of the terminating reagent. formula (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n are as defined above) is described in US Pat. It is disclosed in issued patent number 30186. This process involves esterifying an aromatic polycarboxylic acid anhydride with a hydroxyalkyl acrylate or methacrylate, then converting this esterification product into the corresponding acid chloride derivative, and finally reacting said acid chloride derivative with a diamine. include. The aromatic polycarboxylic anhydride used is of course the formula (wherein R ⁴ and R ⁵ are as defined above). Again, a particularly preferred anhydride is 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, the preparation of which is described above. Suitable diamines include those described in detail in the above-mentioned US patent specifications. A method for producing polymers from diarylfluorinated diamines is based on the structural formula (wherein R ⁴ and R ⁵ are selected from the group consisting of perfluoro and perhalofluoroaliphatic hydrocarbons containing 1 to 8 carbon atoms, and A and
A' is selected from the group consisting of H, Cl, Br, and _NO2 ) and a tetracarboxylic dianhydride. This includes producing epoxide-added products. The organic diamine preferably utilized in the reaction product can be prepared by the method described in detail in US Pat. No. 3,310,573. Particular diamines of interest include: 4,4'-(hexafluoroisopropylidene)
Dianiline, 4,4'-(hexafluoroisopropylidene)-
Bis(2,6-dibromoaniline), 4,4'-(hexafluoroisopropylidene)-
Bis(2-nitroaniline), 4,4'-(hexafluoroisopropylidene)-
Bis(o-phenylenediamine), 4,4'-(hexafluoroisopropylidene)-
Bis(2-aminotoluene), 4,4'-(hexafluoroisopropylidene)-
Bis(aminobenzoic acid), 4,4'-(hexafluoroisopropylidene)-
Bis(2,6-dichloroaniline), 4,4'-(hexafluoroisopropylidene)-
Bis(N-methylaniline), 4,4'-(hexafluoroisopropylidene)-
Bis(N-ethylaniline), 4,4'-(hexafluoroisopropylidene)-
Bis(N-2-cyanoethylaniline), 4,4'-(hexafluoroisopropylidene)-
Bis(2-nitro-6-chloroaniline), 4,4'-(chloropentafluoroisopropylidene)dianiline, 4,4'-(chloropentafluoroisopropylidene)-bis(2,6-dibromoaniline), 4 , 4'-(chloropentafluoroisopropylidene)-bis(N-2-cyanoethylaniline), 4,4'-(chloropentafluoroisopropylidene)-bis(2-aminotoluene), 4,4'-(1 , 3-dichlorotetrafluoroisopropylidene) dianiline, 4,4'-(1,3-dichlorotetrafluoroisopropylidene)-bis(2-aminotoluene). The tetracarboxylic dianhydride suitable for the present invention has the following formula: (wherein R ⁶ is characterized by benzenoid unsaturation and contains at least one six-membered carbocyclic ring whose four carbonyl groups are directly bonded to separate carbon atoms in the ring of the R ⁶ group. is a valent aromatic organic group in which each set of carbonyl groups is directly bonded to an adjacent carbon atom in the R ⁶ group, i.e.

[expression] or

It is characterized by the formation of a 5-membered ring of the formula. Examples of suitable dianhydrides for use in the present invention include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-4,
4'-diphenyltetracarboxylic dianhydride, 1,
2,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride thing, bis(3,4-
dicarboxyphenyl) sulfone dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, naphthalene-1,2,4,5 -tetracarboxylic dianhydride, 2,2-bis(2,3
- dicarboxyphenyl) propane dianhydride,
1,1-bis(2,3-dicarboxyphenyl)
Ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3
-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5, 6-tetracarboxylic dianhydride, thiophene-2,3,4,
5-tetracarboxylic dianhydride, 3,4,3',
Examples include 4'-benzophenonetetracarboxylic dianhydride. Any suitable solvent can be used for the reaction of the diamine and polycarboxylic dianhydride. Such suitable solvents are organic solvents whose functional groups do not react with either the dianhydride or the diamine to the extent that they react with each other. In addition to being inert to the system and preferably a solvent to the product, the organic solvent is a solvent for at least one of the reactants (the dianhydride or the diamine) and preferably for the reactants. Must be a solvent for both. A more detailed description of such suitable solvents can be found in U.S. Pat.
