TW202309657A - Photosensitive polyimide resin composition - Google Patents

Abstract

An object of the present invention is to provide a photosensitive polyimide resin composition which has solubility in developer during development and has insolubility in developer after photocrosslinking, and can attain good membrane property and high sensitivity, and which does not cause membrane loss or crack of a resin coating and warping or destruction of a substrate. The present invention provides a photosensitive polyimide resin composition which comprises a solvent-soluble polyimide and a diazide compound, wherein the solvent-soluble polyimide is a block copolymer having, in the same repeating unit, (a) an alicyclic acid dianhydride residue and (b) a diamine residue selected from the group consisting of an aromatic diamine having an alkyl group at the ortho position of an amino group and an aromatic diamine having an indan structure.

Description

Photosensitive polyimide resin composition

The present invention relates to photosensitive polyimide resin composition.

In recent years, for semiconductor packaging substrates, there have been discussions from FC-CSP or FC-BGA to Fan-out Wafer Level with low profile, improved electrical characteristics (R, L, C), and reduced warpage Package (fan-out wafer-level packaging, FO-WLP), some FO-WLP has been mass-produced. Also, research on Fan-out Panel Level Package (FO-PLP) using panel-level materials is also in vogue. The key materials used in the FO-WLP or FO-PLP, which are made of organic materials, are sealing materials and various protective film materials. The protective film materials use photosensitive polyimide.

The method of imparting photosensitivity to photosensitive polyimide can be roughly divided into positive type and negative type. The method of imparting negative photosensitivity is that photocrosslinking reaction occurs in the exposed part and remains after development treatment, so chemical resistance and heat resistance can be easily improved, so it can provide a material with excellent reliability. Negative photosensitive polyimide can be roughly divided into two types: the method of introducing a photosensitive group into a precursor such as polyamide acid, and then performing heating imidization after photoreaction; A method that is inherently photosensitive.

The representative method that has been put into practice in this field is the method of using precursors such as polyamic acid, for example: those who carry out ester bonding by hydroxyacrylate of polyamic acid (Patent Document 1), and polyamide A photosensitive group is introduced by mixing an acrylate or the like into an acid through a salt bond (Patent Document 2).

Furthermore, as negative photosensitive compositions aiming at lowering the coefficient of thermal expansion, compositions containing polyimide precursors having a benzoxazole skeleton in the main chain have been reported (Patent Documents 3 and 4).

Furthermore, the photosensitive composition aimed at reducing the residual stress has been reported to be a resin composition composed of a polyimide precursor with a photosensitive group, a photoinitiator, and a solvent, and the polyimide precursor As a material system, those synthesized from various aromatic tetracarboxylic dianhydrides and diamines were used (Patent Document 5).

Furthermore, it has been reported that a substrate with metal wiring for a power module having a metal substrate, a polyimide resin layer, and a conductive metal wiring layer can ensure both insulation and thermal conductivity, and the improved power module A substrate with heat dissipation and reliability (Patent Document 6). Here, it is described that the polyimide resin system can preferably use thermoplastic and non-thermoplastic polyimide systems synthesized by using aromatic tetracarboxylic dianhydrides from the viewpoint of achieving heat resistance and low linear thermal expansion coefficient. resin.

On the other hand, a method for making the ring-closed polyimide self-photosensitive has been reported, such as using a polyamide obtained by polycondensation reaction between tetracarboxylic dianhydride and diamine having a benzophenone structure. A method of an imine copolymer (Patent Document 7); and a method of adding an acryl group to the side chain of a solvent-soluble polyimide block copolymer synthesized by two-stage polycondensation (Patent Document 8).

Furthermore, there are disclosed negative photosensitive polyimides containing solvent-soluble polyimides with aromatic or alicyclic tetracarboxylic dianhydride residues and aromatic diamine residues, and photoradical generators. The imine composition has high image resolution capability and is excellent in adhesiveness, heat resistance, mechanical properties, and flexibility (Patent Document 9).

Furthermore, it has been reported that there are aromatic tetracarboxylic acid dianhydride residues with a diphenyl ketone structure in the main chain, aromatic diamines with an alkyl group in the ortho position to the amine group, or aromatic diamines with an indan structure. The solvent-soluble polyimide of the residue of the group diamine and the photosensitive polyimide resin composition of a specific amount of diazide compound have both solvent solubility during development and solvent insolubility after photocrosslinking, Good film physical properties and high sensitivity can be achieved (Patent Document 10). [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. Sho 55-41422 [Patent Document 2] Japanese Patent Laid-Open No. 54-145794 [Patent Document 3] Japanese Patent Laid-Open No. 2005-321648 [Patent Document 4] Japanese Patent Laid-Open No. 2005-321650 [Patent Document 5] Japanese Patent Laid-Open No. 2001-110898 [Patent Document 6] Japanese Patent Laid-Open No. 2015-97258 [Patent Document 7] Japanese Patent Laid-Open No. 5-39281 [Patent Document 8] Japanese Patent Laid-Open No. 2000-147768 [Patent Document 9] International Publication No. 2002/023276 [Patent Document 10] International Publication No. 2020/246565

(Problem to be solved by the invention)

The requirements for semiconductor packaging substrates are becoming more stringent year by year, and even FO-WLP and FO-PLP are no exception, requiring thinner patterns, smaller diameters of connecting through holes, and multilayering. In order to meet these requirements, in addition to the sensitivity improvement and film reliability of photosensitive polyimide, it is also deeply related to the cost reduction of the biggest issue of FO-WLP and FO-PLP. Reduction of warpage of large panel size, and improved dimensional stability. However, one of these elements is low thermal expansion.

Conventional photosensitive polyimide resins have larger thermal expansion coefficients than metal and inorganic materials. When the thermal expansion coefficient of the resin is large, if it is coated on a metal or inorganic material substrate to form a resin film, there will be thermal stress caused by the difference in thermal expansion coefficient, which will lead to cracks in the formed resin film, or resin coating. Potential for the film to peel from the substrate, for the substrate to warp, or for the substrate to be damaged. In addition, if the lithography for patterning is performed in a state where the base material is greatly warped, the patterning resolution may be deteriorated. Especially in the case of using a substrate with a large panel size and coating a thick resin on the substrate, this problem tends to be significant. Therefore, it is expected to develop a photosensitive polyimide resin with a small thermal expansion coefficient. Especially when silicon wafers are used as the base material, since the coefficient of thermal expansion is an extremely small value of 3ppm/°C, the difference in thermal expansion between the polyimide resin and the wafer may cause warping of the wafer, which is considered to be a defect in the manufacturing process. , transportation failure, cause of breakage, or influence on device characteristics (electrical characteristics, resolution), etc. are not good.

In order to meet these requirements, although the polyamic acid-type photosensitive polyimide resin compositions such as the above-mentioned patent documents 3 to 6 have been reviewed, they have not yet achieved sufficient performance. In addition, in the method of using a polyamide photosensitive composition, after coating and drying on the substrate, or after exposure and development, high temperature treatment (for example, 350~450°C) is necessary for imidization At this time, syneresis will occur, and the photosensitive group will detach or volatilize, resulting in a significant reduction in film thickness. This phenomenon greatly affects substrate warping and dimensional stability in semiconductor packaging and electronic component manufacturing processes, and also becomes a factor for lowering storage stability.

