Photosensitive resin composition, varnish, cured product, and semiconductor device

Abstract

A photosensitive resin composition containing a polyimide (A) having a carboxy group in a constitutional unit, a polymerization initiator (B), and a polyfunctional (meth)acrylate (C).

Description

Photosensitive resin composition, varnish, cured product, and semiconductor device

[0001] The present invention relates to a photosensitive resin composition, varnish, cured product, and semiconductor device.

[0002] Polyimide is widely used as a thin film for electronic materials such as semiconductor protective materials, insulating materials, and color filters due to its high mechanical strength, heat resistance, insulating properties, and solvent resistance.

[0003] Patent Document 1 describes a photosensitive adhesive composition that has excellent pattern-forming properties with an alkaline developer and sufficient re-adhesion after exposure, comprising (A) an alkali-soluble resin, (B) an epoxy resin, (C) a radiation-polymerizable compound, and (D) a photopolymerization initiator, wherein the glass transition temperature of the alkali-soluble resin (A) is 150°C or lower, and the epoxy resin (B) comprises (B1) a trifunctional or more functional component and (B2) a liquid component, and part or all of the liquid component (B2) may also be the trifunctional or more functional component (B1).

[0004] Japanese Patent Publication No. 2009-221453

[0005] The present invention provides a photosensitive resin composition with improved chemical resistance after curing.

[0006] The present inventors have discovered that the chemical resistance of a photosensitive resin composition after curing can be improved by using a photosensitive resin composition comprising a polyimide having a carboxyl group in its constituent units, a polymerization initiator, and a polyfunctional (meth)acrylate, and have completed the present invention.

[0007] In other words, the present invention provides the following photosensitive resin composition, varnish, cured product, and semiconductor device.

[0008] [1] A photosensitive resin composition comprising a polyimide (A) having a carboxyl group in its constituent units, a polymerization initiator (B), and a polyfunctional (meth)acrylate (C). [2] The photosensitive resin composition according to [1], wherein the polyimide (A) comprises a constituent unit represented by the following general formula (1). (In general formula (1), X represents a constituent unit (X) which is a divalent organic group, and Y represents a constituent unit (Y) which is a tetravalent organic group, and the constituent unit (X) includes a constituent unit (X-1) which has a carboxyl group.) [3] The photosensitive resin composition according to [2], wherein the constituent unit (X-1) includes a constituent unit represented by the following general formula (x1). (In general formula (x1), Z １ (wherein represents a single bond, an oxygen atom, or a divalent organic group, and * represents a bond.) [4] The photosensitive resin composition according to [2] or [3], wherein the constituent unit (X-1) comprises a constituent unit represented by the following general formula (x2). (In the general formula (x2), * represents a bond.) [5] The photosensitive resin composition according to any one of [2] to [4], wherein the constituent unit (X-1) comprises a constituent unit derived from at least one diamine selected from the group consisting of 5,5'-methylenebis(2-aminobenzoic acid), 1,2-bis(4-amino-2-carboxyphenoxy)benzene, 1,3-bis(4-amino-2-carboxyphenoxy)benzene, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 5-amino-2-(4-aminophenoxy)benzoic acid, 3,5-diaminobenzoic acid, 3,5-diamino-4-methoxybenzoic acid, 3,5-bis(4-aminophenoxy)benzoic acid, N-bis(4-aminophenyl)-4-carboxyaniline, and 4,4'-diamino-N-(4-carboxyphenyl)benzanilide. [6] The photosensitive resin composition according to any one of [2] to [5], wherein the ratio of the constituent unit (X-1) in the constituent unit (X) is 1 mol% or more and 50 mol% or less. [7] The photosensitive resin composition according to any one of [2] to [6], wherein the constituent unit (X) further comprises a constituent unit represented by the following general formula (x3). (In general formula (x3), Z ２ R represents an alkylene group. １Each of these independently represents an alkyl group having 1 to 4 carbon atoms, and * represents a bond.) [8] The photosensitive resin composition according to [7], wherein the ratio of the constituent unit represented by the general formula (x3) in the constituent unit (X) is 50 mol% or more and 99 mol% or less. [9] The photosensitive resin composition according to any one of [2] to [8], wherein the constituent unit (X) further comprises a constituent unit represented by the following general formula (x4). (In the general formula (x4), * represents a bonding bond.)

[10] The photosensitive resin composition according to any one of [2] to [9], wherein the constituent unit (Y) comprises a constituent unit represented by the following formula (y11). (In formula (y11), * represents a bond.)

[11] The photosensitive resin composition according to

[10] , wherein the ratio of the constituent unit represented by formula (y11) in the constituent unit (Y) is 50 mol% or more and 100 mol% or less.

[12] The photosensitive resin composition according to any one of [1] to

[11] , wherein the polyfunctional (meth)acrylate (C) comprises a trifunctional or more (meth)acrylate.

[13] The photosensitive resin composition according to

[12] , wherein the content of the trifunctional or more (meth)acrylate per 100 parts by mass of the polyimide (A) is 100 parts by mass or less.

[14] The photosensitive resin composition according to any one of [1] to

[13] , further comprising an epoxy compound (D).

[15] The photosensitive resin composition according to any one of [1] to

[14] , further comprising a silane coupling agent (E).

[16] The photosensitive resin composition according to

[15] , wherein the silane coupling agent (E) comprises (meth)acrylsilane.

[17] The photosensitive resin composition according to any one of [1] to

[16] , wherein the cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours by the following method has a breaking elongation of more than 23% at 23°C. (Method) A test piece (50 mm × 7 mm × 10 μm thick) is cut from the cured product. In accordance with JIS K 7197:2012, the breaking elongation from the initial position of the test piece to the breaking point is measured using a thermomechanical analyzer under the conditions of air atmosphere, tensile mode, chuck distance of 20 mm, tensile speed of 5 mm / min, and 23°C. The average value of the values ​​obtained by measuring for 10 test pieces is taken as the breaking elongation.

[18] The photosensitive resin composition according to any one of [1] to

[17] , wherein the Δt obtained by the following method is greater than -2.0 μm. (Method) The photosensitive resin composition is spin-coated onto an 8-inch silicon wafer, and then heated at 110°C for 3 minutes to dry the photosensitive resin composition. The spin-coating is performed so that the film thickness after drying is 10 μm. Then, a high-pressure mercury lamp is used to heat the wafer at 600 mJ / cm². ２is exposed, and heated at 230°C for 2 hours in a nitrogen atmosphere to be cured. Using a dicing saw, a test piece with a silicon wafer (20 mm × 20 mm × 10 μm thick) is cut out. The test piece is immersed in dimethyl sulfoxide containing 2.38 mass% of tetramethylammonium hydroxide (TMAH) at 50°C for 20 minutes. Next, after washing with isopropanol and drying by air blowing, heating is performed on a hot plate at 170°C for 5 minutes to obtain the test piece with a silicon wafer after the chemical resistance test. Using an optical interference film thickness measuring device, the film thickness t of the test piece after the chemical resistance test is measured, and the film thickness difference Δt before and after the chemical resistance test is calculated based on the following formula. Δt [μm] = t [μm] − 10 μm

[19] The glass transition temperature (Tg ＤＭＡ ) of a cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours, which is measured by dynamic viscoelasticity measurement (DMA) in accordance with JIS K 7244-4:1999, is 280°C or higher. The photosensitive resin composition according to any one of [1] to

[18] .

[20] The glass transition temperature (Tg ＤＭＡ ) of a cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours, which is measured by dynamic viscoelasticity measurement (DMA) in accordance with JIS K 7244-4:1999, is 280°C or higher and 500°C or lower. The photosensitive resin composition according to

[19] .

[21] The glass transition temperature (Tg ＴＭＡ ) of a cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours, which is measured by thermomechanical analysis (TMA) in accordance with JIS K 7197:2012, is 240°C or higher. The photosensitive resin composition according to any one of [1] to

[20] .

