Photosensitive resin composition, cured product, and semiconductor device

Abstract

The present invention provides a photosensitive resin composition with improved adhesion to copper after curing. [Solution] A photosensitive resin composition comprising: component (A), which is at least one selected from the group consisting of polyimide and its precursors containing a structural unit represented by the following general formula (1), and polybenzoxazole and its precursors containing a structural unit having a ketone group; a polymerization initiator (B); and an aromatic heterocyclic compound (C) having an amino group. TIFF2026109040000049.tif44153 (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 (Y) includes a constituent unit (Y-1) which has a ketone group.)

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 an objective to provide a photosensitive resin composition that does not precipitate during low-temperature storage, has high adhesion to copper or copper alloys, and provides a cured film with suppressed migration. The negative-type photosensitive resin composition is described, comprising (A) at least one resin selected from (A1) a polyimide precursor and (A2) a polyimide, (B) a photopolymerization initiator, (C) a nitrogen-containing heterocyclic compound, and (D) a solvent, wherein the (A1) polyimide precursor is a polyamic acid ester or polyamic acid salt represented by a predetermined formula, the (A2) polyimide is a polyimide resin represented by a predetermined formula, the photosensitive resin composition further contains (E) an inhibitor of precipitation of the (C) nitrogen-containing heterocyclic compound, the (C) nitrogen-containing heterocyclic compound is a tetrazole compound, and the Hansen solubility parameter of the (E) inhibitor is in the following range (△D: 15.2~21.2, △P: 8.9~14.9, △H: 9.0~14.3). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-86702 [Overview of the project] [Problems that the invention aims to solve]

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

[0006] The present inventors have found that in a photosensitive resin composition comprising polyimide and its precursors, and polybenzoxazole and its precursors, and a polymerization initiator, the adhesion of the photosensitive resin composition to copper after curing can be improved if the photosensitive resin composition contains an aromatic heterocyclic compound having an amino group, and if at least one of the polyimide and its precursors, and polybenzoxazole and its precursors, contains a structural unit having a ketone group, thereby completing the present invention.

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

[0008] [1] Component (A) is at least one selected from the group consisting of polyimides and their precursors containing a structural unit represented by the following general formula (1), and polybenzoxazoles and their precursors containing a structural unit having a ketone group. Polymerization initiator (B), A heterocyclic aromatic compound (C) having an amino group, A photosensitive resin composition containing [the specified element]. [ka] (In general formula (1), X represents a divalent organic group (X) and Y represents a tetravalent organic group (Y), The aforementioned constituent unit (Y) includes a constituent unit (Y-1) having a ketone group. [2] The photosensitive resin composition according to [1], wherein the aromatic heterocyclic compound (C) comprises an azole compound having an amino group. [3] The azole compound having an amino group is the photosensitive resin composition according to [2], which contains at least one selected from the group consisting of tetrazole having an amino group, triazole having an amino group, and derivatives thereof. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the ratio of the structural unit (Y-1) in the structural unit (Y) is 10 mol% or more. [5] The structural unit (Y-1) contains at least one selected from the group consisting of a structural unit represented by the following general formula (y11), a structural unit represented by the following general formula (y12), and a structural unit represented by the following general formula (y13). The photosensitive resin composition according to any one of [1] to [4]. [Chemical formula] (In the general formula (y11), * represents a bond.) [Chemical formula] (In the general formula (y12), * represents a bond.) [Chemical formula] (In the general formula (y13), Z 1 represents a single bond, -C(=O)-, -O-, or -S-, * represents a bond.) [6] The photosensitive resin composition according to any one of [1] to [5], further containing a polyfunctional (meth)acrylate (D). [7] The photosensitive resin composition according to [6], wherein the polyfunctional (meth)acrylate (D) contains a (meth)acrylate having 5 or more functional groups. [8] The photosensitive resin composition according to [6] or [7], wherein the polyfunctional (meth)acrylate (D) contains a (meth)acrylate having 2 or more and 4 or less functional groups. [9] The photosensitive resin composition according to any one of [6] to [8], wherein the polyfunctional (meth)acrylate (D) comprises a polyalkylene glycol di(meth)acrylate.

[10] The photosensitive resin composition according to [9], wherein the polyalkylene glycol di(meth)acrylate comprises polyethylene glycol di(meth)acrylate.

[11] The photosensitive resin composition according to any one of [6] to

[10] , wherein the content of the polyfunctional (meth)acrylate (D) per 100 parts by mass of component (A) is 20 parts by mass or more and 150 parts by mass or less.

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

[11] , wherein the aforementioned constituent unit (Y) further comprises a constituent unit (Y-2) represented by the following general formula (y2). [ka] (In general formula (y2), R 4 Each of these independently represents an alkyl group having 1 to 4 carbon atoms. Z 2 This represents a single bond or a divalent organic group. g and h each independently represent integers from 0 to 4. * represents a bond.