Furthermore, the photosensitive compositions of the above-mentioned Patent Documents 7 to 10 using ring-closed polyimides are insufficient from the viewpoint of lowering the thermal expansion coefficient.

According to this, protective film materials such as semiconductor packaging substrates are required to avoid reduction in film thickness and cracking of the resin coating due to the high temperature treatment of imidization and the difference in thermal expansion coefficient between the polyimide resin and the substrate. , The photosensitive polyimide resin composition in which the substrate is warped and destroyed.

The object of the present invention is to provide: having developer solubility during development and developer insolubility after photocrosslinking, which can achieve good film physical properties and high sensitivity, and will not cause film thickness reduction, cracking, or substrate warping of the resin coating. Or damaged photosensitive polyimide resin composition. (technical means to solve the problem)

The inventors of the present invention conducted in-depth research to solve the above problems, and found that the ring-closed solvent-soluble polyimide system used has: (a) alicyclic acid dianhydride residues, and (b) an alkyl group on the ortho-position of the amine group The block copolymer of the same repeating unit of the aromatic diamine or the residue of the aromatic diamine having an indan structure, by using the resin composition containing this solvent-soluble polyimide and diazide compound, it is convenient A resin composition having a remarkably reduced coefficient of thermal expansion can be obtained. Then, it was found that by using this resin composition, the above-mentioned problems can be solved, and it can be provided: it has developer solubility during development and developer insolubility after photocrosslinking, can achieve good film physical properties and high sensitivity, and resin coating A photosensitive polyimide resin composition that does not cause film thickness reduction and cracking, and does not cause warping and damage to the substrate, and thus completed the present invention.

That is, the photosensitive polyimide resin composition provided by the present invention is a photosensitive polyimide resin composition containing a solvent-soluble polyimide and a diazide compound as essential components, wherein the solvent-soluble polyimide The imide has in the same repeating unit: (a) an alicyclic acid dianhydride residue, and (b) an aromatic diamine with an alkyl group at the ortho position of the amine group, and an aromatic diamine with an indan structure. A block copolymer of residues of at least one diamine selected from the group consisting of diamines. Furthermore, the pattern forming method provided by the present invention is characterized in exposing the substrate coated with the above-mentioned resin composition of the present invention by ultraviolet irradiation, and then developing and removing the unexposed portion. Furthermore, the semiconductor package, magnetic element, display element or organic multilayer wiring substrate provided by the present invention has: an interlayer insulating film, a passivation film or a surface protection film formed by using the above-mentioned resin composition of the present invention. (compared to the effect of previous technology)

The present invention can provide: Even if polyamic acid that needs to be imidized at high temperature is not used, it can still have developer solubility during development and developer insolubility after photocrosslinking, and can achieve good film physical properties and high It is a photosensitive polyimide resin composition that does not cause film thickness reduction and cracking in the resin film, does not cause warping and damage to the substrate, and has a low thermal expansion coefficient. Furthermore, when the thickness of the film formed by using the polyimide resin composition is large (for example, the case of 10 μm or more), by making the photosensitive polyimide resin composition of the present invention further contain a photobase generator and For epoxy resins, a photobase generator is used to photocrosslink epoxy resins to achieve a fully crosslinked structure.

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

(A) Solvent-soluble polyimide The (A) solvent-soluble polyimide of the present invention has in the same repeating unit: (a) alicyclic acid dianhydride residues and (b) block copolymers of diamine residues with specific structures. (b) The diamine residue with specific structure is a group formed from (b-1) aromatic diamine with alkyl group on the ortho position of amino group, and (b-2) aromatic diamine with indan structure Select at least one diamine residue.

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

[chemical 1]

(In the formula, ^Z1 is an alicyclic acid dianhydride residue, ^Ar1 is an aromatic diamine residue with an alkyl group on the ortho position of the amino group)

[Chem 2]

(In the formula, ^Z2 is an alicyclic acid dianhydride residue, ^Ar2 is an aromatic diamine residue with an indenane structure)

(a) Alicyclic acid dianhydride residue (a) Alicyclic acid dianhydrides that provide residues of alicyclic acid dianhydrides include, for example: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclobutane Pentane tetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4 ,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane -1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylene- 4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) di anhydride, 1, 1,1,3,3,3-hexafluoro-2,2-propylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy- 4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl -4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride , 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic acid-2,6: 3,5-dianhydride, 3-carboxymethyl-1,2,4-cyclopentanetricarboxylic acid 1 ,4: 2,3-dianhydride. These may be used individually by 1 type, and may use 2 or more types of mixtures. Among them, in order to achieve a low thermal expansion rate, it is preferably a tetracarboxylic dianhydride of a cycloalkane with 4 to 7 carbon atoms, more preferably a 1,2,3,4-cyclobutane tetracarboxylic dianhydride, or 1, 2,3,4-Cyclopentanetetracarboxylic dianhydride.

The 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) polyimide, which belongs to the alicyclic acid dianhydride, has almost no absorption in the visible light region from 300nm to 800nm, and the g-line ( 436nm), i-line (365nm) and other exposure wavelengths are almost all penetrated. If a photosensitive polyimide such as the CBDA-based polyimide is used as a matrix polymer, the exposure wavelength can be effectively utilized, and a high-sensitivity and high-resolution photosensitive polyimide can be obtained.

In the present invention, for achieving increased penetration in the visible light region, high sensitivity and high resolution, and taking into account low thermal expansion rate and solvent solubility, (a) alicyclic acid dianhydride residues (Z ¹ and Z ² ), It accounts for (A) of all acid dianhydride residues constituting the solvent-soluble polyimide, preferably more than 5 mol%, more than 10 mol%, more than 15 mol%, more preferably more than 20 mol%, and more preferably 65 mol% Below, below 60mol%, more preferably below 55mol%.

In addition, other aromatic acid dianhydrides may be used in combination in order to achieve both low thermal expansion coefficient and solvent solubility. Other aromatic acid dianhydrides include, for example: 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-[propane-2,2-diylbis(1,4 -Phenyloxy)] diphthalic dianhydride, 4,4'-oxydiphthalic anhydride, and pyromellitic dianhydride, etc.

Furthermore, in order to further increase the penetration in the visible light region and maintain the solvent solubility of polyimide, fluorine-based acid dianhydrides may also be used in combination. Fluorine-based acid dianhydrides are aromatic acid dianhydrides with fluorine atoms (or substituents containing fluorine atoms). Representative examples include: 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, and 2,2'-bis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, etc.

(b) diamine residue with specific structure (b-1) aromatic diamine residue with alkyl on the ortho position of amine group (general formula [I Ar ¹ ) in ] can be, for example, an aromatic bis having a straight-chain or branched alkyl group with 1 to 12 carbons, preferably 1 to 5 carbons, and more preferably 1 to 3 carbons at the ortho position of the amino group. Specific examples of the amine residues include residues of aromatic diamines having structures represented by the following formulas (1) to (3) and heterocyclic diamines having a dibenzothiophene structure.

