JP2008257210A - Positive-type photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive-type photosensitive resin composition having excellent patterning property and retaining a rectangular pattern form even after heat treatment at a high temperature. <P>SOLUTION: The positive-type photosensitive resin composition comprises (a) a novolac resin, (b) a resin mainly composed of a polyimide precursor of a specific structure, (c) a naphthoquinone-diazido compound of a specific structure, (d) a compound having an alkoxymethyl group, and (e) a solvent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a positive photosensitive resin composition. More specifically, the present invention relates to a positive type photosensitive resin composition suitable for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, etc., wherein a portion exposed to ultraviolet rays is dissolved in an alkali developer.

  Since heat-resistant resins such as polyimide and polybenzoxazole have excellent heat resistance and electrical insulation, they are used for surface protection films and interlayer insulation films of semiconductor elements such as LSI (Large Scale Integration). In recent years, with the miniaturization of semiconductor elements, surface protection films, interlayer insulating films, and the like have been required to have a resolution of several μm. For this reason, positive photosensitive polyimide and polybenzoxazole that can be finely processed are used in such applications.

  In addition, as a method for obtaining a photosensitive resin composition having high pattern processability using these heat resistant resins, a positive photosensitive resin composition containing a novolac resin widely used as a resin for photoresists has been developed. (For example, see Patent Documents 1 to 4). However, when a pattern formed using a positive photosensitive resin containing a heat resistant resin and a novolac resin is heat-treated, there is a problem that the pattern is deformed.

As a method for improving the pattern shape and heat resistance of a novolak resist, a novolak resist containing a specific quinonediazide compound has been proposed (see, for example, Patent Document 5). Moreover, the photosensitive resin precursor composition containing heat-resistant resin precursors, such as a polyimide precursor, and a specific quinonediazide compound is proposed (for example, refer patent document 6). However, when heat treatment is performed at a high temperature of 300 ° C. or higher, there is a problem that the pattern is deformed.
JP 2005-62764 A (Claim 1) Japanese Patent Laying-Open No. 2005-250160 (Claim 1) Japanese Patent Laying-Open No. 2005-352004 (Claim 1) JP 2006-285037 A (Claim 1) JP-A-5-297582 (Claim 1) JP 2000-338666 A (Claim 1)

  As described above, the conventionally known photosensitive resin composition containing a heat-resistant resin such as polyimide or polybenzoxazole and a novolac resin has a problem that the cross-sectional shape of the pattern cannot maintain a rectangular shape when heat treatment is performed at a high temperature. there were. An object of the present invention is to provide a positive photosensitive resin composition that is excellent in pattern processability and can maintain a rectangular pattern shape even after heat treatment at a high temperature.

  The present invention includes (a) a novolak resin, (b) a resin having a structure represented by general formula (1) as a main component, (c) a naphthoquinone diazide compound represented by general formula (2), (d) alkoxy A positive photosensitive resin composition comprising a methyl group-containing compound and (e) a solvent.

In general formula (1), R ¹ and R ² may be the same or different, and represent a divalent to octavalent organic group having 2 or more carbon atoms. R ³ and R ⁴ may be the same or different and each represents hydrogen or an organic group having 1 to 20 carbon atoms. n is in the range of 10 to 100,000, m and f are integers of 0 to 2, and p and q are integers of 0 to 4. However, p + q> 0.

In general formula (2), R ^{5 to} R ⁸ may be the same or different and each represents hydrogen or a monovalent organic group having 1 to 10 carbon atoms. R ⁹ represents a divalent organic group. Q represents a 5-naphthoquinonediazidosulfonyl group, a 4-naphthoquinonediazidesulfonyl group, or hydrogen. However, not all of Q becomes hydrogen. r, s, t, and u represent an integer of 0-4.

  ADVANTAGE OF THE INVENTION According to this invention, the positive photosensitive resin composition which is excellent in pattern workability and can maintain a rectangular pattern shape after heat processing at high temperature can be obtained.

  The positive photosensitive resin composition of the present invention contains (a) a novolak resin and (b) a resin whose main component is a structure represented by the general formula (1).

  (A) The novolac resin is obtained by polycondensing phenols and aldehydes by a known method. Two or more novolac resins may be combined and contained. Preferred examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3 , 5-trimethylphenol, 3,4,5-trimethylphenol and the like. In particular, phenol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol and 2,3,5-trimethylphenol are preferable. Two or more of these phenols may be used in combination. From the viewpoint of solubility in an alkaline developer, m-cresol is preferable, and a combination of m-cresol and p-cresol is also preferable. That is, it is preferable that (a) novolak resin includes an m-cresol residue or a cresol novolak resin containing an m-cresol residue and a p-cresol residue. At this time, the molar ratio of m-cresol residue to p-cresol residue in the cresol novolak resin (m-cresol residue / p-cresol residue, m / p) is preferably 1.8 or more. If it is this range, the moderate solubility to an alkali developing solution will be shown, and favorable sensitivity will be obtained. More preferably, it is 4 or more.

  Preferred examples of the aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like. Of these, formalin is particularly preferred. Two or more of these aldehydes may be used in combination. The amount of the aldehyde used is preferably 0.6 mol or more, and more preferably 0.7 mol or more with respect to 1 mol of the phenol. Moreover, 3 mol or less is preferable and 1.5 mol or less is more preferable.

In the polycondensation reaction between phenols and aldehydes, an acidic catalyst is usually used. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, p-toluenesulfonic acid, and the like. The usage-amount of these acidic catalysts is 1 * 10 < ^-5 > ^-5 * 10 < ^-1 > mol normally with respect to 1 mol of phenols. In the polycondensation reaction, water is usually used as a reaction medium. However, when a heterogeneous system is formed from the beginning of the reaction, a hydrophilic solvent or a lipophilic solvent is used as the reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol, butanol and propylene glycol monomethyl ether; and cyclic ethers such as tetrahydrofuran and dioxane. Examples of the lipophilic solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. The amount of these reaction media used is usually 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw material.

  The reaction temperature of the polycondensation can be appropriately adjusted according to the reactivity of the raw materials, but is usually 10 to 200 ° C. As a polycondensation reaction method, a method in which phenols, aldehydes, acidic catalysts, etc. are charged and reacted together, or a method in which phenols, aldehydes, etc. are added in the presence of an acidic catalyst as the reaction proceeds Etc. can be adopted as appropriate. After completion of the polycondensation reaction, in order to remove unreacted raw materials, acidic catalyst, reaction medium, etc. present in the system, the reaction temperature is generally increased to 130 to 230 ° C., and volatile components are reduced under reduced pressure. Remove and recover novolac resin.

  In the present invention, the polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) of the (a) novolak resin is preferably 1,000 or more, and more preferably 2,000 or more. Moreover, 20,000 or less is preferable and 10,000 or less is more preferable. If it is this range, it is excellent in the workability | operativity at the time of apply | coating the positive photosensitive resin composition of this invention to a base material, and the solubility to an alkali developing solution.

