JP2009258634A - Positive photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition that excels in chemical resistance and adhesion with respect to metallic materials, after curing. <P>SOLUTION: The positive photosensitive resin composition comprises (a) a polymer, having a structure represented by general formula (1) as the main component; (b) a quinone azide compound; (c) an alkoxymethyl group-containing compound; and (d) a solvent, the alkoxymethyl group-containing compound, containing two or more compounds selected from among a group consisting of specific compounds. In the general formula (1), R<SP>1</SP>and R<SP>2</SP>each represent a 2C or more divalent to 8-valent organic group; R<SP>3</SP>and R<SP>4</SP>, which may be the same or different, each represent hydrogen atom or a 1-20C monovalent organic group; n represents an integer of 10-100,000; l and m each represent an integer of 0-2; p and q each represent an integer of 0-4, with p+1>0. <P>COPYRIGHT: (C)2010,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 can be used as surface protection films and interlayer insulation films for semiconductor elements such as LSIs (Large Scale Integrations). It is used. With the miniaturization of semiconductor elements, a surface protection film, an interlayer insulating film and the like are 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 recent years, in order to reduce the mounting area of an LSI package, a bump is formed on the package directly from the method in which pins are provided outside the package such as a conventional QFP (Quad Flat Package) and joined to the substrate. A method of joining packages has come to be used. For this reason, it is necessary to form solder bumps or the like when forming a package, and heat resistance and chemical resistance are required for an insulating material such as polyimide used for protecting an LSI chip. In particular, since the solder bump formation is performed at a high temperature using an organic acid called a flux treatment, chemical resistance higher than the conventional one is required. Furthermore, in applications such as an insulating film between wiring layers of a wafer level package, in addition to the above characteristics, adhesion to metal materials used for electrodes, wirings, and the like is required.

  As means for improving chemical resistance, a photosensitive resin composition containing an alkali-soluble polyamic acid (or an ester thereof), a quinonediazide compound, and a thermally crosslinkable compound having a methylol group substituted with an organic group has been proposed. (For example, refer to Patent Document 1). In addition, a resin composition containing a resin having a cyclic structure or a precursor thereof and a thermal crosslinking agent having a phenol-based specific structure has been proposed (see, for example, Patent Document 2). Although chemical resistance can be improved by using these cross-linking agents, the resin compositions disclosed therein have insufficient adhesion to metal materials.

On the other hand, a method using a specific amino compound, a disulfide compound or a thioether compound has been proposed as a method for improving the adhesion to a metal material (see, for example, Patent Documents 3 to 4). However, the resin compositions disclosed therein are insufficient in chemical resistance.
JP 2002-328472 A JP 2007-16214 A JP 2004-43779 A JP 2007-39486 A

  An object of this invention is to provide the positive photosensitive resin composition excellent in the chemical resistance after hardening, and the adhesiveness with respect to a metal material.

  The present invention relates to a positive photosensitive material comprising (a) a polymer having a structure represented by the general formula (1) as a main component, (b) a quinonediazide compound, (c) an alkoxymethyl group-containing compound and (d) a solvent. A resin composition, wherein (c) an alkoxymethyl group-containing compound is (c1) a compound having a group represented by the following general formula (2), (c2) a compound represented by the following general formula (3), and (C3) A positive photosensitive resin composition containing two or more selected from the group consisting of compounds represented by the following general formula (3).

In General Formula (1), R ¹ and R ² 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. 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.

In General Formula (2), R ⁵ and R ⁶ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms. i represents 2 or 3.

In General Formula (3), R ⁷ and R ⁸ represent an alkyl group having 1 to 6 carbon atoms. R ⁹ represents a hydrogen atom, a methyl group or an ethyl group. R represents a single bond or a divalent to tetravalent organic group. j represents an integer of 2 to 4.

(In the general formula (4), R ^{10 to} R ¹⁵ may be the same or different and each represents a hydrogen atom or CH ₂ OR ¹⁶ (R ¹⁶ is an alkyl group having 1 to 6 carbon atoms), provided that R ¹⁰ to 5 or more in R ¹⁵ is CH ₂ OR ¹⁶ ).

  ADVANTAGE OF THE INVENTION According to this invention, the positive photosensitive resin composition excellent in the chemical resistance after hardening and the adhesiveness with a metal material can be obtained.

