KR20220018957A - Photosensitive polyimide resin composition - Google Patents

Abstract

SUMMARY An object of the present invention is to provide a photosensitive polyimide resin composition which is provided with developer solubility during development and developer insolubility after photocrosslinking, and capable of achieving good film properties and high sensitivity. The present invention contains (A) a solvent-soluble polyimide and (B) a diazide compound as essential components, and (A) the solvent-soluble polyimide contains (a) an aromatic tetracarboxylic acid dianhydride residue having a benzophenone structure. and (b) an aromatic diamine having an alkyl group at the ortho position of the amino group, an aromatic diamine having an indane structure, and a diamine having a polysiloxane structure A block copolymer having a residue in the main chain of at least one diamine selected from the group consisting of and (B) provide the photosensitive polyimide resin composition whose content of a diazide compound is 2.0-150 weight part with respect to 100 weight part of (A) solvent-soluble polyimides.

Description

Photosensitive polyimide resin composition

The present invention relates to a photosensitive polyimide resin composition.

In recent years, in semiconductor package substrates, transition from FC-CSP or FC-BGA to Fan-out Wafer Level Package (FO-WLP) capable of lowering the height, improving electrical characteristics (R, L, C), and reducing warpage. This is being considered in full swing, and a part of FO-WLP is being mass-produced. In the organic material used for this FO-WLP, the key material is a sealing material and various protective film materials, and photosensitive polyimide is used as this protective film material.

It is known that the photosensitive polyimide has several photosensitivity imparting methods (patent document 1), and it is largely divided into a positive type and a negative type from an image forming process. Although the positive type is more sensitive than the negative type, it is difficult to expect improvement in physical properties by the photoreaction because it uses a photolysis reaction. On the other hand, the negative type is characterized in that the exposed portion causes a photocrosslinking reaction and remains after the developing treatment, so that the chemical resistance and heat resistance are easily improved. Therefore, when the negative type is used as a permanent insulating film, although there are some problems in sensitivity, it can provide the thing excellent in reliability.

Negative photosensitive polyimides are broadly classified into a method in which a photosensitive group is introduced into a precursor such as polyamic acid and heat imidization after photoreaction, and a method in which the ring-opened polyimide itself has photosensitivity. Representative methods that have been put to practical use in the above field include ester bonding with hydroxyacrylate of polyamic acid (Patent Document 2), or introducing a photosensitive group by salt bonding by mixing aminoacrylate with polyamic acid (Patent Document) 3) is.

Moreover, as a method of giving photosensitivity to the ring-opened polyimide itself, the method of using the polyimide copolymer obtained by the polycondensation reaction of the tetracarboxylic dianhydride which has a benzophenone structure and diamine (patent document 4), The method of adding an acryloyl group to the side chain of the solvent-soluble polyimide block copolymer synthesize|combined by two-step polycondensation (patent document 5) is reported.

Kenichi Fukuda, Makoto Ueda, Collection of Polymer Papers, vol 63, No. 9, pp.561-576 Japanese Patent Publication No. 55-41422 Gazette Japanese Patent Laid-Open No. 54-145794 Japanese Patent Laid-Open No. 5-39281 Japanese Patent Laid-Open No. 2000-147768

Demands for semiconductor package substrates and the like are getting stricter every year, and FO-WLP is no exception. In order to respond to these demands, also for photosensitive polyimide, in addition to the improvement of sensitivity and the reliability of the thin film, the reduction and dimension of warpage in a large panel size, which is deeply involved in the reduction of cost, which is the biggest problem of FO-WLP, The improvement of stability is calculated|required.

However, the method of heating imidization after photoreaction using polyamic acid that is currently in practical use requires a high temperature (for example, 350 to 450° C.) for imidization, and at that time, dehydration shrinkage or separation of the photosensitive group Or volatilization occurs, and large membrane bearings generate|occur|produce. This had a large influence on warpage and dimensional stability in the manufacturing process of a semiconductor package or an electronic device, and was a factor in which storage stability also fell.

Further, even when a ring-opened polyimide is used, there is a problem that it is necessary to have a structure in which the developer is soluble at the time of development and the photosensitive portion becomes insoluble in the developer after photosensitizing. There was a problem that the sex was insufficient.

As described above, as a material for a protective film such as a semiconductor package substrate, a photosensitive polyimide that has developer solubility during development and developer insolubility after photocrosslinking, and which can achieve good film properties and improved sensitivity has been demanded.

An object of the present invention is to provide a photosensitive polyimide resin composition which is provided with developer solubility at the time of development and developer insolubility after photocrosslinking, and which can achieve good film properties and high sensitivity.

As a result of intensive studies to solve the above problems, the present inventors have used, as a ring-opened polyimide, a block copolymer having a structure having an aromatic acid dianhydride having a benzophenone structure and a specific diamine in the main chain, and this polyimide It was found that by combining the imide and a specific amount of a diazide compound, it was possible to provide a photosensitive polyimide resin composition that was equipped with solvent solubility during development and solvent insolubility after photocrosslinking, and capable of achieving good film properties and high sensitivity. and completed the present invention.

That is, the present invention provides the following.

(1) A photosensitive polyimide resin composition comprising (A) a solvent-soluble polyimide and (B) a diazide compound as essential components, wherein the (A) solvent-soluble polyimide is (a) an aromatic tetra having a benzophenone structure A residue of at least one diamine selected from the group consisting of a carboxylic acid dianhydride residue and (b) an aromatic diamine having an alkyl group at the ortho position of the amino group, an aromatic diamine having an indane structure, and a diamine having a polysiloxane structure as a main chain It is a block copolymer which has in it, Comprising: The photosensitive polyimide resin composition whose content of the said (B) diazide compound is 2.0-150 weight part with respect to 100 weight part of said (A) solvent-soluble polyimides.

(2) The resin composition according to (1), wherein the residue of the at least one diamine is a residue of an aromatic diamine having a phenylindane structure.

(3) The resin composition according to (1) or (2), wherein the (B) diazide compound is 2,6-di(4'-azidebenzal)-4-ethylcyclohexanone.

(4) The said photosensitive polyimide resin composition further contains (C) an epoxy resin and (D) a photobase generator, The resin composition in any one of (1)-(3) characterized by the above-mentioned.

(5) The said photosensitive polyimide resin composition is a negative solvent developing composition, The resin composition in any one of (1)-(4) characterized by the above-mentioned.