No. 3959350 can be found in each specification. Suitable conditions for reacting dianhydrides and diamines are also described in detail in the aforementioned US patents. As previously described, the olefinically unsaturated monoepoxide is added to the reaction product prepared from the dianhydride and diamine. Such monoepoxides have the formula [In the formula, R ⁷ is preferably an olefinic unsaturated group containing a (meth)acrylic ester-containing group]. Preferred olefinically unsaturated monoepoxides are the unsaturated epoxides glycidyl acrylate and chrycidyl methacrylate. Preferably, the composition of addition product in solvent for the dianhydride/diamine reaction is about 10-50% by weight adduct and about 50-90% by weight based on the combined weight of adduct and solvent. Contains solvent. In the production of addition products of monoepoxides to dianhydride/diamine reaction products, dianhydride/diamine
reacting a diamine reaction product (polyamic acid) with hydroxyethyl acrylate, hydroxyethyl methacrylate or a combination of the two;
A subsequent reaction with an olefinically unsaturated monoepoxide is advantageous. In this method,
The terminal acid anhydride groups are interrupted or attached and compounds with well-defined structures are obtained. The solubility is also influenced by this terminating reagent and in particular the photosensitivity of the addition product is enhanced due to the unsaturation of this terminating reagent. Other methods for making polymers from diaryl fluorinated diamines are described in U.S. Reissue Pat.
It is disclosed in specification No. 30186. The method involves esterifying an aromatic polycarboxylic acid anhydride with a hydroxyalkyl acrylate or methacrylate, then converting the esterification product to the corresponding acid chloride derivative, and finally reacting said acid chloride derivative with a diamine. do. In the present invention, the aromatic polycarboxylic acid anhydride is the above-mentioned tetracarboxylic dianhydride, and the diamine has the structural formula (wherein R ⁴ , R ⁵ , A and A' are as defined above). For dianhydride esterification, typical hydroxyalkyl acrylates and methacrylates are as follows. Hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and others. Thionyl chloride can typically be used for converting the esterification product to the corresponding acid chloride. Typical solvents in which the esterification of the dianhydride and subsequent reaction of the acid chloride derivative with the diamine are carried out include butyrolactone, tetrahydrofuran,
Mention may be made of hexamethylphosphoric triamide and combinations of the foregoing. Other suitable solvents include those disclosed in the US patents mentioned above and which do not react with the thionyl chloride or any other reagents used in the preparation of the acid chloride derivative. The conditions that influence such reactions are well known;
These are illustrated in the examples of the above-mentioned US reissue patent specifications. In order to reduce the radiation exposure time and increase the polymerization rate of polymer products of the type and produced by any method, the photopolymerizable polyimide precursor compositions of the present invention also contain the following: 1. Polymer formation 5 to 30% by weight based on the weight of the product, a radiation-sensitive polymerizable polyfunctional acrylate compound;
and 2 from 0.5 to 20% by weight based on the weight of the polymer product,
Polymerization initiator systems including hydrogen donor initiators and aromatic biimidazole may be included. Typical useful radiation sensitive polymerizable multifunctional acrylate compounds are trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane ethoxylate trimethacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane polyethoxylate Trimethacrylate, trimethylolpropane polyethoxylate triacrylate and mixtures thereof. Preferred are trimethylolpropane polyethoxylate triacrylate and trimethylolpropane ethoxylate triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol dimethacrylate having a weight average molecular weight of about 500 to 1500. , polymethylene diacrylate,
These are polyethylene dimethacrylate, trimethylene glycol dimethacrylate, and tetraethylene glycol diacrylate. It is possible to photopolymerize this composition without using the polymerizable polyfunctional acrylate compound described above in the composition. For most practical purposes, the presence of multifunctional acrylate compounds is highly desirable because it reduces photopolymerization time. All molecular weights referenced herein are determined by evaporation pressure method. Typical aromatic biimidazole photoinitiators are described in U.S. Pat.