[22] The glass transition temperature of a cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours, which is measured by dynamic viscoelasticity measurement (DMA) in accordance with JIS K 7244-4:1999, is defined as Tg ＤＭＡ , and the glass transition temperature of a cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours, which is measured by thermomechanical analysis (TMA) in accordance with JIS K 7197:2012, is defined as Tg ＴＭＡ , then Tg ＤＭＡ −Tg ＴＭＡ[1] to

[21] any one of the following photosensitive resin compositions, wherein the temperature is 40°C or higher.

[23] The photosensitive resin composition according to any one of the following, wherein the mean coefficient of linear expansion (CTE) in the range of 50°C to 100°C is 65 ppm / °C or less, as measured by thermomechanical analysis (TMA) in accordance with JIS K 7197:2012, of the cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours.

[24] The photosensitive resin composition according to any one of the following, wherein the storage modulus at 23°C is 2.0 GPa or more and 20.0 GPa or less, as measured by dynamic viscoelasticity measurement (DMA) in accordance with JIS K 7244-4:1999.

[25] The photosensitive resin composition according to any one of the following, wherein the temperature is 40°C or higher. [1] to

[24] any one of the following, wherein the temperature is 40°C or higher.

[26] The photosensitive resin composition according to any one of the following, wherein the temperature is 40°C or higher.

[27] The photosensitive resin composition according to any one of the following, wherein the temperature is 40°C or higher.

[28] The photosensitive resin composition according to any one of the following, wherein the temperature is 40°C or higher.

[299] The photosensitive resin composition according to any one of the following, wherein the temperature is 40°C or higher.

[20]

[26] A varnish comprising a photosensitive resin composition according to any one of [1] to

[25] and a solvent.

[27] A cured product of a photosensitive resin composition according to any one of [1] to

[25] .

[28] A semiconductor device comprising the cured product according to

[27] .

[29] The semiconductor device according to

[28] , comprising an interlayer insulating film, a resin film containing the cured product on the interlayer insulating film, and rewiring embedded in the resin film.

[0009] According to the present invention, a photosensitive resin composition with improved chemical resistance after curing can be provided.

[0010] This is a schematic cross-sectional view illustrating an example of the structure of the semiconductor device according to this embodiment.

[0011] Embodiments of the present invention will be described below. In this specification, "A to B" indicating a numerical range means A or greater and B or less unless otherwise specified. In this specification, the notation "(meth)acrylate" represents a concept that encompasses both acrylate and methacrylate. The same applies to similar notations such as "(meth)acrylic". Also, the figures are schematic diagrams and do not correspond to actual dimensional ratios.

[0012] (Photosensitive resin composition) The photosensitive resin composition of the present embodiment includes a polyimide (A) having a carboxy group in a constitutional unit, a polymerization initiator (B), and a polyfunctional (meth)acrylate (C). The present inventors have found that a photosensitive resin composition comprising a polyimide having a carboxy group in a constitutional unit, a polymerization initiator, and a polyfunctional (meth)acrylate can improve the chemical resistance of the photosensitive resin composition after curing. According to the photosensitive resin composition of the present embodiment, the chemical resistance after curing can be improved. Although such a mechanism is not necessarily clear, according to studies by the present inventors, it is considered that the chemical resistance after curing can be improved because the photosensitive resin composition contains the polyimide (A) having a carboxy group in a constitutional unit.

[0013] (Polyimide (A)) In the present embodiment, the polyimide (A) may include a constitutional unit represented by the following general formula (1).

[0014]

[0015] In general formula (1), X represents a constitutional unit (X) that is a divalent organic group, Y represents a constitutional unit (Y) that is a tetravalent organic group, and the constitutional unit (X) includes a constitutional unit (X-1) having a carboxy group.

[0016] The constitutional unit (X-1) preferably includes a constitutional unit represented by the following general formula (x1). This enables further improvement of the chemical resistance of the photosensitive resin composition after curing.

[0017]

[0018] In general formula (x1), Z １ represents a single bond, an oxygen atom, or a divalent organic group, and * represents a binding site.

[0019] Z １ may be a single bond or a divalent organic group, may be a single bond or an alkylene group, may be a single bond or a methylene group, and may be a methylene group.

[0020] The constituent unit represented by the general formula (x1) may include, for example, the constituent unit represented by the following formula (x11) (a constituent unit derived from 5,5'-methylenebis(2-aminobenzoic acid)).

[0021]

[0022] The constituent unit (X-1) may include the constituent unit represented by the following general formula (x2).

[0023]

[0024] In the general formula (x²), * represents a bond.

[0025] The constituent unit represented by the general formula (x2) may include, for example, the constituent unit represented by the following formula (x21) (a constituent unit derived from 3,5-diaminobenzoic acid).

[0026]

[0027] The constituent unit (X-1) is derived from at least one diamine selected from the group consisting of 5,5'-methylenebis(2-aminobenzoic acid), 1,2-bis(4-amino-2-carboxyphenoxy)benzene, 1,3-bis(4-amino-2-carboxyphenoxy)benzene, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 5-amino-2-(4-aminophenoxy)benzoic acid, 3,5-diaminobenzoic acid, 3,5-diamino-4-methoxybenzoic acid, 3,5-bis(4-aminophenoxy)benzoic acid, N-bis(4-aminophenyl)-4-carboxyaniline, and 4,4'-diamino-N-(4-carboxyphenyl)benzanilide. It may contain constituent units, and may contain constituent units derived from at least one diamine selected from the group consisting of 5,5'-methylenebis(2-aminobenzoic acid), 1,2-bis(4-amino-2-carboxyphenoxy)benzene, 1,3-bis(4-amino-2-carboxyphenoxy)benzene, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, and 3,5-diaminobenzoic acid; it may contain constituent units derived from at least one diamine selected from the group consisting of 5,5'-methylenebis(2-aminobenzoic acid) and 3,5-diaminobenzoic acid; and may contain constituent units derived from 5,5'-methylenebis(2-aminobenzoic acid).

[0028] The ratio of constituent unit (X-1) to constituent unit (X) is preferably 1 mol% to 50 mol%, more preferably 2 mol% to 40 mol%, and even more preferably 5 mol% to 30 mol%. By setting the ratio of constituent unit (X-1) to constituent unit (X) within the above range, the chemical resistance of the photosensitive resin composition after curing can be further improved, and the balance with other physical properties can be improved.

[0029] The constituent unit (X) preferably further comprises a constituent unit represented by the following general formula (x3). This improves the tensile elongation of the photosensitive resin composition after curing and the solvent solubility of the photosensitive resin composition.

[0030]

[0031] In general formula (x3), Z ２R represents an alkylene group. １ Each of these independently represents an alkyl group having 1 to 4 carbon atoms, and * represents a bond.

[0032] Z ２ It may be a methylene group.

[0033] R １ It may contain at least one group selected from the group consisting of methyl groups and ethyl groups.

[0034] The ratio of the constituent unit represented by the general formula (x3) in the constituent unit (X) is preferably 50 mol% to 99 mol%, more preferably 60 mol% to 98 mol%, and even more preferably 70 mol% to 95 mol%. By setting the ratio of the constituent unit represented by the general formula (x3) in the constituent unit (X) within the above range, the balance between the tensile elongation after curing and other physical properties of the photosensitive resin composition can be improved.

[0035] The constituent unit (X) preferably further comprises a constituent unit represented by the following general formula (x4). This improves the solvent solubility of polyimide (A).

[0036]

[0037] In the general formula (x4), * represents a bond.

[0038] The constituent unit represented by the general formula (x4) may include, for example, the constituent unit represented by the following formula (x41) (a constituent unit derived from 1,3-bis(3-aminophenoxy)benzene).

