JP2008225457A - Positive-type photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive-type photosensitive resin composition having good mechanical properties and excellent storage stability by using a novolac resin. <P>SOLUTION: The positive-type photosensitive resin composition comprises (a) the novolac resin, (b) a polymer mainly composed of a structure represented by general formula (1) and/or (2), (c) a quinonediazide compound, (d) a compound having an alkoxymethyl group, and (e) a solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a positive photosensitive resin composition. More specifically, the present invention relates to a positive 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 alkaline 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.

On the other hand, a positive photosensitive resin composition containing a novolak resin widely used as a resin for photoresist, a polyimide precursor or a polybenzoxazole precursor, and a quinonediazide compound has been proposed (for example, Patent Document 1). reference). However, this resin composition is very fragile after thermosetting, and has insufficient mechanical properties, particularly elongation and strength, compared to conventional polyimide and polybenzoxazole. In addition, a positive photosensitive resin composition containing a novolac resin, a polyamide precursor or a polybenzoxazole precursor, a quinonediazide compound, and a polyfunctional methylol compound has been proposed (see, for example, Patent Documents 2 to 4). However, these resin compositions are inferior in mechanical properties and storage stability and have a problem of large sensitivity changes. For the above reasons, it has been difficult to use these resin compositions in place of photosensitive polyimide or photosensitive polybenzoxazole in applications such as surface protection films and interlayer insulating films of semiconductor elements.
Japanese Patent Laying-Open No. 2005-352004 (Claim 1) Japanese Patent Laying-Open No. 2005-062764 (Claim 1) Japanese Patent Laying-Open No. 2005-250160 (Claim 1) JP 2006-285037 A (Claim 1)

  An object of the present invention is to provide a positive photosensitive resin composition having good mechanical properties and excellent storage stability using a novolac resin.

  The present invention includes (a) a novolak resin, (b) a polymer having a structure represented by the general formula (1) and / or (2) as a main component, (c) a quinonediazide compound, and (d) an alkoxymethyl group-containing compound. And (e) a positive photosensitive resin composition containing a solvent.

In general formulas (1) to (2), 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 a monovalent organic group having 1 to 20 carbon atoms. —NH—R ^{5 in} the general formula (1) and —CO—R ^{6 in} the general formula (2) represent a terminal group of the polymer, and R ⁵ and R ⁶ have 2 to 30 carbon atoms having an unsaturated hydrocarbon group. A monovalent organic group is shown. n is in the range of 10 to 100,000, l and m are integers of 0 to 2, and p and q are integers of 0 to 4. However, p + q> 0.

  According to the present invention, a positive photosensitive resin composition having good mechanical properties and excellent storage stability can be obtained.

  The positive photosensitive resin composition of the present invention contains (a) a novolak resin, and (b) a polymer whose main component is a structure represented by the general formula (1) and / or (2).

  (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.

  Preferable examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, and 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 or 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 the reaction medium 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, phenols, aldehydes, acidic catalysts, etc. are charged all at once and reacted, or phenols, aldehydes, etc. are added as the reaction proceeds in the presence of acidic catalysts, 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 polymer having the structure represented by the general formula (1) and / or (2) 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. It is. 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 having n structural units of the structure represented by the general formula (1) and / or (2) in an amount of 50 mol% or more of the structural units of the polymer. 70 mol% or more is preferable and 90 mol% or more is more preferable.

In the above general formulas (1) and (2), 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, trimellitic acid, tricarboxylic acids such as trimesic acid, pyromellitic acid as the acid R ¹ is tetravalent, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid Tetracarboxylic acids such as diphenylsulfonetetracarboxylic acid, diester compounds in which two carboxyl groups are methyl or ethyl groups, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, and carboxyls thereof Examples thereof include diester compounds in which two groups are methyl groups or ethyl groups. 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 formulas (1) and (2) has a structure represented by the general formula (5).