It is disclosed in the specifications of No. 3479185 and No. 3784557. 2,4,5-triphenylimidazolyl dimers having ortho substituents on the 2-phenyl ring are particularly useful initiators. Typical initiators of this type are 2-(o-chlorophenyl)-4,
5-diphenylimidazolyl dimer, 2-(o-
fluorophenyl)-4,5-diphenylimidazolyl dimer, 2-(o-methoxyphenyl)-
4,5-diphenylimidazolyl dimer and mixtures thereof. Particularly preferred are bis(2-o-chlorophenyl-4,5-diphenylimidazolyl) and bis[2-o-chlorophenyl-4,5-di(m-methoxyphenyl)imidazolyl]. The reason is that these initiators are stable and they are excellent photoinitiators. Hexaarylbiimidazole can also be used as a photoinitiator, as shown in US Pat. No. 3,552,973. Typically useful hydrogen donors, photosensitizers and photoinitiators include the following: Aromatic ketones such as benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, 4-acryloxy-4'-diethylaminobenzophenone, 4-methoxy -4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthraquinone, 2-tertiary butylanthraquinone, 1,2-benzanthraquinone,
2,3-benzanthraquinone, 2,3-dichloronaphthoquinone, benzyl dimethyl ketal and other aromatic ketones, such as the aforementioned U.S. Pat.
3552973, benzoyl, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether and benzoin phenyl ether,
Methylbenzoin, ethylbenzoin and other benzoins, mercaptobenzothiazole,
Mercaptobenzoxazole e.g. U.S. Pat.
4291115 and n-phenylglycine. It is also possible to use a combination of both photosensitizers and photoinitiators. Photopolymerization times are generally longer when no photosensitizer is added. Since photopolymerization is enhanced by the addition of photosensitizers, photoinitiators, or mixtures thereof, it is preferable to use such compounds in the composition in an amount of about 0.1 to 15% by weight of the composition. is preferred. It may be desirable to have a compound present that changes color upon completion of polymerization, is a hydrogen donor, and is a chain transfer agent to provide rapid initiation to polymerization. For example, the leuco dyes disclosed in US Pat. No. 3,552,973 (column 6, line 6 to column 11, line 9) can be used. Typically useful dyes are alkylaminoaromatic alkanes such as tris(diethylamino-o-tolyl)methane, tris(dimethylamino-o-oxylyl)methane and tris(dipropylamino-o-tolyl).
It's methane. Plasticizers in amounts of 0.1 to 10% by weight based on the weight of the polymer product may also be included in the compositions of the invention. Typical plasticizers are tricresyl phosphate, dioctyl phthalate, dihexyl phthalate, dinonyl phthalate, polyethylene glycol ether, ethylene glycol dicaprolate. In applying the composition to a substrate, the composition is applied and then dried at about 30-100°C for about 20 minutes to 5 hours depending on the coating thickness to form a film. urge The film is then exposed to actinic radiation through the pattern for about 1 second to 5 minutes. Preferably, exposure times of 1 to 60 seconds are required for industrial processes, and usually exposures of 30 seconds or less are highly preferred. Typical radiation sources used are wavelengths between 250 and 400 nm and wavelengths between 0.5 and 400 nm.
It is an ultraviolet lamp providing an intensity of 60 milliwatts/cm ² (mW/cm ² ). After exposure, the film is then immersed in or sprayed with a developer solution. A typical developer solution is 2/1 to 1/
4-butyrolactone/toluene in a weight ratio of 4, or dimethylformamide/ethanol in a weight ratio of 2/1 to 1/4. The film is then washed with a non-solvent and then dried. This film is cured into a polyimide relief structure by baking at about 150 DEG -450 DEG C. for about 20 minutes to 4 hours. During curing, this acrylate component decomposes leaving a molded polyimide structure. The relief structure obtained has sharp definition and good chemical, electrical and mechanical properties. Typical uses for this composition include protective coatings for semiconductors, dielectric layers for multilayer integrated circuits, high temperature solder masks, bonded multilayer circuits, final passivation coatings on electrical and electronic devices, and others. The following examples are intended to illustrate the invention.