  The positive photosensitive resin composition of the present invention contains (a) a polymer whose main component is a structure represented by the general formula (1). The polymer having the structure represented by the general formula (1) as a main component can be a polymer having an imide ring, an oxazole ring, or other cyclic structures by heating or an appropriate catalyst. Preferred are polyamic acid or polyamic acid ester of a polyimide precursor, and polyhydroxyamide of a polybenzoxazole precursor. Due to the annular structure, the heat resistance and solvent resistance are dramatically improved. Here, the main component means that n structural units of the structure represented by the general formula (1) have 50 mol% or more of all the structural units of the polymer. It is preferable to contain 70 mol% or more, and it is more preferable to contain 90 mol% or more.

In the general formula (1), R ¹ represents a divalent to octavalent organic group having 2 or more carbon atoms, and represents an acid structural component. Examples of acids in which R ¹ is divalent include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, and bis (carboxyphenyl) propane, and aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and adipic acid. And so on. Examples of the acid that makes R ¹ trivalent include tricarboxylic acids such as trimellitic acid and trimesic acid. Examples of acids in which R ¹ is tetravalent include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and other aromatic tetracarboxylic acids, butanetetracarboxylic acid, and cyclopentane. Examples thereof include aliphatic tetracarboxylic acids such as tetracarboxylic acid, diester compounds in which two hydrogen atoms of these carboxyl groups are converted into 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. Two or more of these acid components may be used, but preferably contains 1 to 40 mol% of a tetracarboxylic acid residue. Moreover, it is preferable that the residue of the acid which has a hydroxyl group is contained 50 mol% or more from the point of the solubility with respect to an alkali developing solution, or a photosensitive point.

R ¹ preferably has an aromatic ring from the viewpoint of heat resistance, and more preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms. Preferred examples of the structure of R ¹ (COOR ³ ) _m (OH) _{p in} the general formula (1) include the structures shown below.

In general formula (1), R ² represents a divalent to octavalent organic group having 2 or more carbon atoms and represents a structural component of diamine. R ² preferably has an aromatic ring from the viewpoint of heat resistance. Specific examples of diamines include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone, Bis (amino-hydroxy-phenyl) hexafluoropropane, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybenzidine, diaminobenzoic acid, diaminoterephthalic acid, alkylating the hydrogen of these aromatic rings Compounds substituted with groups or halogen atoms, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, hexamethylene Diamine, ^R 2 (COOR ⁴⁾ of the general formula _{(1) l} (OH) _q can be mentioned is one of the following structures. Among these, it is preferable that R ² (COOR ⁴ ) _l (OH) _{q in} the general formula (1) is represented by the following structure. Two or more of these diamine components may be used, but from the viewpoint of solubility in an alkaline developer, it is preferable that the residue of a diamine having a hydroxyl group is 60 mol% or more.

R ³ and R ^{4 in} the general formula (1) may be the same or different and each represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms. From the viewpoint of solubility in an alkali developer and solution stability of the resulting photosensitive resin composition, it is preferable that 10 mol% to 90 mol% of R ³ and R ⁴ are each hydrogen. Furthermore, it is more preferable that R ³ and R ⁴ each contain at least one monovalent hydrocarbon group having 1 to 16 carbon atoms, and the others are hydrogen atoms.

  Moreover, l and m of General formula (1) show the number of a carboxyl group or an ester group, and show the integer of 0-2. 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 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 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 the polymer which has the structure represented by General formula (1) as a main component. By sealing the end of the polymer with a monoamine having a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group and a thiol group, the dissolution rate of the resin in an aqueous alkaline solution can be adjusted to a preferred range. . Moreover, the dissolution rate with respect to aqueous alkali solution can be adjusted to a preferable range by sealing the terminal of a polymer with an acid anhydride, an acid chloride, and monocarboxylic acid. As for content of terminal blockers, such as a monoamine, an acid anhydride, an acid chloride, and monocarboxylic acid, 5-50 mol% is preferable with respect to all the amine components.

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

  The polymer whose main component is 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, for example, there is 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 method of adding a bisaminophenol compound or monoamino compound to this, or a bisaminophenol compound or monoamino added with a tertiary amine such as pyridine. There is a method of dropping a dicarboxylic acid dichloride solution into a compound solution.

  The polymer having the structure represented by the general formula (1) as a main component is polymerized by the above method, and then poured into a large amount of water or a methanol / water mixture, precipitated, filtered and dried, It is desirable to 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 positive photosensitive resin composition of the present invention may contain a polymer other than the polymer of component (a), and examples thereof include novolak resins. You may contain 2 or more types of novolak resins. The novolak resin can be obtained by polycondensing phenols and aldehydes by a known method.