  (B) The resin having the structure represented by the general formula (1) as a main component can be a resin having an imide ring, an oxazole ring, or other cyclic structure by heating or an appropriate catalyst. Polyamide acid or polyamic acid ester of polyimide precursor and polyhydroxyamide of polybenzoxazole precursor are preferable. Due to the annular structure, the heat resistance and solvent resistance are dramatically improved. Among these, you may contain combining 2 or more types of resin. Here, the main component means that the n structural units represented by the general formula (1) have 50 mol% or more of the structural units of the resin. 70 mol% or more is preferable and 90 mol% or more is more preferable.

In the general formula (1), R ¹ may be the same or different, and represents a divalent to octavalent organic group having 2 or more carbon atoms and represents an acid structural component. Examples of the acid in which R ¹ is divalent include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, aromatic dicarboxylic acid such as bis (carboxyphenyl) propane, and aliphatic dicarboxylic acid such as cyclohexanedicarboxylic acid and adipic acid. And so on. The acid R ¹ is trivalent, as the acid, trimellitic acid, tricarboxylic acids such as trimesic acid, R ¹ is tetravalent, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic Tetracarboxylic acids such as acids, diester compounds in which two carboxyl groups are esterified with methyl or ethyl groups, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, and two carboxyl groups And a diester compound esterified with a methyl group or an ethyl group. Moreover, the acid which has hydroxyl groups, such as a hydroxyphthalic acid and a hydroxy trimellitic acid, can also be mentioned. These acid components may be used alone or in combination of two or more, but preferably contain 1 to 40 mol% of tetracarboxylic acid. Further, from the viewpoint of solubility in an alkali developer and photosensitivity, it is preferable to use 50 mol% or more of an acid component having a hydroxyl group, and 70 mol% or more is more preferable.

R ¹ preferably contains an aromatic ring from the viewpoint of heat resistance, and more preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms. Specifically, it is preferable that R ¹ (COOR ³ ) _m (OH) _p in the general formula (1) has a structure represented by the general formula (5).

In the general formula (5), R ³⁷ and R ³⁹ represent a divalent to tetravalent organic group having 2 to 20 carbon atoms. R ³⁸ represents represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. R ⁴⁰ and R ⁴¹ may be the same or different and each represents hydrogen or an organic group having 1 to 20 carbon atoms. o and x are integers of 0 to 2, and w is an integer of 1 to 4. However, o + x ≦ 2.

R ³⁷ and R ³⁹ are more preferably those containing an aromatic ring from the viewpoint of the heat resistance of the resulting resin, and particularly preferred structures include residues such as trimellitic acid, trimesic acid and naphthalene tricarboxylic acid.

R ³⁸ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. Further, the w hydroxyl groups are preferably located adjacent to the amide bond. As such an example, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-hydroxy-4-aminophenyl) hexafluoropropane containing a fluorine atom, bis ( 3-amino-4-hydroxyphenyl) propane, bis (3-hydroxy-4-aminophenyl) propane, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-dihydroxy-4,4 ′ Examples include diaminobiphenyl, 2,4-diaminophenol, 2,5-diaminophenol, and 1,4-diamino-2,5-dihydroxybenzene having an amino group bonded thereto.

Further, R ⁴⁰ and R ⁴¹ in the general formula (5) may be the same or different, and represent hydrogen or an organic group having 1 to 20 carbon atoms. Hydrogen or a hydrocarbon group having 1 to 20 carbon atoms is preferable. By setting the number of carbon atoms to 20 or less, moderate solubility in an alkali developer can be obtained. o and x represent an integer of 0 to 2, preferably 1 or 2. However, o + x ≦ 2. Moreover, w represents the integer of 1-4. Within this range, good pattern processability can be obtained.

  Among the structures represented by the general formula (5), examples of preferred structures include the following structures, but are not limited thereto.

In the general formula (1), R ² may be the same or different and represents a divalent to octavalent organic group having 2 or more carbon atoms and represents a structural component of diamine. Among these, those having an aromatic ring are preferred from the viewpoint of the heat resistance of the resulting resin. The diamine component may be used alone or in combination of two or more. Specific examples of diamines include fluorine atoms, bis (amino-hydroxy-phenyl) hexafluoropropane, bis (trifluoromethyl) benzidine, no fluorine atoms, phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene , Diaminodiphenylmethane, diaminodiphenylsulfone, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone, or compounds in which these aromatic rings are substituted with alkyl groups or halogen atoms, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy- diamino - pyrimidine, diaminophenol, dihydroxy benzidine, diaminobenzoic acid, and compounds such as di-amino terephthalic acid of the general formula ⁽¹⁾ R ² (CO R ⁴⁾ _f (OH) _q is represented by the general formula (6) can be exemplified ~ structure represented by any one of (8) one. Among these, it is preferable to use 60 mol% or more of a diamine component having a hydroxyl group from the viewpoint of solubility in an alkali developer and photosensitivity.

R ⁴² and R ^{44 in} the general formula (6) represent a trivalent to tetravalent organic group having 2 to 20 carbon atoms, and R ⁴³ represents a divalent organic group having 2 to 30 carbon atoms. aa and bb represent 1 or 2. In the general formula (7), R ⁴⁵ and R ⁴⁷ represent a divalent organic group having 2 to 20 carbon atoms, and R ⁴⁶ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. cc represents an integer of 1 to 4. R ^{48 in the} general formula (8) represents a divalent organic group having 2 to 20 carbon atoms, and R ⁴⁹ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. dd represents an integer of 1 to 4.

In the general formula (6), R ⁴² and R ⁴⁴ denotes a trivalent to tetravalent organic group having 2 to 20 carbon atoms, those having an aromatic ring from the viewpoint of the heat resistance of the resulting resin is preferable. Specific examples of —R ⁴⁴ (OH) _aa — and —R ⁴⁴ (OH) _bb — include hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, Examples thereof include bis (hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) sulfone group, hydroxydiphenyl ether group, and dihydroxydiphenyl ether group. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used. R ⁴³ represents a divalent organic group having 2 to 30 carbon atoms. A divalent group having an aromatic ring is preferable from the viewpoint of heat resistance of the obtained resin. Examples of such a group include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. In addition, an aliphatic cyclohexyl group and the like can also be used.

In the general formula (7), R ⁴⁵ and R ⁴⁷ represent a divalent organic group having 2 to 20 carbon atoms. A divalent group having an aromatic ring is preferred from the heat resistance of the resulting resin. Examples thereof include the groups shown as examples of R ⁴³ described above. R ⁴⁶ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms, and preferably has an aromatic ring from the heat resistance of the obtained resin. Examples of —R ⁴⁶ (OH) _cc — include the groups shown as examples of —R ⁴² (OH) _aa — and —R ⁴⁴ (OH) _bb — described above.