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

[12] , further comprising epoxy compound (E).

[14] The photosensitive resin composition according to

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

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

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

[16] The photosensitive resin composition according to

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

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

[16] , wherein the average value of the peel strength obtained by the following method is greater than 0.7 N / cm. (method) The photosensitive resin composition is applied to a silicon wafer having a copper plating layer with a thickness of 3000 angstroms on its surface, and dried to obtain a photosensitive resin film with a thickness of 10 μm. The obtained photosensitive resin film is subjected to a 300 mJ / cm² test using an i-line stepper. 2 The photosensitive resin film is exposed to light. The exposed photosensitive resin film is developed using a spray developer while rotating at 2500 rpm with cyclopentanone for 30 seconds, followed by propylene glycol monomethyl ether acetate for 10 seconds. After development, the photosensitive resin film is air-dried using a spin dryer, then dried on a hot plate at 120°C for 2 minutes, and heat-treated at 230°C for 2 hours under a nitrogen atmosphere to obtain a cured film. A silicon wafer is cut to obtain a test piece with a width of 7 mm and a length of 50 mm. The end 5 mm of the test piece is immersed in a 2 mass% hydrofluoric acid aqueous solution at 23°C for 6 hours, then washed with water and dried to peel off the cured film from the end of the test piece. The cured film is peeled off at a rate of 90° and a peeling speed of 20 mm / min, and the peel strength is measured. The average value of the three measurements is calculated.

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

[17] , wherein the photosensitive resin composition obtained by the following method is cured at 230°C for 2 hours, and the cured product has a breaking elongation of 10% or more at 23°C. (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. The average value obtained from measurements of 10 test specimens is taken as the elongation at break.

[19] A photosensitive resin composition used in semiconductor devices, according to any one of [1] to

[18] .

[20] A cured product of a photosensitive resin composition described in any one of [1] to

[19] . [twenty one] A semiconductor device comprising the cured product described in

[20] . [twenty two] Interlayer insulating film and A resin film containing the cured product described in

[20] is provided on the interlayer insulating film, The rewiring embedded in the aforementioned resin film, The semiconductor device described in

[21] , comprising: [Effects of the Invention]

[0009] According to the present invention, a photosensitive resin composition with improved adhesion to copper 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 component (A), which is at least one selected from the group consisting of polyimide and its precursors containing a structural unit represented by the following general formula (1), and polybenzoxazole and its precursors containing a structural unit having a ketone group; a polymerization initiator (B); and an aromatic heterocyclic compound (C) having an amino group. [ka]

[0013] In general formula (1), X represents a divalent organic group (X) and Y represents a tetravalent organic group (Y).

[0014] In this embodiment, the constituent unit (Y) includes a constituent unit (Y-1) having a ketone group.

[0015] The adhesion of a photosensitive resin composition to copper after curing can be improved by including component (A), polymerization initiator (B), and aromatic heterocyclic compound (C). Although the mechanism is not entirely clear, the inventors' investigations suggest the following: Component (A) contains a structural unit having a ketone group, and aromatic heterocyclic compound (C) has an amino group. Therefore, dehydration condensation between component (A) and aromatic heterocyclic compound (C) generates an imine. This causes the aromatic heterocycle derived from aromatic heterocyclic compound (C) to bond to component (A) via an imino group. The aromatic heterocycle derived from aromatic heterocyclic compound (C) contributes to the improved adhesion of the photosensitive resin composition to copper after curing. The bonding of the aromatic heterocycle derived from aromatic heterocyclic compound (C) to component (A) via an imino group improves the adhesion of the photosensitive resin composition to copper after curing.

[0016] (Component (A)) Component (A) is at least one selected from the group consisting of polyimides containing a structural unit represented by general formula (1) and their precursors, and polybenzoxazoles containing a structural unit having a ketone group and their precursors. Component (A) may also include polyimides containing a structural unit represented by general formula (1). Polyimide precursors include polyamic acids. Polybenzoxazole precursors include polyhydroxyamides.

[0017] (Polyimide constituent unit (X)) The constituent unit (X) may include at least one selected from the group consisting of the constituent unit (X-1) represented by the following general formula (x1), the constituent unit (X-2) represented by the following general formula (x2), the constituent unit (X-3) represented by the following general formula (x3), and the constituent unit represented by the following formula (x41).

[0018] The constituent unit (X) preferably includes at least one selected from the group consisting of constituent unit (X-1) represented by the following general formula (x1), constituent unit (X-2) represented by the following general formula (x2), and constituent unit (X-3) represented by the following general formula (x3). This improves the elastic modulus of the photosensitive resin composition. Constituent unit (X) may also include constituent unit (X-1) represented by the following general formula (x1).

[0019] The constituent unit (X) may include the constituent unit represented by the following formula (x41).