  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. Two or more of these phenols may be used. Preferred examples of the aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like. Two or more of these aldehydes may be used. The amount of the aldehyde used is preferably 0.6 mol or more, more preferably 0.7 mol or more, per 1 mol of phenols.

  The novolak resin has a polystyrene equivalent weight average molecular weight (hereinafter referred to as “Mw”) of 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.

  The content of the novolak resin is preferably 30 parts by weight or more and preferably 200 parts by weight or less with respect to 100 parts by weight of the polymer of the component (a). If it is this range, a sensitivity will improve.

  The positive photosensitive resin composition of the present invention contains (b) a quinonediazide compound. The quinonediazide compound includes a polyhydroxy compound in which a sulfonic acid of quinonediazide is bonded with an ester, a polyamino compound in which a sulfonic acid of quinonediazide is bonded to a sulfonamide, a sulfonic acid of quinonediazide in an ester bond and / or sulfone Examples include amide-bonded ones. 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 entire functional group is substituted with quinonediazide. Preferably it is. 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. In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. 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, and two or more of these may be contained. Moreover, you may contain the naphthoquinone diazide sulfonyl ester compound which has 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group in the same molecule.

  Polyhydroxy compounds are 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.

  The molecular weight of the quinonediazide compound is preferably 350 or more and 1200 or less.

  The quinonediazide compound used in the present invention can be obtained, for example, by a method of reacting 5-naphthoquinonediazidesulfonyl chloride with a phenol compound in the presence of triethylamine.

  The content of the (b) quinonediazide compound is preferably 1 part by weight or more, more preferably 3 parts by weight or more, and preferably 50 parts by weight or less with respect to 100 parts by weight of the polymer of the component (a). More preferably, it is 40 parts by weight or less.

  The positive photosensitive resin composition of the present invention contains (c) an alkoxymethyl group-containing compound. Since the alkoxymethyl group causes a crosslinking reaction in a temperature range of 150 ° C. or higher, it can be crosslinked by a post-development heat treatment described later to obtain a cured film having excellent chemical resistance. The component (c) preferably has 4 or more alkoxymethyl groups, and can further improve chemical resistance. In the present invention, (c) an alkoxymethyl group-containing compound is (c1) a compound having a group represented by the following general formula (2), (c2) a compound represented by the following general formula (3), and (c3) It is important that there are two or more selected from the group consisting of compounds represented by the following general formula (4). In addition to the improvement in chemical resistance, the compound (c1) can improve adhesion to a metal material after curing because the urea residue strongly interacts with the metal. However, sufficient chemical resistance cannot be obtained with (c1) alone. Although the compound (c2) can greatly improve the chemical resistance, only (c2) cannot provide sufficient adhesion to the metal material. In addition to the improvement in chemical resistance, the compound (c3) has a melamine skeleton that interacts very strongly with the metal, so that it can improve the adhesion to the cured metal material in a smaller amount than (c1). However, sufficient chemical resistance cannot be obtained with (c3) alone. Therefore, in the present invention, by containing two or more of (c1) to (c3), chemical resistance after curing and adhesion to a metal material can be made compatible. Further, one of them is preferably (c3), and a high adhesion effect to a metal can be obtained even with a small amount. Moreover, in order to improve chemical resistance more, it is preferable to contain (c2).

In General Formula (2), R ⁵ and R ⁶ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms. From the viewpoint of solubility in the resin composition, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable. i represents 2 or 3.

In General Formula (3), R ⁷ and R ⁸ represent an alkyl group having 1 to 6 carbon atoms. An alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of solubility in the resin composition. R ⁹ represents a hydrogen atom, a methyl group or an ethyl group. R represents a single bond or a divalent to tetravalent organic group. j represents an integer of 2 to 4. Examples of the divalent to tetravalent organic group of R include the following structures. Here, R ^{17 to} R ³⁴ 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.

In General Formula (4), R ^{10 to} R ¹⁵ may be the same or different and each represents a hydrogen atom or CH ₂ OR ¹⁶ (R ¹⁶ is an alkyl group having 1 to 6 carbon atoms). However, five or more of R ^{10 to} R ¹⁵ are CH ₂ OR ¹⁶ .

  (C1) Specific examples of the compound having a group represented by the general formula (2) include, but are not limited to, the following compounds.

  (C2) Specific examples of the compound 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.