[0039]

[0040] The ratio of the constituent unit represented by the general formula (x4) in the constituent unit (X) may be 1 mol% or more and 25 mol% or less, 2 mol% or more and 20 mol% or less, or 5 mol% or more and 15 mol% or less.

[0041] The constituent unit (X) may include at least one selected from the group consisting of constituent units represented by the following general formula (x5), constituent units represented by the following general formula (x6), and constituent units represented by the following general formula (x7), and may include at least one selected from the group consisting of constituent units represented by the following general formula (x6) and constituent units represented by the following general formula (x7).

[0042]

[0043] In general formula (x5), R ２ Each of the above independently represents an alkyl group having 1 to 4 carbon atoms, a and b each independently represent an integer from 0 to 3, and * represents a bond.

[0044]

[0045] In general formula (x6), R ３ Each of the following independently represents an alkyl group having 1 to 4 carbon atoms, c and d independently represent integers from 0 to 4, and * represents a bond.

[0046]

[0047] In general formula (x7), R ４ Each of the following independently represents an alkyl group having 1 to 4 carbon atoms, e and f independently represent integers from 0 to 4, and * represents a bond.

[0048] In general formula (x5), R ２ Each of these independently represents an alkyl group having 1 to 4 carbon atoms. ２ It may contain at least one group selected from the group consisting of a methyl group, an ethyl group, an isopropyl group, an n-propyl group, and a tert-butyl group, or it may contain at least one group selected from the group consisting of a methyl group and an ethyl group, or it may contain a methyl group. In general formula (x5), a and b each independently represent an integer from 0 to 3. a and b each independently may be 0 or 1, or they may be 1.

[0049] The constituent unit represented by the general formula (x5) may include, for example, the constituent unit represented by the following formula (x51).

[0050]

[0051] In general formula (x6), R ３ Each of these independently represents an alkyl group having 1 to 4 carbon atoms. ３ c may contain at least one group selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, and tert-butyl groups, or it may contain at least one group selected from the group consisting of methyl and ethyl groups, or it may contain a methyl group. In general formula (x6), c and d each independently represent an integer from 0 to 4. c and d each independently may be an integer from 0 to 2, or they may be 0 or 1, or they may be 1.

[0052] The constituent unit represented by the general formula (x6) may include, for example, at least one selected from the group consisting of the constituent unit represented by the following formula (x61) and the constituent unit represented by the following formula (x62).

[0053]

[0054]

[0055] In general formula (x7), R ４ Each of these independently represents an alkyl group having 1 to 4 carbon atoms. ４ It may contain at least one group selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, and tert-butyl groups, or it may contain at least one group selected from the group consisting of methyl and ethyl groups, or it may contain a methyl group. In general formula (x7), e and f each independently represent an integer from 0 to 4. e and f each independently may be 0 or 1, or they may be 0.

[0056] The constituent unit represented by the general formula (x7) may include, for example, the constituent unit represented by the following formula (x71).

[0057]

[0058] The constituent unit (Y) preferably includes a constituent unit represented by the following formula (y11). This improves the tensile elongation of the photosensitive resin composition after curing.

[0059]

[0060] In equation (y11), * represents a bond.

[0061] The ratio of the constituent units represented by formula (y11) in the constituent unit (Y) is preferably 50 mol% to 100 mol%, more preferably 75 mol% to 100 mol%, and even more preferably 90 mol% to 100 mol%. By setting the ratio of the constituent units represented by formula (y11) in the constituent unit (Y) within the above range, the tensile elongation of the photosensitive resin composition after curing can be improved.

[0062] The constituent unit (Y) preferably includes a constituent unit represented by the following general formula (y2). This improves the elastic modulus and tensile elongation of the photosensitive resin composition after curing and reduces the mean coefficient of linear expansion (CTE).

[0063]

[0064] In general formula (y2), R ５ Each of these independently represents an alkyl group having 1 to 4 carbon atoms, Z ３ represents a single bond or a divalent organic group, g and h each independently represent an integer from 0 to 4, and * represents a bond.

[0065] In general formula (y2), R ５ Each of these independently represents an alkyl group having 1 to 4 carbon atoms. ５ Preferably, it comprises at least one group selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, and tert-butyl groups, more preferably at least one group selected from the group consisting of methyl, isopropyl, and tert-butyl groups, and even more preferably a methyl group. This makes it possible to reduce the mean coefficient of linear expansion (CTE) of the photosensitive resin composition after curing.

[0066] In the general formula (y²), g and h each independently represent integers from 0 to 4. g and h may also independently be integers from 0 to 3, or they may be 3.

[0067] In general formula (y2), Z ３ Z represents a single bond or a divalent organic group. ３ Preferably, the component is a single bond, a cyclohexane-1,1-diyl group, a phenylene group, or a biphenyl-4,4'-diyl group, more preferably a single bond or a cyclohexane-1,1-diyl group, and even more preferably a single bond. This reduces the mean coefficient of linear expansion (CTE) of the photosensitive resin composition after curing.

[0068] The constituent unit represented by the general formula (y2) preferably includes the constituent unit represented by the following formula (y21). This improves the elastic modulus and tensile elongation of the photosensitive resin composition after curing and reduces the mean coefficient of linear expansion (CTE).

[0069]

[0070] The constituent unit (Y) may include the constituent unit represented by the following general formula (y3).

[0071]

[0072] In general formula (y3), Z ４ This is a single bond, -C(=O)-, a divalent group represented by the following formula, or -SO ２ The dash (-) represents a hyphen (*), and the asterisk (*) represents a combination.

[0073]

[0074] In the above formula, * represents a bond.

[0075] Z ４ This may be a single bond, a -C(=O)-, or a divalent group represented by the above formula, or it may be a -C(=O)-.

[0076] The constituent unit represented by the general formula (y3) may include, for example, at least one selected from the group consisting of the constituent unit represented by the following formula (y31), the constituent unit represented by the following formula (y32), and the constituent unit represented by the following formula (y33), and may also include the constituent unit represented by the following formula (y31).

[0077]

[0078]

[0079]

[0080] (Polymerization initiator (B)) The photosensitive resin composition of this embodiment contains polymerization initiator (B).

[0081] The content of polymerization initiator (B) per 100 parts by mass of polyimide (A) may be 1 part by mass or more and 50 parts by mass or less, 5 parts by mass or more and 40 parts by mass or less, or 10 parts by mass or more and 30 parts by mass or less.

[0082] The polymerization initiator (B) preferably includes a photoradical generator. This allows the photosensitive resin composition to be cured by exposure.

[0083] Photoradical generators include oxime ester-based photoradical generators such as 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyl oxime) and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetyl oxime); alkylphenone-based photoradical generators such as 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, and 2-benzyl-2-(dimethylamino)-4'-morpholinobtyrophenone; and, It may contain at least one selected from the group consisting of benzophenone and benzophenone-based photoradical generators such as 4,4'-bis(dimethylamino)benzophenone, and may also contain an oxime ester-based photoradical generator, and may also contain 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyloxime).

[0084] The amount of photoradical generator per 100 parts by mass of polyimide (A) may be 1 part by mass or more and 30 parts by mass or 5 parts by mass or more and 20 parts by mass.

[0085] The polymerization initiator (B) preferably includes a thermal radical generator. This allows the photosensitive resin composition to be cured by heating.

[0086] The thermal radical generator may contain organic peroxides such as dicumyl peroxide, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, and tert-butyl=2-ethylperoxyhexanoate, and may also contain dicumyl peroxide.

[0087] The amount of thermal radical generator per 100 parts by mass of polyimide (A) may be 1 part by mass or more and 30 parts by mass or 5 parts by mass or more and 20 parts by mass.

[0088] (Polyfunctional (meth)acrylate (C)) The photosensitive resin composition of this embodiment contains polyfunctional (meth)acrylate (C).