(6) A pattern formation method characterized by exposing the substrate coated with the resin composition according to any one of (1) to (5) by ultraviolet irradiation, and developing and removing the unexposed portion.

(7) A semiconductor package, electronic element, display element, or organic multilayer wiring board having an interlayer insulating film, a passivation film, or a surface protective film formed using the resin composition according to any one of (1) to (5).

According to the present invention, both solvent solubility during development and solvent insolubility after photocrosslinking are provided by using a ring-opened photosensitive polyimide and a specific amount of a diazide compound without using a polyamic acid requiring imidization at high temperature. Furthermore, it is possible to provide a photosensitive polyimide resin composition capable of achieving excellent film properties and high sensitivity equivalent to or higher than those of the photosensitive polyimide using polyamic acid.

When a conventionally used polyimide having a benzophenone skeleton was used, the quantum yield of hydrogen extraction crosslinking between the benzophenone moiety and the adjacent alkyl group was low, and a sufficient crosslinked structure was not obtained. By adding a compound, sufficient crosslinked structure of polyimide can be implement|achieved.

In addition, when the thickness of the film formed using the polyimide resin composition is large, for example, in the case of 10 µm or more, the polyimide resin composition contains a photobase generator and an epoxy resin, and the photobase generator is used to form an epoxy resin. A sufficient crosslinked structure can be realized by photocrosslinking.

The photosensitive polyimide resin composition of this invention is a resin composition containing (A) solvent-soluble polyimide and (B) a diazide compound as essential components.

(A) Solvent-soluble polyimide

(A) solvent-soluble polyimide in this invention, (a) aromatic dianhydride which has a benzophenone structure, (b-1) aromatic diamine which has an alkyl group at the ortho position of an amino group, (b-2) indane It is a block copolymer which has in a principal chain at least 1 sort(s) of diamine (b) selected from the group which consists of aromatic diamine which has a structure, and (b-3) diamine which has polysiloxane structure.

Specifically, the solvent-soluble polyimide (A) of the present invention is at least one of the repeating units represented by the following general formulas [I] to [III], and is a block copolymer having preferably two or more.

(Wherein, Z ¹ is an aromatic tetracarboxylic dianhydride residue, and Ar ¹ is an aromatic diamine residue having an alkyl group at the ortho position of the amino group)

(Wherein, Z ² is an aromatic tetracarboxylic dianhydride residue, and Ar ² is an aromatic diamine residue having an indane structure)

(Wherein, Z ³ is an aromatic tetracarboxylic dianhydride residue, and Ar ³ is a diamine residue having a polysiloxane structure)

In the present invention, at least one of Z ¹ in the general formula [I], Z ² in the general formula [II], and Z ³ in the general formula [III] is (a) aromatic tetra having a benzophenone structure Although it is a carboxylic acid dianhydride residue, it is preferable that Z ¹ , Z ² and Z ³ are all (a) aromatic tetracarboxylic dianhydride residues having a benzophenone structure.

As an aromatic acid dianhydride used as an aromatic acid dianhydride residue having (a) a benzophenone structure in the present invention, 2,2',3,3'-benzophenonetetracarboxylic dianhydride (BTDA), 4, 5,3',4'-benzophenonetetracarboxylic dianhydride (BTDA), 3,3',4,4'- benzophenonetetracarboxylic dianhydride (BTDA), etc. are mentioned. The morphology of the BTDA-based polyimide is also changed by photocrosslinking. That is, it is said that densification of the aggregation state occurs. This also contributes to the improvement of chemical resistance and heat resistance.

It is preferable to make the aromatic acid dianhydride which has a benzophenone structure contain 10 mol% or more, 45 mol% or more, and 50 mol% or more of all the aromatic acid dianhydrides which comprise a solvent-soluble polyimide. When content of the aromatic dianhydride which has a benzophenone structure is less than 10 mol%, the solvent resistance of the polyimide resin composition after photocrosslinking falls, and there exists a tendency for a sensitivity to become low.

Examples other than the aromatic tetracarboxylic dianhydride residue having a benzophenone structure of Z ¹ , Z ² and Z ³ in the general formulas [I] to [III] are not particularly limited, but pyromellitic acid dianhydride; 3,4,3',4'-benzophenonetetracarboxylic dianhydride, 3,4,3',4'-diphenyltetracarboxylic dianhydride, bis-(3,4-dicarboxyphenyl)ether and dianhydride, 2,2-bis-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and 4,4'-oxydiphthalic dianhydride.

Moreover, (A) solvent-soluble polyimide may have repeating units which consist of aromatic tetracarboxylic dianhydride residues and diamine residues other than the said general formula [I] - [III].

(b) diamines

(b-1) aromatic diamine having an alkyl group at the ortho position of the amino group

As the aromatic diamine residue (Ar ¹ ) having an alkyl group at the ortho position of the amino group in the present invention, a linear or branched alkyl group having 1 to 12 carbon atoms at the ortho position of the amino group, preferably 1 to 5 carbon atoms, more preferably The aromatic diamine residue which has a C1-C3 alkyl group is mentioned, The thing of a structure specifically represented by following formula (1)-(3) is mentioned.

In the formula (1), the free bond (two bonding positions to which the amino group is bonded) exists in the meta position or the para position relative to each other.

In the formula (2), the free bond (two bonding positions to which the amino group is bonded) is preferably in the meta position or para position with respect to R ₁₁ , and R ₅ and R ₆ are the two ortho positions of the free bond. is connected to R ₁₁ is -O-, -S-, -SS-, -SO-, -SO ₂ -, -CO-, -COO-, -NH-, -CONH-, -CON-alkyl group- (the number of carbon atoms in the alkyl group n represents 1 to 6), -CON-benzyl group-.

In the above formula (3), the free bond (two bonding positions to which the amino group is bonded) is present at the 2-,3-,6- or 7-position, and R ₅ and R ₆ are the two ortho positions of the free bond. is connected to

In the formulas (1) to (3), R ₅ and R ₆ are a linear or branched alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. .

In the present invention, the aromatic diamine residue (Ar ¹ ) having an alkyl group at the ortho position of the amino group is 30 mol% or more in all the diamines constituting the solvent-soluble polyimide (A), 50 mol% or more, particularly 70 mol% % or more is preferable. If it is less than 50 mol%, there exists a tendency for a crosslinking density to fall.

(b-2) Aromatic diamines having an indane structure

In the present invention, the aromatic diamine residue (Ar ² ) having an indane structure includes those having a structure represented by the following formula (IV) or (V) in the following indane skeleton.

