Photosensitive resin composition

Abstract

To provide a photosensitive resin composition which has high solubility in organic solvents, maintains a glass transition temperature while exhibiting superior dielectric characteristics, and makes it possible to yield a cured product with reduced warpage upon lamination of films.SOLUTION: A photosensitive resin composition comprises (1A) a polyamic acid and / or a polyamic acid ester having a structure derived from a diamine compound with a siloxane structure, a structure derived from a diamine compound with an indane structure, and a structure derived from a tetracarboxylic dianhydride with an alicyclic structure, the polyamic acid ester having an ester residue derived from an epoxy compound with an ethylenically unsaturated bond, (B) a photopolymerization initiator, and (C) a crosslinking agent.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 using the photosensitive resin composition. [Background technology]

[0002] Conventionally, surface protection films and interlayer insulating films for semiconductor devices have required excellent heat resistance, insulating properties, and mechanical properties. Polyimide resins having both of these properties are used. Furthermore, because polyimide resins have low solubility in solvents, they are often used in photosensitive resin compositions in the form of a polyimide precursor. After forming an insulating layer or the like, the polyimide precursor is cyclized to produce a polyimide, which then forms an insulating layer. For example, Patent Document 1 describes a photosensitive polyimide precursor having a skeleton derived from 4,4'-oxydiphthalic dianhydride and a skeleton derived from 4,4'-diaminodiphenyl ether, and a photosensitive polyimide precursor having a skeleton derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride and a skeleton derived from 4,4'-diaminodiphenyl ether. Patent Document 2 describes a positive-type photosensitive resin composition containing a polybenzoxazole precursor. Patent Document 3 describes a positive-type photosensitive polyimide resin composition containing a phenolic hydroxyl group-containing polyimide resin and a diazo-based positive-type photosensitizer. Patent Document 4 also proposes a silicone-modified polyimide resin. Patent Document 5 describes a photosensitive resin composition containing a polyamic acid containing a polymer of a silicone diamine compound. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6419383 [Patent Document 2] Patent No. 5577688 [Patent Document 3] International Publication No. 2010 / 047271 [Patent Document 4] Patent No. 3646947 [Patent Document 5] Patent No. 5393806 Summary of the Invention [Problem to be solved by the invention]

[0004] The photosensitive resin compositions described in Patent Documents 1 to 5 above do not satisfy the dielectric properties required for 5G communication applications, such as low dielectric constant and low dielectric loss. Furthermore, warping of substrates can occur during the manufacture of multilayer films for packages, or due to stress caused by heat or impact, and there is a growing demand for suppressing this warping. In particular, the resin composition described in Patent Document 3 requires the introduction of a large number of phenolic hydroxyl groups to ensure developability in an alkaline aqueous solution, resulting in high polarity of the polyimide resin and unavoidable deterioration of its dielectric and mechanical properties. Furthermore, the polyimide resin described in Patent Document 4 lacks photosensitivity and requires a separate photoresist for pattern formation. The photosensitive resin composition described in Patent Document 5 has problems with poor solubility in organic solvents. Furthermore, the introduction of a silicone structure into the polyimide resin lowers the glass transition temperature, which can lead to deformation of the formed via pattern due to heat sagging when the polyimide resin is heated to cure.

[0005] The present invention has been made in view of the above-mentioned problems, and has an object to provide a photosensitive resin composition that has high solubility in organic solvents, exhibits excellent dielectric properties while maintaining its glass transition temperature, and is capable of giving a cured product that is suppressed in warping during film lamination, as well as a photosensitive film, a semiconductor package substrate, a semiconductor device, and a method for manufacturing a semiconductor package substrate that use the same. [Means for solving the problem]

[0006] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by using a photosensitive resin composition containing a polyamic acid and / or polyamic acid ester having a specific structure, a photopolymerization initiator, and a crosslinking agent, and have thus completed the present invention.

[0007] That is, the present invention includes the following. [1] (1A) A polyamic acid and / or a polyamic acid ester having a structure derived from a diamine compound having a siloxane structure, a structure derived from a diamine compound having an indane structure, and a structure derived from a tetracarboxylic dianhydride having an alicyclic structure, wherein the polyamic acid ester has an ester residue derived from an epoxy compound having an ethylenically unsaturated bond; (B) a photoinitiator, and (C) a crosslinking agent, A photosensitive resin composition comprising: [2] The photosensitive resin composition according to [1], wherein in the component (1A), the diamine compound having a siloxane structure is a compound represented by the following formula (1a), and the diamine compound having an indane structure is a compound represented by the following formula (2a): [ka] (In formula (1a), R a1 , R a2 , R a3 and R a4 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 4 to 20 carbon atoms. 1 and X 2 each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and p represents an integer of 1 to 100. [ka] (In formula (2a), Xa and Xb each independently represent a single bond, a group represented by formula (X-1) below, a group represented by formula (X-2) below, or a group represented by formula (X-3) below. x represents an integer of 0 to 5.) [ka] (In the formula, * represents a bond.) [3] The photosensitive resin composition according to [1] or [2], wherein in the component (1A), the tetracarboxylic acid dianhydride having an alicyclic structure has 10 to 30 carbon atoms and a 6-membered alicyclic structure. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the tetracarboxylic acid dianhydride having an alicyclic structure in the component (1A) is a compound represented by the following formula (3a): [ka] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the epoxy compound having an ethylenically unsaturated bond in the component (1A) is glycidyl (meth)acrylate. [6] The photosensitive resin composition according to any one of [1] to [5], wherein in the component (1A), the number of structures derived from a diamine compound having an indane structure is M1, the number of structures derived from a diamine compound having a siloxane structure is N1, and if a structure derived from another diamine compound is present, the number of structures derived from the other diamine compound is L1, the sum (m1+n1) of m1 defined by the following formula (1) and n1 defined by the following formula (2) is 90 to 100:

number

number

number

[10] In the diamine compound represented by formula (1a) of component (1A), R a1 , R a2 , R a3 and R a4 The photosensitive resin composition according to any one of [2] to [9], wherein is a methyl group.

[11] In the diamine compound represented by formula (1a) of component (1A), R a1 , R a2 , R a3 and R a4 The photosensitive resin composition according to any one of [2] to [9], wherein is a phenyl group.

[12] In the diamine compound represented by formula (1a) of component (1A), X 1 and X 2 The photosensitive resin composition according to any one of [2] to

[11] , wherein is a 1,3-propylene group.

[13] The photosensitive resin composition according to any one of [2] to

[12] , wherein in the component (1A), the diamine compound represented by formula (2a) is a compound represented by the following formula (2a-1): [ka]

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

[13] , further comprising (D) an adhesion aid.

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

[14] , further comprising (E) a sensitizer.

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

[15] , further comprising (F) a surfactant.

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

[16] , which is a negative type.

[18] (2A) A polyamic acid and / or a polyamic acid ester having a structural unit represented by the following formula (A-1), a structural unit represented by the following formula (A-2), and a structural unit represented by the following formula (A-3): (B) a photoinitiator, and (C) a crosslinking agent, A photosensitive resin composition comprising: [ka] (In formula (A-1), each A independently represents a tetravalent organic group having an alicyclic structure. R 1 and R 2 each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms and an ethylenically unsaturated group. [ka] (In formula (A-2), R a1 , R a2 , R a3 and R a4 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 4 to 20 carbon atoms. 1 and X 2 each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and p represents an integer of 1 to 100. [ka] (In formula (A-3), Xa and Xb each independently represent a single bond, a group represented by formula (X-1) below, a group represented by formula (X-2) below, or a group represented by formula (X-3) below. x represents an integer of 0 to 5.) [ka] (In the formula, * represents a bond.)

[19] The photosensitive resin composition according to

[18] , wherein the component (2A) is a polyamic acid and / or a polyamic acid ester having a structural unit represented by the following formula (A-4) and a structural unit represented by the following formula (A-5): [ka] [ka] (In formula (A-4) and formula (A-5), each A independently represents a tetravalent organic group having an alicyclic structure. R 1 and R 2 R each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms and an ethylenically unsaturated group. a1 , R a2 , R a3 and R a4 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 4 to 20 carbon atoms. 1 and X 2 each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms. p represents an integer of 1 to 100. Xa and Xb each independently represent a single bond, a group represented by the above formula (X-1), a group represented by the above formula (X-2), or a group represented by the above formula (X-3). x represents an integer of 0 to 5.

[20] The photosensitive resin composition according to

[19] , wherein the number of repetitions of the structural unit represented by formula (A-5) is M2, the number of repetitions of the structural unit represented by formula (A-4) is N2, and if another structural unit is present, the number of repetitions of the other structural unit is L2, the sum (m2+n2) of m2 defined by the following formula (4) and n2 defined by the following formula (5) is 90 to 100:

number

number

[21] The photosensitive resin composition according to

[20] , wherein m2=40 to 90.

[22] The photosensitive resin composition according to

[20] or

[21] , wherein n2=10 to 60.

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

[19] to

[22] , wherein in formula (A-4) and formula (A-5), A is a tetravalent organic group having 6 to 26 carbon atoms and having a 6-membered alicyclic structure.

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

[19] to

[23] , wherein in formula (A-4) and formula (A-5), A is a group represented by the following formula (X-6): [ka] (In the formula, * represents a bond.)

[25] In formula (A-4) and formula (A-5), R 1 and R 2 are each independently a hydrogen atom, a group represented by the following formula (X-4), or a group represented by the following formula (X-5): [ka] (In formula (X-4), R 24 , R 25 and R 26 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p2 represents an integer of 0 to 10. * represents a bond. [ka] In formula (X-5), ring Z represents an aliphatic hydrocarbon ring having 3 to 20 carbon atoms which may have a substituent. 34 , R 35 and R 36 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p3 represents an integer of 0 to 10. * represents a bond.

[26] In formula (A-4) and formula (A-5), R 1 and R 2 are each independently a hydrogen atom or a group represented by the above formula (X-4), In formula (X-4), R 24 is a hydrogen atom or a methyl group, and R 25 is a hydrogen atom, and R26 is a hydrogen atom, and p2 is 1.

[27] In the component (2A), R 1 and R 2 The total number of R 1 and R 2 The photosensitive resin composition according to any one of

[18] to

[26] , wherein when the total number of monovalent groups having 1 to 20 carbon atoms and an ethylenically unsaturated group among the above is S2, a modification rate u2 (%) defined by the following formula (6) is 20 to 100%:

number

[28] In formula (A-4), R a1 , R a2 , R a3 and R a4 The photosensitive resin composition according to any one of

[19] to

[27] , wherein is a methyl group.

[29] In formula (A-4), R a1 , R a2 , R a3 and R a4 The photosensitive resin composition according to any one of

[19] to

[27] , wherein is a phenyl group.

[30] In formula (A-4), X 1 and X 2 The photosensitive resin composition according to any one of

[19] to

[27] , wherein is a 1,3-propylene group.

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

[19] to

[30] , wherein the structural unit represented by formula (A-5) is a structural unit represented by the following formula (A-5-1): [ka] (In formula (A-5-1), A represents a tetravalent organic group having an alicyclic structure. R 1 and R 2 each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms and an ethylenically unsaturated group.

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

[18] to

[31] , further comprising (D) an adhesion aid.

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

[18] to

[32] , further comprising (E) a sensitizer.

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

[18] to

[33] , further comprising (F) a surfactant.

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

[18] to

[34] , which is a negative type.

[36] 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

[35] .

[37] 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

[35] .

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

[37] .

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

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

[0008] According to the present invention, it is possible to provide a photosensitive resin composition that has high solubility in organic solvents, exhibits excellent dielectric properties while maintaining its glass transition temperature, and is capable of giving a cured product that is suppressed in warping during film lamination, as well as a photosensitive film, a semiconductor package substrate, a semiconductor device, and a method for manufacturing a semiconductor package substrate that use the same. DETAILED DESCRIPTION OF THE INVENTION

[0009] The photosensitive resin composition of the present invention, and the photosensitive film, semiconductor package substrate, semiconductor device, and method for manufacturing a semiconductor package substrate obtained using the photosensitive resin composition will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and can be modified as desired within the scope of the claims and their equivalents.

[0010] In the following description, unless otherwise specified, the expressions "XX to YY" or "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined in any way.

[0011] In the following description, "dielectric constant" refers to "relative dielectric constant" unless otherwise specified.

[0012] In the following description, unless otherwise specified, the term "optionally substituted" used in reference to a compound or group means both a case where the hydrogen atoms of the compound or group are not substituted with substituents and a case where some or all of the hydrogen atoms of the compound or group are substituted with substituents.

[0013] In the following description, the content of each component in the photosensitive resin composition represents a value when the non-volatile components in the photosensitive resin composition are taken as 100 mass %, unless otherwise specified.

[0014] In the following description, the component (1A) and the component (2A) may be collectively referred to as the "component (A)." Furthermore, the photosensitive resin composition of the first embodiment and the photosensitive resin composition of the second embodiment may be collectively referred to as the "photosensitive resin composition."

[0015] [Photosensitive resin composition of the first embodiment] The photosensitive resin composition of the first embodiment of the present invention contains (1A) a polyamic acid and / or polyamic acid ester having a structure derived from a diamine compound having a siloxane structure, a structure derived from a diamine compound having an indane structure, and a structure derived from a tetracarboxylic dianhydride having an alicyclic structure, where the polyamic acid ester has an ester residue derived from an epoxy compound having an ethylenically unsaturated bond (hereinafter also referred to as "polyamic acid and / or polyamic acid ester having a first specific structure"); (B) a photopolymerization initiator; and (C) a crosslinking agent. By incorporating the components (1A) to (C) in combination into the photosensitive resin composition, a cured product can be obtained that has high solubility in organic solvents, exhibits excellent dielectric properties while maintaining a glass transition temperature, and exhibits reduced warping during film lamination.

[0016] The photosensitive resin composition of the first embodiment is suitable as a negative-type photosensitive resin composition. In a negative-type photosensitive resin composition, a crosslinking reaction or the like occurs in the area irradiated with actinic rays, and the composition becomes insoluble in a developer. Therefore, it becomes possible to selectively remove the photosensitive resin composition from areas other than those where the crosslinking reaction has progressed during development, and a negative-type pattern can be advantageously formed. The area remaining after development has sufficient strength due to the crosslinking reaction or the like, and can be used as is as an insulating layer or the like in the form of a permanent film.

[0017] The photosensitive resin composition of the first embodiment may further contain optional components in addition to the components (1A) to (C). Examples of optional components include (D) an adhesion aid, (E) a sensitizer, (F) a surfactant, (G) an organic solvent, and (H) other additives. Each component contained in the photosensitive resin composition of the first embodiment will be described in detail below.

[0018] <(1A) Polyamic Acid and / or Polyamic Acid Ester Having a First Specific Structure> The photosensitive resin composition of the first embodiment contains, as component (1A), a polyamic acid and / or polyamic acid ester having a structure derived from a diamine compound having a siloxane structure, a structure derived from a diamine compound having an indane structure, and a structure derived from a tetracarboxylic dianhydride having an alicyclic structure, wherein the polyamic acid ester has an ester residue derived from an epoxy compound having an ethylenically unsaturated bond. In the present invention, the term "polyamic acid and / or polyamic acid ester" encompasses "polyamic acid," "polyamic acid ester," and "copolymer of polyamic acid and polyamic acid ester." The component (1A) may be used alone or in combination of two or more.

[0019] Polyamic acid can be obtained by reacting a tetracarboxylic dianhydride with a diamine compound, and a portion of the polyamic acid can be converted into a polyamic acid ester by reacting the polyamic acid with an epoxy compound having an ethylenically unsaturated bond.

[0020] When component (A) has a structure derived from a tetracarboxylic dianhydride having an asymmetric structure represented by formula (P-1) below and a structure derived from a diamine compound having an asymmetric structure represented by formula (Q-1) below, the structural units of the polyamic acid and / or polyamic acid ester may be 16 types of positional isomers represented by formulas (PQ-1) to (PQ-16) below. [ka] (In the formula, the numbers 1 to 4 attached to the bonds of the tetravalent substituent P mean that the tetravalent group P is asymmetric and the four bonds can be distinguished.)

[0021] In the following description, polyamic acids and / or polyamic acid esters may be described using structural formulas. Unless otherwise specified, the expression of any one of formulas (PQ-1) to (PQ-16) is considered to encompass all structures of formulas (PQ-1) to (PQ-16). That is, "polyamic acids and / or polyamic acid esters having a structural unit represented by formula (PQ-1)" means "polyamic acids and / or polyamic acid esters having one or more structural units selected from formulas (PQ-1) to (PQ-16)." In the case of polyamic acids and / or polyamic acid esters having two or more structural units selected from formulas (PQ-1) to (PQ-16), this also includes polyamic acids and / or polyamic acid esters in which the two or more structural units are copolymerized in any manner, such as random copolymerization, alternating copolymerization, block copolymerization, graft copolymerization, or ordered copolymerization.