[0020] [ka]

[0021] 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 between 0 and 4. * represents a bond.

[0022] [ka]

[0023] 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.

[0024] [ka]

[0025] In the general formula (x3), R 3 each independently represents an alkyl group having 1 to 4 carbon atoms, e and f each independently represent an integer of 0 to 3, * represents a bond.

[0026]

Chemical formula

[0027] In the formula (x41), * represents a bond.

[0028] In the general formula (x1), R 1 each independently represents an alkyl group having 1 to 4 carbon atoms. R 1 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, may contain at least one group selected from the group consisting of a methyl group and an ethyl group, and may contain a methyl group.

[0029] In the general formula (x1), a and b each independently represent an integer of 0 to 4. a and b may each independently be an integer of 0 to 2, may be 0 or 1, and may be 1.

[0030] The structural unit (X-1) may contain at least one kind selected from the group consisting of, for example, a structural unit represented by the following formula (x11) and a structural unit represented by the following formula (x12), and may contain a structural unit represented by the following formula (x11).

[0031]

Chemical formula

[0032]

Chemical formula

[0033] The ratio of constituent unit (X-1) to constituent unit (X) may be 0 mol% or more and 100 mol% or less, 10 mol% or more and 90 mol% or less, or 20 mol% or more and 80 mol% or less.

[0034] 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.

[0035] In the general formula (x²), c and d each independently represent integers from 0 to 4. C and d can each independently be 0 or 1, or they can be 0.

[0036] The constituent unit (X-2) may include, for example, the constituent unit represented by the following formula (x21).

[0037] [ka]

[0038] In general formula (x3), R 3 Each of these independently represents an alkyl group having 1 to 4 carbon atoms. 3 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.

[0039] In the general formula (x3), e and f each independently represent integers between 0 and 3. E and f can each independently be 0 or 1, or 1.

[0040] The constituent unit (X-3) may include, for example, the constituent unit represented by the following formula (x31).

[0041] [ka]

[0042] The constituent unit (X) may include the constituent unit (X-5) represented by the following general formula (x5).

[0043] [ka]

[0044] In the general formula (x5), * represents a bond.

[0045] The constituent unit (X-5) may include, for example, the constituent unit represented by the following formula (x51).

[0046] [ka]

[0047] (Polyimide constituent unit (Y)) The constituent unit (Y) includes a constituent unit (Y-1) that has a ketone group.

[0048] The constituent unit (Y-1) preferably includes at least one selected from the group consisting of the constituent unit represented by the following general formula (y11), the constituent unit represented by the following general formula (y12), and the constituent unit represented by the following general formula (y13). This further improves the adhesion of the photosensitive resin composition to copper after curing. The constituent unit (Y-1) may also include the constituent unit represented by the following general formula (y11).

[0049] [ka]

[0050] In the general formula (y11), * represents a bond.

[0051] [ka]

[0052] In the general formula (y12), * represents a bond.

[0053] [ka]

[0054] In general formula (y13), Z 1 This represents a single bond, -C(=O)-, -O-, or -S-. * represents a bond.

[0055] The constituent unit represented by the general formula (y11) may include, for example, at least one selected from the group consisting of the constituent unit represented by the following formula (y111) (a constituent unit derived from 3,3',4,4'-benzophenonetetracarboxylic dianhydride) and the constituent unit represented by the following formula (y112) (a constituent unit derived from 2,2',3,3'-benzophenonetetracarboxylic dianhydride), and may also include the constituent unit represented by the following formula (y111).

[0056] [ka]

[0057] [ka]

[0058] The constituent units represented by the general formula (y12) may include, for example, at least one selected from the group consisting of constituent units derived from 1,3-bis(3,4-dicarboxybenzoyl)benzene dianhydride, constituent units derived from 1,4-bis(3,4-dicarboxybenzoyl)benzene dianhydride, constituent units derived from 1,3-bis(2,3-dicarboxybenzoyl)benzene dianhydride, and constituent units derived from 1,4-bis(2,3-dicarboxybenzoyl)benzene dianhydride.

[0059] In general formula (y13), Z 1 represents a single bond, -C(=O)-, -O-, or -S-. That is, the constituent units represented by general formula (y13) may include, for example, at least one selected from the group consisting of constituent units derived from 2,3,6,7-(9-fluorenone)tetracarboxylic dianhydride, constituent units derived from 2,3,6,7-anthraquinonetetracarboxylic dianhydride, constituent units derived from 2,3,6,7-thioxanthonetetracarboxylic dianhydride, and constituent units derived from 2,3,6,7-xanthonetetracarboxylic dianhydride.