[Chem 3]

In the above formula (1), the free bonds (the two bonding positions of the bonded amine groups) exist in the meta-position or para-position opposite to each other, especially in order to achieve a low thermal expansion coefficient and obtain a higher linearity of the main chain skeleton From the point of view of polyimide, it is preferable to exist in the para position. R ⁵ and R ⁶ are bonded to two ortho positions of free bonds. In the above formula (2), the free bond (the two bonding positions of the bonded amine group) is preferably present at the meta-position or the para-position relative to R ¹¹ (linking group), especially for achieving a low thermal expansion coefficient. From the viewpoint of polyimide having a relatively high linearity of the main chain skeleton, it is preferable to exist in the para position. R ⁵ and R ⁶ are bonded to two ortho positions of free bonds. R ¹¹ represents a single bond, -alkyl (alkyl carbon number n is 1~6)-, -fenyl-, -O-, -S-, -SS-, -SO-, -SO ₂ -, A group selected from -CO-, -COO-, -NH-, -CONH-, -CON-alkyl-(alkyl carbon number n is 1 to 6), and -CON-benzyl-. In the above formula (3), the free bond (the two bonding positions of the bonded amine group) is present at the 2-, 3-, 6- or 7-position, and R ⁵ and R ⁶ are bonded to 2 of the free bond. neighbors. In the above formulas (1)~(3), R ⁷ ~R ¹⁰ are linear or branched alkyl groups, alkoxy groups (C series n=1~12) or alkoxyalkyl groups (C n=2~12), preferably an alkyl group with 1~5 carbons, more preferably an alkyl group with 1~3 carbons.

The diamines with dibenzothiophene structure can be, for example: diamines with an alkyl group with 1 to 5 carbons (preferably 1 to 3 carbons) at the ortho-position of the amino group, especially preferably the following formula (4 ) The diamine of the structure shown.

[chemical 4]

In the present invention, the (b-1) aromatic diamine residue (Ar ¹ ) having an alkyl group at the ortho position of the amine group accounts for the proportion of (A) constituting the solvent-soluble polymer in order to increase the crosslink density and achieve a low thermal expansion coefficient. Among all the diamines of imides, it is preferable to contain more than 20 mol%, more than 25 mol%, more than 30 mol%, more than 35 mol%, more preferably more than 40 mol%, and preferably less than 90 mol%, less than 85 mol%, and more preferably The best is below 80mol%. When the aromatic diamine residue (Ar ¹ ) having an alkyl group at the ortho position of the amino group of (b-1) accounts for less than 20 mol% of all diamines, the crosslink density may decrease.

(b-2) Aromatic diamine residue having an indan structure In the basic invention, the aromatic diamine residue having an indan structure (Ar ² in the general formula [II]) may have, for example, the following formula ( 5) or the residue of the amine of the structure shown in (6).

[chemical 5]

In the above formula (5), R ₁ and R ₂ represent an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, or an alkoxyalkyl group with 2 to 12 carbons; R ₁ and R ₂ is preferably bonded to two ortho positions of the free bond (bonding position of the amine group).

[chemical 6]

In the above formula (6), R ₁ , R ₂ and R ₃ represent independent hydrogen atoms or alkyl groups with 1 to 5 carbon atoms, preferably alkyl groups with 1 to 3 carbon atoms. Each R ₄ and each R ₅ respectively represent an independent hydrogen atom or an alkyl group having 1 to 5 carbons, among which a hydrogen atom or a methyl group is preferred. Specific examples of diamines of the formula (6) can include, for example: 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindenane, 6-amino-1 -(4'-Aminophenyl)-1,3,3-trimethylindane. (b-2) The residue of an aromatic diamine having an indan structure is preferably a residue of an aromatic diamine having a phenylindan structure represented by the above formula (6).

In the present invention, (b-2) the aromatic diamine residue (Ar ² ) having an indan structure is capable of increasing the crosslinking density and achieving a low thermal expansion rate, and accounts for (A) constituting the solvent-soluble polyimide Of all the diamines, it is preferably more than 10mol%, more than 15mol%, more than 20mol%, more than 25mol%, more preferably more than 30mol%, and preferably less than 95mol%, less than 90mol%, more preferably 85mol% the following. If it is less than 10 mol%, the crosslink density tends to decrease.

The total diamine containing the above (b-1) aromatic diamine having an alkyl group at the ortho position of the amino group and (b-2) aromatic diamine having an indan structure is used in aromatic diamines in order to achieve a low thermal expansion coefficient. The two amino groups substituted on the ring are preferably substituted at opposite para positions. Two amine groups are substituted for the aromatic diamines at the para-positions opposite to each other, accounting for the total aromatic diamines, preferably containing 30 mol% or more, 40 mol% or more, more preferably 50 mol% or more, and more preferably 90mol% or less, 80mol% or less, more preferably 70mol% or less.

In order to increase the transmittance in the visible light region and achieve both low thermal expansion and solvent solubility, other diamines can be used in combination. Such aromatic diamines may, for example, be aromatic diamines having fluorine atoms or substituents containing fluorine atoms. Representative examples include: 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2-bis[3-(3-aminophenoxy)phenyl ]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3 - Hexafluoropropane and the like.

(A) The solvent-soluble polyimide system may have the repeating unit which consists of an aromatic tetracarboxylic dianhydride residue and a diamine residue other than said general formula [I] and [II].

(A) Synthetic method of solvent-soluble polyimide The synthesis method of the solvent-soluble polyimide can use a known method without special limitation. By using the above-mentioned (a) alicyclic acid dianhydride and (b) diamine in approximately equal amounts, in an organic polar solvent , in the presence of a catalyst and a dehydrating agent, the solvent-soluble polyimide can be synthesized by reacting at 160~200°C for several hours. Organic polar solvents can be used, for example: N-methylpyrrolidone (NMP), γ-butyrolactone, N,N'-dimethylacetamide, N,N'-dimethylformamide, di Methoxyphenone, tetramethylurea, tetrahydrothiophene-1,1-oxide, etc.

(A) The solvent-soluble polyimide-based block copolymer of the present invention can be synthesized by performing a block copolymerization reaction if necessary. For example, it can be produced by using a two-stage batch addition reaction. In the first stage, the polyimide oligomer is first synthesized from the above (a) alicyclic acid dianhydride and (b) diamine, and then in the second stage. In the stage, tetracarboxylic dianhydride and/or aromatic diamine are further added to conduct polycondensation to form block copolymerized polyimide.

啉的二成分系觸媒。如下式所示，隨醯亞胺化的進行會生成水，所生成的水會參予內酯的平衡，成為酸-鹼觸媒而呈現觸媒作用。The catalyst system of the block copolymerization reaction can promote the dehydration imidization reaction by using a two-component system acid-base catalyst utilizing a lactone equilibrium reaction. The specific system can use γ-valerolactone, pyridine or N-methyl

A two-component system catalyst of morphine. As shown in the following formula, water will be generated along with the progress of imidization, and the generated water will participate in the balance of lactone and become an acid-base catalyst to exhibit catalytic effect.

[chemical 7]

啉並被排除於系統外。依此可獲得高純度的聚醯亞胺溶液。The water produced by the imidization reaction is azeotroped by a dehydrating agent such as toluene or xylene that coexists with a polar solvent, and is excluded from the system. If the reaction is over, the water in the solution will be removed, and the acid-base catalyst will become γ-valerolactone, pyridine or N-methyl

phylloline and is excluded from the system. In this way, a high-purity polyimide solution can be obtained.

