Photosensitive resin composition, cured product, and semiconductor device

Abstract

The present invention provides a photosensitive resin composition with improved mechanical properties after curing. [Solution] A photosensitive resin composition comprising the following general formula (1) and a polymerization initiator (B). TIFF2026098251000042.tif44153 (In general formula (1), X represents a divalent organic group (constituent unit (X)), Y represents a tetravalent organic group (constituent unit (Y), and the constituent unit (X) includes the constituent unit (X-1) represented by the following general formula (x1).) TIFF2026098251000043.tif44153

Description

[Technical Field]

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

[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 polyimide resin composition that possesses developer solubility during development and developer insolubility after photocrosslinking, achieving good film properties and high sensitivity, while preventing film beriberi and cracking of the resin coating, and preventing warping and breakage of the substrate. The photosensitive polyimide resin composition is a photosensitive polyimide resin composition containing a solvent-soluble polyimide and a diazide compound as essential components, characterized in that the solvent-soluble polyimide is a block copolymer having (a) an alicyclic acid dianhydride residue and (b) at least one diamine residue selected from the group consisting of aromatic diamines having an alkyl group at the ortho position of the amino group and aromatic diamines having an indane structure in the same repeating unit. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-001636 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention provides a photosensitive resin composition with improved mechanical properties after curing. [Means for solving the problem]

[0006] The inventors of the present invention have found that in a photosensitive resin composition containing a polyimide and a polymerization initiator, when the polyimide contains a predetermined structural unit, the mechanical properties of the photosensitive resin composition after curing can be improved, and thus the present invention has been completed.

[0007] That is, according to the present invention, there are provided a photosensitive resin composition, a cured product, and a semiconductor device as described below.

[0008] [1] A photosensitive resin composition comprising a polyimide (A) containing a structural unit represented by the following general formula (1), a polymerization initiator (B), and. [Chemical formula] (In the general formula (1), X represents a structural unit (X) which is a divalent organic group, Y represents a structural unit (Y) which is a tetravalent organic group, The structural unit (X) contains a structural unit (X-1) represented by the following general formula (x1).) [Chemical formula] (In the general formula (x1), R 1 each independently represents an alkyl group having 1 to 4 carbon atoms, a and b each independently represent an integer of 0 to 4, * represents a bond.) [2] The photosensitive resin composition according to [1], further comprising a polyfunctional (meth)acrylate (C). [3] The photosensitive resin composition according to [2], wherein the polyfunctional (meth)acrylate (C) contains a pentafunctional or higher (meth)acrylate. [4] The photosensitive resin composition according to [2] or [3], wherein the polyfunctional (meth)acrylate (C) contains a bifunctional to tetrafunctional (meth)acrylate. [5] The photosensitive resin composition according to any one of [2] to [4], wherein the polyfunctional (meth)acrylate (C) comprises a polyalkylene glycol di(meth)acrylate. [6] The photosensitive resin composition according to [5], wherein the polyalkylene glycol di(meth)acrylate comprises polyethylene glycol di(meth)acrylate. [7] The photosensitive resin composition according to any one of [2] to [6], wherein the content of the polyfunctional (meth)acrylate (C) per 100 parts by mass of the polyimide (A) is 10 parts by mass or more and 150 parts by mass or less. [8] The photosensitive resin composition according to any one of [1] to [7], wherein the constituent unit (Y) comprises a constituent unit (Y-1) represented by the following general formula (y1). [ka] (In general formula (y1), R 3 Each of these independently represents an alkyl group having 1 to 4 carbon atoms. Z 1 This represents a single bond or a divalent organic group. e and f each independently represent integers from 0 to 4. * represents a bond. [9] The photosensitive resin composition according to [8], wherein the ratio of the constituent unit (Y-1) in the constituent unit (Y) is 10 mol% or more.

[10] The photosensitive resin composition according to any one of [1] to [9], wherein the aforementioned constituent unit (Y) includes a constituent unit (Y-2) represented by the following general formula (y2). [ka] (In general formula (y2), Z 2 This represents a single bond, -C(=O)-, or -SO2-. * represents a bond.

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

[10] , wherein the polyimide (A) is a random copolymer.

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

[11] , further comprising epoxy compound (D).

[13] The photosensitive resin composition according to

[12] , wherein the epoxy compound (D) comprises an epoxy compound having a (meth)acryloyl group.

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

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

[15] The photosensitive resin composition according to

[14] , wherein the silane coupling agent (E) comprises a silane coupling agent having a cyclic anhydride structure.

