JP4548001B2 - Positive photosensitive resin precursor composition - Google Patents

Description

  The present invention relates to a photosensitive resin precursor composition that is suitable for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, etc., and in which a portion exposed to ultraviolet rays is dissolved in an alkaline aqueous solution.

  The positive heat-resistant resin precursor composition in which the exposed part is dissolved by development includes those obtained by adding quinonediazide to polyamic acid, those obtained by adding quinonediazide to a soluble polyimide having a hydroxyl group, and quinonediazide in a polyamide having a hydroxyl group. The thing which added was known. Examples of the quinonediazide compound include a fluorine-containing quinonediazide (see Patent Document 1) and a quinonediazide containing an isopropyl residue (see Patent Document 2).

  However, in the case where quinonediazide is added to normal polyamic acid, the solubility of the carboxyl group of the polyamic acid is higher than the dissolution inhibiting effect of quinonediazide on alkali, so that the desired pattern cannot be obtained in most cases. there were. In addition, with the addition of a soluble polyimide resin having a hydroxyl group, the problems as described above are reduced, but the structure is limited to make it soluble, and the solvent resistance of the resulting polyimide resin is poor. The point was a problem. The addition of quinonediazide to a polyamide resin having a hydroxyl group also has a problem in that the structure is limited in order to obtain solubility and the solvent resistance of the resin obtained after heat treatment is inferior.

  In order to control the alkali solubility of the polyamic acid, a polyamic acid derivative in which the carboxyl group of the polyamic acid is protected with an ester group has been developed. However, when naphthoquinone diazide is added to this polyamic acid derivative, the dissolution inhibition effect of naphthoquinone diazide on alkali becomes very large. In most cases, the desired pattern can be obtained, but the sensitivity is greatly reduced. There was a problem.

Recently, a system in which a novolac resin or a polyhydroxystyrene resin is added to a heat-resistant resin precursor has been studied as a technique for increasing sensitivity. Specifically, those obtained by adding a photosensitive diazoquinone compound and a polyhydroxystyrene resin to a hydroxypolyamide resin (see Patent Document 3), and those obtained by adding a diazonaphthoquinonesulfonic acid ester and a phenol novolac resin to a polyamic acid silyl ester ( Patent Document 4)), the former has a problem in solvent resistance after low-temperature heat treatment at 250 ° C., and the latter has a stable developability because trialkylsilyl ester is easily hydrolyzed in a solution. It was a problem that could not be obtained.
JP-A-4-31860 (Claim 1) JP-A-7-281441 (Claim 1) JP-A-2002-241611 (Claims 1 to 6) Japanese Patent No. 3369344 (Claim 1)

  In consideration of the above points, the present invention uses a novolak resin and / or polyhydroxystyrene resin for the polyimide precursor and polybenzoxazole precursor having a specific structure, and is excellent in high sensitivity and high resolution. It is an object of the present invention to provide a photosensitive composition capable of obtaining sufficient solvent resistance even in heat treatment at ° C.

  That is, the present invention contains (a) a polymer mainly composed of a structural unit represented by the general formula (1), (b) a quinonediazide compound, (c) a novolac resin and / or a polyhydroxystyrene resin, Component (c) is a positive photosensitive resin precursor composition containing 101 parts by weight or more with respect to 100 parts by weight of component (a).

(Wherein R ¹ represents a divalent to octavalent organic group having 2 or more carbon atoms, R ³ represents either hydrogen or an organic group having 1 to 20 carbon atoms. N is in the range of 10 to 100,000. M represents an integer from 0 to 2, and p represents an integer from 0 to 4. )

  According to the present invention, a novolac resin and / or a polyhydroxystyrene resin is used for a polyimide precursor and a polybenzoxazole precursor having a specific structure, so that high sensitivity, high resolution, and high temperature such as 250 ° C. are obtained. Sufficient solvent resistance can be obtained even in heat treatment.

  The polymer having the structural unit represented by the general formula (1) in the present invention as a main component can be a polymer having an imide ring, an oxazole ring, or other cyclic structure by heating or an appropriate catalyst. Includes polyamic acid, polyamic acid ester of polyimide precursor, and polyhydroxyamide of polybenzoxazole precursor. With the ring structure, the heat resistance and solvent resistance are dramatically improved.

R ¹ represents a divalent to octavalent organic group having two or more carbon atoms, R ³ may be the same or different, and represents either hydrogen or an organic group having 1 to 20 carbon atoms. n is in the range of 10 to 100,000, m is an integer from 0 to 2, and p is an integer from 0 to 4 .

In the general formula (1), R ¹ represents a divalent to octavalent organic group having two or more carbon atoms, and represents an acid structural component. Examples of divalent compounds include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, and bis (carboxyphenyl) propane, and aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and adipic acid. Can do. Examples of trivalent compounds include tricarboxylic acids such as trimellitic acid and trimesic acid, and examples of tetravalent compounds include tetracarboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and diphenyl ether tetracarboxylic acid. Can do. Moreover, acids having a hydroxyl group such as hydroxyphthalic acid and hydroxytrimellitic acid can also be used. These acid components may be used alone or in combination of two or more, but it is preferable to use 1 to 40 mol% of tetracarboxylic acid as a copolymer.

