Photosensitive resin composition

Abstract

To provide a photosensitive resin composition that maintains superior dielectric characteristics of a cured product while preventing cracking on an insulating layer surface or vias after exposure even under increased exposure dose, thereby ensuring a wide exposure process window.SOLUTION: A photosensitive resin composition comprises (A) a polyimide precursor, (B) a crosslinking agent, (C) a photo-radical generator, and (D) a compound having a structure represented by the following formula (D-1), where Ar ring represents an aromatic ring which may have a substituent, and * denotes a bond.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, and further to a photosensitive film, a semiconductor package substrate, a semiconductor device, and a method for producing a semiconductor package substrate, all of which are obtained using the photosensitive resin composition. [Background technology]

[0002] Conventionally, polyimide resins, which have excellent heat resistance and insulating properties, have been used for insulating layers of semiconductor devices. In addition, since polyimide resins have low solubility in solvents, they are used in the form of polyimide precursors in photosensitive resin compositions, and after forming an insulating layer or the like, the polyimide precursor is cyclized to form an insulating layer (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-084435 [Patent Document 2] International Publication No. 2020 / 004500 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, as communication speeds and capacities in communication devices have increased, the photosensitive resin compositions used in semiconductor package substrates for communication devices are also required to have excellent resolution, as well as excellent dielectric properties such as low dielectric constant and dielectric dissipation factor after curing, and high optical transparency.

[0005] In order to improve the optical transparency of insulating layers in semiconductor devices, compounds that have low absorption of visible light (wavelengths of 400 to 780 nm) and ultraviolet-A rays (320 to 400 nm), which are close to visible light, are used as components of photosensitive resin compositions. For example, Patent Document 2 describes the use of a polyimide precursor whose i-line absorbance in a 0.1 wt% N-methylpyrrolidone solution is 0.1 to 0.6.

[0006] However, according to the investigations of the present inventors, it has been found that when a photosensitive resin composition with high optical transparency is used for a thin insulating layer, excessive photoradical reaction occurs during exposure due to the high optical transparency, and cracks may occur on the surface of the insulating layer or in vias after exposure due to photocuring shrinkage. While it is conceivable to reduce the exposure dose in order to suppress the excessive photoradical reaction, this narrows the process window for exposure, which may pose a problem in the stable production of semiconductor devices at an industrial level.

[0007] The present invention has been made in view of the above-mentioned problems, and aims to provide a photosensitive resin composition that is less likely to cause cracks on the surface of an insulating layer or in vias after exposure, even when the exposure dose is increased, while maintaining the excellent dielectric properties of the cured product, i.e., has a wide exposure process window. [Means for solving the problem]

[0008] As a result of extensive investigations, the present inventors have found that the above-mentioned problems can be solved by using a photosensitive resin composition containing a polyimide precursor, a crosslinking agent, a photoradical generator, and a compound having a specific structure, and have thus completed the present invention.

[0009] That is, the present invention includes the following. [1] (A) a polyimide precursor, (B) a crosslinking agent, (C) a photoradical generator, and (D) A compound having a structure represented by the following formula (D-1): A photosensitive resin composition comprising: [ka] (In the formula, the ring Ar represents an aromatic ring which may have a substituent, and * represents a bond.) [2] The photosensitive resin composition according to [1], wherein in formula (D-1), the ring Ar is a monocyclic aromatic ring which may have a substituent. [3] The photosensitive resin composition according to [1] or [2], wherein in formula (D-1), the ring Ar is a benzene ring. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the component (D) is a compound represented by the following formula (D-2): [ka] (In the formula, R represents an alkyl group having 1 to 20 carbon atoms.) [5] The photosensitive resin composition according to any one of [1] to [4], wherein the component (D) is a compound represented by the following formula (D-3): [ka] (In the formula, X represents a divalent organic group.) [6] The photosensitive resin composition according to [5], wherein in formula (D-3), X is a divalent saturated chain group having 1 to 50 skeletal atoms and consisting of skeletal atoms selected from carbon atoms, nitrogen atoms, and oxygen atoms. [7] The photosensitive resin composition according to [5] or [6], wherein in formula (D-3), X is a divalent organic group represented by the following formula (D-4): [ka] (In the formula, each Y independently represents an oxygen atom or —NR′— (N represents a nitrogen atom, and R′ represents an alkyl group having 1 to 20 carbon atoms), * represents a bond, each p independently represents an integer of 1 to 10, q represents an integer of 1 to 10, and n′ represents an integer of 0 to 10.) [8] (D) The absorption coefficient ε (L g -1 ·cm -1 ) is 4 L·g -1 ·cm -1 The photosensitive resin composition according to any one of [1] to [7], which is: [9] The photosensitive resin composition according to any one of [1] to [8], wherein the component (C) is an intramolecular cleavage type photoradical generator.

[10] The photosensitive resin composition according to any one of [1] to [9], wherein the component (C) is an oxime ester-based photoradical generator.

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

[10] , wherein the component (A) is a polyimide precursor containing an indane skeleton.

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

[11] , wherein the component (B) has 3 to 6 functional groups.

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

[12] , wherein the component (B) is a (meth)acrylate.

[14] The mass ratio of component (D) to component (A) [component (D) / component (A)] is 10 -4 ~10 -1 The photosensitive resin composition according to any one of [1] to

[13] , wherein

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

[14] , wherein the mass ratio of the component (D) to the component (B) [component (D) / component (B)] is 0.01 to 1.

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

[15] , wherein the mass ratio of the component (D) to the component (C) [component (D) / component (C)] is 0.01 to 10.

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

[16] , wherein the content of component (A) is 70 to 98 mass % when the total non-volatile components of the photosensitive resin composition is 100 mass %.

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

[17] , wherein the content of component (D) is 0.05 to 5 mass % when the total non-volatile components of the photosensitive resin composition is 100 mass %.

[19] A photosensitive film comprising a support and a photosensitive resin composition layer formed on the support, the photosensitive resin composition layer comprising the photosensitive resin composition according to any one of [1] to

[18] .

[20] The photosensitive film according to

[19] , which has a thickness of 1 to 30 μm.

[21] A semiconductor package substrate comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of [1] to

[18] .

[22] A semiconductor device comprising the semiconductor package substrate according to

[21] .

[23] A step of forming a photosensitive resin composition layer containing the photosensitive resin composition according to any one of [1] to

[18] on a circuit board; a step of irradiating the photosensitive resin composition layer with actinic rays; developing the photosensitive resin composition layer; A method for manufacturing a semiconductor package substrate, comprising: [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a photosensitive resin composition that is resistant to cracking on the surface of an insulating layer or in vias after exposure even when the exposure dose is increased while maintaining the excellent dielectric properties of the cured product, i.e., has a wide exposure process window; and a photosensitive film, semiconductor package substrate, semiconductor device, and method for producing a semiconductor package substrate, all of which are obtained using the photosensitive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and can be implemented with any modifications within the scope of the claims and their equivalents.

[0012] In the following description, unless otherwise specified, the expressions "XX to YY" or "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined in any way.

[0013] In the following description, "dielectric constant" refers to "relative dielectric constant" unless otherwise specified.

[0014] In the following description, unless otherwise specified, the term "optionally substituted" used in reference to a compound or group means both a case where the hydrogen atoms of the compound or group are not substituted with substituents and a case where some or all of the hydrogen atoms of the compound or group are substituted with substituents.

[0015] In the following description, the content of each component in the photosensitive resin composition represents a value when the non-volatile components in the photosensitive resin composition are taken as 100 mass %, unless otherwise specified.

[0016] [Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A) a polyimide precursor, (B) a crosslinking agent, (C) a photoradical generator, and (D) a compound having a structure represented by the following formula (D-1): [ka] (In the formula, the ring Ar represents an aromatic ring which may have a substituent, and * represents a bond.)

[0017] By incorporating a combination of components (A) to (D) into the photosensitive resin composition, it is possible to obtain a photosensitive resin composition that is less likely to develop cracks on the insulating layer surface or in vias after exposure, even when the exposure dose is increased, while maintaining the excellent dielectric properties of the cured product, i.e., has a wide exposure process window.

[0018] The photosensitive resin composition of the present invention is suitable as a negative photosensitive resin composition.

[0019] The photosensitive resin composition may further contain optional components in addition to the components (A) to (D). Examples of optional components include (E) a sensitizer, (F) other additives, and (G) a solvent. Each component contained in the photosensitive resin composition will be described in detail below.

[0020] <(A) Polyimide precursor> The photosensitive resin composition contains a polyimide precursor (A) as component (A). The polyimide precursor (A) can undergo ring closure upon heating to form a polyimide. Therefore, a cured product obtained by thermally curing a photosensitive resin composition containing the polyimide precursor (A) can utilize the excellent physical properties of polyimide to form a good insulating layer. Furthermore, the use of the polyimide precursor (A) usually improves the resolution of the photosensitive resin composition. The component (A) may be used alone or in combination of two or more.

[0021] The (A) polyimide precursor can be a resin having a plurality of amic acid structures and / or amic acid ester structures. As the amic acid ester, it is preferable to use a compound having a structure obtained by reacting a carboxyl group of an amic acid structural unit obtained by reacting a tetracarboxylic acid dianhydride with a diamine compound with an epoxy group of an epoxy compound containing an ethylenically unsaturated bond or a hydroxy group of an alcohol containing an ethylenically unsaturated bond.

[0022] The amic acid ester structure contains a residue derived from a structure formed by the reaction of an epoxy group of an epoxy compound or a hydroxy group of an alcohol with a carboxyl group. When the epoxy compound or alcohol contains an ethylenically unsaturated bond, the residue may also contain an ethylenically unsaturated bond. An "ethylenically unsaturated bond" refers to a non-aromatic carbon-carbon unsaturated bond, such as a non-aromatic carbon-carbon double bond or carbon-carbon triple bond. Therefore, the residue can function as a radical-reactive group that can undergo polymerization by radicals generated by heat or light. In this case, a photosensitive resin composition containing (A) a polyimide precursor can be polymerized by exposure to light, thereby more effectively reducing the solubility of the photosensitive resin composition in a developer.

[0023] The polyimide precursor (A) preferably contains an indane skeleton in the amic acid structure and / or amic acid ester structure. The indane skeleton represents the skeleton shown in formula (a1-1) below. When the amic acid structure and / or amic acid ester structure contains an indane skeleton, the solubility of the unexposed areas of the photosensitive resin composition in a developer can be increased. This can shorten the development time, and more preferably improve the resolution. Unless otherwise specified, "resolution" refers to the ability to form small holes in a photosensitive resin composition by exposure and development. Generally, the smaller the diameter of the holes that can be formed, the better the resolution. In particular, the polyimide precursor (A) preferably contains a trimethylindane skeleton represented by formula (a1-2) below. It is more preferable that the amic acid structure and / or amic acid ester structure contain an indane skeleton in the structural portion derived from a diamine compound.

[0024] [ka]

[0025] When component (A) has a structure derived from a tetracarboxylic dianhydride with an asymmetric structure represented by formula (P-1) below and a structure derived from a diamine with an asymmetric structure represented by formula (Q-1) below, the structural units of the polyimide precursor (polyamic acid and / or polyamic acid ester) can be 16 types of positional isomers represented by formulas (PQ-1) to (PQ-16) below. [ka] (In the formula, the numbers 1 to 4 attached to the bonds of the tetravalent substituent P mean that the tetravalent group P is asymmetric and the four bonds can be distinguished.)