[0022] When component (1A) has a structure derived from a diamine compound having a siloxane structure, the dielectric loss tangent of the cured product of the photosensitive resin composition can be reduced. This is thought to be due to the low polarity of the siloxane structure. Furthermore, when component (1A) has a structure derived from a diamine compound having a siloxane structure, warping of the cured product can be suppressed. This is thought to be due to the siloxane structure forming a helical structure, which has stress relaxation properties.

[0023] The component (1A) having a structure derived from a diamine compound having an indane structure can enhance the solubility of the component (1A) in organic solvents and increase the glass transition temperature of the cured product. Furthermore, the component (1A) having a structure derived from a diamine compound having an indane structure can achieve excellent limiting resolution. In other words, small-diameter holes can be formed in the photosensitive resin composition layer by exposure and development.

[0024] When component (1A) has a structure derived from a tetracarboxylic dianhydride having an alicyclic structure, the solubility of component (1A) in organic solvents can be increased, and the glass transition temperature of the cured product can be increased.

[0025] When the polyamic acid ester in component (1A) contains an ester residue derived from an epoxy compound having an ethylenically unsaturated bond, the ethylenically unsaturated bond in component (1A) reacts and polymerizes upon exposure, more effectively reducing the solubility of the cured product of the photosensitive resin composition in a developer. This means that the resolution of the photosensitive resin composition can be ensured. Furthermore, when the polyamic acid ester in component (1A) contains an ester residue derived from an epoxy compound having an ethylenically unsaturated bond, film retention can be improved.

[0026] Component (1A) has a structure derived from a diamine compound having a siloxane structure. The molecular weight of the diamine compound having a siloxane structure in component (1A) is preferably 100 to 5,000, more preferably 500 to 2,000. The side chain of the silicon atom in the siloxane structure is preferably an alkyl group or an aryl group. The alkyl group is preferably methyl, and the aryl group is preferably phenyl.

[0027] In the component (1A), the diamine compound having a siloxane structure is preferably a compound represented by the following formula (1a). [ka] (In formula (1a), R a1 , R a2 , R a3 and R a4 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 4 to 20 carbon atoms. 1 and X 2 each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and p represents an integer of 1 to 100.

[0028] In formula (1a), R a1 , R a2 , R a3 and R a4each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 4 to 20 carbon atoms.

[0029] The alkyl group is a chain (straight-chain or branched) alkyl group or a cyclic alkyl group. The alkyl group has 1 to 20 carbon atoms, preferably 1 to 10, and more preferably 1 to 5. Examples of the chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a decyl group. Preferred are a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, more preferred are a methyl group or an ethyl group, and even more preferred is a methyl group. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

[0030] An aryl group is a group in which one hydrogen atom on an aromatic ring has been removed from an aromatic compound. The number of carbon atoms in the aryl group is 4 to 20, preferably 4 to 10, more preferably 5 to 10, and even more preferably 6 to 10. Examples of the aryl group include a phenyl group, a naphthyl group, a thienyl group, a pyrrolyl group, a furanyl group, a furyl group, a pyridyl group, a pyridazinyl group, a pyrimidyl group, a pyrazinyl group, a triazinyl group, a pyrrolidyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group. A phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred.

[0031] In formula (1a), X 1 and X 2 each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms. From the viewpoint of further reducing the dielectric loss tangent of the cured product of the photosensitive resin composition and further suppressing warpage of the cured product, X 1 and X 2 From the viewpoint of improving the heat resistance and stability of the cured product of the photosensitive resin composition, X is preferably a single bond. 1 and X 2 is preferably an alkylene group having 1 to 20 carbon atoms.

[0032] X 1 and X 2 The lower limit of the number of carbon atoms in the alkylene group in the formula (I) is preferably 2 or more. The upper limit of the number of carbon atoms in the alkylene group is preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less. Examples of the alkylene group include an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,2-butylene group, a 1,3-butylene group, and a 1,4-butylene group. An ethylene group, a 1,3-propylene group, or a 1,4-butylene group is more preferred, an ethylene group or a 1,3-propylene group is even more preferred, and a 1,3-propylene group is particularly preferred.

[0033] Among these, X 1 and X 2 From the viewpoint of further reducing the dielectric loss tangent of the cured product of the photosensitive resin composition and further suppressing warpage of the cured product, X is preferably a single bond or a 1,3-propylene group. 1 and X 2 From the viewpoint of improving the heat resistance and stability of the cured product of the photosensitive resin composition, X is more preferably a single bond. 1 and X 2 is more preferably a 1,3-propylene group.

[0034] In formula (1a), p represents an integer of 1 to 100. The lower limit of p is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. The upper limit of p is preferably 50 or less, more preferably 40 or less or 35 or less, even more preferably 30 or less or 25 or less, and particularly preferably 20 or less or 15 or less.

[0035] Among these, the diamine compounds having a siloxane structure are preferably compounds represented by the following formulas (1a-1) to (1a-4). [ka] (In the formula, p represents an integer of 1 to 100.)

[0036] Component (1A) has a structure derived from a diamine compound having an indane structure. The indane structure represents the structure shown in formula (a1-1) below. When the polyamic acid and / or polyamic acid ester has an indane structure, the solubility of the unexposed areas of the photosensitive resin composition in a developer can be increased. This can shorten the development time and, more preferably, improve the resolution. Unless otherwise specified, "resolution" refers to the ability to form small holes in the photosensitive resin composition layer by exposure and development. Generally, the smaller the diameter of the holes that can be formed, the better the resolution. In particular, the diamine compound having an indane structure in component (1A) preferably has a trimethylindane structure represented by formula (a1-2) below. [ka]

[0037] In the component (1A), the diamine compound having an indane structure is preferably a compound represented by the following formula (2a). [ka] (In formula (2a), Xa and Xb each independently represent a single bond, a group represented by formula (X-1) below, a group represented by formula (X-2) below, or a group represented by formula (X-3) below. x represents an integer of 0 to 5.) [ka] (In the formula, * represents a bond.)

[0038] In formula (2a), Xa and Xb each independently represent a single bond, a group represented by formula (X-1), a group represented by formula (X-2), or a group represented by formula (X-3). Xa and Xb may be bonded to a five-membered ring or a benzene ring.

[0039] Examples of the group represented by formula (X-1) include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group.

[0040] Examples of the group represented by formula (X-2) include groups represented by the following formulae (2-1) to (2-6). [ka]

[0041] Examples of the group represented by formula (X-3) include groups represented by the following formulae (3-1) to (3-3). [ka]

[0042] Among these, Xa is preferably a group represented by formula (X-1) or a group represented by formula (X-2), more preferably a 1,4-phenylene group or a group represented by formula (2-1), and even more preferably a 1,4-phenylene group. Xb is preferably a single bond or a group represented by formula (X-3), more preferably a single bond or a group represented by formula (3-1), and even more preferably a single bond.

[0043] In formula (A-2), x represents an integer of 0 to 5. x is preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably 3.

[0044] Among these, as the diamine compound having an indane structure, the compounds represented by the following formulas (2a-1) to (2a-9) are preferred, the compound represented by the following formula (2a-1) or the compound represented by the following formula (2a-6) is more preferred, and the compound represented by the following formula (2a-1) is even more preferred. [ka]

[0045] The component (1A) has a structure derived from a tetracarboxylic acid dianhydride having an alicyclic structure. In the component (1A), the tetracarboxylic acid dianhydride having an alicyclic structure preferably has 10 to 30 carbon atoms. In addition, in the component (1A), the tetracarboxylic acid dianhydride having an alicyclic structure preferably has a six-membered alicyclic structure.

[0046] Examples of acid dianhydrides having an alicyclic structure include 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-exo-3-exo-5-exo-6-exo-2,3,5,6-tetracarboxylic dianhydride, and bicyclo[2.2 1]Heptane-2,3,5,6-tetracarboxylic dianhydride, 2-(3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthyl)succinic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, decahydro-dimethanonaphthalenetetracarboxylic dianhydride, etc., are listed, and 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride is preferred. 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride is a compound represented by the following formula (3a): [ka]

[0047] The polyamic acid ester in component (1A) has an ester residue derived from an epoxy compound having an ethylenically unsaturated bond. The epoxy compound having an ethylenically unsaturated bond is preferably glycidyl (meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate, more preferably glycidyl (meth)acrylate, and even more preferably glycidyl methacrylate. "(Meth)acrylate" encompasses methacrylate and acrylate.

[0048] Among these, preferred examples of component (1A) include polyamic acids and / or polyamic acid esters having a structure derived from a diamine compound having a siloxane structure represented by formula (1a-2) above, a structure derived from a diamine compound having an indane structure represented by formula (2a-1) above, and a structure derived from a tetracarboxylic acid dianhydride having an alicyclic structure represented by formula (3a) above, wherein the polyamic acid ester has an ester residue derived from glycidyl methacrylate.

[0049] Another preferred example of component (1A) is a polyamic acid and / or polyamic acid ester having a structure derived from a diamine compound having a siloxane structure represented by formula (1a-4) above, a structure derived from a diamine compound having an indane structure represented by formula (2a-1) above, and a structure derived from a tetracarboxylic acid dianhydride having an alicyclic structure represented by formula (3a) above, wherein the polyamic acid ester has an ester residue derived from glycidyl methacrylate.

[0050] In component (1A), when the number of structures derived from a diamine compound having an indane structure is M1, the number of structures derived from a diamine compound having a siloxane structure is N1, and if there is a structure derived from another diamine compound, the number of structures derived from the other diamine compound is L1, the sum of m1 defined in formula (1) below and n1 defined in formula (2) below (m1+n1) is preferably 90 to 100. m1+n1 is more preferably 95 or more or 96 or more, even more preferably 97 or more, and particularly preferably 98 or more or 99 or more. m1, n1, and l1 described below are 1 It can be measured by H-NMR.

number

number

[0051] I1 defined by the following formula (7) is more preferably 10 or less, more preferably 5 or less or 4 or less, even more preferably 3 or less, and particularly preferably 2 or less or 1 or less.

number

[0052] From the viewpoints of improving solubility in organic solvents, increasing the glass transition temperature of the cured product, and obtaining excellent limiting resolution, m1 is preferably 40 to 90. The lower limit of m1 is more preferably 45 or more, even more preferably 50 or more or 55 or more, and particularly preferably 60 or more or 65 or more. The upper limit of m1 is more preferably 85 or less, even more preferably 80 or less, and particularly preferably 75 or less.

[0053] From the viewpoint of reducing the dielectric loss tangent of the cured product and suppressing warpage of the cured product, n1 is preferably 10 to 60. The lower limit of n1 is more preferably 15 or more, even more preferably 20 or more, and particularly preferably 25 or more. The upper limit of n1 is more preferably 55 or less, even more preferably 50 or less or 45 or less, and particularly preferably 40 or less or 35 or less.

[0054] In component (1A), when the total number of polyamic acid moieties and the number of polyamic acid ester moieties is T1 and the number of polyamic acid ester moieties having an ester residue derived from an epoxy compound having an ethylenically unsaturated bond is S1, the modification rate u1 (%) defined by the following formula (3) is preferably 20 to 100% from the viewpoint of improving film retention. The lower limit of u1 is more preferably 25% or more, even more preferably 30% or more, and particularly preferably 35% or more. The upper limit of u1 is more preferably 90% or less, 80% or less, or 70%, more preferably 60% or less, or 50% or less, and particularly preferably 45% or less, or 40% or less. u1 is 1 It can be measured by H-NMR.

number

[0055] From the viewpoint of obtaining excellent limiting resolution, the weight average molecular weight of component (1A) is preferably 3,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, and particularly preferably 6,000 or more, and is preferably 1,000,000 or less, more preferably 500,000 or less, even more preferably 200,000 or less, or 100,000 or less, and particularly preferably 50,000 or less, 20,000 or less, 10,000 or less, 9,000 or less, or 8,000 or less. The weight average molecular weight of component (1A) can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0056] From the viewpoint of obtaining excellent limiting resolution and a cured product with good physical properties, the content of component (1A) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, based on 100% by mass of the non-volatile components of the photosensitive resin composition. The upper limit is preferably 99% by mass or less, more preferably 97% by mass or less or 95% by mass or less, and even more preferably 93% by mass or less or 90% by mass or less.

[0057] <Method of manufacturing component (1A)> There are no particular limitations on the method for producing component (1A). Component (1A) can be obtained, for example, by reacting a tetracarboxylic acid dianhydride having an alicyclic structure, a diamine compound having a siloxane structure, a diamine compound having an indane structure, and an epoxy compound having an ethylenically unsaturated bond.

[0058] Examples of tetracarboxylic acid dianhydrides having an alicyclic epoxy structure include the tetracarboxylic acid dianhydrides having an alicyclic structure described above. Examples of diamine compounds having a siloxane structure include the compounds represented by the above formulas (1a-1) to (1a-4). Examples of diamine compounds having an indane structure include the compounds represented by the above formulas (2a-1) to (2a-9). In addition, when component (1A) also has a structure derived from a diamine compound that does not fall into either the diamine compound having a siloxane structure or the diamine compound having an indane structure, diamine compounds represented by the following formulas (4a-1) to (4a-18) can also be used. Examples of epoxy compounds having an ethylenically unsaturated bond include glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate. [ka]

[0059] Specifically, for example, component (1A) is (i) a step of charging a diamine compound, a tetracarboxylic dianhydride, and an organic solvent into a reaction vessel and heating the mixture; (ii) adding a polymerization inhibitor and an epoxy compound having an ethylenically unsaturated bond to a reaction vessel and heating the mixture; The composition can be produced by a production method including the steps of:

[0060] In step (i), a diamine compound having a siloxane structure, a diamine compound having an indane structure, a tetracarboxylic dianhydride having an alicyclic epoxy structure, and an organic solvent are charged into a reaction vessel and heated to produce a polyamic acid. For example, a separable flask can be used as the reaction vessel, and an oil bath or the like can be used for heating. As the organic solvent, a ketone-based organic solvent is preferred, and cyclohexanone is more preferred. The heating temperature is preferably 50 to 60°C, and the reaction time is preferably 15 to 20 hours.

[0061] In step (ii), a polymerization inhibitor and an epoxy compound having an ethylenically unsaturated bond are added and heated to esterify a part of the polyamic acid. In step (ii), it is preferable to add the polymerization inhibitor and then add the epoxy compound having an ethylenically unsaturated bond.

[0062] The polymerization inhibitor is preferably diluted and dissolved in an organic solvent before addition. Examples of the polymerization inhibitor include 4-tert-butylpyrocatechol, tert-butylhydroquinone, 1,4-benzoquinone, dibutylhydroxytoluene, 1,1-diphenyl-2-picrylhydrazyl free radical, hydroquinone, mequinol, phenothiazine, and 4-methoxyphenol, with 4-methoxyphenol being preferred. The amount of the polymerization inhibitor added is preferably 0.01 to 5% by mass, more preferably 0.03 to 0.1% by mass, based on 100% by mass of the total amount of the diamine compound and the tetracarboxylic acid anhydride, in order to prevent gelation of the polymer components during the reaction.

[0063] The amount of the epoxy compound having an ethylenically unsaturated bond added is preferably 0.3 to 2.0 equivalents, more preferably 0.5 to 1.0 equivalents, relative to the carboxylic acid group of the polyamic acid. The epoxy compound having an ethylenically unsaturated bond is preferably added using a dropping funnel or the like.

[0064] In step (ii), it is preferable to add an epoxy compound having an ethylenically unsaturated bond, followed by the addition of a base catalyst and heating. The heating temperature is preferably 70 to 100°C, and the heating time is preferably 15 to 20 hours. Examples of the base catalyst include 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), N,N-dimethylaminopyridine (DMAP), N-methylimidazole (MIMZ), triethylamine, tributylamine, pyridine, quaternary onium salts such as tetrabutylammonium bromide (Bu4NBr), and crown ethers such as 18-crown-6-ether, with 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) being preferred. From the viewpoint of efficiently proceeding with the esterification reaction, the amount of the base catalyst added is preferably 0.01 to 5 mass%, more preferably 0.1 to 2.0 mass%, and even more preferably 0.5 to 1.5 mass%, based on 100 mass% of the total amount of the diamine compound and tetracarboxylic acid anhydride.