[16] A photosensitive resin composition according to any one of [1] to

[15] , wherein the storage modulus at 23°C 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, is greater than 2.8 GPa.

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

[16] , wherein the temperature is greater than 313°C.

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

[17] , wherein the temperature is greater than 259°C.

[19] In accordance with JIS K 7244-4:1999, the glass transition temperature (Tg) of the cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours is measured by dynamic viscoelasticity measurement (DMA). DMAand 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) in accordance with JIS K 7197:2012, is designated as Tg TMA When it is DMA -Tg TMA is 25°C or higher, the photosensitive resin composition according to any one of [1] to

[18] .

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

[19] , wherein the average coefficient of linear expansion (CTE) in the range from 50°C to 100°C of the cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours, measured by thermomechanical analysis (TMA) in accordance with JIS K 7197:2012, is less than 61 ppm / °C.

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

[20] , wherein the average value of the elongation at break at 23°C of the cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours, obtained by the following method, is 3% or more. (Method) Cut out a test piece (50 mm × 7 mm × 10 μm thick) from the cured product. In accordance with JIS K 7197:2012, using a thermomechanical analyzer, measure the elongation at break from the initial position to the break point of the test piece under an air atmosphere, in tension mode, with a chuck distance of 20 mm, a tensile speed of 5 mm / min, and at 23°C. Measure 10 test pieces and obtain the average value of the elongation at break.

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

[21] , which is used in a semiconductor device.

[23] The cured product of the photosensitive resin composition according to any one of [1] to

[22] .

[24] A semiconductor device comprising the cured product described in

[23] .

[25] An interlayer insulating film, A resin film containing the cured product described in

[23] on the interlayer insulating film, A rewiring embedded in the resin film, and the semiconductor device described in

[24] . [Effects of the Invention]

[0009] According to the present invention, a photosensitive resin composition with improved mechanical properties after curing can be provided. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic cross-sectional view illustrating an example of the structure of the semiconductor device according to this embodiment. [Modes for carrying out the invention]

[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 this embodiment comprises a polyimide (A) containing a structural unit represented by the following general formula (1), and a polymerization initiator (B).

[0013] [ka]

[0014] In general formula (1), X represents a divalent organic group (X) and Y represents a tetravalent organic group (Y).

[0015] In this embodiment, the constituent unit (X) includes the constituent unit (X-1) represented by the following general formula (x1).

[0016] [ka]

[0017] In general formula (x1), R 1 Each of these independently represents an alkyl group having 1 to 4 carbon atoms. a and b each independently represent integers from 0 to 4. * represents a bond.

[0018] Because the constituent unit (X) contains the constituent unit (X-1), the polyimide (A) of this embodiment has a rigid cardo structure, which is thought to improve the mechanical properties of the photosensitive resin composition after curing. In particular, it is thought that the elastic modulus of the photosensitive resin composition after curing can be improved. Furthermore, it is thought that the heat resistance of the photosensitive resin composition after curing can be improved.

[0019] In general formula (x1), R 1 Each of these independently represents an alkyl group having 1 to 4 carbon atoms. 1 It may contain at least one group selected from the group consisting of methyl group, ethyl group, isopropyl group, n-propyl group, and tert-butyl group, and may contain at least one group selected from the group consisting of methyl group and ethyl group, and may contain a methyl group.

[0020] In the general formula (x1), a and b each independently represent integers from 0 to 4. A and b can each independently be 0 or 1, or they can be 0.

[0021] The constituent unit (X-1) may include, for example, the constituent unit represented by the following formula (x11).

[0022] [ka]

[0023] The ratio of constituent unit (X-1) to constituent unit (X) is preferably 5 mol% to 100 mol%, more preferably 10 mol% to 90 mol%, even more preferably 15 mol% to 80 mol%, even more preferably 20 mol% to 70 mol%, and even more preferably 25 mol% to 60 mol%. By setting the ratio of constituent unit (X-1) to constituent unit (X) within the above range, the mechanical properties of the photosensitive resin composition after curing can be further improved.

[0024] The constituent units included in the polyimide (A) of this embodiment will be described in more detail below.

[0025] (Polyimide (A) constituent unit (X)) The constituent unit (X) preferably further comprises a constituent unit (X-2) represented by the following general formula (x2).

[0026] [ka]

[0027] In general formula (x2), R 2 Each of these independently represents an alkyl group having 1 to 4 carbon atoms. c and d each independently represent integers from 0 to 4. * represents a bond.