In the general formula (8), R ⁴⁸ represents a divalent organic group having 2 to 20 carbon atoms. From the heat resistance of the resulting resin, a divalent group having an aromatic ring is preferred. Examples thereof include the groups shown as examples of R ⁴³ described above. R ⁴⁹ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms, and preferably has an aromatic ring from the heat resistance of the obtained resin. Examples of —R ⁴⁹ (OH) _dd — include the groups shown as examples of —R ⁴² (OH) _aa — and —R ⁴⁴ (OH) _bb — described above.

  Of the structures represented by the general formula (6), examples of preferable structures include the following structures, but are not limited thereto.

  Of the structures represented by the general formula (7), examples of preferred structures include the following structures, but are not limited thereto.

  Of the structures represented by the general formula (8), examples of preferred structures include the structures shown below, but are not limited thereto.

R ³ and R ^{4 in} the general formula (1) may be the same or different, and represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms. From the viewpoint of the solution stability of the resulting photosensitive resin composition solution, R ³ and R ⁴ are preferably organic groups, but hydrogen is preferable from the viewpoint of solubility in an alkali developer. In the present invention, hydrogen and an organic group can be mixed. By adjusting the amounts of hydrogen and organic groups of R ³ and R ^4, the dissolution rate with respect to the aqueous alkali solution is changed, so that a photosensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment. A preferred range is that 10 mol% to 90 mol% of each of R ³ and R ⁴ is hydrogen. Further, from the viewpoint of solubility in an alkali developer, the organic group has 20 or less carbon atoms. From the above, R ³ and R ⁴ preferably contain at least one hydrocarbon group having 1 to 16 carbon atoms, and the others are hydrogen.

  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. P and q of General formula (1) show the integer of 0-4, and are p + q> 0. In the general formula (1), n represents the number of repeating structural units of the resin, and is in the range of 10 to 100,000. If n is less than 10, the solubility of the resin in an alkaline developer becomes too high, and the desired pattern may not be formed because the contrast between the exposed and unexposed areas cannot be obtained. On the other hand, if n is larger than 100,000, the solubility of the resin in the alkaline developer becomes too small, the exposed portion is not dissolved, and a desired pattern cannot be formed. From the viewpoint of the solubility of the resin in an alkaline developer, n is preferably 1,000 or less, and more preferably 100 or less. Further, n is preferably 20 or more from the viewpoint of improving the elongation.

  N in the general formula (1) can be easily calculated by measuring the weight average molecular weight (Mw) by gel permeation chromatography (GPC), light scattering method, X-ray small angle scattering method or the like. When the molecular weight of the repeating unit is M and the weight average molecular weight of the polymer is Mw, n = Mw / M. The number of repetitions n in the present invention refers to a value calculated using the simplest GPC measurement in terms of polystyrene.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized in R ¹ and / or R ² of the general formula (1) within a range that does not reduce the heat resistance. Specific 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.

  Moreover, terminal blocker can be made to react with the terminal of resin which has the structure represented by General formula (1) as a main component. By sealing the terminal of the resin with a monoamine having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group, and an allyl group, an alkaline aqueous solution of the resin Can be adjusted to a preferable range. Moreover, the dissolution rate with respect to aqueous alkali solution can be adjusted to a preferable range by sealing the terminal of resin with the acid anhydride, acid chloride, and monocarboxylic acid which have the said functional group. The content of the end-capping agent such as monoamine, acid anhydride, acid chloride, monocarboxylic acid is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, based on the total amine component. is there. By setting it as such a range, the viscosity of the solution at the time of apply | coating a resin composition can be obtained, and the resin composition which had the outstanding film | membrane physical property can be obtained.

The end-capping agent introduced into the resin can be easily detected by the following method. For example, by dissolving the resin into which the end-capping agent has been introduced in an acidic solution and decomposing it into an amine component and an acid anhydride component that are the structural units of the resin, this is measured by gas chromatography (GC) or NMR measurement, The end capping agent can be easily detected. Apart from this, it is possible to directly detect the resin into which the end-capping agent is introduced by pyrolysis gas chromatography (PGC), infrared spectrum and ¹³ C NMR spectrum measurement.

  (B) The resin mainly composed of the structure represented by the general formula (1) is synthesized by the following method. In the case of polyamic acid or polyamic acid ester, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound and a monoamino compound used for terminal blocking at a low temperature, a diester is obtained by tetracarboxylic dianhydride and an alcohol, Thereafter, a method of reacting a diamine compound, a monoamino compound and a condensing agent, a method of obtaining a diester by tetracarboxylic dianhydride and an alcohol, and then converting the remaining dicarboxylic acid to an acid chloride and reacting with the diamine compound or the monoamino compound. and so on. In the case of polyhydroxyamide, it can be obtained by a production method in which a bisaminophenol compound, a dicarboxylic acid, and a monoamino compound are subjected to a condensation reaction. Specifically, a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid, and a bisaminophenol compound or monoamino compound is added thereto, or a bisaminophenol compound added with a tertiary amine such as pyridine, There is a method of dropping a dicarboxylic acid dichloride solution into a monoamino compound solution.

  (B) The resin having the structure represented by the general formula (1) as a main component is polymerized by the above-described method, and then charged into a large amount of water or a methanol / water mixture and precipitated, and separated by filtration. It is desirable to dry and isolate. By this precipitation operation, unreacted monomers and oligomer components such as dimers and trimers are removed, and film properties after thermosetting are improved.

  (B) The content of the polymer whose main component is the structure represented by the general formula (1) is preferably 30 parts by weight or more and more preferably 40 parts by weight or more with respect to (a) 100 parts by weight of the novolak resin. If it is 30 parts by weight or more, the pattern shape is good. Moreover, if it is 100 weight part or less, pattern workability will become favorable.

  The positive photosensitive resin composition of the present invention contains (c) a naphthoquinonediazide compound represented by the general formula (2). Like the positive photosensitive resin composition of the present invention, a positive photosensitive resin composition containing a novolak resin and a polyimide precursor or a polybenzoxazole precursor heats the polyimide precursor or the polybenzoxazole precursor. Heat treatment is performed to close and cure the ring. In particular, in applications such as a surface protective film and an interlayer insulating film of a semiconductor element, the cured film is usually treated at a high temperature of 180 to 290 ° C. in a subsequent process. For this reason, in order to prevent generation | occurrence | production of the gas in a post-processing process, when hardening a resin composition, the temperature higher than the heat processing temperature in a post-processing process, ie, 300 degreeC or more, is often performed. In general, a pattern formed using (a) a novolak resin and (b) a positive photosensitive resin containing a resin whose main component is the structure represented by the general formula (1) is heated at a high temperature of 300 ° C. or higher. When the heat treatment is carried out, the pattern is deformed because the softening point of the novolak resin is low. In the present invention, by using the naphthoquinone diazide compound represented by the general formula (3), it is possible to suppress deformation of the pattern even in a heat treatment at 300 ° C. or higher even in a resin composition containing a novolac resin. it can.