[0065] <(B) Photopolymerization initiator> The photosensitive resin composition of the first embodiment contains a (B) photopolymerization initiator as the (B) component. The (B) component generates radicals when irradiated with actinic rays, and the portions of the photosensitive resin composition where a crosslinking reaction or the like has occurred due to the radicals do not dissolve in a developer. Therefore, during development, it becomes possible to selectively remove the photosensitive resin composition from the portions other than those where the crosslinking reaction has progressed, and a negative pattern can be advantageously formed. The (B) component may be used alone or in combination of two or more. Furthermore, the (B) component is a component different from the (A) and (C) components.

[0066] (B) Photopolymerization initiators include intramolecular cleavage-type photopolymerization initiators and hydrogen abstraction-type photopolymerization initiators, with intramolecular cleavage-type photopolymerization initiators being preferred. Intramolecular cleavage-type photopolymerization initiators are photopolymerization initiators that generate radicals by intramolecular cleavage, while hydrogen abstraction-type photopolymerization initiators are photopolymerization initiators that generate radicals by exchanging hydrogen or electrons between two molecules.

[0067] Examples of the intramolecular cleavage photopolymerization initiator include an α-aminoketone-based photopolymerization initiator, a phosphine oxide-based photopolymerization initiator, an α-hydroxyketone-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, a benzyl-based photopolymerization initiator, a benzyl ketal-based photopolymerization initiator, a benzoin-based photopolymerization initiator, a peroxide-based photopolymerization initiator, a titanocene-based photopolymerization initiator, and a cyanide-based photopolymerization initiator. From the viewpoint of photosensitivity, an oxime ester-based photopolymerization initiator or a phosphine oxide-based photopolymerization initiator is preferred.

[0068] Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and aromatic biimidazole-based photopolymerization initiators.

[0069] Examples of the α-aminoketone photopolymerization initiator include 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-methyl-1-(4-hexylphenyl)-2-morpholinopropan-1-one, 2-ethyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and N-arylglycines such as N-phenylglycine.

[0070] The phosphine oxide photopolymerization initiator is preferably an acylphosphine photopolymerization initiator. Examples of the acylphosphine photopolymerization agent include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, and polyoxyethylene glycerin ether tris[phenyl(2,4,6-trimethylbenzoyl)phosphinate] (Polymeric TPO-L), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is preferred.

[0071] Examples of the α-hydroxyketone photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropanone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one.

[0072] Examples of the oxime ester photopolymerization initiator include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (OXE01), [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino]acetate (OXE02), 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, and 1-phenyl-1,2 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide, and the like are included, and 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (OXE01) or [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino]acetate (OXE02) is preferred.

[0073] Examples of the benzyl-based photopolymerization initiator include benzyl.

[0074] Examples of the benzyl ketal photopolymerization initiator include benzyl dimethyl ketal (2,2-dimethoxy-2-phenylacetophenone) and benzyl-β-methoxyethyl acetal.

[0075] Examples of the benzoin-based photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0076] Examples of peroxide-based photopolymerization initiators include benzoyl perchloride.

[0077] Examples of the titanocene photopolymerization initiator include bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanocene. Examples of the cyanide-based photopolymerization initiator include α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide.

[0078] Examples of the benzophenone-based photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone.

[0079] Examples of the acetophenone-based photopolymerization initiator include 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone.

[0080] Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone.

[0081] Examples of aromatic biimidazole photopolymerization initiators include 2,2'-bis-(2-chlorophenyl)4,5,4',5'-tetraphenyl-1,2'-biimidazole.

[0082] Component (B) can be a commercially available product, such as "Irgacure-OXE01," "Irgacure-OXE02," "Irgacure-OXE04," and "IrgacureTPO" manufactured by BASF, "Omnirad907," "Omnirad369," "Omnirad379," "Omnirad379EG," "Omnirad819," and "OmniradTPO" manufactured by IGM, and "N-1919" manufactured by ADEKA.

[0083] From the viewpoints of improving photosensitivity, patterning ability, and physical properties of the photosensitive resin composition layer after curing of the photosensitive resin composition, the mass ratio of component (B) to component (1A) [component (B) / component (1A)] is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and particularly preferably 0.02 or more. The upper limit is preferably 0.2 or less, more preferably 0.1 or less, and even more preferably 0.05 or less.

[0084] From the viewpoints of improving photosensitivity, improving patterning ability, and improving the physical properties of the photosensitive resin composition layer after curing the photosensitive resin composition, the lower limit of the mass ratio of component (1A) to component (B) [component (1A) / component (B)] is preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more. The upper limit is preferably 60 or less, more preferably 50 or less, and even more preferably 45 or less.

[0085] From the viewpoints of improving photosensitivity, improving patterning ability, and improving the physical properties of the photosensitive resin composition layer after curing the photosensitive resin composition, the content of component (B) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 2% by mass or more, based on 100% by mass of the nonvolatile components of the photosensitive resin composition. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less.

[0086] To achieve the effects of the present invention more significantly, the total content of the components (1A) and (B) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more or 85% by mass or more, based on 100% by mass of the nonvolatile components of the photosensitive resin composition. The upper limit is preferably 99% by mass or less, more preferably 97% by mass or less or 95% by mass or less, and even more preferably 93% by mass or less or 90% by mass or less.

[0087] <(C) Crosslinking Agent> The photosensitive resin composition of the first embodiment contains a crosslinking agent (C) as component (C). When the photosensitive resin composition is irradiated with actinic rays and radicals are generated from the photopolymerization initiator (B), a crosslinking reaction of component (C) occurs, rendering the composition insoluble in the developer. This makes it possible to selectively remove the photosensitive resin composition from areas other than those where the crosslinking reaction has progressed during development, advantageously forming a negative pattern. Furthermore, by including component (C) in the photosensitive resin composition, the residual film rate can be increased. The component (C) may be used alone or in combination of two or more. Furthermore, component (C) does not include components that correspond to component (A).

[0088] As component (C), a compound capable of causing a crosslinking reaction during development can be used. The lower limit of the number of reactive sites per molecule of component (C) that undergo a crosslinking reaction (hereinafter sometimes referred to as the "number of functional groups") is preferably 1 or more, more preferably 2 or more. The upper limit of the number of functional groups is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 6 or less, 4 or less, or 3 or less. Examples of component (C) include (C1) a compound having an ethylenically unsaturated bond, (C2) a compound having two or more epoxy groups, a nitrogen-containing compound containing two or more methylol groups and / or alkoxymethyl groups, a condensate of a nitrogen-containing compound containing two or more methylol groups and / or alkoxymethyl groups, and a phenol compound having two or more methylol groups or alkoxymethyl groups. Examples of nitrogen-containing compounds containing two or more methylol groups and / or alkoxymethyl groups include melamine compounds containing two or more methylol groups and / or alkoxymethyl groups, guanamine compounds containing two or more methylol groups and / or alkoxymethyl groups, glycoluril compounds containing two or more methylol groups and / or alkoxymethyl groups, etc. As component (C), (C1) a compound having an ethylenically unsaturated bond or (C2) a compound having two or more epoxy groups is preferred, and (C1) a compound having an ethylenically unsaturated bond is more preferred.

[0089] <(C1) Compound having an ethylenically unsaturated bond> In one embodiment of the present invention, component (C) preferably includes (C1) a compound having an ethylenically unsaturated bond. When component (C) is a compound having (C1) an ethylenically unsaturated bond, it is more preferable that at least one of the carbon atoms at the α-position of the ethylenically unsaturated bond is a carbon atom of a carbonyl group or a carbon atom of an aromatic group. The carbon atom at the α-position of the ethylenically unsaturated bond refers to the first carbon atom adjacent to the carbon atom bonded by a carbon-carbon double bond.

[0090] The ethylenically unsaturated bond represents a carbon-carbon double bond. Therefore, component (C1) may contain a group having an ethylenically unsaturated bond (hereinafter, referred to as "ethylenically unsaturated group" as appropriate). The ethylenically unsaturated group is typically a monovalent group, such as a vinyl group, allyl group, propargyl group, butenyl group, styryl group, ethynyl group, phenylethynyl group, maleimide group, nadimide group, or (meth)acryloyl group. From the viewpoint of photoradical polymerization reactivity, a (meth)acryloyl group or an allyl group is preferred. The term "(meth)acryloyl group" encompasses methacryloyl groups, acryloyl groups, and combinations thereof. Since component (C1) contains an ethylenically unsaturated group, it is photoradical polymerizable. For photoradical polymerization under general conditions, compounds having a carbonyl group or an aromatic group at at least one α-position of the ethylenically unsaturated bond are preferred. The lower limit for the number of ethylenically unsaturated groups per molecule of component (C1) is preferably at least 1, and more preferably at least 2. The upper limit is preferably at most 30, more preferably at most 20, even more preferably at most 10, and particularly preferably at most 6, 4, or 3. Furthermore, when component (C1) contains two or more ethylenically unsaturated groups per molecule, these ethylenically unsaturated groups may be the same or different.

[0091] In one embodiment of the present invention, the component (C1) is preferably a compound represented by the following formula (C-1). [ka] (In formula (C-1), R 1c each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms; Z 1c 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 1c represents an organic group with a valence of nc, where nc is a positive integer of 2 to 6.

[0092] R1c are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1-butyl group, a s-butyl group, and a t-butyl group. Among these, R 1c is preferably a hydrogen atom or a methyl group, more preferably a methyl group.

[0093] Z 1c 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.

[0094] As the linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkylene group having 1 to 10 carbon atoms is preferred, and a linear or branched alkylene group having 1 to 6 carbon atoms is more preferred. Examples of such alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group, with a methylene group being preferred. The alkylene group may also be an oxyalkylene group containing an oxygen atom, and specific examples of such groups include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 20. [ka]

[0095] The arylene group which may contain an oxygen atom is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, still more preferably an arylene group having 6 to 12 carbon atoms, and particularly preferably an arylene group having 6 to 10 carbon atoms. Examples of such arylene groups include a phenylene group and a naphthylene group. The arylene group may also contain an oxygen atom, and specific examples of such groups include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 4. [ka]

[0096] As the linear or branched alkenylene group having 2 to 20 carbon atoms which may contain an oxygen atom, a linear or branched alkenylene group having 2 to 10 carbon atoms is preferred, and a linear or branched alkenylene group having 2 to 6 carbon atoms is more preferred. Examples of such alkenylene groups include ethenylene, propenylene, butenylene, pentenylene, and hexenylene. The alkenylene group may also be an oxyalkenylene group containing an oxygen atom, and specific examples of such groups include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 10. The alkenylene group is preferably a propenylene group. [ka]

[0097] Among them, Z 1c As the alkyl group, a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom is preferred, a methylene group or an oxyalkylene group is more preferred, and a methylene group is even more preferred.

[0098] A 1c represents an organic group with a valence of nc. 1cExamples of A include linear, cyclic, or branched C1-10 nc-valent hydrocarbon groups which may contain an oxygen atom, nc-valent groups derived from bisphenol, nc-valent groups derived from fluorene, nc-valent groups derived from tricyclodecane, and nc-valent groups derived from an isocyanuric group. Examples of nc-valent hydrocarbon groups which may contain an oxygen atom include nc-valent aliphatic hydrocarbon groups which may contain an oxygen atom, and nc-valent aromatic hydrocarbon groups which may contain an oxygen atom. nc-valent aliphatic hydrocarbon groups which may contain an oxygen atom are preferred, and when nc is 2, for example, an alkylene group is preferred. A 1c Specific examples of the group represented by include the following: In the formula, "*" represents a bond. [ka]

[0099] nc represents a positive integer of 2 to 6. nc is preferably a positive integer of 2 to 5, more preferably a positive integer of 2 to 4, and even more preferably 2 or 3.

[0100] In one embodiment of the present invention, the component (C1) is preferably a compound represented by the following formula (C-2). [ka] (In formula (C-2), R 2c each independently represents a hydrogen atom or a methyl group.

[0101] R 2c represents a hydrogen atom or a methyl group, and a methyl group is preferred.

[0102] Specific examples of the component (C1) represented by formula (C-1) include the following compounds (CL-1) to (CL-13). As the component (C1), the compound (CL-1), the compound (CL-2), the compound (CL-12) or the compound (CL-13) is preferred, the compound (CL-1) or the compound (CL-2) is more preferred, and the compound (CL-2) is even more preferred. [ka]

[0103] Component (C1) can be a commercially available product. Examples of commercially available products of component (C1) represented by formula (C-1) above include NK Ester D-TMP, TMPT, A-TMPT, 4G, 9G, 14G, 23G, and DCP manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd., and SR209, CN2301, and CN2304 manufactured by Sartomer Japan.

[0104] In one embodiment of the present invention, the component (C1) is preferably a compound represented by the following formula (C-3). [ka] (In the formula, R 11c , R 12c , R 13c , R 14c , R 15c and R 16c each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; Z c represents a divalent organic group.

[0105] R 11c , R 12c , R 13c , R 14c , R 15c and R 16c 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, such as 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 an isopropyl group, with a methyl group being preferred. 11c , R 12c , R 13c , R 14c , R15c and R 16c 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.

[0106] Z c represents a divalent organic group. Examples of divalent organic groups include divalent aliphatic hydrocarbon groups, divalent aromatic hydrocarbon groups, divalent groups containing heteroatoms, and divalent groups consisting of a combination of two or more of these. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms.

[0107] The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic. The divalent aliphatic hydrocarbon group may be saturated or unsaturated. The divalent aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Examples of the divalent aliphatic hydrocarbon group include alkylene groups, alkenylene groups, and alkynylene groups. Examples of the alkylene group include methylene groups, ethylene groups, propylene groups, butylene groups, pentylene groups, and hexylene groups. Examples of the alkenylene group include ethenylene groups, propenylene groups, butenylene groups, pentenylene groups, and hexenylene groups. Examples of the alkynylene group include ethynylene groups and propynylene groups.

[0108] The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. 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.

[0109] Examples of the divalent group containing a hetero atom include -O-, -S-, -NH-, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -C(=O)-NH-, -S(=O)2-, -S(=O)2-O-, and the groups shown below. [ka] (* represents a bond.)

[0110] Examples of divalent groups formed by a combination of two or more groups include those formed by bonding a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, and a divalent group containing a heteroatom; those formed by bonding a divalent aromatic hydrocarbon group and a divalent group containing a heteroatom; and those formed by bonding a divalent aliphatic hydrocarbon group and a divalent group containing a heteroatom. Specific examples of the divalent groups formed by a combination of two or more groups include the following groups (X-7) to (X-13). In the groups (X-7) to (X-13), * represents a bond. As the divalent group formed by a combination of two or more groups, groups (X-7) to (X-10) are preferred, groups (X-7) and (X-8) are more preferred, and groups (X-7) are even more preferred. [ka]

[0111] Z c The divalent organic group in the formula (I) 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, isopropyl, n-butyl, and t-butyl; halogen atoms such as fluorine, chlorine, and bromine; alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, and propoxy; hydroxy groups; and halogen-substituted alkyl groups, such as trifluoromethyl. The above-mentioned substituents may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). The substituent may be contained alone or in combination of two or more types. When the divalent organic group has a substituent, the substituent is preferably a hydroxy group.

[0112] Specific examples of the component (C1) represented by formula (C-3) 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 compounds represented by the following formulas (C-3-1) to (C-3-4). Of these, the compound represented by formula (C-3-1) or the compound represented by formula (C-3-2) is preferred, and the compound represented by formula (C-3-1) is more preferred. [ka]

[0113] The component (C1) represented by formula (C-3) can be a commercially available product, such as "BANI-X" and "BANI-M" manufactured by Maruzen Petrochemical Co., Ltd., "DAD" manufactured by Nisshoku Techno Fine Chemical Co., Ltd., or "DPNG" manufactured by Kuraray Co., Ltd.

[0114] When component (C) contains a compound (C1) having an ethylenically unsaturated bond, from the viewpoint of achieving remarkable effects of the present invention and excellent limiting resolution, the mass ratio of component (C1) to component (1A) [component (C1) / component (1A)] is preferably 0.01 or more, more preferably 0.03 or more, even more preferably 0.05 or more, and particularly preferably 0.1 or more. The upper limit is preferably 1 or less, more preferably 0.5 or less, even more preferably 0.2 or less, and particularly preferably 0.15 or less.

[0115] When the component (C) includes a compound (C1) having an ethylenically unsaturated bond, from the viewpoint of significantly achieving the effects of the present invention and obtaining excellent limiting resolution, the lower limit of the mass ratio of the component (1A) to the component (C1) [component (1A) / component (C1)] is preferably at least 1, more preferably at least 3, and even more preferably at least 5. The upper limit is preferably at most 25, more preferably at most 20, and even more preferably at most 15.