[0028] By including constituent unit (X-2) within constituent unit (X), the mechanical properties of the photosensitive resin composition after curing can be further improved.

[0029] In general formula (x2), 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 methyl group, ethyl group, isopropyl group, n-propyl group, and tert-butyl group, and may contain at least one group selected from the group consisting of methyl group and ethyl group, and may contain a methyl group.

[0030] In the general formula (x2), c and d each independently represent an integer from 0 to 4. From the viewpoint of improving the elastic modulus and tensile elongation of the photosensitive resin composition after curing, c and d are each independently preferably integers from 0 to 2, more preferably 0 or 1.

[0031] From the viewpoint of improving the elastic modulus and tensile elongation of the photosensitive resin composition after curing, the constituent unit (X-2) preferably includes at least one selected from the group consisting of constituent units represented by the following formula (x21) and constituent units represented by the following formula (x22).

[0032] [ka]

[0033] [ka]

[0034] The ratio of constituent unit (X-2) to constituent unit (X) is preferably greater than 0 mol% and 95 mol% or less, more preferably 10 mol% to 90 mol%, even more preferably 20 mol% to 85 mol%, even more preferably 30 mol% to 80 mol%, and even more preferably 40 mol% to 75 mol%. By setting the ratio of constituent unit (X-2) to constituent unit (X) within the above range, the mechanical properties of the photosensitive resin composition after curing can be further improved.

[0035] The ratio of constituent unit (X-2) to constituent unit (X-1) in constituent unit (X) is preferably greater than 0 mol% and 500 mol% or less, more preferably 25 mol% to 450 mol%, even more preferably 50 mol% to 400 mol%, even more preferably 75 mol% to 350 mol%, and even more preferably 100 mol% to 300 mol%. By setting the ratio of constituent unit (X-2) to constituent unit (X-1) within the above range, the mechanical properties of the photosensitive resin composition after curing can be further improved.

[0036] The constituent unit (X) may further include the constituent unit (X-3) represented by the following general formula (x3).

[0037] [ka]

[0038] In the general formula (x3), * represents a bond.

[0039] (Polyimide (A) constituent unit (Y)) The constituent unit (Y) preferably includes a constituent unit (Y-1) represented by the following general formula (y1).

[0040] [ka]

[0041] In general formula (y1), R 3 Each of these independently represents an alkyl group having 1 to 4 carbon atoms. Z 1 This represents a single bond or a divalent organic group. e and f each independently represent integers from 0 to 4. * represents a bond.

[0042] By including constituent unit (Y-1) within constituent unit (Y), the elastic modulus and tensile elongation of the photosensitive resin composition after curing can be improved, and the mean coefficient of linear thermal expansion (CTE) can be reduced.

[0043] In general formula (y1), R 3 Each of these independently represents an alkyl group having 1 to 4 carbon atoms. 3 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.

[0044] In the general formula (y1), e and f each independently represent integers from 0 to 4. e and f may also independently be integers from 0 to 3, or they may be 3.

[0045] In general formula (y1), Z 1 Z represents a single bond or a divalent organic group. 1 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.

[0046] The constituent unit (Y-1) preferably includes a constituent unit represented by the following formula (y11). This improves the elastic modulus and tensile elongation of the photosensitive resin composition after curing and reduces the mean coefficient of linear expansion (CTE).

[0047] [ka]

[0048] The ratio of constituent unit (Y-1) to constituent unit (Y) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, and even more preferably 50 mol% or more. By setting the ratio of constituent unit (Y-1) to constituent unit (Y) to the above lower limit or higher, the elastic modulus and tensile elongation after curing of the photosensitive resin composition can be improved, and the mean coefficient of linear expansion (CTE) can be reduced. The upper limit of the ratio of constituent unit (Y-1) to constituent unit (Y) is not particularly limited, but for example, it may be 100 mol% or less, 95 mol% or less, or 90 mol% or less.

[0049] The ratio of the constituent unit represented by formula (y11) in the constituent unit (Y) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, and even more preferably 50 mol% or more. By setting the ratio of the constituent unit represented by formula (y11) in the constituent unit (Y) to be above the lower limit, the elastic modulus and tensile elongation after curing of the photosensitive resin composition can be improved, and the mean coefficient of linear expansion (CTE) can be reduced. The upper limit of the ratio of the constituent unit represented by formula (y11) in the constituent unit (Y) is not particularly limited, but for example, it may be 100 mol% or less, 95 mol% or less, or 90 mol% or less.

[0050] The constituent unit (Y) preferably includes the constituent unit (Y-2) represented by the following general formula (y2).