[0060] The ratio of constituent unit (Y-1) to constituent unit (Y) is preferably 10 mol% to 100 mol%, more preferably 20 mol% to 95 mol%, even more preferably 30 mol% to 90 mol%, even more preferably 40 mol% to 80 mol%, and even more preferably 50 mol% to 75 mol%. By setting the ratio of constituent unit (Y-1) to constituent unit (Y) within the above range, the adhesion of the photosensitive resin composition to copper after curing can be further improved.

[0061] The constituent unit (Y) preferably further comprises a constituent unit (Y-2) 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).

[0062] [ka]

[0063] In general formula (y2), R 4 Each of these independently represents an alkyl group having 1 to 4 carbon atoms. Z 2 This represents a single bond or a divalent organic group. g and h each independently represent integers from 0 to 4. * represents a bond.

[0064] In general formula (y2), R 4 Each of these independently represents an alkyl group having 1 to 4 carbon atoms. 4 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.

[0065] In the general formula (y²), g and h each independently represent an integer between 0 and 4. g and h may also independently be an integer between 0 and 3, or they may be 3.

[0066] In general formula (y2), Z 2 Z represents a single bond or a divalent organic group. 2 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.

[0067] The constituent unit (Y-2) preferably includes a 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).

[0068] [ka]

[0069] The ratio of constituent unit (Y-2) to constituent unit (Y) is preferably greater than 0 mol% and 90 mol% or less, more preferably 5 mol% to 80 mol%, even more preferably 10 mol% to 70 mol%, even more preferably 20 mol% to 60 mol%, and even more preferably 25 mol% to 50 mol%. By setting the ratio of constituent unit (Y-2) to constituent unit (Y) within the above range, 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.

[0070] (Other components of polyimide) The polyimide is preferably a random copolymer. Being a random copolymer reduces the likelihood of structural bias within the polyimide molecule, thereby improving its solvent solubility.

[0071] (Polymerization initiator (B)) The photosensitive resin composition of this embodiment contains a polymerization initiator (B).

[0072] The amount of polymerization initiator (B) per 100 parts by mass of component (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.

[0073] The polymerization initiator (B) preferably includes a photoradical generator. This allows the photosensitive resin composition to be cured by exposure.

[0074] 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).

[0075] The amount of photoradical generator per 100 parts by mass of component (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.

[0076] The polymerization initiator (B) preferably includes a thermal radical generator. This allows the photosensitive resin composition to be cured by heating.

[0077] 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.

[0078] The amount of thermal radical generator per 100 parts by mass of component (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.

[0079] (Aromatic heterocyclic compounds (C)) The photosensitive resin composition of this embodiment contains an aromatic heterocyclic compound (C) having an amino group.

[0080] The content of aromatic heterocyclic compound (C) per 100 parts by mass of component (A) is preferably more than 0 parts by mass and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 15 parts by mass or less, even more preferably 0.5 parts by mass or more and 10 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 aromatic heterocyclic compound (C) per 100 parts by mass of component (A) within the above range, the adhesion of the photosensitive resin composition to copper after curing can be further improved.

[0081] The aromatic heterocyclic compound (C) may include an azole compound having an amino group.

[0082] Azole compounds having an amino group, 5-aminotetrazole and tetrazoles containing an amino group, such as 5-amino-1-methyltetrazole; Triazoles having an amino group, such as 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, and 3-amino-5-mercapto-1,2,4-triazole; and It may also include at least one selected from the group consisting of these derivatives.

[0083] The azole compound having an amino group may include at least one selected from the group consisting of 5-aminotetrazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole.

[0084] When the aromatic heterocyclic compound (C) contains an azole compound having an amino group, the content of the azole compound having an amino group per 100 parts by mass of component (A) is preferably more than 0 parts by mass and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 15 parts by mass or less, even more preferably 0.5 parts by mass or more and 10 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 azole compound having an amino group per 100 parts by mass of component (A) to the above range, the adhesion of the photosensitive resin composition to copper after curing can be further improved.

[0085] In this embodiment, the aromatic heterocyclic compound (C) preferably does not have a carboxyl group. This further improves the adhesion of the photosensitive resin composition to copper after curing.

[0086] (Polyfunctional (meth)acrylate (D)) The photosensitive resin composition of this embodiment preferably further comprises a polyfunctional (meth)acrylate (D). This improves the curing properties of the photosensitive resin composition.

[0087] Polyfunctional (meth)acrylates (D) 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.

[0088] The content of polyfunctional (meth)acrylate (D) per 100 parts by mass of component (A) is preferably 20 parts by mass or more and 150 parts by mass or less, more preferably 25 parts by mass or more and 100 parts by mass or less, and even more preferably 30 parts by mass or more and 75 parts by mass or less. By setting the content of polyfunctional (meth)acrylate (D) per 100 parts by mass of component (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.

[0089] The polyfunctional (meth)acrylate (D) 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.