[0116] When the component (C) includes a compound (C1) having an ethylenically unsaturated bond, from the viewpoint of significantly achieving the effects of the present invention and obtaining excellent limiting resolution, the lower limit of the mass ratio of the component (C1) to the component (B) [component (C1) / component (B)] is preferably at least 1, more preferably at least 2, even more preferably at least 3, and particularly preferably at least 3.5. The upper limit is preferably at most 20, more preferably at most 10, even more preferably at most 8, and particularly preferably at most 6.

[0117] When component (C) includes a compound (C1) having an ethylenically unsaturated bond, the content of component (C1) is, from the viewpoint of significantly achieving the effects of the present invention and obtaining excellent limiting resolution, preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, particularly preferably 7% by mass or more or 9% by mass or more, based on 100% by mass of the non-volatile components of the photosensitive resin composition. The upper limit is preferably 40% by mass or less, 30% by mass or less, or 20% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less.

[0118] <(C2) Compounds having two or more epoxy groups> In one embodiment of the present invention, component (C) may contain (C2) a compound having two or more epoxy groups. By including (C2) a compound having two or more epoxy groups in the photosensitive resin composition, the strength of the cured product of the photosensitive resin composition can be improved. The compound having two or more epoxy groups may be used alone or in combination of two or more.

[0119] (C2) The number of epoxy groups contained in one molecule of the compound having two or more epoxy groups is 2 or more, and preferably 10 or less, more preferably 8 or less, and even more preferably 4 or less, from the viewpoint of obtaining excellent limiting resolution of the photosensitive resin composition and improving the mechanical strength of a cured product of the photosensitive resin composition.

[0120] (C2) Examples of compounds having two or more epoxy groups include aromatic epoxy compounds such as bixylenol-type epoxy compounds, bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol S-type epoxy compounds, bisphenol AF-type epoxy compounds, trisphenol-type epoxy compounds, naphthol novolac-type epoxy compounds, phenol novolac-type epoxy compounds, tert-butyl-catechol-type epoxy compounds, naphthalene-type epoxy compounds, naphthol-type epoxy compounds, anthracene-type epoxy compounds, cresol novolac-type epoxy compounds, biphenyl-type epoxy compounds, and naphthylene ether-type epoxy compounds; aliphatic epoxy compounds such as epoxy compounds having a butadiene structure, cyclohexane-type epoxy compounds, cyclohexanedimethanol-type epoxy compounds, trimethylol-type epoxy compounds, and tetraphenylethane-type epoxy compounds; alicyclic epoxy compounds; heterocyclic epoxy compounds; glycidyl ether-type epoxy compounds; and glycidylamine-type epoxy compounds. Among these, from the viewpoint of significantly obtaining the effects of the present invention, aromatic epoxy compounds are preferred, and among aromatic epoxy compounds, naphthalene-type epoxy compounds or bisphenol A-type epoxy compounds are preferred, with naphthalene-type epoxy compounds being more preferred.

[0121] Specific examples of aromatic epoxy compounds include "HP4032," "HP4032D," and "HP4032SS" (naphthalene-type epoxy compounds) manufactured by DIC Corporation; "828US," "jER828EL," "825," and "Epikote 828EL" (bisphenol A-type epoxy compounds) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F-type epoxy compounds) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; and "ZX105" manufactured by Nippon Steel Chemical & Material Co., Ltd. 9 (a mixture of bisphenol A and bisphenol F epoxy compounds); DIC's "HP4032H" (a naphthalene-type epoxy compound); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy compounds); DIC's "N-690" (a cresol novolac-type epoxy compound); DIC's "N-695" (a cresol novolac-type epoxy compound); Nippon Kayaku's "EPPN-502H" (a trisphenol-type epoxy compound); Nippon Kayaku's "NC7000L" " (naphthol novolac type epoxy compound); "NC3000H", "NC3000", "NC3000L", and "NC3100" (biphenyl type epoxy compounds) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthol type epoxy compound) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol novolac type epoxy compound) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YL6121" (biphenyl type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "YX4000H", "YX4000", and "YX4000HK" manufactured by Mitsubishi Chemical Corporation (bixylenol-type epoxy compound); "YX8800" manufactured by Mitsubishi Chemical Corporation (anthracene-type epoxy compound); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd.; "YL7760" manufactured by Mitsubishi Chemical Corporation (bisphenol AF-type epoxy compound); "YL7800" manufactured by Mitsubishi Chemical Corporation (fluorene-type epoxy compound); "jER1010" manufactured by Mitsubishi Chemical Corporation (solid bisphenol A-type epoxy compound); and "jER1031S" manufactured by Mitsubishi Chemical Corporation (tetraphenylethane-type epoxy compound).

[0122] The epoxy equivalent of the (C2) compound having two or more epoxy groups is preferably 50 g / eq to 5000 g / eq, more preferably 50 g / eq to 3000 g / eq, even more preferably 80 g / eq to 2000 g / eq, and even more preferably 110 g / eq to 1000 g / eq. Within this range, the crosslink density of the cured product of the photosensitive resin composition is sufficient, resulting in an insulating layer with low surface roughness. The epoxy equivalent is the mass of a resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0123] From the viewpoint of significantly achieving the desired effects of the present invention, the weight-average molecular weight (Mw) of the compound (C2) having two or more epoxy groups is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. The weight-average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0124] When component (C) contains a compound (C2) having two or more epoxy groups, the content of component (C2) 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, based on 100% by mass of the nonvolatile components of the photosensitive resin composition, from the viewpoints of obtaining excellent limiting resolution and improving the mechanical strength of the cured product. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0125] From the viewpoint of achieving significant effects of the present invention and excellent limiting resolution, the mass ratio of component (C) to component (1A) [component (C) / component (1A)] is preferably 0.01 or more, more preferably 0.03 or more, even more preferably 0.05 or more, and particularly preferably 0.1 or more, and the upper limit is preferably 1 or less, more preferably 0.5 or less, even more preferably 0.2 or less, and particularly preferably 0.15 or less.

[0126] From the viewpoint of achieving significant effects of the present invention and excellent limiting resolution, the lower limit of the mass ratio of the component (1A) to the component (C) [component (1A) / component (C)] is preferably at least 1, more preferably at least 3, and even more preferably at least 5. The upper limit is preferably at most 25, more preferably at most 20, and even more preferably at most 15.

[0127] From the viewpoint of achieving significant effects of the present invention and excellent limiting resolution, the lower limit of the mass ratio of component (C) to component (B) [component (C) / component (B)] is preferably at least 1, more preferably at least 2, even more preferably at least 3, and particularly preferably at least 3.5. The upper limit is preferably at most 20, more preferably at most 10, even more preferably at most 8, and particularly preferably at most 6.

[0128] From the viewpoint of achieving a significant effect of the present invention and an excellent limiting resolution, the content of component (C) is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more or 9% by mass or more, based on 100% by mass of the nonvolatile components of the photosensitive resin composition. The upper limit is preferably 40% by mass or less, 30% by mass or less, or 20% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less.

[0129] To achieve the effects of the present invention more significantly, the total content of components (1A) and (C) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more or 80% by mass or more, and particularly preferably 85% by mass or more, 90% by mass or more, or 95% by mass or more, based on 100% by mass of the non-volatile components of the photosensitive resin composition. The upper limit is preferably 99% by mass or less, more preferably 98% by mass or less or 97% by mass or less, and even more preferably 96% by mass or less.

[0130] To achieve the effects of the present invention more significantly, the total content of components (1A), (B), and (C) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more or 80% by mass or more, and particularly preferably 85% by mass or more, 90% by mass or more, 95% by mass or more, or 97% by mass or more, based on 100% by mass of the non-volatile components of the photosensitive resin composition. There is no particular upper limit, but it may be 100% by mass, or may be 99.9% by mass or less, 99.5% by mass or less, or 99% by mass or less, for example.

[0131] <(D) Adhesion aid> The photosensitive resin composition of the first embodiment may contain an adhesion aid (D) as an optional component, and preferably contains an adhesion aid (D). By including the adhesion aid (D) in the photosensitive resin composition, the adhesion strength between the substrate and the cured product of the photosensitive resin composition can be improved. The component (D) may be used alone or in combination of two or more. Furthermore, the component (D) is a component different from the components (A) to (C).

[0132] As the (D) adhesion aid, a compound that improves the adhesive strength between the substrate and the film formed using the photosensitive resin composition can be used. Examples of such compounds include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-3-triethoxysilyl]propylamide)-2,5-Dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propyl succinic anhydride, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, 3- Mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2- Mercaptoethyl tripropoxysilane, 2-mercaptoethyl tripropoxysilane, 2-mercaptoethyl ethoxydipropoxysilane, 2-mercaptoethyl dimethoxypropoxysilane, 2-mercaptoethyl methoxydipropoxysilane, 4-mercaptobutyl trimethoxysilane, 4-mercaptobutyl triethoxysilane, 4-mercaptobutyl tripropoxysilane, N-(3-triethoxysilylpropyl)urea, N-(3-trimethoxysilylpropyl)urea, aminotriazine ring and ethoxysilyl Silane coupling agents such as compounds having a hydroxyl group; aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate; 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-amino-5-mercapto-1H-1,2,4-triazole, 5-amino-1,2,4-triazole-3-carboxylic acid, 3,5-diphenyl-1,2,Examples of the adhesion aid include triazole-based adhesion aids such as 4-triazole. Among these, from the viewpoint of significantly achieving the effects of the present invention, the adhesion aid (D) is preferably a silane coupling agent or a triazole-based adhesion aid, and more preferably a triazole-based adhesion aid. Furthermore, among the triazole-based adhesion aids, 3,5-diamino-1,2,4-triazole is preferred.

[0133] (D) The adhesion aid can be a commercially available product. Examples of commercially available products include "KBM-403" (3-glycidoxypropyltriethoxysilane), "KBM-803" (3-mercaptopropyltrimethoxysilane), "LS-1375" (3-mercaptopropylmethyldimethoxysilane), and "LS-3610" (N-(3-triethoxysilylpropyl)urea) manufactured by Shin-Etsu Chemical Co., Ltd.; "Sila-Ace S810" (3-mercaptopropyltrimethoxysilane) manufactured by Chisso Corporation; and "SIM6475.0" (3-mercaptopropyltriethoxysilane) and "SIM6474" manufactured by Azmax Corporation. .0" (3-mercaptopropylmethyldimethoxysilane), "SIM6473.5C" (mercaptomethyltrimethoxysilane), "SIM6473.0" (mercaptomethylmethyldimethoxysilane), "SIU9055.0" (N-(3-triethoxysilylpropyl)urea), "SIU9058.0" (N-(3-trimethoxysilylpropyl)urea); "VD-5" (compound having an aminotriazine ring and an ethoxysilyl group) manufactured by Shikoku Chemical Industry Co., Ltd.; 3,5-diamino-1,2,4-triazole manufactured by Tokyo Chemical Industry Co., Ltd., etc.

[0134] When the photosensitive resin composition contains component (D), the content of component (D) is, from the viewpoints of substrate adhesion and mechanical strength, preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.02% by mass or more, particularly preferably 0.05% by mass or more or 0.08% by mass or more, based on 100% by mass of the non-volatile components of the photosensitive resin composition. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less or 0.5% by mass or less, particularly preferably 0.2% by mass or less.

[0135] When the photosensitive resin composition contains the component (D), from the viewpoint of substrate adhesion and mechanical strength, the lower limit of the mass ratio of the component (D) to the component (1A) [component (D) / component (1A)] is preferably 10 -5 More than or equal to 10 -4 More preferably, 2×10 -4 More preferably, 5 × 10 -4 The upper limit is preferably 10 -1 Less than or equal to 10, more preferably -2 Less than 5 × 10, more preferably -3 Below 2 × 10, particularly preferably -3 The following is the result.

[0136] When the photosensitive resin composition contains component (D), from the viewpoints of substrate adhesion and mechanical strength, the mass ratio of component (D) to component (B) [component (D) / component (B)] is preferably 0.001 or 0.005, more preferably 0.01, and even more preferably 0.02. The upper limit is preferably 1 or less, more preferably 0.5 or less, even more preferably 0.1 or less, and particularly preferably 0.05 or less.

[0137] When the photosensitive resin composition contains component (D), from the viewpoints of substrate adhesion and mechanical strength, the mass ratio of component (D) to component (C) [component (D) / component (C)] is preferably 0.0001 or 0.0005, more preferably 0.001, even more preferably 0.004, and particularly preferably 0.006. The upper limit is preferably 0.1, more preferably 0.05, even more preferably 0.02, and particularly preferably 0.01.

[0138] <(E) Sensitizer> The photosensitive resin composition of the first embodiment may contain a sensitizer (E) as an optional component, and preferably contains a sensitizer (E). When the photosensitive resin composition contains a sensitizer (E), the photosensitivity of the photosensitive resin composition can be further improved. The component (E) may be used alone or in combination of two or more. Furthermore, the component (E) does not include components that fall under the category of component (B), and is a component that is different from the components (A), (C), and (D).

[0139] The component (E) can be a compound that can improve 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; p-dimethylaminocinnamic acid indanones such as 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, etc.; acetones such as 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, etc.; 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminobenzyl Coumarins such as coumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, and 3-ethoxycarbonyl-7-diethylaminocoumarin; amines such as N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, and isoamyl diethylaminobenzoate; 2-mercaptobenzimidazoline heterocycles such as 1-phenyl-5-mercaptotetrazole, 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. Amines are preferred, ethanolamines are more preferred, and N-phenyldiethanolamine is even more preferred.

[0140] In one embodiment of the present invention, the component (E) is preferably a heterocycle, and more preferably a compound represented by the following formula (E-1), from the viewpoint of achieving the effects of the present invention more significantly. [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.

[0141] R 1e represents a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, a halogen atom, a hydroxy group, a methoxy group, or a t-butoxy group. Examples of the linear or branched alkyl group having 1 to 7 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a t-butyl group. Among these, R 1e is preferably a hydrogen atom, a hydroxy group, a methoxy group, or a t-butoxy group, more preferably a hydrogen atom or a hydroxy group, and even more preferably a hydrogen atom.

[0142] R 1e The bonding position of may be any of the ortho-position, meta-position, and para-position based on the position of the phenylene group bonding to the nitrogen atom of mercaptotetrazole, but the para-position is preferred from the viewpoint of significantly obtaining the effects of the present invention.

[0143] The compound represented by formula (E-1) is preferably any compound selected from the group consisting of compounds represented by formula (E-2) below and compounds represented by formula (E-3) below. [ka]

[0144] In one embodiment of the present invention, the component (E) is preferably an ethanolamine, and more preferably a compound represented by the following formula (E-4), from the viewpoint of significantly achieving the effects of the present invention. [ka] (In formula (E-4), R 2e represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a hydroxyalkyl group having 1 to 10 carbon atoms. 3e represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0145] In formula (E-4), R 2e represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a hydroxyalkyl group having 1 to 10 carbon atoms.

[0146] The alkyl group is a chain (straight-chain or branched) alkyl group or a cyclic alkyl group. The number of carbon atoms in the alkyl group is 1 to 10, preferably 1 to 5, and more preferably 1 to 3. Examples of the chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a decyl group. Of these, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is preferred, a methyl group or an ethyl group is more preferred, and an ethyl group is even more preferred. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

[0147] A hydroxyalkyl group is a compound in which some of the hydrogen atoms of the alkyl group are substituted with hydroxy groups. The number of hydroxy groups in the hydroxyalkyl group is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 1. The number of carbon atoms in the hydroxyalkyl group is 1 to 10, preferably 1 to 5, and more preferably 1 to 3. Examples of chain hydroxyalkyl groups include a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 2-hydroxy-n-propyl group, with a 2-hydroxyethyl group or a 3-hydroxy-n-propyl group being preferred, and a 2-hydroxyethyl group being more preferred. Furthermore, examples of cyclic hydroxyalkyl groups include a 4-hydroxycyclohexyl group.

[0148] Among these, R 2e is preferably a hydrogen atom, an ethyl group or a 2-hydroxyethyl group, more preferably an ethyl group or a 2-hydroxyethyl group, and even more preferably a 2-hydroxyethyl group.

[0149] In formula (E-4), R 3e represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0150] The alkyl group is a chain (straight-chain or branched) alkyl group or a cyclic alkyl group. The number of carbon atoms in the alkyl group is 1 to 10, preferably 1 to 5, and more preferably 1 to 3. Examples of the chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a decyl group. Preferred are a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. More preferred are a methyl group or an ethyl group, and even more preferred is a methyl group. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

[0151] Among these, R 3eis preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0152] R 3e The bonding position of may be any of the ortho-position, meta-position, and para-position with respect to the position of the phenylene group bonded to the nitrogen atom clearly shown in formula (E-4), and the para-position is preferred from the viewpoint of significantly obtaining the effects of the present invention.