[0026] In the following description, polyimide precursors may be described using structural formulas. Unless otherwise specified, the expression of any one of formulas (PQ-1) to (PQ-16) is considered to encompass all structures of formulas (PQ-1) to (PQ-16). That is, a "polyimide precursor having a structural unit represented by formula (PQ-1)" means a "polyimide precursor having one or more structural units selected from formulas (PQ-1) to (PQ-16)." In the case of a polyimide precursor having two or more structural units selected from formulas (PQ-1) to (PQ-16), this also includes polyimide precursors in which the two or more structural units are copolymerized in any of the following ways: random copolymerization, alternating copolymerization, block copolymerization, graft copolymerization, and ordered copolymerization.

[0027] From the viewpoint of obtaining a cured product that is excellent in limiting resolution and dielectric properties, the component (A) preferably has a structural unit represented by the following formula (A-1). [ka] (In the formula, each A independently represents a tetravalent organic group, each B independently represents a divalent organic group which may have a substituent, and R 1 and R 2 each independently represents a hydrogen atom or a monovalent organic group, and n represents an integer of 5 to 200.

[0028] In formula (A-1), each A independently represents a tetravalent organic group. The tetravalent organic group is preferably a tetravalent organic group having 6 to 40 carbon atoms. Examples of the tetravalent organic group having 6 to 40 carbon atoms include -COOR 1 Group and -COOR 2 and an aromatic group (R 1 and R 2 is R in formula (A-1) 1 and R 2and an alicyclic aliphatic group. Examples of such groups include the following groups (i) to (xiii). In the formula, * represents a bond. As A, a group (ii), a group (viii), a group (ix), a group (x), a group (xi), or a group (xii) is preferred, a group (ii), a group (viii), a group (x), a group (xi), or a group (xii) is more preferred, and a group (ii), a group (x), a group (xi), or a group (xii) is even more preferred. [ka] [ka]

[0029] The tetravalent organic group may have a substituent. Examples of the substituent include linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, 2-propyl, n-butyl, s-butyl, i-butyl, t-butyl, cyclopentyl, and cyclohexyl; halogen atoms such as fluorine, chlorine, and bromine; alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, t-butoxy, and phenoxy; hydroxy; and halogen-substituted alkyl groups such as trifluoromethyl. The above-mentioned substituents may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). The substituent may be contained alone or in combination of two or more.

[0030] In formula (A-1), each B independently represents a divalent organic group. The divalent organic group preferably has an aromatic ring. Examples of the divalent organic group include groups (1a) to (26a) exemplified below. In the formula, * represents a bond. The group may also be a combination of two or more of the groups (1a) to (26a). The divalent organic group is preferably a group (2a) or a group (20a) to (26a). Furthermore, B more preferably has an indane skeleton. That is, as the divalent organic group, groups (20a) to (26a) are more preferred, and group (23a) is even more preferred. [ka] [ka]

[0031] The divalent organic group may have a substituent. Examples of the substituent include linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, 2-propyl, n-butyl, s-butyl, i-butyl, t-butyl, cyclopentyl, and cyclohexyl; halogen atoms such as fluorine, chlorine, and bromine; alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, t-butoxy, and phenoxy; hydroxy; and halogen-substituted alkyl groups such as trifluoromethyl. The above-mentioned substituents may further have a secondary substituent. The substituents may be contained alone or in combination of two or more.

[0032] R in formula (A-1) 1 and R 2 Each of R in formula (A-1) independently represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include saturated aliphatic groups having 1 to 4 carbon atoms; and reactive groups that can be polymerized by radicals generated by heat or light, i.e., radical reactive groups. The radical reactive groups are preferred. 1 and R 2 and each independently, at least one of them is preferably a radical reactive group, and more preferably both of them are radical reactive groups.

[0033] The saturated aliphatic group having 1 to 4 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, an n-butyl group, and a t-butyl group.

[0034] The radical reactive group is preferably a group represented by the following formula (A-2-1), (A-2-2) or (A-2-3). [ka] (In the formula, R 14 ~R 16 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p1 represents an integer of 1 to 10. * represents a bond. [ka] (In the formula, R 24 ~R 26 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p2 represents an integer of 0 to 10. * represents a bond. [ka] (In the formula, ring Z represents an aliphatic hydrocarbon ring having 5 to 20 carbon atoms which may have a substituent. R 34 ~R 36 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p3 represents an integer of 0 to 10. * represents a bond.

[0035] R in formula (A-2-1) 14 ~R 16 R each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and a 2-propyl group. 14 ~R 16 is preferably a hydrogen atom or a methyl group.

[0036] In formula (A-2-1), p1 represents an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 2.

[0037] R in formula (A-2-2) 24 ~R 26R each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and a 2-propyl group. 24 ~R 26 is preferably a hydrogen atom or a methyl group.

[0038] In formula (A-2-2), p2 represents an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 1.

[0039] Ring Z in formula (A-2-3) represents an aliphatic hydrocarbon ring having 5 to 20 carbon atoms, which may have a substituent. The aliphatic hydrocarbon ring may be monocyclic or polycyclic. The aliphatic hydrocarbon ring may be a saturated aliphatic hydrocarbon ring such as a cycloalkane ring, or an unsaturated aliphatic hydrocarbon ring such as a cycloalkene ring. The number of carbon atoms in the aliphatic hydrocarbon ring is preferably 3 to 10. Examples of the aliphatic hydrocarbon ring include monocycloalkane rings such as a cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, and cyclooctane ring; bicycloalkane rings such as a decalin ring and a norbornane ring; spiroalkane rings such as a spirononane ring; monocycloalkene rings such as a cyclobutene ring, cyclopropene ring, cyclohexene ring, cyclohexadiene ring, cycloheptene ring, and cyclooctene ring; bicycloalkene rings such as a norbornene ring and a norbornadiene ring; and spiroalkene rings such as a spirononene ring. Of these, a cycloalkane ring is preferred, a monocycloalkane ring is more preferred, and a cyclohexane ring is even more preferred.

[0040] Examples of substituents that the aliphatic hydrocarbon ring in ring Z may have include linear, branched, or cyclic C1-C10 alkyl groups such as methyl, ethyl, n-propyl, 2-propyl, n-butyl, s-butyl, i-butyl, t-butyl, cyclopentyl, and cyclohexyl; halogen atoms such as fluorine, chlorine, and bromine; alkoxy groups having C1-C10 such as methoxy, ethoxy, propoxy, t-butoxy, and phenoxy; hydroxy; and halogen-substituted alkyl groups such as trifluoromethyl, with alkyl groups being preferred. The above-mentioned substituents may have a secondary substituent. The substituents may be contained alone or in combination of two or more.

[0041] R in formula (A-2-3) 34 ~R 36 R each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and a 2-propyl group. 24 ~R 26 is preferably a hydrogen atom or a methyl group.

[0042] In formula (A-2-3), p3 represents an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 1.

[0043] Examples of the radical reactive group represented by formula (A-2-3) include groups represented by formula (A-2-4) and groups represented by formula (A-2-5), etc. In the formula, * represents a bond. [ka]

[0044] R in formula (A-1) 1 and R 2are each independently preferably a radical reactive group, more preferably at least one of which is a group represented by formula (A-2-1), formula (A-2-2), or formula (A-2-3), and R 1 and R 2 and are more preferably both groups represented by formula (A-2-1), formula (A-2-2), or formula (A-2-3).

[0045] In formula (A-1), n represents an integer of 5 to 200. The upper limit of n is preferably 150 or less, more preferably 100 or less, even more preferably 70 or less, or 50 or less, and particularly preferably 30 or less. The lower limit of n is preferably 7 or more, more preferably 10 or more, even more preferably 12 or more, and particularly preferably 15 or more.

[0046] The component (A) preferably has a structural unit represented by formula (A-3). [ka] (In the formula, A 1 each independently represents a tetravalent organic group, R 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group, R 13 represents a methyl group; each Xa independently represents a single bond, a group represented by the following formula (1) or a group represented by formula (2); each Xb independently represents a single bond, a group represented by formula (3) or a group represented by formula (4); m1 represents an integer of 0 to 5; and n1 represents an integer of 5 to 200. [ka] (In formulas (1) to (4), * represents a bond.)

[0047] A in formula (A-3) 1 each independently represents a tetravalent organic group, A 1 is the same as A in formula (A-1).

[0048] R in formula (A-3) 11 and R 12each independently represents a hydrogen atom or a monovalent organic group, and R in formula (A-1) 1 and R 2 is the same as

[0049] Each Xa independently represents a single bond, a group represented by formula (1), or a group represented by formula (2). Xa may be bonded to a five-membered ring or a benzene ring.

[0050] Examples of the group represented by formula (1) include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group.

[0051] Examples of the group represented by formula (2) include the following groups (2-1) to (2-6). [ka]

[0052] Among these, Xa is preferably a single bond or a group represented by formula (1), more preferably a single bond or a 1,4-phenylene group.

[0053] Each Xb independently represents a single bond, a group represented by formula (3), or a group represented by formula (4). Xb may be bonded to a five-membered ring or a benzene ring.

[0054] Examples of the group represented by formula (3) include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group.

[0055] Examples of the group represented by formula (4) include the following groups. [ka]

[0056] Among these, Xb is preferably a single bond or a group represented by formula (3), more preferably a single bond or a 1,4-phenylene group.

[0057] R13 represents a methyl group. 13 indicates bonding to a five-membered ring.

[0058] m1 represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 2 or 3, and even more preferably 3.

[0059] n1 represents an integer of 5 to 200 and is the same as n in formula (A-1).

[0060] Specific examples of the component (A) include the following compounds (A1) to (A12). However, the component (A) is not limited to these specific examples. In the formula, n represents an integer of 5 to 200. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0061] From the viewpoint of obtaining excellent limiting resolution, the weight average molecular weight of component (A) is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 13,000 or more, and particularly preferably 15,000 or more, and is preferably 1,000,000 or less, more preferably 500,000 or less, even more preferably 200,000 or less or 100,000 or less, and particularly preferably 50,000 or less or 20,000 or less. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0062] There are no particular restrictions on the method for producing component (A), which can usually be obtained by reacting a tetracarboxylic dianhydride with a diamine compound.

[0063] For example, a polyamic acid structure is formed by a method of reacting a tetracarboxylic dianhydride with a diamine compound, and then a specific polyamic acid ester structural unit can be formed by a method of reacting a carboxyl group of this polyamic acid structural unit with an epoxy group of an epoxy compound containing an ethylenically unsaturated bond.

[0064] Alternatively, a tetracarboxylic dianhydride may be reacted with an alcohol, the acid anhydride may be ring-opened to produce an ester and a carboxylic acid, the carboxylic acid may be reacted with thionyl chloride to produce an acid chloride, and the acid chloride may be reacted with a diamine to form an amic acid ester structural unit.

[0065] The component (A) can also be produced by the production methods described in, for example, JP-A No. 2015-209461, JP-A No. 2015-214680, JP-A No. 2017-219850, or JP-A No. 2018-146964.