In the general formula (2), R ^{5 to} R ⁸ may be the same or different and each represents hydrogen or a monovalent organic group having 1 to 10 carbon atoms. As an organic group, hydrocarbon groups, such as a C1-C10 alkyl group and an alkenyl group, and a C1-C10 alkoxy group are mentioned, for example. More specifically, the alkyl group is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a butyl group, a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a t-butyl group. The alkoxy group is a carbon such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an isopropoxy group, an isobutoxy group, an n-butoxy group, a sec-butoxy group, or a t-butoxy group. The alkoxy group of number 1-4 is preferable. The alkenyl group is preferably an alkenyl group having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group or a butenyl group. R ⁹ represents a divalent organic group and is preferably a hydrocarbon group having 1 to 30 carbon atoms.

  In the said General formula (2), Q shows 5-naphthoquinone diazide sulfonyl group, 4-naphthoquinone diazide sulfonyl group, or hydrogen. However, not all of Q becomes hydrogen. In the present invention, the molar ratio of naphthoquinonediazidesulfonyl group to hydrogen (naphthoquinonediazidesulfonyl group / hydrogen) in Q is preferably 3/5 or more because the pattern shape is good. Moreover, since pattern workability improves that it is 3 or less, 5/3 or less is more preferable. In addition, a naphthoquinone diazide sulfonyl group points out the total amount of 5-naphthoquinone diazide sulfonyl group and 4-naphthoquinone diazide sulfonyl group here.

  (C) The molecular weight of the quinonediazide compound represented by the general formula (2) is preferably 2500 or less, and preferably 1600 or less. When the molecular weight is 2500 or less, the quinonediazide compound is sufficiently thermally decomposed in the heat treatment after pattern formation, and a cured film having excellent heat resistance, mechanical properties, and adhesiveness can be obtained. On the other hand, 800 or more is preferable and 900 or more is more preferable.

  (C) The naphthoquinone diazide compound represented by the general formula (2) can be obtained by esterifying a corresponding polyhydroxy compound and naphthoquinone diazide sulfonic acid. The polyhydroxy compound can be synthesized, for example, according to the method described in JP-A-49-250, and includes a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst. It is done. Specific examples of the polyhydroxy compound preferably used in the present invention include the following compounds. Two or more of these polyhydroxy compounds may be combined.

  (C) The naphthoquinone diazide compound represented by the general formula (2) is, for example, a part or all of the hydroxyl groups of the polyhydroxy compound, 1,2-naphthoquinone diazide-5- (and / or -4-) sulfonyl. It can be obtained by carrying out a usual esterification reaction in the presence of chloride and a basic catalyst. That is, a predetermined amount of a polyhydroxy compound, 1,2-naphthoquinonediazide-5- (and / or-4-) sulfonyl chloride, and a solvent are charged into a flask, and a basic catalyst is dropped to condense. Examples of the solvent include dioxane, acetone, methyl ethyl ketone, N-methylpyrrolidone and the like. Examples of the basic catalyst include sodium hydroxide, sodium hydrogen carbonate, triethylamine and the like. The reaction temperature is generally −20 ° C. to 60 ° C., preferably 0 ° C. to 40 ° C. The obtained product is generally produced after washing with water and dried.

  In the esterification reaction, mixtures with different esterification numbers and esterification positions are obtained. The esterification rate (molar ratio of naphthoquinonediazidosulfonyl group to hydrogen in Q) as used in the present invention is defined as the average value of this mixture. The esterification rate defined in this way can be adjusted by the mixing ratio of the raw material polyhydroxy compound and 1,2-naphthoquinonediazide-5- (and / or-4-) sulfonyl chloride. That is, since the added 1,2-naphthoquinonediazide-5- (and / or-4-) sulfonyl chloride substantially undergoes an esterification reaction, in order to obtain a mixture having a desired esterification rate, What is necessary is just to adjust the molar ratio. Specifically, the molar amount of the quinonediazide compound is preferably 1 mol or more, and more preferably 1.5 mol or more with respect to the polyhydroxy compound mol. Moreover, 3 mol or less is preferable and 2.5 mol or less is more preferable.

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazide sulfonyl ester compound in which 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound. Can also be used together.

  Further, the content of (c) quinonediazide compound is preferably 1 part by weight or more, more preferably 3 parts by weight from the viewpoint of pattern processability with respect to 100 parts by weight of the total amount of (a) novolak resin and (b) component resin. Part or more, preferably 50 parts by weight or less, more preferably 40 parts by weight or less.

  The positive photosensitive resin composition of the present invention contains (d) an alkoxymethyl group-containing compound. Since the alkoxymethyl group causes a crosslinking reaction in a temperature range of 150 ° C. or higher, it contains the compound, so that the polyimide precursor or the polybenzoxazole precursor is crosslinked by heat and cured by heat treatment to form a favorable pattern shape. Can be obtained. When the component (d) is not used, a good pattern shape cannot be obtained. The component (d) is preferably a compound having two or more alkoxymethyl groups in order to increase the crosslink density, and more preferably a compound having four or more alkoxymethyl groups from the viewpoint of increasing the crosslink density and further improving chemical resistance. . In the present invention, the alkoxymethyl group-containing compound is preferably a compound having a group represented by the general formula (3) or a compound represented by the general formula (4), and these may be used in combination.

In General Formula (3), R ¹⁰ and R ¹¹ represent an alkyl group having 1 to 20 carbon atoms. A C1-C10 alkyl group is preferable from a soluble point with a resin composition, and a C1-C3 alkyl group is more preferable.

In General Formula (4), R ¹² and R ¹³ represent CH ₂ OR ³⁶ (R ³⁶ is an alkyl group having 1 to 6 carbon atoms), and have 1 to 3 carbon atoms in terms of solubility with the resin composition. An alkyl group is more preferred. R ¹⁴ represents hydrogen, a methyl group or an ethyl group. R ^{15 to} R ³⁵ may be the same or different and each represents hydrogen, an organic group having 1 to 20 carbon atoms, Cl, Br, I, or F. j represents an integer of 1 to 4;

  Specific examples of the compound containing the group represented by the general formula (3) include, but are not limited to, the following compounds.

  Specific examples of the compound represented by the general formula (4) include the following compounds, but are not limited thereto.

  (D) The content of the alkoxymethyl group-containing compound is 5% by weight with respect to 100 parts by weight of the total amount of (a) novolac resin and (b) resin from the viewpoint of increasing the crosslink density and further improving the pattern shape. Part or more is preferred. Furthermore, if it is 10 parts by weight or more, a better pattern shape can be obtained. Moreover, from the surface of pattern workability, 50 weight part or less is preferable, 40 weight part or less is more preferable, and 30 weight part or less is further more preferable.

  The positive photosensitive resin composition of the present invention contains (e) a solvent. Solvents include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, etc. Ethers, 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. In the present invention, two or more of these solvents can be used. The content of the solvent is preferably 50 parts by weight or more, more preferably 100 parts by weight or more with respect to 100 parts by weight of the total amount of the (a) novolak resin and the resin of the component (b), and preferably 2, 000 parts by weight or less, more preferably 1,500 parts by weight or less.