[0153] Specific examples of the compound represented by formula (E-4) include N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, and N-phenylethanolamine, with N-phenyldiethanolamine being preferred.

[0154] When the photosensitive resin composition contains component (E), the content of component (E) is, from the viewpoint of significantly achieving the effects of the present invention and obtaining appropriate photosensitivity, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 1.5% by mass or more, based on 100% by mass of the non-volatile components of the photosensitive resin composition. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less or 2% by mass or less.

[0155] When the photosensitive resin composition contains component (E), from the viewpoint of significantly achieving the effects of the present invention and obtaining appropriate photosensitivity, the mass ratio of component (E) to component (1A) [component (E) / component (1A)] is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and particularly preferably 0.015 or more. The upper limit is preferably 1 or less, more preferably 0.5 or less, even more preferably 0.1 or less, and particularly preferably 0.05 or less or 0.03 or less.

[0156] When the photosensitive resin composition contains the component (E), from the viewpoint of significantly achieving the effects of the present invention and obtaining appropriate photosensitivity, the mass ratio of the component (E) to the component (B) [component (E) / component (B)] is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, particularly preferably 0.3 or more or 0.5 or more. The upper limit is preferably 10 or less, more preferably 5 or less, even more preferably 1 or less, particularly preferably 0.8 or less.

[0157] When the photosensitive resin composition contains component (E), from the viewpoint of significantly achieving the effects of the present invention and obtaining appropriate photosensitivity, the mass ratio of component (E) to component (C) [component (E) / component (C)] is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.08 or more or 0.1 or more, and particularly preferably 0.15 or more. The upper limit is preferably 10 or less, more preferably 5 or less, even more preferably 1 or less, and particularly preferably 0.5 or less or 0.3 or less.

[0158] When the photosensitive resin composition contains the component (D) and the component (E), from the viewpoint of significantly achieving the effects of the present invention and obtaining appropriate photosensitivity, the lower limit of the mass ratio of the component (E) to the component (D) [component (E) / component (D)] is preferably at least 1, more preferably at least 5, even more preferably at least 10, and particularly preferably at least 15. The upper limit is preferably at most 1,000, more preferably at most 100, even more preferably at most 50, and particularly preferably at most 40, 30, or 25.

[0159] <(F) Surfactant> The photosensitive resin composition of the first embodiment may contain a surfactant (F) as an optional component, and preferably contains a surfactant (F). By including the component (F) in the resin composition, a more uniform coating film can be formed when the resin composition is applied. The surfactant (F) may be used alone or in combination of two or more. Furthermore, the component (F) is a component different from the components (A) to (E).

[0160] Examples of the (F) surfactant include fluorine-based surfactants, silicone-based surfactants, polyether-based surfactants, poly(meth)acrylate-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, etc. Among these, polyether-based surfactants are preferred as the (F) component.

[0161] Examples of fluorosurfactants include fluorosurfactants composed of a compound having a fluoroalkyl group or a fluoroalkylene chain at least at any one of the terminal, main chain, and side chain. Specific examples include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol bis(1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol bis(1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol bis(1,1,2,2-tetrafluorobutyl) ether, and hexapropylene glycol bis(1,1,2,2-tetrafluorobutyl) ether. Examples of such perfluoroalkyl esters include glycol bis(1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N-[3-(perfluorooctanesulfonamido)propyl]-N,N'-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salts, perfluoroalkyl-N-ethylsulfonylglycine salts, bis(N-perfluorooctylsulfonyl-N-ethylaminoethyl)phosphate, and monoperfluoroalkylethyl phosphate esters.

[0162] Commercially available fluorine-based surfactants include "Megafac (registered trademark) F-142D", "Megafac (registered trademark) F-172", "Megafac (registered trademark) F-173", "Megafac (registered trademark) F-183", "Megafac (registered trademark) F-444", "Megafac (registered trademark) F-445", "Megafac (registered trademark) F-470", "Megafac (registered trademark) F-475", "Megafac (registered trademark) F-477", "Megafac (registered trademark) F-555", and "Megafac (registered trademark) F-559" (all trade names, manufactured by DIC Corporation), "Ftop (registered trademark) EF301", "Ftop (registered trademark) 303", and "Ftop (registered trademark) 352" (all trade names, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), "Florald (registered trademark) FC-430", "Florald (registered trademark) FC-431" (all trade names, manufactured by Sumitomo 3M Limited), and "Asahiguard (registered trademark) Examples of such polyolefin resins include "AG710" (trade name, manufactured by Asahi Glass Co., Ltd.), "Surflon (registered trademark) S-382", "Surflon (registered trademark) SC-101", "Surflon (registered trademark) SC-102", "Surflon (registered trademark) SC-103", "Surflon (registered trademark) SC-104", "Surflon (registered trademark) SC-105", and "Surflon (registered trademark) SC-106" (all trade names, manufactured by AGC Seimi Chemical Co., Ltd.), "BM-1000", "BM-1100" (all trade names, manufactured by Yusho Co., Ltd.), "NBX-15", "FTX-218", and "DFX-218" (all trade names, manufactured by Neos Corporation).

[0163] Commercially available silicone surfactants include, for example, "SH28PA," "SH7PA," "SH21PA," "SH30PA," and "ST94PA" (all trade names, manufactured by Dow Corning Toray Co., Ltd.), "BYK-301," "BYK-307," "BYK-331," "BYK-333," and "BYK-345" (all trade names, manufactured by BYK-Chemie Japan K.K.).

[0164] Commercially available polyether surfactants include, for example, "KP-341," "KP-360A," "KP-101," "KP-106," "KP-109," "KP-110," "KP-112," "KP-118," "KP-120," "KP-121," "KP-124," "KP-125," "KP-126," "KP-301," and "KP-306" (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), with "KP-341" being preferred.

[0165] When the photosensitive resin composition contains component (F), the content of component (F) is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more or 0.015% by mass or more, and particularly preferably 0.02% by mass or more, when the total components of the resin composition is taken as 100% by mass, from the viewpoint of forming a more uniform coating film when the resin composition is applied. The upper limit is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less.

[0166] When the photosensitive resin composition contains component (F), the content of component (F) is, from the viewpoint of forming a more uniform coating film when the resin composition is applied, preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more or 0.03% by mass or more, particularly preferably 0.05% by mass or more or 0.08% by mass or more, based on 100% by mass of the nonvolatile components of the resin composition. The upper limit is preferably 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, particularly preferably 0.3% by mass or less or 0.2% by mass or less.

[0167] When the photosensitive resin composition contains the component (F), from the viewpoint of forming a more uniform coating film when the resin composition is applied, the lower limit of the mass ratio of the component (F) to the component (1A) [component (F) / component (1A)] is preferably 10 -5 More than or equal to 10 -4 More preferably, 2×10 -4 More preferably, 5 × 10 -4The upper limit is preferably 10 -1 Less than or equal to 10, more preferably -2 Less than 5 × 10, more preferably -3 Below 2 × 10, particularly preferably -3 The following is the result.

[0168] When the photosensitive resin composition contains the component (F), from the viewpoint of forming a more uniform coating film when the resin composition is applied, the lower limit of the mass ratio of the component (F) to the component (B) [component (F) / component (B)] is preferably 0.001 or more or 0.005 or more, more preferably 0.01 or more, and even more preferably 0.02. The upper limit is preferably 1 or less, more preferably 0.5 or less, even more preferably 0.1 or less, and particularly preferably 0.05 or less.

[0169] When the photosensitive resin composition contains the component (F), from the viewpoint of forming a more uniform coating film when the resin composition is applied, the mass ratio of the component (F) to the component (C) [component (F) / component (C)] is preferably 0.0001 or 0.0005, more preferably 0.001, even more preferably 0.004, and particularly preferably 0.006. The upper limit is preferably 0.1, more preferably 0.05, even more preferably 0.02, and particularly preferably 0.01.

[0170] When the photosensitive resin composition contains the component (D) and the component (F), from the viewpoint of forming a more uniform coating film when the resin composition is applied, the mass ratio of the component (F) to the component (D) [component (F) / component (D)] is preferably 0.01 or 0.1 or more, more preferably 0.5 or more, even more preferably 0.7 or more, and particularly preferably 0.9 or more. The upper limit is preferably 100 or less, more preferably 10 or less, even more preferably 5 or less, and particularly preferably 3 or 2 or less.

[0171] When the photosensitive resin composition contains the component (E) and the component (F), from the viewpoint of forming a more uniform coating film when the resin composition is applied, the mass ratio of the component (F) to the component (E) [component (F) / component (E)] is preferably 0.001 or more or 0.005 or more, more preferably 0.01 or more, even more preferably 0.02 or more, and particularly preferably 0.04 or more. The upper limit is preferably 5 or less, more preferably 1 or less, even more preferably 0.5 or less, and particularly preferably 0.1 or less or 0.08 or less.

[0172] <(G) Organic Solvent> The photosensitive resin composition of the first embodiment may contain an organic solvent (G) as an optional component. The organic solvent (G) is a volatile component, and any organic solvent that can dissolve at least one of the components (A) to (F) and the component (H) can be used. The component (G) may be used alone or in combination of two or more.

[0173] Examples of component (G) include organic solvents composed of atoms selected from carbon, oxygen, nitrogen, phosphorus, sulfur, halogen, and hydrogen atoms. From the viewpoint of safety, component (G) is preferably an organic solvent composed of atoms selected from carbon, oxygen, and hydrogen atoms, and more preferably an organic solvent composed of carbon, oxygen, and hydrogen atoms.

[0174] Examples of component (G) include glycol-based organic solvents, glycol ether-based organic solvents, glycol ether ester-based organic solvents, ketone-based organic solvents, ester-based organic solvents, ether-based organic solvents, alcohol-based organic solvents, aliphatic hydrocarbon-based organic solvents, aromatic organic solvents, nitrogen-based organic solvents, sulfur-based organic solvents, and halogen-based organic solvents. Examples of nitrogen-based organic solvents include amide-based organic solvents, urea-based organic solvents, and nitrile-based organic solvents. From the viewpoint of safety, component (G) is preferably an ester-based organic solvent, ketone-based organic solvent, glycol-based organic solvent, glycol ether-based organic solvent, or glycol ether ester-based organic solvent, more preferably an ester-based organic solvent or ketone-based organic solvent, and particularly preferably a ketone-based organic solvent.

[0175] Examples of glycol-based organic solvents include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and trimethylene glycol.

[0176] Examples of glycol ether organic solvents include cellosolves such as ethylene glycol monomethyl ether (also known as methyl cellosolve), ethylene glycol monoethyl ether (also known as cellosolve), ethylene glycol monopropyl ether (also known as propyl cellosolve), ethylene glycol monobutyl ether (also known as butyl cellosolve), ethylene glycol monoisobutyl ether (also known as isobutyl cellosolve), ethylene glycol mono-tert-butyl ether (also known as tert-butyl cellosolve), and ethylene glycol monohexyl ether; diethylene glycol monomethyl ether (also known as methyl carbitol), diethylene glycol monoethyl ether ( carbitols such as diethylene glycol monopropyl ether (also known as propyl carbitol) and diethylene glycol monobutyl ether (DB) (also known as butyl carbitol); propylene glycol ethers such as propylene glycol monomethyl ether (PGM), propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; and dipropylene glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether.

[0177] Examples of glycol ether ester organic solvents include cellosolve esters such as ethylene glycol monomethyl ether acetate (also known as methyl cellosolve acetate), ethylene glycol monoethyl ether acetate (also known as cellosolve acetate), and ethylene glycol monobutyl ether acetate (also known as butyl cellosolve acetate); carbitol esters such as diethylene glycol monoethyl ether acetate (EDGAc) (also known as carbitol acetate) and diethylene glycol monobutyl ether acetate (also known as butyl carbitol acetate); propylene glycol ether esters such as propylene glycol monomethyl ether acetate (PGMEAc) and propylene glycol monoethyl ether acetate; and dipropylene glycol ether esters such as dipropylene glycol monomethyl ether acetate.

[0178] Examples of ketone-based organic solvents include aliphatic acyclic ketones such as acetone, methyl ethyl ketone (MEK), diethyl ketone, 2-pentanone, methyl isobutyl ketone, 2-hexanone, 2-heptanone (MAK), and diisobutyl ketone; aliphatic cyclic ketones such as cyclopentanone, cyclohexanone (Anone), and 2-methylcyclohexanone; and aromatic ketones such as acetophenone. The lower limit of the number of carbon atoms in the ketone-based organic solvent is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. The upper limit of the number of carbon atoms in the ketone-based organic solvent is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.

[0179] Ester-based organic solvents are organic solvents having an ester structure that do not fall under the category of glycol ether ester-based organic solvents. Examples include fatty acid alkyl esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-pentyl acetate, isopentyl acetate, ethyl propionate, propyl propionate, and isopropyl propionate; hydroxy acid alkyl esters such as methyl lactate, ethyl lactate, and butyl lactate; keto acid alkyl esters such as methyl acetoacetate and ethyl acetoacetate; lactones such as γ-butyrolactone and α-acetyl-γ-butyrolactone; and aromatic esters such as methyl benzoate and ethyl benzoate. Lactones are preferred as ester-based organic solvents. Furthermore, the number of carbon atoms in the ester-based organic solvent is preferably 3 to 9.

[0180] The ether-based organic solvent is an organic solvent having an ether structure that does not fall under the category of glycol ether-based organic solvents or glycol ether ester-based organic solvents, and examples thereof include aliphatic acyclic ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; aliphatic cyclic ethers such as tetrahydrofuran, 1,4-dioxane, and 1,3-dioxolane; and aromatic ethers such as anisole and phenetole. The number of carbon atoms in the ether-based organic solvent is preferably 2 to 9.

[0181] Alcohol-based organic solvents are organic solvents having an alcohol structure that does not fall under the category of glycol-based organic solvents and glycol ether-based organic solvents, and examples thereof include aliphatic acyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-pentyl alcohol, isopentyl alcohol, sec-pentyl alcohol, tert-pentyl alcohol, neopentyl alcohol, n-hexyl alcohol, n-heptyl alcohol, isoheptyl alcohol, n-octyl alcohol, and 2-ethylhexyl alcohol; aliphatic cyclic alcohols such as cyclohexanol; and aromatic alcohols such as benzyl alcohol and phenethyl alcohol.

[0182] Examples of aliphatic hydrocarbon organic solvents include n-pentane, n-hexane, 2-methylpentane (also known as isohexane), n-heptane, n-octane, cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin, etc. The aliphatic hydrocarbon organic solvent preferably has 5 to 10 carbon atoms.

[0183] Examples of aromatic organic solvents include C benzene, toluene, o-xylene, m-xylene, p-xylene, and ethylbenzene. 6-8 Aromatic hydrocarbons: C9 aromatic hydrocarbons such as 1,2,3-trimethylbenzene, 1,3,5-trimethylbenzene (also known as mesitylene), 1,2,4-trimethylbenzene, 4-ethyltoluene, 3-ethyltoluene, and 2-ethyltoluene; C1 aromatic hydrocarbons such as 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, 3-ethyl-o-xylene, 4-ethyl-o-xylene, 2-ethyl-p-xylene, 1,2,3,5-tetramethylbenzene, and tetralin. 10 Examples include aromatic hydrocarbons and aromatic heterocyclic compounds such as pyridine, furan, thiophene, etc. The aromatic organic solvent preferably has 6 to 10 carbon atoms.

[0184] Examples of amide-based organic solvents include aliphatic acyclic amides such as N,N-dimethylacetamide and N,N-dimethylformamide, lactams such as N-methyl-2-pyrrolidone and N-cyclohexyl-2-pyrrolidone, and phosphoric acid amides such as hexamethylphosphoramide. The number of carbon atoms in the amide-based organic solvent is preferably 2 to 10.

[0185] Examples of urea-based organic solvents include tetramethylurea and 1,3-dimethyl-2-imidazolinone.

[0186] Examples of the nitrile organic solvent include acetonitrile, propionitrile, benzonitrile, etc. The nitrile organic solvent preferably has 2 to 10 carbon atoms.

[0187] An example of the sulfur-based organic solvent is dimethyl sulfoxide.

[0188] Examples of halogen-based organic solvents include chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, etc. The halogen-based organic solvent preferably has 1 to 10 carbon atoms.

[0189] Among these, γ-butyrolactone, cyclopentanone, cyclohexanone, propylene glycol, or propylene glycol monomethyl ether acetate is preferred, cyclohexanone or γ-butyrolactone is more preferred, and cyclohexanone is even more preferred.