  The tetracarboxylic acid used in the present invention is preferably a trivalent to octavalent organic group having 2 or more carbon atoms containing an aromatic ring and having 1 to 4 hydroxyl groups. A trivalent or tetravalent organic group of several 6 to 30 is more preferable. Specifically, a structure as shown in the general formula (2) is preferable.

R ⁵ and R ⁷ represent a divalent to tetravalent organic group selected from 2 to 20 carbon atoms, and R ⁶ represents a trivalent to 8 valent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. . R ⁸ , R ⁹ , and R ¹⁰ may be the same or different and each represents hydrogen or an organic group having 1 to 20 carbon atoms. o, s, and t are integers from 0 to 2, and r is an integer from 1 to 4.

R ⁵ and R ⁷ represent a divalent to tetravalent organic group selected from 2 to 20 carbon atoms. Those containing an aromatic ring are more preferred from the heat resistance of the resulting polymer, and among them, particularly preferred structures include those such as trimellitic acid, trimesic acid and naphthalene tricarboxylic acid residues.

R ⁶ represents a trivalent to octavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. The hydroxyl group in R ⁶ is preferably located adjacent to the amide bond. When the amide group and the hydroxyl group are adjacent to each other, a ring closing reaction occurs during heating, and the heat resistance is further improved. For example, when it contains a fluorine atom, it does not contain bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-hydroxy-4-aminophenyl) hexafluoropropane, or a fluorine atom. In the case, bis (3-amino-4-hydroxyphenyl) propane, bis (3-hydroxy-4-aminophenyl) propane, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-diamino Examples include -4,4'-dihydroxybiphenyl, 2,4-diamino-phenol, 2,5-diaminophenol, and those in which the amino group of 1,4-diamino-2,5-dihydroxybenzene is bonded.

Moreover, R < ⁸ >, R < ⁹ >, R < ¹⁰ > of General formula (2) has shown either hydrogen and the organic group to C1-C20. When the number of carbon atoms exceeds 20, the solubility in an alkaline developer is lowered. o, s, and t represent integers of 0 to 2, and are preferably selected from 1 and 2. R represents an integer of 1 to 4. When r is 5 or more, the properties of the resulting heat-resistant resin film deteriorate.

  Among the compounds represented by the general formula (2), examples of preferred compounds include those having the structures shown below, but are not limited thereto.

R ²⁷ to R ³⁶ represents any one of hydrogen, an organic group having from 1 to 10 carbon atoms.

In the general formula (1), R ² represents a divalent to octavalent organic group having 2 or more carbon atoms, and represents a structural component of diamine. Among these, preferred examples of R ² have the aromatic than heat resistance of the resulting polymer, and preferably has a hydroxyl group or a carboxyl group, one general formula (3), (4), (5) The thing of the structure shown in can be mention | raise | lifted.

R ¹¹ and R ¹³ represent a trivalent to hexavalent organic group having a hydroxyl group selected from 2 to 20 carbon atoms, and R ¹² represents a divalent to tetravalent organic group selected from 2 to 30 carbon atoms. . R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different and each represents hydrogen or an organic group having 1 to 20 carbon atoms. u and v are 1 or 2, and g, h, and i are integers from 0 to 2, respectively. R ¹⁷ and R ¹⁹ represent a divalent to tetravalent organic group having 2 to 20 carbon atoms, and R ¹⁸ represents a trivalent to octavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. R ²⁰ , R ²¹ and R ²² may be the same or different and each represents hydrogen or an organic group having 1 to 20 carbon atoms. j, k, and l are integers from 0 to 2, and w is an integer from 1 to 4. R ²³ represents a divalent to tetravalent organic group selected from 2 to 20 carbon atoms, and R ²⁴ represents a trivalent to octavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. R ²⁵ and R ²⁶ may be the same or different and each represents hydrogen or an organic group having 1 to 20 carbon atoms. d and e are integers of 0 to 2, and x is an integer of 1 to 4.

In the general formula (3), R ¹¹ and R ¹³ represent a trivalent to hexavalent organic group having a hydroxyl group selected from 2 to 20 carbon atoms, and have an aromatic ring due to the heat resistance of the resulting polymer. Is preferred. Specifically, hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) ) Represents a sulfone group, a hydroxydiphenyl ether group, a dihydroxydiphenyl ether group, and the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used. R ¹² represents a divalent to tetravalent organic group selected from 2 to 30 carbon atoms. A divalent to tetravalent group having an aromatic is better than the heat resistance of the obtained polymer, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone. Examples thereof include those having up to two substituted carboxyl groups, and aliphatic cyclohexyl groups can also be used.