[0089] The polyfunctional (meth)acrylate (C) includes, for example, at least one selected from the group consisting of: difunctional (meth)acrylates such as polyalkylene glycol di(meth)acrylate and alkyl di(meth)acrylate; trifunctional (meth)acrylates such as tris(2-(meth)acryloyloxyethyl) isocyanurate, optionally alkoxylated pentaerythritol tri(meth)acrylate, optionally alkoxylated trimethylolpropane tri(meth)acrylate and alkoxylated glycerin tri(meth)acrylate; tetrafunctional (meth)acrylates such as optionally alkoxylated pentaerythritol tetra(meth)acrylate and optionally alkoxylated ditrimethylolpropane tetra(meth)acrylate; and quintafunctional or more (meth)acrylates such as optionally alkoxylated dipentaerythritol penta(meth)acrylate and optionally alkoxylated dipentaerythritol hexa(meth)acrylate.

[0090] The content of polyfunctional (meth)acrylate (C) per 100 parts by mass of polyimide (A) is preferably 10 parts by mass or more and 150 parts by mass or less, more preferably 15 parts by mass or more and 100 parts by mass or less, and even more preferably 20 parts by mass or more and 75 parts by mass or less. By setting the content of polyfunctional (meth)acrylate (C) per 100 parts by mass of polyimide (A) within the above range, the balance between the photosensitivity of the photosensitive resin composition and the mechanical properties of the photosensitive resin composition after curing can be improved.

[0091] The polyfunctional (meth)acrylate (C) preferably comprises a trifunctional (meth)acrylate, more preferably a pentafunctional (meth)acrylate, and even more preferably at least one selected from the group consisting of dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate. This further improves the chemical resistance of the photosensitive resin composition after curing. It also improves the heat resistance of the photosensitive resin composition after curing and reduces the mean coefficient of linear expansion (CTE).

[0092] The content of trifunctional or more (meth)acrylate per 100 parts by mass of polyimide (A) is preferably more than 0 parts by mass and 100 parts by mass or less, more preferably 5 parts by mass or more and 80 parts by mass or less, even more preferably 10 parts by mass or more and 70 parts by mass or less, even more preferably 15 parts by mass or more and 65 parts by mass or less, and even more preferably 20 parts by mass or more and 60 parts by mass or less. By setting the content of trifunctional or more (meth)acrylate per 100 parts by mass of polyimide (A) to the above range, the chemical resistance of the photosensitive resin composition after curing can be further improved. In addition, the heat resistance of the photosensitive resin composition after curing can be improved, the mean coefficient of linear expansion (CTE) can be reduced, and the balance with other physical properties can be improved.

[0093] The content of trifunctional or more (meth)acrylates per 100 parts by mass of polyfunctional (meth)acrylate (C) is preferably 30 parts by mass or more and 100 parts by mass or less, more preferably 40 parts by mass or more and 100 parts by mass or less, and even more preferably 50 parts by mass or more and 100 parts by mass or less. By setting the content of trifunctional or more (meth)acrylates per 100 parts by mass of polyfunctional (meth)acrylate (C) to the above range, the chemical resistance of the photosensitive resin composition after curing can be further improved. In addition, the heat resistance of the photosensitive resin composition after curing can be improved, the mean coefficient of linear expansion (CTE) can be reduced, and the balance with other physical properties can be improved.

[0094] The polyfunctional (meth)acrylate (C) preferably comprises a bifunctional (meth)acrylate, more preferably a polyalkylene glycol di(meth)acrylate, even more preferably a polyethylene glycol di(meth)acrylate, and even more preferably a triethylene glycol di(meth)acrylate. This improves the tensile elongation of the photosensitive resin composition after curing.

[0095] The polyfunctional (meth)acrylate (C) preferably includes a (meth)acrylate having an isocyanurate skeleton. This improves the tensile elongation after curing of the photosensitive resin composition and the solvent solubility of the photosensitive resin composition. The (meth)acrylate having an isocyanurate skeleton may include, for example, at least one selected from the group consisting of tris(2-(meth)acryloyloxyethyl) isocyanurate and 2-hydroxyethylbis(2-(meth)acryloyloxyethyl) isocyanurate, and may also include tris(2-(meth)acryloyloxyethyl) isocyanurate.

[0096] (Epoxy compound (D)) The photosensitive resin composition of this embodiment preferably further comprises epoxy compound (D). Epoxy compound (D) is a compound having epoxy groups. It is believed that the epoxy groups of epoxy compound (D) react with the acid anhydride groups, which are terminal groups of polyimide (A), to form ester bonds, thereby improving the tensile elongation of the photosensitive resin composition after curing.

[0097] The content of epoxy compound (D) per 100 parts by mass of polyimide (A) is preferably 0.1 parts by mass or more and 25 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less, and even more preferably 1 part by mass or more and 15 parts by mass or less. By setting the content of epoxy compound (D) per 100 parts by mass of polyimide (A) within the above range, the balance between the tensile elongation after curing and other physical properties of the photosensitive resin composition can be improved.

[0098] The epoxy compound (D) preferably includes an epoxy compound having a (meth)acryloyl group. It is believed that the epoxy compound having a (meth)acryloyl group polymerizes with the polyfunctional (meth)acrylate (C), thereby crosslinking the polyfunctional (meth)acrylate (C) and the polyimide (A). This is thought to improve the mechanical properties of the photosensitive resin composition after curing. The epoxy compound having a (meth)acryloyl group may include, for example, at least one selected from the group consisting of 4-hydroxybutyl (meth)acrylate glycidyl ether, glycidyl (meth)acrylate, and (3,4-epoxycyclohexyl)methyl (meth)acrylate, and may also include 4-hydroxybutyl (meth)acrylate glycidyl ether.

[0099] (Silane coupling agent (E)) The photosensitive resin composition of this embodiment preferably further comprises a silane coupling agent (E). This improves the compatibility of polyimide (A) and polyfunctional (meth)acrylate (C), and improves the solvent solubility of the photosensitive resin composition.

[0100] Silane coupling agents (E) include, for example, silane coupling agents having a cyclic anhydride structure such as 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, and 3-dimethylmethoxysilylpropyl succinic anhydride; (meth)acryloylsilanes such as 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, and 3-(meth)acryloyloxypropyltriethoxysilane; epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; It comprises at least one selected from the group consisting of aminosilanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine; mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; and ureidosilanes such as 3-ureidopropyltrialkoxysilane.

[0101] The content of the silane coupling agent (E) per 100 parts by mass of polyimide (A) is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass or less, and even more preferably 2 parts by mass or more and 7 parts by mass or less. By setting the content of the silane coupling agent (E) per 100 parts by mass of polyimide (A) to the above range, the compatibility between polyimide (A) and polyfunctional (meth)acrylate (C) can be improved, and the solvent solubility of the photosensitive resin composition can be improved.

[0102] The silane coupling agent (E) preferably includes a silane coupling agent having a cyclic anhydride structure. It is believed that the cyclic anhydride structure reacts with the amino groups that are terminal groups of polyimide (A) or with the epoxy compound (D), thereby improving the adhesion between the cured photosensitive resin composition and the adherend (e.g., substrate). The silane coupling agent having a cyclic anhydride structure may include at least one selected from the group consisting of 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, and 3-dimethylmethoxysilylpropyl succinic anhydride, and may also include 3-trimethoxysilylpropyl succinic anhydride.

[0103] The silane coupling agent (E) preferably contains (meth)acrylsilane. Polymerization of (meth)acrylsilane with the polyfunctional (meth)acrylate (C) can improve the compatibility of polyimide (A) and the polyfunctional (meth)acrylate (C), thereby improving the solvent solubility of the photosensitive resin composition. The (meth)acrylsilane may contain at least one selected from the group consisting of 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, and 3-(meth)acryloyloxypropyltriethoxysilane, and may also contain 3-(meth)acryloyloxypropyltrimethoxysilane.