[0066] The tetracarboxylic acid dianhydride may be an aliphatic tetracarboxylic acid dianhydride or an aromatic tetracarboxylic acid dianhydride, and preferably an aliphatic tetracarboxylic acid dianhydride. Examples of the aliphatic tetracarboxylic acid dianhydride include 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, bicyclo[2.2.1]heptane-2-endo-3-endo-5-exo-6-exo-2,3,5,6-tetracarboxylic acid dianhydride, and bicyclo[2.2.1]heptane-2-exo-3-exo-5- Exo-6-exo-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic dianhydride, 2-(3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthyl)succinic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 1,2,3,4-butanetetracarboxylic dianhydride anhydride, N,N'-1,4-phenylenebis[octahydro-1,3-dioxo-5-isobenzofurancarboxamide], decahydro-dimethanonaphthalenetetracarboxylic dianhydride, bis[2-(3-aminopropoxy)ethyl]ether, 1,4-butanediol-bis(3-aminopropyl)ether, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro-5,5-undecane, 1,2-bis(2-aminoethoxy)ethane, 1,2-bis(3-aminopropoxy)ethane, triethylene glycol-bis(3-aminopropyl)ether, polyethylene glycol-bis(3-aminopropyl)ether, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro-5,5-undecane, 1,4-butanediol-bis(3-aminopropyl)ether, and the like.

[0067] Examples of aromatic tetracarboxylic dianhydrides include 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-para-terphenyltetracarboxylic dianhydride, 3,3',4,4'-meta-terphenyltetracarboxylic dianhydride, and 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride. One type of tetracarboxylic dianhydride may be used alone, or two or more types may be used in combination.

[0068] The diamine compound can be an aliphatic diamine or an aromatic ring-containing diamine compound, and the aromatic ring-containing diamine compound is preferred.The aliphatic diamine compound can be, for example, bis[2-(3-aminopropoxy)ethyl]ether, 1,4-butanediol-bis(3-aminopropyl)ether, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro-5,5-undecane, 1,2-bis(2-aminoethoxy)ethane, 1,2-bis(3-aminopropoxy)ethane, triethylene glycol-bis(3-aminopropyl)ether, polyethylene glycol-bis(3-aminopropyl)ether, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro-5,5-undecane, 1,4-butanediol-bis(3-aminopropyl)ether, etc.

[0069] Examples of diamine compounds containing an aromatic ring include 4,4'-diaminodiphenyl ether and diamine compounds represented by the following formulas (a2-1) to (a2-26). One type of diamine compound may be used alone, or two or more types may be used in combination. Of these, diamine compounds containing an indane skeleton are preferred. Examples of diamine compounds containing an indane skeleton include diamine compounds represented by the following formulas (a2-20) to (a2-26). Of these, diamine compounds represented by formulas (a2-23) to (a2-26) are preferred, and diamine compounds represented by formula (a2-23) are more preferred. [ka] [ka]

[0070] As the epoxy compound containing an ethylenically unsaturated bond, a compound containing an ethylenically unsaturated bond and an epoxy group can be used. The epoxy group may be contained as a glycidyl group. Examples of the epoxy compound containing an ethylenically unsaturated bond include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl methacrylate. The epoxy compound containing an ethylenically unsaturated bond may be used alone or in combination of two or more.

[0071] The alcohol may be an alcohol containing an ethylenically unsaturated bond or a saturated aliphatic alcohol having 1 to 4 carbon atoms. One type of alcohol may be used alone, or two or more types may be used in combination.

[0072] As the alcohol containing an ethylenically unsaturated bond, a compound containing an ethylenically unsaturated bond and a hydroxy group can be used. Examples of the ethylenically unsaturated alcohol include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl acrylate, with 2-hydroxyethyl methacrylate being preferred. One type of alcohol containing an ethylenically unsaturated bond may be used alone, or two or more types may be used in combination.

[0073] Examples of saturated aliphatic alcohols having 1 to 4 carbon atoms include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and t-butanol.

[0074] From the viewpoint of obtaining excellent limiting resolution, the content of the component (A), when the non-volatile components of the photosensitive resin composition are taken as 100% by mass, is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, particularly preferably 80% by mass or more, 90% by mass or more, and is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 96% by mass or less.

[0075] <(B) Crosslinking Agent> The photosensitive resin composition contains a crosslinking agent (B) as component (B). However, component (B) excludes components (A) and (D), which will be described later. When the photosensitive resin composition is irradiated with actinic rays and radicals are generated from the photoradical generator, a crosslinking reaction occurs in component (B), rendering the composition insoluble in the developer. This makes it possible to selectively remove the photosensitive resin composition from areas other than those where the crosslinking reaction has progressed during development, thereby advantageously forming a negative pattern. The component (B) may be used alone or in combination of two or more.

[0076] As component (B), a compound capable of causing a crosslinking reaction during development can be used. The lower limit of the number of reactive sites per molecule of component (B) at which a crosslinking reaction occurs (hereinafter sometimes referred to as the "number of functional groups") is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. The upper limit of the number of functional groups is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 6 or less or 4 or less.

[0077] Component (B) is preferably a compound having an ethylenically unsaturated bond, and more preferably a compound having an ethylenically unsaturated bond in which at least one of the carbon atoms at the α-position of the ethylenically unsaturated bond is a carbon atom of a carbonyl group or a carbon atom of an aromatic group. The carbon atom at the α-position of the ethylenically unsaturated bond refers to the first carbon atom adjacent to the carbon atom bonded by the carbon-carbon double bond.

[0078] The ethylenically unsaturated bond represents a carbon-carbon double bond. Therefore, component (B) may contain a group having an ethylenically unsaturated bond (hereinafter, occasionally referred to as an "ethylenically unsaturated group"). The ethylenically unsaturated group is typically a monovalent group, such as a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, or a (meth)acryloyl group. From the viewpoint of photoradical polymerization reactivity, a (meth)acryloyl group or a phenylethynyl group is preferred, a (meth)acryloyl group is more preferred, and a methacryloyl group is even more preferred. The term "(meth)acryloyl group" encompasses a methacryloyl group, an acryloyl group, and a combination thereof. Since component (B) contains an ethylenically unsaturated bond, it is photoradical polymerizable. However, for photoradical polymerization under general conditions, a compound having a carbonyl group or an aromatic group at at least one α-position of the ethylenically unsaturated bond is preferred. The lower limit for the number of ethylenically unsaturated bonds per molecule of component (B) is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and the upper limit is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 6 or less or 4 or less. Furthermore, when component (B) contains two or more ethylenically unsaturated groups per molecule, those ethylenically unsaturated groups may be the same or different.

[0079] The component (B) is preferably a compound represented by the following formula (B-1). [ka] (In the formula, R 1b each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms; Z 1b each independently represents a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, an arylene group which may contain an oxygen atom, or a linear or branched alkenylene group having 2 to 20 carbon atoms which may contain an oxygen atom; A 1b represents a linear, cyclic or branched nb-valent organic group having 1 to 10 carbon atoms, where nb represents an integer of 2 to 6.

[0080] R 1b are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1-butyl group, a s-butyl group, and a t-butyl group. Among these, R 1b is preferably a hydrogen atom or a methyl group.

[0081] Z 1b each independently represents a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, an arylene group which may contain an oxygen atom, or a linear or branched alkenylene group having 2 to 20 carbon atoms which may contain an oxygen atom.

[0082] As the linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkylene group having 1 to 10 carbon atoms is preferred, and a linear or branched alkylene group having 1 to 6 carbon atoms is more preferred. Examples of such alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group, with a methylene group being preferred. The alkylene group may also be an oxyalkylene group containing an oxygen atom, and specific examples of such groups include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 20. [ka]

[0083] The arylene group which may contain an oxygen atom is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, and even more preferably an arylene group having 6 to 12 carbon atoms. Examples of such arylene groups include a phenylene group and a naphthylene group. The arylene group may also contain an oxygen atom, and specific examples of such groups include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 4. [ka]

[0084] As the linear or branched alkenylene group having 2 to 20 carbon atoms which may contain an oxygen atom, a linear or branched alkenylene group having 2 to 10 carbon atoms is preferred, and a linear or branched alkenylene group having 2 to 6 carbon atoms is more preferred. Examples of such alkenylene groups include ethenylene, propenylene, butenylene, pentenylene, and hexenylene. The alkenylene group may also be an oxyalkenylene group containing an oxygen atom, and specific examples of such groups include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 10. The alkenylene group is preferably a propenylene group. [ka]

[0085] Among them, Z 1b As the alkyl group, a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom is preferred, and a methylene group is more preferred.

[0086] A 1brepresents a linear, cyclic, or branched nb-valent organic group having 1 to 10 carbon atoms. Examples of the nb-valent organic group include an nb-valent hydrocarbon group which may contain an oxygen atom, an nb-valent group derived from bisphenol, an nb-valent group derived from fluorene, an nb-valent group derived from tricyclodecane, or an nb-valent group derived from an isocyanuric group. Examples of the nb-valent hydrocarbon group which may contain an oxygen atom include an nb-valent aliphatic hydrocarbon group which may contain an oxygen atom, and an nb-valent aromatic hydrocarbon group which may contain an oxygen atom, with an nb-valent aliphatic hydrocarbon group which may contain an oxygen atom being preferred. A 1b Specific examples of the group represented by include the following: In the formula, "*" represents a bond. [ka]

[0087] nb represents an integer of 2 to 6, preferably an integer of 3 to 6, more preferably an integer of 3 to 5, further preferably 3 or 4, and particularly preferably 3.

[0088] The component (B) is preferably a compound represented by the following formula (B-2). [ka] (In the formula, R 2b each independently represents a hydrogen atom or a methyl group.

[0089] R 2b represents a hydrogen atom or a methyl group, and a methyl group is preferred.

[0090] Specific examples of the component (B) include the following compounds (CL-1) to (CL-13), and the component (B) is preferably the compound (CL-1), the compound (CL-2), or the compound (CL-12), although the component (B) is not limited to these. [ka] [ka] [ka]

[0091] Component (B) can be a commercially available product, such as NK Ester D-TMP, TMPT, A-TMPT, 4G, 9G, 14G, 23G, and DCP manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd., and SR209, CN2301, and CN2304 manufactured by Sartomer Japan.

[0092] From the viewpoint of obtaining excellent limiting resolution, the content of the component (B) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, 2% by mass or more, or 3% by mass or more, and is preferably 20% by mass or less, more preferably 18% by mass or less, 16% by mass or less, even more preferably 14% by mass or less, 12% by mass or less, or 10% by mass or less, and particularly preferably 8% by mass or less, 6% by mass or less, or 4% by mass or less, when the total amount of non-volatile components in the photosensitive resin composition is taken as 100% by mass.

[0093] From the viewpoint of obtaining excellent limiting resolution, the lower limit of the mass ratio of the component (B) to the component (A) [component (B) / component (A)] is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and particularly preferably 0.03 or more, and the upper limit is preferably 0.2 or less, more preferably 0.17 or less or 0.15 or less, even more preferably 0.1 or less or 0.05 or less, and particularly preferably 0.04 or less.

[0094] <(C) Photoradical generator> The photosensitive resin composition contains (C) a photoradical generator. Component (C) generates radicals upon irradiation with actinic rays, and these radicals can cause a crosslinking reaction. In the photosensitive resin composition, the portions where the radical-induced crosslinking reaction occurs are cured to form a cured product, improving resistance to the developer. Therefore, during development, it becomes possible to selectively remove the photosensitive resin composition from portions other than those where the crosslinking reaction has progressed, advantageously forming a negative pattern. Component (C) may be used alone or in combination of two or more. Component (C) excludes components (A), (B), and (D), which will be described later.

[0095] (C) Examples of the photoradical generator include an intramolecular cleavage-type photoradical generator and a hydrogen abstraction-type photoradical generator, with an intramolecular cleavage-type photoradical generator being preferred. An intramolecular cleavage-type photoradical generator is a type of photoradical generator that generates radicals by intramolecular cleavage, and a hydrogen abstraction-type photoradical generator is a type of photoradical generator that generates radicals by exchanging hydrogen or electrons between two molecules.