In General formula (4), R < ¹⁷ >, R < ¹⁹ > represents the bivalent-tetravalent organic group chosen from C2-C20. A divalent to tetravalent group having aromaticity is better than the heat resistance of the obtained polymer, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. These may be substituted with up to 2 carboxyl groups, but in addition to these, aliphatic cyclohexyl groups may also be used. R ¹⁸ represents a trivalent to octavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms, and preferably has an aromatic ring from the heat resistance of the resulting polymer. Specifically, hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) ) Represents a sulfone group, a hydroxydiphenyl ether group, a dihydroxydiphenyl ether group, and the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.

In the general formula (5), R ²³ represents a divalent to tetravalent organic group selected from 2 to 20 carbon atoms. From the heat resistance of the polymer obtained, a divalent to tetravalent group having an aromatic group is preferable, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. These may be substituted with up to 2 carboxyl groups, but in addition to these, aliphatic cyclohexyl groups may also be used. R ²⁴ represents a trivalent to octavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms, and preferably has an aromatic ring from the heat resistance of the resulting polymer. Specifically, hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) ) Represents a sulfone group, a hydroxydiphenyl ether group, a dihydroxydiphenyl ether group, and the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.

R ¹⁴ , R ¹⁵ , R ¹⁶ in general formula (3), R ²⁰ , R ²¹ , R ²² in general formula (4), and R ²⁵ , R ^{26 in} general formula (5) may be the same or different. One of hydrogen and an organic group having 1 to 20 carbon atoms is shown. When the number of carbon atoms exceeds 20, the solubility in an alkaline developer is lowered. Further, g, h, i in the general formula (3), j, k, l in the general formula (4), d and e in the general formula (5) represent integers of 0 to 2, but preferably 1 2 is selected. In the general formula (3), u and v are 1 or 2, w in the general formula (4) and x in the general formula (5) are integers of 1 to 4.

  Specific examples of the structure represented by the general formula (3) are shown below.

  Moreover, the specific example represented by General formula (4) is shown below.

  Specific examples represented by the general formula (5) are shown below.

  It can also modify | denature using the other diamine component of the range of 1-40 mol% with respect to the diamine represented by General formula (3), (4), (5). Examples of these are phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone or their aromatics. Examples thereof include compounds in which the aromatic ring is substituted with an alkyl group or a halogen atom, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, hexamethylenediamine, and the like. When the aliphatic diamine component is copolymerized in an amount of 40 mol% or more, the heat resistance of the resulting polymer may be lowered.

R ³ and R ^{4 in} the general formula (1) may be the same or different and each represents hydrogen or an organic group having 1 to 20 carbon atoms. In view of the stability of the resulting positive photosensitive resin precursor solution, R ³ and R ⁴ are preferably organic groups, but hydrogen is more preferable than the solubility in an aqueous alkali solution. In the present invention, a hydrogen atom and an alkyl group can be mixed. By controlling the amounts of hydrogen and organic groups of R ³ and R ^4, the dissolution rate in the aqueous alkali solution is changed. By this adjustment, a positive photosensitive resin precursor composition having an appropriate dissolution rate is obtained. be able to. As a preferable range, 10% to 90% of R ³ and R ⁴ are each a hydrogen atom. When the number of carbon atoms in R ³ and R ⁴ exceeds 20, it will not dissolve in the alkaline aqueous solution. From the above, R ³ and R ⁴ preferably contain one or more hydrocarbon groups having 1 to 16 carbon atoms, and the others are hydrogen atoms.

  Moreover, m and f of General formula (1) have shown the number of the carboxyl groups, and have shown the integer of 0-2. More preferably, it is 1 or 2. In the general formula (1), n represents the number of repeating structural units of the polymer of the present invention, and is preferably in the range of 10 to 100,000.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with R ¹ and R ² in the general formula (1) within a range that does not decrease the heat resistance. Specifically, examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like. The positive photosensitive resin composition may be composed only of the structural unit represented by the general formula (1), or may be a copolymer or blend with other structural units. In that case, it is preferable to contain 70 mol% or more of the structural unit represented by General formula (1), and it is more preferable to contain 90 mol% or more . The type and amount of structural units used for copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polyimide polymer obtained by final heat treatment.

  The heat resistant resin precursor of the present invention is synthesized by a known method. In the case of polyamic acid or polyamic acid ester, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound at a low temperature, a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then in the presence of an amine and a condensing agent It can be synthesized by a method of reacting with a tetracarboxylic dianhydride and alcohol to obtain a diester, then converting the remaining dicarboxylic acid into an acid chloride and reacting with an amine.

  In the case of polyhydroxyamide, it can be obtained by a condensation reaction of a bisaminophenol compound and a dicarboxylic acid. Specifically, a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid, and a bisaminophenol compound is added thereto, or a solution of a bisaminophenol compound added with a tertiary amine such as pyridine is added to a dicarboxylic acid. For example, a solution of dichloride is dropped.