[0090] The content of 5- or more functional (meth)acrylate per 100 parts by mass of component (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 component (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 component (A) to be below the upper limit, the tensile elongation of the photosensitive resin composition after curing can be improved.

[0091] The content of five- or more functional (meth)acrylates per 100 parts by mass of polyfunctional (meth)acrylate (D) is preferably 20 parts by mass or more and 100 parts by mass or less, more preferably 30 parts by mass or more and 99 parts by mass or less, and even more preferably 40 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 (D) 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 (D) to be below the upper limit, the tensile elongation of the photosensitive resin composition after curing can be improved.

[0092] The polyfunctional (meth)acrylate (D) 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 of the photosensitive resin composition after curing.

[0093] The content of bifunctional to tetrafunctional (meth)acrylate per 100 parts by mass of component (A) is preferably more than 0 parts by mass and 40 parts by mass or less, more preferably 1 part by mass and 35 parts by mass or less, and even more preferably 2 parts by mass and 30 parts by mass or less. By setting the content of bifunctional to tetrafunctional (meth)acrylate per 100 parts by mass of component (A) within the above range, the mechanical properties of the photosensitive resin composition after curing can be improved.

[0094] The content of bifunctional to tetrafunctional (meth)acrylate per 100 parts by mass of polyfunctional (meth)acrylate (D) is preferably greater than 0 parts by mass and 80 parts by mass or less, more preferably 1 part by mass and 70 parts by mass or less, and even more preferably 2 parts by mass and 60 parts by mass or less. By setting the content of bifunctional to tetrafunctional (meth)acrylate per 100 parts by mass of polyfunctional (meth)acrylate (D) 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 (D) 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.

[0095] The polyfunctional (meth)acrylate (D) 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.

[0096] The polyfunctional (meth)acrylate (D) 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.

[0097] 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.

[0098] (Epoxy compound (E)) The photosensitive resin composition of this embodiment preferably further comprises an epoxy compound (E). The epoxy compound (E) is a compound having an epoxy group. It is believed that the epoxy group of the epoxy compound (E) reacts with the acid anhydride group or carboxyl group, which are terminal groups of component (A), to form an ester bond, thereby improving the tensile elongation of the photosensitive resin composition after curing.

[0099] The content of epoxy compound (E) per 100 parts by mass of component (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 (E) per 100 parts by mass of component (A) within the above range, the balance between the tensile elongation and heat resistance after curing of the photosensitive resin composition can be improved.

[0100] The epoxy compound (E) 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 (D), causing crosslinking between the polyfunctional (meth)acrylate (D) and component (A). This is thought to further improve the mechanical properties of the photosensitive resin composition after curing.

[0101] 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.

[0102] (Silane coupling agent (F)) The photosensitive resin composition of this embodiment preferably further comprises a silane coupling agent (F). This further improves the adhesion of the photosensitive resin composition to copper after curing.

[0103] Silane coupling agent (F) 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.

[0104] The content of the silane coupling agent (F) per 100 parts by mass of component (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 (F) per 100 parts by mass of component (A) within the above range, the adhesion of the photosensitive resin composition to copper after curing can be further improved.

[0105] The silane coupling agent (F) preferably includes a silane coupling agent having a cyclic anhydride structure. It is believed that the cyclic anhydride structure reacts with the amino group, which is the terminal group of component (A), and with the epoxy compound (E), thereby further improving the adhesion of the photosensitive resin composition to copper after curing.

[0106] 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.

[0107] The content of the silane coupling agent having a cyclic anhydride structure per 100 parts by mass of component (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 component (A) to the above range, the adhesion of the photosensitive resin composition to copper after curing can be further improved.

[0108] The silane coupling agent (F) preferably contains (meth)acrylicsilane. It is believed that the polymerization of (meth)acrylicsilane with the polyfunctional (meth)acrylate (D) can further improve the adhesion of the photosensitive resin composition to copper after curing.

[0109] (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.

[0110] The content of (meth)acrylsilane per 100 parts by mass of component (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 component (A) within the above range, the adhesion of the photosensitive resin composition to copper after curing can be further improved.

[0111] (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 (E) and a curing catalyst. By including a curing catalyst in the photosensitive resin composition, the reaction between the epoxy group of the epoxy compound (E) and the acid anhydride group or carboxyl group which are terminal groups of component (A) proceeds sufficiently, and the elongation at break after curing of the photosensitive resin composition can be improved.

[0112] 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.

[0113] The content of the curing catalyst per 100 parts by mass of component (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.

[0114] (Antioxidant) The photosensitive resin composition of this embodiment preferably further contains an antioxidant. This helps to suppress the degradation of the photosensitive resin composition.

[0115] 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].

[0116] The amount of antioxidant per 100 parts by mass of component (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.

[0117] (Surfactants) The photosensitive resin composition of this embodiment preferably further contains a surfactant. This improves the applicability of the photosensitive resin composition.