In the above formula ^{(5), R 33} and ^{R 35} represents a divalent to tetravalent organic group having 2 to 20 carbon atoms. R ³⁴ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. R ³⁶ and R ³⁷ may be the same or different and each represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms. o and t are integers of 0 to 2, and r is an integer of 1 to 4. However, o + t ≦ 2.

From the viewpoint of the heat resistance of the resulting polymer, R ³³ and R ³⁵ preferably contain an aromatic ring, and particularly preferred structures include residues such as trimellitic acid, trimesic acid and naphthalene tricarboxylic acid.

R ³⁴ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. Furthermore, the r 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-diamino-phenol, 2,5-diaminophenol, and 1,4-diamino-2,5-dihydroxybenzene having an amino group bonded thereto.

R ³⁶ and R ³⁷ in the general formula (5) may be the same or different and represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and hydrogen or carbon atoms having 1 to 20 carbon atoms. A hydrogen group is preferred. By setting the number of carbon atoms to 20 or less, moderate solubility in an alkali developer can be obtained. o and t each represent an integer of 0 to 2, preferably 1 or 2. However, o + t ≦ 2. R represents an integer of 1 to 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 formulas (1) and (2), 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. Of these, those having an aromatic ring are preferred from the viewpoint of the heat resistance of the resulting polymer. 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 an alkyl group or a halogen atom, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy- Compounds such as diamino-pyrimidine, diaminophenol, dihydroxybenzidine, diaminobenzoic acid, diaminoterephthalic acid, cyclohexyldiamine, Ren bis cyclohexylamine, aliphatic diamines such as _{^{hexamethylenediamine, R 2 (COOR 4) l}} (OH) q in general formula (1) and (2), one of the general formulas (6) - (8) Mention may be made of the structures shown. 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.

In the general formula (6), R ³⁸ and R ⁴⁰ represent a trivalent to tetravalent organic group having 2 to 20 carbon atoms, and R ³⁹ represents a divalent organic group having 2 to 30 carbon atoms. u and v represent 1 or 2. R ⁴¹ and R ^{43 in} the general formula (7) represent a divalent organic group having 2 to 20 carbon atoms, and R ⁴² represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. w shows the integer of 1-4. R ^{44 in the} general formula (8) represents a divalent organic group having 2 to 20 carbon atoms, and R ⁴⁵ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. x shows the integer of 1-4.

In the general formula (6), R ³⁸ and R ⁴⁰ 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 polymer. Specific examples of —R ³⁸ (OH) _u — and —R ⁴⁰ (OH) _v — include hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (Hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) sulfone group, hydroxydiphenyl ether group, dihydroxydiphenyl ether group and the like can be mentioned. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used. R ³⁹ represents a divalent organic group having 2 to 30 carbon atoms. What has an aromatic ring from the heat resistant point of the polymer obtained is preferable. 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 or the like can also be used.

In the general formula (7), R ⁴¹ and R ⁴³ 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 polymer. Examples thereof include the groups shown as examples of R ³⁹ described above. R ⁴² 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 resulting polymer. Examples of the aforementioned _{^{-R 35 (OH) u - -}} -R 42 (OH) w include groups shown as examples of - and ^-R 40 _{(OH) v.}

In the general formula (8), R ⁴⁴ represents a divalent organic group having 2 to 20 carbon atoms. Those having an aromatic ring are preferred from the heat resistance of the resulting polymer. Examples thereof include the groups shown as examples of R ³⁹ described above. R ⁴⁵ 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 resulting polymer. Examples of -R ⁴⁵ (OH) x-, aforementioned ^-R 38 _{(OH) u} - include the groups shown as examples of - and ^-R 40 _{(OH) v.}

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

  Further, among the structures represented by the general formula (7), examples of preferable 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 formulas (1) and (2) may be the same or different from each other, and represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms. From the viewpoint of 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 alkaline aqueous solution. 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 preferable range is that 10 mol% to 90 mol% of each of R ³ and R ⁴ is a hydrogen atom. 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 atoms.