[0051] [ka]

[0052] In general formula (y2), Z 2 This represents a single bond, -C(=O)-, or -SO2-. * represents a bond.

[0053] The inclusion of constituent unit (Y-2) in the constituent unit (Y) improves the flexibility of the molecular structure of polyimide (A), thereby improving the tensile elongation of the photosensitive resin composition after curing. Furthermore, because constituent unit (Y-2) contains a polar structure, the solvent solubility of the photosensitive resin composition can be improved.

[0054] Z 2 This can be a single bond, or it can be -C(=O)-, or it can be -C(=O)-.

[0055] The constituent unit (Y-2) may include, for example, at least one selected from the group consisting of the constituent unit represented by the following formula (y21) and the constituent unit represented by the following formula (y22), and may also include the constituent unit represented by the following formula (y21).

[0056] [ka]

[0057] [ka]

[0058] The constituent unit (Y) may include the constituent unit represented by the following formula (y31).

[0059] [ka]

[0060] (Other components of polyimide(A)) The polyimide (A) is preferably a random copolymer. Being a random copolymer reduces the likelihood of structural bias within the polyimide (A) molecule, thereby improving its solvent solubility.

[0061] (Polymerization initiator (B)) The photosensitive resin composition of this embodiment contains a polymerization initiator (B).

[0062] 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.

[0063] The polymerization initiator (B) preferably includes a photoradical generator. This allows the photosensitive resin composition to be cured by exposure.

[0064] Photoradical generators are 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).

[0065] 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.

[0066] The polymerization initiator (B) preferably includes a thermal radical generator. This allows the photosensitive resin composition to be cured by heating.

[0067] 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.

[0068] 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.

[0069] (Polyfunctional (meth)acrylate (C)) The photosensitive resin composition of this embodiment preferably further comprises a polyfunctional (meth)acrylate (C). This improves the curing properties of the photosensitive resin composition.

[0070] Polyfunctional (meth)acrylates (C) are, for example, Difunctional (meth)acrylates such as polyalkylene glycol di(meth)acrylates and alkyl di(meth)acrylates; 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 pentaerythritol tetra(meth)acrylate which may be alkoxylated, and ditrimethylolpropane tetra(meth)acrylate which may be alkoxylated; and It comprises at least one selected from the group consisting of five or more functional (meth)acrylates, such as dipentaerythritol penta(meth)acrylate which may be alkoxylated, and dipentaerythritol hexa(meth)acrylate which may be alkoxylated.

[0071] 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.

[0072] The polyfunctional (meth)acrylate (C) preferably comprises a (meth)acrylate with five or more functions, and more preferably comprises at least one selected from the group consisting of dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate. This improves the photosensitivity of the photosensitive resin composition. It also improves the chemical resistance of the photosensitive resin composition after curing.

[0073] The content of 5- or more functional (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 5- or more functional (meth)acrylate per 100 parts by mass of polyimide (A) to be above the lower limit, the photosensitivity of the photosensitive resin composition can be improved. In addition, the chemical resistance of the photosensitive resin composition after curing can be improved. By setting the content of 5- or more functional (meth)acrylate per 100 parts by mass of polyimide (A) to be below the upper limit, the tensile elongation of the photosensitive resin composition after curing can be improved.

[0074] The content of five- or more functional (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 99 parts by mass or less, and even more preferably 50 parts by mass or more and 98 parts by mass or less. By setting the content of five- or more functional (meth)acrylates per 100 parts by mass of polyfunctional (meth)acrylate (C) to be above the lower limit, the photosensitivity of the photosensitive resin composition can be improved. Furthermore, the chemical resistance of the photosensitive resin composition after curing can be improved. By setting the content of five- or more functional (meth)acrylates per 100 parts by mass of polyfunctional (meth)acrylate (C) to be below the upper limit, the tensile elongation of the photosensitive resin composition after curing can be improved.

[0075] The polyfunctional (meth)acrylate (C) preferably comprises a (meth)acrylate with two to four functionalities, and more preferably a (meth)acrylate with two or three functionalities. This improves the elongation at break after curing of the photosensitive resin composition.

[0076] The content of bifunctional to tetrafunctional (meth)acrylate per 100 parts by mass of polyimide (A) is preferably more than 0 parts by mass and 30 parts by mass or less, more preferably 1 part by mass and 25 parts by mass or less, and even more preferably 2 parts by mass and 20 parts by mass or less. By setting the content of bifunctional to tetrafunctional (meth)acrylate per 100 parts by mass of polyimide (A) to the above range, the mechanical properties of the photosensitive resin composition after curing can be further improved.