  (C) The content of the alkoxymethyl group-containing compound is 0.5 parts by weight of the total amount of (c) with respect to 100 parts by weight of the polymer of component (a) from the viewpoint of increasing the crosslinking density and further improving chemical resistance. The above is preferable. Further, if it is 10 parts by weight or more, higher chemical resistance can be obtained. Therefore, 10 parts by weight or more is preferable for more severe processing conditions such as flux treatment for lead-free solder heated at around 260 ° C. Moreover, 100 weight part or less is preferable from the surface of the mechanical characteristic of a cured film, 50 weight part or less is more preferable, 40 weight part or less is more preferable, and 30 weight part or less is further more preferable. When the component (c2) is contained, the content of (c2) is preferably 5 parts by weight or more with respect to 100 parts by weight of the polymer of the component (a) from the viewpoint of chemical resistance. Is preferably 10 parts by weight or more. Moreover, when (c3) is contained, from the viewpoint of maintaining sensitivity, the content of (c3) is preferably in the range of 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the polymer of component (a).

  The positive photosensitive resin composition of the present invention contains (d) 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 or less, more preferably 1500 parts by weight with respect to 100 parts by weight of the polymer of component (a). Or less.

  The positive photosensitive resin composition of the present invention may further contain (e) a silane compound. Examples of the silane compound include compounds having the following structures, vinylsilane compounds such as vinyltrimethoxysilane and vinyltriethoxysilane, N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, and N-phenylaminopropyltrimethoxy. Aminosilane compounds such as silane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- Silane compounds having an epoxy group such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-ethyl-[( Silane compound having an oxetane such as Li triethoxysilyl propoxy) methyl] oxetane are preferred. By containing such a silane compound, the adhesion to the silicon substrate is improved. You may contain 2 or more types of these silane compounds.

  0.005 weight part or more is preferable with respect to 100 weight part of polymers of (a) component, and, as for content of said (e) silane compound, 0.01 weight part or more is more preferable. Moreover, 20 weight part or less is preferable and 15 weight part or less is more preferable.

  The positive photosensitive resin composition of the present invention may contain (f) a photoacid generator. As the photoacid generator, a sulfonium salt, a phosphonium salt or a diazonium salt is preferable, and two or more of these may be contained. By containing a photoacid generator, it acts as a dissolution regulator for an alkaline developer. Of these, a sulfonium salt is preferable, and a triarylsulfonium salt is more preferable. Specific examples of the triarylsulfonium salt are shown below.

  In the positive photosensitive resin composition of the present invention, the content of the (f) photoacid generator is preferably 0.01 parts by weight or more, more preferably 0 with respect to 100 parts by weight of the polymer of the component (a). 0.05 parts by weight or more, preferably 50 parts by weight or less, more preferably 10 parts by weight or less.

  Moreover, the compound which has a phenolic hydroxyl group can be contained for the purpose of improving the sensitivity of the said photosensitive resin composition as needed. Examples of the compound having a phenolic hydroxyl group include Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, and BIR-BIPC-F. be able to. By containing a compound having a phenolic hydroxyl group, the obtained resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. Therefore, film loss due to development is small. In addition, development is easy in a short time.

  The content of the compound having a phenolic hydroxyl group is preferably 1 part by weight or more, more preferably 3 parts by weight or more, and preferably 50 parts by weight or less, with respect to 100 parts by weight of the polymer of component (a). More preferably, it is 40 parts by weight or less.

  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 (d) components, and if necessary, other components 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.

  In the present invention, the component (e) is preferably added to the composition after the completion of polymerization of the polymer. When a compound corresponding to the component (e) is added at the time of polymer polymerization, it may be incorporated into the polymer main chain by a covalent bond in the polymer, and the adhesion effect with the Si substrate may be reduced. In addition, when the polymer was reprecipitated, it was reprecipitated in order to prevent problems such as removal of unreacted compounds of the above compound during the reprecipitation and lowering the adhesion effect, and gelation due to condensation of alkoxy groups. The component (e) is preferably added when the polymer is dissolved together with other components, or after the components (a) to (c) are dissolved in the solvent (d).

  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, a silicon wafer sputtered with metal, ceramics, gallium arsenide, metal, glass, metal oxide insulating film, silicon nitride, ITO, or the like is used, but not limited thereto. Since the positive photosensitive resin composition of the present invention is excellent in adhesion to a metal material, it is particularly preferable to use it for a metal substrate or a silicon wafer sputtered with a metal. 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, it is preferable to 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 generally carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, a method of performing heat treatment at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each, or linearly raising the temperature from room temperature to 400 ° C. over 2 hours may 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 semiconductor elements, an interlayer insulating film for multilayer wiring for high-density mounting, an insulating layer for organic electroluminescent elements, etc. It is suitably used for applications. In particular, since it has excellent adhesion to a metal material, it is suitably used for an interlayer insulating film of a multilayer wiring for high-density mounting.

