Photosensitive resin composition

Abstract

To provide a photosensitive resin composition that can give a cured product having excellent limiting resolution and dielectric properties, and provide a photosensitive resin composition or the like that can give a cured product having excellent limiting resolution and via hole shapes and having excellent dielectric properties.SOLUTION: A photosensitive resin composition contains (A) a polyimide precursor having an indan skeleton, (B) a crosslinker, and (C) a photoradical generator. Alternatively, a photosensitive resin composition contains (A) a polyimide precursor having an indan skeleton, (B) a crosslinker, (C) a photoradical generator, and (D) an allyl compound having ethylenically unsaturated bonds, wherein carbon atoms at α-positions of the ethylenically unsaturated bonds are bound to groups selected from hydrocarbon groups and hydrogen atoms, and wherein at least one of groups bound to the carbon atoms at α-positions of the ethylenically unsaturated bonds is a hydrogen atom.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, which are obtained by 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 and the like 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 insulating layers and the like, the polyimide precursors are cyclized to form insulating layers (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2003-084435 A DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0004] In recent years, with the increase in communication speed and capacity in communication devices, photosensitive resin compositions used in semiconductor package substrates for communication devices are also required to have excellent dielectric properties, such as low dielectric constant and dielectric dissipation factor of the cured product, as well as excellent resolution.

[0005] The present invention has been made in consideration of the above problems, and has an object to provide a photosensitive resin composition excellent in limiting resolution and dielectric properties of a cured product, and 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.

[0006] In addition, when a via hole is formed by exposing and developing a photosensitive resin composition, it is not easy to control the shape of the via hole. For example, in a negative photosensitive resin composition, if the radical reaction due to exposure is insufficient or excessive, the shape of the via hole may deteriorate.

[0007] The present invention has been made in consideration of the above problems, and has an object to provide a photosensitive resin composition capable of obtaining a cured product having good limiting resolution and via hole shape and excellent dielectric properties, and 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. [Means for solving the problem]

[0008] As a result of intensive research, the present inventors have found that the above object can be achieved by incorporating a specific polyimide precursor, a crosslinking agent and a photoradical generator into a photosensitive resin composition, and have thus completed the present invention.

[0009] That is, the present invention includes the following. [1] (1A) a polyimide precursor having an indane skeleton, (1B) a crosslinking agent, and (1C) a photoradical generator, A photosensitive resin composition comprising: [2] The photosensitive resin composition according to [1], further comprising (1D) an allyl compound having an ethylenically unsaturated bond, in which the carbon atom at the α-position of the ethylenically unsaturated bond is bonded to a group selected from a hydrocarbon group and a hydrogen atom, and at least one of the groups bonded to the carbon atom at the α-position of the ethylenically unsaturated bond is a hydrogen atom. [3] The photosensitive resin composition according to [2], wherein the component (1D) is represented by the following formula (D-1): [ka] (In the formula, R 1d , R 2d , and R 3deach independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. * represents a bond.) [4] The photosensitive resin composition according to [2] or [3], wherein the component (1D) is represented by the following formula (D-2): [ka] (In the formula, R 11d , R 12d , R 13d , R 14d , R 15d and R 16d each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; Z d represents a divalent organic group. [5] The photosensitive resin composition according to any one of [1] to [4], further comprising (1E) a sensitizer. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the component (1A) 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 having an indane skeleton, 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. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the component (1A) has a structural unit represented by the following formula (A-3): [ka] (In the formula, each A1 independently represents a tetravalent organic group, R 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group; R 13each independently represents a hydrogen atom or 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 1 to 5, and n1 represents an integer of 5 to 200. [ka] (In formulas (1) to (4), * represents a bond.) [8] R in formula (A-1) 1 and R 2 each independently represents a hydrogen atom or a radically reactive group. [9] R in formula (A-1) 1 and R 2 each independently represents a hydrogen atom or a radical reactive group represented by the following formula (A-2): [ka] (In the formula, R 4 ~R 6 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p represents an integer of 1 to 10.

[10] The photosensitive resin composition according to any one of [1] to [9], wherein the component (1A) has a structural unit represented by the following formula (A-4): [ka] (In the formula, each A2 independently represents a tetravalent organic group, R 21 or R 22 each independently represents a hydrogen atom or a group represented by the following formula (A-5), and n2 represents an integer of 5 to 200. [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.

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

[10] , wherein the weight average molecular weight of the component (1A) is 5,000 or more and 1,000,000 or less.

[12] (2A) polyimide precursor, (2B) a crosslinking agent, (2C) a photoradical generator, and (2D) Allyl compounds having an ethylenically unsaturated bond, in which the carbon atom at the α-position of the ethylenically unsaturated bond is bonded to a group selected from a hydrocarbon group and a hydrogen atom, and at least one of the groups bonded to the carbon atom at the α-position of the ethylenically unsaturated bond is a hydrogen atom. A photosensitive resin composition comprising:

[13] The photosensitive resin composition according to

[12] , wherein the component (2D) is represented by the following formula (D-1): [ka] (In the formula, R 1d , R 2d , and R 3d each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. * represents a bond.)

[14] The photosensitive resin composition according to

[12] or

[13] , wherein the component (2D) is represented by the following formula (D-2): [ka] (In the formula, R 11d , R 12d , R 13d , R 14d , R 15d and R 16d each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; Z d represents a divalent organic group.

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

[12] to

[14] , wherein the component (2A) 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, and R 1 and R2 each independently represents a hydrogen atom or a monovalent organic group, and n represents an integer of 5 to 200.

[16] R in formula (A-1) 1 and R 2 and each independently represent at least one radical reactive group.

[17] The photosensitive resin composition according to

[16] , wherein the radical reactive group is represented by the following formula (A-2): [ka] (In the formula, R 4 ~R 6 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p represents an integer of 1 to 10.

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

[15] to

[17] , wherein B in formula (A-1) is a divalent organic group having an indane skeleton.

[19] The photosensitive resin composition according to any one of

[12] to

[18] , wherein the component (2A) has a structural unit represented by the following formula (A-3): [ka] (In the formula, each A1 independently represents a tetravalent organic group, R 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group; R 13 each independently represents a hydrogen atom or 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 1 to 5, and n1 represents an integer of 5 to 200. [ka] (In formulas (1) to (4), * represents a bond.)

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

[12] to

[19] , wherein the component (2B) is a compound having an ethylenically unsaturated bond, and at least one of the carbon atoms at the α-position of the ethylenically unsaturated bond is bonded to a carbonyl group or an aromatic group.

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

[12] to

[20] , further comprising a sensitizer (2E).

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

[12] to

[21] , wherein the content of the component (2D) is 0.1% by mass or more and 15% by mass or less, when the total amount of non-volatile components of the photosensitive resin composition is 100% by mass.

[23] The photosensitive resin composition according to any one of

[12] to

[22] , wherein the content of the component (2A) is 70% by mass or more and 98% by mass or less, when the total amount of non-volatile components in the photosensitive resin composition is 100% by mass.

[24] 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

[23] .

[25] 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

[23] .

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

[25] .

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

[23] on a circuit board; A step of irradiating the photosensitive resin composition layer with actinic rays; and developing the photosensitive resin composition layer. Effect of the Invention

[0010] According to the present invention, it is possible to provide a photosensitive resin composition having excellent limiting resolution and dielectric properties of a cured product, and a photosensitive film, a semiconductor package substrate, a semiconductor device, and a method for producing a semiconductor package substrate, each of which is obtained using the photosensitive resin composition.

[0011] Furthermore, according to the present invention, it is possible to provide a photosensitive resin composition capable of obtaining a cured product having good limiting resolution, good via hole shape, and excellent dielectric properties, and a photosensitive film, a semiconductor package substrate, a semiconductor device, and a method for producing a semiconductor package substrate, each of which is obtained using the photosensitive resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The first and second photosensitive resin compositions, the photosensitive film, the semiconductor package substrate, the semiconductor device, and the method for producing the semiconductor package substrate of the present invention will be described in detail below.

[0013] In this specification, the (1A) and (2A) components are sometimes collectively referred to as the "(A) component", the (1B) and (2B) components are sometimes collectively referred to as the "(B) component", the (1C) and (2C) components are sometimes collectively referred to as the "(C) component", the (1D) and (2D) components are sometimes collectively referred to as the "(D) component", the (1E) and (2E) components are sometimes collectively referred to as the "(E) component", the (1F) and (2F) components are sometimes collectively referred to as the "(F) component", and the (1G) and (2G) components are sometimes collectively referred to as the "(G) component".

[0014] [Photosensitive resin composition of the first embodiment] The photosensitive resin composition of the first embodiment of the present invention contains (1A) a polyimide precursor having an indane skeleton, (1B) a crosslinking agent, and (1C) a photoradical generator. By incorporating the components (1A) to (1C) in combination in the photosensitive resin composition, a cured product having excellent limit resolution and dielectric properties can be obtained. In addition, the photosensitive resin composition of the first embodiment can usually provide a cured product having a good via hole shape and excellent warpage.

[0015] The photosensitive resin composition of the first embodiment of the present invention is suitable as a negative photosensitive resin composition.

[0016] The photosensitive resin composition of the first embodiment may further contain an optional component in combination with the components (1A) to (1C). Examples of the optional component include (1D) an allyl compound having an ethylenically unsaturated bond, the α-position of which is a group selected from a hydrocarbon group and a hydrogen atom, and at least one of the groups at the α-position of the ethylenically unsaturated bond is a hydrogen atom, (1E) a sensitizer, (1F) other additives, and (1G) a solvent. Each component contained in the photosensitive resin composition of the first embodiment will be described in detail below.

[0017] <(1A) Polyimide precursor having an indane skeleton> The photosensitive resin composition contains a polyimide precursor having an indane skeleton (1A) as the component (1A). By including the component (1A) in the photosensitive resin composition, a cured product having excellent limit resolution and excellent dielectric properties can be obtained. The component (1A) may be used alone or in combination of two or more.

[0018] The component (1A) may be a resin having an indane skeleton and a plurality of amic acid and / or amic acid ester structures. The indane skeleton is the skeleton shown in the following formula (a1), and is preferably a trimethylindane skeleton shown in the following formula (a2). The amic acid and amic acid ester are compounds obtained by reacting a tetracarboxylic dianhydride with a diamine compound. [ka]

[0019] Examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides are preferred. Examples of the tetracarboxylic dianhydride include 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3,3',4 ,4'-para-terphenyltetracarboxylic dianhydride, 3,3',4,4'-meta-terphenyltetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2-endo-3-endo-5-exo-6-exo-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2-endo-3-endo-5-exo-6-exo-2,3,5,6-tetracarboxylic dianhydride 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, 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-tetracarboxylic dianhydride Examples of the tetrahydrofuran are tetrahydrofuran, ...

[0020] As the diamine compound, for example, a diamine having an indane skeleton is preferably used. Examples of the diamine having an indane skeleton include the diamines exemplified below. [ka]

[0021] From the viewpoint of obtaining a cured product that has excellent limiting resolution and excellent dielectric properties, the component (1A) 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 having an indane skeleton, 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.