[0077] The content of bifunctional to tetrafunctional (meth)acrylate per 100 parts by mass of polyfunctional (meth)acrylate (C) is preferably greater than 0 parts by mass and 70 parts by mass or less, more preferably 1 part by mass and 60 parts by mass or less, and even more preferably 2 parts by mass and 50 parts by mass or less. By setting the content of bifunctional to tetrafunctional (meth)acrylate per 100 parts by mass of polyfunctional (meth)acrylate (C) to above the lower limit, the tensile elongation after curing of the photosensitive resin composition can be improved. By setting the content of bifunctional to tetrafunctional (meth)acrylate per 100 parts by mass of polyfunctional (meth)acrylate (C) to below the upper limit, the photosensitivity of the photosensitive resin composition can be improved. Furthermore, the chemical resistance of the photosensitive resin composition after curing can be improved.

[0078] The polyfunctional (meth)acrylate (C) preferably comprises polyalkylene glycol di(meth)acrylate, more preferably at least one selected from the group consisting of polyethylene glycol di(meth)acrylate and polypropylene glycol di(meth)acrylate, even more preferably polyethylene glycol di(meth)acrylate, even more preferably at least one selected from the group consisting of diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate and tetraethylene glycol di(meth)acrylate, and even more preferably triethylene glycol di(meth)acrylate. This improves the balance between the tensile elongation and heat resistance of the photosensitive resin composition after curing.

[0079] 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, and reduces oxygen permeability.

[0080] 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.

[0081] (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.

[0082] 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 and heat resistance after curing of the photosensitive resin composition can be improved.

[0083] 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), resulting in crosslinking between the polyfunctional (meth)acrylate (C) and the polyimide (A). This is thought to further improve the mechanical properties of the photosensitive resin composition after curing.

[0084] 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.

[0085] (Silane coupling agent (E)) The photosensitive resin composition of this embodiment preferably further comprises a silane coupling agent (E). This improves the adhesion between the cured photosensitive resin composition and the adherend (e.g., a substrate).

[0086] Silane coupling agent (E) is, 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)acrylsilanes 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; 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, It contains at least one selected from the group consisting of ureidosilanes, such as 3-ureidopropyltrialkoxysilane.

[0087] 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) within the above range, the adhesion between the cured product of the photosensitive resin composition and the adherend (e.g., substrate) can be improved.

[0088] 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).

[0089] The silane coupling agent having a cyclic anhydride structure may contain 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 contain 3-trimethoxysilylpropyl succinic anhydride.

[0090] The content of the silane coupling agent having a cyclic anhydride structure 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 the silane coupling agent having a cyclic anhydride structure per 100 parts by mass of polyimide (A) to the above range, the adhesion between the cured product of the photosensitive resin composition and the adherend (e.g., substrate) can be improved.

[0091] The silane coupling agent (E) preferably contains (meth)acrylicsilane. It is believed that the polymerization of (meth)acrylicsilane with the polyfunctional (meth)acrylate (C) can improve the adhesion between the cured photosensitive resin composition and the adherend (e.g., substrate).

[0092] (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.

[0093] 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 adhesion between the cured product of the photosensitive resin composition and the adherend (e.g., substrate) can be improved.

[0094] (Adhesion enhancer) The photosensitive resin composition of this embodiment preferably further contains an adhesion aid. This improves the adhesion between the cured photosensitive resin composition and the adherend (e.g., a substrate).

[0095] The adhesion aids include, for example, nitrogen atom-containing heteroaromatic compounds 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-triazol)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.

[0096] 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.

[0097] (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 groups of the epoxy compound (D) and the acid anhydride groups, which are terminal groups of the polyimide (A), proceeds sufficiently, and the elongation at break after curing of the photosensitive resin composition can be improved.

[0098] The curing catalyst is Phosphonium salts such as tetraphenylphosphonium·4,4'-sulfonyl diphenolate, 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, It may contain at least one selected from the group consisting of imidazoles such as 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole and 2-ethyl-4-methylimidazole, and may also contain a phosphonium salt, or tetraphenylphosphonium·4,4'-sulfonyl diphenolate.

[0099] 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.

[0100] (Antioxidant) The photosensitive resin composition of this embodiment preferably further contains an antioxidant. This helps to suppress the degradation of the photosensitive resin composition.

[0101] 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].

[0102] 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.

[0103] (Surfactants) The photosensitive resin composition of this embodiment preferably further contains a surfactant. This improves the applicability of the photosensitive resin composition.