啉。在160~200℃反應溶液中，草酸鹽或丙二酸鹽成為酸觸媒，促進醯亞胺化反應。所生成的聚醯亞胺溶劑中會殘留觸媒量的草酸或丙二酸。當該聚醯亞胺溶液塗佈於基材後，加熱至200℃以上施行脫溶劑而製膜時，在聚醯亞胺中殘存的草酸或丙二酸，會依如下述式般進行熱分解形成氣體並被排除於系統外。Other two-component catalyst systems can use oxalic acid or malonic acid, and pyridine or N-methyl

phylloline. In the reaction solution at 160~200°C, oxalate or malonate becomes an acid catalyst to promote imidization reaction. Catalytic amounts of oxalic acid or malonic acid remain in the resulting polyimide solvent. When the polyimide solution is coated on the substrate and heated to above 200°C to remove the solvent and form a film, the oxalic acid or malonic acid remaining in the polyimide will be thermally decomposed according to the following formula Gas is formed and is excluded from the system.

[chemical 8]

By the above method, high-purity (A) solvent-soluble polyimide can be obtained. The activity of the oxalic acid-pyridine catalyst is stronger than that of the valerolactone-pyridine catalyst, and it can generate high molecular weight polyimide in a short time.

The term "solvent solubility" in the present invention refers to the organic polar solvent used in the synthesis of polyimide and the solvent used in the film described later, and refers to polyimide that can dissolve more than 5 g in 100 g of solvent. The solvent system here can be exemplified for example: N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylformamide, dimethylacetamide, dimethyloxide, cyclobutane, Polar solvents such as methylurea.

The (A) solvent-soluble polyimide synthesized as above can be used in a solution state of, for example, a solid content of 10 to 30% by weight in the above-mentioned organic polar solvent or the solvent used for the membrane as described later. (A) The molecular weight of the solvent-soluble polyimide is preferably 10,000 to 400,000 in terms of weight average molecular weight in terms of polystyrene. If within this range, good solvent solubility, film physical properties and insulation properties can be achieved. (A) The proper viscosity of the solvent-soluble polyimide is preferably 2-10 Pa·s/25°C when the solid content is 20-40% by weight. Also, the glass transition temperature (Tg) (measured by TMA) of the solvent-soluble polyimide is preferably 200°C or higher, more preferably 250°C or higher.

The concentration of (A) solvent-soluble polyimide in the solution is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. In addition, using the catalyst system formed by the above-mentioned lactone and alkali, the polyimide obtained by direct imidization reaction can be obtained in the form of a solution dissolved in a polar solvent, and the concentration of the polyimide can also be in the range of Within the above preferred range, the prepared polyimide solution is preferably directly used in this state.

The prepared polyimide solution may be further diluted with a diluent as needed. The diluent is a solvent that does not significantly impair solubility, for example: dioxane, dioxolane, N-methyl-2-pyrrolidone, γ-butyrolactone, cyclohexanone, cyclopentanone , propylene glycol monomethyl ether acetate, methyl lactate, anisole, methyl benzoate, ethyl acetate, etc., but are not limited to these.

(B) Diazide compound In the present invention, another essential component of the photosensitive polyimide resin composition is to add (B) a diazide compound. (B) The diazide compound is a photocrosslinking agent for crosslinking (A) solvent-soluble polyimide between polymers, by (B) the diazide compound and (A) ) Solvent-soluble polyimide used in combination can significantly improve exposure and developability.

(B) Diazide compounds can be exemplified by: 4,4'-diazidebenzylidene acetophenone, 2,6-bis(4'-azidobenzylidene)cyclohexanone, 2,6- Bis(4'-azidobenzylidene)-4-methylcyclohexanone, 2,6-bis(4'-azidobenzylidene)-4-ethylcyclohexanone, 2,6-bis( 4'-azidobenzylidene)-4-tertiary amylcyclohexanone, 4,4'-diazidodiphenylene, 4,4'-diazidodiphenyl ether, 4,4'-bis Azide phenylene sulfide, 4,4'-diazide diphenylmethane, etc. Among them, those having a diazidebenzylidene cyclohexanone structure are preferable, and 2,6-bis(4'-azidobenzylidene) is more preferable from the viewpoint of cross-linkability and storage stability. -4-Ethylcyclohexanone.

(B) The diazide compound is contained in the photosensitive polyimide resin composition, preferably 2.0-150 parts by weight, more preferably 5.0-100 parts by weight, relative to 100 parts by weight of (A) solvent-soluble polyimide. Parts by weight, especially 10.0-80 parts by weight. When it is less than 2.0 parts by weight, the crosslink density tends to decrease, and when it exceeds 150 parts by weight, the physical properties of the film tend to decrease. In order to complement the crosslinkability, a diazacyclopropene compound, a maleimide compound, or a bismaleimide compound may be used in combination.

In the photosensitive polyimide resin composition of the present invention containing the above-mentioned (A) solvent-soluble polyimide and the above-mentioned (B) diazide compound, the (A) solvent-soluble polyimide in the exposed part will The photocrosslinking reaction is initiated, and the exposed part remains even after developing treatment, so it can be used as a negative photosensitive polyimide resin composition.

If the photosensitive polyimide resin composition of the present invention is at the low wavelength end, the light penetration is poor, especially in the case of thick film specifications, and the pattern shape tends to show the reverse push-pull that is common in negative solvent development. In order to improve this phenomenon, it is found that different photosensitive cross-linking photosensitive monomers or polymers are also effective. In particular, when it is found that it can be particularly effective as a component of the photosensitive polyimide resin composition of the present invention, it is (C) epoxy resin and (D) photobase with excellent compatibility with the photosensitive polyimide resin composition A combination of generators.

(C) epoxy resin (C) The epoxy resin is not particularly limited, it can be selected according to the reactivity with the photobase generator, or the compatibility with the photosensitive polyimide resin composition, and the epoxy resin can be used for example: phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, epoxy resin containing three 𠯤 skeleton, epoxy resin containing 錀 skeleton, naphthalene type epoxy resin, biphenyl type epoxy resin, Crystalline epoxy resins, bisphenol A type epoxy resins, etc., and these high molecular weight epoxy resins can also be used. The content of (C) epoxy resin in the photosensitive polyimide resin composition is preferably 2-50 parts by weight, more preferably 2-20 parts by weight relative to 100 parts by weight of (A) solvent-soluble polyimide share.

(D) Photobase Generator (D) The photobase generator is a component that generates an anion (base) by ultraviolet irradiation, and is roughly classified into a nonionic type and an ionic type. The light absorption of the non-ionic system will generate primary amines, secondary amines, imidazoles, etc., while the ionic system will generate strong organic bases such as amidine, guanidine, and phosphazene. (D) The photobase generator will generate primary amines and secondary amines in the reaction with (C) epoxy resin, and it is not easy to cause a chain reaction. Therefore, the non-ionic type is better to generate imidazole, and the ionic type is better. Will produce amidine, guanidine and so on.

(D) The photobase generator of this invention can use a commercial item. For example: WPBG-018, WPBG-140, WPBG-266, WPBG-300, WPBG-345, WPBG-027, WPBG-165 (the above are all manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), etc. The (D) photobase generator content in the photosensitive polyimide resin composition is preferably 0.1 to 3% by weight relative to the (C) epoxy resin.