[0022] 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 an aromatic group in which the -CONH- group and the -CONH- group are in the ortho position with respect to each other, or an alicyclic aliphatic group (R 1 and R 2 is R in formula (A-1) 1 and R 2 (which is the same as the above). Examples of such groups include groups (i) to (ix). Among them, A is preferably a tetravalent organic group exemplified below, and more preferably a group (viii) or a group (ix). In the formula, * represents a bond. [ka]

[0023] In formula (A-1), each B independently represents a divalent organic group having an indane skeleton. The divalent organic group having an indane skeleton preferably has an aromatic ring in addition to the indane skeleton. Examples of the divalent organic group having an indane skeleton include the groups (1a) to (7a) shown below, with the group (7a) being preferred. In the formula, * represents a bond. [ka]

[0024] R in formula (A-1) 1 and R 2 each independently represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include a saturated aliphatic group having 1 to 4 carbon atoms; a reactive group that can be polymerized by a radical generated by heat or light, i.e., a radical reactive group, and the like, and a radical reactive group is preferable. Examples of the radical reactive group include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, a (meth)acryloyl group, and a group represented by formula (A-2) described below. The "(meth)acryloyl group" includes a methacryloyl group, an acryloyl group, and a combination thereof. R in formula (A-1) 1 and R 2 is preferably at least one of, and more preferably both of, independently represent a radical reactive group. The radical reactive group is preferably a group represented by the following formula (A-2). [ka] (In the formula, R 4 ~R 6 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p represents an integer of 1 to 10.

[0025] R in formula (A-2) 4 ~R 6each 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, and among these, a methyl group is preferred.

[0026] As the saturated aliphatic group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, and an n-butyl group.

[0027] In the formula (A-2), p 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.

[0028] R in formula (A-1) 1 and R 2 is preferably at least one of a radical reactive group, more preferably at least one of a group represented by formula (A-2), R 1 and R 2 It is more preferable that both of are groups represented by formula (A-2).

[0029] In the formula (A-1), n ​​represents an integer of 5 to 200, preferably an integer of 5 to 150, more preferably an integer of 5 to 100, and further preferably an integer of 5 to 70.

[0030] The component (1A) preferably has a structural unit represented by formula (A-3). [ka] (In the formula, each A1 independently represents a tetravalent organic group, R 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group; R 13each independently represents a hydrogen atom or 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 1 to 5, and n1 represents an integer of 5 to 200. [ka] (In formulas (1) to (4), * represents a bond.)

[0031] Each A1 in formula (A-3) independently represents a tetravalent organic group, and A1 is the same as A in formula (A-1).

[0032] R in formula (A-3) 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group, and R in formula (A-1) 1 and R 2 is the same as:

[0033] Each Xa independently represents a single bond, a group represented by formula (1), or a group represented by formula (2).

[0034] 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.

[0035] Examples of the group represented by formula (2) include the following groups (2-1) to (2-6). [ka]

[0036] Among them, Xa is preferably a group represented by formula (2), more preferably a group represented by formula (2-1).

[0037] Each Xb independently represents a single bond, a group represented by formula (3), or a group represented by formula (4).

[0038] 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.

[0039] Examples of the group represented by formula (4) include the following groups. [ka]

[0040] Among these, Xb is preferably a group represented by formula (3), and more preferably a 1,4-phenylene group.

[0041] R 13 each independently represents a hydrogen atom or a methyl group, and preferably represents a methyl group.

[0042] m1 represents an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably 3.

[0043] n1 represents an integer of 5 to 200 and is the same as n in formula (A-1).

[0044] The component (1A) preferably has a structural unit represented by the following (A-4). [ka] (In the formula, each A2 independently represents a tetravalent organic group, R 21 or R 22 each independently represents a hydrogen atom or a group represented by the following formula (A-5), and n2 represents an integer of 5 to 200. [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.

[0045] Each A2 in formula (A-4) independently represents a tetravalent organic group and is the same as A in formula (A-1).

[0046] R in formula (A-4) 21 and R 22 R each independently represents a hydrogen atom or a group represented by formula (A-5), and a group represented by formula (A-5) is preferable. 14 ~R 16 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R in the group represented by formula (A-2) 4 ~R 6 In the group represented by formula (A-5), p1 represents an integer of 1 to 10 and is the same as p in the group represented by formula (A-2).

[0047] n2 represents an integer of 5 to 200 and is the same as n in formula (A-1).

[0048] The component (1A) may be a copolymer containing a structural unit having an indane skeleton and a structural unit not containing an indane skeleton. For example, the component (1A) may contain a structural unit other than the structural unit represented by formula (A-1) (a structural unit not containing an indane skeleton) in addition to the structural unit represented by formula (A-1).

[0049] Specific examples of the component (1A) include the following compounds (A1) to (A5). However, the component (1A) is not limited to these specific examples. In the formula, n is an integer of 5 to 200. [ka]

[0050] From the viewpoint of obtaining the remarkable effects of the present invention, the weight average molecular weight of the (1A) component is preferably at least 5,000, more preferably at least 10,000, and even more preferably at least 50,000, and is preferably at most 1,000,000, more preferably at most 500,000, and even more preferably at most 200,000. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0051] The method for producing the component (1A) is not particularly limited. The component (1A) can usually be obtained by reacting the above-mentioned tetracarboxylic dianhydride with a diamine compound. The component (1A) can be produced, for example, by the production method described in JP-A-2015-209461 or JP-A-2015-214680.

[0052] From the viewpoint of obtaining the effects of the present invention significantly, the content of the (1A) component 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, 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 non-volatile components of the photosensitive resin composition are taken as 100% by mass, in the present invention. Note that, in the present invention, the content of each component in the photosensitive resin composition is the value when the non-volatile components in the photosensitive resin composition are taken as 100% by mass, unless otherwise specified.

[0053] <(1B) Crosslinking Agent> The photosensitive resin composition contains a crosslinking agent (1B) as the component (1B). However, the component (1B) does not include those corresponding to the components (1A) and (1D). When the photosensitive resin composition is irradiated with actinic rays and radicals are generated from the photoradical generator, a crosslinking reaction of the component (1B) occurs, and the composition becomes insoluble in the developer. Therefore, during development, the photosensitive resin composition can be selectively removed from areas other than those where the crosslinking reaction has progressed, and a negative pattern can be advantageously formed. The component (1B) may be used alone or in combination of two or more.

[0054] As the component (1B), a compound capable of promoting a crosslinking reaction during development can be used. Such a compound is preferably a compound having an ethylenically unsaturated bond, and more preferably a compound having an ethylenically unsaturated bond and at least one of the carbon atoms at the α-position of the ethylenically unsaturated bond is bonded to a carbonyl group or 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 a carbon-carbon double bond.

[0055] The ethylenically unsaturated bond represents a carbon-carbon double bond. Therefore, the (1B) component may contain a group having an ethylenically unsaturated bond (hereinafter, may be referred to as "ethylenically unsaturated group" as appropriate). The ethylenically unsaturated group is usually a monovalent group, and examples thereof include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, and a (meth)acryloyl group. From the viewpoint of reactivity of photoradical polymerization, a (meth)acryloyl group and a phenylethynyl group are preferred, and a (meth)acryloyl group is particularly preferred. The "(meth)acryloyl group" includes a methacryloyl group, an acryloyl group, and a combination thereof. The (1B) component contains an ethylenically unsaturated group, and therefore is capable of photoradical polymerization. However, in order to perform photoradical polymerization under general conditions, a compound having a carbonyl group or an aromatic group at at least one of the α positions of the ethylenically unsaturated bond is preferred. The number of ethylenically unsaturated groups per molecule of component (1B) is preferably at least 1, and more preferably at least 2. Furthermore, when component (1B) contains two or more ethylenically unsaturated groups per molecule, those ethylenically unsaturated groups may be the same or different.

[0056] The component (1B) is preferably a compound represented by the following general formula (B-1). [ka] (In formula (B-1), R 31each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms; 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 1 represents a linear, cyclic or branched nb-valent organic group having 1 to 10 carbon atoms, and nb represents a positive integer of 2 to 6.

[0057] R 31 each independently represents 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 them, R 31 is preferably a hydrogen atom or a methyl group.

[0058] Each Z 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. 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, and a methylene group is preferred. The alkylene group may also be an oxyalkylene group containing an oxygen atom, and specific examples of such groups include the following. In the formula, "*" represents a bond, and a represents an integer of 1 to 23. [ka]

[0059] The arylene group which may contain an oxygen atom is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 15 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. Examples of such an arylene group 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 23. [ka]

[0060] 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 an alkenylene group include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, and a hexenylene group. The alkenylene group may also be an oxyalkenylene group containing an oxygen atom, and specific examples of such groups include the following. In the formula, "*" represents a bond, and a represents an integer of 1 to 23. The alkenylene group is preferably a propenylene group. [ka]

[0061] Among these, Z is preferably a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, and more preferably an oxyalkylene group.

[0062] A 1represents 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. An nb-valent aliphatic hydrocarbon group which may contain an oxygen atom is preferred, and when nb is 2, for example, an alkylene group is preferred. A 1 Specific examples of the group represented by include the following: In the formula, "*" represents a bond. [ka]

[0063] nb represents a positive integer of 2 to 6, preferably a positive integer of 2 to 5, more preferably a positive integer of 2 to 4, and further preferably 2 or 3.

[0064] The component (1B) is preferably a compound represented by the following general formula (B-2). [ka] (In formula (B-2), R 32 each independently represents a hydrogen atom or a methyl group.

[0065] R 32 represents a hydrogen atom or a methyl group, and a methyl group is preferable.

[0066] Specific examples of the component (1B) include the following compounds (CL-1) to (CL-11), however, the component (1B) is not limited to these. [ka] [ka]

[0067] As the component (1B), commercially available products can be used, such as NK Ester D-TMP, 4G, 9G, 14G, 23G, and DCP manufactured by Shin-Nakamura Chemical Co., Ltd.

[0068] In order to prominently obtain the effects of the present invention, the content of the (1B) component, per 100 parts by mass of the (1A) component, is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more, and is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less.

[0069] From the viewpoint of obtaining the effects of the present invention prominently, the content of the component (1B) 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, and even more preferably 15% by mass or less, when the non-volatile components of the photosensitive resin composition are taken as 100% by mass.

[0070] <(1C) Photoradical generator> The photosensitive resin composition contains a photoradical generator (1C). The component (1C) generates radicals when irradiated with actinic rays, and the portion of the photosensitive resin composition where crosslinking reaction or the like has occurred due to the radicals does not dissolve in the developer. Therefore, during development, it becomes possible to selectively remove the photosensitive resin composition from the portion other than where the crosslinking reaction has progressed, and a negative pattern can be advantageously formed. The component (1C) may be used alone or in combination of two or more. In addition, the component (1C) does not include those corresponding to the components (1A) to (1B) and the components (1D) to (1E) described below.

[0071] Examples of the (1C) component include benzophenone, o-benzoylbenzoic acid methyl, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone and other acetophenone derivatives, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and other thioxanthone derivatives; benzil, benzil dimethyl ketal, benzyl-β-methoxyethyl acetal and other benzyl derivatives; benzoin, benzoin methyl ether and other benzoin derivatives; 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, 1-phenyl-1,2-propanedione-2-(o-benzoyl) oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl) oxime and other oximes; N-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazoles; titanocenes; α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide; and the like. Among these, oximes are preferred as the component (1C) from the viewpoint of photosensitivity.

[0072] Commercially available products can be used as the component (1C), such as "Irgacure-OXE02" and "Irgacure-OXE04" manufactured by BASF.

[0073] In order to prominently obtain the effects of the present invention, the content of the component (1C) is preferably at least 0.1 part by mass, more preferably at least 0.5 part by mass, and even more preferably at least 1 part by mass, per 100 parts by mass of the component (1A), 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.

[0074] From the viewpoint of prominently obtaining the effects of the present invention, the content of the component (1C) 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, based on 100% by mass of the non-volatile components of the photosensitive resin composition.