[0104] Surfactants are, 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, It includes at least one selected from the group consisting of fluorine-based surfactants.

[0105] 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.

[0106] (solvent) The photosensitive resin composition of this embodiment preferably further contains a solvent. This improves the coatability of the photosensitive resin composition.

[0107] The solvent includes, for example, at least one selected from the group consisting of acetone, methyl ethyl ketone, toluene, propylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol 1-monomethyl ether 2-acetate, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzyl alcohol, propylene carbonate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, butyl acetate, γ-butyrolactone, methyl lactate, ethyl lactate, and butyl lactate.

[0108] If the photosensitive resin composition of this embodiment further contains a solvent, the total solid content (non-volatile component) in the photosensitive resin composition may be 10% by mass or more and 50% by mass or less.

[0109] (Physical properties of photosensitive resin compositions) The physical properties of the photosensitive resin composition of this embodiment will be described below.

[0110] According to 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), is preferably greater than 2.8 GPa and less than or equal to 20.0 GPa, more preferably between 3.0 GPa and 15.0 GPa, even more preferably between 3.2 GPa and 10.0 GPa, and even more preferably between 3.4 GPa and 8.0 GPa. Having the storage modulus at 23°C within the above range improves the rigidity and strength of the cured photosensitive resin composition, suppressing crack formation during the manufacture of semiconductor devices.

[0111] 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) in accordance with JIS K 7244-4:1999.DMA The temperature is preferably more than 313°C and 500°C or less, more preferably 315°C to 475°C, and even more preferably 320°C to 450°C. In this embodiment, Tg DMA This is thought to mainly reflect the glass transition temperature of polyimide (A). Tg DMA As long as 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.

[0112] 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 between 259°C and 500°C, more preferably between 265°C and 475°C, and even more preferably between 270°C and 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 As long as the above range is maintained, it is possible to manufacture semiconductor devices with minimal film thickness changes due to chemical treatment.

[0113] 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 25°C to 100°C, more preferably 30°C to 90°C, and even more preferably 35°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, it is possible to achieve both the elongation at break and the elastic modulus after curing of the photosensitive resin composition, thereby enabling the manufacture of semiconductor devices with good connection reliability.

[0114] In accordance with JIS K 7197:2012, the mean coefficient of linear expansion (CTE) of a cured product obtained by curing a photosensitive resin composition at 230°C for 2 hours, measured by thermomechanical analysis (TMA), in the range of 50°C to 100°C, is preferably 20 ppm / °C or more and less than 61 ppm / °C, more preferably 25 ppm / °C or more and 60 ppm / °C or less, and even more preferably 30 ppm / °C or more and 58 ppm / °C or less. Having a mean coefficient of linear expansion (CTE) within this range suppresses warping of the semiconductor device, enabling the manufacture of a semiconductor device with good connection reliability.

[0115] The average value of 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 3% to 70%, more preferably 4% to 60%, and even more preferably 5% to 50%. Having the average elongation at break at 23°C within this range suppresses the occurrence of cracks during the manufacturing of semiconductor devices, enabling the production of semiconductor devices with good connection reliability.

[0116] (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 to the breaking point of the test specimen 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. Measurements are performed on 10 test specimens, and the average value of the elongation at break is calculated.

[0117] (Method for preparing a 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.

[0118] (Uses of photosensitive resin compositions) The photosensitive resin composition of this embodiment is preferably used in semiconductor devices. It 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., in semiconductor devices.

[0119] (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.

[0120] (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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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. [Examples]

[0125] 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.

[0126] (1) Raw materials for polyimide (A) The raw materials used in the synthesis of polyimide (A) are listed below.

[0127] (Diamine) BPF-AN: Represented by the following formula, 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene [ka]

[0128] OTBAF: 9,9-bis(4-amino-3-methylphenyl)fluorene, represented by the following formula. [ka]

[0129] BAF: 9,9-bis(4-aminophenyl)fluorene, represented by the following formula. [ka]

[0130] DABA: 3,5-diaminobenzoic acid, represented by the following formula. [ka]

[0131] MED-J: 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane, represented by the following formula. [ka]

[0132] (acid dianhydride) 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.) [ka]

[0133] PMDA: Pyromellitic anhydride, represented by the following formula. [ka]

[0134] BTDA: A dianhydride of 3,3',4,4'-benzophenonetetracarboxylic acid, represented by the following formula. [ka]

[0135] (2) Synthesis of polyimide (A) In a flask equipped with a Dean-Stark apparatus, 9.0 g of diamine, 11.0 g of acidic dianhydride, and solvents (91.1 g of 3-methyl-2-oxazolidone and 5.5 g of cyclopentyl methyl ether) were added. 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 at 150°C for 1 hour. 3.3 g of 2,6-lutidine was added as a dehydration catalyst, and the mixture was further reacted 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).