  In the general formulas (1) and (2), l and m represent the number of carboxyl groups or esters, and are integers of 0 to 2. Preferably it is 1 or 2. P and q of General formula (1) and (2) show the integer of 0-4, and it is p + q> 0. In the general formulas (1) and (2), n represents the number of repeating structural units of the polymer, and is in the range of 10 to 100,000. If n is less than 10, the solubility of the polymer in an alkaline developer becomes too high, and the contrast between the exposed area and the unexposed area cannot be obtained, and a desired pattern may not be formed. On the other hand, if n is larger than 100,000, the solubility of the polymer in an alkali developer becomes too small, the exposed portion is not dissolved, and a desired pattern cannot be formed. From the viewpoint of solubility of the polymer 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 formulas (1) and (2) 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 used for R ¹ and / or R ² in the general formulas (1) and (2) as long as the heat resistance is not lowered. Good. 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.

In the general formulas (1) and (2), —NH—R ⁵ and —CO—R ⁶ represent end groups of the polymer. General formula (1) shows the case where a monoamino compound is used at the terminal, and general formula (2) shows the case where a monoacid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound is used at the terminal. . R ⁵ and R ⁶ represent a monovalent organic group having 2 to 30 carbon atoms and having an unsaturated hydrocarbon group. From the viewpoint of the heat resistance of the resulting polymer, those having an aromatic ring are preferred. The unsaturated hydrocarbon group in R ⁵ and R ⁶ reacts and crosslinks during heat curing, whereby good mechanical properties are obtained. Since the novolak resin as the component (a) is brittle, the conventionally known resin composition containing the novolak resin and the polyimide precursor or polybenzoxazole precursor and the quinonediazide compound has insufficient mechanical properties after thermosetting. Had problems. For this reason, satisfactory mechanical properties cannot be obtained particularly in the use of a permanent film such as a protective film of a semiconductor element. In the positive photosensitive resin composition of the present invention, since the polymer of the component (b) has the above end group, the crosslinking reaction proceeds by heat treatment, so that even a resin composition containing a novolak resin is subjected to heat curing. Mechanical properties can be improved dramatically.

Examples of R ⁵ and R ⁶ include o-vinylphenyl group, m-vinylphenyl group, p-vinylphenyl group, o-ethynylphenyl group, m-ethynylphenyl group, p-ethynylphenyl group, o-propynylphenyl. Group, m-propynylphenyl group, p-propynylphenyl group, o-allylphenyl group, m-allylphenyl group, p-allylphenyl group, o- (3-hydroxy-3-methyl-1-butynyl) phenyl group, m- (3-hydroxy-3-methyl-1-butynyl) phenyl group, p- (3-hydroxy-3-methyl-1-butynyl) phenyl group, o- (3-hydroxy-3-methyl-1-pentynyl) ) Phenyl group, m- (3-hydroxy-3-methyl-1-pentynyl) phenyl group, p- (3-hydroxy-3-methyl-1-pentynyl) Enyl group, o- (3-hydroxy-3-ethyl-1-pentynyl) phenyl group, m- (3-hydroxy-3-ethyl-1-pentynyl) phenyl group, p- (3-hydroxy-3-ethyl- 1-pentynyl) phenyl group, o-nitrophenyl group, m-nitrophenyl group, p-nitrophenyl group, o-methylolphenyl group, m-methylolphenyl group, p-methylolphenyl group, o-methylbenzoate group, m -A methyl benzoate group and p-methyl benzoate group are mentioned. Examples of the substituent having no aromatic ring include a 3-vinylcyclohexyl group, a 4-vinylcyclohexyl group, a 3-ethynylcyclohexyl group, a 4-ethynylcyclohexyl group, a 3-propynylcyclohexyl group, and a 4-propynylcyclohexyl group. . More preferably, m-vinylphenyl group, p-vinylphenyl group, m-ethynylphenyl group, p-ethynylphenyl group, m-propynylphenyl group, p-propynylphenyl group, m-allylphenyl group, p-allylphenyl. Group, m- (3-hydroxy-3-methyl-1-pentynyl) phenyl group, p- (3-hydroxy-3-methyl-1-pentynyl) phenyl group. Further, from the viewpoint of heat resistance, m-ethynylphenyl group, p-ethynylphenyl group, m-propynylphenyl group, p-propynylphenyl group, m- (3-hydroxy-3-methyl-1-pentynyl) phenyl group, p A group having an unsaturated triple bond of-(3-hydroxy-3-methyl-1-pentynyl) phenyl group is more preferable. R ⁵ and R ⁶ may have two or more unsaturated bonds.