[0118] 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.

[0119] The amount of surfactant per 100 parts by mass of component (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.

[0120] (Precipitation inhibitor) The photosensitive resin composition of this embodiment does not necessarily contain an inhibitor of precipitation with Hansen solubility parameters (HSP) of △D: 15.2 to 21.2, △P: 8.9 to 14.9, and △H: 9.0 to 14.3. △D represents the energy due to intermolecular dispersion forces, △P represents the energy due to intermolecular dipole interactions, and △H represents the energy due to intermolecular hydrogen bonding.

[0121] (solvent) The photosensitive resin composition of this embodiment preferably further contains a solvent. This improves the coatability of the photosensitive resin composition.

[0122] 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.

[0123] 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.

[0124] (Physical properties of photosensitive resin compositions) The physical properties of the photosensitive resin composition of this embodiment will be described below.

[0125] The average peel strength of the photosensitive resin composition of this embodiment can be obtained by the following method.

[0126] (method) A photosensitive resin composition is applied to a silicon wafer having a 3000 angstrom thick copper plating layer on its surface, and dried to obtain a photosensitive resin film with a thickness of 10 μm. The obtained photosensitive resin film is then subjected to a 300 mJ / cm² test using an i-line stepper. 2 The photosensitive resin film is exposed to light. The exposed photosensitive resin film is developed using a spray developer while rotating at 2500 rpm with cyclopentanone for 30 seconds, followed by propylene glycol monomethyl ether acetate for 10 seconds. After development, the photosensitive resin film is air-dried using a spin dryer, then dried on a hot plate at 120°C for 2 minutes, and heat-treated at 230°C for 2 hours under a nitrogen atmosphere to obtain a cured film. A silicon wafer is cut to obtain a test piece measuring 7 mm wide x 50 mm long. The end 5 mm of the test piece is immersed in a 2 mass% hydrofluoric acid aqueous solution at 23°C for 6 hours, then washed with water and dried to peel off the cured film from the end of the test piece. The cured film is peeled 1 cm at a 90° angle and a peeling speed of 20 mm / min, and the peel strength is measured. The average value of the three measurements is taken.

[0127] In the photosensitive resin composition of this embodiment, the average value of the peel strength is preferably greater than 0.7 N / cm, more preferably 0.8 N / cm or more, even more preferably 0.9 N / cm or more, and even more preferably 1.0 N / cm or more. Having an average value of peel strength greater than or equal to the above lower limit further improves the adhesion of the photosensitive resin composition to copper after curing. The upper limit of the average value of the peel strength is not particularly limited, but for example, it may be 3.0 N / cm or less, 2.5 N / cm or less, or 2.0 N / cm or less.

[0128] Furthermore, the adhesion evaluated by the above method differs from the adhesion evaluated by the cross-cut method specified in JIS K 5600-5-6:1999. Specifically, the above method differs from the cross-cut method specified in JIS K 5600-5-6:1999 in that it measures the stress at the edges of the interface when peeling the hardened film from the copper plating layer. In addition, the above method is preferable as a method for measuring the peel strength of the photosensitive resin composition of this embodiment because it can evaluate a higher level of adhesion that cannot be evaluated by a normal peel resistance test (for example, the cross-cut method specified in JIS K 5600-5-6:1999). In the cross-cut method specified in JIS K 5600-5-6:1999, a photosensitive resin composition that is evaluated as having sufficient adhesion to copper may be evaluated as having insufficient adhesion to copper by the above method.

[0129] The elongation at break of the cured product obtained by curing the photosensitive resin composition, obtained by the following method, at 230°C for 2 hours is preferably 10% to 80%, more preferably 12% to 70%, even more preferably 14% to 60%, and still more preferably 16% to 55%. Having the 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.

[0130] (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. The average value obtained from measurements of 10 test specimens is taken as the elongation at break.

[0131] (Method for preparing a photosensitive resin composition) The photosensitive resin composition of this embodiment can be prepared, for example, by mixing the above-mentioned components in a solvent. By polymerizing component (A) with a diamine and an acidic dianhydride, polyamic acid, a precursor of polyimide, is obtained. By heating the polyamic acid to carry out a dehydration and cyclization reaction, polyimide is obtained. Alternatively, by polymerizing a bis(aminophenol) compound with a dicarbonyl chloride or dicarboxylic acid, polyhydroxyamide, a precursor of polybenzoxazole, is obtained. By heating the polyhydroxyamide to carry out a dehydration and cyclization reaction, polybenzoxazole is obtained.

[0132] (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.

[0133] (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.

[0134] (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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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]

[0139] 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.

[0140] (1) Raw materials for polyimide The raw materials used in the synthesis of polyimide are listed below.