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

(1) Sensitivity evaluation Preparation of photosensitive resin film A photosensitive resin composition (hereinafter referred to as varnish) was applied onto a 6-inch silicon wafer so that the film thickness after pre-baking was 8 μm, and then hot plate (Tokyo Electron) A photosensitive resin film was obtained by pre-baking at 120 ° C. for 3 minutes using a coating and developing apparatus Mark-7 manufactured by Co., 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 70 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) Eop in which a 50 μm line-and-space pattern (1L / 1S) is formed in a one-to-one width was determined. A good value was obtained when this value was 600 mJ / cm ² or less, and a defective product was obtained when it exceeded 600 mJ / cm ² .

(2) Adhesive evaluation with metal material On a silicon wafer sputtered with copper, varnish was applied using a spinner so that the film thickness after pre-baking would be 10 μm, and then hot plate (manufactured by Tokyo Electron Ltd.) A photosensitive resin film was obtained by prebaking at 120 ° C. for 3 minutes using a coating and developing apparatus D-SPIN. The prepared photosensitive resin film was exposed and developed (dip development), and then using an inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd., under a nitrogen stream (oxygen concentration of 20 ppm or less) at 170 ° C. for 30 minutes, and thereafter The temperature was raised to 320 ° C. over 1 hour, and heat treatment was performed at 320 ° C. for 1 hour to produce a heat resistant resin film (cured film).

  The cured film was immersed in a 10% by mass sulfuric acid aqueous solution, treated at 23 ° C. for 3 minutes, and then washed with water. An optical microscope was used to observe whether there was any penetration between the cured film and the silicon wafer. If there was no soaking at all, ◎, if there was a slight soaking, ○, if there was a lot of soaking, it was rated as x.

  Further, a peeling test using “cello tape (registered trademark)” was performed on the pattern of the cured film. Thereafter, the film was immersed in a 10% by mass sulfuric acid aqueous solution, treated at 23 ° C. for 3 minutes, and then subjected to a peeling test using “Cellotape (registered trademark)” in the same manner as described above to evaluate the adhesion before and after the treatment. If there was no peeling in the peeling test, ◎, if it was slight peeling, it was judged as bad, and if many peelings were observed, it was judged as bad, and ○ or more was judged as acceptable.

(3) Evaluation of chemical resistance The silicon wafer patterned in (1) is cured under the conditions described in (2), immersed in a stripping solution 106 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), and at 70 ° C. for 10 minutes. After the treatment, it was washed with water. The pattern was observed for abnormalities such as cracks with an optical microscope.

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 more 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) Under a dry nitrogen stream, 16.10 g (0.05 mol) of BisP-RS (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.86 g of 5-naphthoquinonediazidesulfonyl acid chloride (0.1 mol) 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 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-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. A quinonediazide compound (f) represented by the following formula was obtained in the same manner as in Synthesis Example 5 using 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 7 Synthesis of quinonediazide compound (g) 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 (g) 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 8 Synthesis of quinonediazide compound (h) In a dry nitrogen stream, 11.41 g (0.05 mol) of bisphenol A and 26.86 g (0.1 mol) of 4-naphthoquinonediazidesulfonyl acid chloride were added to 1,4-dioxane. Dissolved in 450 g and brought to room temperature. A quinonediazide compound (h) represented by the following formula was obtained in the same manner as in Synthesis Example 5 using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 9 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 hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 was added thereto together with 14 g of NMP, and reacted at 20 ° C. for 1 hour, and then reacted at 40 ° C. for 2 hours. . Thereafter, 0.65 g (0.006 mol) of 4-aminophenol was added as a terminal blocking agent, and the mixture was further reacted at 40 ° C. for 1 hour. Thereafter, a solution prepared by diluting 7.14 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 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 10 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 hydroxyl 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 4-aminophenylacetylene was added as a terminal blocking agent, and the mixture was further reacted at 40 ° C. for 1 hour. 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 11 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, reacted at 20 ° C. for 1 hour, and then at 50 ° C. for 2 hours. Reacted. Thereafter, a solution obtained by diluting 14.7 g (0.1 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 12 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. 28.57 g (0.040 mol) of hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA). 41 g (0.010 mol) was added at room temperature together with 25 g of NMP, and the mixture was stirred at room temperature for 1 hour and then at 50 ° 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 with a vacuum dryer at 80 ° C. for 72 hours to obtain a polyimide precursor polymer D.