  When using polyhydroxyamide, a positive photosensitive heat-resistant resin precursor that can be removed with an alkaline aqueous solution by adding a photosensitizer such as naphthoquinonediazide sulfonate to the polyhydroxyamide solution. A composition can be obtained.

  The quinonediazide compound (b) added to the present invention is preferably a compound in which a sulfonic acid of naphthoquinonediazide is bonded with an ester to a compound having a phenolic hydroxyl group. As the compound having a phenolic hydroxyl group used here, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-PHBA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP -IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-p-CR, Methylenetetra-p-CR, BisRS-26X, Bis-PFP-PC Manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A ( Above, trade name, manufactured by Asahi Organic Materials Co., Ltd.), naphthol, Tet 4-Naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid by ester bond to a compound such as hydroxybenzophenone, gallic acid methyl ester, bisphenol A, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) The introduced compounds can be exemplified as preferable ones, but other compounds can also be used.

  Further, when the molecular weight of the naphthoquinone diazide compound used in the present invention exceeds 3000, the naphthoquinone diazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that the heat resistance of the resulting film is lowered, the mechanical properties are lowered, and the adhesion There is a possibility that problems such as a decrease in performance occur. From this point of view, the molecular weight of the preferred naphthoquinonediazide compound is 300 to 3000. More preferably, it is 350 to 2000. The addition amount of such a naphthoquinonediazide compound is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the polymer.

  If necessary, the compound having a phenolic hydroxyl group may be used as it is without being esterified with naphthoquinone diazide for the purpose of supplementing the alkali developability of the photosensitive heat-resistant precursor composition. By adding this phenolic hydroxyl group-containing compound, the resulting resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. Development is easy in a short time. In this case, the addition amount of the compound having a phenolic hydroxyl group is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight with respect to 100 parts by weight of the polymer.

  The novolak resin and / or polyhydroxystyrene resin of component (c) used in the present invention is preferably blended in a polyamide resin in an amount of 101 to 1000 parts by weight with respect to 100 parts by weight of the polyamide resin. If it is less than 101 parts by weight, sufficient solvent resistance cannot be obtained at low-temperature curing at 250 ° C., which is not preferable. Moreover, since heat resistance will fall when it exceeds 1000 weight part, it is unpreferable. Furthermore, these can be used alone or as a mixture.

  In addition, novolak resins preferably used in the present invention include novolak phenol resins and resol phenol resins, and various phenols alone or a mixture of plural kinds thereof are polycondensed with aldehydes such as formalin by a known method. Is obtained.

  Examples of phenols constituting the novolak phenol resin and resol phenol resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, and 2,5-dimethylphenol. 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, , 4,5-trimethylphenol, methylene bisphenol, methylene bis p-cresol, resorcin, catechol, 2-methyl resorcin, 4-methyl resorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichloro Phenol m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α -Naphthol, (beta) -naphthol etc. are mentioned, These can be used individually or as a mixture of several.

  In addition to formalin, examples of aldehydes include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like. These can be used alone or as a mixture of a plurality of them.

  And the preferable weight average molecular weight of the novolak resin used in the positive photosensitive resin composition of the present invention is 2,000 to 50,000 in terms of polystyrene by GPC (gel permeation chromatography), preferably 3,000 to 40,000. The preferred weight average molecular weight of the polyhydroxystyrene resin is 500 to 10,000, preferably 1,000 to 5,000 in terms of polystyrene by GPC (gel permeation chromatography).

  As the polyhydroxystyrene resin used in the present invention, a vinylphenol homopolymer or a copolymer with styrene can also be used.

  Solvents used in the present invention are polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene Ethers such as glycol monomethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone and diacetone alcohol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate and ethyl lactate, and aromatic hydrocarbons such as toluene and xylene These solvents can be used alone or in combination.

  The amount of the solvent used in the present invention is preferably 50 to 2000 parts by weight, particularly 100 to 1500 parts by weight with respect to 100 parts by weight of the polymer having the structural unit represented by the general formula (1) as a main component. preferable.

  Next, a method for forming a heat resistant resin pattern using the photosensitive resin precursor composition of the present invention will be described.

  A photosensitive heat resistant precursor composition is applied onto a substrate. A silicon wafer, ceramics, gallium arsenide, or the like is used as the substrate, but is not limited thereto. Examples of the application method include spin coating using a spinner, spray coating, and roll coating. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 150 μm.

  Next, the substrate coated with the photosensitive heat-resistant precursor composition is dried to obtain a photosensitive heat-resistant precursor composition film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like at a temperature of 50 ° C. to 150 ° C. for 1 minute to several hours.

  Next, the photosensitive heat-resistant precursor composition film is exposed to actinic radiation through a mask having a desired pattern. As the actinic radiation used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays and the like. In the present invention, it is preferable to use i-ray (365 nm), h-ray (405 nm), and g-ray (436 nm) of a mercury lamp. .