All parts and percentages are by weight unless otherwise noted and molecular weights are determined by vapor pressure osmosis. Example Composition A (polymer product) 16.35 g in 115 ml dimethylacetamide
18.70 g (0.056 mol) of 4,4'-(hexafluoroisopropylidene) dianiline was added to a stirred solution of 1,2,4,5-benzenetetracarboxylic anhydride (0.075 mol) at an internal reaction temperature of 35°C. The amount was added in approximately 2g portions so as not to exceed the amount. The mixture was then stirred at room temperature for 2 hours, after which 0.5 g (0.004
mol) of hydroxyethyl methacrylate were added and the mixture was stirred for a further 2 hours at room temperature. Then 37.5ml glycidyl methacrylate (GMA), 0.4g benzyldimethylamine and
0.03g of hydroquinone was added in this order. This mixture was then warmed to between about 50-60°C and 15
Stir for hours. The reaction solution was then allowed to cool to room temperature and washed with 5 x 50 ml of petroleum ether to remove unreacted GMA.
was removed. The polymer product is prepared by dissolving the reaction solution in 1000 ml of an aromatic hydrocarbon blend (such as that sold by Union Oil Company as "Super High Flash Naphtha H-596"). Isolated by dropwise addition using vigorous stirring. The resulting gelatinous precipitate was triturated with 2 x 500 ml of petroleum ether and filtered off with suction to yield the product (composition A) as a white solid. Composition B The photopolymerizable polyimide precursor composition of the present invention was prepared by charging the following ingredients into a container and placing the container on rollers where it was mixed for 2 hours.

[Table] The composition B was passed through a 1 μm filter. Two inch diameter silicone wafers were coated with the aminosilane adhesion promoter solution by spin coating techniques. In this case, after application of the adhesion promoter solution, the wafer was
Rotated for seconds. Composition B was then applied to the wafer by the spin technique described above for 60 seconds at 3000 rpm. A wafer having a coating of this composition B was heated at 50°C.
for 2 hours, after which it was exposed to a UV light source through the mask template at 365 nm and an intensity of about 5 mW/cm ² . The wafer was then treated by dipping it in a 4-butyrolactone/toluene (1/1) solution for 20 seconds and then washing with toluene spray for 10 seconds to remove any unexposed composition. Then this wafer
Spin dry at 3000 rpm for 60 seconds. Finally, the wafer was heated and held at about 300° C. for 1 hour to produce a polyimide relief structure for electronic circuits with sharp, clean lines. Example Composition A (polymer product) 33.3 g (0.075 g) in 115 ml dimethylacetamide
11.26 g (0.056 mol) of 4,4'-diamino-diphenyl ether was added to a stirred solution of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (mol) at its internal reaction temperature. is 35℃
The amount was added in approximately 2g portions so as not to exceed the amount. The mixture was then stirred at room temperature for 2 hours, after which 0.5 g
(0.004 mol) of hydroxyethyl methacrylate was added and the mixture was stirred for a further 2 hours at room temperature. Then 37.5ml glycidyl methacrylate (GMA), 0.4g benzyldimethylamine and
0.03g of hydroquinone was added in this order. This mixture was then warmed to between about 50-60°C and 15
Stir for hours. The reaction solution was then cooled to room temperature and washed with 5 x 50 ml of petroleum ether to remove unreacted GMA. This polymer product was prepared by adding 1000 ml of this reaction solution to an aromatic hydrocarbon blend (e.g. the aforementioned "Super High Flush Naphtha H-596").
The solution was isolated by dropwise addition using vigorous stirring. The resulting gelatinous precipitate was divided into 2 x 500
Trituration with ml of petroleum ether and suction gave the product (composition A) as a white solid with an acid number of 77.5. The infrared spectrum is
It showed carbonyl vibrations at 1720 and 1630 cm ^-1 . Composition B The photopolymerizable polyimide precursor composition of the present invention was prepared by charging the following ingredients into a container and placing the container on rollers where it was mixed for 2 hours.