系敏化劑等。光敏化劑含量相對於感光性聚醯亞胺樹脂組成物，較佳係0.05~2重量%左右。 (Photosensitizer) In the photosensitive polyimide resin composition of the present invention, a photosensitizer can be included in order to improve the sensitivity of pattern analysis according to the respective end uses. The best photosensitizers are those that act on the long wavelength (>350nm) side. Photosensitizers can be for example: anthracene sensitizers, oxysulfur

Department of sensitizers, etc. The content of the photosensitizer is preferably about 0.05 to 2% by weight relative to the photosensitive polyimide resin composition.

Specific examples of anthracene sensitizers include: 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene Base anthracene, 9,10-dibutoxyanthracene, 9,10-dipentyloxyanthracene, 9,10-dihexyloxyanthracene, 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-diisopropoxyanthracene, 2-methyl- or 2-ethyl-9,10 - Dibutoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene, etc. As anthracene-based sensitizers, commercially available ones can be used. Examples of commercially available products include "ANTHRACURE UVS-1331", "ANTHRACURE UVS-1101", and "ANTHRACURE UVS-1221" (all of which are manufactured by Kawasaki Chemical Industry Co., Ltd.).

系敏化劑係可舉例如：2-異丙基氧硫

、4-異丙基氧硫

、2,4-二乙基氧硫𠮿

、氯丙氧基氧硫𠮿

等。氧硫

系敏化劑係可使用市售物。市售物係可舉例如：「KAYACURE DETX-S」(日本化藥公司製)、「Speedcure ITX」、「Speedcure DETX」、「Speedcure CPTX」(以上均為LAMBSON公司製)等。Furthermore, oxygen sulfur

The sensitizer system can be for example: 2-isopropyl oxysulfur

, 4-isopropyl oxysulfide

, 2,4-Diethylsulfuric acid 𠮿

, Chloropropoxysulfur

wait. Oxygen sulfur

As a sensitizer, a commercially available thing can be used. Commercially available products include, for example, "KAYACURE DETX-S" (manufactured by Nippon Kayaku Co., Ltd.), "Speedcure ITX", "Speedcure DETX", and "Speedcure CPTX" (all of which are made by LAMBSON Co., Ltd.).

(other additives) In the photosensitive polyimide resin composition of the present invention, modifiers usually added to photosensitive polyimide resin compositions, such as coupling agents, plasticizers, film-forming resins, and surfactants, may also be added. , stabilizer, spectral sensitivity regulator, etc. Especially when the adhesion of polyimide to the substrate is not good, by adding a coupling agent, especially for example: ethylene trimethoxy silane, 3-glycidoxy propyl methyl dimethoxy silane, para Styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, tris(trimethoxysilylpropylisocyanurate), 3 -Ureapropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, hexamethyldimethoxysilane Siloxane, Hexamethyldisilazane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, N-[3-(triethoxysilyl)propyl]phthalein Amino acid, 7-octenyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, 8-Methacryloxyoctyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, 3-trimethoxysilyl-N-( 1,3-Dimethyl-butylene)propylamine, N-(1-phenylethylidene)-3-(triethoxysilyl)-1-propylamine, N-(1-phenylethylidene) )-3-(trimethoxysilyl)-1-propylamine and other silane coupling agents can make the adhesion to the substrate good. In this case, the added amount of the silane coupling agent is preferably 0.1-5% by weight of the photosensitive polyimide resin composition. When the adhesion is not good even with the addition of silane coupling agents, it is effective to use these coupling agents to perform substrate surface treatment.

Furthermore, when using a substrate made of copper or a copper alloy, an azole compound may be blended into the photosensitive polyimide resin composition in order to suppress discoloration of the substrate. Azole compounds can be exemplified as: 1H-benzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 5-carboxy-1H-benzo Triazole, and 4-carboxy-1H-benzotriazole, etc. In this case, the added amount of the azole compound is preferably 0.1 to 1% by weight of the photosensitive polyimide resin composition.

Furthermore, in order to suppress discoloration on copper, a hindered phenolic compound may be blended into the photosensitive polyimide resin composition. Hindered phenolic compounds can be, for example: 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4, 6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3 ,5-tris-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-triethylmethyl-3-hydroxy-2,6-dimethyl Benzyl)-1,3,5-trione-2,4,6-(1H,3H,5H)-trione, etc. In this case, the added amount of the hindered phenol compound is preferably 0.1-2% by weight of the photosensitive polyimide resin composition. In addition, other resins that can be used in combination can be, for example, polyarylate resin, polyethersulfone resin, and the like.

The photosensitive polyimide resin composition system of the present invention can form a solution state suitable for substrates. In this case, solvents that can be used for imidization reactions can be used, such as: N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylformamide, dimethylacetamide , dimethyl sulfide, cyclobutane, tetramethyl urea and other polar solvents.

[Manufacturing method of photosensitive polyimide pattern] Using the photosensitive polyimide resin composition containing the above components, the photosensitive polyimide pattern can be produced on the substrate. Specifically, by including: (1) coating the photosensitive polyimide resin composition of the present invention on a substrate to form a resin layer on the substrate; (2) exposing the resin layer to light. Step; (3) developing the exposed resin layer to form photosensitive polyimide patterns such as insulating materials for electronic parts, passivation films, buffer coating films, and interlayer insulating films for semiconductor packaging; and (4) The step of forming a permanent insulating film by applying heat treatment to the photosensitive polyimide pattern; the photosensitive polyimide pattern can be manufactured.

Hereinafter, typical aspects of each step will be described. (1) A step of forming a resin layer on the substrate by coating the photosensitive resin composition on the substrate: In this step, the photosensitive resin composition of the present invention is coated on substrates such as silicon wafers, metal substrates, ceramic substrates, organic substrates, etc., and then dried if necessary to form a resin layer. The coating method can be a known method for coating photosensitive resin compositions, such as: spin coater, bar coater, knife coater, curtain coater, screen printing machine, etc. The method of cloth, and the method of spray coating using a spray coater, etc.

The coating film formed from the photosensitive resin composition can be dried as needed. As a drying method, methods such as air drying, heat drying in an oven or a hot plate, and vacuum drying can be used. Specifically, when performing air drying or heat drying, the drying may be performed under the conditions of 20-140° C. and 1-30 minutes. On the premise of not hindering various properties of the photosensitive resin composition of the present invention, it is not limited to this range.

(2) The step of exposing the resin layer: In this step, for the resin layer formed in the above step (1), use exposure devices such as contact aligners, projection exposure equipment, steppers, etc., through a patterned mask or grating, or directly use Exposure to an ultraviolet light source or the like is performed. Then, post-exposure baking and/or pre-development baking may be performed according to any combination of temperature and time if necessary for the purpose of increasing photosensitivity. The range of baking conditions is preferably temperature 40~120° C., time 10~240 seconds, but it is not limited to this range as long as the properties of the photosensitive resin composition of the present invention are not hindered.

(3) Developing the exposed resin layer to form a photosensitive polyimide pattern: In this step, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As the development method, a well-known photoresist development method can be used, for example, any method can be selected from spin spray method, flat paddle method, dipping method by ultrasonic treatment, and the like. In addition, after development, for the purpose of adjusting the shape of the photosensitive polyimide pattern, etc., post-development baking may be performed at any combination of temperature and time if necessary.

The developing solution used during development is preferably a good solvent for the photosensitive resin composition, or a combination of the good solvent and the poor solvent. For example, good solvents are preferably N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. Poor solvents are preferably toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate and propylene glycol methyl ether acetate. When the good solvent and the poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent by utilizing the solubility of the polymer in the photosensitive resin composition. In addition, two or more solvents may be used for each of the good solvent and the poor solvent, for example, several kinds may be used in combination.