[0075] <(1D) Allyl compounds having an ethylenically unsaturated bond, in which the carbon atom at the α-position of the ethylenically unsaturated bond is bonded to a group selected from a hydrocarbon group and a hydrogen atom, and at least one of the groups bonded to the carbon atom at the α-position of the ethylenically unsaturated bond is a hydrogen atom> The photosensitive resin composition may contain, as an optional component, an allyl compound (1D) having an ethylenically unsaturated bond, the carbon atom at the α-position of the ethylenically unsaturated bond being bonded to a group selected from a hydrocarbon group and a hydrogen atom, and at least one of the groups bonded to the carbon atom at the α-position of the ethylenically unsaturated bond being a hydrogen atom. The component (1D) excludes the above-mentioned components (1A) to (1C) and the component (1E) described below. The carbon atom at the α-position of the ethylenically unsaturated bond is the first carbon atom adjacent to the carbon atom bonded by a carbon-carbon double bond, and specifically, for example, as shown in the following formula (d1), it indicates the carbon atom (C1 to C4) adjacent to the carbon atom bonded by a carbon-carbon double bond. [ka]

[0076] When the photosensitive resin composition is a negative type, by including the (1D) component in the photosensitive resin composition, it is possible to prevent the radical reaction from progressing to the unexposed areas, and it is possible to obtain a cured product with a good via hole shape.

[0077] When the component (1D) has multiple ethylenically unsaturated bonds, it is sufficient that at least one of the multiple α-position carbon atoms is bonded to a hydrogen atom, and in this case, the other α-position carbon atoms may be bonded to groups other than a carbonyl group and an aromatic group. The component (1D) is preferably an allyl compound in which the carbon atom at the α-position of the ethylenically unsaturated bond is composed only of groups selected from a hydrocarbon group and a hydrogen atom, and at least one of the groups bonded to the carbon atom at the α-position of the ethylenically unsaturated bond is a hydrogen atom.

[0078] The component (1D) is preferably represented by the following formula (D-1). [ka] (In the formula, R 1d , R 2d , and R 3d each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. * represents a bond.)

[0079] In formula (D-1), R 1d , R 2d , and R 3d R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. Examples of the hydrocarbon group having 1 to 3 carbon atoms include an aliphatic hydrocarbon group having 1 to 3 carbon atoms. Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include a saturated aliphatic hydrocarbon group, for example, 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, an isopropyl group, and among these, a methyl group is preferred. 1d , R 2d , and R 3d is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0080] The number of structures represented by formula (D-1) per molecule of component (1D) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The number of structures represented by formula (D-1) per molecule of component (1D) is preferably 2 or 3, and more preferably 2. In addition, when the number of structures represented by formula (D-1) per molecule of component (D) is 2 or more, those structures represented by formula (D-1) may be the same or different.

[0081] The component (1D) is preferably a compound represented by the following formula (D-2). [ka] (In the formula, R 11d , R 12d , R 13d , R 14d , R 15d and R 16d each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; Z d represents a divalent organic group.

[0082] R 11d , R 12d , R 13d , R 14d , R 15d and R 16d each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; 1d , R 2d , and R 3d is the same as:

[0083] Z d represents a divalent organic group. Examples of the divalent organic group include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent group containing a heteroatom, and a divalent group consisting of a combination of two or more of these. Examples of the heteroatom include an oxygen atom, a sulfur atom, a nitrogen atom, and a halogen atom.

[0084] The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic. The divalent aliphatic hydrocarbon group may be saturated or unsaturated. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 5. Examples of the divalent aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. Examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, and a hexenylene group. Examples of the alkynylene group include an ethynylene group, a propenylene group, and the like.

[0085] The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 to 20, and more preferably 6 to 15. Examples of the divalent aromatic hydrocarbon group include an arylene group, and examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group, and a 9,9-diphenyl-9H-fluorenylene group.

[0086] Examples of the divalent group containing a heteroatom include -O-, -S-, -NH-, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -C(=O)-NH-, -S(=O) 2 -, -S(=O) 2 -O-, the groups shown below, and the like. [ka] (* represents a bond.)

[0087] Examples of the divalent group consisting of two or more combinations include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, and a divalent group containing a heteroatom bonded thereto; a divalent aromatic hydrocarbon group and a divalent group containing a heteroatom bonded thereto; and a divalent aliphatic hydrocarbon group and a divalent group containing a heteroatom bonded thereto. Specific examples of the divalent group consisting of two or more combinations as described above include the following groups (d-1) to (d-6), but the present invention is not limited thereto. In the groups (d-1) to (d-6), * represents a bond. The divalent group consisting of two or more combinations is preferably the groups (d-1) to (d-3). [ka]

[0088] 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, and n-butyl groups; halogen atoms, such as fluorine, chlorine, and bromine; alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, and propoxy; hydroxyl groups; and halogen-substituted alkyl groups, such as trifluoromethyl groups. The above-mentioned substituents may further have a substituent (hereinafter, sometimes referred to as "secondary substituents"). The substituents may be contained alone or in combination of two or more kinds. When the divalent organic group has a substituent, the substituent is preferably a hydroxyl group.

[0089] Specific examples of the component (1D) include triallyl isocyanurate, triallyl cyanurate, 1,3,5-triallylhexahydro-1,3,5-triazine, diallylpropyl isocyanurate, diallyl 1,4-cyclohexanedicarboxylate, 9,9-bis(4-allyloxyphenyl)fluorene, 2,2-bis(allyloxymethyl)-1-butanol, and the following compounds (D1) to (D3), etc. However, the component (1D) is not limited to these specific examples. [ka]

[0090] The component (1D) may be a commercially available product, such as "BANI-X" or "BANI-M" manufactured by Maruzen Petrochemical Co., Ltd., "DAD" manufactured by Nisshoku Techno Fine Chemical Co., Ltd., or "DPNG" manufactured by Kuraray Co., Ltd.

[0091] In order to prominently obtain the effects of the present invention, the content of the component (1D) is preferably at least 0.1 part by mass, more preferably at least 0.5 part by mass, and even more preferably at least 1 part by mass, per 100 parts by mass of the component (1A), and is preferably at most 20 parts by mass, more preferably at most 15 parts by mass, and even more preferably at most 10 parts by mass.

[0092] When the total amount of non-volatile components in the photosensitive resin composition is taken as 100 mass%, from the viewpoint of obtaining a cured product with excellent via hole shape, the content of the (1D) component is preferably 0.1 mass% or more, more preferably 0.13 mass% or more, even more preferably 0.15 mass% or more, 0.17 mass% or more, or 0.2 mass% or more, and is preferably 15 mass% or less, more preferably 13 mass% or less, even more preferably 11 mass% or less, or 10 mass% or less.

[0093] When the content of the component (1A) when the nonvolatile components of the photosensitive resin composition are taken as 100 mass % is a1 and the content of the component (1D) when the nonvolatile components of the photosensitive resin composition are taken as 100 mass %, d1, from the viewpoint of significantly obtaining the effects of the present invention, a1 / d1 is preferably 1 or more, more preferably 3 or more, and even more preferably 5 or more, and is preferably 600 or less, more preferably 100 or less, and even more preferably 500 or less, 400 or less, 300 or less, 200 or less, or 100 or less.

[0094] <(1E) Sensitizer> The photosensitive resin composition may contain a sensitizer (1E) as an optional component. By containing the sensitizer (1E) in the photosensitive resin composition, it is possible to improve the photosensitivity of the photosensitive resin composition. The component (1E) may be used alone or in combination of two or more kinds. In addition, the component (1E) excludes those corresponding to the components (1A) to (1D).

[0095] The component (1E) may 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; chalcones such as 4,4'-bis(dimethylamino)chalcone and 4,4'-bis(diethylamino)chalcone; -Dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, and other indanones; 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, and other thiazoles; 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, and other acetones; 3,3'-carbonyl-bis(7-diethylaminobenzal)acetone, and other acetones; coumarins such as 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, and 3-ethoxycarbonyl-7-diethylaminocoumarin; N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, diethyl amines such as isoamyl ethylaminobenzoate; 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.

[0096] Of these, from the viewpoint of achieving remarkable effects of the present invention, the component (1E) is preferably a heterocyclic compound, and more preferably a compound represented by the following general formula (D-1). [ka] (In formula (D-1), R 41 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.

[0097] R 41 represents a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, a halogen atom, a hydroxyl 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, a propyl group, an isopropyl group, and a t-butyl group. Among these, R 41 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 more preferably a hydrogen atom.

[0098] R 41 The bonding position of may be any of the ortho-position, meta-position, and para-position based on the site of the phenylene group bonding to the nitrogen atom of mercaptotetrazole, but the para-position is preferred from the viewpoint of significantly obtaining the effects of the present invention.

[0099] The compound represented by (D-1) is preferably either a compound represented by the following (D-2) or a compound represented by the following (D-3). [ka]

[0100] In order to prominently obtain the effects of the present invention, the content of the (1E) component is preferably at least 0.1 part by mass, more preferably at least 0.5 part by mass, and even more preferably at least 1 part by mass, per 100 parts by mass of the (1A) 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.

[0101] From the viewpoint of obtaining the effects of the present invention prominently, the content of the component (1E) 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, based on 100% by mass of the non-volatile components of the photosensitive resin composition, from the viewpoint of obtaining the effects of the present invention prominently.

[0102] <(1F) Other Additives> The photosensitive resin composition may further contain (1F) other additives to the extent that the object of the present invention is not hindered. Examples of (1F) 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.

[0103] <(1G) Solvent> The photosensitive resin composition may contain a (1G) solvent as an optional component in combination with the non-volatile components such as the above-mentioned components (1A) to (1F). The (1G) solvent is a volatile component that can uniformly dissolve at least one of the components (1A) to (1C) and the optional components (1D) to (1F). Examples of such a solvent 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; and benzene, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. aromatic hydrocarbon compounds having 6 to 10 carbon atoms, such as benzene, 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.

[0104] Examples of the (1G) component 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 (1G) component may be used alone or in combination of two or more.

[0105] The content of the (1G) component 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 the component (1G) is taken as 100% by mass. The content of the (1G) component in the photosensitive resin composition layer of the photosensitive film 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 the component (1G) is taken as 100% by mass.

[0106] The photosensitive resin composition can be produced by mixing the above-mentioned components (1A) to (1C) as essential components, appropriately mixing the above-mentioned components (1D) to (1G) as optional components, and kneading or stirring, as necessary, with kneading means such as a triple roll mill, a ball mill, a bead mill, or a sand mill, or with stirring means such as a super mixer or a planetary mixer.

[0107] [Photosensitive resin composition of the second embodiment] The photosensitive resin composition of the second embodiment of the present invention contains (2A) a polyimide precursor, (2B) a crosslinking agent, (2C) a photoradical generator, and (2D) an allyl compound having an ethylenically unsaturated bond, the α-position of the ethylenically unsaturated bond being a group selected from a hydrocarbon group and a hydrogen atom, and at least one of the groups at the α-position of the ethylenically unsaturated bond being a hydrogen atom. By incorporating the components (2A) to (2D) in combination into the photosensitive resin composition, a cured product having good limiting resolution and via hole shape and excellent dielectric properties can be obtained. In addition, the photosensitive resin composition of the second embodiment can usually obtain a cured product having excellent warpage.

[0108] The photosensitive resin composition of the second embodiment of the present invention is suitable as a negative photosensitive resin composition.

[0109] The photosensitive resin composition of the second embodiment may further contain optional components in addition to the components (2A) to (2D), such as a sensitizer (2E), other additives (2F), and a solvent (2G).

[0110] <(2A) Polyimide precursor> The photosensitive resin composition contains a polyimide precursor (2A) as the component (2A). By adding the component (2A) to the photosensitive resin composition, a cured product having excellent dielectric properties can be obtained. The component (2A) may be used alone or in combination of two or more.

[0111] The component (2A) may be a resin having a plurality of amic acid structures and / or amic acid ester structures, specifically, a compound obtained by reacting a tetracarboxylic dianhydride with a diamine compound.