【table】

[Table] The composition B was passed through a 1 μm filter. Two inch diameter silicone wafers were coated with the aminosilane adhesion promoter solution by spin coating techniques. In this case, after applying the adhesion promoter solution, the wafer was
Rotated for seconds. Composition B was then applied to the wafer by the spin technique described above for 60 seconds at 3000 rpm. The wafer with the composition B coating was dried at 50° C. for 2 hours, after which it was exposed to a UV light source through a mask template at 365 nm and an intensity of about 5 mW/cm ² . The wafer was then developed by dipping it in a 4-butyrolactone/toluene (1/1) solution for 20 seconds and then rinsing with a 10 second toluene spray to remove all unexposed composition. Then this wafer
Spin dry at 3000 rpm for 60 seconds. Finally, heat and hold this wafer at about 300℃ for 1 hour.
They produced polyimide relief structures for electronic circuits with sharp, clean lines spaced only 3 microns apart when examined at 150x magnification.

Claims (1)

[Claims] 1 (a) Formula (where n corresponds to the number of units in the polymer and is a positive integer sufficiently large to produce a polymer having a number average molecular weight of 1500 to 15000 as measured by vapor pressure osmometry, and The → symbol for a particular unit in the polymer represents isomerization, R ¹ is a divalent aromatic, aliphatic or cycloaliphatic group containing at least 2 carbon atoms, and R ² and R ³ are selected from the group consisting of a hydrogen group (radical) and any organic group containing a photopolymerizable olefinic double bond ^;
and at least one of R ³ is the organic group,
and R ⁴ and R ⁵ are selected from the group consisting of perfluoro and perhalofluoroaliphatic hydrocarbons containing 1 to 8 carbon atoms; (where n corresponds to the number of units in the polymer and is a positive integer sufficiently large to produce a polymer having a number average molecular weight of 1,500 to 15,000 as measured by vapor pressure osmosis; and The → symbol for a particular unit in the incorporation represents isomerization, R ⁶ contains at least one 6-membered carbon atom ring characterized by benzenoid unsaturation, and the R ⁶ group A tetravalent aromatic organic group in which four carbonyl groups are directly bonded to separate carbon atoms in the ring, and R ² and R ³ contain a hydrogen group and a photopolymerizable olefinic double bond. selected from the group consisting of any organic group that
At least one of R ² and R ³ is the above-mentioned organic group, R ⁴ and R ⁵ are selected from the group consisting of perfluoro and perhalofluoroaliphatic hydrocarbons containing 1 to 8 carbon atoms, And A
and A′ is selected from the group consisting of H, Cl, Br and NO ₂ ), (b) a radiation-sensitive polymerizable polyfunctional acrylate compound, and (c) a hydrogen donor initiator and an aromatic biimidazole. A radiation-sensitive polyimide precursor composition comprising a photoinitiator system. 2 R ⁴ and R ⁵ are −CF ₃ , −CClF ₂ and −
A radiation-sensitive polyimide precursor composition according to claim 1, selected from the group consisting of _CBrF2 . 3. The radiation-sensitive polyimide precursor according to claim 2, wherein R ² and R ³ are selected from the group consisting of a hydrogen group, a hydroxyalkyl acrylate group, a hydroxyalkyl methacrylate group, an alkyl acrylate group, and an alkyl methacrylate group. Composition. 4. The radiation-sensitive polymerizable polyfunctional acrylate compound is present in an amount equal to 5-30% by weight of the polymer and the photoinitiator system is present in an amount equal to 0.5-30% by weight of the polymer. A radiation-sensitive polyimide precursor composition according to claim 3. 5 The radiation-sensitive polymerizable polyfunctional acrylate compound is trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane ethoxylate trimethacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane polyethoxylate trimethacrylate, Methylolpropane polyethoxylate triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate,
Triethylene glycol diacrylate, polyethylene glycol dimethacrylate, polymethylene diacrylate, polymethylene dimethacrylate, trimethylene glycol dimethacrylate,
A radiation-sensitive polyimide precursor composition according to claim 4 selected from the group consisting of tetraethylene glycol diacrylate and mixtures thereof. 6 The aromatic biimidazole of the photopolymerization initiator is bis(2-o-chlorophenyl-4,5-diphenyl and imidazolyl) and bis[2-
The radiation-sensitive polyimide precursor composition according to claim 5, which is selected from the group consisting of o-chlorophenyl-4,5-di(m-methoxyphenyl)imidazolyl. 7 The composition may further contain from 0.1 to 0.1 based on the weight of the polymer.