[0104] The content of (meth)acrylsilane per 100 parts by mass of polyimide (A) is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 7.5 parts by mass or less, and even more preferably 1 part by mass or more and 5 parts by mass or less. By setting the content of (meth)acrylsilane per 100 parts by mass of polyimide (A) within the above range, the compatibility between polyimide (A) and polyfunctional (meth)acrylate (C) can be improved, and the solvent solubility of the photosensitive resin composition can be improved.

[0105] (Adhesion enhancer) The photosensitive resin composition of this embodiment preferably further contains an adhesion enhancer. This improves the adhesion between the cured photosensitive resin composition and the adherend (e.g., a substrate).

[0106] The adhesion aid includes, for example, a nitrogen atom-containing heteroaromatic compound having at least one group selected from the group consisting of (1H-tetrazol-5-yl)amino group, 1-(1H-tetrazol-5-yl)methyl-amino group, 3-(1H-tetrazol-5-yl)benz-amino group, 1-(5-1H-triazoyl)methylamino group, 3-(1H-pyrazoyl)amino group, 4-(1H-pyrazoyl)amino group, 5-(1H-pyrazoyl)amino group, 1-(3-1H-pyrazoyl)methylamino group, 1-(4-1H-pyrazoyl)methylamino group, and 1-(5-1H-pyrazoyl)methylamino group.

[0107] The content of the adhesion aid per 100 parts by mass of polyimide (A) is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 5 parts by mass or less. By setting the content of the adhesion aid per 100 parts by mass of polyimide (A) within the above range, the adhesion between the cured product of the photosensitive resin composition and the adherend (e.g., substrate) can be improved.

[0108] (Curing Catalyst) The photosensitive resin composition of this embodiment preferably further comprises a curing catalyst. This can accelerate the curing reaction of the photosensitive resin composition. In particular, the photosensitive resin composition of this embodiment preferably further comprises an epoxy compound (D) and a curing catalyst. By including a curing catalyst in the photosensitive resin composition, the reaction between the epoxy group of the epoxy compound (D) and the acid anhydride group which is the terminal group of the polyimide (A) proceeds sufficiently, and the tensile elongation of the photosensitive resin composition after curing can be improved.

[0109] The curing catalyst may contain at least one selected from the group consisting of phosphonium salts such as tetraphenylphosphonium-4,4'-sulfonyldiphenolate, tetraphenylphosphonium-tetraphenylborate, and tetraphenylphosphonium bromide; phosphines such as triphenylphosphine and methyldiphenylphosphine; tertiary amines and tertiary amine salts such as 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, and 2,4,6-tris(dimethylaminomethyl)phenol; and imidazoles such as 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole and 2-ethyl-4-methylimidazole, and may contain phosphonium salts, and may also contain tetraphenylphosphonium-4,4'-sulfonyldiphenolate.

[0110] The content of the curing catalyst per 100 parts by mass of polyimide (A) may be 1 part by mass or more and 50 parts by mass or less, or 5 parts by mass or more and 30 parts by mass or less.

[0111] (Antioxidant) The photosensitive resin composition of this embodiment preferably further contains an antioxidant. This helps to suppress the deterioration of the photosensitive resin composition.

[0112] The antioxidant includes, for example, at least one selected from the group consisting of hindered phenol antioxidants such as tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid and 2,2'-methylenebis(6-tert-butyl-4-ethylphenol); and thioether antioxidants such as pentaerythritol tetrakis[3-laurylthiopropionate].

[0113] The amount of antioxidant per 100 parts by mass of polyimide (A) may be 0.1 parts by mass or more and 10 parts by mass or less, or 1 part by mass or more and 5 parts by mass or less.

[0114] (Surfactant) The photosensitive resin composition of this embodiment preferably further contains a surfactant. This improves the applicability of the photosensitive resin composition.

[0115] The surfactant includes, for example, silicone-based surfactants such as polyether-modified siloxanes, polyester-modified siloxanes, and aralkyl-modified siloxanes; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; and at least one selected from the group consisting of fluorine-based surfactants.

[0116] The amount of surfactant per 100 parts by mass of polyimide (A) may be 0.01 parts by mass or more and 1 part by mass or less, or 0.05 parts by mass or more and 0.5 parts by mass or less.

[0117] (Physical properties of the photosensitive resin composition) The physical properties of the photosensitive resin composition of this embodiment will be described below.

[0118] In accordance with JIS K 7244-4:1999, the storage modulus at 23°C of a cured product obtained by curing a photosensitive resin composition at 230°C for 2 hours, as measured by dynamic viscoelasticity measurement (DMA), may be 2.0 GPa or more and 20.0 GPa or less, 2.0 GPa or more and 15.0 GPa or less, 2.5 GPa or more and 10.0 GPa or less, or 2.8 GPa or more and 8.0 GPa or less.

[0119] The glass transition temperature (Tg) of a cured product obtained by curing a photosensitive resin composition at 230°C for 2 hours, as measured by dynamic viscoelasticity measurement (DMA) in accordance with JIS K 7244-4:1999, is determined. ＤＭＡ The temperature is preferably 280°C to 500°C, more preferably 290°C to 475°C, and even more preferably 295°C to 450°C. In this embodiment, Tg ＤＭＡ This is thought to mainly reflect the glass transition temperature of polyimide (A). Tg ＤＭＡ Because the above range is maintained, it is possible to manufacture semiconductor devices with small dimensional changes during high-temperature reflow processing and good connection reliability.

[0120] The glass transition temperature (Tg) of a cured product obtained by curing a photosensitive resin composition at 230°C for 2 hours is measured by thermomechanical analysis (TMA) in accordance with JIS K 7197:2012. ＴＭＡ The temperature is preferably 240°C to 500°C, more preferably 245°C to 475°C, and even more preferably 250°C to 450°C. In this embodiment, Tg ＴＭＡ This is thought to mainly reflect the glass transition temperature of the cured polyfunctional (meth)acrylate (C). ＴＭＡ By keeping the above range, it is possible to manufacture semiconductor devices with minimal film thickness changes due to chemical treatment.

[0121] In accordance with JIS K 7244-4:1999, the glass transition temperature (Tg) of a cured product obtained by curing a photosensitive resin composition at 230°C for 2 hours is measured by dynamic viscoelasticity measurement (DMA). ＤＭＡ The glass transition temperature (Tg) of the cured product obtained by curing a photosensitive resin composition at 230°C for 2 hours is determined by thermomechanical analysis (TMA) in accordance with JIS K 7197:2012. ＴＭＡ Let's assume that Tg ＤＭＡ -Tg ＴＭＡ The temperature is preferably 40°C to 100°C, more preferably 42°C to 90°C, and even more preferably 44°C to 80°C. In this embodiment, Tg ＤＭＡ -Tg ＴＭＡ The magnitude of the value is considered to be an indicator of the magnitude of the glass transition temperature of polyimide (A) relative to the glass transition temperature of the cured polyfunctional (meth)acrylate (C). ＤＭＡ -Tg ＴＭＡ By keeping the above range, the balance between the tensile elongation and elastic modulus after curing of the photosensitive resin composition can be improved, making it possible to manufacture semiconductor devices with good connection reliability.

[0122] In accordance with JIS K 7197:2012, the mean linear thermal expansion coefficient (CTE) of a cured product obtained by curing a photosensitive resin composition at 230°C for 2 hours, measured by thermomechanical analysis (TMA), is preferably 20 ppm / °C to 65 ppm / °C, more preferably 25 ppm / °C to 64 ppm / °C, and even more preferably 30 ppm / °C to 63 ppm / °C. Having a mean linear thermal expansion coefficient (CTE) within this range suppresses warping of the semiconductor device, enabling the manufacture of a semiconductor device with good connection reliability.