In the formula (IV), R ₁ and R ₂ represent an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkoxyalkyl group having 2 to 12 carbon atoms, R ₁ and R ₂ are a free bond (amino group It is preferably bonded at two ortho positions of the two bonding sites to be bonded).

In the formula (V), R ₁ , R ₂ and R ₃ independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and each of R ₄ and R ₅ is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. represents an alkyl group of Specific examples include 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane and 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane. can

In this invention, the solvent-soluble polyimide which has in a principal chain the aromatic diamine residue which has a phenylindane structure represented by the said Formula (V) is preferable.

The aromatic diamine residue (Ar ² ) having an indane structure in the present invention is 50 mol% or more, more 60 mol% or more, particularly 70 mol% or more in all the diamines constituting the solvent-soluble polyimide (A). it is preferable If it is less than 50 mol%, there exists a tendency for a crosslinking density to fall.

(b-3) a diamine residue having a polysiloxane structure (Ar ³ )

As the diamine residue (Ar ³ ) having a polysiloxane structure in the present invention, α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω -bis(4-aminophenyl)polydimethylsiloxane, α,ω-bis(4-amino-3-methylphenyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydiphenylsiloxane, α,ω- Bis(4-aminobutyl)polydimethylsiloxane etc. are mentioned.

The diamine residue (Ar ³ ) having a polysiloxane structure in the present invention is preferably contained in 2.0 to 30 mol% in all the diamines constituting the (A) solvent-soluble polyimide, more preferably contained in 5.0 to 20 mol% desirable. When content of the diamine which has a polysiloxane structure exceeds 30 mol%, solvent solubility may become high too much, and there exists a tendency for Tg to also fall.

(A) Synthesis method of solvent-soluble polyimide

The method for synthesizing the solvent-soluble polyimide may use a known method, and is not particularly limited, but using approximately equal amounts of the above-described tetracarboxylic dianhydride and aromatic diamine, in an organic polar solvent in the presence of a catalyst and a dehydrating agent, By making it react at 160-200 degreeC for several hours, a solvent-soluble polyimide can be synthesize|combined. Examples of the organic polar solvent include N-methylpyrrolidone (NMP), γ-butyrolactone, N,N'-dimethylacetamide, N,N'-dimethylformamide, dimethyl sulfoxide, tetramethylurea, tetrahydroti Offene-1,1-oxide and the like are used.

The (A) solvent-soluble polyimide in this invention is a block copolymer, and is compoundable by performing a block copolymerization reaction as needed. For example, it can be prepared by the sequential addition reaction of two steps, and in the first step, a polyimide oligomer is synthesized from tetracarboxylic dianhydride and aromatic diamine, and then in the second step, tetracarboxylic dianhydride is synthesized. And/or aromatic diamine can be added, it can be polycondensed and it can be set as a block copolymerization polyimide.

As a catalyst for the block copolymerization reaction, a dehydration imidation reaction can be promoted by using a two-component acid-base catalyst using an equilibrium reaction of lactones. Specifically, a two-component catalyst of γ-valerolactone and pyridine or N-methylmorpholine is used. As shown in the following formula, as imidation proceeds, water is produced, and the produced water participates in the equilibrium of lactones, becomes an acid-base catalyst, and exhibits a catalytic action.

Water generated by the imidization reaction is removed out of the system by azeotroping with a dehydrating agent such as toluene or xylene coexisting in a polar solvent. When the reaction is completed, water in the solution is removed, and the acid-base catalyst is removed out of the system as γ-valerolactone and pyridine or N-methylmorpholine. In this way, a high-purity polyimide solution can be obtained.

As another two-component catalyst, oxalic acid or malonic acid and pyridine or N-methylmorpholine can be used. In the reaction solution at 160-200°C, oxalate or malonate promotes the imidation reaction as an acid catalyst. A catalytic amount of oxalic acid or malonic acid remains in the resulting polyimide solvent. When this polyimide solution is applied to a substrate and then heated to 200° C. or higher and solvent is removed to form a film, the oxalic acid or malonic acid remaining in the polyimide is thermally decomposed as shown in the following formula, and removed out of the system as a gas do.

By the above method, the high-purity (A) solvent-soluble polyimide can be obtained.

The oxalic acid-pyridine-based catalyst has a stronger activity than the valerolactone-pyridine-based catalyst and can produce a high molecular weight polyimide in a short time.

The term "solvent solubility" in this invention is a term used with respect to the organic polar solvent used in the synthesis|combination of a polyimide, and the solvent used for the film|membrane mentioned later, The polyimide which melt|dissolves 5 g or more in 100 g of solvent. means to be Here, examples of the solvent include polar solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, and tetramethylurea.

The solvent-soluble polyimide (A) synthesized as described above can be used in the state of a solution in which, for example, the solid content is 10 to 30% by weight in the organic polar solvent or a solvent used for a film to be described later. . (A) As for the molecular weight of a solvent-soluble polyimide, 10,000-400,000 are preferable as a weight average molecular weight of polystyrene conversion. If it is this range, good solvent solubility, film|membrane physical property, and insulation can be achieved. (A) When the appropriate viscosity of a solvent-soluble polyimide is 20 to 40 weight% of solid content, Preferably it is 2-10 Pa*g/25 degreeC. Moreover, 200 degreeC or more is preferable and, as for the glass transition temperature (Tg) (by a TMA measurement method) of a solvent-soluble polyimide, 250 degreeC or more is more preferable.

As for the density|concentration of (A) solvent-soluble polyimide in a solution, 5 to 50 weight% is preferable, More preferably, it is 10 to 40 weight%. In addition, the polyimide obtained by the direct imidation reaction using the catalyst system consisting of a lactone and a base can be obtained in the form of a solution dissolved in a polar solvent, and the concentration of the polyimide can also be within the above preferred range. The polyimide solution prepared can be preferably used as it is.

If desired, the manufactured polyimide solution can be further diluted using a diluent. As the diluent, a solvent that does not significantly impair solubility, for example, dioxane, dioxolane, N-methyl-2-pyrrolidone, γ-butyrolactone, cyclohexanone, cyclopentanone, propylene glycol mono Although methyl ether acetate, methyl lactate, anisole, methyl benzoate, ethyl acetate, etc. are mentioned, It is not specifically limited to these.