[0190] When the photosensitive resin composition contains component (G), the content of component (G) may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, etc., based on 100% by mass of the entire photosensitive resin composition. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less. By keeping the content of component (G) within the above range, the photosensitive resin composition can be made into a varnish with an appropriate viscosity.

[0191] When the photosensitive resin composition contains component (G), from the viewpoint of obtaining a varnish with an appropriate viscosity, the lower limit of the mass ratio of component (G) to component (1A) [component (G) / component (1A)] is preferably 0.1 or more or 0.5 or more, more preferably 1 or more, even more preferably 1.5 or more, and particularly preferably 2 or more or 2.5 or more. The upper limit is preferably 10 or less, more preferably 8 or less, even more preferably 5 or less, and particularly preferably 4 or less or 3 or less.

[0192] <(H) Other Additives> The photosensitive resin composition of the first embodiment may further contain (H) other additives to the extent that the object of the present invention is not impaired. Examples of (H) other additives include 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 antifoaming agents; 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 phenolic curing agents and cyanate ester-based curing agents. Furthermore, the components (A) to (G) may also function as thermoplastic resins, colorants, polymerization inhibitors, thickeners, antifoaming agents, flame retardants, or curing agents. In this case, the component in question is considered to be one of components (A) to (G), not component (H).

[0193] [Photosensitive resin composition of second embodiment] The photosensitive resin composition of the second embodiment of the present invention contains (2A) a polyamic acid and / or polyamic acid ester having a structural unit represented by the following formula (A-1), a structural unit represented by the following formula (A-2), and a structural unit represented by the following formula (A-3) (hereinafter also referred to as "a polyamic acid and / or polyamic acid ester having a second specific structure"), (B) a photopolymerization initiator, and (C) a crosslinking agent. By incorporating the components (2A) to (C) in combination into the photosensitive resin composition, it is possible to obtain a cured product that has high solubility in organic solvents, exhibits excellent dielectric properties while maintaining a glass transition temperature, and exhibits reduced warping during film lamination.

[0194] The photosensitive resin composition of the second embodiment is suitable as a negative-type photosensitive resin composition. In a negative-type photosensitive resin composition, a crosslinking reaction or the like occurs in the area irradiated with actinic rays, and the area becomes insoluble in a developer. Therefore, it becomes possible to selectively remove the photosensitive resin composition from areas other than those where the crosslinking reaction has progressed during development, and a negative-type pattern can be advantageously formed. The area remaining after development has sufficient strength due to the crosslinking reaction or the like, and can be used as is as an insulating layer or the like in the form of a permanent film.

[0195] The photosensitive resin composition of the second embodiment may further contain optional components in addition to the components (2A) to (C). Examples of optional components include (D) an adhesion aid, (E) a sensitizer, (F) a surfactant, (G) an organic solvent, and (H) other additives. Each component contained in the photosensitive resin composition of the second embodiment will be described in detail below.

[0196] <(2A) Polyamic Acid and / or Polyamic Acid Ester Having a Second Specific Structure> The photosensitive resin composition of the second embodiment contains, as component (2A), a polyamic acid and / or a polyamic acid ester having a structural unit represented by the following formula (A-1), a structural unit represented by the following formula (A-2), and a structural unit represented by the following formula (A-3): [ka] (In formula (A-1), A represents a tetravalent organic group having an alicyclic structure. R 1 and R 2 each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms and an ethylenically unsaturated group. [ka] (In formula (A-2), R a1 , R a2 , R a3 and R a4 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 4 to 20 carbon atoms. 1 and X 2 each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and p represents an integer of 1 to 100. [ka] (In formula (A-3), Xa and Xb each independently represent a single bond, a group represented by formula (X-1) below, a group represented by formula (X-2) below, or a group represented by formula (X-3) below. x represents an integer of 0 to 5.) [ka] (In the formula, * represents a bond.)

[0197] The (2A) component contains a structural unit represented by formula (A-2), which can reduce the dielectric loss tangent of the cured product of the photosensitive resin composition. This is thought to be due to the low polarity of the structural unit represented by formula (A-2). Furthermore, the (2A) component contains a structural unit represented by formula (A-2), which can suppress warpage of the cured product. This is thought to be due to the structural unit represented by formula (A-2) forming a helical structure and having stress relaxation properties.

[0198] The structural unit represented by formula (A-3) in component (2A) enhances the solubility of component (2A) in organic solvents and increases the glass transition temperature of the cured product. Furthermore, the structural unit represented by formula (A-3) in component (2A) provides excellent limiting resolution. This means that small holes can be formed in the photosensitive resin composition by exposure and development.

[0199] In formula (A-1), each A independently represents a tetravalent organic group having an alicyclic structure. The alicyclic structure of A can enhance the solubility of component (2A) in organic solvents and increase the glass transition temperature of the cured product. The lower limit for the number of carbon atoms in A is preferably 6 or more, more preferably 7 or more, and even more preferably 8 or more. The upper limit for the number of carbon atoms in A is preferably 26 or less, more preferably 22 or less, even more preferably 18 or less, and particularly preferably 14 or less or 10 or less. Furthermore, A is preferably a tetravalent organic group having a 6-membered alicyclic structure.

[0200] Examples of A include the following groups (i) to (iii), with group (i) being preferred: In the formula, * represents a bond. [ka]

[0201] In formula (A-1), R 1 and R 2 each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms and an ethylenically unsaturated group. The monovalent group having 1 to 20 carbon atoms and an ethylenically unsaturated group preferably has 3 to 15 carbon atoms, more preferably 5 to 10 carbon atoms, and even more preferably 6 to 8 carbon atoms.

[0202] The monovalent group having 1 to 20 carbon atoms and an ethylenically unsaturated group is preferably a group represented by the following formula (X-4) or a group represented by the following formula (X-5). [ka] (In formula (X-4), R24 , R 25 and R 26 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p2 represents an integer of 0 to 10. * represents a bond. [ka] In formula (X-5), ring Z represents an aliphatic hydrocarbon ring having 3 to 20 carbon atoms which may have a substituent. 34 , R 35 and R 36 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p3 represents an integer of 0 to 10. * represents a bond.

[0203] R in formula (X-4) 24 , R 25 and R 26 R each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and a 2-propyl group. 24 , R 25 and R 26 is preferably a hydrogen atom or a methyl group. 24 is preferably a hydrogen atom or a methyl group, more preferably a methyl group. 25 R is more preferably a hydrogen atom. 26 is more preferably a hydrogen atom.

[0204] In formula (X-4), p2 represents an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 1.

[0205] Ring Z in formula (X-5) represents an aliphatic hydrocarbon ring having 3 to 20 carbon atoms, which may have a substituent. The aliphatic hydrocarbon ring may be monocyclic or polycyclic. The aliphatic hydrocarbon ring may be a saturated aliphatic hydrocarbon ring such as a cycloalkane ring, or an unsaturated aliphatic hydrocarbon ring such as a cycloalkene ring. The number of carbon atoms in the aliphatic hydrocarbon ring is preferably 3 to 10. Examples of the aliphatic hydrocarbon ring include monocycloalkane rings such as a cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, and cyclooctane ring; bicycloalkane rings such as a decalin ring and a norbornane ring; spiroalkane rings such as a spirononane ring; monocycloalkene rings such as a cyclobutene ring, cyclopropene ring, cyclohexene ring, cyclohexadiene ring, cycloheptene ring, and cyclooctene ring; bicycloalkene rings such as a norbornene ring and a norbornadiene ring; and spiroalkene rings such as a spirononene ring. Of these, a cycloalkane ring is preferred, a monocycloalkane ring is more preferred, and a cyclohexane ring is even more preferred.

[0206] Examples of substituents that the aliphatic hydrocarbon ring in ring Z may have include linear, branched, or cyclic C1-C10 alkyl groups such as methyl, ethyl, n-propyl, 2-propyl, n-butyl, s-butyl, i-butyl, t-butyl, cyclopentyl, and cyclohexyl; halogen atoms such as fluorine, chlorine, and bromine; alkoxy groups having C1-C10 such as methoxy, ethoxy, propoxy, t-butoxy, and phenoxy; hydroxy; and halogen-substituted alkyl groups such as trifluoromethyl, with alkyl groups being preferred. The above-mentioned substituents may have a secondary substituent. The substituents may be contained alone or in combination of two or more.

[0207] R in formula (X-5) 34 , R 35 and R 36R 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. 34 , R 35 and R 36 is preferably a hydrogen atom or a methyl group. 34 is preferably a hydrogen atom or a methyl group, more preferably a methyl group. 35 R is more preferably a hydrogen atom. 36 is more preferably a hydrogen atom.

[0208] In formula (X-5), p3 represents an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 1.

[0209] Examples of the group represented by formula (X-5) include a group represented by formula (X-5-1) and a group represented by formula (X-5-2), etc. In the formula, * represents a bond. [ka]

[0210] In the component (2A), when the number of repeating structural units represented by formula (A-1) is M3, R in the M3 structural units represented by formula (A-1) 1 and R 2 At least one of the M structural units represented by formula (A-1) is preferably a monovalent group having 1 to 20 carbon atoms and having an ethylenically unsaturated group, and at least one of the M structural units represented by formula (A-2) is more preferably a group represented by formula (X-4) or a group represented by formula (X-5). 1 and R 2When at least one of the R groups in the structural unit (A-1) has an ethylenically unsaturated group, the ethylenically unsaturated bond in the component (2A) reacts and polymerizes upon exposure, and the solubility of the cured product of the photosensitive resin composition in a developer can be more effectively reduced. In other words, the resolution of the photosensitive resin composition can be ensured. Furthermore, when the R groups in the structural unit (A-1) are M, the number of R groups in the structural unit (A-1) is M. 1 and R 2 When at least one of them has an ethylenically unsaturated group, the film retention can be further improved.

[0211] R in formula (A-1) 1 and R 2 and R are each independently a monovalent group having 1 to 20 carbon atoms and having an ethylenically unsaturated group, and it is more preferable that at least one of them is a group represented by formula (X-4) or a group represented by formula (X-5). 1 and R 2 When at least one of R has an ethylenically unsaturated group, the ethylenically unsaturated bond in component (2A) reacts and polymerizes upon exposure, further effectively reducing the solubility of the cured product of the photosensitive resin composition in a developer. In other words, the resolution of the photosensitive resin composition can be ensured. 1 and R 2 When at least one of them has an ethylenically unsaturated group, the film retention can be further improved.

[0212] In formula (A-2), R a1 , R a2 , R a3 and R a4 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 4 to 20 carbon atoms, and R in formula (1a) a1 , R a2 , R a3 and R a4 is the same as

[0213] In formula (A-2), X 1 and X 2each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and X in formula (1a) 1 and X 2 is the same as

[0214] In formula (A-2), p represents an integer of 1 to 100, and is the same as p in formula (1a).

[0215] In formula (A-3), Xa and Xb each independently represent a single bond, a group represented by formula (X-1), a group represented by formula (X-2), or a group represented by formula (X-3). Xa and Xb may be bonded to a five-membered ring or a benzene ring. Xa and Xb in formula (A-3) are the same as Xa and Xb in formula (2a).

[0216] In formula (A-3), x represents an integer of 0 to 5 and is the same as x in formula (2a).

[0217] The component (2A) is preferably a polyamic acid and / or a polyamic acid ester having a structural unit represented by the following formula (A-4) and a structural unit represented by the following formula (A-5). [ka] [ka] (In formula (A-4) and formula (A-5), each A independently represents a tetravalent organic group having an alicyclic structure. R 1 and R 2 R each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms and an ethylenically unsaturated group. a1 , R a2 , R a3 and R a4 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 4 to 20 carbon atoms. 1 and X 2each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms. p represents an integer of 1 to 100. Xa and Xb each independently represent a single bond, a group represented by the above formula (X-1), a group represented by the above formula (X-2), or a group represented by the above formula (X-3). x represents an integer of 0 to 5.

[0218] In formula (A-4) and formula (A-5), each A independently represents a tetravalent organic group having an alicyclic structure, and is the same as A in formula (A-1).

[0219] In formula (A-4) and formula (A-5), R 1 and R 2 each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms and an ethylenically unsaturated group, and R 1 and R 2 is the same as

[0220] In the component (2A), when the number of repeating structural units represented by formula (A-5) is M2 and the number of repeating structural units represented by formula (A-4) is N2, there are M2+N2 structural units represented by formula (A-4) and R in the structural units represented by formula (A-5). 1 and R 2 At least one of the M2+N2 structural units represented by formula (A-4) and the R in the structural unit represented by formula (A-5) is preferably a monovalent group having 1 to 20 carbon atoms and having an ethylenically unsaturated group, and more preferably at least one of the M2+N2 structural units represented by formula (A-4) and the R in the structural unit represented by formula (A-5) is more preferably a monovalent group having 1 to 20 carbon atoms and having an ethylenically unsaturated group. 1 and R 2 When at least one of the structural units (A-4) and (A-5) has an ethylenically unsaturated group, the ethylenically unsaturated bond in component (2A) reacts and polymerizes upon exposure, more effectively reducing the solubility of the cured product of the photosensitive resin composition in a developer. In other words, the resolution of the photosensitive resin composition can be ensured. Furthermore, when the number of R in the structural units (A-4) and (A-5) is M2+N2, the number of R in the structural units (A-5) is M2+N2. 1 and R 2When at least one of them has an ethylenically unsaturated group, the film retention can be further improved.

[0221] In formula (A-4), R a1 , R a2 , R a3 and R a4 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 4 to 20 carbon atoms, and R in formula (1a) a1 , R a2 , R a3 and R a4 is the same as

[0222] In formula (A-4), X 1 and X 2 each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and X in formula (1a) 1 and X 2 is the same as

[0223] In formula (A-4), p represents an integer of 1 to 100 and is the same as p in formula (1a).

[0224] In formula (A-5), Xa and Xb each independently represent a single bond, a group represented by formula (X-1), a group represented by formula (X-2), or a group represented by formula (X-3). Xa and Xb may be bonded to a five-membered ring or a benzene ring. Xa and Xb in formula (A-5) are the same as Xa and Xb in formula (2a).

[0225] In formula (A-5), x represents an integer of 0 to 5 and is the same as x in formula (2a).

[0226] The structural unit represented by formula (A-5) is preferably a structural unit represented by the following formula (A-5-1). [ka] (In formula (A-5-1), A represents a tetravalent organic group having an alicyclic structure. R 1 and R 2each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms and an ethylenically unsaturated group.

[0227] In formula (A-5-1), each A independently represents a tetravalent organic group having an alicyclic structure, and is the same as A in formula (A-1).

[0228] In formula (A-5-1), R 1 and R 2 each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms and an ethylenically unsaturated group, and R 1 and R 2 is the same as

[0229] In component (2A), the structural units represented by formula (A-4) and the structural units represented by formula (A-5) may be bonded in any order, and examples of the bonding mode include random copolymerization, alternating copolymerization, block copolymerization, graft copolymerization, and ordered copolymerization.

[0230] Specific examples of the component (2A) include polyamic acids and / or polyamic acid esters having a structural unit represented by the following formula (A-5-2) and a structural unit represented by the following formula (A-4-2). [ka]

[0231] Further, other specific examples of the component (2A) include polyamic acids and / or polyamic acid esters having a structural unit represented by the following formula (A-5-2) and a structural unit represented by the following formula (A-4-3). [ka]

[0232] Further, other specific examples of the component (2A) include polyamic acids and / or polyamic acid esters having a structural unit represented by the following formula (A-5-2) and a structural unit represented by the following formula (A-4-5). [ka]

[0233] Further, other specific examples of the component (2A) include polyamic acids and / or polyamic acid esters having a structural unit represented by the following formula (A-5-2) and a structural unit represented by the following formula (A-4-6). [ka]

[0234] In the component (2A), when the number of repeats of the structural unit represented by formula (A-5) is M2, the number of repeats of the structural unit represented by formula (A-4) is N2, and if another structural unit is present, the number of repeats of the other structural unit is L2, the sum of m2 defined by the following formula (4) and n2 defined by the following formula (5) (m2+n2) is preferably 90 to 100. m2+n2 is more preferably 95 or more or 96 or more, even more preferably 97 or more, and particularly preferably 98 or more or 99 or more. m2 and n2 are 1 It can be measured by H-NMR.

number

number

[0235] I2 defined by the following formula (8) is more preferably 10 or less, more preferably 5 or less or 4 or less, even more preferably 3 or less, and particularly preferably 2 or less or 1 or less.

number

[0236] From the viewpoints of improving solubility in organic solvents, increasing the glass transition temperature of the cured product, and obtaining excellent limiting resolution, m2 is preferably 40 to 90. The lower limit of m2 is more preferably 45 or more, even more preferably 50 or more or 55 or more, and particularly preferably 60 or more or 65 or more. The upper limit of m2 is more preferably 85 or less, even more preferably 80 or less, and particularly preferably 75 or less.