[0096] Examples of the intramolecular cleavage-type photoradical generator include an α-aminoketone-based photoradical generator, a phosphine oxide-based photoradical generator, an α-hydroxyketone-based photoradical generator, an oxime ester-based photoradical generator, a benzyl-based photoradical generator, a benzyl ketal-based photoradical generator, a benzoin-based photoradical generator, a peroxide-based photoradical generator, and a titanocene-based photoradical generator. From the viewpoint of photosensitivity, an oxime ester-based photoradical generator is preferred.

[0097] Examples of the hydrogen abstraction type photoradical generator include benzophenone-based photoradical generators, acetophenone-based photoradical generators, thioxanthone-based photoradical generators, and aromatic bisimidazole-based photoradical generators.

[0098] Examples of α-aminoketone photoradical generators include 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-methyl-1-(4-hexylphenyl)-2-morpholinopropan-1-one, 2-ethyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and N-phenylglycine.

[0099] Examples of phosphine oxide photoradical generators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, and polyoxyethylene glycerin ether tris[phenyl(2,4,6-trimethylbenzoyl)phosphinate] (Polymeric TPO-L).

[0100] Examples of α-hydroxyketone-based photoradical generators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropanone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one.

[0101] Examples of oxime ester-based photoradical generators include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (OXE01), [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino]acetate (OXE02), 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, and 1-phenyl-1, Examples include 2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide, and the like, with 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (OXE01) or [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino]acetate (OXE02) being preferred.

[0102] Examples of benzyl-based photoradical generators include benzyl.

[0103] Examples of benzyl ketal photoradical generators include benzyl dimethyl ketal (2,2-dimethoxy-2-phenylacetophenone) and benzyl-β-methoxyethyl acetal.

[0104] Examples of benzoin-based photoradical generators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0105] Examples of peroxide-based photoradical generators include benzoyl perchloride.

[0106] Examples of titanocene-based photoradical generators include bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanocene.

[0107] Examples of benzophenone-based photoradical generators include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone.

[0108] Examples of acetophenone-based photoradical generators include 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone.

[0109] Examples of thioxanthone-based photoradical generators include thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone.

[0110] Examples of aromatic bisimidazole-based photoradical generators include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole.

[0111] Component (C) can be a commercially available product, such as "Irgacure-OXE01," "Irgacure-OXE02," "Irgacure-OXE04," and "IrgacureTPO" manufactured by BASF, "Omnirad907," "Omnirad369," "Omnirad379," "Omnirad379EG," "Omnirad819," and "OmniradTPO" manufactured by IGM, and "N-1919" manufactured by ADEKA.

[0112] From the viewpoint of obtaining excellent limiting resolution, the content of component (C) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of the non-volatile components of the photosensitive resin composition.

[0113] From the viewpoint of obtaining excellent limiting resolution, the lower limit of the mass ratio of the component (C) to the component (A) [component (C) / component (A)] is preferably 0.001 or more, more preferably 0.005 or more, and even more preferably 0.01 or more, and the upper limit is preferably 0.2 or less, more preferably 0.17 or less or 0.15 or less, even more preferably 0.1 or less or 0.05 or less, and particularly preferably 0.02 or less.

[0114] From the viewpoint of obtaining excellent limiting resolution, the lower limit of the mass ratio of the component (C) to the component (B) [component (C) / component (B)] is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and particularly preferably 0.2 or more, and the upper limit is preferably 2 or less, more preferably 1.7 or less or 1.5 or less, even more preferably 1 or less or 0.7 or less, and particularly preferably 0.5 or less.

[0115] <(D) Compound having a structure represented by formula (D-1)> The photosensitive resin composition contains a compound having a structure represented by the following formula (D-1) as component (D). However, component (D) does not include components that fall under component (A). By including component (D) in the photosensitive resin composition, component (D) gently absorbs ultraviolet light during exposure, preventing excessive photoradical reactions from occurring during exposure even under conditions of high exposure dose, and preventing cracks from occurring on the insulating layer surface or in vias after exposure due to photocure shrinkage. The component (D) may be used alone or in combination of two or more. [ka] (In the formula, the ring Ar represents an aromatic ring which may have a substituent, and * represents a bond.)

[0116] In formula (D-1), the ring Ar represents an aromatic ring which may have a substituent. The term "aromatic ring" refers to a ring conforming to Hückel's rule, in which the number of electrons contained in the π-electron system on the ring is 4r + 2 (r is a natural number), and includes monocyclic aromatic rings and fused aromatic rings in which two or more monocyclic aromatic rings are fused. The aromatic ring is preferably a monocyclic aromatic ring. The aromatic ring may be an aromatic carbocycle having only carbon atoms as ring-constituting atoms, or an aromatic heterocycle having heteroatoms such as oxygen, nitrogen, or sulfur atoms as ring-constituting atoms in addition to carbon atoms. The aromatic ring is preferably an aromatic carbocycle. The number of carbon atoms in the aromatic ring is preferably 3 or more, more preferably 4 or more or 5 or more, and even more preferably 6 or more, with the upper limit being preferably 24 or less, more preferably 18 or less or 14 or less, and even more preferably 10 or less. The number of carbon atoms does not include the number of carbon atoms of substituents.

[0117] Examples of the monocyclic aromatic ring include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a furazan ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, an imidazole ring, a triazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a pyridazine ring. Examples of fused aromatic rings in which two or more monocyclic aromatic rings are fused include a naphthalene ring, an anthracene ring, a phenanthrene ring, a benzofuran ring, an isobenzofuran ring, an indole ring, an isoindole ring, a benzothiophene ring, a benzimidazole ring, an indazole ring, a benzoxazole ring, a benzisoxazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring, a phthalazine ring, a pyridothiazole ring, a benzotriazole ring, an imidazopyridine ring, a triazopyridine ring, a purine ring, etc. As the aromatic ring, a benzene ring is preferred.

[0118] The aromatic ring may have a substituent in addition to the dimethylamino group and ester group of formula (D-1). Examples of the substituent include linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, n-butyl, s-butyl, i-butyl, t-butyl, cyclopentyl, and cyclohexyl; halogen atoms such as fluorine, chlorine, and bromine; alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, t-butoxy, and phenoxy; hydroxy; and halogen-substituted alkyl groups such as trifluoromethyl. The above-mentioned substituents may further have a secondary substituent. The substituents may be contained alone or in combination of two or more.

[0119] The aromatic ring preferably has no substituents other than the dimethylamino group and the ester group of formula (D-1).

[0120] From the viewpoint of absorbing ultraviolet rays appropriately, the component (D) is preferably a compound represented by the following formula (D-2) or (D-3). [ka] (In the formula, R represents an alkyl group having 1 to 20 carbon atoms.) [ka] (In the formula, X represents a divalent organic group.)

[0121] In formula (D-2), the substitution positions of the dimethylamino group and the ester group are not particularly limited, and may be any of the ortho, meta, and para positions, with the para position being preferred.

[0122] In formula (D-2), R represents an alkyl group having 1 to 20 carbon atoms. The alkyl group is a chain (straight-chain or branched) alkyl group or a cyclic alkyl group. An alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 1 to 5 carbon atoms is even more preferred. Examples of the chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a decyl group. Methyl group, ethyl group, an n-propyl group, an isopropyl group, and a 2-ethylhexyl group are preferred, a methyl group or an ethyl group is more preferred, and an ethyl group is even more preferred. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

[0123] Specific examples of the component (D) represented by formula (D-2) include the following compounds (D2-1) to (D2-5), although the component (D) is not limited to these specific examples. [ka]

[0124] In formula (D-3), the substitution positions of the dimethylamino group and the ester group are not particularly limited and may be any of the ortho, meta, and para positions, with the para position being preferred. Furthermore, the substitution positions of the dimethylamino group and the ester group on the two benzene rings may be the same or different, but are preferably the same. That is, it is more preferred that both of the substitution positions of the dimethylamino group and the ester group on the two benzene rings are para positions.

[0125] In formula (D-3), X represents a divalent organic group. The number of carbon atoms in X is preferably 1 to 50. The lower limit of the number of carbon atoms in X is more preferably 2 or more, even more preferably 3 or more, and particularly preferably 4 or more. The upper limit of the number of carbon atoms in X is more preferably 30 or less, even more preferably 16 or less, and particularly preferably 12 or less. X is preferably a divalent aliphatic group, and more preferably a divalent saturated chain group having 1 to 50 skeletal atoms composed of skeletal atoms selected from carbon atoms, nitrogen atoms, and oxygen atoms. The lower limit of the number of skeletal atoms is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more or 6 or more. The upper limit of the number of skeletal atoms is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 10 or less. "Saturated" means that the group does not contain a double bond or a triple bond, and "chain group" means a straight-chain group or a branched-chain group.

[0126] In formula (D-3), X is more preferably a divalent organic group represented by the following formula (D-4). [ka] (In the formula, each Y independently represents an oxygen atom or —NR′— (N is a nitrogen atom, and R′ is an alkyl group having 1 to 20 carbon atoms), * represents a bond, each p independently represents an integer of 1 to 10, q represents an integer of 1 to 10, and n′ represents an integer of 0 to 10.)

[0127] In formula (D-4), each Y independently represents an oxygen atom or -NR'- (N is a nitrogen atom, and R' is an alkyl group having 1 to 20 carbon atoms). R' is a chain (straight-chain or branched) alkyl group or a cyclic alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 5 carbon atoms. Examples of the chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a decyl group. Methyl, ethyl, n-propyl, and isopropyl groups are preferred, with methyl and ethyl groups being more preferred, and methyl being even more preferred. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

[0128] In formula (D-4), each p independently represents an integer of 1 to 10. p is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 2.

[0129] In formula (D-4), q represents an integer of 1 to 10. q is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 2.

[0130] In formula (D-4), n' represents an integer of 0 to 10. n' is preferably an integer of 0 to 5, more preferably an integer of 1 to 4, and even more preferably an integer of 3 or 4.

[0131] Specific examples of the component (D) represented by formula (D-3) include the following compounds (D3-1) to (D3-3), although the component (D) is not limited to these specific examples. [ka]

[0132] (D) The extinction coefficient ε (L g) of the component at a wavelength of 365 nm -1 ·cm -1 ) upper limit is 100L·g -1 ·cm -1 It is preferable that the extinction coefficient ε is 100 L g or less. -1 ·cm -1 By ensuring that the absorption coefficient ε is equal to or less than 10 L g, not only the component (D) but also the photoradical generator (C) can absorb ultraviolet light during exposure, allowing photocuring to proceed sufficiently. -1 ·cm -1 It is preferably 4 L g or less. -1 ·cm -1 Below, 2L g -1 ·cm -1 Less than or equal to 1 L·g -1 ·cm -1 It is particularly preferably 0.5 L g -1 ·cm -1 Below, 0.1L g -1 ·cm -1 Less than or equal to 0.02 L g -1 ·cm -1 The absorption coefficient ε (L g) of component (D) at a wavelength of 365 nm is -1 ·cm -1 ) lower limit is 0.001 L g -1 ·cm -1 It is preferable that the extinction coefficient ε is 0.001 L g -1 ·cm -1 By satisfying this condition, component (D) sufficiently absorbs ultraviolet light during exposure, preventing excessive photoradical reactions even under conditions of high exposure doses, and more effectively preventing cracks on the insulating layer surface and vias after exposure due to photocure shrinkage. The lower limit of the absorption coefficient ε is preferably 0.005 L g -1 ·cm -1 More preferably, it is 0.01 L g -1 ·cm -1 More preferably, it is 0.05 L g -1 ·cm -1 That's all.