[0123] The elongation at break at 23°C of the cured product obtained by curing the photosensitive resin composition obtained by the following method at 230°C for 2 hours is preferably more than 23% and 85% or less, more preferably 25% to 80%, even more preferably 30% to 75%, even more preferably 35% to 70%, and even more preferably 40% to 65%. Having the elongation at break at 23°C within the above range suppresses the occurrence of cracks during the manufacturing of semiconductor devices, enabling the production of semiconductor devices with good connection reliability.

[0124] (Method) A test specimen (50 mm × 7 mm × 10 μm thick) is cut from the cured material. In accordance with JIS K 7197:2012, the elongation at break from the initial position of the test specimen to the point of fracture is measured using a thermomechanical analyzer under air atmosphere, tensile mode, chuck distance of 20 mm, tensile speed of 5 mm / min, and 23°C. The average value obtained from measurements of 10 test specimens is taken as the elongation at break.

[0125] The Δt obtained by the following method is preferably greater than -2.0 μm and less than or equal to 0 μm, more preferably between -1.5 μm and less than or equal to -0.01 μm, even more preferably between -1.0 μm and less than or equal to -0.1 μm, and even more preferably between -0.8 μm and less than or equal to -0.2 μm. By having Δt within the above range, it is possible to manufacture semiconductor devices with minimal film thickness changes due to chemical treatment.

[0126] (Method) The photosensitive resin composition was spin-coated onto an 8-inch silicon wafer, and then heated at 110°C for 3 minutes to dry the photosensitive resin composition. The spin-coating was performed so that the film thickness after drying was 10 μm. Then, a high-pressure mercury lamp was used to heat the wafer at 600 mJ / cm². ２ The specimen is exposed to light and cured by heating at 230°C for 2 hours under a nitrogen atmosphere. A test specimen (20 mm × 20 mm × 10 μm thick) with a silicon wafer is cut out using a dicing saw. The test specimen is immersed in dimethyl sulfoxide containing 2.38 mass% tetramethylammonium hydroxide (TMAH) at 50°C for 20 minutes. Then, it is washed with isopropanol, dried with an air blower, and heated on a hot plate at 170°C for 5 minutes to obtain a test specimen with a silicon wafer after the chemical resistance test. The film thickness t of the test specimen after the chemical resistance test is measured using an optical interferometry film thickness analyzer, and the difference in film thickness Δt before and after the chemical resistance test is calculated based on the following formula: Δt [μm] = t [μm] - 10 μm

[0127] (Method for preparing the photosensitive resin composition) The photosensitive resin composition of this embodiment can be prepared, for example, by imidizing a diamine and an acidic dianhydride in an organic solvent to obtain polyimide (A), and then mixing the above-mentioned components in a solvent.

[0128] (Varnish) The varnish of this embodiment comprises the photosensitive resin composition of this embodiment and a solvent.

[0129] The total solid content (non-volatile components) in the varnish of this embodiment may be 10% by mass or more and 50% by mass or less.

[0130] In accordance with JIS K 7117-2:1999, the viscosity of the varnish measured using a cone rotor with a radius of 14 mm and an angle of 3° at 25°C and a rotation speed of 20 rpm may be between 100 mPa·s and 3,000 mPa·s, between 750 mPa·s and 2,500 mPa·s, or between 1,000 mPa·s and 2,000 mPa·s.

[0131] (Uses of the photosensitive resin composition) The photosensitive resin composition of this embodiment is preferably used in semiconductor devices. The photosensitive resin composition of this embodiment is preferably used to form a resin film for semiconductor devices, and more preferably to form a permanent film. The permanent film is used as a protective film, interlayer film, dam material, etc., for semiconductor devices.

[0132] (Cured product) The cured product of this embodiment is a cured product of the photosensitive resin composition of this embodiment. The cured product of this embodiment can be obtained, for example, by applying the photosensitive resin composition of this embodiment to a substrate, pre-baking to dry and form a resin film, then exposing and developing the resin film to a desired shape, and finally post-baking to cure it. Pre-baking may be, for example, a heat treatment at 90°C to 130°C for 30 seconds to 1 hour. Post-baking may be, for example, a heat treatment at 150°C to 250°C for 30 minutes to 10 hours.

[0133] (Semiconductor device) The semiconductor device of this embodiment includes the cured product of this embodiment. More specifically, the semiconductor device of this embodiment may include an interlayer insulating film, a resin film containing the cured product of this embodiment on the interlayer insulating film, and rewiring embedded in the resin film.

[0134] Figure 1 is a schematic cross-sectional view illustrating an example of the structure of a semiconductor device according to this embodiment. As shown in Figure 1, the semiconductor device 100 of this embodiment comprises a semiconductor substrate on which semiconductor elements such as transistors are provided, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. The uppermost layer of the multilayer wiring layer is provided with an interlayer insulating film 30 and an uppermost wiring 34 provided on the interlayer insulating film 30. A passivation film 32 is provided on the interlayer insulating film 30 and the uppermost wiring 34. An opening is provided in a part of the passivation film 32 to expose the uppermost wiring 34. A rewiring layer 40 is provided on the passivation film 32. The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, rewiring 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and the rewiring 46. An opening is formed in the insulating layer 42 that connects to the uppermost wiring 34. The rewiring 46 is formed on the insulating layer 42 and within openings provided in the insulating layer 42, and is connected to the uppermost wiring 34. The insulating layer 44 is provided with openings for connection to the rewiring 46. Within the openings provided in the insulating layer 44, for example, bumps 52 are formed via a UBM (Under Bump Metallurgy) layer 50. The semiconductor device 100 is connected to a wiring board or the like via, for example, the bumps 52.

[0135] In the semiconductor device 100, at least one selected from the group consisting of a passivation film 32, an insulating layer 42, and an insulating layer 44 may be a resin film containing the cured product of this embodiment. The resin film may be a permanent film.

[0136] The semiconductor device 100 may be a semiconductor chip. In this case, for example, a semiconductor package can be obtained by mounting the semiconductor device 100 on a wiring board via bumps 52.

[0137] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and modifications, improvements, etc., within the scope that can achieve the objectives of the present invention are included in the present invention.

[0138] The present invention will be described in detail below with reference to examples. However, the present invention is not limited in any way to the descriptions in these examples.

[0139] (1) Raw materials for polyimide (A) The raw materials used in the synthesis of polyimide (A) are shown below.

[0140] (Diamine) MBAA: 5,5'-methylenebis(2-aminobenzoic acid), represented by the following formula.

[0141] DABA: 3,5-diaminobenzoic acid, represented by the following formula.

[0142] MED-J: 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane, represented by the following formula.

[0143] ATEPM: 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, represented by the following formula.

[0144] APB: 1,3-bis(3-aminophenoxy)benzene, represented by the following formula.

[0145] BPF-AN: 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene, represented by the following formula.

[0146] OTBAF: 9,9-bis(4-amino-3-methylphenyl)fluorene, represented by the following formula.

[0147] (Acid dianhydride) ODPA: 4,4'-oxydiphthalic acid anhydride, represented by the following formula.

[0148] TMPBP-TME: Represented by the following formula, 2,2',3,3',5,5'-hexamethyl[1,1'-biphenyl]-4,4'-diyl=bis(1,3-dioxo-1,3-dihydro-2-benzofuran-5-carboxylate) (manufactured by Honshu Chemical Industry Co., Ltd.)

[0149] BTDA: 3,3',4,4'-benzophenonetetracarboxylic dianhydride, represented by the following formula.