Synthesis Example 13 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, 2.96 g (0.020 mol) of maleic 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 14 Synthesis of Polymer F In a 0.5 liter flask equipped with a stirrer and a thermometer, 24.82 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, s-butyl alcohol 11 .86 g, 0.40 g of triethylamine, and 110.03 g of NMP were added, and the mixture was stirred and reacted at 60 ° C. for 24 hours to obtain 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid dis-butyl ester. Then, after cooling the flask to 5 ° C., 18.08 g of thionyl chloride was added dropwise and reacted for 1 hour to obtain a solution of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid dis-butyl ester dichloride. It was.

  Next, 47.97 g of NMP was charged into a 0.5 liter flask equipped with a stirrer, a thermometer, and a Dimroth condenser, and 4.33 g of 4,4′-diaminodiphenyl ether, 7.67 g of 3,5-diaminobenzoic acid. After stirring and dissolving, 24.05 g of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid dis-butyl ester dichloride was prepared. After dropwise addition in 1 hour, stirring was continued for 1 hour. The solution was poured into 4 liters of water, and the precipitates were collected and washed, and then dried under reduced pressure to obtain a polyimide precursor polymer F.

Synthesis Example 15 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 4 to 7 kPa, 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 16 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 15, a polymer solid of novolak resin B was obtained. From GPC, the weight average molecular weight was 4,000.

Example 1
10 g of the polymer A solid obtained in Synthesis Example 9 was weighed, and 2.0 g of the quinonediazide compound (e) obtained in Synthesis Example 5 and “Nicarac” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) 1 0.0 g and 1.0 g of HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) were dissolved in 30 g of GBL to obtain a varnish of a photosensitive polyimide precursor composition. Using the obtained varnish, sensitivity evaluation, metal adhesion evaluation, and chemical resistance evaluation were performed as described above.

Example 2
10 g of the polymer B solid obtained in Synthesis Example 10 was weighed, and 2.0 g of the quinonediazide compound (f) obtained in Synthesis Example 6 and “Nicarac” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) 1 0.0 g and 1.0 g of HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) were dissolved in 20 g of GBL and 10 g of ethyl lactate (EL) to obtain a varnish of a photosensitive polyimide precursor composition. Using the obtained varnish, sensitivity evaluation, metal adhesion evaluation, and chemical resistance evaluation were performed as described above.

Example 3
10 g of the polymer C solid obtained in Synthesis Example 11 was weighed, and 2.0 g of the quinonediazide compound (g) obtained in Synthesis Example 7 and “Nicarac” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) 1 0.0 g and 1.0 g of HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) were dissolved in 30 g of NMP to obtain a varnish of a photosensitive polyimide precursor composition. Using the obtained varnish, sensitivity evaluation, metal adhesion evaluation, and chemical resistance evaluation were performed as described above.

Example 4
10 g of the solid of the polymer D obtained in Synthesis Example 12 was weighed, and 2.0 g of the quinonediazide compound (h) obtained in Synthesis Example 8 and “Nicarac” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) 1 0.0 g and 1.0 g of HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) were dissolved in 30 g of GBL to obtain a varnish of a photosensitive polyimide precursor composition. Using the obtained varnish, sensitivity evaluation, metal adhesion evaluation, and chemical resistance evaluation were performed as described above.

Example 5
10 g of the polymer A solid obtained in Synthesis Example 9 was weighed, and 2.0 g of the quinonediazide compound (e) obtained in Synthesis Example 5 and “Nicarac” MW-30HM (trade name, manufactured by Sanwa Chemical Co., Ltd.) 1 0.0 g and 1.0 g of HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) were dissolved in 30 g of GBL to obtain a varnish of a photosensitive polyimide precursor composition. Using the obtained varnish, sensitivity evaluation, metal adhesion evaluation, and chemical resistance evaluation were performed as described above.

Example 6
10 g of the polymer A solid obtained in Synthesis Example 9 was weighed, and 2.0 g of the quinonediazide compound (e) obtained in Synthesis Example 5 and “Nicarac” MW-390 (trade name, manufactured by Sanwa Chemical Co., Ltd.) 1 0.0 g and 1.0 g of HMOM-TPPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) were dissolved in 30 g of GBL to obtain a varnish of a photosensitive polyimide precursor composition. Using the obtained varnish, sensitivity evaluation, metal adhesion evaluation, and chemical resistance evaluation were performed as described above.