(B) diazide compound

In this invention, there exists an effect that exposure and developability improve remarkably by adding (B) diazide compound as another essential component to the photosensitive polyimide resin composition.

(B) As the diazide compound, 4,4'-diazidebenzalacetophenone, 2,6-di(4'-azidebenzal)cyclohexanone, 2,6-di(4'-azidebenzal)- 4-Methylcyclohexanone, 2,6-di(4'-azidebenzal)-4-ethylcyclohexanone, 2,6-di(4'-azidebenzal)-4-t-amylcyclohexanone , 4,4'- diazide diphenyl sulfone, 4,4'- diazide diphenyl ether, 4,4'- diazide phenyl sulfide, 4,4'- diazide diphenylmethane, etc. are mentioned. Among these, those having an azidebenzalcyclohexanone structure are preferable, and 2,6-di(4'-azidebenzal)-4-ethylcyclohexanone is particularly excellent from the viewpoint of crosslinking properties and storage stability.

(B) The diazide compound is 2.0 to 150 parts by weight, 5.0 to 100 parts by weight, particularly 10.0 to 80 parts by weight based on 100 parts by weight of (A) solvent-soluble polyimide in the photosensitive polyimide resin composition. desirable. When it is less than 2.0 parts by weight, the crosslinking density tends to decrease, and when it exceeds 150 parts by weight, the film properties tend to decrease. In order to supplement crosslinkability, you may use together a diazirine compound, a maleimide, or a bismaleimide compound.

Since the photosensitive polyimide resin composition of the present invention has poor light transmittance on the low-wavelength side, especially in the case of a thick film specification, the pattern shape tends to be reverse-tapered, which is seen as a negative solvent phenomenon. In order to improve this, it was found that it is also effective to use other photosensitive monomers or polymers of a photosensitive crosslinking method in combination. Among them, it was found that a combination of (C) an epoxy resin and (D) a photobase generator having excellent compatibility with the photosensitive polyimide resin composition is particularly effective as a component of the photosensitive polyimide resin composition of the present invention. .

(C) Epoxy resin

(C) It is not necessary to specifically limit as an epoxy resin, It can select by the reactivity with a photobase generator or compatibility with the photosensitive polyimide resin composition, As an epoxy resin, For example, a phenol novolak-type epoxy resin , Cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, crystalline epoxy resin, bisphenol A type epoxy Resin etc. can be used and those polymeric epoxy resins can also be used. 2-50 weight part is preferable with respect to 100 weight part of (A) solvent-soluble polyimides, and, as for content of (C) epoxy resin in the photosensitive polyimide resin composition, 2-20 parts are the most preferable.

(D) photobase generator

(D) A photobase generator is a component which generate|occur|produces an anion (base) by irradiation of an ultraviolet-ray, and is largely divided into a nonionic type and an ionic type. Nonionic types include those that absorb light to generate primary amines, secondary amines, imidazoles, and the like, while ionic types generate organic strong bases such as amidine, guanidine and phosphazene.

(D) The photobase generator (C) in the reaction with the epoxy resin, since a chain reaction does not easily occur in generating a primary amine or a secondary amine, imidazole or ionic type in nonionic type It is suitable to generate amidine, guanidine, and the like.

A commercial item can be used as (D) photobase generator in this invention. For example, WPBG-018, WPBG-140, WPBG-266, WPBG-300, WPBG-345, WPBG-027, WPBG-165 (above, the Fujifilm Wako Junyaku company make) etc. are mentioned.

0.5 to 8 weight% is preferable with respect to (C) epoxy resin, and, as for content of (D) photobase generator in the photosensitive polyimide resin composition, 1 to 6 weight% is more preferable.

(photosensitizer)

In the photosensitive polyimide resin composition of this invention, in order to suit each end use, a photosensitizer can be contained, and the sensitivity of pattern resolution can be raised. As a photosensitizer, it is preferable to act especially on the long-wavelength (>350 nm) side. As a photosensitizer, an anthracene type sensitizer, a thioxanthone type sensitizer, etc. are mentioned, for example. As for content of a photosensitizer, about 0.3 to 2 weight% is preferable with respect to the photosensitive polyimide resin composition.

Specific examples of the anthracene-based sensitizer include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10 -dibutoxyanthracene, 9,10-dipentyloxideanthracene, 9,10-dihexyloxideanthracene, 9,10-bis(2-methoxyethoxy)anthracene, 9,10-bis(2-ethoxyethoxy) ) anthracene, 9,10-bis (2-butoxyethoxy) anthracene, 9,10-bis (3-butoxypropoxy) anthracene, 2-methyl- or 2-ethyl-9,10 dimethoxyanthracene, 2 -methyl- or 2-ethyl-9,10-diethoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipropoxyanthracene, 2-methyl- or 2-ethyl-9,10-diisopro Foxyanthracene, 2-methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10 -dihexyloxy anthracene, etc. are mentioned.

As anthracene-type sensitizer, a commercial item can be used. As a commercial item, "Anthracure UVS-1331", "Anthracure UVS-1101", "Anthracure UVS-1221" (above, the Kawasaki Kasei Kogyo Co., Ltd. make) etc. are mentioned, for example.

Moreover, as a thioxanthone type sensitizer, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, chloropropoxy thioxanthone etc. are mentioned, for example. have. A commercial item can be used as a thioxanthone type sensitizer. As a commercial item, "KAYACURE DETX-S" (made by Nippon Kayaku Corporation), "Speedcure ITX", "Speedcure DETX", "Speedcure CPTX" (above, LAMBSON company make) etc. are mentioned, for example.

(Other additives)

To the photosensitive polyimide resin composition of the present invention, a modifier that is added in a normal photosensitive polyimide resin composition, for example, a coupling agent, a plasticizer, a film-forming resin, a surfactant, a stabilizer, a spectral sensitivity adjuster, etc. may be added. In particular, when the adhesion of the polyimide to the substrate is not good, a coupling agent, particularly, for example, vinyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, p-styryltrimethoxysilane, 3- Methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane , 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, hexamethyldisiloxane, hexamethyldisilazane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, N-[ Adhesiveness to a board|substrate can be made favorable by adding silane coupling agents, such as 3-(triethoxysilyl) propyl] phthalamic acid. In this case, as for the addition amount of a silane coupling agent, 0.1 to 5 weight% of the photosensitive polyimide resin composition is preferable.