[0112] Among them, the (2A) component preferably has a radical reactive group from the viewpoint of obtaining a cured product having excellent limit resolution and excellent dielectric properties. Examples of the radical reactive group include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, a (meth)acryloyl group, and a group represented by formula (A-2) described later, and the group represented by formula (A-2) is preferable. The "(meth)acryloyl group" includes a methacryloyl group, an acryloyl group, and a combination thereof. In addition, the (2A) component is preferably a polyimide precursor having an indane skeleton, and more preferably a polyimide precursor having an indane skeleton and a radical reactive group, from the viewpoint of obtaining a cured product having excellent limit resolution and excellent dielectric properties. As the polyimide precursor having an indane skeleton, a compound having an indane skeleton and obtained by reacting a tetracarboxylic dianhydride with a diamine compound can be used. The indane skeleton represents a skeleton shown in the following formula (a1), and is preferably a trimethylindane skeleton shown in the following formula (a2). [ka]

[0113] Examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides are preferred. Examples of the tetracarboxylic dianhydride include 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3,3',4 ,4'-para-terphenyltetracarboxylic dianhydride, 3,3',4,4'-meta-terphenyltetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2-endo-3-endo-5-exo-6-exo-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2-endo-3-endo-5-exo-6-exo-2,3,5,6-tetracarboxylic dianhydride 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, 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-tetracarboxylic dianhydride Examples of the tetrahydrofuran are tetrahydrofuran, ...

[0114] When the component (2A) is a polyimide precursor having an indane skeleton, it is preferable to use a diamine having an indane skeleton as the diamine compound. Examples of the diamine having an indane skeleton include the diamines exemplified below. [ka]

[0115] From the viewpoint of obtaining a cured product that has excellent limiting resolution and excellent dielectric properties, the component (2A) 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, 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.

[0116] 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 an aromatic group in which the -CONH- group and the -CONH- group are in the ortho position with respect to each other, or an alicyclic aliphatic group (R 1 and R 2 is R in formula (A-1) 1 and R 2 (which is the same as the above). Examples of such groups include groups (i) to (ix). Among them, A is preferably a tetravalent organic group exemplified below, and more preferably a group (viii) or a group (ix). In the formula, * represents a bond. [ka]

[0117] In formula (A-1), each B independently represents a divalent organic group. The divalent organic group preferably has an aromatic ring, more preferably has a divalent organic group having an indane skeleton, and further preferably has an aromatic ring in addition to the indane skeleton. Examples of the divalent organic group include groups (1a) to (27a) exemplified below, of which groups (1a) to (7a) (divalent organic groups having an indane skeleton) are preferred, and group (7a) is more preferred. In the formula, * represents a bond. [ka] [ka] [ka] [ka]

[0118] R in formula (A-1) 1 and R 2 Each of R independently represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include a saturated aliphatic group having 1 to 4 carbon atoms; a reactive group that can be polymerized by a radical generated by heat or light, i.e., a radical reactive group, and the like. The radical reactive group is preferably a radical reactive group. The radical reactive group is as described above. R in formula (A-1) 1 and R 2 is preferably at least one of, and more preferably both of, independently represent a radical reactive group. The radical reactive group is preferably a group represented by the following formula (A-2). [ka] (In the formula, R 4 ~R 6 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p represents an integer of 1 to 10.

[0119] R in formula (A-2) 4 ~R6 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, and among these, a methyl group is preferred.

[0120] As the saturated aliphatic group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, and an n-butyl group.

[0121] In the formula (A-2), p 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.

[0122] R in formula (A-1) 1 and R 2 is preferably at least one of a radical reactive group, more preferably at least one of a group represented by formula (A-2), R 1 and R 2 It is more preferable that both of are groups represented by formula (A-2).

[0123] In the formula (A-1), n ​​represents an integer of 5 to 200, preferably an integer of 5 to 150, more preferably an integer of 5 to 100, and further preferably an integer of 5 to 70.

[0124] The component (2A) preferably has a structural unit represented by formula (A-3). [ka] (In the formula, each A1 independently represents a tetravalent organic group, R 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group; R 13each independently represents a hydrogen atom or 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 1 to 5, and n1 represents an integer of 5 to 200. [ka] (In formulas (1) to (4), * represents a bond.)

[0125] Each A1 in formula (A-3) independently represents a tetravalent organic group, and A1 is the same as A in formula (A-1).

[0126] R in formula (A-3) 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group, and R in formula (A-1) 1 and R 2 is the same as:

[0127] Each Xa independently represents a single bond, a group represented by formula (1), or a group represented by formula (2).

[0128] 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.

[0129] Examples of the group represented by formula (2) include the following groups (2-1) to (2-6). [ka]

[0130] Among them, Xa is preferably a group represented by formula (2), more preferably a group represented by formula (2-1).

[0131] Each Xb independently represents a single bond, a group represented by formula (3), or a group represented by formula (4).

[0132] 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.

[0133] Examples of the group represented by formula (4) include the following groups. [ka]

[0134] Among these, Xb is preferably a group represented by formula (3), and more preferably a 1,4-phenylene group.

[0135] R 13 each independently represents a hydrogen atom or a methyl group, and preferably represents a methyl group.

[0136] m1 represents an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably 3.

[0137] n1 represents an integer of 5 to 200 and is the same as n in formula (A-1).

[0138] The component (2A) preferably has a structural unit represented by the following (A-4). [ka] (In the formula, each A2 independently represents a tetravalent organic group, R 21 or R 22 each independently represents a hydrogen atom or a group represented by the following formula (A-5), and n2 represents an integer of 5 to 200. [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.

[0139] Each A2 in formula (A-4) independently represents a tetravalent organic group and is the same as A in formula (A-1).

[0140] R in formula (A-4) 21 and R 22 R each independently represents a hydrogen atom or a group represented by formula (A-5), and a group represented by formula (A-5) is preferable. 14 ~R 16 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R in the group represented by formula (A-2) 4 ~R 6 In the group represented by formula (A-5), p1 represents an integer of 1 to 10 and is the same as p in the group represented by formula (A-2).

[0141] n2 represents an integer of 5 to 200 and is the same as n in formula (A-1).

[0142] The component (2A) may be a copolymer containing a structural unit having an indane skeleton and a structural unit not having an indane skeleton. For example, the component (2A) may contain a structural unit having no indane skeleton and ...

[0143] Specific examples of the component (2A) include the following compounds (A1) to (A7). However, the component (2A) is not limited to these specific examples. In the formula, n is an integer of 5 to 200. [ka] [ka]

[0144] From the viewpoint of obtaining the remarkable effects of the present invention, the weight average molecular weight of the (2A) component is preferably at least 5,000, more preferably at least 10,000, and even more preferably at least 50,000, and is preferably at most 1,000,000, more preferably at most 500,000, and even more preferably at most 200,000. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0145] The method for producing the component (2A) is not particularly limited. The component (2A) can usually be obtained by reacting the above-mentioned tetracarboxylic dianhydride with a diamine compound. The component (2A) can be produced, for example, by the production method described in JP-A-2015-209461 or JP-A-2015-214680.

[0146] From the viewpoint of obtaining the effects of the present invention significantly, the content of the (2A) component 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, preferably 98% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less, when the non-volatile components of the photosensitive resin composition are taken as 100% by mass. In the present invention, the content of each component in the photosensitive resin composition is the value when the non-volatile components in the photosensitive resin composition are taken as 100% by mass, unless otherwise specified.

[0147] <(2B) Crosslinking agent> The photosensitive resin composition contains a crosslinking agent (2B) as the component (2B). However, the component (2B) does not include those corresponding to the components (2A) and (2D). When the photosensitive resin composition is irradiated with actinic rays and radicals are generated from the photoradical generator, a crosslinking reaction of the component (2B) occurs, and the composition becomes insoluble in the developer. Therefore, during development, the photosensitive resin composition can be selectively removed from areas other than those where the crosslinking reaction has progressed, and a negative pattern can be advantageously formed. The component (2B) may be used alone or in combination of two or more.

[0148] As the component (2B), a compound capable of promoting a crosslinking reaction during development can be used. Such a compound is preferably a compound having an ethylenically unsaturated bond, and more preferably a compound having an ethylenically unsaturated bond and at least one carbon atom at the α-position of the ethylenically unsaturated bond is bonded to a carbonyl group or an aromatic group.

[0149] The ethylenically unsaturated bond represents a carbon-carbon double bond. Therefore, the (2B) component may contain a group having an ethylenically unsaturated bond (hereinafter, may be referred to as "ethylenically unsaturated group" as appropriate). The ethylenically unsaturated group is usually a monovalent group, and examples thereof include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, and a (meth)acryloyl group. From the viewpoint of reactivity of photoradical polymerization, a (meth)acryloyl group and a phenylethynyl group are preferred, and a (meth)acryloyl group is particularly preferred. The "(meth)acryloyl group" includes a methacryloyl group, an acryloyl group, and a combination thereof. The (2B) component contains an ethylenically unsaturated group, and therefore is capable of photoradical polymerization. However, in order to perform photoradical polymerization under general conditions, a compound having a carbonyl group or an aromatic group at at least one of the α positions of the ethylenically unsaturated bond is preferred. The number of ethylenically unsaturated groups per molecule of component (2B) is preferably at least 1, and more preferably at least 2. Furthermore, when component (2B) contains two or more ethylenically unsaturated groups per molecule, those ethylenically unsaturated groups may be the same or different.

[0150] The component (2B) is preferably a compound represented by the following general 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 1beach 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, and nb represents a positive integer of 2 to 6.

[0151] R 1b each independently represents 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 them, R 1b is preferably a hydrogen atom or a methyl group.

[0152] 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. 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, and a methylene group is preferred. The alkylene group may also be an oxyalkylene group containing an oxygen atom, and specific examples of such groups include, for example, those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 23. [ka]

[0153] The arylene group which may contain an oxygen atom is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 15 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. Examples of such an arylene group 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 23. [ka]

[0154] 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 an alkenylene group include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, and a hexenylene group. The alkenylene group may also be an oxyalkenylene group containing an oxygen atom, and specific examples of such groups include the following. In the formula, "*" represents a bond, and a represents an integer of 1 to 23. The alkenylene group is preferably a propenylene group. [ka]

[0155] 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 preferable, and a methylene group is more preferable.

[0156] 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]

[0157] nb represents a positive integer of 2 to 6, preferably a positive integer of 2 to 5, more preferably a positive integer of 2 to 4, and further preferably 2 or 3.

[0158] The component (2B) is preferably a compound represented by the following general formula (B-2). [ka] (In the formula, R 2b each independently represents a hydrogen atom or a methyl group.

[0159] R 2b represents a hydrogen atom or a methyl group, and a methyl group is preferable.

[0160] Specific examples of the component (2B) include the following compounds (CL-1) to (CL-11), although the component (2B) is not limited thereto. [ka] [ka]

[0161] As the component (2B), commercially available products can be used, such as NK Ester-D-TMP, 4G, 9G, 14G, 23G, and DCP manufactured by Shin-Nakamura Chemical Co., Ltd.

[0162] In order to prominently obtain the effects of the present invention, the content of the (2B) component, per 100 parts by mass of the (2A) component, is preferably at least 1 part by mass, more preferably at least 2 parts by mass, and even more preferably at least 3 parts by mass, and is preferably at most 25 parts by mass, more preferably at most 20 parts by mass, and even more preferably at most 15 parts by mass.

[0163] From the viewpoint of obtaining the effects of the present invention prominently, the content of the (2B) component, when the non-volatile components of the photosensitive resin composition are taken as 100 mass%, is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, even more preferably 1 mass% or more, 2 mass% or more, or 3 mass% or more, and is preferably 20 mass% or less, more preferably 18 mass% or less, and even more preferably 15 mass% or less.

[0164] <(2C) Photoradical generator> The photosensitive resin composition contains a photoradical generator (2C) as the component (2C). The component (2C) generates radicals when irradiated with actinic rays, and the portion of the photosensitive resin composition where crosslinking reaction or the like has occurred due to the radicals does not dissolve in the developer. Therefore, during development, it becomes possible to selectively remove the photosensitive resin composition from the portion other than the portion where the crosslinking reaction has progressed, and a negative pattern can be advantageously formed. The component (2C) may be used alone or in combination of two or more. In addition, the component (2C) does not include those corresponding to the above-mentioned components (2A) to (2B) and the below-mentioned components (2D) to (2E).