  The introduction ratio of the polymer terminal component is preferably in the range of 0.1 to 40 mol%, particularly preferably 1 to 30 mol% with respect to the diamine component.

The end group introduced into the polymer can be easily detected by the following method. For example, a resin in which a terminal component has been introduced is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component, which are constituent units of the resin, and this is analyzed by gas chromatography (GC) or NMR measurement to obtain a terminal component. Can be easily detected. Apart from this, it is possible to directly detect the resin into which the terminal group has been introduced by pyrolysis gas chromatography (PGC), infrared spectrum and ¹³ C NMR spectrum measurement.

  The polymer whose main component is the structure represented by the general formula (1) and / or (2) 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 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.

  The polymer having the structure represented by the general formula (1) and / or (2) as a main component is polymerized by the above method, and then poured into a large amount of water or a methanol / water mixture to cause precipitation. It is desirable to filter, 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.

  The content of the polymer whose main component is the structure represented by the general formula (1) and / or (2) is preferably 30 parts by weight or more, and 40 parts by weight or more with respect to 100 parts by weight of the (a) novolak resin. More preferred. If it is this range, the mechanical characteristic after thermosetting will improve more. Moreover, in order to improve a sensitivity, 100 weight part or less is preferable and 80 weight part or less is more preferable.

  The positive photosensitive resin composition of the present invention contains (c) a quinonediazide compound. Two or more quinonediazide compounds may be contained. As quinonediazide compounds, quinonediazide sulfonic acid bonded to a polyhydroxy compound with an ester, quinonediazide sulfonic acid bonded to a polyamino compound with a sulfonamide bond, and a quinonediazide sulfonic acid bonded to a polyhydroxypolyamino compound with an ester bond and / or sulfone Examples include amide-bonded ones. The quinonediazide compound can be obtained, for example, by reacting 5-naphthoquinonediazidesulfonyl chloride with a polyhydroxy compound in the presence of triethylamine. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, from the viewpoint of the contrast between the exposed part and the unexposed part, 50 mol% or more of the whole functional group is substituted with quinonediazide. It is preferable. By using such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. it can.

  Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPPHAP (trade name, 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, 46DMOC, 46DMOEP, TM-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.) 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A , Bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Manufactured by Manabu Kogyo Co.) and the like, but not limited to.

  Polyamino compounds are 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl. Although sulfide etc. are mentioned, it is not limited to these.

  Examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited thereto.

  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 in combination.

  Further, the molecular weight of the quinonediazide compound is preferably 2500 or less, more preferably 1500 or less, and even more preferably 1200 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, 300 or more is preferable and 350 or more is more preferable.

  The content of the (c) quinonediazide compound 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 polymer (a) novolac resin and component (b). , Preferably 50 parts by weight or less, more preferably 40 parts by weight or less.

  The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, there is a method of reacting 5-naphthoquinonediazide sulfonyl chloride and a phenol compound in the presence of triethylamine. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

  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, by containing the compound, heat treatment in which the polyimide precursor or the polybenzoxazole precursor is cyclized by heat and cured is mainly (a) novolak. The resin or (b) is crosslinked by adding to the ortho position of the phenolic hydroxyl group of the polymer having the structure represented by the general formula (1) or (2) as a main component. For this reason, excellent mechanical properties can be obtained. Since the novolak resin is brittle, when the component (d) is not contained, the cured film becomes brittle and a self-supporting film cannot be obtained. The component (d) is preferably a compound having two or more alkoxymethyl groups in order to increase the crosslinking density. Furthermore, the compound which has 4 or more of alkoxymethyl groups from the point which raises a crosslinking density and improves a mechanical characteristic more is more preferable. 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 ⁷ represents a monovalent 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 the general formula (4), R ⁸ and R ⁹ represent CH ₂ OR ³² . R ³² represents an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is more preferable from the viewpoint of solubility with the resin composition. R ¹⁰ represents a hydrogen atom, a methyl group or an ethyl group. R ^{11 to} R ³¹ may be the same or different and each represents a hydrogen atom, a monovalent 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.