Moreover, when using the board|substrate which consists of copper or a copper alloy, in order to suppress the discoloration of a board|substrate, an azole compound can be mix|blended with the photosensitive polyimide resin composition. Examples of the azole compound include 1H-benzotriazole, tolyltriazole, 5-methyl-1H-benzotrial, 4-methyl-1H-benzotrial, 5-carboxy-1H-benzotrial and 4- Carboxy-1H-benzotrial etc. are mentioned. In this case, as for the addition amount of an azole compound, 0.1 to 1 weight% of the photosensitive polyimide resin composition is preferable.

Moreover, in order to suppress discoloration of a copper phase, a hindered phenol compound can be mix|blended with the photosensitive polyimide resin composition.

Examples of the hindered phenol compound include 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4; 6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5- triazine-2,4,6-(1H,3H,5H)-trione and 1,3,5-tris(4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl)-1; 3,5-triazine-2,4,6-(1H,3H,5H)-trione etc. are mentioned.

In this case, as for the addition amount of a hindered phenol compound, 0.1 to 2 weight% of the photosensitive polyimide resin composition is preferable. Moreover, polyarylate resin, polyether sulfone resin, etc. are mentioned as other resin which can be used together.

The photosensitive polyimide resin composition of this invention can be made into the form of a solution suitable for application on a base material. In this case, as the solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, tetramethylurea, etc. used as a solvent for the imidation reaction of polar solvents can be used.

Manufacturing method of photosensitive polyimide pattern

A photosensitive polyimide pattern can be produced on a substrate by using the photosensitive polyimide resin composition containing the above-mentioned components. Specifically, (1) the process of forming a resin layer on the said board|substrate by apply|coating the photosensitive polyimide resin composition of this invention mentioned above on the board|substrate, (2) the process of exposing the said resin layer, (3) A step of developing the resin layer after exposure to form an insulating material for an electronic component and a photosensitive polyimide pattern such as a passivation film, a buffer coat film, and an interlayer insulating film in a semiconductor package; (4) the photosensitive polyimide pattern A photosensitive polyimide pattern can be manufactured by the method including the process of completing as a permanent insulating film by heat-processing.

Hereinafter, the typical form of each process is demonstrated.

(1) A step of forming a resin layer on the substrate by applying the photosensitive resin composition on the substrate:

In this process, the photosensitive resin composition of this invention is apply|coated on base materials, such as a silicon wafer, a metal substrate, a ceramic substrate, and an organic board|substrate, and it is made to dry after that as needed, and a resin layer is formed. As a coating method, a method conventionally used for application of the photosensitive resin composition, for example, a method of application with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, etc., a method of spray application with a spray coater, etc. are used. can

The coating film which consists of a photosensitive resin composition can be dried as needed. As a drying method, methods, such as air drying, heat drying by oven or a hot plate, and vacuum drying, are used. When air-drying or heat-drying specifically, it can dry under the conditions for 1 to 30 minutes at 20-140 degreeC. Unless the various characteristics of the photosensitive resin composition of this invention are impaired, it is not limited to this range.

(2) Step of exposing the resin layer:

In this step, the resin layer formed in the step (1) is exposed through an exposure apparatus such as a contact aligner, mirror projection, or stepper through a photomask or reticle having a pattern or directly or directly with an ultraviolet light source or the like. do. After that, for the purpose of improving the photosensitivity or the like, if necessary, post-exposure baking and/or pre-development baking may be performed by any combination of temperature and time. As for the range of baking conditions, although temperature is 40-120 degreeC, and time is 10-240 second, unless various characteristics of the photosensitive resin composition of this invention are impaired, it is not limited to this range.

(3) A step of developing a resin layer after exposure to form a photosensitive polyimide pattern:

In this process, the unexposed part of the photosensitive resin layer after exposure is developed and removed. As a developing method, arbitrary methods can be selected and used from the conventionally known photoresist developing method, for example, the rotation spray method, the paddle method, the immersion method accompanying ultrasonic treatment, etc. In addition, after image development, for the purpose of adjusting the shape of the photosensitive polyimide pattern, you may perform post-development baking by arbitrary combinations of temperature and time as needed.

As a developing solution used for image development, the good solvent with respect to the photosensitive resin composition, or the combination of the said good solvent and a poor solvent is preferable. Examples of the good solvent include N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α- Acetyl-γ-butyrolactone and the like are preferred. As a poor solvent, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, etc. are preferable. When mixing and using a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent with respect to a good solvent with the solubility of the polymer in the photosensitive resin composition. Moreover, about each of a good solvent and a poor solvent, 2 or more types of solvents, for example, can also be used combining several types.

(4) A step of heat-treating the photosensitive polyimide pattern to complete it as a permanent insulating film:

In this process, by heating the photosensitive polyimide pattern obtained by the said image development, it completes as a permanent insulating film. That is, unlike the polyamic acid type, since imidization has already been completed, it can be completed as a permanent insulating film by removing residues, such as a solvent. As a method of heat-hardening, various methods, such as using a thing with a hot plate, using an oven, and using a temperature rising type oven which can set a temperature program, can be selected. Heating is sufficient conditions for evaporating a contained solvent etc., for example, can be performed under the conditions of about 30 minutes - 2 hours at 150-250 degreeC. As atmospheric gas at the time of heating, air may be used and inert gas, such as nitrogen and argon, can also be used.

The photosensitive polyimide pattern formed as mentioned above can be used as an interlayer insulating film, a passivation film, or a surface protection film of a semiconductor package, an electronic element, a display element, or an organic multilayer wiring board.

(Example)

Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to these.

(Synthesis of block copolymer polyimide)

Synthesis Example 1

A cooling tube equipped with a stirrer, a nitrogen introduction tube, and a water receiver was attached to a glass separable three-necked flask. 3,4,3',4'-benzophenonetetracarboxylic acid dianhydride (hereinafter referred to as BTDA) 64.45 g (0.2 mol), 1,3-bis (3-aminophenoxy) benzene 29.23 g (0.1 mol) ), valerolactone 1.5 g (0.015 mol), pyridine 2.4 g (0.03 mol), NMP 200 g, and toluene 30 g were added, stirred at 200 rpm at room temperature under nitrogen atmosphere for 30 minutes, and then heated to 180 ° C. for 1 hour It was heated and stirred. During the reaction, the azeotrope of toluene-water was removed.