[0133] Component (D) is preferably a compound that does not react with the photoradical generator (C) when excited by ultraviolet light. Here, "reaction" includes the transfer of energy from the excited component (D) to component (C) and the exchange of hydrogen atoms or electrons between the excited component (D) and component (C). By not reacting with the photoradical generator (C), the excited component (D) returns to its ground state upon thermal deactivation, preventing excessive photoradical reactions.

[0134] Component (D) can be a commercially available product, such as "Omnipol ASA," "Omnirad EDB," "Esacure A 198," or "Omnirad EHA," manufactured by IGM.

[0135] From the viewpoint of significantly achieving the effects of the present invention, the content of component (D) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, or 0.4% by mass or more, when the total amount of non-volatile components in the photosensitive resin composition is taken as 100% by mass, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, 1% by mass or less, or 0.7% by mass or less. is.

[0136] From the viewpoint of significantly achieving the effects of the present invention, the lower limit of the mass ratio of the component (D) to the component (A) [component (D) / component (A)] is preferably 10 -4 More than 10, more preferably -3 More preferably, 2 × 10 -3 More preferably, 5 × 10 -3 The upper limit is preferably 10 -1 Less than or equal to 5 × 10 -2 More preferably, 10 -2 Below, particularly preferably 8 × 10 -3 The following is the result.

[0137] From the viewpoint of achieving a significant effect of the present invention, the lower limit of the mass ratio of the component (D) to the component (B) [component (D) / component (B)] is preferably 0.01 or more, more preferably 0.03 or more, even more preferably 0.05 or more, and particularly preferably 0.1 or more or 0.15 or more, and the upper limit is preferably 1 or less, more preferably 0.8 or less, even more preferably 0.5 or less, and particularly preferably 0.2 or less.

[0138] From the viewpoint of achieving a significant effect of the present invention, the lower limit of the mass ratio of the component (D) to the component (C) [component (D) / component (C)] is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, particularly preferably 0.2 or more or 0.4 or more, and the upper limit is preferably 10 or less, more preferably 5 or less, even more preferably 3 or less, particularly preferably 1 or less or 0.6 or less.

[0139] <(E) Sensitizer> The photosensitive resin composition may contain a sensitizer (E) as an optional component. By including a sensitizer (E) in the photosensitive resin composition, it is possible to improve the photosensitivity of the photosensitive resin composition. The component (E) may be used alone or in combination of two or more. In addition, the component (E) does not include components (A) to (D) described above.

[0140] The component (E) can be a compound capable of improving the photosensitivity of the photosensitive resin composition. Examples of such compounds include benzophenones such as Michler's ketone, 4,4'-bis(diethylamino)benzophenone, and 4-morpholinobenzophenone; cyclic alkanes such as 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, and 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone; and chalcones such as 4,4'-bis(dimethylamino)chalcone and 4,4'-bis(diethylamino)chalcone. indanones such as p-dimethylaminocinnamylidene indanone and p-dimethylaminobenzylidene indanone; thiazoles such as 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, and 2-(p-dimethylaminophenylvinylene)isonaphthothiazole; acetones such as 1,3-bis(4'-dimethylaminobenzal)acetone and 1,3-bis(4'-diethylaminobenzal)acetone; 3,3'-carbonyl -bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, etc.; N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, diethylamine amines such as isoamyl benzoate; heterocyclic compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 1-phenyl-5-mercaptotetrazole, and 1-p-hydroxyphenyl-5-mercaptotetrazole; and styrenes such as 2-(p-dimethylaminobenzoyl)styrene.

[0141] Of these, from the viewpoint of obtaining excellent limiting resolution, heterocyclic compounds are preferred as the component (E), and compounds represented by the following general formula (E-1) are more preferred. [ka] (In formula (E-1), R 1e represents a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, a halogen atom, a hydroxy group, a methoxy group, or a t-butoxy group.

[0142] R 1e represents a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, a halogen atom, a hydroxy group, a methoxy group, or a t-butoxy group. Examples of the linear or branched alkyl group having 1 to 7 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a t-butyl group. Among these, R 1e is preferably a hydroxy group, a methoxy group, or a t-butoxy group having an oxygen atom, more preferably a hydrogen atom or a hydroxy group, and even more preferably a hydrogen atom.

[0143] R 1e The bonding position of may be any of the ortho-position, meta-position, and para-position based on the position of the phenylene group bonding to the nitrogen atom of the mercaptotetrazole, but the para-position is preferred from the viewpoint of obtaining excellent limiting resolution.

[0144] The compound represented by (E-1) is preferably either a compound represented by the following (E-2) or a compound represented by the following (E-3). [ka]

[0145] From the viewpoint of obtaining excellent limiting resolution, the content of the (E) component is preferably at least 0.1 part by mass, more preferably at least 0.5 parts by mass, and even more preferably at least 1 part by mass, per 100 parts by mass of the (A) component, and is preferably at most 20 parts by mass, more preferably at most 17 parts by mass, and even more preferably at most 15 parts by mass.

[0146] From the viewpoint of obtaining excellent limiting resolution, the content of the component (E) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 20% by mass or less, more preferably 17% by mass or less, and even more preferably 15% by mass or less, when the total non-volatile components of the photosensitive resin composition is taken as 100% by mass.

[0147] <(F) Other additives> The photosensitive resin composition may further contain (F) other additives to the extent that the object of the present invention is not impaired. Examples of (F) other additives include adhesion aids; surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants; thermoplastic resins; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black; polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; thickeners such as bentone and montmorillonite; silicone-based, fluorine-based, and vinyl resin-based defoamers; flame retardants such as epoxy resins, antimony compounds, phosphorus-based compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters; and thermosetting resins such as phenol-based curing agents and cyanate ester-based curing agents.

[0148] <(G) Solvent> The photosensitive resin composition may optionally contain a solvent (G) in combination with the nonvolatile components (A) to (F). The solvent (G) is preferably a volatile component that can uniformly dissolve at least one of the components (A) to (D) and the optional components (E) and (F). Examples of such solvents include ether compounds having 2 to 9 carbon atoms, such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; ketone compounds having 2 to 6 carbon atoms, such as acetone and methyl ethyl ketone; saturated hydrocarbon compounds having 5 to 10 carbon atoms, such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, and decalin; aromatic hydrocarbon compounds having 6 to 10 carbon atoms, such as benzene, toluene, xylene, mesitylene, and tetralin; ester compounds having 3 to 9 carbon atoms, such as methyl acetate, ethyl acetate, γ-butyrolactone, and methyl benzoate; halogen-containing compounds having 1 to 10 carbon atoms, such as chloroform, methylene chloride, and 1,2-dichloroethane; nitrogen-containing compounds having 2 to 10 carbon atoms, such as acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and sulfur-containing compounds, such as dimethyl sulfoxide.

[0149] Examples of the component (G) include N-ethyl-2-pyrrolidone, tetrahydrofuran, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, cyclopentanone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, anisole, ethyl acetate, ethyl lactate, and butyl lactate. The component (G) may be used alone or in combination of two or more.

[0150] The content of component (G) is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less, when the entire photosensitive resin composition including component (G) is taken as 100% by mass. The content of component (G) in the photosensitive resin composition layer of the photosensitive film described below is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, when the entire photosensitive resin composition including component (G) is taken as 100% by mass.

[0151] <Method for producing photosensitive resin composition> The photosensitive resin composition can be produced by mixing the essential components (A) to (D) described above, and optionally mixing the optional components (E) to (G) described above, and kneading or stirring the mixture, if necessary, using a kneading device such as a triple roll mill, a ball mill, a bead mill, or a sand mill, or a stirring device such as a super mixer or a planetary mixer.

[0152] <Physical properties and applications of photosensitive resin compositions> Photosensitive resin compositions exhibit excellent limiting resolution. For example, exposure and development are performed using a mask that creates circular holes with opening diameters of 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm. In this case, the limiting resolution, which is the minimum size of the opening, is preferably 25 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less.

[0153] The photosensitive resin composition exhibits the property that cracks are unlikely to occur on the surface of the insulating layer or in the vias after exposure even when the exposure dose is increased, i.e., the exposure process window is wide. For example, when the exposure dose is set to 50 mJ / cm using a mask that draws round holes (vias) with an opening diameter of 20 μm in the exposure pattern, 2 , 100mJ / cm 2, 200mJ / cm 2 , 300mJ / cm 2 and ultraviolet light (wavelength 365 nm, intensity 40 mW / cm 2 ) and development. Then, the 10 vias are observed with a scanning electron microscope (SEM) (magnification 1000x) to check for the presence or absence of cracks in the vias. The number of cracks in the vias is preferably 3 or less, more preferably 2 or less, even more preferably 1 or less, and particularly preferably 0, at any exposure dose. The evaluation of the exposure process window can be carried out according to the method described in the Examples below.

[0154] A cured product obtained by thermally curing a photosensitive resin composition at 250°C for 2 hours exhibits the characteristic of a low dielectric constant (Dk). The dielectric constant at 23°C is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. The lower limit is not particularly limited, but may be 1 or more, for example. The dielectric constant can be measured according to the method described in the examples below.

[0155] A cured product obtained by thermally curing a photosensitive resin composition at 250°C for 2 hours exhibits the characteristic of a low dielectric loss tangent (Df). The dielectric loss tangent at 23°C is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0.03 or less. The lower limit is not particularly limited, but may be 0.0001 or more, 0.001 or more, or 0.01 or more, for example. The dielectric loss tangent can be measured according to the method described in the Examples below.

[0156] The photosensitive resin composition of the present invention is not particularly limited in its applications, but can be used in a wide range of applications where photosensitive resin compositions are used, such as photosensitive films, insulating resin sheets such as prepregs, silicon wafers, circuit boards (for laminates, multilayer printed wiring boards, etc.), solder resists, buffer coating films, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, and component-embedding resins. Among these, photosensitive resin compositions for insulating layers of printed wiring boards (printed wiring boards in which a cured product of the photosensitive resin composition is used as an insulating layer), photosensitive resin compositions for interlayer insulating layers (printed wiring boards in which a cured product of the photosensitive resin composition is used as an interlayer insulating layer), photosensitive resin compositions for plating (printed wiring boards in which plating is formed on a cured product of the photosensitive resin composition), and photosensitive resin compositions for solder resists (printed wiring boards in which a cured product of the photosensitive resin composition is used as a solder resist), photosensitive resin compositions for rewiring formation layers of wafer-level packages (wafer-level packages in which a cured product of the photosensitive resin composition is used as a rewiring formation layer), The photosensitive resin composition can be suitably used as a photosensitive resin composition for a rewiring formation layer in a fan-out wafer-level package (a fan-out wafer-level package in which a cured product of the photosensitive resin composition serves as a rewiring formation layer), a photosensitive resin composition for a rewiring formation layer in a fan-out panel-level package (a fan-out panel-level package in which a cured product of the photosensitive resin composition serves as a rewiring formation layer), a photosensitive resin composition for a buffer coat (a semiconductor device in which a cured product of the photosensitive resin composition serves as a buffer coat), or a photosensitive resin composition for an insulating layer in a display (a display in which a cured product of the photosensitive resin composition serves as an insulating layer).

[0157] [Photosensitive film] The photosensitive resin composition of the present invention can be applied to a photosensitive film. The photosensitive film can include a support and a photosensitive resin composition layer formed on the support. The photosensitive resin composition layer is a layer made of the above-mentioned photosensitive resin composition. The photosensitive film may also include a support, a photosensitive resin composition layer, and a protective film in this order.