[0237] From the viewpoint of reducing the dielectric loss tangent of the cured product and suppressing warpage of the cured product, n2 is preferably 10 to 60. The lower limit of n2 is more preferably 15 or more, even more preferably 20 or more, and particularly preferably 25 or more. The upper limit of n2 is more preferably 55 or less, even more preferably 50 or less or 45 or less, and particularly preferably 40 or less or 35 or less.

[0238] In the component (2A), R of the structural unit represented by formula (A-1) 1 and R 2 The total number of R 1 and R 2 When the total number of monovalent groups having 1 to 20 carbon atoms and an ethylenically unsaturated group is S2, the modification rate u2 (%) defined by the following formula (6) is preferably 20 to 100% from the viewpoint of improving film retention. The lower limit of u2 is more preferably 25% or more, even more preferably 30% or more, and particularly preferably 35% or more. The upper limit of u2 is more preferably 90% or less, 80% or less, or 70%, more preferably 60% or less, or 50% or less, and particularly preferably 45% or less, or 40% or less. u2 is 1 It can be measured by H-NMR.

number

[0239] From the viewpoint of obtaining excellent limiting resolution, the weight average molecular weight of component (2A) is preferably 3,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, and particularly preferably 6,000 or more, and is preferably 1,000,000 or less, more preferably 500,000 or less, even more preferably 200,000 or less or 100,000 or less, and particularly preferably 50,000 or less, 20,000 or less, 10,000 or less, 9,000 or less, or 8,000 or less. The weight average molecular weight of component (2A) can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0240] From the viewpoint of obtaining excellent limiting resolution and a cured product with good physical properties, the content of component (2A) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, based on 100% by mass of the nonvolatile components of the resin composition. The upper limit is preferably 99% by mass or less, more preferably 97% by mass or less or 95% by mass or less, and even more preferably 93% by mass or less or 90% by mass or less.

[0241] <Method of manufacturing component (2A)> The method for producing component (2A) is the same as the method for producing component (1A).

[0242] <(B) Photopolymerization initiator> The photosensitive resin composition of the second embodiment contains a (B) photopolymerization initiator as the (B) component. The (B) photopolymerization initiator of the second embodiment is the same as the (B) photopolymerization initiator of the first embodiment.

[0243] <(C) Crosslinking Agent> The photosensitive resin composition of the second embodiment contains a crosslinking agent (C) as the component (C). The crosslinking agent (C) of the second embodiment is the same as the crosslinking agent (C) of the first embodiment.

[0244] <(D) Adhesion aid> The photosensitive resin composition of the second embodiment may contain, and preferably contains, an adhesion aid (D) as an optional component. The adhesion aid (D) according to the second embodiment is the same as the adhesion aid (D) according to the first embodiment.

[0245] <(E) Sensitizer> The photosensitive resin composition of the second embodiment may contain a sensitizer (E) as an optional component, and preferably contains a sensitizer (E). The sensitizer (E) according to the second embodiment is the same as the sensitizer (E) according to the first embodiment.

[0246] <(F) Surfactant> The photosensitive resin composition of the second embodiment may contain, and preferably contains, a surfactant (F) as an optional component. The surfactant (F) according to the second embodiment is the same as the surfactant (F) according to the first embodiment.

[0247] <(G) Organic Solvent> The photosensitive resin composition of the second embodiment may contain an organic solvent (G) as an optional component. The organic solvent (G) according to the second embodiment is the same as the organic solvent (G) according to the first embodiment.

[0248] <(H) Other Additives> The photosensitive resin composition of the second embodiment may further contain (H) other additives to the extent that the object of the present invention is not impaired. The (H) other additives of the second embodiment are the same as the (H) other additives of the first embodiment.

[0249] [Method for producing photosensitive resin composition] The photosensitive resin composition can be produced by mixing the essential components (A) to (C) described above, and optionally mixing the optional components (D) to (H) described above, and kneading or stirring the mixture, if necessary, using a kneading device such as a triple roll mill, a ball mill, a bead mill, or a sand mill, or a stirring device such as a super mixer or a planetary mixer.

[0250] [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.

[0251] Examples of the support include polyethylene terephthalate (PET) film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, and triacetyl acetate film, with polyethylene terephthalate film being particularly preferred.

[0252] Examples of commercially available supports include polypropylene films manufactured by Oji Paper Co., Ltd. under the product names "Alphan MA-410" and "E-200C," manufactured by Tamapoly Co., Ltd. under the product names "GF-1" and "GF-8," manufactured by Shin-Etsu Film Co., Ltd., and the like; PS series manufactured by Teijin Limited under the product name "PS-25," and polyethylene terephthalate films manufactured by Toray Industries, Inc. under the product name "Lumirror T6AM," and the like.

[0253] The support may also be a support with a release layer, which has a release layer on the surface that bonds to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available release agents include "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation. The support with a release layer may also be a commercially available product, such as "Lumirror T60" and "Lumirror R80" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, or "Uni-Peel" manufactured by Unitika Limited, which are PET films having a release layer primarily composed of an alkyd resin-based release agent.

[0254] 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.

[0255] 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, and 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, and even more preferably 20 μm or less.

[0256] The photosensitive resin composition layer may be protected by a protective film. Protecting the photosensitive resin composition layer with a protective film can prevent dust from adhering to the surface of the photosensitive resin composition layer and scratches. The protective film may be made of the same material as the support. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and even more preferably in the range of 10 μm to 30 μm. The protective film is preferably one in which the adhesive strength between the photosensitive resin composition layer and the protective film is smaller than the adhesive strength between the photosensitive resin composition layer and the support.

[0257] An example of a commercially available protective film is "MA-411" (biaxially oriented polypropylene film) manufactured by Oji F-Tex Co., Ltd.

[0258] The photosensitive film can be produced, for example, by applying the photosensitive resin composition onto a support using a die coater or the like, and then drying off the (G) organic solvent as necessary.

[0259] Drying may be carried out by known methods such as heating, hot air blowing, etc. The drying conditions are not particularly limited, but drying is carried out so that the content of the organic solvent in the resin composition layer is preferably 10% by mass or less, more preferably 5% by mass or less.

[0260] [Physical properties and applications of photosensitive resin compositions] In one embodiment, the photosensitive resin composition exhibits excellent limiting resolution. For example, exposure and development are performed using a mask that draws circular holes with opening diameters of 5 μm, 7 μm, 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm in the exposure pattern. In this case, the limiting resolution, which is the minimum size that can be opened, is preferably 25 μm or less, more preferably 20 μm or less, even more preferably 15 μm or less or 10 μm or less, and particularly preferably 7 μm or less or 5 μm or less. The limiting resolution can be evaluated according to the method described in the Examples below.

[0261] In one embodiment, the photosensitive resin composition exhibits excellent film retention (film thickness reduction rate). For example, the film thickness of a photosensitive resin composition layer coated on a silicon wafer is measured, and the film thickness of the photosensitive resin composition layer after development is measured. In this case, when applying the formula: film thickness reduction rate = film thickness after development / film thickness after coating × 100 (%), the film thickness reduction rate is preferably 70% or more, more preferably 90% or more. Film retention can be measured according to the method described in the Examples below.

[0262] In one embodiment, a cured product obtained by thermally curing a photosensitive resin composition at 200°C for 120 minutes exhibits the characteristic of having a small amount of warpage. A 100 μm-thick photosensitive film produced using the photosensitive resin composition is laminated onto an 8-inch silicon wafer, and the cured product preferably has a warpage of 1000 μm or less, more preferably 900 μm or less, even more preferably 800 μm or less, and particularly preferably 700 μm or less or 600 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more, 1 μm or more, 10 μm or more, 100 μm or more, etc. The amount of warpage can be measured according to the method described in the Examples below.

[0263] In one embodiment, a cured product obtained by thermally curing a photosensitive resin composition at 180°C for 180 minutes exhibits the property of a high glass transition temperature. The glass transition temperature when thermally cured at 180°C for 180 minutes is preferably 150°C or higher, more preferably 160°C or higher, even more preferably 170°C or higher or 180°C or higher, and particularly preferably 190°C or higher or 200°C or higher. The upper limit is not particularly limited, but may be 400°C or lower, 300°C or lower, etc. The glass transition temperature can be measured according to the method described in the examples below.

[0264] In one embodiment, a cured product obtained by thermally curing a photosensitive resin composition at 250°C for 120 minutes exhibits the property of a high glass transition temperature. The glass transition temperature when thermally cured at 250°C for 120 minutes is preferably 180°C or higher, more preferably 190°C or higher, even more preferably 200°C or higher or 210°C or higher, and particularly preferably 220°C or higher or 230°C or higher. The upper limit is not particularly limited, but may be 400°C or lower, 300°C or lower, etc. The glass transition temperature can be measured according to the method described in the examples below.

[0265] In one embodiment, the absolute value of the difference between the glass transition temperature Tg(250°C) when the photosensitive resin composition is thermally cured at 250°C for 120 minutes and the glass transition temperature Tg(180°C) when the photosensitive resin composition is thermally cured at 180°C for 180 minutes, |Tg(250°C)-Tg(180°C)|, is preferably 70°C or less, more preferably 60°C or less or 50°C or less, even more preferably 45°C or less or 40°C or less, and particularly preferably 35°C or less. The lower limit is not particularly limited, but may be 1°C or more, 2°C or more, etc. A small absolute value |Tg(250°C)-Tg(180°C)| means that the glass transition temperature has little dependency on the curing temperature. From the viewpoint of obtaining a cured product of stable quality in an industrial process, it is preferable that the glass transition temperature has little dependency on the curing temperature.

[0266] In one embodiment, a cured product obtained by thermally curing the photosensitive resin composition at 180°C for 180 minutes exhibits the characteristic of a low dielectric constant (Dk). The dielectric constant when thermally cured at 180°C for 180 minutes is preferably 4 or less, more preferably 3 or less, and even more preferably 2.8 or less. The lower limit is not particularly limited, but may be 0.01 or more, 0.1 or more, 1 or more, etc. The dielectric constant can be measured according to the method described in the examples below.

[0267] In one embodiment, a cured product obtained by thermally curing the photosensitive resin composition at 250°C for 120 minutes exhibits the characteristic of a low dielectric constant (Dk). The dielectric constant when thermally cured at 250°C for 120 minutes is preferably 4 or less, more preferably 3 or less, and even more preferably 2.8 or less. The lower limit is not particularly limited, but may be 0.01 or more, 0.1 or more, 1 or more, etc. The dielectric constant can be measured according to the method described in the examples below.

[0268] In one embodiment, the absolute value of the difference between the dielectric constant Dk(250°C) when the photosensitive resin composition is thermally cured at 250°C for 120 minutes and the dielectric constant Dk(180°C) when the photosensitive resin composition is thermally cured at 180°C for 180 minutes, |Dk(250°C)-Dk(180°C)|, is preferably 0.2 or less, more preferably 0.15 or less, even more preferably 0.12 or less or 0.1 or less, and particularly preferably 0.08 or less. The lower limit is not particularly limited, but may be 0.001 or more, 0.01 or more, etc. A small absolute value |Dk(250°C)-Dk(180°C)| means that the dielectric constant has little dependency on the curing temperature. From the viewpoint of obtaining a cured product of stable quality in an industrial process, a small dependency of the dielectric constant on the curing temperature is preferred.

[0269] In one embodiment, a cured product obtained by thermally curing a photosensitive resin composition at 180°C for 180 minutes exhibits the characteristic of a low dielectric loss tangent (Df). The dielectric loss tangent when thermally cured at 180°C for 180 minutes is preferably 0.03 or less or 0.025 or less, more preferably 0.02 or less or 0.015 or less, and even more preferably 0.01 or less. The lower limit is not particularly limited, but may be 0.0005 or more, 0.001 or more, etc. The dielectric loss tangent can be measured according to the method described in the examples below.

[0270] In one embodiment, a cured product obtained by thermally curing a photosensitive resin composition at 250°C for 120 minutes exhibits the characteristic of a low dielectric loss tangent (Df). The dielectric loss tangent when thermally cured at 250°C for 120 minutes is preferably 0.03 or less or 0.025 or less, more preferably 0.02 or less or 0.015 or less, and even more preferably 0.01 or less. The lower limit is not particularly limited, but may be 0.0005 or more, 0.001 or more, etc. The dielectric loss tangent can be measured according to the method described in the examples below.

[0271] In one embodiment, the absolute value of the difference between the dielectric loss tangent Df(250°C) when the photosensitive resin composition is thermally cured at 250°C for 120 minutes and the dielectric loss tangent Df(180°C) when the photosensitive resin composition is thermally cured at 180°C for 180 minutes, |Df(250°C)-Df(180°C)|, is preferably 0.01 or less, more preferably 0.007 or less, even more preferably 0.005 or less or 0.004 or less, and particularly preferably 0.003 or less or 0.002 or less. The lower limit is not particularly limited and may be 0 or more. A small absolute value |Df(250°C)-Df(180°C)| means that the dielectric loss tangent has little dependency on the curing temperature. From the viewpoint of obtaining a cured product of stable quality in an industrial process, it is preferable that the dielectric loss tangent has little dependency on the curing temperature.

[0272] In one embodiment, the photosensitive resin composition exhibits the property of being able to be handled as a solution dissolved in an organic solvent. When the varnish-like photosensitive resin composition is stored at 5°C, the time until a precipitate forms is preferably 10 hours or more, more preferably 1 month or more. The upper limit is not particularly limited, but it may be within 1 year, for example. The time until a precipitate forms when the varnish-like photosensitive resin composition is stored at 5°C can be measured according to the method described in the Examples below.

[0273] The photosensitive resin composition of the present invention is not particularly limited in its applications, but can be used in a wide range of applications where photosensitive resin compositions are used, such as a photosensitive film with a support, an insulating resin sheet such as a prepreg, a silicon wafer, a circuit board (for laminates, multilayer printed wiring boards, etc.), a solder resist, a buffer coating film, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, a component embedding resin, etc. Among these, photosensitive resin compositions for insulating layers of printed wiring boards (printed wiring boards in which a cured product of the photosensitive resin composition is used as an insulating layer), photosensitive resin compositions for interlayer insulating layers (printed wiring boards in which a cured product of the photosensitive resin composition is used as an interlayer insulating layer), photosensitive resin compositions for plating formation (printed wiring boards in which plating is formed on a cured product of the photosensitive resin composition), and photosensitive resin compositions for solder resists (printed wiring boards in which a cured product of the photosensitive resin composition is used as a solder resist), photosensitive resin compositions for rewiring formation layers of wafer-level packages (wafer-level packages in which a cured product of the photosensitive resin composition is used as a rewiring formation layer), The photosensitive resin composition can be suitably used as a photosensitive resin composition for a rewiring formation layer in a fan-out wafer-level package (a fan-out wafer-level package in which a cured product of the photosensitive resin composition serves as a rewiring formation layer), a photosensitive resin composition for a rewiring formation layer in a fan-out panel-level package (a fan-out panel-level package in which a cured product of the photosensitive resin composition serves as a rewiring formation layer), a photosensitive resin composition for a buffer coat (a semiconductor device in which a cured product of the photosensitive resin composition serves as a buffer coat), or a photosensitive resin composition for an insulating layer in a display (a display in which a cured product of the photosensitive resin composition serves as an insulating layer).

[0274] [Semiconductor package substrate and its manufacturing method] The semiconductor package substrate of the present invention includes an insulating layer formed from a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a rewiring formation layer, an interlayer insulating layer, a buffer coating film, or a solder resist.

[0275] In particular, the semiconductor package substrate of the first embodiment of the present invention can be manufactured using the above-mentioned photosensitive resin composition, and the cured product of the photosensitive resin composition is used as an insulating layer. Specifically, the manufacturing method of the semiconductor package substrate includes: (I) forming a photosensitive resin composition layer containing the photosensitive resin composition of the present invention on a circuit board; (II) a step of irradiating the photosensitive resin composition layer with actinic rays; and (III) Step of developing the photosensitive resin composition layer The method for manufacturing a semiconductor package substrate preferably includes steps (I) to (III) in the order of step (I), step (II), and step (III).

[0276] <Process (I)> In step (I), a photosensitive resin composition layer containing the photosensitive resin composition of the present invention is formed on a circuit board. Examples of a method 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.

[0277] When a resin varnish containing a photosensitive resin composition is applied directly onto a circuit board, a photosensitive resin composition layer can be formed on the circuit board by drying and volatilizing the (G) organic solvent.