After cooling to room temperature, 48.33 g (0.15 mol) of BTDA, 44.57 g (0.25 mol) of 2,4-diethyl-6-methyl-1,3-benzenediamine (aromatic diamine having an alkyl group ortho to N-) After adding 360 g of NMP and 90 g of toluene and stirring at room temperature for 30 minutes, it heated up at 180 degreeC and heat-stirred for 1 hour. The reaction was terminated by heating and stirring at 180°C for 2 hours and 30 minutes while removing the water-toluene azeotropic reflux from the system. NMP was added and diluted to the obtained product, and the block copolymerization polyimide solution of 20 weight% of solid content was obtained.

Synthesis Example 2

A cooling tube equipped with a stirrer, a nitrogen introduction tube, and a water receiver was attached to a glass separable three-necked flask. 64.45 g (0.2 mol) of 3,4,3',4'-benzophenonetetracarboxylic acid dianhydride (hereinafter referred to as BTDA), 29.23 g (0.1 mol) of 1,3-bis(3-aminophenoxy)benzene , 1.5 g (0.015 mol) of valerolactone, 2.4 g (0.03 mol) of pyridine, 200 g of NMP, and 30 g of toluene were added, stirred at 200 rpm at room temperature under nitrogen atmosphere for 30 minutes, then heated to 180 ° C. and heated for 1 hour stirred. During the reaction, the azeotrope of toluene-water was removed.

After cooling to room temperature, 48.33 g (0.15 mol) of BTDA, 51.08 g (0.25 mol) of 5,7-diamino-1,1,4,6-tetramethylindane (aromatic diamine having an alkyl group ortho to N-) ), NMP360g, and toluene 90g were added, and after stirring at room temperature for 30 minutes, it heated up at 180 degreeC, and heat-stirred for 1 hour. The reaction was terminated by heating and stirring at 180°C for 2 hours and 30 minutes while removing the azeotropic reflux of water-toluene out of the system. NMP was added and diluted to the obtained product, and the block copolymerization polyimide solution of 20 weight% of solid content was obtained.

Synthesis Example 3

A cooling tube equipped with a stirrer, a nitrogen introduction tube, and a water receiver was attached to a glass separable three-necked flask. 64.45 g (0.2 mol) of 3,4,3',4'-benzophenonetetracarboxylic acid dianhydride (hereinafter referred to as BTDA), 29.23 g (0.1 mol) of 1,3-bis(3-aminophenoxy)benzene , 1.5 g (0.015 mol) of valerolactone, 2.4 g (0.03 mol) of pyridine, 200 g of NMP, and 30 g of toluene were added, stirred at 200 rpm at room temperature under nitrogen atmosphere for 30 minutes, then heated to 180 ° C. and heated for 1 hour stirred. During the reaction, the azeotrope of toluene-water was removed.

After cooling to room temperature, 44.13 g (0.15 mol) of 3,4,3',4'-biphenyltetracarboxylic acid dianhydride, 44.57 g of 2,4-diethyl-6-methyl-1,3-benzenediamine ( 0.25 mol) (aromatic diamine having an alkyl group at the ortho position with respect to N-), 360 g of NMP, and 90 g of toluene were added, stirred at room temperature for 30 minutes, then heated to 180° C., and heated and stirred for 1 hour. The reaction was terminated by heating and stirring at 180°C for 2 hours and 30 minutes while removing the water-toluene azeotropic reflux from the system. NMP was added and diluted to the obtained product, and the block copolymerization polyimide solution of 20 weight% of solid content was obtained.

Synthesis Example 4

A cooling tube equipped with a stirrer, a nitrogen introduction tube, and a water receiver was attached to a glass separable three-necked flask. 3,4,3',4'-benzophenonetetracarboxylic acid dianhydride (hereinafter referred to as BTDA) 64.45 g (0.2 mol), 5-amino-1-(4'-aminophenyl)-1,3,3 - 26.64 g (0.1 mol) of trimethylindane (aromatic diamine containing phenylindane structure), 1.5 g (0.015 mol) of valerolactone, 2.4 g (0.03 mol) of pyridine, 200 g of NMP, and 30 g of toluene were added, and under a nitrogen atmosphere at room temperature , after stirring at 200 rpm for 30 minutes, the temperature was raised to 180° C. and the mixture was heated and stirred for 1 hour. During the reaction, the azeotrope of toluene-water was removed.

After cooling to room temperature, 48.33 g (0.15 mol) of BTDA, 66.60 g (0.25 mol) of 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 360 g of NMP, and 90 g of toluene were added. , after stirring at room temperature for 30 minutes, the temperature was raised to 180° C. and the mixture was heated and stirred for 1 hour. The reaction was terminated by heating and stirring at 180°C for 2 hours and 30 minutes while removing the water-toluene azeotropic reflux from the system. NMP was added and diluted to the obtained product, and the block copolymerization polyimide solution of 20 weight% of solid content was obtained.

Synthesis Example 5

A cooling tube equipped with a stirrer, a nitrogen introduction tube, and a water receiver was attached to a glass separable three-necked flask. 64.45 g (0.2 mol) of 3,4,3',4'-benzophenonetetracarboxylic acid dianhydride (hereinafter referred to as BTDA), 12.22 g (0.1 mol) of 2,4-diaminotoluene (ortho to N- Aromatic diamine having an alkyl group at the position), valerolactone 1.5 g (0.015 mol), pyridine 2.4 g (0.03 mol), NMP 200 g, and toluene 30 g were added, and stirred at room temperature under nitrogen atmosphere at 200 rpm for 30 minutes at 200 rpm, It heated up to 180 degreeC and heat-stirred for 1 hour. During the reaction, the azeotrope of toluene-water was removed.

After cooling to room temperature, 48.33 g (0.15 mol) of BTDA, 66.60 g (0.25 mol) of 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 360 g of NMP, and 90 g of toluene were added. , after stirring at room temperature for 30 minutes, the temperature was raised to 180°C, and the mixture was heated and stirred for 1 hour. The reaction was terminated by heating and stirring at 180°C for 2 hours and 30 minutes while removing the water-toluene azeotropic reflux from the system. NMP was added and diluted to the obtained product, and the block copolymerization polyimide solution of 20 weight% of solid content was obtained.