[0150] (2) Synthesis of Polyimide (A) Diamine: 9.0 g, acidic dianhydride: 11.0 g, and solvent (3-methyl-2-oxazolidone: 91.1 g, and cyclopentyl methyl ether: 5.5 g) were placed in a flask equipped with a Dean-Stark apparatus. The starting material compositions of the diamine and acidic dianhydride are shown in Table 1 (units are molar ratios). The mixture was then stirred at room temperature for 10 minutes under a nitrogen atmosphere, and then heated in an oil bath and reacted at 150°C for 1 hour. 2,6-lutidine: 3.3 g was added as a dehydration catalyst, and the reaction was further carried out at 190°C for 4 hours. After the reaction solution was cooled to room temperature, it was diluted with tetrahydrofuran, and isopropanol was added dropwise to precipitate a solid. The obtained solid was filtered, washed, and vacuum dried at 60°C to obtain polyimide (A).

[0151] (3) Evaluation of Polyimide (A) (Evaluation of solubility in TMAH aqueous solution) When polyimide (A) from each example and comparative example was mixed with a 2.38% by mass aqueous solution of tetramethylammonium hydride (TMAH), none of them dissolved.

[0152] (Evaluation of solubility in γ-butyrolactone) A solution was prepared by dissolving 2 g of polyimide (A) in 8 g of γ-butyrolactone. The solution was visually observed, and the solubility of polyimide (A) in γ-butyrolactone was evaluated according to the following criteria: A: The solution was clear. B: The solution was cloudy.

[0153] (Evaluation of solubility in N-methylpyrrolidone) A solution was prepared by dissolving 2 g of polyimide (A) in 8 g of N-methylpyrrolidone. The solution was visually observed, and the solubility of polyimide (A) in N-methylpyrrolidone was evaluated according to the following criteria: A: The solution was clear. B: The solution was cloudy.

[0154] Table 1 shows the evaluation results for each example and comparative example.

[0155] (4) Preparation of Photosensitive Resin Composition Each raw material was mixed in a solvent to prepare a photosensitive resin composition. The types and amounts of raw materials other than polyimide (A), and the types and amounts of solvents are shown below. The amounts of polyfunctional (meth)acrylate (C) and epoxy compound (D) are shown in Table 1. The amounts of each raw material and solvent are relative to 100 parts by mass of polyimide (A).

[0156] (Polymerization initiator (B)) b1: 10 parts by mass of 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyloxime), represented by the following formula ("Irgacure OXE01" manufactured by BASF Japan).

[0157] b2: Dicumyl peroxide represented by the following formula (Parcadox BC-FF, manufactured by Kayaku Nurion Co., Ltd.), 10 parts by mass

[0158] (Polyfunctional (meth)acrylate (C)) c1: Dipentaerythritol polyacrylate represented by the following formula (A-DPH, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0159] c2: A polyfunctional acrylate compound represented by the following formula (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat #802)

[0160] c3: Tris(2-acryloyloxyethyl) isocyanurate (A-9300NT, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) c4: Triethylene glycol dimethacrylate (3G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0161] (Epoxy compound (D)) d1: 4-hydroxybutyl acrylate glycidyl ether represented by the following formula (Shinryo Co., Ltd. "4HBAGE")

[0162] d2: A trifunctional epoxy compound represented by the following formula (Printec Co., Ltd., VG3101L)

[0163] (Silane coupling agent (E)) e1: 2 parts by mass of 3-trimethoxysilylpropyl succinic anhydride (Shin-Etsu Chemical Co., Ltd. "X-12-967C"), represented by the following formula.

[0164] e2: 2 parts by mass of 3-methacryloyloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), represented by the following formula.

[0165] (Other raw materials) Adhesion aid: 5-aminotetrazol monohydrate (manufactured by Masuda Chemical Industries, Ltd.), 2 parts by mass Curing catalyst: Tetraphenylphosphonium 4,4'-sulfonyl diphenolate (manufactured by Sumitomo Bakelite Co., Ltd.), represented by the following formula, 10 parts by mass

[0166] Antioxidant: Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid (KEMINOX179, manufactured by Chemipro Chemical Co., Ltd.), 2 parts by mass, represented by the following formula.

[0167] Surfactant: Polyether-modified siloxane (BYK-349, manufactured by BYK Corporation), 0.1 parts by mass; Solvent: γ-butyrolactone (manufactured by Sanwa Oil & Chemical Industry Co., Ltd.), 600 parts by mass

[0168] (5) Evaluation of the photosensitive resin composition (Preparation of cured product) The photosensitive resin composition was spin-coated onto an 8-inch silicon wafer, and then heated at 110°C for 3 minutes to dry the photosensitive resin composition (pre-bake). The spin-coating was performed so that the film thickness after drying was 10 μm. Then, a high-pressure mercury lamp was used to heat the wafer at 600 mJ / cm². ２ The silicon wafer was exposed to light and then heated at 230°C for 2 hours under a nitrogen atmosphere to cure it (post-bake). The silicon wafer was cut to a width of 7 mm using a dicing saw. The cut silicon wafer was immersed in a 2 mass% hydrofluoric acid aqueous solution and the cured material was peeled off the silicon wafer. The peeled cured material was dried at 80°C for 90 minutes to obtain a cured product.

[0169] (Dynamic Viscoelasticity Measurement) A test specimen (30 mm × 7 mm × 10 μm thick) was cut from the obtained cured material. In accordance with JIS K 7244-4:1999, dynamic viscoelasticity measurement (DMA) was performed using a dynamic viscoelasticity measuring device (TA Instruments "Q800") under the conditions of air atmosphere, frequency 1 Hz, tensile mode, heating rate 5 °C / min, chuck distance 20 mm, and 23 °C, and the storage modulus at 23 °C was measured. Furthermore, dynamic viscoelasticity measurement (DMA) was performed under the conditions of heating from 23 °C to 400 °C. In the obtained temperature-loss tangent (tanδ) graph, the temperature at which the loss tangent (tanδ) is maximum was defined as the glass transition temperature (Tg). ＤＭＡ )

[0170] (Thermomechanical Analysis) A test specimen (20 mm × 4 mm × 10 μm thick) was cut from the obtained hardened material. Thermomechanical analysis (TMA) was performed in accordance with JIS K 7197:2012 using a thermomechanical analyzer (Hitachi High-Tech Corporation "TMA-7100C") under nitrogen atmosphere, tensile mode, heating rate of 10°C / min, chuck distance of 10 mm, and heating from 23°C to 400°C. The glass transition temperature (Tg) was determined from the obtained temperature-displacement graph. ＴＭＡ ), and the average coefficient of linear thermal expansion (CTE) in the range of 50°C to 100°C were determined.

[0171] (Measurement of Elongation at Break) A test specimen (50 mm × 7 mm × 10 μm thick) was cut from the hardened material. In accordance with JIS K 7197:2012, the elongation at break from the initial position to the breaking point of the test specimen was measured using a thermomechanical analyzer (A&D Corporation "STB-1225S") under the conditions of air atmosphere, tensile mode, chuck distance of 20 mm, tensile speed of 5 mm / min, and 23°C. The average value obtained from measurements of 10 test specimens was taken as the elongation at break.

[0172] (Chemical Resistance Test) The photosensitive resin composition was spin-coated onto an 8-inch silicon wafer, and then heated at 110°C for 3 minutes to dry the photosensitive resin composition (pre-bake). The spin-coating was performed so that the film thickness after drying was 10 μm. Then, a high-pressure mercury lamp was used to test at 600 mJ / cm². ２The specimens were exposed to light and then heated at 230°C for 2 hours under a nitrogen atmosphere to cure them (post-bake). A test specimen with a silicon wafer (20 mm × 20 mm × 10 μm thick) was cut out using a dicing saw. The test specimen was immersed in dimethyl sulfoxide containing 2.38 mass% tetramethylammonium hydroxide (TMAH) at 50°C for 20 minutes. Next, it was washed with isopropanol, dried with an air blower, and then heated on a hot plate at 170°C for 5 minutes to obtain a silicon wafer-attached test specimen after the chemical resistance test. The film thickness t of the test specimen after the chemical resistance test was measured using an optical interferometry film thickness analyzer (VM-1020, manufactured by SCREEN Semiconductor Solutions Inc.), and the difference in film thickness Δt before and after the chemical resistance test was calculated based on the following formula: Δt [μm] = t [μm] - 10 μm

[0173] Table 1 shows the evaluation results for each example and comparative example.