  The positive photosensitive resin composition of the present invention can contain (f) a silane compound. (F) By containing a silane compound, adhesiveness with a base substrate improves. (F) Specific examples of the silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, and N-phenyl. Aminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-acryl Roxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and the following silane compounds Can be are not limited thereto.

  The (f) silane compound is preferably contained in an amount of 0.001 parts by weight or more, more preferably 0.005 parts by weight, based on 100 parts by weight of the total amount of the resin (a) novolak resin and component (b). As mentioned above, More preferably, it is 0.01 weight part or more. Moreover, 30 weight part or less is preferable, More preferably, it is 20 weight part or less, More preferably, it is 15 weight part or less. If it is in this range, a sufficient effect as an adhesion aid can be obtained while maintaining the heat resistance of the composition.

  Moreover, the positive photosensitive resin composition of this invention can contain the compound which has a phenolic hydroxyl group as needed. By containing a compound having a phenolic hydroxyl group, the resulting positive photosensitive resin composition is hardly dissolved in an alkali developer before exposure, and easily dissolved in an alkali developer upon exposure. Less film loss and easy development in a short time. For this reason, pattern workability improves. Particularly preferred compounds having a phenolic hydroxyl group are, for example, Bis-Z, TekP-4HPA, TRisP-HAP, TRisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-BIPC-F. is there.

  The content of such a compound having a phenolic hydroxyl group is preferably 1 part by weight or more, more preferably 3 parts by weight or more with respect to 100 parts by weight of the total amount of the resin (a) novolak resin and component (b). In addition, it is preferably 50 parts by weight or less, more preferably 40 parts by weight or less. In addition, in this invention, even if it is a compound which has a phenolic hydroxyl group, when it has a quinone diazide, it shall classify | categorize into (c) quinone diazide compound.

  In addition, if necessary, for the purpose of improving the wettability between the photosensitive composition and the substrate, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, methyl isobutyl You may contain ketones, such as a ketone, and ethers, such as tetrahydrofuran and a dioxane. Further, inorganic particles such as silicon dioxide and titanium dioxide, polyimide powder, and the like can also be contained.

  The manufacturing method of the positive photosensitive resin composition of this invention is illustrated. For example, (a) to (e), and if necessary, other components are placed in a glass flask or stainless steel container and stirred and dissolved with a mechanical stirrer, etc., ultrasonically dissolved, planetary stirring and defoaming The method of stirring and dissolving with an apparatus is mentioned. The viscosity of the composition is preferably 1 to 10,000 mPa · s. Moreover, you may filter with the filter of 0.1 micrometer-5 micrometers pore size in order to remove a foreign material.

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

  A photosensitive resin composition is applied onto a substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, metal, glass, metal oxide insulating film, silicon nitride, ITO, or the like is used, but not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, and slit die coating. Further, 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 resin composition is dried to obtain a photosensitive resin film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like in the range of 50 ° C to 150 ° C for 1 minute to several hours.

  Next, the photosensitive resin 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 rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp. .

  In order to form a pattern of a heat resistant resin from the photosensitive resin film, the exposed portion may be removed using a developer after exposure. The developer is an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamino An aqueous solution of a compound exhibiting alkalinity such as ethyl 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, dimethyl sulfoxide, γ-butyrolactone, 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 increasing the temperature stepwise or by selecting a certain temperature range and continuously increasing 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 320 ° C. over 2 hours can be mentioned.

  The heat-resistant resin film formed by the positive photosensitive resin composition of the present invention includes a semiconductor passivation film, a protective film for a semiconductor element, an interlayer insulating film for a multilayer wiring for high-density mounting, an insulating layer for an organic electroluminescent element, etc. It is suitably used for applications.

  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 composition in an Example was performed with the following method.

(1) Evaluation of pattern processability Production of photosensitive resin film On a 6-inch silicon wafer, a photosensitive resin composition (hereinafter referred to as varnish) was applied so that the film thickness after pre-baking T1 = 8.0 μm, and then A photosensitive resin film was obtained by pre-baking at 120 ° C. for 3 minutes using a hot plate (a coating and developing apparatus Mark-7 manufactured by Tokyo Electron Ltd.).

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

Exposure The reticle from which the pattern was cut was set in an exposure machine (i-line stepper DSW-8570i manufactured by GCA), and the photosensitive resin film was exposed to i-line by changing the exposure time at an intensity of 365 nm.

Development Using a developing device of Mark-7 manufactured by Tokyo Electron Ltd., a 2.38% aqueous solution of tetramethylammonium hydroxide was sprayed on the exposed film for 10 seconds at 50 revolutions. Then, it was allowed to stand for 30 seconds at 0 rotation, rinsed with water at 400 rotation, and then shaken and dried for 10 seconds at 3,000 rotation.

Calculation of pattern workability After exposure and development, an exposure time (hereinafter referred to as an optimum exposure time) Eop in which a 50 μm line-and-space pattern (1L / 1S) is formed in a one-to-one width was obtained. . If Eop is 400 mJ / cm ² or less, the pattern workability is good, and 200 mJ / cm ² or less is more preferable.

(2) Evaluation of pattern shape characteristics after thermosetting Thermosetting treatment The photosensitive resin precursor film developed and produced by the above-described method was subjected to a nitrogen stream using an inert oven CLH-21CD manufactured by Koyo Thermo System Co., Ltd. (Oxygen concentration: 20 ppm or less) The solution was introduced into 150 ° C., heated to 320 ° C. in 30 minutes at the same time as the addition, and heat-treated at 320 ° C. for 30 minutes to produce a heat resistant resin coating (cured film).

Pattern shape evaluation After thermosetting, the pattern cross section was observed using FE-SEM manufactured by Hitachi High-Technologies Corporation. As the evaluation criteria, a pattern having a cross section close to a rectangle was accepted, and a pattern having no corners and a circle was rejected. FIG. 1 shows the evaluation criteria for pattern shape characteristics after thermosetting.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride (a) In a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) Allyl glycidyl ether 34.2 g (0.3 mol) was dissolved in 100 g of gamma butyrolactone and cooled to -15 ° C. Thereto was added dropwise 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of gamma butyrolactone 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 a hydroxyl group-containing acid anhydride (a).

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (b) 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 3-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 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 as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound (b). The obtained solid was used for the reaction as it was.

Synthesis Example 3 Synthesis of hydroxyl group-containing diamine (c) 15.4 g (0.1 mol) of 2-amino-4-nitrophenol was dissolved in 50 mL of acetone and 30 g (0.34 mol) of propylene oxide. 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 of γ-butyrolactone (GBL), 3 g of 5% palladium-carbon 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 for recrystallization to obtain a hydroxyl group-containing diamine (c) crystal.