[0165] Examples of the (2C) component include benzophenone, o-benzoylbenzoic acid methyl, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone and other acetophenone derivatives, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and other thioxanthone derivatives; benzil, benzil dimethyl ketal, benzyl-β-methoxyethyl acetal and other benzyl derivatives; benzoin, benzoin methyl ether and other benzoin derivatives; 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, 1-phenyl-1,2-propanedione-2-(o-benzoyl) oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl) oxime and other oximes; N-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazoles; titanocenes; α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide; and the like. Among these, oximes are preferred as the component (C) from the viewpoint of photosensitivity.

[0166] The component (2C) may be a commercially available product, such as "Irgacure-OXE02" or "Irgacure-OXE04" manufactured by BASF.

[0167] In order to prominently obtain the effects of the present invention, the content of the component (2C) per 100 parts by mass of the component (2A) 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, 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.

[0168] From the viewpoint of prominently obtaining the effects of the present invention, the content of the component (2C) 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, when the non-volatile components of the photosensitive resin composition are taken as 100% by mass, and is preferably 20% by mass or less, more preferably 17% by mass or less, and even more preferably 15% by mass or less.

[0169] <(2D) Allyl compounds having an ethylenically unsaturated bond, in which the carbon atom at the α-position of the ethylenically unsaturated bond is bonded to a group selected from a hydrocarbon group and a hydrogen atom, and at least one of the groups bonded to the carbon atom at the α-position of the ethylenically unsaturated bond is a hydrogen atom> The photosensitive resin composition contains, as component (2D), an allyl compound having an ethylenically unsaturated bond, the carbon atom at the α-position of the ethylenically unsaturated bond being bonded to a group selected from a hydrocarbon group and a hydrogen atom, and at least one of the groups bonded to the carbon atom at the α-position of the ethylenically unsaturated bond being a hydrogen atom. The component (2D) excludes the above-mentioned components (2A) to (2C) and the component (2E) described below. The carbon atom at the α-position of the ethylenically unsaturated bond is the first carbon atom adjacent to the carbon atom bonded by a carbon-carbon double bond, and specifically, for example, as shown in the following formula (d1), it indicates the carbon atom (C1 to C4) adjacent to the carbon atom bonded by a carbon-carbon double bond. [ka]

[0170] When the photosensitive resin composition is negative type, the exposed portion is usually less soluble in the developer due to the radical reaction. Therefore, the unexposed portion is removed by the developer, and only the exposed portion remains. The present inventors have found that if the radical reaction proceeds excessively, the radical reaction proceeds to the unexposed portion as well. The unexposed portion where the radical reaction has proceeded is not sufficiently cured because the amount of exposure is less than that of the exposed portion, but the solubility in the developer is reduced due to the progress of the radical reaction. Therefore, the unexposed portion where the radical reaction has proceeded dissolves slower in the developer than the unexposed portion. In addition, development is usually carried out from the mask side surface of the photosensitive resin composition layer. Therefore, in the unexposed portion where the radical reaction has proceeded during development, the portion near the mask side surface can be removed by development, while the portion near the surface opposite to the mask side (the via bottom) can remain without being removed by development. In this case, the via hole shape obtained by exposure and development is tapered, with the diameter larger closer to the mask side surface and smaller closer to the via bottom. Conventionally, this has resulted in a deterioration in the shape of the via hole. In contrast, in the present invention, the (2D) component functions as a chain transfer agent by the hydrogen atom bonded to the carbon atom at the α-position of the ethylenically unsaturated bond, and can control the radical reaction. Therefore, by including the (2D) component in the photosensitive resin composition, the radical reaction is controlled. As a result, it is possible to prevent the radical reaction from progressing to the unexposed portion, and it is possible to obtain a cured product with a good via hole shape. Note that, since the (2E) component functions as a crosslinking agent when the carbon atom at the α-position of the ethylenically unsaturated bond is bonded to a carbonyl group or an aromatic group, the carbon atom at the α-position of the ethylenically unsaturated bond present in the molecule is not bonded to a carbonyl group or an aromatic group.

[0171] When the component (2D) has multiple ethylenically unsaturated bonds, it is sufficient that at least one of the multiple α-position carbon atoms is bonded to a hydrogen atom, and in this case, the other α-position carbon atoms may be bonded to groups other than a carbonyl group and an aromatic group. The component (2D) is preferably an allyl compound in which the carbon atoms at the α-position of the ethylenically unsaturated bonds are composed only of groups selected from hydrocarbon groups and hydrogen atoms, and at least one of the groups bonded to the carbon atoms at the α-position of the ethylenically unsaturated bonds is a hydrogen atom.

[0172] The component (2D) is preferably represented by the following formula (D-1). [ka] (In the formula, R 1d , R 2d , and R 3d each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. * represents a bond.)

[0173] In formula (D-1), R 1d , R 2d , and R 3d R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. Examples of the hydrocarbon group having 1 to 3 carbon atoms include an aliphatic hydrocarbon group having 1 to 3 carbon atoms. Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include a saturated aliphatic hydrocarbon group, for example, 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, an isopropyl group, and among these, a methyl group is preferred. 1d , R 2d , and R 3d is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0174] The number of structures represented by formula (D-1) per molecule of component (2D) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The number of structures represented by formula (D-1) per molecule of component (2D) is preferably 2 or 3, and more preferably 2. In addition, when the number of structures represented by formula (D-1) per molecule of component (2D) is 2 or more, those structures represented by formula (D-1) may be the same or different.

[0175] The component (2D) is preferably a compound represented by the following formula (D-2). [ka] (In the formula, R 11d , R 12d , R 13d , R 14d , R 15d and R 16d each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; Z d represents a divalent organic group.

[0176] R 11d , R 12d , R 13d , R 14d , R 15d and R 16d each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; 1d , R 2d , and R 3d is the same as:

[0177] Z d represents a divalent organic group. Examples of the divalent organic group include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent group containing a heteroatom, and a divalent group consisting of a combination of two or more of these. Examples of the heteroatom include an oxygen atom, a sulfur atom, a nitrogen atom, and a halogen atom.

[0178] The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic. The divalent aliphatic hydrocarbon group may be saturated or unsaturated. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 5. Examples of the divalent aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. Examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, and a hexenylene group. Examples of the alkynylene group include an ethynylene group, a propenylene group, and the like.

[0179] The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 to 20, and more preferably 6 to 15. Examples of the divalent aromatic hydrocarbon group include an arylene group, and examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group, and a 9,9-diphenyl-9H-fluorenylene group.

[0180] Examples of the divalent group containing a heteroatom include -O-, -S-, -NH-, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -C(=O)-NH-, -S(=O) 2 -, -S(=O) 2 -O-, the groups shown below, and the like. [ka] (* represents a bond.)

[0181] Examples of the divalent group consisting of two or more combinations include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, and a divalent group containing a heteroatom bonded thereto; a divalent aromatic hydrocarbon group and a divalent group containing a heteroatom bonded thereto; and a divalent aliphatic hydrocarbon group and a divalent group containing a heteroatom bonded thereto. Specific examples of the divalent group consisting of two or more combinations as described above include the following groups (d-1) to (d-6), but the present invention is not limited thereto. In the groups (d-1) to (d-6), * represents a bond. The divalent group consisting of two or more combinations is preferably the groups (d-1) to (d-3). [ka]

[0182] 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, and n-butyl groups; halogen atoms, such as fluorine, chlorine, and bromine; alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, and propoxy; hydroxyl groups; and halogen-substituted alkyl groups, such as trifluoromethyl groups. The above-mentioned substituents may further have a substituent (hereinafter, sometimes referred to as "secondary substituents"). The substituents may be contained alone or in combination of two or more kinds. When the divalent organic group has a substituent, the substituent is preferably a hydroxyl group.

[0183] Specific examples of the (2D) component include triallyl isocyanurate, triallyl cyanurate, 1,3,5-triallylhexahydro-1,3,5-triazine, diallylpropyl isocyanurate, diallyl 1,4-cyclohexanedicarboxylate, 9,9-bis(4-allyloxyphenyl)fluorene, 2,2-bis(allyloxymethyl)-1-butanol, and the following compounds (D1) to (D3), etc. However, the (2D) component is not limited to these specific examples. [ka]

[0184] The (2D) component may be a commercially available product, such as "BANI-X" or "BANI-M" manufactured by Maruzen Petrochemical Co., Ltd., "DAD" manufactured by Nisshoku Techno Fine Chemical Co., Ltd., or "DPNG" manufactured by Kuraray Co., Ltd.

[0185] In order to prominently obtain the effects of the present invention, the content of the component (2D) is preferably at least 0.1 part by mass, more preferably at least 0.5 part by mass, and even more preferably at least 1 part by mass, per 100 parts by mass of the component (2A), and is preferably at most 20 parts by mass, more preferably at most 15 parts by mass, and even more preferably at most 10 parts by mass.

[0186] When the non-volatile components of the photosensitive resin composition are taken as 100 mass%, from the viewpoint of obtaining a cured product with excellent via hole shape, the content of the (2D) component is preferably 0.1 mass% or more, more preferably 0.13 mass% or more, even more preferably 0.15 mass% or more, 0.17 mass% or more, or 0.2 mass% or more, and is preferably 15 mass% or less, more preferably 13 mass% or less, even more preferably 11 mass% or less, or 10 mass% or less.

[0187] When the content of the component (2A) when the nonvolatile components of the photosensitive resin composition are taken as 100 mass % is a1 and the content of the component (2D) when the nonvolatile components of the photosensitive resin composition are taken as 100 mass %, d1, from the viewpoint of significantly obtaining the effects of the present invention, a1 / d1 is preferably 1 or more, more preferably 3 or more, and even more preferably 5 or more, and is preferably 600 or less, more preferably 100 or less, and even more preferably 500 or less, 400 or less, 300 or less, 200 or less, or 100 or less.

[0188] <(2E) Sensitizer> The photosensitive resin composition may contain a sensitizer (2E) as an optional component. By containing the sensitizer (2E) in the photosensitive resin composition, it is possible to improve the photosensitivity of the photosensitive resin composition. The component (2E) may be used alone or in combination of two or more. In addition, the component (2E) does not include those corresponding to the above-mentioned components (2A) to (2D).

[0189] The (2E) component may 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; chalcones such as 4,4'-bis(dimethylamino)chalcone and 4,4'-bis(diethylamino)chalcone; -Dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, and other indanones; 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, and other thiazoles; 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, and other acetones; 3,3'-carbonyl-bis(7-diethylaminobenzal)acetone, and other acetones; coumarins such as 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, and 3-ethoxycarbonyl-7-diethylaminocoumarin; N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, diethyl amines such as isoamyl ethylaminobenzoate; 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.

[0190] Of these, from the viewpoint of achieving remarkable effects of the present invention, the component (2E) is preferably a heterocyclic compound, and more preferably a compound represented by the following general formula (E-1). [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.

[0191] R 1e represents a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, a halogen atom, a hydroxyl 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, a 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 more preferably a hydrogen atom.

[0192] R 1e The bonding position of may be any of the ortho-position, meta-position, and para-position based on the site of the phenylene group bonding to the nitrogen atom of mercaptotetrazole, but the para-position is preferred from the viewpoint of significantly obtaining the effects of the present invention.

[0193] 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]

[0194] In order to prominently obtain the effects of the present invention, the content of the (2E) component, per 100 parts by mass of the (2A) 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, and is preferably at most 20 parts by mass, more preferably at most 15 parts by mass, and even more preferably at most 10 parts by mass.