  The content of the (d) alkoxymethyl group-containing compound is preferably 5 parts by weight or more with respect to 100 parts by weight of the total amount of the polymer of (a) novolac resin and component (b) from the viewpoint of mechanical properties. The above is more preferable. Moreover, from the point of mechanical characteristics, 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 may be contained. The content of the solvent is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, and preferably 2000 parts by weight with respect to 100 parts by weight of the total amount of the polymer of (a) novolak resin and component (b). Part or less, more preferably 1500 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 (a) novolak resin and the component (b) polymer. 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 can be obtained as an adhesion assistant while maintaining the heat resistance of the positive photosensitive resin composition.

  Moreover, the positive photosensitive resin composition of this invention can contain the compound which has a phenolic hydroxyl group as needed. By containing the compound having a phenolic hydroxyl group, the sensitivity of the obtained positive photosensitive resin composition is improved. That is, it hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer when exposed to light. Therefore, film loss due to development is small, and development in a short time becomes easy. Particularly preferred compounds having a phenolic hydroxyl group include, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-PC, BIR-PTBP, BIR-BIPC-F (trade name, manufactured by Asahi Organic Materials Co., Ltd.).

  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 polymer (a) novolac 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, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, You may contain 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 generally used, but is not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, and slit die coating. Moreover, although a coating film thickness changes with application methods, solid content concentration of composition, viscosity, etc., it is normally 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 passivation film for a semiconductor element, a protective film for a semiconductor element, an interlayer insulating film for 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 shaken and dried for 10 seconds at 3000 rotation.

Calculation of Sensitivity After exposure and development, an exposure time (hereinafter referred to as an optimal exposure time) Eop1 at which a 50 μm line and space pattern (1L / 1S) is formed in a one-to-one width was determined. If Eop1 was 400 mJ / cm ² or less, the pattern workability was judged to be good. 200 mJ / cm ² or less is more preferable.

(2) Storage Stability Evaluation After leaving the varnish at 23 ° C. for 14 days under a yellow light, a coating film was prepared at the same rotational speed as the evaluation described in (1) above, and the film thickness T2 after application was measured. Subsequently, exposure and development were performed, and the optimum exposure time Eop2 was determined. The value of T1-T2 was calculated, and if the absolute value of this value was 0.3 μm or less, it was judged as good, and if it exceeded 0.3 μm, it was judged as bad. Furthermore, the value of Eop2-Eop1 was calculated, and when the absolute value of this value was 50 mJ / cm ² or less, it was judged as good, and when it exceeded 50 mJ / cm ² , it was judged as bad.

(3) Evaluation of mechanical properties Preparation of heat-resistant resin film On a 6-inch silicon wafer, varnish was applied so that the film thickness after pre-baking would be 13 μm, and then hot plate (Coating and developing device Mark manufactured by Tokyo Electron Ltd.) The photosensitive resin precursor film | membrane was obtained by prebaking for 3 minutes at 120 degreeC using -7). Thereafter, the photosensitive resin precursor film developed by the method described in the above (1) was prepared using an inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd., under a nitrogen stream (oxygen concentration of 20 ppm or less), 150 The temperature was raised to 30 ° C. for 30 minutes and then to 320 ° C. over 1 hour, followed by heat treatment at 320 ° C. for 30 minutes to produce a heat resistant resin film (cured film).