A radiation-sensitive polyimide precursor composition according to claim 6, which also contains 10% by weight of leuco dye. 8 The composition may further contain from 0.1 to 0.1 based on the weight of the polymer.
A radiation-sensitive polyimide precursor composition according to claim 7, which also contains 15% by weight of a photosensitizer. 9 (1) Equation (wherein R ⁶ is characterized by benzenoid unsaturation and whose four carbonyl groups are at least one bonded directly to separate carbon atoms in the ring of the R ⁶ group)
A tetracarboxylic dianhydride of the formula (wherein R ⁴ and R ⁵ are selected from the group consisting of perfluoro and perhalofluoroaliphatic hydrocarbons containing 1 to 8 carbon atoms, and A
and A' is selected from the group consisting of H, Cl, Br, and _NO2 ) in a suitable solvent at a temperature of about 75°C or less to form a carboxyl group-containing reaction product. (2) reacting the reaction product with an olefinically unsaturated monoepoxide in an organic solvent at a temperature between room temperature and 100°C to produce an addition product; (3) producing an addition product of the addition product; adding a radiation-sensitive polymerizable multifunctional acrylate compound to the solution; and (4) also adding to the solution a photoinitiator system comprising a hydrogen donor initiator and an aromatic biimidazole. a) Equation (where n corresponds to the number of units in the polymer and is a positive integer sufficiently large to produce a polymer having a number average molecular weight of 1500 to 15000 as measured by vapor pressure osmosis; and The → symbol for a specific unit in the formula represents isomerization, R ⁶ is a group as described above, and R ² and R ³ contain a hydrogen group and a photopolymerizable olefinic double bond. selected from the group consisting of any organic group consisting of R ² and
At least one of R ³ is the above-mentioned organic group,
R ⁴ and R ⁵ are groups as described above,
and (A and A' are groups as described above); (b) a radiation-sensitive polymerizable polyfunctional acrylate compound; and (c) a photopolymerization initiator comprising a hydrogen donor initiator and an aromatic biimidazole. A method of producing a radiation-sensitive polyimide precursor composition comprising a system. 10 (1) Equation (wherein R ⁶ is characterized by benzenoid unsaturation and whose four carbonyl groups are at least one bonded directly to separate carbon atoms in the ring of the R ⁶ group)
a tetracarboxylic dianhydride (a tetravalent aromatic non-halogen-containing organic group containing six-membered carbon rings) is reacted with a compound selected from the group consisting of hydroxyalkyl acrylate and hydroxyalkyl methacrylate. (2) producing an acid chloride derivative of the esterification product; (3) producing an acid chloride derivative of the esterification product; (4) the acid chloride derivative. , the expression (wherein R ⁴ and R ⁵ are selected from the group consisting of perfluoro and perhalofluoroaliphatic hydrocarbons containing 1 to 8 carbon atoms, and A
and A′ is selected from the group consisting of H, Cl, Br, and NO ₂ ) to form an addition product; (5) adding a radiation-sensitive polymerizable polymer to a solution of the addition product; adding a functional acrylate compound; and (6) also adding to said solution a photoinitiator system comprising a hydrogen donor initiator and an aromatic biimidazole. (where n corresponds to the number of units in the polymer and is a positive integer sufficiently large to produce a polymer having a number average molecular weight of 1,500 to 15,000 as measured by vapor pressure osmosis; and The → symbol for a specific unit in the coalescence represents isomerization, R ⁶ is a group as described above, and R ² and R ³ represent a hydrogen group and a photopolymerizable olefinic double bond. selected from the group consisting of any organic group contained, at least one of R ² and R ³ being the above-mentioned organic group,
R ⁴ and R ⁵ are groups as described above,