[0136] (3) 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), as well as 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).

[0137] (Polymerization initiator (B)) b1: 10 parts by mass of 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyloxime) (BASF Japan's "Irgacure OXE01"), represented by the following formula. [ka]

[0138] b2: Dicumyl peroxide (Parcadox BC-FF, manufactured by Nuurion Pharmaceuticals), 10 parts by mass, represented by the following formula. [ka]

[0139] (Polyfunctional (meth)acrylate (C)) c1: Dipentaerythritol polyacrylate (A-DPH, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), represented by the following formula. [ka]

[0140] c2: A polyfunctional acrylate compound represented by the following formula ("Viscote #802" manufactured by Osaka Organic Chemical Industry Co., Ltd.) [ka]

[0141] c3: Tris(2-acryloyloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "A-9300NT") c4: Triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "3G")

[0142] (Epoxy compound (D)) d1: 4-hydroxybutyl acrylate glycidyl ether (Shinryo Co., Ltd. "4HBAGE"), represented by the following formula. [ka]

[0143] d2: A trifunctional epoxy compound represented by the following formula (VG3101L, manufactured by Printec Co., Ltd.) [ka]

[0144] (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. [ka]

[0145] e2: 2 parts by mass of 3-methacryloyloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), represented by the following formula. [ka]

[0146] (Other ingredients) Adhesion aid: 5-aminotetrazol monohydrate (manufactured by Masuda Chemical Industries Co., Ltd.), 5 parts by mass Curing catalyst: 10 parts by mass of tetraphenylphosphonium·4,4'-sulfonyl diphenolate (manufactured by Sumitomo Bakelite Co., Ltd.), represented by the following formula. [ka]

[0147] 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. [ka]

[0148] Surfactant: Polyether-modified siloxane (BYK-349, manufactured by BYK), 0.1 parts by mass Solvent: γ-Butyrolactone (manufactured by Sanwa Oil & Chemical Industry Co., Ltd.), 600 parts by mass

[0149] (4) Evaluation of photosensitive resin composition (Preparation of hardened material) 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 to achieve a film thickness of 10 μm after drying. Subsequently, a high-pressure mercury lamp was used to apply 600 mJ / cm² of heat. 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.

[0150] (Dynamic viscoelasticity measurement) A test specimen (30 mm × 7 mm × 10 μm thick) was cut from the obtained cured material. Dynamic viscoelasticity (DMA) measurements were performed using a dynamic viscoelasticity analyzer (TA Instruments "Q800") in accordance with JIS K 7244-4:1999, under the conditions of air atmosphere, frequency 1 Hz, tensile mode, heating rate 5 °C / min, chuck distance 20 mm, and 23 °C, to measure the storage modulus at 23 °C. Furthermore, dynamic viscoelasticity (DMA) measurements were performed under 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) was maximum was defined as the glass transition temperature (Tg). DMA)

[0151] (Thermomechanical analysis) A test specimen (20 mm × 4 mm × 10 μm thick) was cut from the obtained cured 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 mean coefficient of linear thermal expansion (CTE) in the range of 50°C to 100°C were determined.

[0152] (Measurement of elongation at break) From the resulting cured material, test specimens (50 mm × 7 mm × 10 μm thick) were cut out. In accordance with JIS K 7197:2012, a thermomechanical analyzer (A&D Co., Ltd. "STB-1225S") was used to measure the elongation at break from the initial position of the test specimen to the point of fracture under the conditions of air atmosphere, tensile mode, chuck distance of 20 mm, tensile speed of 5 mm / min, and 23°C. Measurements were performed on 10 test specimens, and the average value of the elongation at break was calculated.

[0153] [Table 1] [Explanation of symbols]

[0154] 30 Interlayer insulating film 32 Passivation membrane 34 Top layer wiring 40 Redistribution layer 42 Insulating layer 44 Insulating layer 46 Rewiring 50 UBM layers 52 Bump 100 Semiconductor Devices

Claims

1. A polyimide (A) containing a constituent unit represented by the following general formula (1), Polymerization initiator (B), A photosensitive resin composition containing [the specified element]. 【Chemistry 1】 (In general formula (1), X represents a divalent organic group (X) and Y represents a tetravalent organic group (Y), The aforementioned constituent unit (X) includes the constituent unit (X-1) represented by the following general formula (x1). 【Chemistry 2】 (In general formula (x1), R １ Each of these independently represents an alkyl group having 1 to 4 carbon atoms. a and b each independently represent integers from 0 to 4. * indicates a bonding operation.