[0158] Examples of the support include polyethylene terephthalate (PET) film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, and triacetyl acetate film, with polyethylene terephthalate film being particularly preferred.

[0159] Examples of commercially available supports include, but are not limited to, polypropylene films such as those manufactured by Oji Paper Co., Ltd. under the product names "Alphan MA-410" and "E-200C," those manufactured by Tamapoly Co., Ltd. under the product names "GF-1" and "GF-8," and those manufactured by Shin-Etsu Film Co., Ltd.; the PS series manufactured by Teijin Limited under the product name "PS-25," and polyethylene terephthalate films such as those manufactured by Toray Industries, Inc. under the product name "Lumirror T6AM." These supports are preferably coated on the surface with a release agent, such as a silicone or non-silicone coating, to facilitate removal. Examples of supports whose surfaces have been treated with such a release agent include "AL-5" manufactured by Lintec Corporation. The thickness of the support is preferably in the range of 5 μm to 100 μm, and more preferably in the range of 10 μm to 50 μm.

[0160] The thickness of the photosensitive resin composition layer is not particularly limited and can be, for example, 1 μm or more and 100 μm or less, preferably 2 μm or more, more preferably 4 μm or more, and preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less.

[0161] The photosensitive resin composition layer may be protected by a protective film. Protecting the photosensitive resin composition layer with a protective film can prevent dust from adhering to the surface of the photosensitive resin composition layer and scratches. The protective film may be made of the same material as the support. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and even more preferably in the range of 10 μm to 30 μm. The protective film is preferably one in which the adhesive strength between the photosensitive resin composition layer and the protective film is smaller than the adhesive strength between the photosensitive resin composition layer and the support.

[0162] An example of a commercially available protective film is "MA-411" (biaxially oriented polypropylene film) manufactured by Oji F-Tex Co., Ltd.

[0163] The photosensitive film can be produced, for example, by applying the photosensitive resin composition onto a support and, if necessary, drying off the (G) solvent.

[0164] [Semiconductor package substrate] The semiconductor package substrate of the present invention includes an insulating layer formed from a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a rewiring formation layer, an interlayer insulating layer, a buffer coating film, or a solder resist.

[0165] In particular, the semiconductor package substrate of the first embodiment of the present invention can be manufactured using the above-mentioned photosensitive resin composition, and the cured product of the photosensitive resin composition is used as an insulating layer. Specifically, the manufacturing method of the semiconductor package substrate includes: (I) forming a photosensitive resin composition layer containing the photosensitive resin composition of the present invention on a circuit board; (II) a step of irradiating the photosensitive resin composition layer with actinic rays; and (III) a step of developing the photosensitive resin composition layer; Contains, in this order:

[0166] <Process (I)> Methods for forming the photosensitive resin composition layer include a method in which a resin varnish containing the photosensitive resin composition is directly applied onto the circuit board, and a method in which the photosensitive film is used.

[0167] When the resin varnish containing the photosensitive resin composition is applied directly onto the circuit board, the (G) solvent is dried and evaporated to form a photosensitive resin composition layer on the circuit board.

[0168] Examples of resin varnish application methods include gravure coating, microgravure coating, reverse coating, kiss reverse coating, die coating, slot die coating, lip coating, comma coating, blade coating, roll coating, knife coating, curtain coating, chamber gravure coating, slot orifice coating, spin coating, slit coating, spray coating, dip coating, hot melt coating, bar coating, applicator coating, air knife coating, curtain flow coating, offset printing, brush coating, and full-surface printing using screen printing.

[0169] The resin varnish may be applied in several batches, in one application, or by a combination of several different methods. Among these, the die coating method is preferred because it provides excellent uniformity. Furthermore, to avoid contamination, it is preferable to carry out the application process in an environment where foreign matter is less likely to be generated, such as a clean room.

[0170] After the resin varnish is applied, it is dried, if necessary, in a hot air oven or far-infrared oven. The drying conditions are preferably 80°C to 120°C for 3 to 13 minutes. In this way, a photosensitive resin composition layer is formed on the circuit board.

[0171] Examples of circuit boards include glass epoxy boards, metal boards, polyester boards, polyimide boards, BT resin boards, and thermosetting polyphenylene ether boards. Here, the term "circuit board" refers to a board in which a patterned conductor layer (circuit) is formed on one or both sides of a support substrate such as those described above. Also included in the term "circuit board" is a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, in which one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits). The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

[0172] On the other hand, when a photosensitive film is used, the photosensitive resin composition layer is laminated on one or both sides of the circuit board using a vacuum laminator. In the laminating step, if the photosensitive film has a protective film, the protective film is removed, and then the photosensitive film and the circuit board are preheated as necessary, and the photosensitive resin composition layer is pressure-bonded to the circuit board while being pressurized and heated. For the photosensitive film, a method of laminating the film to the circuit board under reduced pressure by a vacuum lamination method is preferably used.

[0173] The lamination conditions are not particularly limited, but for example, the pressure-bonding temperature (lamination temperature) is preferably 70°C to 140°C, and the pressure-bonding pressure is preferably 1 kgf / cm. 2 ~11kgf / cm 2 (9.8×10 4 N / m 2 ~107.9×10 4 N / m 2), the pressure bonding time is preferably 5 to 300 seconds, and lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The lamination process may be a batch process or a continuous process using rolls. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nikko Materials Co., Ltd., a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a roll-type dry coater manufactured by Hitachi Industries Co., Ltd., and a vacuum laminator manufactured by Hitachi AIC Corporation.

[0174] <Process (II)> After the photosensitive resin composition layer is provided on the circuit board, an exposure step is then performed in which actinic rays are irradiated to predetermined portions of the photosensitive resin composition layer through a mask pattern. Examples of actinic rays include ultraviolet rays, visible rays, electron beams, and X-rays, with ultraviolet rays being particularly preferred. The irradiation dose of ultraviolet rays is approximately 10 mJ / cm. 2 ~1000mJ / cm 2 The photosensitive resin composition layer produced using the photosensitive resin composition or photosensitive film according to the present invention has a wide process window during exposure, and therefore a cured product having good physical properties can be obtained with a wide range of ultraviolet irradiation doses. Exposure methods include contact exposure, in which a mask pattern is closely attached to the circuit board, and non-contact exposure, in which exposure is performed using parallel light without close contact, and either method may be used.

[0175] In step (II), vias can be formed using a via pattern such as a round hole pattern as a mask pattern. The via diameter (opening diameter) is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. The lower limit is not particularly limited, but can be 0.1 μm or more, 0.5 μm or more, etc.

[0176] <Process (III)> After the exposure step, a development step is carried out in which the unexposed portions of the photosensitive resin composition layer are removed with a developer, thereby forming a pattern. The development is usually carried out by wet development.

[0177] In the case of the wet development, a developer that is safe, stable, and easy to handle is used, such as an alkaline solution, an aqueous developer, an organic solvent, etc. As the developing method, a known method such as spraying, shaking immersion, brushing, scraping, etc. is suitably adopted.

[0178] Examples of alkaline aqueous solutions used as the developer include aqueous solutions of alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; alkali metal phosphates such as sodium phosphate and potassium phosphate; and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; and aqueous solutions of organic bases that do not contain metal ions, such as tetraalkylammonium hydroxide. Of these, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred because it does not contain metal ions and does not affect the semiconductor chip.

[0179] These alkaline aqueous solutions may contain a surfactant, an antifoaming agent, etc. to improve the development effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8 to 12, more preferably in the range of 9 to 11. The base concentration of the alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected depending on the developability of the photosensitive resin composition layer, but is preferably 20°C to 50°C.

[0180] Examples of organic solvents used as developers include acetone, ethyl acetate, alkoxyethanols having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclopentanone, and cyclohexanone.

[0181] The concentration of such organic solvents is preferably 2% by mass to 100% by mass, more preferably 2% by mass to 90% by mass, based on the total amount of the developer. The temperature of such organic solvents can be adjusted according to the developability. These organic solvents can be used alone or in combination of two or more. Examples of organic solvent-based developers that can be used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, cyclopentanone, methyl isobutyl ketone, and γ-butyrolactone.

[0182] In forming a pattern, two or more development methods may be used in combination as needed. Development methods include dipping, bathing, spraying, high-pressure spraying, brushing, and slapping, with the high-pressure spraying method being preferred for improving resolution. When using a spraying method, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

[0183] <Thermal curing (post-bake) process> After the completion of the step (III), a thermal curing (post-baking) step is carried out as necessary. Although the curing of the photosensitive resin composition layer may proceed in the steps (I) to (III) described above, the thermal curing step can further promote the curing of the photosensitive resin composition, thereby obtaining an insulating layer with excellent mechanical strength. Examples of the post-baking step include a heating step using a clean oven. The thermal curing atmosphere may be air or an inert gas atmosphere such as nitrogen. The heating conditions may be appropriately selected depending on the type and content of the resin component in the photosensitive resin composition, but are preferably selected within the range of 150°C to 250°C for 20 to 180 minutes, and more preferably 160°C to 230°C for 30 to 120 minutes.

[0184] <Other processes> The method for producing a semiconductor package substrate may further include a drilling step and a desmearing step after forming an insulating layer as a cured photosensitive resin composition layer. These steps may be performed according to various methods used in the production of semiconductor package substrates and known to those skilled in the art.

[0185] After forming the insulating layer, if desired, via holes or through holes are formed in the insulating layer formed on the circuit board by a drilling process. The drilling process can be performed by a known method such as a drill, a laser, or plasma, or by a combination of these methods as needed, but a drilling process using a laser such as a carbon dioxide laser or a YAG laser is preferred.

[0186] The desmearing process is a process of performing a desmear treatment. Generally, resin residue (smear) adheres to the inside of the opening formed in the drilling process. Since such smear can cause poor electrical connection, a process of removing the smear (desmearing process) is performed in this process.

[0187] The desmearing treatment may be performed by a dry desmearing treatment, a wet desmearing treatment, or a combination thereof.

[0188] An example of the dry desmear treatment is a desmear treatment using plasma. The desmear treatment using plasma can be performed using a commercially available plasma desmear treatment apparatus. Among the commercially available plasma desmear treatment apparatuses, examples suitable for use in manufacturing semiconductor package substrates include a microwave plasma apparatus manufactured by Nissin Corporation and an atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Co., Ltd.

[0189] Examples of wet desmear treatments include desmear treatments using an oxidizing agent solution. When desmear treatments are performed using an oxidizing agent solution, it is preferable to perform a swelling treatment using a swelling solution, an oxidation treatment using an oxidizing agent solution, and a neutralization treatment using a neutralizing solution in this order. Examples of swelling solutions include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing a substrate having via holes or the like formed therein in a swelling solution heated to 60°C to 80°C for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganate aqueous solution, such as a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous sodium hydroxide solution. The oxidation treatment using an oxidizing agent solution is preferably performed by immersing the substrate after the swelling treatment in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Commercially available alkaline permanganate aqueous solutions include, for example, "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan. The neutralization treatment using a neutralizing solution is preferably carried out by immersing the substrate after oxidation treatment in the neutralizing solution at 30°C to 50°C for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and a commercially available product thereof is, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan.

[0190] When the dry desmear treatment and the wet desmear treatment are performed in combination, the dry desmear treatment may be performed first, or the wet desmear treatment may be performed first.

[0191] In any case where the insulating layer is formed as a rewiring formation layer, an interlayer insulating layer, or a solder resist, a drilling step and a desmearing step may be performed after the thermal curing step. In addition, in the manufacturing method of a semiconductor package substrate, a plating step may be further performed.