Synthesis Example 4 Synthesis of Hydroxyl Group-Containing Diamine (d) 2-Amino-4-nitrophenol 15.4 g (0.1 mol) was dissolved in acetone 100 mL and propylene oxide 17.4 g (0.3 mol), 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, a hydroxyl group-containing diamine (d) crystal was obtained in the same manner as in Synthesis Example 2.

Synthesis Example 5 Synthesis of quinonediazide compound (e) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.31 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride (NAC5) under a dry nitrogen stream 40.28 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 in the system would not be 35 ° C. or higher. It stirred at 30 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 (e).

Synthesis Example 6 Synthesis of quinonediazide compound (f) TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol) and NAC5 26.86 g (0.10 mol) in a dry nitrogen stream ), 14.43 g (0.05 mol) of 4-naphthoquinonediazide sulfonyl chloride was dissolved in 450 g of 1,4-dioxane and brought to room temperature. A quinonediazide compound (f) was obtained in the same manner as in Synthesis Example 5 using 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 7 Synthesis of quinonediazide compound (g) TekP-4HBPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.): 57.67 g (0.1 mol), NAC5: 26.87 g (0.1 mol) in a 2 L flask It was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° 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 (g).

Synthesis Example 8 Synthesis of quinonediazide compound (h) TekP-4HBPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.): 57.67 g (0.1 mol), NAC5: 40.30 g (0.15 mol) in a 2 L flask It 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 in the system would not be 35 ° 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 (h).

Synthesis Example 9 Synthesis of quinonediazide compound (i) TekP-4HBPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.): 57.67 g (0.1 mol), NAC5: 53.74 g (0.2 mol) in a 2 L flask It was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 20.24 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° 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 (i).

Synthesis Example 10 Synthesis of quinonediazide compound (j) TekP-4HBPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.): 57.67 g (0.1 mol), NAC5: 67.17 g (0.25 mol) in a 2 L flask It was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 25.30 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° 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 (j).

Synthesis Example 11 Synthesis of quinonediazide compound (k) TekP-4HBPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.): 57.67 g (0.1 mol), NAC5: 80.60 g (0.3 mol) in a 2 L flask It was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 30.36 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° 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 (k).

Synthesis Example 12 Synthesis of Novolak Resin A Under a dry nitrogen stream, 70.2 g (0.65 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 75.5 g of a 37 wt% formaldehyde aqueous solution (formaldehyde 0) .93 mol), 0.63 g (0.005 mol) of oxalic acid dihydrate, and 264 g of methyl isobutyl ketone, and then immersed in an oil bath to conduct a polycondensation reaction for 4 hours while refluxing the reaction solution. It was. Thereafter, the temperature of the oil bath is raised over 3 hours, and then the pressure in the flask is reduced to 40 to 67 hPa, the volatile matter is removed, the dissolved resin is cooled to room temperature, and a novolak resin is obtained. A polymer solid of A was obtained. From GPC, the weight average molecular weight was 3,500.

Synthesis Example 13 Synthesis of Novolak Resin B 108 g (1.00 mol) of m-cresol was used instead of 70.2 g (0.65 mol) of m-cresol and 37.8 g (0.35 mol) of p-cresol. Otherwise in the same manner as in Synthesis Example 12, a polymer solid of novolak resin B was obtained. From GPC, the weight average molecular weight was 4,000.

Synthesis Example 14 Synthesis of Novolak Resin C Instead of 70.2 g (0.65 mol) of m-cresol and 37.8 g (0.35 mol) of p-cresol, 86.4 g (0.80 mol) of m-cresol, A novolak resin C polymer solid was obtained in the same manner as in Synthesis Example 12 except that 21.6 g (0.20 mol) of p-cresol was used. From GPC, the weight average molecular weight was 5,000.

Synthesis Example 15 Synthesis of Novolak Resin D Instead of 70.2 g (0.65 mol) of m-cresol and 37.8 g (0.35 mol) of p-cresol, 54 g (0.50 mol) of m-cresol, p- A novolak resin D polymer solid was obtained in the same manner as in Synthesis Example 12 except that 54 g (0.50 mol) of cresol was used. From GPC, the weight average molecular weight was 3,500.

Synthesis Example 16 Synthesis of Polymer A 4.4 g (0.023 mol) of 4,4′-diaminophenyl ether (DAE), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (SiDA) under a dry nitrogen stream ) 1.24 g (0.005 mol) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). 21.4 g (0.030 mol) of the hydroxy group-containing acid anhydride (a) obtained in Synthesis Example 1 was added thereto together with 14 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour, and then reacted at 40 ° C. for 2 hours. . Thereafter, a solution obtained 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 40 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and a precipitate of polymer solid was collected by filtration. The polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polyimide precursor polymer A.

Synthesis Example 17 Synthesis of Polymer B Under a dry nitrogen stream, 13.90 g (0.023 mol) of hydroxyl group-containing diamine (b) obtained in Synthesis Example 2 was dissolved in 50 g of NMP. 17.5 g (0.025 mol) of the hydroxy group-containing acid anhydride (a) obtained in Synthesis Example 1 was added thereto together with 30 g of pyridine, and reacted at 40 ° C. for 2 hours. Thereafter, a solution obtained by diluting 7.35 g (0.05 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 40 ° C. for 2 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 72 hours to obtain a polyimide precursor polymer B.

Synthesis Example 18 Synthesis of Polymer C Under dry nitrogen stream, 15.13 g (0.040 mol) of hydroxyl group-containing diamine compound (c) obtained in Synthesis Example 3 and 1.24 g (0.005 mol) of SiDA were dissolved in 50 g of NMP. I let you. To this, 15.51 g (0.05 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic anhydride (ODPA) was added together with 21 g of NMP and reacted at 20 ° C. for 1 hour, and then at 50 ° C. for 1 hour. Reacted. Thereafter, a solution obtained by diluting 13.2 g (0.09 mol) of N, N-dimethylformamide diethyl acetal with 15 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 72 hours to obtain a polyimide precursor polymer C.

Synthesis Example 19 Synthesis of Polymer D 4.37 g (0.018 mol) of hydroxyl group-containing diamine compound (d) obtained in Synthesis Example 4 under a stream of dry nitrogen, 4.51 g (0.0225 mol) of DAE and 0.62 g of SiDA (0.0025 mol) was dissolved in 70 g of NMP. Here, 24.99 g (0.035 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) 4. 41 g (0.010 mol) was added together with 25 g of NMP at room temperature, and the mixture was stirred at room temperature for 1 hour and then at 40 ° C. for 1 hour. Thereafter, a solution obtained by diluting 13.09 g (0.11 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 72 hours to obtain a polyimide precursor polymer D.

Synthesis Example 20 Synthesis of Polymer E 19.70 g of a dicarboxylic acid derivative obtained by reacting 1 mol of diphenyl ether-4,4′-dicarboxylic acid dichloride (DEDC) with 2 mol of 1-hydroxybenzotriazole under a dry nitrogen stream ( 0.040 mol) and 18.31 g (0.050 mol) of BAHF were dissolved in 200 g of NMP and stirred at 75 ° C. for 12 hours to complete the reaction. After the completion of the reaction, the solution was put into 3 L of a solution of water / methanol = 3/1, and a polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours to obtain a polybenzoxazole precursor polymer E.