Synthesis Example 6

A cooling tube equipped with a stirrer, a nitrogen introduction tube, and a water receiver was attached to a glass separable three-necked flask. 3,4,3',4'-benzophenonetetracarboxylic acid dianhydride (hereinafter referred to as BTDA) 64.45 g (0.2 mol), 5-amino-1-(4'-aminophenyl)-1,3,3 - Trimethylindane 15.98 g (0.06 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 9.94 g (0.04 mol), valerolactone 1.5 g (0.015 mol), pyridine 2.4 g (0.03 mol), After adding NMP 200g and toluene 30g, and stirring at room temperature for 30 minutes, it heated up at 180 degreeC and stirred for 1 hour. During the reaction, the azeotrope of toluene-water was removed.

After cooling to room temperature, 48.33 g (0.15 mol) of BTDA, 66.60 g (0.25 mol) of 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 360 g of NMP, and 90 g of toluene were added. , after stirring at room temperature for 30 minutes, the temperature was raised to 180° C. and the mixture was heated and stirred for 1 hour. The reaction was terminated by heating and stirring at 180°C for 2 hours and 30 minutes while removing the water-toluene azeotropic reflux from the system. NMP was added and diluted to the obtained product, and the block copolymerization polyimide solution of 20 weight% of solid content was obtained.

Synthesis Comparative Example 1

A cooling tube equipped with a stirrer, a nitrogen introduction tube, and a water receiver was attached to a glass separable three-necked flask. 58.84 g (0.2 mol) of 3,4,3',4'-biphenyltetracarboxylic acid dianhydride, 29.23 g (0.1 mol) of 1,3-bis(3-aminophenoxy)benzene, 1.5 g of valerolactone (0.015 mol), pyridine 2.4 g (0.03 mol), NMP 200 g, and toluene 30 g were added, stirred at 200 rpm at room temperature under nitrogen atmosphere for 30 minutes, and then heated to 180° C. and heated and stirred for 1 hour. During the reaction, the azeotrope of toluene-water was removed.

After cooling to room temperature, 48.33 g (0.15 mol) of 3,4,3',4'-benzophenonetetracarboxylic dianhydride, 44.57 g of 2,4-diethyl-6-methyl-1,3-benzenediamine ( 0.25 mol) (aromatic diamine having an alkyl group ortho to N-), 360 g of NMP, and 90 g of toluene were added and stirred at room temperature for 30 minutes, then heated to 180° C. and stirred with heat for 1 hour. The reaction was terminated by heating and stirring at 180°C for 2 hours and 30 minutes while removing the azeotropic reflux of water-toluene out of the system. NMP was added and diluted to the obtained product, and the block copolymerization polyimide solution of 20 weight% of solid content was obtained.

Synthesis Comparative Example 2

A cooling tube equipped with a stirrer, a nitrogen introduction tube, and a water receiver was attached to a glass separable three-necked flask. 64.45 g (0.2 mol) of 3,4,3',4'-benzophenonetetracarboxylic acid dianhydride (hereinafter referred to as BTDA), 12.22 g (0.1 mol) of 2,4-diaminotoluene (ortho to N- Aromatic diamine having an alkyl group at the position), valerolactone 1.5 g (0.015 mol), pyridine 2.4 g (0.03 mol), NMP 200 g, and toluene 30 g were added, and stirred at room temperature under nitrogen atmosphere at 200 rpm for 30 minutes at 200 rpm, It heated up to 180 degreeC and heat-stirred for 1 hour. During the reaction, the azeotrope of toluene-water was removed.

After air cooling, 48.33 g (0.15 mol) of BTDA, 73.08 g (0.25 mol) of 1,3-bis(3-aminophenoxy)benzene (aromatic diamine containing an aromatic ether bond), 360 g of NMP, and 90 g of toluene were added, and the mixture was cooled to room temperature. After stirring for 30 minutes, it heated up to 180 degreeC and heat-stirred for 1 hour. The reaction was terminated by heating and stirring at 180°C for 2 hours and 30 minutes while removing the water-toluene azeotropic reflux from the system. NMP was added and diluted to the obtained product, and the block copolymerization polyimide solution of 20 weight% of solid content was obtained.

(Preparation of photosensitive polyimide resin composition)

In the following examples and comparative examples, "part" means "part by weight".

Examples 1-6

500 parts of block copolymer polyimide solutions of Synthesis Examples 1 to 6 (solid content 20 wt%), 2,6-di(4'-azidebenzal)-4-ethylcyclohexanone 20 parts, 9,10-di parts Toxanthracene 1 part, 3-glycidoxypropylmethyldimethoxysilane 1 part, 5-methyl-1H-benzotrial 0.1 part, 1,3,5-tris(4-triethylmethyl-3-hydroxy-2 1 part of ,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione was added and dissolved in methyl benzoate to obtain a photosensitive resin composition having a solid content of 20% did.

Example 7

In Example 1 (using the polyimide solution of Synthesis Example 1), 2,6-di(4'-a) instead of 2,6-di(4'-azidebenzal)-4-ethylcyclohexanone The photosensitive resin composition was prepared using the same method except having used zidbenzal)-4-methylcyclohexanone.

Example 8

In Example 1 (using the polyimide solution of Synthesis Example 1), 4,4'-diazidebenzalacetophenone instead of 2,6-di(4'-azidebenzal)-4-ethylcyclohexanone The photosensitive resin composition was prepared using the same method except having used.

Example 9

In Example 1 (using the polyimide solution of Synthesis Example 1), 16.7 parts of YX-6954BH30 (polymer epoxy; manufactured by Mitsubishi Chemical Corporation), 0.25 parts of WPBG-300 (photobase generator: manufactured by Fujifilm Wako Junyaku) Except having further added, the photosensitive resin composition was prepared using the same method.

Example 10

In Example 1 (using the polyimide solution of Synthesis Example 1), 5 parts of TEPIC-VL (trifunctional epoxy: manufactured by Nissan Chemical Industries, Ltd.), WPBG-300 (photobase generator: manufactured by FUJIFILM Wako Junyaku Co., Ltd.) ) The photosensitive resin composition was prepared using the same method except having added 0.25 part.

Comparative Example 1

In Example 7 (using the polyimide solution of Synthesis Example 1), the same method was used except that 2,6-di(4'-azidebenzal)-4-methylcyclohexanone was not used. Thus, the photosensitive resin composition was prepared.