[0192] The plating process is a process of forming a conductor layer on an insulating layer. The conductor layer may be formed by sputtering after the insulating layer is formed, or by a combination of electroless plating and electrolytic plating. Alternatively, a plating resist having a reverse pattern to the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. Subsequent pattern formation methods that can be used include, for example, subtractive methods and semi-additive methods known to those skilled in the art.

[0193] The semiconductor package substrate according to the second embodiment of the present invention can be manufactured using the above-described photosensitive resin composition, and the cured product of the photosensitive resin composition is used as a rewiring formation layer. Specifically, the manufacturing method of the semiconductor package substrate includes: (A) a step of laminating a temporary fixing film on a substrate; (B) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (C) forming an encapsulation layer on the semiconductor chip; (D) peeling the substrate and the temporary fixing film from the semiconductor chip; (E) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; (F) forming a rewiring layer as a conductor layer on the rewiring formation layer; and (G) forming a solder resist layer on the rewiring layer; The method for manufacturing the semiconductor chip package also includes: (H) dicing and singulating the plurality of semiconductor chip packages into individual semiconductor chip packages; may also include:

[0194] <Process (A)> Step (A) is a step of laminating a temporary fixing film on a substrate. The lamination conditions for the substrate and the temporary fixing film are not particularly limited, but for example, the pressure-bonding temperature (lamination temperature) is preferably 70°C to 140°C, and the pressure-bonding pressure is preferably 1 kgf / cm. 2 ~11kgf / cm 2 (9.8×10 4 N / m 2 ~107.9×10 4 N / m 2 ), and the pressure bonding time is preferably 5 to 300 seconds, and lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg or less. The lamination process may be a batch process or a continuous process using rolls. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nikko Materials Co., Ltd., a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a roll-type dry coater manufactured by Hitachi Industries Co., Ltd., and a vacuum laminator manufactured by Hitachi AIC Corporation.

[0195] Examples of the substrate include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); substrates such as FR-4 substrates in which glass fibers are impregnated with epoxy resin or the like and then thermoset; and substrates made of bismaleimide triazine resins such as BT resin.

[0196] The temporary fixing film may be made of any material that can be peeled off from the semiconductor chip and can temporarily fix the semiconductor chip. Commercially available products include "Riva Alpha" manufactured by Nitto Denko Corporation.

[0197] <Process (B)> Step (B) is a step of temporarily fixing semiconductor chips on a temporary fixing film. Temporarily fixing semiconductor chips can be performed using a device such as a flip chip bonder or a die bonder. The layout and number of semiconductor chips can be appropriately set depending on the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, and the like. For example, the semiconductor chips may be temporarily fixed by arranging them in a matrix of multiple rows and multiple columns.

[0198] <Process (C)> Step (C) is a step of forming an encapsulating layer on the semiconductor chip. Any insulating material can be used for the encapsulating layer, and the above-mentioned photosensitive resin composition can also be used. The encapsulating layer is usually formed by a method including a step of forming an encapsulating resin composition layer on the semiconductor chip and a step of thermally curing this resin composition layer to form the encapsulating layer.

[0199] The encapsulating resin composition layer is preferably formed by a compression molding method, in which a semiconductor chip and the encapsulating resin composition are typically placed in a mold, and pressure and, if necessary, heat are applied to the encapsulating resin composition in the mold to form an encapsulating resin composition layer that covers the semiconductor chip.

[0200] Specific operations of the compression molding method can be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. An encapsulating resin composition is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip to which the encapsulating resin composition has been applied is attached to the lower mold together with the substrate and the temporary fixing film. Thereafter, the upper and lower molds are clamped together, and heat and pressure are applied to the encapsulating resin composition to perform compression molding.

[0201] Furthermore, specific operations of the compression molding method may be, for example, as follows: An upper mold and a lower mold are prepared as molds for compression molding. An encapsulating resin composition is placed on the lower mold. A semiconductor chip is attached to the upper mold together with a substrate and a temporary fixing film. Thereafter, the upper and lower molds are clamped together so that the encapsulating resin composition placed on the lower mold contacts the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

[0202] The molding conditions vary depending on the composition of the encapsulating resin composition, and appropriate conditions can be adopted to achieve good encapsulation. For example, the mold temperature during molding is preferably a temperature at which the encapsulating resin composition exhibits excellent compression moldability, and is preferably 80°C or higher, more preferably 100°C or higher, particularly preferably 120°C or higher, and preferably 200°C or lower, more preferably 170°C or lower, and particularly preferably 150°C or lower. The pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, particularly preferably 5 MPa or higher, and preferably 50 MPa or lower, more preferably 30 MPa or lower, and particularly preferably 20 MPa or lower. The cure time is preferably 1 minute or longer, more preferably 2 minutes or longer, particularly preferably 5 minutes or longer, and preferably 60 minutes or shorter, more preferably 30 minutes or shorter, and particularly preferably 20 minutes or shorter. Typically, the mold is removed after the encapsulating resin composition layer is formed. The mold may be removed before or after the encapsulating resin composition layer is thermally cured.

[0203] The compression molding method may be carried out by discharging the encapsulating resin composition filled in a cartridge into a lower mold.

[0204] <Process (D)> Step (D) is a step of peeling the substrate and the temporary fixing film from the semiconductor chip. It is desirable to adopt an appropriate peeling method depending on the material of the temporary fixing film. Examples of peeling methods include a method in which the temporary fixing film is heated, foamed, or expanded to peel it off. Another example of a peeling method is a method in which the temporary fixing film is irradiated with ultraviolet light through the substrate to reduce the adhesive strength of the temporary fixing film, thereby peeling it off.

[0205] In the method of peeling off the temporary fixing film by heating, foaming or expanding it, the heating conditions are usually 100°C to 250°C for 1 second to 90 seconds or 5 minutes to 15 minutes. In the method of peeling off the temporary fixing film by irradiating it with ultraviolet light to reduce the adhesive strength of the temporary fixing film, the irradiation dose of ultraviolet light is usually 10 mJ / cm. 2 ~1000mJ / cm 2 is.

[0206] <Process (E)> Step (E) is a step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off. The rewiring formation layer uses the photosensitive resin composition of the present invention. The method for forming the rewiring formation layer is the same as the method for forming the photosensitive resin composition layer in step (I) in the first embodiment.

[0207] When forming the rewiring formation layer, via holes may be formed in the rewiring formation layer to connect the semiconductor chip and the rewiring layer to each other.

[0208] The via hole can usually be formed by performing an exposure step in which the surface of the photosensitive resin composition layer for forming the rewiring formation layer is irradiated with actinic rays through a mask pattern, and a development step in which the non-exposed portion not irradiated with actinic rays is developed and removed. The dose and duration of actinic rays can be appropriately set depending on the photosensitive resin composition layer. Examples of the exposure method include a contact exposure method in which a mask pattern is brought into close contact with the photosensitive resin composition layer and exposed, and a non-contact exposure method in which a mask pattern is not brought into close contact with the photosensitive resin composition layer and exposed using parallel rays. The actinic rays, developer, and exposure and development method are as described above for the semiconductor package substrate of the first embodiment.

[0209] The shape of the via hole is not particularly limited, but is generally circular (approximately circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less, and is preferably 0.1 μm or more, preferably 0.5 μm or more, and more preferably 1.0 μm or more. Here, the top diameter of the via hole refers to the diameter of the opening of the via hole on the surface of the rewiring formation layer.

[0210] <Process (F)> Step (F) is a step of forming a redistribution layer as a conductor layer on the redistribution formation layer. The method of forming the redistribution layer on the redistribution formation layer can be the same as the method of forming a conductor layer on an insulating layer in the first embodiment. Steps (E) and (F) may be repeated to alternately stack (build up) the redistribution layers and the redistribution formation layers.

[0211] <Process (G)> Step (G) is a step of forming a solder resist layer on the rewiring layer. Any insulating material can be used as the material for the solder resist layer. Among them, photosensitive resins and thermosetting resins are preferred from the viewpoint of ease of manufacturing a semiconductor chip package. The photosensitive resin composition of the present invention may also be used.

[0212] In step (G), bumping processing may be performed to form bumps, if necessary. The bumping processing can be performed by a method such as solder balls or solder plating. In addition, the formation of via holes in the bumping processing can be performed in the same manner as in step (E).

[0213] The method for manufacturing a semiconductor chip package may include a step (H) in addition to the steps (A) to (G). The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages. The method for dicing the semiconductor chip packages into individual semiconductor chip packages is not particularly limited.

[0214] [Semiconductor Devices] Examples of semiconductor devices on which the above-mentioned semiconductor chip package is mounted include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft). [Example]

[0215] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[0216] <Synthesis Example 1: Synthesis of Polyimide Precursor A1 (Containing Indane Skeleton)> Under a nitrogen stream, 105.6 g (399.7 mmol) of 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (MCTC) and 500 g of γ-butyrolactone were dissolved in a 1 L separable flask. 104.3 g (391.5 mmol) of 1-(4-aminophenyl)-1,3,3-trimethylindanamine (PIDA) was added and reacted at 50 °C for 20 hours to obtain polyamic acid. 111.3 g (783.0 mmol) of glycidyl methacrylate (GMA) and 0.42 g of 4-methoxyphenol were added and reacted at 50 °C for 20 hours to obtain a solution of polyimide precursor A1. The molecular weight of polyimide precursor A1 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 16,000. The structural unit of polyimide precursor A1 is shown below (n represents an integer of 5 to 200). [ka]

[0217] <Synthesis Example 2: Synthesis of Polyimide Precursor A2 (Containing Indane Skeleton)> Under a nitrogen stream, 79.2 g (399.7 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride (BT-100) and 500 g of γ-butyrolactone were dissolved in a 1 L separable flask. 104.3 g (391.5 mmol) of 1-(4-aminophenyl)-1,3,3-trimethylindanamine (PIDA) was added and reacted at 50 °C for 20 hours to obtain polyamic acid. 111.3 g (783.0 mmol) of glycidyl methacrylate (GMA) and 0.42 g of 4-methoxyphenol were added and reacted at 50 °C for 20 hours to obtain a solution of polyimide precursor A2. The molecular weight of polyimide precursor A2 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight-average molecular weight (Mw) of 14,000. The structural unit of polyimide precursor A2 is shown below (n represents an integer of 5 to 200). [ka]

[0218] <Synthesis Example 3: Synthesis of Polyimide Precursor A3 (Containing Indane Skeleton)> Under a nitrogen stream, 120.0 g (399.7 mmol) of 2-(3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthyl)succinic dianhydride (TDA-100) and 500 g of γ-butyrolactone were dissolved in a 1 L separable flask. 104.3 g (391.5 mmol) of 1-(4-aminophenyl)-1,3,3-trimethylindanamine (PIDA) was added and reacted at 50 °C for 20 hours to obtain polyamic acid. 153.7 g (843.5 mmol) of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100) and 0.42 g of 4-methoxyphenol were added and reacted at 50 °C for 20 hours to obtain a solution of polyimide precursor A3. The molecular weight of Polyimide Precursor A3 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 16,000. The structural units of Polyimide Precursor A3 are shown below (n represents an integer of 5 to 200). [ka]

[0219] <Synthesis Example 4: Synthesis of Polyimide Precursor A4 (Not Containing Indane Skeleton)> 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride was suspended in 140 mL of diglyme while removing moisture in a dry reactor equipped with a stirrer, a condenser, and an internal thermometer. 16.8 g (129.1 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of purified water, and 10.7 g (135.3 mmol) of pyridine were subsequently added and stirred at 60°C for 18 hours. The mixture was then cooled to -20°C, and 16.1 g (135.3 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride formed. The mixture was then warmed to room temperature and stirred for 2 hours. 9.7 g (122.6 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were then added, resulting in a clear solution. Next, 11.8 g (58.9 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise to the resulting clear solution over 1 hour. Next, 5.6 g (174.8 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. The mixture was then added to 4 L of water to precipitate Polyimide Precursor A4, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. Polyimide Precursor A4 was collected by filtration, added again to 4 L of water, stirred for 30 minutes, and filtered again. The resulting Polyimide Precursor A-4 was then dried under reduced pressure at 45°C for 3 days. The weight-average molecular weight (Mw) of the resulting Polyimide Precursor A4 was 24,800. The structural units of Polyimide Precursor A4 are shown below (n represents an integer between 5 and 200). [ka]

[0220] <Preparation of Photosensitive Resin Composition> Each component was mixed according to the blending amounts (unit: parts by mass) in Table 1 below, and stirred using a high-speed rotary mixer to prepare a varnish-like photosensitive resin composition. Solutions (non-volatile content: 30%) of the polyimide precursors A1 to A4 obtained in the above-mentioned Synthesis Examples 1 to 4 were prepared, and these solutions were used.