Example 7
10 g of the polymer A solid obtained in Synthesis Example 9 was weighed, and 2.0 g of the quinonediazide compound (e) obtained in Synthesis Example 5 and “Nicarac” MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.) 1 0.0 g and 1.0 g of HMOM-TPPHBA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) were dissolved in 30 g of GBL to obtain a varnish of a photosensitive polyimide precursor composition. Using the obtained varnish, sensitivity evaluation, metal adhesion evaluation, and chemical resistance evaluation were performed as described above.

Example 8
10 g of the polymer A solid obtained in Synthesis Example 9 was weighed, 2 g of the quinonediazide compound (e) obtained in Synthesis Example 5 and “Nicarac” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) 1.5 g "Nicarac" MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.) (1.0 g) was dissolved in GBL (30 g) to obtain a varnish of a photosensitive polyimide precursor composition. Using the obtained varnish, sensitivity evaluation, metal adhesion evaluation, and chemical resistance evaluation were performed as described above.

Example 9
10 g of the polymer A solid obtained in Synthesis Example 9 was weighed, and 2.0 g of the quinonediazide compound (e) obtained in Synthesis Example 5 and “Nicarac” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) 1 0.0 g and 1.0 g of TMOM-BP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) were dissolved in 30 g of GBL to obtain a varnish of a photosensitive polyimide precursor composition. Using the obtained varnish, sensitivity evaluation, metal adhesion evaluation, and chemical resistance evaluation were performed as described above.

Example 10
A varnish was obtained in the same manner as in Example 1 except that “Nicarac” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) was 0.3 g, and as described above, sensitivity evaluation and adhesion to metal were performed. Evaluation and chemical resistance evaluation were performed.

Example 11
“Nicarac” MW-30HM (trade name, manufactured by Sanwa Chemical Co., Ltd.) was changed to 0.15 g, and a varnish was obtained in the same manner as in Example 5. As described above, sensitivity evaluation and adhesion to metal were performed. Evaluation and chemical resistance evaluation were performed.

Example 12
“Nikarak” MW-30HM (trade name, manufactured by Sanwa Chemical Co., Ltd.) was changed to 0.06 g, and a varnish was obtained in the same manner as in Example 5. As described above, sensitivity evaluation and adhesion to metal were performed. Evaluation and chemical resistance evaluation were performed.

Example 13
A varnish was obtained in the same manner as in Example 1 except that 0.5 g of N-phenyl-3-aminopropyltrimethoxysilane was added, and sensitivity evaluation, metal adhesion evaluation, and chemical resistance evaluation were performed as described above. went.

Example 14
A varnish was obtained in the same manner as in Example 5 except that 0.5 g of vinyltrimethoxysilane was added. As described above, sensitivity evaluation, metal adhesion evaluation, and chemical resistance evaluation were performed.

Example 15
A varnish was obtained in the same manner as in Example 1 except that 4 g of the polymer A obtained in Synthesis Example 9 was added and 6 g of the novolak resin A was added. As described above, sensitivity evaluation, evaluation of adhesion to metal, chemical resistance Sex evaluation was performed.

Example 16
A varnish was obtained in the same manner as in Example 5 except that 4 g of the polymer A obtained in Synthesis Example 9 and 6 g of the novolak resin B were added. As described above, sensitivity evaluation, metal adhesion evaluation, chemical resistance Sex evaluation was performed.

Example 17
A varnish was obtained in the same manner as in Example 15 except that 0.5 g of N-phenyl-3-aminopropyltrimethoxysilane was added. As described above, sensitivity evaluation, adhesion evaluation with metal, and chemical resistance evaluation were performed. went.

Example 18
A varnish was obtained in the same manner as in Example 15 except that 0.5 g of 3-glycidoxypropyltrimethoxysilane was added, and sensitivity evaluation, adhesion evaluation with metal, and chemical resistance evaluation were performed as described above. .

Example 19
A varnish was obtained in the same manner as in Example 15 except that 0.5 g of vinyltrimethoxysilane was added. As described above, sensitivity evaluation, adhesion evaluation with metal, and chemical resistance evaluation were performed.

Example 20
A varnish was obtained in the same manner as in Example 15 except that 0.5 g of m-acetylaminophenyltrimethoxysilane was added, and sensitivity evaluation, metal adhesion evaluation, and chemical resistance evaluation were performed as described above.

Comparative Example 1
A varnish was obtained in the same manner as in Example 1 except that no alkoxymethyl group-containing compound was used, and sensitivity evaluation, metal adhesion evaluation, and chemical resistance evaluation were performed as described above.