(4) A step of forming a permanent insulating film by applying heat treatment to the photosensitive polyimide pattern: In this step, the permanent insulating film can be formed by applying heat to the photosensitive polyimide pattern obtained by the above-mentioned development. That is, unlike the polyamic acid formula, since the imidization has been completed, the permanent insulating film can be completed by removing residues such as solvents. The method of heating and hardening can be selected from various methods such as using a heating plate, using an oven, and using a heating-type oven with a temperature program that can be set. Heating can be carried out under sufficient conditions for evaporating the contained solvent, for example, at 150 to 300° C. for 30 minutes to 2 hours. Air can be used as the ambient gas system during heating, and inert gases such as nitrogen and argon can also be used.

The photosensitive polyimide pattern formed as above can be used as an interlayer insulating film, passivation film or surface protection film of semiconductor packages, electronic components, display components or organic multilayer wiring substrates. [Example]

Hereinafter, the examples of the present invention will be described in detail, but the present invention is not limited thereto.

(Synthesis of block copolymerized polyimide) Synthesis Example 1 A cooling pipe equipped with a stirrer, a nitrogen introduction pipe, and a moisture receiver was installed in a glass-made separable three-necked flask. Filling: 14.39g (0.046 moles) of 4,4-oxydiphthalic anhydride (hereinafter referred to as "ODPA"), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter referred to as "CBDA") ) 9.10g (0.046 moles), 3,7-diamino-2,8-dimethyldibenzothiophene (hereinafter referred to as "TSN") (aromatic diamine with an alkyl group in the ortho position of the amino group ) 21.64g (0.079 mol), valerolactone 1.9g (0.019 mol), pyridine 3.0g (0.04 mol), NMP: 125g, and toluene 50g, at room temperature, nitrogen environment, according to 180rpm stirring for 30 minutes Then, the temperature was raised to 180° C. and heated and stirred for 1.5 hours. During the reaction, the toluene-water azeotrope was removed. Cool to room temperature, add: pyromellitic anhydride (hereinafter referred to as "PMDA") 21.32g (0.098 mol), 2,2-bis(trifluoromethyl)benzidine (hereinafter referred to as "TFMB") 34.17g ( 0.107 mol), and NMP: 400 g, after stirring at room temperature for 30 minutes, the temperature was raised to 180° C. and heated and stirred for 1 hour. While removing the water-toluene azeotropic reflux from the system, the reaction was terminated by heating and stirring at 180°C for 5 hours. A block copolymerized polyimide solution with a solid content of 15% by weight was obtained.

Synthesis Example 2 A cooling pipe equipped with a stirrer, a nitrogen introduction pipe, and a moisture receiver was installed in a glass-made separable three-necked flask. Filling: 14.39g (0.046 moles) of 4,4-oxydiphthalic anhydride (hereinafter referred to as "ODPA"), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter referred to as "CBDA") ) 9.10g (0.046 moles), 3,7-diamino-2,8-dimethyldibenzothiophene (hereinafter referred to as "TSN") (aromatic diamine with an alkyl group in the ortho position of the amino group ) 21.64g (0.079 mol), valerolactone 1.9g (0.019 mol), pyridine 3.0g (0.04 mol), NMP: 125g, and toluene 50g, at room temperature, nitrogen environment, according to 180rpm stirring for 30 minutes Then, the temperature was raised to 180° C. and heated and stirred for 1.5 hours. During the reaction, the toluene-water azeotrope was removed. Cool to room temperature, add: ODPA: 15.33g (0.049 mol), CBDA: 9.69g (0.049 mol), 2,2-bis (trifluoromethyl) benzidine (hereinafter referred to as "TFMB") 34.17g ( 0.107 mol), and NMP: 420 g, after stirring at room temperature for 30 minutes, the temperature was raised to 180° C. and heated and stirred for 1 hour. While removing the water-toluene azeotropic reflux from the system, the reaction was terminated by heating and stirring at 180°C for 5 hours. A block copolymerized polyimide solution with a solid content of 15% by weight was obtained.

Synthesis Example 3 A cooling pipe equipped with a stirrer, a nitrogen introduction pipe, and a moisture receiver was installed in a glass-made separable three-necked flask. Loading: 14.39g (0.046 moles) of 4,4-oxydiphthalic anhydride (hereinafter referred to as "ODPA"), 9.75g (0.046 moles) of trans-1,2,3,4-cyclopentane tetracarboxylic dianhydride mole), 3,7-diamino-2,8-dimethyldibenzothiophene (hereinafter referred to as "TSN") (aromatic diamine with an alkyl group adjacent to the amino group) 21.64g (0.079 mol), valerolactone 1.9g (0.019 mol), pyridine 3.0g (0.04 mol), NMP: 130g, and toluene 50g, at room temperature, under nitrogen environment, according to 180rpm after stirring for 30 minutes, the temperature was raised to 180 °C and stirred for another 1.5 hours. During the reaction, the toluene-water azeotrope was removed. Cool to room temperature, add: pyromellitic anhydride (hereinafter referred to as "PMDA") 21.32g (0.098 mol), 2,2-bis(trifluoromethyl)benzidine (hereinafter referred to as "TFMB") 34.17g ( 0.107 mol), and NMP: 400 g, after stirring at room temperature for 30 minutes, the temperature was raised to 180° C. and heated and stirred for 1 hour. While removing the water-toluene azeotropic reflux from the system, the reaction was terminated by heating and stirring at 180°C for 5 hours. A block copolymerized polyimide solution with a solid content of 15% by weight was obtained.

Synthesis Example 4 A cooling pipe equipped with a stirrer, a nitrogen introduction pipe, and a moisture receiver was installed in a glass-made separable three-necked flask. Filling: 14.39g (0.046 moles) of 4,4-oxydiphthalic anhydride (hereinafter referred to as "ODPA"), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter referred to as "CBDA") ) 9.10g (0.046 moles), 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindenane 21.04g (0.079 moles) (containing phenylindenes aromatic diamine), valerolactone 1.9g (0.019 mol), pyridine 3.0g (0.04 mol), NMP: 125g, and toluene 50g, stirred at room temperature and nitrogen environment at 180rpm for 30 minutes , heated to 180°C and then heated and stirred for 1.5 hours. During the reaction, the toluene-water azeotrope was removed. Cool to room temperature, add: pyromellitic anhydride (hereinafter referred to as "PMDA") 21.32g (0.098 mol), 2,2-bis(trifluoromethyl)benzidine (hereinafter referred to as "TFMB") 34.17g ( 0.107 mol), and NMP: 400 g, after stirring at room temperature for 30 minutes, the temperature was raised to 180° C. and heated and stirred for 1 hour. While removing the water-toluene azeotropic reflux from the system, the reaction was terminated by heating and stirring at 180°C for 5 hours. A block copolymerized polyimide solution with a solid content of 15% by weight was obtained.