[0141] (Diamine) OTBAF: 9,9-bis(4-amino-3-methylphenyl)fluorene, represented by the following formula. [ka]

[0142] BPF-AN: Represented by the following formula, 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene [ka]

[0143] TSN: 3,7-diamino-2,8-dimethyldibenzothiofensulfone, represented by the following formula. [ka]

[0144] DABA: 3,5-diaminobenzoic acid, represented by the following formula. [ka]

[0145] MED-J: 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane, represented by the following formula. [ka]

[0146] (acid dianhydride) BTDA: A dianhydride of 3,3',4,4'-benzophenonetetracarboxylic acid, represented by the following formula. [ka]

[0147] 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]

[0148] PMDA: Pyromellitic anhydride, represented by the following formula. [ka]

[0149] (2) Synthesis of polyimides 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.

[0150] (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, as well as the types and amounts of solvents, are shown below. The amounts of aromatic heterocyclic compounds (C), polyfunctional (meth)acrylates (D), and epoxy compounds (E) are shown in Table 1. The amounts of each raw material and solvent are relative to 100 parts by mass of polyimide.

[0151] (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]

[0152] b2: Dicumyl peroxide (Parcadox BC-FF, manufactured by Nuurion Pharmaceuticals), 10 parts by mass, represented by the following formula. [ka]

[0153] (Aromatic heterocyclic compounds (C)) c1:5-aminotetrazole (manufactured by Masuda Chemical Industries Co., Ltd.) c2:3-amino-1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.) c3: 3,5-diamino-1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0154] (Polyfunctional (meth)acrylate (D)) d1: Dipentaerythritol polyacrylate (A-DPH, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), represented by the following formula. [ka]

[0155] d2: A polyfunctional acrylate compound represented by the following formula ("Viscote #802" manufactured by Osaka Organic Chemical Industry Co., Ltd.) [ka]

[0156] d3: Tris(2-acryloyloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "A-9300NT") d4: Triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "3G")

[0157] (Epoxy compound (E)) e1: 4-hydroxybutyl acrylate glycidyl ether represented by the following formula (Shinryo Co., Ltd. "4HBAGE") [ka]

[0158] e2: A trifunctional epoxy compound represented by the following formula (Printec Co., Ltd. "VG3101L") [ka]

[0159] (Silane coupling agent (F)) f1: 2 parts by mass of 3-trimethoxysilylpropyl succinic anhydride (Shin-Etsu Chemical Co., Ltd. "X-12-967C"), represented by the following formula. [ka]

[0160] f2: 2 parts by mass of 3-methacryloyloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), represented by the following formula. [ka]

[0161] (Other ingredients) Curing catalyst: 10 parts by mass of tetraphenylphosphonium·4,4'-sulfonyl diphenolate (manufactured by Sumitomo Bakelite Co., Ltd.), represented by the following formula. [ka]

[0162] 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]

[0163] 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

[0164] (4) Evaluation of photosensitive resin composition (Measurement of peel strength) A photosensitive resin composition was applied to a silicon wafer having a 3000 angstrom thick copper plating layer on its surface, and dried to obtain a photosensitive resin film with a thickness of 10 μm. The obtained photosensitive resin film was subjected to a 300 mJ / cm² test using an i-line stepper (Canon FPA-5550iX). 2The photosensitive resin film was exposed to light. The exposed photosensitive resin film was developed using a spray developer while rotating at 2500 rpm with cyclopentanone for 30 seconds, followed by propylene glycol monomethyl ether acetate for 10 seconds. After development, the photosensitive resin film was air-dried using a spin dryer, then dried on a hot plate at 120°C for 2 minutes, and heat-treated at 230°C for 2 hours under a nitrogen atmosphere to obtain a cured film. A silicon wafer was cut to obtain a test piece measuring 7 mm wide x 50 mm long. The end 5 mm of the test piece was immersed in a 2 mass% hydrofluoric acid aqueous solution at 23°C for 6 hours, then washed with water and dried to peel off the cured film from the end of the test piece. Using a precision universal tester (Shimadzu Corporation "AUTOGRAPH AG-Xplus"), the cured film was peeled 1 cm at a 90° angle and a peeling speed of 20 mm / min, and the peel strength was measured. The average value of the three measurements was calculated.

[0165] Furthermore, the photosensitive resin compositions of each example and comparative example exhibited sufficient adhesion to copper, as evaluated by the cross-cut method specified in JIS K 5600-5-6:1999.

[0166] (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.

[0167] (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 )

[0168] (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.

[0169] (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. The average value obtained from measurements of 10 test specimens was defined as the elongation at break.

[0170] Table 1 shows the evaluation results for each example and comparative example.