Preparation of Measurement Sample A cured film prepared on a silicon wafer was immersed in 47% hydrofluoric acid at room temperature for 7 minutes, washed with water, and carefully peeled from the silicon wafer. The peeled cured film was cut into a strip shape having a width of 1 cm and a length of about 9 cm with a single blade to obtain a measurement sample.

Measurement The Tensylon RTM-100 manufactured by Orientec was set with the measurement sample at an initial sample length of 50 mm, and a tensile test was performed at a tensile speed of 50 mm / min. Measurement was performed at n = 12, and the average value of the top five points of the maximum stress, elastic modulus, and elongation obtained was obtained.

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) 34.2 g (0.3 mol) of allyl glycidyl ether was dissolved in 100 g of gamma butyrolactone (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 a hydroxyl group-containing acid anhydride (a) represented by the following formula.

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 palladium compound as a catalyst was removed by filtration, and concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound (b) represented by the following formula.

Synthesis Example 3 Synthesis of hydroxyl group-containing diamine (c) 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 of 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 represented by the following formula.

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 represented by the following formula 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 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) represented by the following formula.

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 5-naphthoquinonediazidesulfonyl chloride 26. 86 g (0.10 mol) and 13.43 g (0.05 mol) of 4-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and brought to room temperature. A quinonediazide compound (f) represented by the following formula 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 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 30 to 50 mmHg, volatile components are 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 8 Synthesis of Novolak Resin B 108 g (1.00 mol) of m-cresol was used in place 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 7, a polymer solid of novolak resin B was obtained. From GPC, the weight average molecular weight was 4,000.

Synthesis Example 9 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 7 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 10 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 polymer solid of novolak resin D was obtained in the same manner as in Synthesis Example 7 except that 54 g (0.50 mol) of cresol was used. From GPC, the weight average molecular weight was 3,500.

Synthesis Example 11 Synthesis of Polymer A 4.4 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 A.

Synthesis Example 12 Synthesis of Polymer B In a dry nitrogen stream, 13.6 g (0.0225 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, 0.58 g (0.005 mol) of 3-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 7.35 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 13 Synthesis of Polymer C In a 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, 0.95 g (0.008 mol) of 4-allylaniline was added as a terminal blocking agent, and the mixture was further reacted at 50 ° C. for 1 hour. 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 14 Synthesis of Polymer D Under a dry nitrogen stream, the hydroxyl group-containing diamine compound (d) obtained in Synthesis Example 4 (6.08 g, 0.025 mol), DAE 4.51 g (0.0225 mol), and SiDA 0.62 g (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, 1.72 g (0.010 mol) of 3-ethynylbenzenedicarboxylic acid anhydride 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 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 15 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 in 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. Next, 3.76 g (0.020 mol) of 3-allylbenzenedicarboxylic anhydride dissolved in 30 g of NMP was added as a terminal blocking agent, and the mixture was further 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 16 Synthesis of polymer F Under a dry nitrogen stream, 4.10 g (0.0205 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 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 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 50 ° 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 17 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, 105 g of ODPA was added, and the mixture was stirred for 8 hours while adjusting to 10 ° C. or more and 30 ° C. or less to obtain a polyimide precursor. A polymer solution G was obtained.

Synthesis Example 18 Synthesis of Polymer H 49.6 g of BAHF and 3.74 g of SiDA were dissolved in 400 g of NMP under a dry nitrogen stream, 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 19 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 to 10 ° C. or higher and 30 ° C. or lower. A polymer solution I of polyimide precursor was obtained.