Comparative Example 2

In Example 7 (using the polyimide solution of Synthesis Example 1), 2,6-di(4'-azidebenzal)-4-methylcyclohexanone was used instead of 20 parts, except that 1.5 parts was used The photosensitive resin composition was prepared using the method of

(Evaluation of performance of polyimide resin composition)

1. Mechanical strength, coefficient of thermal expansion and 5% thermogravimetric reduction temperature

The resin compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 2 were spin-coated on a 6-inch silicon wafer to a film thickness of 15 to 17 μm after final drying, and prebaked at 90° C. for 360 seconds, followed by a high-pressure mercury lamp 2,500 mJ/cm 2 full-wavelength exposure in i-line conversion, immersed in a cyclopentanone solution for 120 seconds, and then heat-dried at 200°C (or 180°C) for 90 minutes to prepare a dried resin film.

This resin dried film was peeled off from the wafer with hydrofluoric acid, and it was set as the test sample for mechanical strength, thermal expansion coefficient, and 5% thermogravimetric decrease temperature measurement.

2. Adhesion strength

The dried resin film formed on the silicon wafer produced above is used.

(1) Using a cutter knife on the test surface, make 11 cut marks reaching the base to make 100 checkerboard eyes. Using a cutter guide, the interval between cuts is 1 mm.

(2) The cello-tape (registered trademark) is strongly pressed on the checkerboard part, the ends of the tape are removed at a time at an angle of 45°, and the condition of the checkerboard is evaluated by comparing it with the standard diagram. The adhesion strength after 240 hours in a state and HAST (80 degreeC x 85 %RH) is judged.

3. Remaining film rate

The resin compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 2 were spin-coated on a 6-inch silicon wafer so that the film thicknesses after final drying were 5 to 7 µm and 10 to 12 µm, and 90° C. for 240 seconds and 90 After pre-baking at ℃ for 300 seconds, the thickness (t ₁ ) is measured with a film thickness meter. Then, using a high-pressure mercury lamp, 1,000 (or 2,500) mJ/cm 2 full-wavelength exposure is performed in i-line conversion, and after immersion in a cyclopentanone solution for 120 seconds, the thickness (t ₂ ) is measured with a film thickness meter. Moreover, heat-drying is performed at 200 degreeC (or 180 degreeC) for 90 minutes, _and thickness (t3) is measured with a film thickness meter after that. From these measured values, t ₂ /t ₁ , t ₃ /t ₁ , and t ₃ /t ₂ were calculated and set as the remaining film rates.

4. Exposure and developability

Pattern evaluation was performed with the following method.

(1) Resolution

The resin compositions obtained in Examples 1-10 and Comparative Examples 1-2 were dripped on a 6-inch silicon wafer, spin-coated for 30 seconds, and then, prebaked on a 90 degreeC hotplate for 240 second. At this time, the coating rotation was adjusted so that the film thickness after baking might be set to about 6-8 micrometers. Then, exposure was performed using a high-pressure mercury lamp. The exposure dose measured by the i-line was 1,000 mJ/cm 2 . After that, it developed with cyclopentanone, rinsed, and heat-dried at 200 degreeC (or 180 degreeC) for 90 minutes. L/S=5/5, 10/10, 15/15, 20/20, 30/30, 50/50㎛, the smallest resolution among square via hole patterns 10, 15, 20, 30, 40, 50㎛ was the resolution.

(2) Pattern edge residue, cracks

Pattern processing was performed by the method similar to said (1), and it visually observed whether there was any abnormality in the film|membrane surface after image development first. Next, a 15-micrometer square via-hole pattern was observed with an optical microscope, and the case where there was a crack in the corner of a pattern was set as the presence of a crack. Moreover, the pattern edge of L/S=15/15 was observed, and the case where the development residue generate|occur|produced was set as the presence of a residue.

The evaluation results of the resin compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 2 are shown in Tables 1 and 2 below. The resin composition obtained in Comparative Examples 1-2 was immersed in the cyclopentanone solution after exposure in evaluation of a residual-film rate and exposure developability, and the film|membrane melt|dissolved. This result has shown that the resin composition obtained by Comparative Examples 1-2 was not equipped with favorable solvent insolubility after photocrosslinking. Therefore, Tg, coefficient of thermal expansion, 5% thermogravimetric decrease temperature, mechanical strength, and adhesion strength of the resin composition obtained in Comparative Examples 1 and 2 were evaluated by making a sample without immersing the resin composition in a cyclopentanone solution. . On the other hand, while the resin composition obtained in Examples 1-10 is equipped with both the solvent solubility at the time of image development and the solvent insolubility after photocrosslinking, it turns out that favorable film|membrane physical property and high sensitivity were achieved.

(Industrial Applicability)

The negative photosensitive polyimide resin composition of the present invention is, for example, a semiconductor package such as FO-WLP or WLP, a thin film magnetic element such as a thin film magnetic head, a thin film inductor, a common mode choke coil, etc. Electronic elements such as a TFT liquid crystal element It is useful for manufacturing display elements, such as a color filter element, an organic electroluminescent element, and an organic multilayer wiring board, etc., and can be used suitably in the field|area of a photosensitive material.

Claims (7)

A photosensitive polyimide resin composition comprising (A) a solvent-soluble polyimide and (B) a diazide compound as essential components,
(A) the solvent-soluble polyimide is (a) an aromatic tetracarboxylic dianhydride residue having a benzophenone structure, (b) an aromatic diamine having an alkyl group at the ortho position of the amino group, an aromatic diamine having an indane structure, and It is a block copolymer having in the main chain the residue of at least one diamine selected from the group consisting of diamines having a polysiloxane structure,
The photosensitive polyimide resin composition in which content of the said (B) diazide compound is 2.0-150 weight part with respect to 100 weight part of said (A) solvent-soluble polyimides. The method of claim 1,
The resin composition characterized in that the residue of the at least one diamine is a residue of an aromatic diamine having a phenylindane structure. 3. The method of claim 1 or 2,
(B) The resin composition, characterized in that the diazide compound is 2,6-di(4'-azidebenzal)-4-ethylcyclohexanone. 4. The method according to any one of claims 1 to 3,
The said photosensitive polyimide resin composition further contains (C) an epoxy resin and (D) a photobase generator, The resin composition characterized by the above-mentioned. 5. The method according to any one of claims 1 to 4,
The said photosensitive polyimide resin composition is a negative solvent developing composition, The resin composition characterized by the above-mentioned. A pattern forming method characterized by exposing the substrate coated with the resin composition according to any one of claims 1 to 5 to ultraviolet irradiation, and developing and removing the unexposed portion. A semiconductor package, an electronic element, a display element, or an organic multilayer wiring board having an interlayer insulating film, a passivation film, or a surface protective film formed using the resin composition according to any one of claims 1 to 5.