Synthesis Example 21 Synthesis of Polymer F Under a dry nitrogen stream, 4.40 g (0.022 mol) of DAE and 1.24 g (0.005 mol) of SiDA were dissolved in 50 g of NMP. 21.4 g (0.030 mol) of the hydroxy group-containing acid anhydride (a) obtained in Synthesis Example 1 was added thereto together with 14 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour, and then reacted at 40 ° C. for 2 hours. . Thereafter, 0.71 g (0.006 mol) of 4-ethynylaniline was added as a terminal blocking agent, and the mixture was further reacted at 40 ° C. for 1 hour. Thereafter, a solution obtained 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 40 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polyimide precursor polymer F.

Synthesis Example 22 Synthesis of Polymer G In a dry nitrogen stream, 48.1 g of DAE and 25.6 g of SiDA were dissolved in 820 g of NMP, added with 105 g of ODPA, and stirred for 8 hours while adjusting the liquid temperature to be 10 ° C. or higher and 30 ° C. or lower. A polymer solution G of polyimide precursor was obtained.

Synthesis Example 23 Synthesis of Polymer H In a dry nitrogen stream, 49.6 g of BAHF and 3.74 g of SiDA were dissolved in 400 g of NMP, 46.7 g of ODPA was added and stirred, and the mixture was allowed to react at room temperature for 5 hours. Obtained.

Synthesis Example 24 Synthesis of Polymer I In a dry nitrogen stream, 198 g of SiDA was dissolved in 600 g of NMP, 123.6 g of ODPA and 78.2 g of maleic anhydride were added, and the mixture was stirred for 8 hours while adjusting the liquid temperature to be 10 ° C. or higher and 30 ° C. or lower. As a result, a polyimide precursor polymer solution I was obtained.

Synthesis Example 25 Synthesis of Polymer J 4.40 g (0.022 mol) of 4,4′-diaminophenyl ether (DAE), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (SiDA) under a dry nitrogen stream ) 1.24 g (0.005 mol) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). 21.4 g (0.030 mol) of the hydroxy group-containing acid anhydride (a) obtained in Synthesis Example 1 was added thereto together with 14 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour, and then reacted at 40 ° C. for 2 hours. . Thereafter, 0.71 g (0.006 mol) of 4-ethynylaniline was added as a terminal blocking agent, and the mixture was further reacted at 40 ° C. for 1 hour. Thereafter, a solution obtained 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 40 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polyimide precursor polymer J.

  The structure of the alkoxymethyl group-containing compound used in each example and comparative example is shown below.

Example 1
6 g of novolak resin A, 4 g of polymer A solid, 2 g of quinonediazide compound (g), 2.5 g of Nicalac MX-270, 0.3 g of vinyltrimethoxysilane, and dissolved in 30 g of GBL to obtain a photosensitive resin composition A varnish was obtained. As described above, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed using the obtained varnish.

Example 2
Novolak resin B: 6 g, polymer B: 4 g, quinonediazide compound (h): 2 g, Nicalac MX-270: 2.5 g, vinyltrimethoxysilane: 0.3 g are measured and dissolved in GBL 25 g + EL 5 g. A varnish of the composition was obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Example 3
Novolak resin C: 6 g, polymer C: 4 g, quinonediazide compound (i): 2 g, Nicalak MX-270: 2.5 g, N-phenylaminopropyltrimethoxysilane: 0.3 g are measured and dissolved in GBL 30 g. Thus, a varnish of the photosensitive resin composition was obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Example 4
Novolak resin A: 6 g, polymer D: 4 g, quinonediazide compound (j): 2 g, Nicalak MX-270: 2.5 g, vinyltrimethoxysilane: 0.3 g are measured and dissolved in NMP 30 g to obtain a photosensitive resin. A varnish of the composition was obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Example 5
Novolak resin A: 6 g, polymer A: 4 g, quinonediazide compound (k): 2 g, Nicalak MX-270: 2.5 g, vinyltrimethoxysilane: 0.3 g are measured and dissolved in GBL 30 g to obtain a photosensitive resin. A varnish of the composition was obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Example 6
Novolak resin A: 6 g, polymer F: 4 g, quinonediazide compound (i): 2 g, Nicarax MX-270: 2.5 g, vinyltrimethoxysilane: 0.3 g are measured and dissolved in 30 g of GBL. A varnish of the composition was obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Example 7
Novolak resin C: 6 g, polymer C: 4 g, quinonediazide compound (i): 2 g, HMOM-TPHAP: 2.5 g, vinyltrimethoxysilane: 0.3 g were measured and dissolved in GBL 30 g to obtain a photosensitive resin composition. A varnish was obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Example 8
Novolac resin C: 6 g, polymer E: 4 g, quinonediazide compound (i): 1.5 g, Nicarax MX-290: 1.5 g, m-acetylaminophenyltrimethoxysilane: 0.3 g were measured, and these were converted to GBL 30 g. The varnish of the photosensitive resin composition was obtained by dissolving. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Example 9
Novolak resin A: 4 g, polymer F: 6 g, quinonediazide compound (i): 2 g, Nicalak MX-270: 2.5 g, vinyltrimethoxysilane: 0.3 g are measured and dissolved in GBL 30 g to obtain a photosensitive resin composition. The varnish was obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Example 10
Novolak resin A: 7 g, polymer F: 3 g, quinonediazide compound (i): 2.2 g, Nicalac MX-270: 1.0 g, vinyltrimethoxysilane: 0.3 g are measured and dissolved in 30 g of GBL. The varnish of the functional resin composition was obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Example 11
Novolak resin A: 7 g, polymer J: 3 g, quinonediazide compound (g): 2 g, Nicarax MX-270: 2.5 g, vinyltrimethoxysilane: 0.3 g are measured and dissolved in GBL 30 g to obtain a photosensitive resin composition. The varnish was obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Example 12
A varnish was obtained in the same manner as in Example 11 except that 7 g of novolak resin B was used instead of 7 g of novolak resin A, and pattern workability evaluation and pattern shape evaluation after thermosetting were performed as described above.

Example 13
A varnish was obtained in the same manner as in Example 11 except that 7 g of novolak resin C was used instead of 7 g of novolak resin A, and pattern workability evaluation and pattern shape evaluation after thermosetting were performed as described above.

Example 14
A varnish was obtained in the same manner as in Example 11 except that 7 g of novolak resin D was used instead of 7 g of novolak resin A, and pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Example 15
Novolak resin A: 6 g, polymer J: 4 g, quinonediazide compound (g): 2 g, Nicarax MX-270: 2.5 g, vinyltrimethoxysilane: 0.3 g were measured and dissolved in GBL 30 g to obtain a photosensitive resin composition. The varnish was obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Example 16
A varnish was obtained in the same manner as in Example 15 except that 2 g of the quinonediazide compound (h) was used instead of 2 g of the quinonediazide compound (g), and the pattern workability evaluation and the pattern shape evaluation after thermosetting were performed as described above. .