[0221] [Table 1]

[0222] The abbreviations in the table are as follows: Component (A) A1 (containing indan skeleton): Solution of polyimide precursor A1 synthesized in Synthesis Example 1 (non-volatile content 30%) A2 (containing indane skeleton): Solution of polyimide precursor A2 synthesized in Synthesis Example 2 (non-volatile content 30%) A3 (containing indan skeleton): Solution of polyimide precursor A3 synthesized in Synthesis Example 3 (non-volatile content 30%) A4 (non-indan skeleton): Solution of polyimide precursor A4 synthesized in Synthesis Example 4 (non-volatile content 30%)

[0223] (B) Component TMPT: A compound represented by the following structural formula ("TMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.) [ka] A-TMPT: A compound represented by the following structural formula ("A-TMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.) [ka] DPHA: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., penta- to hexafunctional acrylate)

[0224] (C) Component Irgacure Oxe02: An oxime ester photoradical generator represented by the following structural formula (BASF's "Irgacure OXE02") [ka] Irgacure Oxe01: An oxime ester photoradical generator represented by the following structural formula (BASF's "Irgacure OXE01") [ka]

[0225] (D) Component Omnipol ASA: A compound represented by the following structural formula (IGM's "Omnipol ASA", extinction coefficient ε = 0.088 L g -1 ·cm -1 ) [ka] Omnirad EDB: A compound represented by the following structural formula ("Omnirad EDB" manufactured by IGM, extinction coefficient ε = 0.010 L g -1 ·cm -1 ) [ka] Esacure A 198: A compound represented by the following structural formula (IGM's "Esacure A 198") [ka] (D') component Omnirad EMK: The compound represented by the following structural formula (IGM's "Omnirad EMK"; extinction coefficient ε = 125 L g -1 ·cm -1 ) [ka]

[0226] <Preparation of photosensitive film> A PET film ("Lumirror T6AM" manufactured by Toray Industries, Inc., thickness 38 μm) was prepared as a support. The photosensitive resin composition prepared in each example and comparative example was uniformly applied to the PET film using a die coater so that the film thickness of the photosensitive resin composition layer after drying would be 10 μm, and the film was dried at 80 to 120°C for 6 minutes to form a photosensitive resin composition layer on the PET. Next, a protective film (biaxially oriented polypropylene film, "MA-411" manufactured by Oji F-Tex Co., Ltd.) was placed on the surface of the photosensitive resin composition layer and laminated at 80°C to produce a photosensitive film with a three-layer structure of support / photosensitive resin composition layer / protective film.

[0227] <Evaluation of via cracks> A 5 μm-thick copper plating was laminated on a silicon wafer, and the substrate was roughened with a 1% hydrochloric acid aqueous solution for 60 seconds. The photosensitive resin composition layer of the photosensitive film was then placed on the substrate so that it was in contact with the surface of the copper layer, and laminated using a vacuum laminator (VP160, manufactured by Nikko Materials Co., Ltd.) to form a laminate in which the copper plating, the photosensitive resin composition layer, and the support were laminated in this order. The pressure bonding conditions were a vacuum evacuation time of 30 seconds, a pressure bonding temperature of 60°C, a pressure bonding pressure of 0.7 MPa, and a pressure bonding time of 30 seconds. After leaving the laminate at room temperature for 30 minutes, the support was peeled off. The laminate from which the support had been peeled off was then exposed to ultraviolet light (wavelength 365 nm, intensity 40 mW / cm). 2 The exposure was performed at a dose of 50 mJ / cm. 2 The exposure time was set within the range of 1.25 seconds. A quartz glass mask was used for the exposure pattern, which drew round holes (vias) with an opening diameter of 20 μm. After leaving the mask at room temperature for 5 minutes, a heat treatment was carried out at 100°C for 3 minutes. The entire surface of the photosensitive resin composition layer on the laminate was spray-developed with cyclopentanone at 23°C as a developer at a spray pressure of 0.1 MPa for an optimal time between 30 and 100 seconds, followed by a spray rinse with propylene glycol monomethyl ether acetate at a spray pressure of 0.1 MPa for 30 seconds. After the spray rinse, 1000 mJ / cm 2The photosensitive resin composition layer was then cured by irradiating it with ultraviolet light (a mixture of I-rays (wavelength 365 nm) and H-rays (wavelength 405 nm)) for 180 minutes at 200°C. The 10 vias were observed with a scanning electron microscope (SEM) (magnification 1000x) to check for the presence or absence of cracks in the vias. Evaluation was based on the following criteria. Good: 0-1 cracked vias. △: 2-3 cracked vias. ×: 4 or more cracked vias. The results are shown in Table 1 above.

[0228] In addition, the exposure dose when using a quartz glass mask to draw a round hole (via) with an opening diameter of 20 μm was 100 mJ / cm 2 (Exposure time 2.5 seconds), 200mJ / cm 2 (exposure time 5 seconds), and 300 mJ / cm 2 The same evaluation was also carried out when the exposure time was set within the range of 7.5 seconds.

[0229] <Measurement of dielectric properties (dielectric constant, dielectric loss tangent)> The photosensitive resin composition was coated onto a release-treated PET film using a blade to a film thickness of 140 μm. The solution on the PET was heated at 80°C for 15 minutes using a heater to form a photosensitive film having a photosensitive resin composition layer. The photosensitive resin composition layer was peeled from the PET film, and the photosensitive resin composition layer was attached to a metal frame using heat-resistant tape. The photosensitive resin composition layer was then heated at 1000 mJ / cm. 2 The film was then irradiated with ultraviolet light for 100 seconds, and cured at 200°C for 2 hours to prepare a film for measuring physical properties.

[0230] A test piece measuring 2 mm in width and 80 mm in length was cut from the film for measuring physical properties. The dielectric constant Dk and dielectric loss tangent Df of the cut test piece were measured by the cavity resonance perturbation method using an Agilent Technologies HP8362B measuring device at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. The results are shown in Table 1.

[0231] In Table 1, Examples 1 to 11 containing components (A), (B), (C), and (D) were able to reduce the number of cracked vias even under high exposure dose conditions while maintaining excellent dielectric properties. This indicates a wide process window for the exposure dose. Comparative Example 1, which did not contain component (D), produced a small number of cracked vias under a low exposure dose of 50 mJ, but the number of cracked vias increased under exposure doses of 100 mJ or more, which was unsatisfactory. Comparative Example 2, which contained component (D') not having the structure represented by formula (D-1) instead of component (D), was unable to form vias due to insufficient photocuring, causing the resin layer to flow out in the developer.

Claims

1. (A) a polyimide precursor; (B) a crosslinking agent, (C) a photoradical generator, and (D) a compound having a structure represented by the following formula (D-1): A photosensitive resin composition comprising: 【Chemical 1】 (In the formula, ring Ar represents an aromatic ring which may have a substituent, and * represents a bond.)

2. 2. The photosensitive resin composition according to claim 1, wherein in formula (D-1), ring Ar is a monocyclic aromatic ring which may have a substituent.

3. 2. The photosensitive resin composition according to claim 1, wherein in formula (D-1), ring Ar is a benzene ring.

4. The photosensitive resin composition according to claim 3, wherein the component (D) is a compound represented by the following formula (D-2): 【Chemistry 2】 (wherein R represents an alkyl group having 1 to 20 carbon atoms).

5. The photosensitive resin composition according to claim 3, wherein the component (D) is a compound represented by the following formula (D-3): 【Chemistry 3】 (In the formula, X represents a divalent organic group.)

6. 6. The photosensitive resin composition according to claim 5, wherein in formula (D-3), X is a divalent saturated chain group having 1 to 50 skeletal atoms selected from carbon atoms, nitrogen atoms, and oxygen atoms.

7. The photosensitive resin composition according to claim 5, wherein in formula (D-3), X is a divalent organic group represented by the following formula (D-4): 【Chemistry 4】 (In the formula, each Y independently represents an oxygen atom or —NR′— (N is a nitrogen atom, and R′ is an alkyl group having 1 to 20 carbon atoms), * represents a bond, each p independently represents an integer of 1 to 10, q is an integer of 1 to 10, and n′ is an integer of 0 to 10.)

8. (D) The absorption coefficient ε (L g －１ ・cm －１ ) is 4 L.g －１ ・cm －１ The photosensitive resin composition according to claim 1, wherein:

9. 2. The photosensitive resin composition according to claim 1, wherein the component (C) is an intramolecular cleavage-type photoradical generator.

10. 2. The photosensitive resin composition according to claim 1, wherein the component (C) is an oxime ester-based photoradical generator.

11. 2. The photosensitive resin composition according to claim 1, wherein the component (A) is a polyimide precursor containing an indane skeleton.

12. 2. The photosensitive resin composition according to claim 1, wherein the component (B) has 3 to 6 functional groups.

13. 2. The photosensitive resin composition according to claim 1, wherein the component (B) is a (meth)acrylate.

14. The mass ratio of the component (D) to the component (A) [component (D) / component (A)] is 10 －４ ~10 －１ The photosensitive resin composition according to claim 1, wherein

15. 2. The photosensitive resin composition according to claim 1, wherein the mass ratio of the component (D) to the component (B) [component (D) / component (B)] is 0.01 to 1.

16. 2. The photosensitive resin composition according to claim 1, wherein the mass ratio of the component (D) to the component (C) [component (D) / component (C)] is 0.01 to 10.

17. 2. The photosensitive resin composition according to claim 1, wherein the content of the component (A) is 70 to 98% by mass, when the total non-volatile components of the photosensitive resin composition is 100% by mass.

18. 2. The photosensitive resin composition according to claim 1, wherein the content of the component (D) is 0.05 to 5% by mass, relative to 100% by mass of the nonvolatile components of the photosensitive resin composition.

19. A photosensitive film comprising a support and a photosensitive resin composition layer formed on the support, the photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 18.

20. 20. The photosensitive film of claim 19, having a thickness of 1 to 30 μm.

21. A semiconductor package substrate comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of claims 1 to 18.

22. A semiconductor device comprising the semiconductor package substrate of claim 21.

23. forming a photosensitive resin composition layer containing the photosensitive resin composition according to any one of claims 1 to 18 on a circuit board; a step of irradiating the photosensitive resin composition layer with actinic rays; developing the photosensitive resin composition layer; A method for manufacturing a semiconductor package substrate, comprising:

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