[0195] From the viewpoint of achieving remarkable effects of the present invention, the content of the (2E) component 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, when the total amount of non-volatile components in the photosensitive resin composition is taken as 100% by mass, and is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0196] <(2F) Other Additives> The photosensitive resin composition may further contain (2F) other additives to the extent that the object of the present invention is not impaired. (2F) Other additives are the same as (1F) Other additives.

[0197] <(2G) Solvent> The photosensitive resin composition may contain a solvent (2G) as an optional component in addition to the non-volatile components (2A) to (2F) described above. The solvent (2G) is the same as the solvent (1G).

[0198] The photosensitive resin composition can be produced by mixing the above-mentioned components (2A) to (2E) as essential components, appropriately mixing the above-mentioned components (2F) and (2G) as optional components, and kneading or stirring, as necessary, with kneading means such as a triple roll mill, a ball mill, a bead mill, or a sand mill, or with stirring means such as a super mixer or a planetary mixer.

[0199] <Properties and Applications of the Photosensitive Resin Compositions of the First and Second Embodiments> The photosensitive resin compositions of the first and second embodiments exhibit the characteristic of excellent limit resolution. For example, exposure and development are performed using a mask that draws round holes with an opening diameter of 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm in the exposure pattern. In this case, the limit resolution, which is the minimum size that can be opened in the photosensitive resin composition of the first embodiment, is preferably less than 30 μm, more preferably 25 μm or less, even more preferably 20 μm or less, less than 20 μm, or 15 μm or less. The limit resolution, which is the minimum size that can be opened in the photosensitive resin composition of the second embodiment, is preferably less than 30 μm, more preferably 25 μm or less, even more preferably 20 μm or less, less than 20 μm, or 15 μm or less. The evaluation of the limit resolution can be measured according to the method described in the examples below.

[0200] By using the photosensitive resin composition of the second embodiment, the shape of the via hole can be easily controlled. In addition, usually, by using the photosensitive resin composition of the first embodiment, the shape of the via hole can be easily controlled. Therefore, the formation of a via hole with a tapered cross section is suppressed. For example, a photosensitive resin composition layer provided on the surface of a substrate such as a silicon wafer is exposed and developed using a mask that draws round holes with an opening diameter of 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm in the exposure pattern. The cross section of the via hole is observed, and the angle α between the surface of the substrate and the wall surface of the via hole is measured. In this case, the angle α is preferably 45° or more, more preferably 50° or more, and even more preferably 60° or more, and is preferably 95° or less, more preferably 93° or less, and even more preferably 90° or less. The evaluation of the via hole shape can be measured according to the method described in the examples described below.

[0201] The cured products obtained by thermally curing the photosensitive resin compositions of the first and second embodiments at 250° C. for 2 hours exhibit the characteristic of having 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. The dielectric constant can be measured according to the method described in the examples below.

[0202] The photosensitive resin compositions of the first and second embodiments are thermally cured at 250° C. for 2 hours to exhibit a low dielectric loss tangent (Df). The dielectric loss tangent at 23° C. is preferably 0.015 or less, more preferably 0.012 or less, and even more preferably 0.09 or less. The lower limit is not particularly limited, but may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in the examples below.

[0203] The cured product obtained by thermally curing the photosensitive resin composition of the first and second embodiments at 200° C. for 120 minutes exhibits the characteristic of suppressing the amount of warping. The amount of warping of the cured product having a thickness of 30 μm is preferably less than 150 μm, more preferably 140 μm or less, and even more preferably 130 μm or less, less than 130 μm. There is no particular lower limit, but it may be 0 μm or more, 1 μm or more, etc. The amount of warping can be measured by the method described in the examples below.

[0204] The photosensitive resin composition of the present invention is not particularly limited in its application, but it can be used in a wide range of applications in which 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 coat films, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, and component-embedding resins. Among them, the photosensitive resin composition can be used in a wide range of applications in which photosensitive resin compositions are used, such as a photosensitive resin composition for insulating layers of printed wiring boards (printed wiring boards in which a cured product of a photosensitive resin composition is used as an insulating layer), a photosensitive resin composition for interlayer insulating layers (printed wiring boards in which a cured product of a photosensitive resin composition is used as an interlayer insulating layer), a photosensitive resin composition for plating (printed wiring boards in which plating is formed on a cured product of a photosensitive resin composition), and a photosensitive resin composition for solder resists (printed wiring boards in which a cured product of a photosensitive resin composition is used as a solder resist), a photosensitive resin composition for rewiring formation layers of wafer-level packages (wafer-level packages in which a cured product of a 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 for a display (a display in which a cured product of the photosensitive resin composition serves as an insulating layer).

[0205] [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.

[0206] Examples of the support include a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, a triacetyl acetate film, and the like, with a polyethylene terephthalate film being particularly preferred.

[0207] Examples of commercially available supports include, but are not limited to, polypropylene films such as those manufactured by Oji Paper under the product names "Alphan MA-410" and "E-200C," those manufactured by Tamapoly under the product names "GF-1" and "GF-8," those manufactured by Shin-Etsu Film, and those manufactured by Teijin under the product name "PS-25" and other polyethylene terephthalate films in the PS series. These supports are preferably coated on the surface with a release agent such as a silicone coating agent or a non-silicone coating agent in order to facilitate removal. Examples of supports whose surfaces have been treated with such release agents include "AL-5" manufactured by Lintec. 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.

[0208] The thickness of the photosensitive resin composition layer is not particularly limited and may be, for example, 1 μm or more and 100 μm or less. In particular, it is preferably 2 μm or more, more preferably 4 μm or more, and is preferably 50 μm or less, more preferably 30 μm or less.

[0209] The photosensitive resin composition layer may be protected by a protective film. By protecting the photosensitive resin composition layer with a protective film, adhesion of dust and scratches on the surface of the photosensitive resin composition layer can be suppressed. As the protective film, for example, a film made of the same material as the above-mentioned support can be used. 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 further preferably in the range of 10 μm to 30 μm. It is preferable that 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.

[0210] The photosensitive film can be produced, for example, by coating the photosensitive resin composition on a support and, if necessary, drying the component (F).

[0211] [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 layer, an interlayer insulating layer, a buffer coat film, or a solder resist.

[0212] In detail, 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. (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) developing the photosensitive resin composition layer; Includes, in this order.

[0213] <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 above-mentioned photosensitive film is used.

[0214] When the resin varnish containing the photosensitive resin composition is directly applied onto the circuit board, the component (F) is dried and volatilized to form a photosensitive resin composition layer on the circuit board.

[0215] Examples of methods for applying resin varnish include gravure coating, microgravure coating, reverse coating, kiss reverse coating, die coating, slot die, lip coating, comma coating, blade coating, roll coating, knife coating, curtain coating, chamber gravure coating, slot orifice, spin coating, slit coating, spray coating, dip coating, hot melt coating, bar coating, applicator, air knife coating, curtain flow coating, offset printing, brush coating, and full-surface printing using screen printing.

[0216] The resin varnish may be applied in several steps, may be applied in one step, or may be applied by combining a plurality of different methods. Among them, the die coating method is preferable because of its excellent uniformity of application. In addition, in order to avoid contamination by foreign matter, it is preferable to carry out the application process in an environment where foreign matter is unlikely to be generated, such as a clean room.

[0217] After the resin varnish is applied, it is dried, if necessary, in a hot air oven or far-infrared oven, etc. The drying conditions are preferably 80° C. to 120° C. for 3 minutes to 13 minutes. In this manner, a photosensitive resin composition layer is formed on the circuit board.

[0218] Examples of the circuit board include a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board. The circuit board here refers to a board in which a patterned conductor layer (circuit) is formed on one or both sides of the support board as described above. In addition, in a multilayer printed wiring board formed by alternately laminating a conductor layer and an insulating layer, a board in which one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits) is also included in the circuit board referred to here. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

[0219] On the other hand, when a photosensitive film is used, the photosensitive resin composition layer side is laminated on one or both sides of the circuit board using a vacuum laminator. In the lamination process, 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.

[0220] 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 seconds 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 Co., Ltd.

[0221] <Process (II)> After the photosensitive resin composition layer is provided on the circuit board, an exposure step is then performed in which a predetermined portion of the photosensitive resin composition layer is irradiated with active light through a mask pattern. Examples of active light include ultraviolet light, visible light, electron beams, and X-rays, and ultraviolet light is particularly preferred. The irradiation dose of ultraviolet light is approximately 10 mJ / cm. 2 ~1000mJ / cm 2There are two types of exposure methods: contact exposure, in which a mask pattern is brought into close contact with the circuit board, and non-contact exposure, in which parallel light is used for exposure without contact, and either method may be used.

[0222] 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 may be 0.1 μm or more, 0.5 μm or more, etc.

[0223] <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.

[0224] In the case of the wet development, a developer that is safe, stable, and easy to operate is used, such as an alkaline solution, an aqueous developer, an organic solvent, etc. As a developing method, a known method such as spraying, rocking immersion, brushing, scraping, etc. is appropriately adopted.

[0225] 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. An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred because it does not contain metal ions and does not affect the semiconductor chip.

[0226] 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 according to the developability of the photosensitive resin composition layer, but is preferably 20°C to 50°C.

[0227] 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.

[0228] The concentration of such an organic solvent is preferably 2% by mass to 90% by mass based on the total amount of the developer. The temperature of such an organic solvent can be adjusted according to the developability. Furthermore, such an organic solvent can be used alone or in combination of two or more kinds. Examples of organic solvent-based developers used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0229] In forming a pattern, two or more kinds of developing methods may be used in combination as necessary. The developing methods include a dip method, a bath method, a spray method, a high-pressure spray method, brushing, slapping, etc., and the high-pressure spray method is suitable for improving resolution. When adopting a spray method, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

[0230] <Thermal curing (post-bake) process> After the above step (III) is completed, a thermal curing (post-baking) step is performed as necessary. Although the curing of the photosensitive resin composition layer may proceed in the above steps (I) to (III), the curing of the photosensitive resin composition can be further promoted by the thermal curing step to obtain an insulating layer having excellent mechanical strength. Examples of the post-baking step include a heating step using a clean oven. The atmosphere during thermal curing may be in air or in 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, and are preferably selected in the range of 150°C to 250°C for 20 minutes to 180 minutes, and more preferably in the range of 160°C to 230°C for 30 minutes to 120 minutes.

[0231] <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 carried out according to various methods used in the production of semiconductor package substrates and known to those skilled in the art.

[0232] After forming the insulating layer, if desired, a hole-making process is performed on the insulating layer formed on the circuit board to form via holes and through holes. The hole-making process can be performed by a known method such as a drill, a laser, or plasma, or by a combination of these methods as necessary, but a hole-making process using a laser such as a carbon dioxide laser or a YAG laser is preferred.

[0233] The desmear process is a process of performing a desmear treatment. Generally, resin residue (smear) adheres to the inside of the opening formed in the hole drilling process. Since such smear can cause poor electrical connection, a process of removing the smear (desmear treatment) is performed in this process.

[0234] The desmear treatment may be performed by a dry desmear treatment, a wet desmear treatment, or a combination thereof.

[0235] 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 device. Among the commercially available plasma desmear treatment devices, examples suitable for manufacturing semiconductor package substrates include a microwave plasma device manufactured by Nissin Co., Ltd. and an atmospheric pressure plasma etching device manufactured by Sekisui Chemical Co., Ltd.

[0236] The wet desmear treatment may be, for example, a desmear treatment using an oxidizing agent solution. When the desmear treatment is performed using an oxidizing agent solution, it is preferable to perform a swelling treatment using a swelling liquid, an oxidation treatment using an oxidizing agent solution, and a neutralization treatment using a neutralizing liquid in this order. Examples of the swelling liquid include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing a substrate on which via holes or the like are formed in a swelling liquid heated to 60°C to 80°C for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganate solution, and examples of the solution include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The oxidation treatment using an oxidizing agent solution is preferably performed by immersing a 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 the 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.