Synthetic Comparative Example 1 A cooling pipe equipped with a stirrer, a nitrogen introduction pipe, and a moisture receiver was installed in a glass-made separable three-necked flask. Filling: 64.45g (0.2 moles) of 3,4,3',4'-benzophenone tetracarboxylic dianhydride (hereinafter referred to as "BTDA"), 1,3-bis(3-aminophenoxy Base) benzene 29.23g (0.1 mol), valerolactone 1.5g (0.015 mol), pyridine 2.4g (0.03 mol), NMP: 200g, and toluene 30g, stir at 200rpm at room temperature and nitrogen environment After 30 minutes, the temperature was raised to 180° C. and heated and stirred for 1 hour. During the reaction, the toluene-water azeotrope was removed. Cool to room temperature, add: BTDA: 48.33g (0.15 mol), 2,4-diethyl-6-methyl-1,3-phenylenediamine 44.57g (0.25 mol) (in the N- Aromatic diamine having an alkyl group), NMP: 360 g, and toluene 90 g were stirred at room temperature for 30 minutes, then heated to 180° C. and heated and stirred for 1 hour. While removing the azeotropic reflux of water-toluene from the system, the reaction was terminated by heating and stirring at 180° C. for 2 hours and 30 minutes. NMP was added to the obtained product for dilution to obtain a block copolymerized polyimide solution with a solid content of 20% by weight.

(Preparation of photosensitive polyimide resin composition) In the following examples and comparative examples, "parts" means "parts by weight".

Example 1~4 In 500 parts of the block copolymerization polyimide solution (solid content 15% by weight) of Synthesis Examples 1~4, add: 2,6-bis(4'-azidobenzylidene)-4-ethyl 40 parts of cyclohexanone and 0.06 parts of 9,10-dibutoxyanthracene were dissolved by NMP to form a photosensitive resin composition with a solid content of 20 wt%.

Embodiment 5~8 In 500 parts of the block copolymerization polyimide solution (solid content 15% by weight) of Synthesis Examples 1~4, add: 2,6-bis(4'-azidobenzylidene)-4-ethyl 40 parts of cyclohexanone, 0.06 parts of 9,10-dibutoxyanthracene, 0.75 parts of 3-glycidoxypropylmethyldimethoxysilane, 0.075 parts of 5-methyl-1H-benzotriazole , and 1,3,5-tris(4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H, 0.75 part of 3H,5H)-triketone was dissolved by NMP to form a photosensitive resin composition with a solid content of 20%.

Example 9 In 500 parts of the block copolymerization polyimide solution (solid content 15% by weight) of Synthesis Example 1, add: 2,6-bis(4'-azidobenzylidene)-4-ethylcyclohexyl 40 parts of ketone, 0.06 parts of 9,10-dibutoxyanthracene, 0.75 parts of 3-glycidoxypropylmethyldimethoxysilane, 0.075 parts of 5-methyl-1H-benzotriazole, 1 ,3,5-tris(4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H 0.75 parts of )-triketone, 4 parts of TEPIC-VL (trifunctional epoxy: manufactured by Nissan Chemical Industry Co., Ltd.), and 0.075 parts of WPBG (photobase generator: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were dissolved in NMP to form a solid content 20% photosensitive resin composition.

Comparative example 1 In 500 parts of the block copolymerization polyimide solution (solid content 20% by weight) of Synthetic Comparative Example 1, add: 2,6-bis(4'-azidobenzylidene)-4-ethylcyclohexyl 20 parts of ketone, 1 part of 9,10-dibutoxyanthracene, 1 part of 3-glycidoxypropylmethyldimethoxysilane, 0.1 part of 5-methyl-1H-benzotriazole, and 1,3,5-tris(4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H, 1 part of 5H)-triketone, dissolved in methyl benzoate to form a photosensitive resin composition with a solid content of 25%.

(Performance Evaluation of Polyimide Resin Composition) 1. Mechanical Strength, Thermal Expansion Coefficient, and 5% Thermogravimetric Reduction Temperature Mixture-treated resin composition), spin-coat on a 6-inch silicon wafer so that the film thickness after final drying becomes 15-17 μm, perform pre-baking at 90°C for 360 seconds, use a high-pressure mercury lamp, and follow the i-line Converted to 2,500mJ/ ^cm2 full-wavelength exposure, dipped in NMP solution (comparative example is cyclopentanone solution) for 120 seconds, then heated and dried at 250°C (or 200°C) for 90 minutes to obtain a dry resin film. This dried resin film was peeled from the wafer with hydrofluoric acid or the like, and used as a test sample for measuring mechanical strength, thermal expansion coefficient, and 5% thermogravimetric reduction temperature.

2. Adhesive strength Use the dry resin film formed on the silicon wafer fabricated as described above. (1) Use a utility knife to make 11 cuts reaching the base on the test surface to make 100 checkerboards. Using the tool guide, set the kerf spacing to 1mm. (2) Strongly crimp cello tape (registered trademark) on the checkerboard part, then tear off the end of the tape at a 45° angle, and then compare and evaluate the checkerboard state with the standard diagram. Determine the normal state and the adhesive strength after 240 hours under HAST (80°C×85%RH).

3. Residual film rate The resin compositions obtained in the above-mentioned examples and comparative examples (Examples 1-3 are resin compositions treated with a silane coupling agent in advance) were placed on a 6-inch silicon wafer according to the final dried film Spin-coating was performed in the thickness of 5~7μm and 10~12μm, and the thickness (t ₁ ) was measured with a film thickness meter after prebaking at 90°C for 240 seconds and 90°C for 300 seconds. Next, use a high-pressure mercury lamp to perform full-wavelength exposure at 1,000 (or 2,500) mJ/cm ² according to the i-line conversion, immerse in NMP solution (comparative example is cyclopentanone solution) for 120 seconds, and measure the thickness (t ₂ ). It is further carried out at 250°C (or 200°C) for 90 minutes, and then the thickness (t ₃ ) is measured with a film thickness gauge. From these values, t ₂ /t _{1 ,} t ₃ /t ₁ , and t ₃ /t ₂ were calculated and set as the residual film rate.

4. Exposure and developability pattern evaluation was carried out in accordance with the following method. (1) Resolution The resin compositions obtained in the above-mentioned Examples and Comparative Examples (Examples 1-3 are resin compositions treated with a silane coupling agent in advance) were dropped onto a 6-inch silicon wafer and rotated for 30 seconds. Coating was followed by a 240 second prebake using a 90°C hot plate. At this time, the coating rotation is adjusted so that the film thickness after baking becomes about 6 to 8 μm. Next, exposure is performed using a high-pressure mercury lamp. The exposure dose measured by the i-line was 1,000 mJ/cm ² . Then, development was performed using an NMP solution (a comparative example is a cyclopentanone solution), followed by rinsing, followed by heat drying at 250° C. (or 200° C.) for 90 minutes. The smallest resolution among L/S=5/5, 10/10, 15/15, 20/20, 30/30, 50/50μm, square through-hole pattern 10, 15, 20, 30, 40, 50μm, Set to resolution.

(2) Residue and cracks on the edge of the pattern Patterning was performed in the same manner as in (1) above, and first, the film surface after development was visually observed for abnormalities. Next, observe the 15 μm square through-hole pattern with an optical microscope, and if there are cracks at the corners of the pattern, it will be judged as having cracks. Also, the edge of the pattern of L/S=15/15 was observed, and when there was residual development, it was judged as having residue.

The evaluation results of the resin compositions obtained in the above-mentioned examples and comparative examples are shown in Table 1 and Table 2 below.