and (A and A' are groups as described above); (b) a radiation-sensitive polymerizable polyfunctional acrylate compound; and (c) a photopolymerization initiator comprising a hydrogen donor initiator and an aromatic biimidazole. A method of producing a radiation-sensitive polyimide precursor composition comprising a system. 11 (1) Equation (wherein R ⁴ and R ⁵ are selected from the group consisting of perfluoro and perhalofluoroaliphatic hydrocarbons containing 1 to 8 carbon atoms) with at least one structure Formula H ₂ N−R ¹ −NH ₂ (wherein R ¹ is a divalent group containing at least 2 carbon atoms, and the two amino groups of the diamine are each of the divalent group bonded to separate carbon atoms) in a suitable solvent at a temperature of 75°C or below to produce a carboxyl group-containing reaction product; (2) reacting the reaction product at room temperature to reacting with an olefinically unsaturated monoepoxide in an organic solvent at a temperature of 100° C. to form an addition product; (3) adding a radiation-sensitive polymerizable polyfunctional acrylate compound to a solution of said addition product; and (4) also adding to the solution a photoinitiator system comprising a hydrogen donor initiator and an aromatic biimidazole, (where n corresponds to the number of units in the polymer and is 1500 to 15000 as determined by vapor pressure osmosis)
is ^a positive integer sufficiently large to produce a polymer having a number average molecular weight of R ² and ^{R 3} are selected from the group consisting of a hydrogen group (radical) and any organic group containing ^a photopolymerizable olefinic double bond; ( ^b ) a radiation-sensitive polymerizable polyfunctional acrylate compound, and ( ^c ) a hydrogen donor initiator and an aromatic biimidazole. A method for producing a radiation-sensitive polyimide precursor composition comprising a photopolymerization initiator system. 12. The method of claim 11, wherein the polycarboxylic dianhydride is 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride. 13. The method of claim 12, wherein said olefinically unsaturated monoepoxide is selected from the group consisting of glycidyl acrylate and glycidyl methacrylate. 14. Claim 1, wherein the organic diamine is 4,4'-diaminodiphenyl ether.
The method described in Section 3. 15. reacting the reaction product of dianhydride and diamine with a compound selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, and combinations of the two, prior to reacting the reaction product with the olefinically unsaturated monoepoxide;
A method according to claim 11. 16 (1) Equation hydroxyalkyl ^{acrylate and} hydroxyalkyl methacrylates to form an esterified product; (2) forming an acid chloride derivative of said esterified product; (3) converting said acid chloride derivative to the formula H ₂ N-R ¹ -NH ₂ (wherein R ¹ is a divalent group containing at least two carbon atoms, and the two amino groups of the diamine are each a separate carbon group of the two groups) (4) adding a radiation-sensitive polymerizable polyfunctional acrylate compound to a solution of said addition product; and (5) said (a) characterized in that a photoinitiator system comprising a hydrogen donor initiator and an aromatic biimidazole is also added to the solution; (where n corresponds to the number of units in the polymer and is 1500 to 15000 as determined by vapor pressure osmosis)
is ^a positive integer sufficiently large to produce a polymer having a number average molecular weight of , R ² and R ³ are hydrogen groups (radicals)
and any organic group containing a photopolymerizable olefinic double bond, in which at least one of R ² and R ³ is the above-mentioned organic group, and R ⁴ and R ⁵ are the above-mentioned organic groups. (b) a radiation-sensitive polymerizable polyfunctional acrylate compound; and (c) a photoinitiator system consisting of a hydrogen donor initiator and an aromatic biimidazole. A method for producing a sensitive polyimide precursor composition. 17. The method of claim 16, wherein the polycarboxylic dianhydride is 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride. 18 Claim 1, wherein the organic diamine is 4,4'-diaminodiphenyl ether.
The method described in Section 7.