[0237] 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.

[0238] In the case where the insulating layer is formed as any of a redistribution layer, an interlayer insulating layer, and a solder resist, a hole drilling step and a desmearing step may be performed after the thermal curing step. In addition, in the manufacturing method of the semiconductor package substrate, a plating step may be further performed.

[0239] 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 may be formed by a combination of electroless plating and electrolytic plating, or a plating resist having a reverse pattern to the conductor layer may be formed by electroless plating alone. Subsequent pattern formation methods include, for example, subtractive methods and semi-additive methods known to those skilled in the art.

[0240] The semiconductor package substrate according to the second 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 a rewiring formation layer. Specifically, the manufacturing method of the semiconductor package substrate includes the following steps: (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) 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; (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 further comprises: (H) dicing the plurality of semiconductor chip packages into individual semiconductor chip packages; may also include

[0241] <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 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 Co., Ltd.

[0242] Examples of the substrate include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel (SPCC); substrates such as FR-4 substrates in which glass fibers are impregnated with epoxy resin or the like and then heat-cured; and substrates made of bismaleimide triazine resins such as BT resin.

[0243] 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.

[0244] <Process (B)> Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. The temporary fixing of the semiconductor chip can be performed using, for example, a device such as a flip chip bonder or a die bonder. The layout and number of the 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, etc. For example, the semiconductor chips may be temporarily fixed by arranging them in a matrix shape of multiple rows and multiple columns.

[0245] <Process (C)> Step (C) is a step of forming an encapsulating layer on the semiconductor chip. The encapsulating layer can be made of any material having insulating properties, and the above-mentioned photosensitive resin composition can 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 the resin composition layer to form the encapsulating layer.

[0246] The formation of the encapsulating resin composition layer is preferably carried out by a compression molding method, in which a semiconductor chip and an encapsulating resin composition are usually 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.

[0247] A specific operation 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 is applied is attached to the lower mold together with the substrate and the temporary fixing film. Then, the upper mold and the lower mold are clamped, and heat and pressure are applied to the encapsulating resin composition to perform compression molding.

[0248] A specific operation 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. Then, the upper mold and the lower mold 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.

[0249] The molding conditions vary depending on the composition of the encapsulating resin composition, and appropriate conditions can be adopted so that good encapsulation is achieved. For example, the temperature of the mold during molding is preferably a temperature at which the encapsulating resin composition can exhibit 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 more, more preferably 2 minutes or more, particularly preferably 5 minutes or more, and preferably 60 minutes or lower, more preferably 30 minutes or lower, and particularly preferably 20 minutes or lower. Usually, 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.

[0250] The compression molding method may be performed by discharging the encapsulating resin composition filled in a cartridge into a lower mold.

[0251] <Process (D)> Step (D) is a step of peeling off the substrate and the temporary fixing film from the semiconductor chip. It is desirable to adopt an appropriate peeling method according to the material of the temporary fixing film. For example, the peeling method may be a method of heating, foaming or expanding the temporary fixing film to peel it off. In addition, for example, the peeling method may be a method of irradiating the temporary fixing film with ultraviolet light through the substrate to reduce the adhesive strength of the temporary fixing film to peel it off.

[0252] 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 reducing the adhesive strength of the temporary fixing film by irradiating it with ultraviolet light, the irradiation amount of ultraviolet light is usually 10 mJ / cm 2 ~1000mJ / cm 2 It is.

[0253] <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 of forming the rewiring formation layer is the same as the method of forming the photosensitive resin composition layer in step (I) in the first embodiment.

[0254] When forming the rewiring formation layer, via holes may be formed in the rewiring formation layer to provide interlayer connection between the semiconductor chip and the rewiring layer.

[0255] The via hole can be formed by carrying out an exposure step of irradiating the surface of the photosensitive resin composition layer for forming the rewiring formation layer with active light through a mask pattern, and a development step of developing and removing the non-exposed portion not irradiated with active light. The amount and time of irradiation of active light can be appropriately set according to the photosensitive resin composition layer. Examples of the exposure method include a contact exposure method in which a mask pattern is closely attached to the photosensitive resin composition layer and exposed, and a non-contact exposure method in which a mask pattern is not closely attached to the photosensitive resin composition layer and exposed using parallel light. The active light, the alkaline aqueous solution, and the exposure and development method are as described above.

[0256] 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.

[0257] <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 may 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.

[0258] <Process (G)> Step (G) is a step of forming a solder resist layer on the rewiring layer. The material of the solder resist layer can be any material having insulating properties. Among them, photosensitive resins and thermosetting resins are preferred from the viewpoint of ease of manufacturing the semiconductor chip package. The photosensitive resin composition of the present invention may also be used.

[0259] 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).

[0260] 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 to separate them. The method for dicing the semiconductor chip packages into individual semiconductor chip packages is not particularly limited.

[0261] [Semiconductor Devices] Examples of semiconductor devices in which the above-mentioned semiconductor chip package is mounted include various semiconductor devices used in electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.). EXAMPLES

[0262] 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.

[0263] <Synthesis Example 1: Synthesis of Polyimide Precursor A-1> 29.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA) was placed in a 2 L separable flask, and then 500 mL of N-methyl-2-pyrrolidone was placed in the 2 L separable flask and stirred at room temperature. 45.0 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindan (INDAN) was added to the separable flask, and the separable flask was heated in an oil bath until the internal temperature reached 40°C, and polymerization was carried out for 20 hours.

[0264] Next, 1.12 g of potassium hydroxide was added to the reaction solution and stirred at room temperature, and 8.8 g of ethylene carbonate was added, and at the same time, the separable flask was heated in an oil bath until the internal temperature reached 80°C and stirred for 10 hours. The resulting reaction solution was brought to 40°C, and 18.1 g of acrylic acid chloride, 0.5 g of dimethylaminopyridine, and 20 g of triethylamine were added and stirred for 3 hours.

[0265] Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate a polymer. The precipitated polymer was filtered and then dried under heating at 80°C in a vacuum dryer to obtain 71 g of polyimide precursor A-1. The weight average molecular weight of polyimide precursor A-1 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 50,000 (Mw). The structural formula of polyimide precursor A-1 is shown below (n represents an integer of 5 to 200). [ka]

[0266] <Synthesis Example 2: Synthesis of Polyimide Precursor A-2> 29.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA) was placed in a 2 L separable flask, and then 500 mL of N-methyl-2-pyrrolidone was placed in the separable flask and stirred at room temperature. 45.0 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindan (INDAN) was added to the separable flask, and the flask was heated in an oil bath until the internal temperature reached 40°C, and polymerization was carried out for 20 hours.

[0267] Next, 1.12 g of potassium hydroxide was added to the reaction solution and stirred at room temperature, and 8.8 g of ethylene carbonate was added, and at the same time, the separable flask was heated in an oil bath until the internal temperature reached 80°C and stirred for 10 hours. The resulting reaction solution was brought to 40°C, and 20.6 g of methacrylic acid chloride, 0.5 g of dimethylaminopyridine, and 20 g of triethylamine were added and stirred for 3 hours.

[0268] Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate a polymer. The precipitated polymer was filtered and then dried under heating at 80°C in a vacuum dryer to obtain 70 g of polyimide precursor A-2. The weight average molecular weight of polyimide precursor A-2 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 52,000. The structural formula of polyimide precursor A-2 is shown below (n represents an integer of 5 to 200). [ka]

[0269] <Synthesis Example 3: Synthesis of Polyimide Precursor A-3> 51.8 g of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) was placed in a 2 L separable flask, and then 500 mL of N-methyl-2-pyrrolidone was placed in the separable flask and stirred at room temperature. 45.0 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindan (INDAN) was added to the separable flask, and the separable flask was heated in an oil bath until the internal temperature reached 40°C, and polymerization was carried out for 20 hours.

[0270] Next, 1.12 g of potassium hydroxide was added to the reaction solution and stirred at room temperature, and 8.8 g of ethylene carbonate was added, and at the same time, the separable flask was heated in an oil bath until the internal temperature reached 80°C and stirred for 10 hours. The resulting reaction solution was brought to 40°C, and 18.1 g of acrylic acid chloride, 0.5 g of dimethylaminopyridine, and 20 g of triethylamine were added, and stirred for 3 hours.

[0271] Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate a polymer. The precipitated polymer was filtered and then dried under heating at 80°C in a vacuum dryer to obtain 90 g of polyimide precursor A-3. The weight average molecular weight of polyimide precursor A-3 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 40,000. The structural formula of polyimide precursor A-3 is shown below (n represents an integer of 5 to 200). [ka]

[0272] <Synthesis Example 4: Synthesis of Polyimide Precursor A-4> 51.8 g of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) was placed in a 2 L separable flask, and then 500 mL of N-methyl-2-pyrrolidone was placed in the separable flask and stirred at room temperature. 45.0 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindan (INDAN) was added, and the separable flask was heated in an oil bath until the internal temperature reached 40°C, and polymerization was carried out for 20 hours.

[0273] Next, 1.12 g of potassium hydroxide was added to the reaction solution and stirred at room temperature, and 8.8 g of ethylene carbonate was added, and at the same time, the separable flask was heated in an oil bath until the internal temperature reached 80°C and stirred for 10 hours. The resulting reaction solution was brought to 40°C, and 20.6 g of methacrylic acid chloride, 0.5 g of dimethylaminopyridine, and 20 g of triethylamine were added and stirred for 3 hours.

[0274] Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate a polymer. The precipitated polymer was filtered and then dried under heating at 80°C in a vacuum dryer to obtain 92 g of polyimide precursor A-4. The weight average molecular weight of polyimide precursor A-4 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 42,000. The structural formula of polyimide precursor A-4 is shown below (n represents an integer of 5 to 200). [ka]

[0275] <Synthesis Example 5: Synthesis of Polyimide Precursor A-5> 51.8 g of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) was placed in a 2 L separable flask, and 500 mL of N-methyl-2-pyrrolidone was placed in the separable flask and stirred at room temperature. 22.5 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindan (INDAN) and 5.4 g of p-phenylenediamine (PDA) were added, and the separable flask was heated in an oil bath until the internal temperature reached 40°C, and polymerization was carried out for 20 hours.

[0276] Next, 1.12 g of potassium hydroxide was added to the reaction solution and stirred at room temperature, and 8.8 g of ethylene carbonate was added, and at the same time, the separable flask was heated in an oil bath until the internal temperature reached 80°C and stirred for 10 hours. The resulting reaction solution was heated to 40°C, and 18.1 g of acrylic acid chloride, 0.5 g of dimethylaminopyridine, and 20 g of triethylamine were added and stirred for 3 hours.

[0277] Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate a polymer. The precipitated polymer was filtered and then dried under heating at 80°C in a vacuum dryer to obtain 90 g of polyimide precursor A-5. The molecular weight of polyimide precursor A-5 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 45,000. [ka]

[0278] <Synthesis Example 6: (A) Synthesis of Polyimide Precursor A-6> 29.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA) was placed in a 2 L separable flask, 500 mL of N-methyl-2-pyrrolidone was added, and the mixture was stirred at room temperature. 10.8 g of p-phenylenediamine (PDA) was then added. At the same time, the reaction vessel was heated in an oil bath until the internal temperature reached 40°C, and polymerization was carried out for 20 hours.

[0279] Next, 1.12 g of potassium hydroxide was added to the reaction solution, and the mixture was stirred at room temperature, followed by the addition of 8.8 g of ethylene carbonate. At the same time, the reaction vessel was heated in an oil bath until the internal temperature reached 80°C, and the mixture was stirred for 10 hours. The resulting reaction solution was heated to 40°C, and 18.1 g of acrylic acid chloride, 0.5 g of dimethylaminopyridine, and 20 g of triethylamine were added and stirred for 3 hours.