[Table 1] project Example 1 Example 2 Example 3 Example 4 Example 5 polyimide Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 1 (a) Acid dianhydride/full acid mol% twenty four 50 twenty four twenty four twenty four (b) diamine/fullamine mol% 42 42 42 42 42 P-site (b) diamine/full amine mol% 58 58 58 58 58 (d) Diazide compound/polyimide share 53 53 53 53 53 drying temperature °C 250 250 250 250 250 Tg (TMA) °C 280 260 270 290 280 Coefficient of Thermal Expansion (TMA) ppm/°C 18 30 19 30 18 5% thermal weight reduction temperature °C 361 350 355 370 361 Mechanical strength modulus of elasticity GPa 4.7 4.0 4.6 4.7 4.7 extend % 5.2 8.1 5.3 5.0 5.2 breaking strength MPa 173 140 170 165 173 Adhesive strength A - 100/100 100/100 100/100 100/100 100/100 HAST - 100/100 100/100 100/100 100/100 100/100 Residual film rate t ₂ /t _{1 (6μm)(11μm)} % 99 99 99 99 99 99 99 99 99 99 t ₃ /t _{1 (6μm)(11μm)} % 90 81 90 81 90 81 90 81 91 82 t ₃ /t _{2 (6μm)(11μm)} % 93 84 93 84 93 84 93 84 94 85 Exposure developability resolution - L/S=10/10 L/S=10/10 L/S=10/10 L/S=10/10 L/S=10/10 15μm 15μm 15μm 15μm 10μm Pattern edge residual - none none none none none crack - none none none none none

[Table 2] project Example 6 Example 7 Example 8 Example 9 Comparative example 1 polyimide Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 1 Synthetic Comparative Example 1 (a) Acid dianhydride/full acid mol% 50 twenty four twenty four twenty four 0 (b) diamine/fullamine mol% 42 42 42 42 71 P-site (b) diamine/full amine mol% 58 58 58 58 0 (d) Diazide compound/polyimide share 53 53 53 53 20 drying temperature °C 250 250 250 250 200 Tg (TMA) °C 260 270 290 270 287 Coefficient of Thermal Expansion (TMA) ppm/°C 30 19 30 19 56 5% thermal weight reduction temperature °C 350 355 370 355 390 Mechanical strength modulus of elasticity GPa 4.0 4.6 4.7 4.5 2.5 extend % 8.1 5.3 5.0 5.0 12.0 Breaking strength MPa 140 170 165 170 115 Adhesive strength A - 100/100 100/100 100/100 100/100 100/100 HAST - 100/100 100/100 100/100 100/100 100/100 Residual film rate t ₂ /t _{1 (6μm)(11μm)} % 99 99 99 99 99 99 99 99 99 99 t ₃ /t _{1 (6μm)(11μm)} % 91 82 91 82 91 82 90 89 92 83 t ₃ /t _{2 (6μm)(11μm)} % 94 85 94 85 94 85 93 91 95 85 Exposure developability resolution - L/S=10/10 L/S=10/10 L/S=10/10 L/S=10/10 L/S=10/10 10μm 10μm 10μm 10μm 15μm Pattern edge residual - none none none none none crack - none none none none none

From the results of the above Table 1 and Table 2, it can be seen that the comparative example using a polyimide containing only aromatic acid dianhydride residues without acid dianhydride residues (a) alicyclic acid dianhydride residues The composition of 1 has a coefficient of thermal expansion of 56ppm/°C, a modulus of elasticity of 2.5GPa, and a breaking strength of 115MPa. In contrast, the compositions of Examples 1 to 9 using polyimides having (a) alicyclic acid dianhydride residues The composition can achieve a thermal expansion coefficient of 18~30ppm/℃, an elastic modulus of 4.0~4.7GPa, and a breaking strength of 140~173MPa. In addition, it is known that the compositions of Examples 1 to 9 maintain high adhesive strength, high residual film rate, and good exposure and developability. From these results, it was found that a composition containing: a solvent-soluble polyimide having (a) an alicyclic acid dianhydride residue and (b) a specific diamine residue in the same repeating unit, and a diazide compound, It is soluble in the developing solution during development and insoluble in the developing solution after photocrosslinking. It can achieve good film physical properties and high sensitivity, and has a low thermal expansion coefficient and excellent mechanical strength. (industrial availability)

The photosensitive polyimide resin composition of the present invention is soluble in the developer solution during development and insoluble in the developer solution after photocrosslinking, can achieve good film physical properties and high sensitivity, and has low thermal expansion coefficient and high mechanical strength. Excellent, so it can be effectively used in electronic components such as semiconductor packages such as FO-WLP, FO-PLP, and WLP, thin-film magnetic heads, thin-film inductors, and common-mode choke coils, TFT liquid crystal elements, and color filter elements. , Organic EL elements and other display elements and the manufacture of organic multilayer wiring substrates, etc., are quite suitable for the field of photosensitive materials.

Claims (12)

A photosensitive polyimide resin composition, which is a photosensitive polyimide resin composition containing solvent-soluble polyimide and a diazide compound as essential components, wherein the above-mentioned solvent-soluble polyimide is in the same The repeating unit has: (a) an alicyclic acid dianhydride residue, and (b) an aromatic diamine with an alkyl group at the ortho position of the amine group, and an aromatic diamine with an indan structure. A block copolymer of residues of at least one diamine selected among them. The resin composition according to claim 1, wherein the solvent-soluble polyimide has (b) the residue of an aromatic diamine having an alkyl group at the ortho position of the amine group, and the two amine groups of the aromatic diamine Department of mutual existence in the para-position of the benzene ring. The resin composition according to claim 1, wherein the above-mentioned solvent-soluble polyimide has (b) residues of aromatic diamines having an alkyl group at the ortho-position of the amine groups, and the aromatic diamines have a linking group The two linked benzene rings and the two amine groups of the aromatic diamine exist at the para position with respect to the linking group. The resin composition according to any one of claims 1 to 3, wherein the (a) alicyclic acid dianhydride residue is a residue of 1,2,3,4-cyclobutanetetracarboxylic dianhydride. The resin composition according to any one of claims 1 to 4, wherein the residue of at least one diamine in (b) is 3,7-diamino-2,8-dimethyldibenzothiophene residues. The resin composition according to any one of claims 1 to 5, wherein the diazide compound is 2,6-bis(4'-azidobenzylidene)-4-ethylcyclohexanone. The resin composition according to any one of claims 1 to 6, wherein the content of the diazide compound is 5.0 to 100 parts by weight relative to 100 parts by weight of the solvent-soluble polyimide. The resin composition according to any one of claims 1 to 7, wherein the thermal expansion coefficient of the photosensitive polyimide resin composition is 20 ppm/°C or less. The resin composition according to any one of claims 1 to 8, wherein the photosensitive polyimide resin composition further contains an epoxy resin and a photobase generator. The resin composition according to any one of claims 1 to 9, wherein the photosensitive polyimide resin composition is a negative solvent developing composition. A method for forming a pattern, comprising exposing the substrate coated with the resin composition according to any one of claims 1 to 10 by ultraviolet radiation, and then developing and removing the unexposed portion. A semiconductor package, a magnetic element, a display element, or an organic multilayer wiring substrate, having an interlayer insulating film, a passivation film, or a surface protection film formed using the resin composition according to any one of claims 1 to 10.