  Formation of the heat-resistant resin pattern is achieved by removing the exposed portion using a developer after exposure. Developers include tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl An aqueous solution of a compound showing alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolaclone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. Good. After development, rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  After development, a temperature of 200 ° C. to 500 ° C. is applied to convert it to a heat resistant resin film. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be mentioned. The curing conditions in the present invention are preferably 200 ° C. or higher and 300 ° C. or lower, and more preferably 200 ° C. or higher and 250 ° C.

  The heat-resistant resin film formed from the photosensitive resin precursor composition according to the present invention is used for applications such as a semiconductor passivation film, a protective film for semiconductor elements, and an interlayer insulating film for multilayer wiring for high-density mounting.

  Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples. In addition, evaluation of the photosensitive resin precursor composition in an Example was performed based on the following method.

Preparation of photosensitive resin precursor film A photosensitive resin precursor composition (hereinafter referred to as varnish) was applied on a 6-inch silicon wafer so that the film thickness after pre-baking was 7 μm, and then a hot plate (Tokyo Electron ( Photosensitive resin precursor film was obtained by prebaking at 120 ° C. for 3 minutes using Mark-7).

Film thickness measurement method Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., after pre-baking and after development, with a refractive index of 1.629, and with a cured film at a refractive index of 1.773 It was.

Exposure A reticle with a cut pattern was set in an exposure machine (i-line stepper DSW-8000 manufactured by GCA), and i-line exposure (intensity of 365 nm) was performed by changing the exposure time.

Development A 2.38% aqueous solution of tetramethylammonium hydroxide was sprayed for 10 seconds at 50 revolutions using a Mark-7 developing device manufactured by Tokyo Electron Ltd. Then, it was allowed to stand for 60 seconds at 0 rotation, rinsed with water at 400 rotation, and shaken and dried for 10 seconds at 3000 rotation.

Calculation of Sensitivity After exposure and development, an exposure time for forming a 50 μm line-and-space pattern (1L / 1S) in a one-to-one width (hereinafter referred to as an optimum exposure time) was determined.

Cure Using the inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd., nitrogen gas flow (oxygen concentration 20 ppm or less) at 140 ° C. for 30 minutes, and then to 250 ° C. for 1 hour. Was heated at 250 ° C. for 1 hour to produce a cured film.

Evaluation of solvent resistance Pure water is obtained by immersing a 7μm thick photosensitive polyimide film prepared on a 6-inch silicon wafer by the above-mentioned coating and curing in N-methyl-pyrrolidone (hereinafter referred to as NMP) at room temperature for 3 minutes. Process immediately. Thereafter, the state of the film was observed with an optical microscope, the film thickness was measured, and the solvent resistant residual film ratio was calculated. The film thickness was 0 μm when cracks occurred, and in other cases, the average value was measured at 9 points in total, 0 cm, ± 2.5 cm, and ± 5 cm from the center in the diameter direction parallel to and perpendicular to the orientation flat of the wafer. The solvent resistant residual film ratio was calculated according to the following formula.
Solvent resistance residual film ratio (%) = film thickness after treatment / film thickness before treatment × 100.

Appearance The state of the film obtained by the solvent resistance evaluation (photosensitive polyimide film immersed in NMP for 3 minutes at room temperature and rinsed with pure water) was observed with an optical microscope. Changes such as cracks and white turbidity were confirmed, and no change was considered good.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride Under dry nitrogen flow, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and allyl glycidyl ether 34.2 g (0.3 mol) was dissolved in 100 g of gamma butyrolactone (hereinafter referred to as GBL) and cooled to −15 ° C. To this, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of GBL was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the reaction was carried out at 0 ° C. for 4 hours. This solution was concentrated with a rotary evaporator and charged into 1 L of toluene to obtain an acid anhydride.

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (1) 18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the solid was placed in a 300 mL GBL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the catalyst was filtered to remove the palladium compound, and the mixture was concentrated with a rotary evaporator to obtain a diamine compound (1). The obtained solid was used for the reaction as it was.

Synthesis Example 3 Synthesis of hydroxyl group-containing diamine (2) 2-Amino-4-nitrophenol (15.4 g, 0.1 mol) was dissolved in acetone (50 mL) and propylene oxide (30 g, 0.34 mol). Cooled down. A solution prepared by dissolving 11.2 g (0.055 mol) of isophthalic acid chloride in 60 mL of acetone was gradually added dropwise thereto. After completion of dropping, the reaction was carried out at −15 ° C. for 4 hours. Thereafter, the precipitate formed by returning to room temperature was collected by filtration.