[0280] Next, the resulting reaction solution was dropped into 6 L of ultrapure water to precipitate the polymer, which was then purified. The purified polymer was filtered and then dried under heating at 80°C in a vacuum dryer to obtain 30 g of polymer A-6. The molecular weight of polyimide precursor A-6 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 50,000. [ka]

[0281] <Synthesis Example 7: Synthesis of Polyimide Precursor A-7> 29.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA) was placed in a 2 L separable flask, followed by 500 mL of N-methyl-2-pyrrolidone and stirring at room temperature. 20.0 g of 4,4'-diaminophenyl ether (ODA) was then added, and the separable flask was heated in an oil bath until the internal temperature reached 40°C, and polymerization was carried out for 20 hours.

[0282] Next, 1.12 g of potassium hydroxide was added to the reaction solution and stirred at room temperature, and 8.8 g of ethylene carbonate was added, and at the same time, the separable flask was heated in an oil bath until the internal temperature reached 80°C and stirred for 10 hours. The resulting reaction solution was heated to 40°C, and 18.1 g of acrylic acid chloride, 0.5 g of dimethylaminopyridine, and 20 g of triethylamine were added and stirred for 3 hours.

[0283] Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate a polymer. The precipitated polymer was filtered and then dried under heating at 80°C in a vacuum dryer to obtain 45 g of polyimide precursor A-7. The molecular weight of polyimide precursor A-7 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 50,000. [ka]

[0284] <Preparation of negative type photosensitive resin composition (Examples a-1 to a-5, b-1 to b-6, Comparative Examples c-1 to c-2)> Each photosensitive resin composition was prepared by dissolving each component in 280 parts by mass of a solvent, γ-butyrolactone (GBL), according to the blending amounts (unit: parts by mass) in the table below. In the table, the contents of component (A) and component (D) represent the contents when the non-volatile components of the photosensitive resin composition are taken as 100% by mass.

[0285] [Table 1]

[0286] The abbreviations in the table are as follows: B-1: A compound represented by the following formula: [ka] C-1: Compound represented by the following formula (Irgacure-OXE02, manufactured by BASF) [ka] D-1: A compound represented by the following formula (BANI-X, manufactured by Maruzen Petrochemical Co., Ltd.) [ka] D-2: Compound represented by the following formula (DAD, manufactured by Nisshoku Techno Fine Chemical Co., Ltd.) [ka] D-3: Compound represented by the following formula (DPNG, manufactured by Kuraray Co., Ltd.) [ka] E-1: A compound represented by the following formula: [ka]

[0287] <Evaluation of limiting resolution and via hole shape> A copper plating layer with a thickness of 10 μm was laminated on the surface of a silicon wafer, and the substrate was subjected to a phobic treatment with a 1% hydrochloric acid aqueous solution for 10 seconds. Each photosensitive resin composition was applied to the substrate with a spin coater at a rotation speed appropriate for a film thickness of 15 μm, and the coating was heated on a hot plate at 120° C. for 5 minutes to form a photosensitive resin composition layer. This is called a laminate.

[0288] The laminate produced by the above method was irradiated with ultraviolet light (wavelength 365 nm, intensity 40 mW / cm 2 The exposure was 50 mJ / cm 2 to 1000mJ / cm 2 The optimum value was set in the range of 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm. A quartz glass mask was used for the exposure pattern, which allows drawing of circular holes (via holes) with openings of 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm.

[0289] Next, the entire surface of the photosensitive resin composition layer on the laminate was spray-developed with cyclopentanone as a developer at a spray pressure of 0.2 MPa for an optimal time between 30 and 200 seconds, followed by spray rinsing with 2-methoxy-1-methylethyl acetate (PGMEA) at a spray pressure of 0.2 MPa for 30 seconds.Furthermore, the photosensitive resin composition layer was cured by performing a heat treatment at 200°C for 120 minutes.

[0290] The diameters of the bottoms of via holes with openings of 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm in the exposure pattern were observed and measured by SEM (magnification 1000 times). The smallest size that can be opened is defined as the limiting resolution. The limiting resolution was also evaluated according to the following criteria. ○: Limiting resolution is less than 20 μm △: Limiting resolution is 20μm or more and less than 30μm ×: Limiting resolution is 30 μm or more

[0291] The shape of the via hole was evaluated by observing the cross section of the via hole and measuring the angle α between the surface of the silicon wafer and the wall surface of the via hole. ○:60°≦α≦95 △:45°≦α<60° ×: 45°>α, or α>95°

[0292] <Measurement of dielectric properties (dielectric constant, dielectric tangent)> The dielectric properties were measured by coating the photosensitive resin composition on a peel-treated PET film with a blade to a film thickness of 140 μm. The solution on the PET was heated at 80° C. for 20 minutes using a heater to form a photosensitive film having a photosensitive resin composition layer. The photosensitive resin composition layer was peeled off from the PET film, and the photosensitive resin composition layer was attached to a metal frame using heat-resistant tape, and cured for an additional 2 hours at 250° C. to prepare a film for measuring physical properties.

[0293] A test piece measuring 2 mm in width and 80 mm in length was cut out from the film for measuring physical properties. The dielectric constant and dielectric loss tangent of the cut out test piece were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by a cavity resonance perturbation method using a measuring device "HP8362B" manufactured by Agilent Technologies.

[0294] <Warpage evaluation (warpage test)> The photosensitive resin compositions produced in the Examples and Comparative Examples were applied onto a 12-inch silicon wafer using a spin coater at a rotation speed appropriate for a film thickness of 30 μm, and then heated on a hot plate at 120° C. for 5 minutes to form a photosensitive resin composition layer. Thereafter, the wafer was irradiated with ultraviolet light (wavelength 365 nm, intensity 40 mW / cm 2 ). 2 The exposure was 1000 mJ / cm 2The exposure was performed on the front surface of the photosensitive resin layer through quartz glass. The photosensitive resin composition layer was further cured by heating at 200°C for 120 minutes. This resulted in a sample substrate including a silicon wafer and a cured layer of the photosensitive resin composition. The amount of warping of the sample substrate at 25°C was measured using a shadow moire measuring device ("ThermoireAXP" manufactured by Akorometrix). The measurement was performed in accordance with JEITA EDX-7311-24, a standard of the Japan Electronics and Information Technology Industries Association. Specifically, a virtual plane calculated by the least squares method of all data on the substrate surface in the measurement area was used as a reference plane, and the difference between the minimum value and the maximum value in the vertical direction from the reference plane was calculated as the amount of warping. The amount of warping was also evaluated according to the following criteria. ○: Warpage is less than 130 μm △: Warpage is 130μm or more and less than 150μm ×: Warpage is 150 μm or more

[0295] [Table 2]

Claims

1. (1A) a polyimide precursor having an indane skeleton, (1B) a crosslinking agent, and (1C) a photoradical generator, Contains The component (1A) is a photosensitive resin composition having a structural unit represented by the following formula (A-3): 【Chemistry 1】 (In the formula, each A1 independently represents a tetravalent organic group, R １１ and R １２ each independently represents a hydrogen atom or a monovalent organic group; R １３ each independently represents a methyl group, Xa represents a group represented by formula (2) bonded to the 3-position of indan, and Xb represents a group represented by formula (4) bonded to the 5-position of indan. m1 represents the integer 3, and n1 represents an integer from 5 to 200. 【Chemistry 2】 (In the formula, * represents a bond, and the bond and the oxygen atom are bonded at the para position.)

2. The photosensitive resin composition according to claim 1, further comprising (1D) an allyl compound which has an ethylenically unsaturated bond, in which the carbon atom at the α-position of the ethylenically unsaturated bond is bonded to a group selected from a hydrocarbon group and a hydrogen atom, and in which at least one of the groups bonded to the carbon atom at the α-position of the ethylenically unsaturated bond is a hydrogen atom.

3. The photosensitive resin composition according to claim 2, wherein the component (1D) is represented by the following formula (D-1): 【Chemistry 3】 (In the formula, R １ｄ , R ２ｄ , and R ３ｄ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. * represents a bond.

4. The photosensitive resin composition according to claim 2 or 3, wherein the component (1D) is represented by the following formula (D-2): 【Chemistry 4】 (In the formula, R １１ｄ , R １２ｄ , R １３ｄ , R １４ｄ , R １５ｄ and R １６ｄ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; Z ｄ represents a divalent organic group.

5. The photosensitive resin composition according to any one of claims 1 to 4, further comprising (1E) a sensitizer.

6. R in formula (A-3) １１ and R １２ The photosensitive resin composition according to any one of claims 1 to 5, wherein each independently represents a hydrogen atom or a radically reactive group.

7. R in formula (A-3) １１ and R １２ each independently represents a hydrogen atom or a radical reactive group represented by the following formula (A-2): 【Chemistry 5】 (In the formula, R ４ ~R ６ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p represents an integer of 1 to 10.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the component (1A) has a structural unit represented by the following formula (A-4): 【Chemistry 6】 (In the formula, each A2 independently represents a tetravalent organic group, R ２１ Or R ２２ each independently represents a hydrogen atom or a group represented by the following formula (A-5); and n2 represents an integer of 5 to 200. 【Chemistry 7】 (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.

9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the weight average molecular weight of the component (1A) is 5,000 or more and 1,000,000 or less.

10. (2A) a polyimide precursor, (2B) a crosslinking agent, (2C) a photoradical generator, and (2D) Allyl compounds which have an ethylenically unsaturated bond, the carbon atom at the α-position of the ethylenically unsaturated bond is bonded to a group selected from a hydrocarbon group and a hydrogen atom, and at least one of the groups bonded to the carbon atom at the α-position of the ethylenically unsaturated bond is a hydrogen atom. Contains The component (2A) has a structural unit represented by the following formula (A-3): The component (2D) is a photosensitive resin composition represented by the following formula (D-2): 【Chemistry 8】 (In the formula, each A1 independently represents a tetravalent organic group, R １１ and R １２ each independently represents a hydrogen atom or a monovalent organic group; R １３ each independently represents a hydrogen atom or 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 1 to 5, and n1 represents an integer of 5 to 200. 【Chemistry 9】 (In the formula, * represents a bond.) 【Chemistry 10】 (In the formula, R １１ｄ , R １２ｄ , R １３ｄ , R １４ｄ , R １５ｄ and R １６ｄ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; Z ｄ represents a divalent organic group represented by any one of the following formulas (d-1) to (d-3). 【Chemistry 11】

11. R in formula (A-3) １１ and R １２ and each independently represent at least one radically reactive group.

12. The photosensitive resin composition according to claim 11, wherein the radical reactive group is represented by the following formula (A-2): 【Chemistry 12】 (In the formula, R ４ ~R ６ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p represents an integer of 1 to 10.

13. The photosensitive resin composition according to any one of claims 10 to 12, wherein the component (2B) is a compound having an ethylenically unsaturated bond, and at least one carbon atom at the α-position of the ethylenically unsaturated bond is bonded to a carbonyl group or an aromatic group.

14. The photosensitive resin composition according to any one of claims 10 to 13, further comprising (2E) a sensitizer.

15. The photosensitive resin composition according to any one of claims 10 to 14, wherein the content of the component (2D) is 0.1 mass% to 15 mass% when the total amount of non-volatile components in the photosensitive resin composition is 100 mass%.

16. The photosensitive resin composition according to any one of claims 10 to 15, wherein the content of the component (2A) is 70% by mass or more and 98% by mass or less, when the total amount of non-volatile components of the photosensitive resin composition is 100% by mass.

17. 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 16.

18. 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 16.

19. A semiconductor device comprising the semiconductor package substrate according to claim 18.

20. A step of forming a photosensitive resin composition layer containing the photosensitive resin composition according to any one of claims 1 to 16 on a circuit board; A step of irradiating the photosensitive resin composition layer with actinic rays; and developing the photosensitive resin composition layer.

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