[0174]

[0175] The photosensitive resin compositions of each example and comparative example were spin-coated onto an 8-inch silicon wafer, and then heated at 110°C for 3 minutes to dry the photosensitive resin compositions (pre-bake). The spin-coating was performed so that the film thickness after drying was 10 μm. Subsequently, when immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydride (TMAH) at 23°C for 30 minutes, none of the compositions dissolved, and no change in film thickness was observed.

[0176] This application claims priority based on Japanese Patent Application No. 2025-049623, filed on 25 March 2025, and incorporates all of its disclosures herein.

[0177] 30 Interlayer insulating film 32 Passivation film 34 Top layer wiring 40 Redistribution layer 42 Insulating layer 44 Insulating layer 46 Redistribution 50 UBM layer 52 Bump 100 Semiconductor equipment

Claims

1. A photosensitive resin composition comprising a polyimide (A) having a carboxyl group in its constituent units, a polymerization initiator (B), and a polyfunctional (meth)acrylate (C).

2. The photosensitive resin composition according to claim 1, wherein the polyimide (A) comprises a constituent unit represented by the following general formula (1). (In general formula (1), X represents a constituent unit (X) which is a divalent organic group, and Y represents a constituent unit (Y) which is a tetravalent organic group, and the constituent unit (X) includes a constituent unit (X-1) which has a carboxyl group.) 3. The photosensitive resin composition according to claim 2, wherein the constituent unit (X-1) includes a constituent unit represented by the following general formula (x1). (In general formula (x1), Z １ (where * represents a single bond, oxygen atom, or divalent organic group, and * represents a bond.) 4. The photosensitive resin composition according to claim 2 or 3, wherein the constituent unit (X-1) includes a constituent unit represented by the following general formula (x2). (In the general formula (x²), * represents a bond.) 5. The photosensitive resin composition according to claim 2 or 3, wherein the constituent unit (X-1) comprises a constituent unit derived from at least one diamine selected from the group consisting of 5,5'-methylenebis(2-aminobenzoic acid), 1,2-bis(4-amino-2-carboxyphenoxy)benzene, 1,3-bis(4-amino-2-carboxyphenoxy)benzene, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 5-amino-2-(4-aminophenoxy)benzoic acid, 3,5-diaminobenzoic acid, 3,5-diamino-4-methoxybenzoic acid, 3,5-bis(4-aminophenoxy)benzoic acid, N-bis(4-aminophenyl)-4-carboxyaniline, and 4,4'-diamino-N-(4-carboxyphenyl)benzanilide.

6. The photosensitive resin composition according to claim 2 or 3, wherein the constituent unit (X) further comprises a constituent unit represented by the following general formula (x3). (In general formula (x3), Z ２ R represents an alkylene group. １ Each of these independently represents an alkyl group having 1 to 4 carbon atoms, and * represents a bond.

7. The photosensitive resin composition according to claim 2 or 3, wherein the constituent unit (X) further comprises a constituent unit represented by the following general formula (x4). (In the general formula (x4), * represents a bond.) 8. The photosensitive resin composition according to claim 2 or 3, wherein the constituent unit (Y) includes a constituent unit represented by the following formula (y11). (In equation (y11), * represents a coupling.) 9. The photosensitive resin composition according to any one of claims 1 to 3, wherein the polyfunctional (meth)acrylate (C) comprises a trifunctional or more (meth)acrylate.

10. The photosensitive resin composition according to any one of claims 1 to 3, further comprising epoxy compound (D).

11. The photosensitive resin composition according to any one of claims 1 to 3, further comprising a silane coupling agent (E).

12. The photosensitive resin composition according to claim 11, wherein the silane coupling agent (E) comprises (meth)acrylsilane.

13. A photosensitive resin composition according to any one of claims 1 to 3, wherein the photosensitive resin composition obtained by curing the photosensitive resin composition at 230°C for 2 hours by the following method has a fracture elongation of more than 23% at 23°C. (Method) A test piece (50 mm × 7 mm × 10 μm thick) is cut from the cured product. In accordance with JIS K 7197:2012, the fracture elongation from the initial position of the test piece to the breaking point is measured using a thermomechanical analyzer under the conditions of air atmosphere, tensile mode, chuck distance of 20 mm, tensile speed of 5 mm / min, and 23°C. The average value obtained from measurements of 10 test pieces is taken as the fracture elongation.

14. The photosensitive resin composition according to any one of claims 1 to 3, wherein the Δt obtained by the following method is greater than -2.0 μm. (Method) The photosensitive resin composition is spin-coated onto an 8-inch silicon wafer, and then heated at 110°C for 3 minutes to dry the photosensitive resin composition. The spin-coating is performed so that the film thickness after drying is 10 μm. Next, using a high-pressure mercury lamp, 600 mJ / cm² was measured. ２ The material is exposed to light and then heated at 230°C for 2 hours under a nitrogen atmosphere to cure it. Using a dicing saw, cut out a test piece (20 mm x 20 mm x 10 μm thick) with a silicon wafer attached. The test specimen is immersed in dimethyl sulfoxide containing 2.38% by mass of tetramethylammonium hydroxide (TMAH) at 50°C for 20 minutes. Then, it is washed with isopropanol, dried with an air blower, and heated on a hot plate at 170°C for 5 minutes to obtain the test specimen with a silicon wafer after the chemical resistance test. The film thickness t of the test specimen after the chemical resistance test is measured using an optical interferometry film thickness analyzer, and the difference in film thickness Δt before and after the chemical resistance test is calculated based on the following formula: Δt [μm] = t [μm] - 10 μm 15. The glass transition temperature (Tg) of the cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours, as measured by dynamic viscoelasticity measurement (DMA) in accordance with JIS K 7244-4:1999. ＤＭＡ A photosensitive resin composition according to any one of claims 1 to 3, wherein the temperature is 280°C or higher.

16. The glass transition temperature (Tg) of the cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours, as measured by thermomechanical analysis (TMA) in accordance with JIS K 7197:2012. ＴＭＡ A photosensitive resin composition according to any one of claims 1 to 3, wherein the temperature is 240°C or higher.

17. When, in accordance with JIS K 7244-4:1999, the glass transition temperature of the cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours measured by dynamic viscoelasticity measurement (DMA) is defined as Tg ＤＭＡ , and in accordance with JIS K 7197:2012, the glass transition temperature of the cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours measured by thermomechanical analysis (TMA) is defined as Tg ＴＭＡ , Tg ＤＭＡ -Tg ＴＭＡ is 40°C or higher, the photosensitive resin composition according to any one of claims 1 to 3.

18. The photosensitive resin composition according to any one of claims 1 to 3, wherein the mean coefficient of linear expansion (CTE) in the range of 50°C to 100°C of the cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours, as measured by thermomechanical analysis (TMA) in accordance with JIS K 7197:2012, is 65 ppm / °C or less.

19. A photosensitive resin composition according to any one of claims 1 to 3, used in semiconductor devices.

20. A varnish comprising the photosensitive resin composition according to any one of claims 1 to 3, and a solvent.

21. A cured product of the photosensitive resin composition according to any one of claims 1 to 3.

22. A semiconductor device comprising the cured product described in claim 21.

23. The semiconductor device according to claim 22, comprising: an interlayer insulating film; a resin film containing the cured product on the interlayer insulating film; and rewiring embedded in the resin film.

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