Example 1
7 g of novolak resin A, 3 g of polymer A solid, 2.2 g of MG-300 (trade name, manufactured by Toyo Gosei Co., Ltd.) as a quinonediazide compound, Nicalac MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.) 5 g and 0.3 g of vinyltrimethoxysilane were dissolved in 30 g of GBL to obtain a varnish of a photosensitive resin composition. Using the obtained varnish, pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Example 2
6 g of novolak resin B, 4 g of polymer B solid, 2 g of quinonediazide compound (f), Nicalac MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) 2.5 g, 0.3 g of N-phenylaminopropyltrimethoxysilane GBL 30 g The varnish of the photosensitive resin composition was obtained. Using the obtained varnish, pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Example 3
6 g of novolak resin C, 4 g of polymer C, 1.5 g of quinonediazide compound (e), 2.0 g of HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 0.3 g of m-acetylaminophenyltrimethoxysilane The varnish of the photosensitive resin composition was obtained by dissolving in 25 g of GBL and 5 g of ethyl lactate (EL). Using the obtained varnish, pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Example 4
6.5 g of novolak resin B, 3.5 g of polymer D solid, 2 g of MG-300 as a quinonediazide compound, 1.0 g of HMOM-TPPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), N-phenylaminopropyltrimethoxysilane 0 .2 g was dissolved in 30 g of GBL to obtain a varnish of a photosensitive resin composition. Using the obtained varnish, pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Example 5
8 g of novolak resin A, 2 g of polymer E solid, 2 g of quinonediazide compound (e), 1.0 g of Nicalac MX-270, 1.5 g of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 0.1 g of vinyltriethoxysilane. 2 g was dissolved in 30 g of NMP to obtain a varnish of a photosensitive resin composition. Using the obtained varnish, pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Example 6
A varnish was obtained in the same manner as in Example 1 except that 4 g of the novolak resin A and 6 g of the polymer A were used, and the pattern processability evaluation, the storage stability evaluation, and the mechanical property evaluation were performed as described above.

Example 7
A varnish was obtained in the same manner as in Example 1 except that 7 g of novolak resin D was used instead of 7 g of novolak resin A, and pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Example 8
A varnish was obtained in the same manner as in Example 2 except that 2.5 g of Nicalac MX-270 was used instead of 2.5 g of Nicalac MX-270. As described above, pattern workability evaluation, storage stability evaluation, machine Characterization was performed.

Example 9
Varnish was obtained in the same manner as in Example 1 except that 7 g of novolak resin B was used instead of 7 g of novolak resin A, and pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Example 10
A varnish was obtained in the same manner as in Example 1 except that 7 g of novolak resin C was used instead of 7 g of novolak resin A, and pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Example 11
A varnish was obtained in the same manner as in Example 1 except that 5 g of the novolak resin A and 5 g of the solid of the polymer A were used, and pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Example 12
A varnish was obtained in the same manner as in Example 1 except that 5.6 g of the novolak resin A and 4.4 g of the polymer A were used, and the pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above. It was.

Example 13
A varnish was obtained in the same manner as in Example 1 except that 7.4 g of the novolak resin A and 2.6 g of the solid of the polymer A were used, and the pattern processability evaluation, the storage stability evaluation, and the mechanical property evaluation were performed as described above. It was.

Example 14
A varnish was obtained in the same manner as in Example 3 except that HMOM-TPHAP was changed to 0.5 g, and pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Example 15
A varnish was obtained in the same manner as in Example 3 except that HMOM-TPHAP was changed to 1.0 g, and pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Example 16
A varnish was obtained in the same manner as in Example 3 except that HMOM-TPHAP was changed to 3.0 g, and pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Example 17
A varnish was obtained in the same manner as in Example 3 except that HMOM-TPHAP was changed to 4.0 g, and pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Example 18
A varnish was obtained in the same manner as in Example 3 except that HMOM-TPHAP was changed to 5.0 g, and pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Comparative Example 1
A varnish was obtained in the same manner as in Example 1 except that 3 g of the solid of polymer F was used instead of 3 g of the solid of polymer A, and pattern processability evaluation, storage stability evaluation and mechanical property evaluation were performed as described above. .

Comparative Example 2
A varnish was obtained in the same manner as in Example 2 except that 22.3 g of the polymer G solution was used instead of 4 g of the polymer B solid and GBL was changed to 15 g. As described above, the pattern processability evaluation, the storage stability evaluation, Mechanical property evaluation was performed.