Comparative Example 2
A varnish was obtained in the same manner as in Example 1 except that HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) was removed. As described above, sensitivity evaluation, metal adhesion evaluation, and chemical resistance evaluation were performed. Went.

Comparative Example 3
A varnish was obtained in the same manner as in Example 1 except that Nicalak MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) was excluded. As described above, sensitivity evaluation, adhesion evaluation with metal, and chemical resistance were obtained. Evaluation was performed.

Comparative Example 4
Except for HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), a varnish was obtained in the same manner as in Example 5. As described above, sensitivity evaluation, metal adhesion evaluation, and chemical resistance evaluation were performed. Went.

Comparative Example 5
The same procedure as in Example 1 was used except that “Nicalac” MX-280 (trade name, manufactured by Sanwa Chemical Co., Ltd.) was used instead of “Nicalac” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.). The varnish was obtained, and as described above, sensitivity evaluation, adhesion evaluation with metal, and chemical resistance evaluation were performed.

Comparative Example 6
The same procedure as in Example 1 was used except that “Nicalac” MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.) was used instead of “Nicalac” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.). The varnish was obtained, and as described above, sensitivity evaluation, adhesion evaluation with metal, and chemical resistance evaluation were performed.

Comparative Example 7
The same procedure as in Example 5 except that 8.0 g of “Nicarac” MW-30HM (trade name, manufactured by Sanwa Chemical Co., Ltd.) was used and HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) was excluded. The varnish was obtained, and as described above, sensitivity evaluation, adhesion evaluation with metal, and chemical resistance evaluation were performed.

Comparative Example 8
A varnish was obtained in the same manner as in Example 1 except that 1,3-diphenylurea was used instead of “Nicalac” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.), and sensitivity evaluation was performed as described above. Evaluation of adhesion to metal and chemical resistance were performed.

Comparative Example 9
N, N′-ethylenediamine diacetate was used in place of “Nicalac” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.), and HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) was excluded. The others were obtained in the same manner as in Example 1, and the sensitivity stability evaluation and the adhesion evaluation with metal were performed as described above.

Comparative Example 10
Bis (4-acetamidophenyl) disulfide was used instead of “Nicalac” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.), and HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) was excluded. The others were obtained in the same manner as in Example 1, and the sensitivity stability evaluation and the adhesion evaluation with metal were performed as described above.

  The alkoxymethyl group-containing compounds and other compounds used in each Example and Comparative Example are shown below.

  Tables 1 to 4 show the compositions and evaluation results of Examples 1 to 20 and Comparative Examples 1 to 10.

Claims (3)

(A) a positive photosensitive resin composition containing a polymer having a structure represented by the general formula (1) as a main component, (b) a quinonediazide compound, (c) an alkoxymethyl group-containing compound, and (d) a solvent. And (c) an alkoxymethyl group-containing compound is (c1) a compound having a group represented by the following general formula (2), (c2) a compound represented by the following general formula (3), and (c3) A positive photosensitive resin composition comprising two or more selected from the group consisting of compounds represented by formula (4).

(In the general formula (1), R ¹ and R ² 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 may be hydrogen or 1 carbon atom. Represents a monovalent organic group of ˜20, n is in the range of 10 to 100,000, l and m are integers of 0 to 2, p and q are integers of 0 to 4, provided that p + q> 0. )

(In general formula (2), R ⁵ and R ⁶ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms. I represents 2 or 3.)

(In General Formula (3), R ⁷ and R ⁸ represent an alkyl group having 1 to 6 carbon atoms. R ⁹ represents a hydrogen atom, a methyl group or an ethyl group. R represents a single bond or a divalent to tetravalent group. Represents an organic group, j represents an integer of 2 to 4)

(In the general formula (4), R ^{10 to} R ¹⁵ may be the same or different and each represents a hydrogen atom or CH ₂ OR ¹⁶ (R ¹⁶ is an alkyl group having 1 to 6 carbon atoms), provided that R ¹⁰ to 5 or more in R ¹⁵ is CH ₂ OR ¹⁶ ) 2. The positive photosensitive resin composition according to claim 1, wherein at least one of the (c) alkoxymethyl group-containing compound is (c3). (A) 0.5 to 100 parts by weight of (c) an alkoxymethyl group-containing compound is contained with respect to 100 parts by weight of a polymer having a structure represented by the general formula (1) as a main component. The positive photosensitive resin composition according to 1 or 2.