[0171] [Table 1]

Explanation of Symbols

[0172] 30 Interlayer Insulation Film 32 Passivation Film 34 Topmost Layer Wiring 40 Rewiring Layer 42 Insulation Layer 44 Insulation Layer 46 Rewiring 50 UBM Layer 52 Bump 100 Semiconductor Device

Claims

1. Component (A) is at least one selected from the group consisting of polyimides and their precursors containing a structural unit represented by the following general formula (1), and polybenzoxazoles and their precursors containing a structural unit having a ketone group. Polymerization initiator (B), A heterocyclic aromatic compound (C) having an amino group, 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 (Y) includes a constituent unit (Y-1) having a ketone group.

2. The photosensitive resin composition according to claim 1, wherein the aromatic heterocyclic compound (C) comprises an azole compound having an amino group.

3. The photosensitive resin composition according to claim 2, wherein the azole compound having an amino group comprises at least one selected from the group consisting of tetrazoles having an amino group, triazoles having an amino group, and derivatives thereof.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the ratio of the constituent unit (Y-1) in the constituent unit (Y) is 10 mol% or more.

5. The photosensitive resin composition according to any one of claims 1 to 3, wherein the constituent unit (Y-1) includes at least one selected from the group consisting of a constituent unit represented by the following general formula (y11), a constituent unit represented by the following general formula (y12), and a constituent unit represented by the following general formula (y13). 【Chemistry 2】 (In the general formula (y11), * represents a bond.) 【Transformation 3】 (In the general formula (y12), * represents a bond.) 【Chemistry 4】 (In general formula (y13), Z １ This represents a single bond, -C(=O)-, -O-, or -S-. * indicates a bonding operation.

6. A photosensitive resin composition according to any one of claims 1 to 3, further comprising a polyfunctional (meth)acrylate (D).

7. The photosensitive resin composition according to claim 6, wherein the polyfunctional (meth)acrylate (D) comprises a (meth)acrylate with five or more functionalities.

8. The photosensitive resin composition according to claim 6, wherein the polyfunctional (meth)acrylate (D) comprises a (meth)acrylate with two or more functions and four or fewer functions.

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

10. The photosensitive resin composition according to claim 9, wherein the polyalkylene glycol di(meth)acrylate comprises polyethylene glycol di(meth)acrylate.

11. The photosensitive resin composition according to claim 6, wherein the content of the polyfunctional (meth)acrylate (D) per 100 parts by mass of component (A) is 20 parts by mass or more and 150 parts by mass or less.

12. The photosensitive resin composition according to any one of claims 1 to 3, wherein the constituent unit (Y) further comprises a constituent unit (Y-2) represented by the following general formula (y2). 【Transformation 5】 (In general formula (y2), R ４ Each of these independently represents an alkyl group having 1 to 4 carbon atoms. Z ２ This represents a single bond or a divalent organic group. g and h each independently represent integers from 0 to 4. * indicates a bonding operation.

13. A photosensitive resin composition according to any one of claims 1 to 3, further comprising an epoxy compound (E).

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

15. A photosensitive resin composition according to any one of claims 1 to 3, further comprising a silane coupling agent (F).

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

17. A photosensitive resin composition according to any one of claims 1 to 3, wherein the average value of the peel strength obtained by the following method is greater than 0.7 N / cm. (method) The photosensitive resin composition is applied to a silicon wafer having a copper plating layer with a thickness of 3000 angstroms on its surface, and dried to obtain a photosensitive resin film with a thickness of 10 μm. The obtained photosensitive resin film is subjected to a 300 mJ / cm² test using an i-line stepper. ２ The photosensitive resin film is exposed to light. The exposed photosensitive resin film is developed using a spray developer while rotating at 2500 rpm with cyclopentanone for 30 seconds, and then with propylene glycol monomethyl ether acetate for 10 seconds. After development, the photosensitive resin film is air-dried using a spin dryer, then dried on a hot plate at 120°C for 2 minutes, and then heat-treated at 230°C for 2 hours under a nitrogen atmosphere to obtain a cured film. The silicon wafer is cut to obtain a test piece with a width of 7 mm and a length of 50 mm. The end 5 mm of the test specimen is immersed in a 2% by mass hydrofluoric acid aqueous solution at 23°C for 6 hours, then washed with water and dried to remove the hardened film from the end of the test specimen. The hardened film is peeled off at a 90° angle and a peeling speed of 20 mm / min to a depth of 1 cm, and the peel strength is measured. The average value of the three measurements is then calculated.

18. A photosensitive resin composition according to any one of claims 1 to 3, wherein the photosensitive resin composition obtained by the following method is cured at 230°C for 2 hours, and the cured product has a breaking elongation of 10% or more at 23°C. (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. The average value obtained from measurements of 10 test specimens is taken as the elongation at break.

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

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

21. A semiconductor device comprising the cured product described in claim 20.

22. Interlayer insulating film and A resin film containing the cured product described in claim 20 is provided on the interlayer insulating film, The rewiring embedded in the aforementioned resin film, The semiconductor device according to claim 21, comprising:

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