Example 17
A varnish was obtained in the same manner as in Example 15 except that 2 g of the quinonediazide compound (i) was used instead of 2 g of the quinonediazide compound (g), and the pattern workability evaluation and the pattern shape evaluation after thermosetting were performed as described above. .

Example 18
A varnish was obtained in the same manner as in Example 15 except that 2 g of the quinonediazide compound (j) was used instead of 2 g of the quinonediazide compound (g), and the pattern workability evaluation and the pattern shape evaluation after thermosetting were performed as described above. .

Example 19
A varnish was obtained in the same manner as in Example 15 except that 2 g of the quinonediazide compound (k) was used instead of 2 g of the quinonediazide compound (g), and the pattern workability evaluation and the pattern shape evaluation after thermosetting were performed as described above. .

Comparative Example 1
Novolak resin A: 7 g, quinonediazide compound (g): 2 g, Nicalac MX-270: 2.5 g, vinyltrimethoxysilane: 0.3 g were measured and dissolved in GBL 30 g to obtain a varnish of the photosensitive resin composition. Obtained. As described above, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed using the obtained varnish.

Comparative Example 2
Novolac resin B: 6 g, quinonediazide compound (h): 2 g, Nicalac MX-270: 2.5 g, vinyltrimethoxysilane: 0.3 g were measured and dissolved in GBL25 g + EL5 g to obtain a varnish of the photosensitive resin composition. Obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Comparative Example 3
Polymer C: 10 g, quinonediazide compound (i): 2 g, Nicarax MX-270: 2.5 g, N-phenylaminopropyltrimethoxysilane: 0.3 g were measured and dissolved in GBL 30 g to obtain a photosensitive resin composition. The varnish was obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Comparative Example 4
Polymer D: 10 g, quinonediazide compound (j): 2 g, Nicalak MX-270: 2.5 g, vinyltrimethoxysilane: 0.3 g are measured and dissolved in NMP 30 g to obtain a varnish of a photosensitive resin composition. It was. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Comparative Example 5
Novolak resin C: 6 g, polymer C: 4 g, quinonediazide compound (e): 2 g, Nicarax MX-270: 2.5 g, N-phenylaminopropyltrimethoxysilane: 0.3 g are measured and dissolved in GBL 30 g for photosensitivity. The varnish of the functional resin composition was obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Comparative Example 6
Novolak resin C: 6 g, polymer C: 4 g, quinonediazide compound (i): 2 g, Nicalak MX-270: 2.5 g, N-phenylaminopropyltrimethoxysilane: 0.3 g are measured and dissolved in GBL 30 g for photosensitivity. The varnish of the functional resin composition was obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Comparative Example 7
Novolak resin A: 6 g, polymer G solution: 22.3 g, quinonediazide compound (f): 2 g, Nicalak MX-270: 2.5 g, vinyltrimethoxysilane: 0.3 g are measured and dissolved in 30 g of NMP. A varnish of the photosensitive resin composition was obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Comparative Example 8
Novolak resin A: 6 g, polymer H solution: 20 g, quinonediazide compound (f): 2 g, 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenine) propane: 2.0 g were measured and they were measured. The varnish of the photosensitive resin composition was obtained by dissolving in 30 g of NMP. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

Comparative Example 9
Novolak resin A: 6.5 g, polymer I solution: 8.7 g, quinonediazide compound (e): 2 g, Nicalak MX-270: 2.5 g, vinyltrimethoxysilane: 0.3 g are measured and dissolved in NMP 30 g. Thus, a varnish of the photosensitive resin composition was obtained. Thereafter, pattern workability evaluation and post-thermosetting pattern shape evaluation were performed as described above.

  The compositions of Examples 1 to 19 and Comparative Examples 1 to 9 are shown in Tables 1 and 2, and the evaluation results are shown in Table 3.

It is a figure which shows the pattern shape characteristic evaluation criteria after thermosetting.

Claims (5)

(A) a novolak resin, (b) a resin having a structure represented by the general formula (1) as a main component, (c) a naphthoquinone diazide compound represented by the general formula (2), and (d) an alkoxymethyl group-containing compound And (e) a positive photosensitive resin composition comprising a solvent.
(In general formula (1), R ¹ and R ² may be the same or different, and represent a divalent to octavalent organic group having 2 or more carbon atoms. R ³ and R ⁴ are the same or different. It may be hydrogen or an organic group having 1 to 20 carbon atoms, n is in the range of 10 to 100,000, m and f are integers of 0 to 2, and p and q are integers of 0 to 4. p + q> 0.)
(In General Formula (2), R ^{5 to} R ⁸ may be the same or different and each represents hydrogen or a monovalent organic group having 1 to 10 carbon atoms. R ⁹ represents a divalent organic group. Q represents a 5-naphthoquinonediazidosulfonyl group, a 4-naphthoquinonediazidesulfonyl group, or hydrogen, provided that not all of Q is hydrogen, and r, s, t, and u represent integers of 0 to 4. .) (A) 100 to 100 parts by weight of novolak resin, (b) 30 to 100 parts by weight of resin mainly composed of the structure represented by general formula (1), (a) novolac resin and (b) general formula (C) 1 to 50 parts by weight of a naphthoquinonediazide compound represented by the general formula (2) with respect to 100 parts by weight of the resin having the structure represented by (1) as a main component, (d) an alkoxymethyl group The positive photosensitive resin composition according to claim 1, comprising 5 to 50 parts by weight of the containing compound. (D) The alkoxymethyl group-containing compound comprises a compound having a group represented by the general formula (3) and / or a compound represented by the general formula (4). Positive photosensitive resin composition.
(In General Formula (3), R ¹⁰ and R ¹¹ represent an alkyl group having 1 to 20 carbon atoms.)
(In General Formula (4), R ¹² and R ¹³ represent CH ₂ OR ³⁶ (R ³⁶ is an alkyl group having 1 to 6 carbon atoms) R ¹⁴ represents hydrogen, a methyl group, or an ethyl group, R ¹⁵ -R ³⁵ may be the same or different and each represents hydrogen, an organic group having 1 to 20 carbon atoms, Cl, Br, I or F. j represents an integer of 1 to 4. (C) The molar ratio of naphthoquinonediazidesulfonyl group to hydrogen (naphthoquinonediazidesulfonyl group / hydrogen) in Q of the naphthoquinonediazide compound represented by the general formula (2) is 3/5 or more and 3 or less, The positive photosensitive resin composition according to any one of claims 1 to 3. The positive photosensitive resin according to any one of claims 1 to 4, wherein (a) the novolak resin contains a cresol novolak resin having a molar ratio (m / p) of m-cresol residue to p-cresol residue of 1.8 or more. Resin composition.