  This precipitate was dissolved in 200 mL, 5 g palladium-carbon 3 g was added, and the mixture was vigorously stirred. A balloon filled with hydrogen gas was attached thereto, and stirring was continued until the balloon of hydrogen gas did not contract any further at room temperature, and further stirred for 2 hours with the balloon of hydrogen gas attached. After completion of the stirring, the palladium compound was removed by filtration, and the solution was concentrated to half by a rotary evaporator. Ethanol was added thereto and recrystallization was performed to obtain crystals of the target compound.

Synthesis Example 4 Synthesis of hydroxyl group-containing diamine (3) 15.4 g (0.1 mol) of 2-amino-4-nitrophenol was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and −15 Cooled to ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 mL of acetone was gradually added dropwise thereto. After completion of dropping, the reaction was carried out at −15 ° C. for 4 hours. Thereafter, the precipitate formed by returning to room temperature was collected by filtration. Thereafter, the target compound crystal was obtained in the same manner as in Synthesis Example 2.

Synthesis Example 5 Synthesis of quinonediazide compound (1) Under a dry nitrogen stream, TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 15.31 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 40.2 g (0.15 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system would not be 45 ° C. or higher. It stirred at 40 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (1).

Synthesis Example 6 Synthesis of quinonediazide compound (2) Under a dry nitrogen stream, 11.41 g (0.05 mol) of bisphenol A and 26.86 g (0.1 mol) of 5-naphthoquinonediazidesulfonyl chloride were converted to 450 g of 1,4-dioxane. Dissolved and brought to room temperature. A quinonediazide compound (2) was obtained in the same manner as in Synthesis Example 5 using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane.

Reference example 1
Under a dry nitrogen stream, 4.1 g (0.0205 mol) of 4,4′-diaminodiphenyl ether and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane are dissolved in 50 g of NMP. I let you. To this, 21.4 g (0.03 mol) of the hydroxy group-containing acid anhydride obtained in Synthesis Example 1 was added together with 14 g of NMP, and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, a solution prepared by diluting 7.14 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours to obtain a polymer solution having a polymer concentration of 26.8%.

  40 g of the obtained polymer solution was measured, 8 g of the quinonediazide compound (1) obtained in Synthesis Example 5 and a novolak resin (trade name, XPS-4958G, m-cresol / p-cresol ratio = 55/45, Gunei Chemical Co., Ltd.) 11.8 g of Kogyo Co., Ltd. was added to obtain a photosensitive polyimide precursor composition varnish A. Using the obtained varnish, a photosensitive polyimide precursor film was prepared on a silicon wafer as described above, exposed and developed, and the sensitivity of the varnish was evaluated. Thereafter, the film was cured, and the solvent-resistant residual film ratio was evaluated and the appearance was confirmed.

Example 1
Under a dry nitrogen stream, 13.6 g (0.0225 mol) of diamine (1) obtained in Synthesis Example 2 and 4-ethynylaniline (trade name: P-APAC, Fuji Photo Film Co., Ltd.) as a terminal blocking agent 0.29 g (0.0025 mol) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). 17.5 g (0.025 mol) of the hydroxy group-containing acid anhydride obtained in Synthesis Example 1 was added thereto together with 30 g of pyridine, and the mixture was reacted at 60 ° C. for 6 hours. After completion of the reaction, the solution was poured into 2 liters of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours.

  In 10 g of the polymer solid thus obtained, 2 g of the quinonediazide compound (1) obtained in Synthesis Example 5 and the novolac resin XPS-4958G15 g were dissolved in 29 g of GBL to obtain a varnish B of a photosensitive polyimide precursor composition. Using the obtained varnish, a photosensitive polyimide precursor film was prepared on a silicon wafer as described above, exposed and developed, and the sensitivity of the varnish was evaluated. Thereafter, the film was cured, and the solvent-resistant residual film ratio was evaluated and the appearance was confirmed.

Example 2
Under a dry nitrogen stream, 20.78 g (0.055 mol) of the diamine compound (2) obtained in Synthesis Example 3 and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane ) Was dissolved in 50 g of NMP. To this, 13.95 g (0.045 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride was added together with 21 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. It was. After stirring at 50 ° C. for 2 hours, a solution obtained by diluting 14.7 g (0.1 mol) of N, N-dimethylformamide diethyl acetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours to obtain a polymer solution having a polymer concentration of 30.6%.

  40 g of the obtained polymer solution was weighed and 8 g of the quinonediazide compound (1) obtained in Synthesis Example 6 and 24.5 g of novolac resin XPS-4958G were added to obtain a varnish C of a photosensitive polyimide precursor composition. Using the obtained varnish, a photosensitive polyimide precursor film was prepared on a silicon wafer as described above, exposed and developed, and the sensitivity of the varnish was evaluated. Thereafter, the film was cured, and the solvent-resistant residual film ratio was evaluated and the appearance was confirmed.