2. The photosensitive resin composition according to claim 1, further comprising a polyfunctional (meth)acrylate (C).

3. The photosensitive resin composition according to claim 2, wherein the polyfunctional (meth)acrylate (C) comprises a (meth)acrylate with five or more functions.

4. The photosensitive resin composition according to claim 2 or 3, wherein the polyfunctional (meth)acrylate (C) comprises a bifunctional (meth)acrylate with or without four functionalities.

5. The photosensitive resin composition according to claim 2 or 3, wherein the polyfunctional (meth)acrylate (C) comprises polyalkylene glycol di(meth)acrylate.

6. The photosensitive resin composition according to claim 5, wherein the polyalkylene glycol di(meth)acrylate comprises polyethylene glycol di(meth)acrylate.

7. The photosensitive resin composition according to claim 2 or 3, wherein the content of the polyfunctional (meth)acrylate (C) per 100 parts by mass of the polyimide (A) is 10 parts by mass or more and 150 parts by mass or less.

8. The photosensitive resin composition according to claim 1 or 2, wherein the constituent unit (Y) includes a constituent unit (Y-1) represented by the following general formula (y1). 【Transformation 3】 (In general formula (y1), R ３ Each of these independently represents an alkyl group having 1 to 4 carbon atoms. Z １ This represents a single bond or a divalent organic group. e and f each independently represent integers from 0 to 4. * indicates a bonding operation.

9. The photosensitive resin composition according to claim 8, wherein the ratio of the constituent unit (Y-1) in the constituent unit (Y) is 10 mol% or more.

10. The photosensitive resin composition according to claim 1 or 2, wherein the constituent unit (Y) includes a constituent unit (Y-2) represented by the following general formula (y2). 【Chemistry 4】 (In general formula (y2), Z ２ This is a single bond, -C(=O)-, or -SO ２ - represents, * indicates a bonding operation.

11. The photosensitive resin composition according to claim 1 or 2, wherein the polyimide (A) is a random copolymer.

12. The photosensitive resin composition according to claim 1 or 2, further comprising epoxy compound (D).

13. The photosensitive resin composition according to claim 12, wherein the epoxy compound (D) comprises an epoxy compound having a (meth)acryloyl group.

14. The photosensitive resin composition according to claim 1 or 2, further comprising a silane coupling agent (E).

15. The photosensitive resin composition according to claim 14, wherein the silane coupling agent (E) comprises a silane coupling agent having a cyclic anhydride structure.

16. The photosensitive resin composition according to claim 1 or 2, wherein the storage modulus of elasticity at 23°C is greater than 2.8 GPa 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.

17. The glass transition temperature (Tg) of the cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours is measured by dynamic viscoelasticity measurement (DMA) in accordance with JIS K 7244-4:1999. ＤＭＡ The photosensitive resin composition according to claim 1 or 2, wherein the temperature is greater than 313°C.

18. The glass transition temperature (Tg) of the cured product obtained by curing the photosensitive resin composition at 230°C for 2 hours is measured by thermomechanical analysis (TMA) in accordance with JIS K 7197:2012. ＴＭＡ The photosensitive resin composition according to claim 1 or 2, wherein the temperature is greater than 259°C.

19. Based on 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 based on 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 When so defined, Tg ＤＭＡ - Tg ＴＭＡ is 25°C or higher. The photosensitive resin composition according to claim 1 or 2

20. The photosensitive resin composition according to claim 1 or 2, wherein the mean coefficient of linear thermal 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 less than 61 ppm / °C.

21. The photosensitive resin composition according to claim 1 or 2, wherein the average value of 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 3% or more. (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 to the breaking point of the test specimen 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. Measurements are performed on 10 test specimens, and the average value of the elongation at break is calculated.

22. A photosensitive resin composition according to claim 1 or 2, used in semiconductor devices.

23. A cured product of the photosensitive resin composition according to claim 1 or 2.

24. A semiconductor device comprising the cured product described in claim 23.

25. Interlayer insulating film and A resin film containing the cured product described in claim 23 is provided on the interlayer insulating film, The rewiring embedded in the aforementioned resin film, The semiconductor device according to claim 24, comprising:

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