Comparative Example 3
A varnish was obtained in the same manner as in Example 3 except that 20 g of the polymer H was used instead of 4 g of the solid of the polymer C, and 10 g of GBL was used. As described above, pattern processability evaluation, storage stability evaluation, mechanical properties Evaluation was performed.

Comparative Example 4
A varnish was obtained in the same manner as in Example 4 except that 8.7 g of the polymer I solution was used instead of 3.5 g of the polymer D solid, and 25 g of GBL was used. As described above, evaluation of pattern processability and storage stability were performed. Evaluation and mechanical property evaluation were performed.

Comparative Example 5
A varnish was obtained in the same manner as in Example 2 except that Nicarax MX-270 was not used, and pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Comparative Example 6
A varnish was obtained in the same manner as in Example 3 except that 4 g of polymer F solid was used instead of 4 g of polymer C and HMOM-TPHAP was not used. As described above, pattern processability evaluation, storage stability evaluation, Mechanical property evaluation was performed.

Comparative Example 7
The same procedure as in Example 2 was repeated except that 22.3 g of the polymer G solution was used instead of 4 g of the polymer B solid, 2,6-dimethylol-p-cresol was used instead of Nicalac MX-270, and the GBL was 15 g. The varnish was obtained, and pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed as described above.

Comparative Example 8
20 g of polymer H solution was used instead of 4 g of polymer C solid, and 2.0 g of 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane was used instead of 2.0 g of HMOM-TPHAP. The varnish was obtained in the same manner as in Example 3 except that the GBL was changed to 10 g, and the pattern processability evaluation, the storage stability evaluation, and the mechanical property evaluation were performed as described above.

Comparative Example 9
A varnish was obtained in the same manner as in Example 2 except that 2.5 g of 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane was used instead of 2.5 g of Nicalac MX-270, As described above, pattern processability evaluation, storage stability evaluation, and mechanical property evaluation were performed.

  Photosensitizers, compounds having phenolic hydroxyl groups, and alkoxymethyl group-containing compounds used in Examples and Comparative Examples are shown below.

  Tables 1 to 3 show the compositions and evaluation results of Examples 1 to 18 and Comparative Examples 1 to 9.

Claims (4)

(A) a novolak resin, (b) a polymer having a structure represented by the general formula (1) and / or (2) as a main component, (c) a quinonediazide compound, (d) an alkoxymethyl group-containing compound, and (e) A positive photosensitive resin composition comprising a solvent.

(In the general formulas (1) to (2), 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 each These may be the same or different and each represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, —NH—R ^{5 in the} general formula (1) and —CO—R ⁶ in the general formula (2) are R ⁵ and R ⁶ each represent a terminal group, and R ⁵ and R ⁶ each represent a monovalent organic group having 2 to 30 carbon atoms having an unsaturated hydrocarbon group, n is in the range of 10 to 100,000, and l and m are 0 to 2. Integers, p and q are integers from 0 to 4, provided that p + q> 0. (A) 30 to 100 parts by weight of a polymer whose main component is the structure represented by the general formula (1) and / or (2) is contained with respect to 100 parts by weight of the novolak resin, and (a) the novolak resin. And (b) 1 to 50 parts by weight of (c) quinonediazide compound with respect to 100 parts by weight of the total amount of the polymer having the structure represented by the general formula (1) and / or (2) as a main component, and (d) alkoxy The positive photosensitive resin composition according to claim 1, comprising 5 to 50 parts by weight of a methyl group-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 the general formula (3), R ⁷ may be the same or different and represents an alkyl group having 1 to 20 carbon atoms.)

(In General Formula (4), R ⁸ and R ⁹ represent CH ₂ OR ³² (R ³² is an alkyl group having 1 to 6 carbon atoms), and R ¹⁰ represents a hydrogen atom, a methyl group, or an ethyl group. ^{11 to} R ³¹ may be the same or different and each represents a hydrogen atom, an organic group having 1 to 20 carbon atoms, Cl, Br, I or F. j represents an integer of 1 to 4. The positive photosensitive resin according to any one of claims 1 to 3, 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.