Example 3
Under a dry nitrogen stream, 6.08 g (0.025 mol) of the diamine compound (3) obtained in Synthesis Example 4, 4.21 g (0.021 mol) of 4,4′-diaminodiphenyl ether, 1,3-bis ( 3-aminopropyl) tetramethyldisiloxane 0.806 g (0.00325 mol) was dissolved in 70 g NMP. 24.99 g (0.035 mol) of the hydroxyl group-containing acid anhydride obtained in Synthesis Example 1 and 4.41 g (0.015 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride were obtained. The mixture was added together with 25 g of NMP at room temperature, and stirred as it was at room temperature for 1 hour and then at 50 ° C. for 2 hours. Next, a solution obtained by diluting 17.6 g (0.2 mol) of glycidyl methyl ether with 10 g of NMP was added and stirred at 70 ° C. for 6 hours to obtain a polymer solution having a polymer concentration of 25.3%.

  40 g of the obtained polymer solution was weighed, and 8 g of the quinonediazide compound (2) obtained in Synthesis Example 6 and 15.18 g of novolac resin XPS-4958G were added to obtain varnish D of a photosensitive polyimide precursor composition. Using the obtained varnish, a photosensitive polyimide precursor film was prepared on a silicon wafer as described above, exposed and developed, and the sensitivity of the varnish was evaluated. Thereafter, the film was cured, and the solvent-resistant residual film ratio was evaluated and the appearance was confirmed.

Reference example 2
40 g of the polymer solution obtained in Reference Example 1 was weighed, 8 g of the quinonediazide compound (1) obtained in Synthesis Example 5 and polyhydroxystyrene (trade name, Marcalinker M, manufactured by Maruzen Petrochemical Co., Ltd., weight average molecular weight) 5100) 11.8 g was added to obtain a varnish E of a photosensitive polyimide precursor composition. Using the obtained varnish, a photosensitive polyimide precursor film was prepared on a silicon wafer as described above, exposed and developed, and the sensitivity of the varnish was evaluated. Thereafter, the film was cured, and the solvent-resistant residual film ratio was evaluated and the appearance was confirmed.

Example 4
The polymer solids 10g obtained in Example 1, quinonediazide compound obtained in Synthesis Example 5 (1) 2 g and, varnish F of dissolved Marukalyncur M15g a polyhydroxystyrene GBL29g photosensitive polyimide precursor composition Got. Using the obtained varnish, a photosensitive polyimide precursor film was prepared on a silicon wafer as described above, exposed and developed, and the sensitivity of the varnish was evaluated. Thereafter, the film was cured, and the solvent-resistant residual film ratio was evaluated and the appearance was confirmed.

Example 5
40 g of the polymer solution obtained in Example 2 was weighed, 8 g of the quinonediazide compound (1) obtained in Synthesis Example 6 and 24.5 g of Marcalinker M, which is polyhydroxystyrene, were added, and the varnish of the photosensitive polyimide precursor composition was added. G was obtained. Using the obtained varnish, a photosensitive polyimide precursor film was prepared on a silicon wafer as described above, exposed and developed, and the sensitivity of the varnish was evaluated. Thereafter, the film was cured, and the solvent-resistant residual film ratio was evaluated and the appearance was confirmed.

Example 6
40 g of the polymer solution obtained in Example 3 was weighed, 8 g of the quinonediazide compound (2) obtained in Synthesis Example 6 and 15.18 g of Marcalinker M which was polyhydroxystyrene were added, and the photosensitive polyimide precursor composition was added. Varnish H was obtained. Using the obtained varnish, a photosensitive polyimide precursor film was prepared on a silicon wafer as described above, exposed and developed, and the sensitivity of the varnish was evaluated. Thereafter, the film was cured, and the solvent-resistant residual film ratio was evaluated and the appearance was confirmed.

Reference example 3
40 g of the polymer solution obtained in Reference Example 1 was weighed, 8 g of the quinonediazide compound (1) obtained in Synthesis Example 5, 5.9 g of XPS-4958G which is a novolac resin, and 7.08 g of Marcalinker M which is polyhydroxystyrene. Was added to obtain a varnish I of a photosensitive polyimide precursor composition. Using the obtained varnish, a photosensitive polyimide precursor film was prepared on a silicon wafer as described above, exposed and developed, and the sensitivity of the varnish was evaluated. Thereafter, the film was cured, and the solvent-resistant residual film ratio was evaluated and the appearance was confirmed.

Comparative Example 1
443.2 g (0.9 mol) of a dicarboxylic acid derivative (active ester) obtained by reacting 1 mol of diphenyl ether 4,4′-dicarboxylic acid with 2 mol of 1-hydroxy-1,2,3-benzotriazole And 66.3 g (1 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet pipe It put into the flask and 3000 g of N-methyl-2-pyrrolidone was added and dissolved. Then, it was made to react at 75 degreeC for 12 hours using the oil bath. Next, 32.8 g (0.2 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 500 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum to obtain the desired polyamide resin. Obtained.

  A photosensitive polyamide precursor composition obtained by dissolving 2 g of the quinonediazide compound (1) obtained in Synthesis Example 5 and 1 g of Marcalinker M, which is polyhydroxystyrene, in 29 g of gamma-butyrolactone in 10 g of the polymer solid thus obtained. Varnish J was obtained. Using the obtained varnish, a photosensitive polyamide precursor film was produced on a silicon wafer as described above, exposed and developed, and the sensitivity of the varnish was evaluated. Thereafter, the film was cured, and the solvent-resistant residual film ratio was evaluated and the appearance was confirmed.

Comparative Example 2
Under a nitrogen atmosphere, 2,2-bis (3,4-dicarboxyphenyl) perfluoropropanoic anhydride 22.2 g (0.05 mol), 39.5 g of diethylene glycol dimethyl ether and N, N′-bis (triethylsilyl) ) -4,4'-diaminodiphenyl ether 15.51 g (0.045 mol) and 1,3-bis [3- (N-trimethylsilyl) aminopropyl] -1,1,3,3-tetramethyl Zizi Loki San 1 A solution prepared by dissolving .98 g (0.005 mol) in 20 g of diethylene glycol dimethyl ether and 20 g of N, N′-dimethylacetamide was added dropwise while cooling so that the reaction temperature did not reach 40 ° C. After completion of dropping, the mixture was further stirred for 12 hours to obtain a polymer solution having a polymer concentration of 33.3%.

  40 g of the obtained polymer solution was weighed, and 8 g of the quinonediazide compound (1) obtained in Synthesis Example 5 and 1.63 g of novolak resin XPS-4958G were added to obtain a varnish K of a photosensitive polyimide precursor composition. Using the obtained varnish, a photosensitive polyimide precursor film was prepared on a silicon wafer as described above, exposed and developed, and the sensitivity of the varnish was evaluated. Thereafter, the film was cured, and the solvent-resistant residual film ratio was evaluated and the appearance was confirmed.

Comparative Example 3
40 g of the polymer solution obtained in Reference Example 1 was weighed, and 8 g of the quinonediazide compound (1) obtained in Synthesis Example 5 was added to obtain a varnish L of a photosensitive polyimide precursor composition. Using the obtained varnish, a photosensitive polyimide precursor film was prepared on a silicon wafer as described above, exposed and developed, and the sensitivity of the varnish was evaluated. Thereafter, the film was cured, and the solvent-resistant residual film ratio was evaluated and the appearance was confirmed.

Claims (2)

A polymer composed mainly of structural units represented by (a) the general formula (1), (b) and a quinonediazide compound, containing (c) a novolac resin and / or polyhydroxy styrene resins, the general formula (1) R ² (COOR ⁴ ) f (OH) q in the formula has at least one selected from the structures represented by the general formulas (3) to (5), and the component (c) is 100 parts by weight of the component (a). 101 parts by weight or more of the positive photosensitive resin precursor composition.

(Wherein R ¹ represents a divalent to octavalent organic group having 2 or more carbon atoms, R ³ represents either hydrogen or an organic group having 1 to 20 carbon atoms. N is in the range of 10 to 100,000. , m is 0 to 2 integer, p is an integer of 0 to 4.)

(R ¹¹ and R ¹³ represent a trivalent to hexavalent organic group having a hydroxyl group selected from 2 to 20 carbon atoms, and R ¹² represents a divalent to tetravalent organic group selected from 2 to 30 carbon atoms. R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different and each represents hydrogen or an organic group having 1 to 20 carbon atoms, u and v are 1 or 2, g, h and i are from 0 R represents an integer of 2. R ¹⁷ and R ¹⁹ represent a divalent to tetravalent organic group having 2 to 20 carbon atoms, and R ¹⁸ represents a trivalent to octavalent group having a hydroxyl group selected from 3 to 20 carbon atoms. R ²⁰ , R ²¹ and R ²² may be the same or different and each represents hydrogen or an organic group having 1 to 20 carbon atoms, j, k and l are integers of 0 to 2, w is ^{.R 23} represents an integer of 1 to 4 is a divalent to tetravalent organic radical selected from 2 to 20 carbon ^{atoms, R 24} is a carbon Is ^{.R 25, R 26} which represents a trivalent to octavalent organic group having a hydroxyl group selected from 3-20 may be the same or different represents hydrogen, any of an organic group having 1 to 20 carbon atoms. d and e are integers from 0 to 2, and x is an integer from 1 to 4.) 2. The positive photosensitive resin precursor composition according to claim 1, wherein R ¹ (COOR ³ ) m (OH) p in the general formula (1) is represented by the general formula (2).

(R ⁵ and R ⁷ represent a divalent to tetravalent organic group selected from 2 to 20 carbon atoms, and R ⁶ represents a trivalent to octavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each represents hydrogen or an organic group having 1 to 20 carbon atoms, o, s and t are integers from 0 to 2, and r is 1 Represents an integer of ~ 4.)