[0278] Examples of resin varnish application methods include gravure coating, microgravure coating, reverse coating, kiss reverse coating, die coating, slot die coating, lip coating, comma coating, blade coating, roll coating, knife coating, curtain coating, chamber gravure coating, slot orifice coating, spin coating, slit coating, spray coating, dip coating, hot melt coating, bar coating, applicator coating, air knife coating, curtain flow coating, offset printing, brush coating, and full-surface printing using screen printing.

[0279] The resin varnish may be applied in several batches, in one application, or by a combination of several different methods. Among these, the die coating method is preferred because it provides excellent uniformity. Furthermore, to avoid contamination, it is preferable to carry out the application process in an environment where foreign matter is less likely to be generated, such as a clean room.

[0280] After the resin varnish is applied, it is dried, if necessary, in a hot air oven or far-infrared oven. The drying conditions are preferably 80°C to 120°C for 3 to 13 minutes. In this way, a photosensitive resin composition layer is formed on the circuit board.

[0281] Examples of circuit boards include glass epoxy boards, metal boards, polyester boards, polyimide boards, BT resin boards, and thermosetting polyphenylene ether boards. Here, the term "circuit board" refers to a board in which a patterned conductor layer (circuit) is formed on one or both sides of a support substrate such as those described above. Also included in the term "circuit board" is a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, in which one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits). The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

[0282] <Process (II)> In step (II), the photosensitive resin composition layer is irradiated with actinic rays. In step (II), it is preferable to irradiate the photosensitive resin composition layer with actinic rays after the photosensitive resin composition layer is provided on the circuit board in step (I). It is also preferable to carry out an exposure step in which actinic rays are irradiated to predetermined portions of the photosensitive resin composition layer through a mask pattern. Examples of actinic rays include ultraviolet rays, visible rays, electron beams, and X-rays, with ultraviolet rays being particularly preferred. The irradiation dose of ultraviolet rays is 10 mJ / cm. 2 ~1000mJ / cm 2 The exposure method includes a contact exposure method in which a mask pattern is brought into close contact with the circuit board, and a non-contact exposure method in which exposure is carried out using parallel light without contact, and either method may be used.

[0283] In step (II), vias can be formed using a via pattern such as a round hole pattern as the mask pattern. The via diameter (opening diameter) is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 30 μm or less, and particularly preferably 25 μm or less, 20 μm or less, 15 μm or less, 10 μm or less, 7 μm or less, or 5 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more, 0.5 μm or more, etc.

[0284] <Process (III)> In step (III), the photosensitive resin composition layer is developed. After step (II), a development step is performed in which the unexposed portions of the photosensitive resin composition layer are removed with a developer, thereby forming a pattern. Development is usually preferably performed by wet development.

[0285] In the case of the wet development, the developer may be a safe, stable, and easy-to-use developer such as an alkaline solution, an aqueous developer, or an organic solvent. Examples of the alkaline solution include an alkaline aqueous solution. The developer is preferably an alkaline aqueous solution or an organic solvent, more preferably an alkaline aqueous solution from the viewpoint of safety, and more preferably an organic solvent from the viewpoint of improving developability (efficiently removing the unexposed portion of the photosensitive resin composition layer). Furthermore, known methods such as spraying, swing immersion, brushing, and scraping may be appropriately employed as the development method.

[0286] Examples of alkaline aqueous solutions used as the developer include aqueous solutions of alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; alkali metal phosphates such as sodium phosphate and potassium phosphate; and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; and aqueous solutions of organic bases that do not contain metal ions, such as tetraalkylammonium hydroxide. Of these, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred because it does not contain metal ions and does not affect the semiconductor chip.

[0287] These alkaline aqueous solutions may contain a surfactant, an antifoaming agent, etc. to improve the development effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8 to 12, more preferably in the range of 9 to 11. The base concentration of the alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected depending on the developability of the photosensitive resin composition layer, but is preferably 20°C to 50°C.

[0288] Examples of organic solvents used as developers include acetone, ethyl acetate, alkoxyethanols having an alkoxy group with 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monomethyl ether (PGME).

[0289] 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. Such organic solvents can be used alone or in combination of two or more. Examples of organic solvent-based developers that can be used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0290] In forming a pattern, two or more development methods may be used in combination as needed. Development methods include dipping, bathing, spraying, high-pressure spraying, brushing, and slapping, with the high-pressure spraying method being preferred for improving resolution. When using a spraying method, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

[0291] After development, the resist may be rinsed with an organic solvent, such as propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME). A preferred rinse method is a spray method.

[0292] <Thermal curing (post-bake) process> After completion of the step (III), a thermal curing (post-baking) step may be carried out as necessary. While the curing of the photosensitive resin composition layer may proceed in the steps (I) to (III), the thermal curing step can further promote the curing of the photosensitive resin composition layer, thereby obtaining an insulating layer with superior mechanical strength. Examples of the post-baking step include a heating step using a clean oven. The thermal curing atmosphere may be an air atmosphere or an inert gas atmosphere such as nitrogen. The heating conditions may be appropriately selected depending on the type and content of the resin component in the photosensitive resin composition, but are preferably selected within the range of 150°C to 250°C for 20 to 240 minutes, and more preferably 160°C to 230°C for 30 to 180 minutes.

[0293] <Other processes> The method for manufacturing a semiconductor package substrate according to the first embodiment may further include a drilling step and a desmearing step after forming an insulating layer as a cured photosensitive resin composition layer. These steps may be performed according to various methods used in manufacturing semiconductor package substrates and known to those skilled in the art.

[0294] After forming the insulating layer, if desired, via holes or through holes may be formed in the insulating layer formed on the circuit board by a drilling process. The drilling process can be performed by a known method such as a drill, a laser, or plasma, or by a combination of these methods as needed, but a drilling process using a laser such as a carbon dioxide laser or a YAG laser is preferred.

[0295] The desmearing step is a step of performing a desmear treatment. Generally, resin residue (smear) adheres to the inside of the opening formed in the drilling step. Since such smear can cause poor electrical connection, it is preferable to perform a treatment to remove the smear (desmearing treatment) in this step.

[0296] The desmearing treatment may be performed by a dry desmearing treatment, a wet desmearing treatment, or a combination thereof.

[0297] An example of the dry desmear treatment is a desmear treatment using plasma. The desmear treatment using plasma can be performed using a commercially available plasma desmear treatment apparatus. Among the commercially available plasma desmear treatment apparatuses, examples suitable for use in manufacturing semiconductor package substrates include a microwave plasma apparatus manufactured by Nissin Corporation and an atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Co., Ltd.

[0298] Examples of wet desmear treatments include desmear treatments using an oxidizing agent solution. When desmear treatments are performed using an oxidizing agent solution, it is preferable to perform a swelling treatment using a swelling solution, an oxidation treatment using an oxidizing agent solution, and a neutralization treatment using a neutralizing solution in this order. Examples of swelling solutions include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing a substrate having via holes or the like formed therein in a swelling solution heated to 60°C to 80°C for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganate aqueous solution, such as a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous sodium hydroxide solution. The oxidation treatment using an oxidizing agent solution is preferably performed by immersing the substrate after the swelling treatment in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Commercially available alkaline permanganate aqueous solutions include, for example, "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan. The neutralization treatment using a neutralizing solution is preferably carried out by immersing the substrate after oxidation treatment in the neutralizing solution at 30°C to 50°C for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and a commercially available product thereof is, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan.

[0299] 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.

[0300] When the insulating layer is formed as any of a rewiring formation layer, an interlayer insulating layer, and a solder resist, a drilling step and a desmearing step may be performed after the thermal curing step. Furthermore, in the method for manufacturing a semiconductor package substrate of the first embodiment, a plating step may be further performed.

[0301] The plating process is a process of forming a conductor layer on an insulating layer. Examples of methods for forming the conductor layer include a method of forming the conductor layer by sputtering after forming the insulating layer, a method of forming the conductor layer by combining electroless plating and electrolytic plating, and a method of forming a plating resist with a reverse pattern to the conductor layer and then forming the conductor layer by electroless plating alone. Subsequent pattern formation methods that can be used include, for example, subtractive methods and semi-additive methods.

[0302] The semiconductor package substrate of 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 of the second embodiment 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) 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 a semiconductor chip package according to the second embodiment includes: (H) A process of dicing and separating a plurality of semiconductor chip packages into individual semiconductor chip packages. may also include:

[0303] <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 Preferably, the pressure bonding time is set to 5 to 300 seconds, and lamination is performed under reduced pressure with an air pressure of 20 mmHg or less. The lamination process may be a batch process or a continuous process using rolls. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nikko Materials Co., Ltd., a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a roll-type dry coater manufactured by Hitachi Industries Co., Ltd., and a vacuum laminator manufactured by Hitachi AIC Corporation.

[0304] Examples of the substrate include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); substrates such as FR-4 substrates in which glass fibers are impregnated with epoxy resin or the like and then thermoset; and substrates made of bismaleimide triazine resins such as BT resin.

[0305] 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.

[0306] <Process (B)> Step (B) is a step of temporarily fixing semiconductor chips on a temporary fixing film. Temporarily fixing semiconductor chips can be performed using a device such as a flip chip bonder or a die bonder. The layout and number of semiconductor chips can be appropriately set depending on the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, and the like. For example, the semiconductor chips may be temporarily fixed by arranging them in a matrix of multiple rows and multiple columns.

[0307] <Process (C)> Step (C) is a step of forming an encapsulating layer on the semiconductor chip. Any insulating material can be used for the encapsulating layer, and the above-mentioned photosensitive resin composition may also be used. The encapsulating layer is usually formed by a method including a step of forming an encapsulating resin composition layer on the semiconductor chip and a step of thermally curing this resin composition layer to form the encapsulating layer.

[0308] The encapsulating resin composition layer is preferably formed by a compression molding method, in which a semiconductor chip and the encapsulating resin composition are typically placed in a mold, and pressure and, if necessary, heat are applied to the encapsulating resin composition in the mold to form an encapsulating resin composition layer that covers the semiconductor chip.

[0309] Specific operations of the compression molding method can be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. An encapsulating resin composition is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip to which the encapsulating resin composition has been applied is attached to the lower mold together with the substrate and the temporary fixing film. Thereafter, the upper and lower molds are clamped together, and heat and pressure are applied to the encapsulating resin composition to perform compression molding.

[0310] Furthermore, specific operations of the compression molding method may be, for example, as follows: An upper mold and a lower mold are prepared as molds for compression molding. An encapsulating resin composition is placed on the lower mold. A semiconductor chip is attached to the upper mold together with a substrate and a temporary fixing film. Thereafter, the upper and lower molds are clamped together so that the encapsulating resin composition placed on the lower mold contacts the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

[0311] The molding conditions vary depending on the composition of the encapsulating resin composition, and appropriate conditions can be adopted to achieve good encapsulation. For example, the mold temperature during molding is preferably a temperature at which the encapsulating resin composition exhibits excellent compression moldability, and is preferably 80°C or higher, more preferably 100°C or higher, particularly preferably 120°C or higher, and preferably 200°C or lower, more preferably 170°C or lower, and particularly preferably 150°C or lower. The pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, particularly preferably 5 MPa or higher, and preferably 50 MPa or lower, more preferably 30 MPa or lower, and particularly preferably 20 MPa or lower. The cure time is preferably 1 minute or longer, more preferably 2 minutes or longer, particularly preferably 5 minutes or longer, and preferably 60 minutes or shorter, more preferably 30 minutes or shorter, and particularly preferably 20 minutes or shorter. Typically, the mold is removed after the encapsulating resin composition layer is formed. The mold may be removed before or after the encapsulating resin composition layer is thermally cured.

[0312] The compression molding method may be carried out by discharging the encapsulating resin composition filled in a cartridge into a lower mold.

[0313] <Process (D)> Step (D) is a step of peeling the substrate and the temporary fixing film from the semiconductor chip. It is desirable to adopt an appropriate peeling method depending on the material of the temporary fixing film. Examples of peeling methods include a method in which the temporary fixing film is heated, foamed, or expanded to peel it off. Another example of a peeling method is a method in which the temporary fixing film is irradiated with ultraviolet light through the substrate to reduce the adhesive strength of the temporary fixing film, thereby peeling it off.

[0314] In the method of peeling off the temporary fixing film by heating, foaming or expanding it, the heating temperature is preferably 100° C. to 250° C. The heating time is preferably 1 second to 15 minutes, and may be, for example, a relatively short time such as 1 second to 90 seconds, or a relatively long time such as 5 minutes to 15 minutes. In the method of peeling off the temporary fixing film by irradiating it with ultraviolet light to reduce the adhesive strength of the temporary fixing film, the irradiation dose of ultraviolet light is 10 mJ / cm. 2~1000mJ / cm 2 is preferred.

[0315] <Process (E)> Step (E) is a step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off. The rewiring formation layer uses the photosensitive resin composition of the present invention. The method for forming the rewiring formation layer is the same as the method for forming the photosensitive resin composition layer in step (I) in the first embodiment.

[0316] When forming the rewiring formation layer, via holes may be formed in the rewiring formation layer to connect the semiconductor chip and the rewiring layer to each other.

[0317] The via hole can usually be formed by performing an exposure step in which the surface of the photosensitive resin composition layer for forming the rewiring formation layer is irradiated with actinic rays through a mask pattern, and a development step in which the non-exposed portion not irradiated with actinic rays is removed with a developer. The dose and duration of actinic rays can be appropriately set depending on the photosensitive resin composition layer. Examples of exposure methods include a contact exposure method in which a mask pattern is brought into close contact with the photosensitive resin composition layer and exposed, and a non-contact exposure method in which a mask pattern is not brought into close contact with the photosensitive resin composition layer and exposed using parallel rays. The actinic rays are the same as those used in step (II) of the first embodiment. The developer is the same as that used in step (III) of the first embodiment. The exposure and development method is the same as that used in steps (II) and (III) of the first embodiment.

[0318] The shape of the via hole is not particularly limited, but is preferably circular or 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.

[0319] <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.

[0320] <Process (G)> Step (G) is a step of forming a solder resist layer on the rewiring layer. Any insulating material can be used as the material for the solder resist layer. Among these, from the viewpoint of ease of manufacturing a semiconductor chip package, a photosensitive resin or a thermosetting resin is preferred. The photosensitive resin composition of the present invention may also be used.

[0321] 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).

[0322] The method for manufacturing a semiconductor chip package may include a step (H) in addition to the steps (A) to (G). The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages. The method for dicing the semiconductor chip packages into individual semiconductor chip packages is not particularly limited.

[0323] [Semiconductor Devices] Examples of semiconductor devices on which the above-mentioned semiconductor chip package is mounted include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft). [Example]

[0324] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In the following description, m1 and m2 will be collectively referred to as "m", n1 and n2 will be collectively referred to as "n", and l1 and l2 will be collectively referred to as "l". In addition, for polyamic acids and / or polyesters having two repeating units corresponding to l, each will be referred to as l. m , l n That is, l=l m +l n is.

[0325] <Synthesis Example 1: Synthesis of polyamic acid and / or polyamic acid ester (A1)> A 3 L separable flask was charged with 185.3 g of 6-(2,5-dioxolan-3-yl)-4-methyl-3a,6,7,7a-tetrahydroisobenzofuran-1,3-dione (MCTC) and 1159 g of cyclohexanone and stirred at room temperature. 180.9 g of KF-8010 (Shin-Etsu Chemical Co., Ltd.) and 130.7 g of 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (PIDA) were then added, and the separable flask was heated in an oil bath until the internal temperature reached 50°C. Polymerization was carried out for 20 hours to obtain polyamic acid.

[0326] Next, 24.8 g of 4-methoxyphenol (1% solution in cyclohexanone), 129.2 g of glycidyl methacrylate (GMA), and 5.0 g of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, yielding polyamic acid and / or polyamic acid ester (A1).

[0327] The molecular weight of (A1) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 6,000 in weight average molecular weight (Mw). 1H-NMR analysis revealed that the copolymer had a structural unit represented by the following formula (A-5-2) and a structural unit represented by the following formula (A-4-2), with a copolymerization ratio of m=69.5 (structural unit represented by formula (A-5-2)) and n=30.5 (structural unit represented by formula (A-4-2)). Furthermore, the modification rate u was 37.2%. [ka]

[0328] <Synthesis Example 2: Synthesis of polyamic acid and / or polyamic acid ester (A2)> A 3 L separable flask was charged with 65.6 g of 6-(2,5-dioxolan-3-yl)-4-methyl-3a,6,7,7a-tetrahydroisobenzofuran-1,3-dione (MCTC) and 490 g of cyclohexanone and stirred at room temperature. 85.3 g of KF-8010 (Shin-Etsu Chemical Co., Ltd.) and 39.7 g of 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (PIDA) were then added, and the separable flask was heated in an oil bath until the internal temperature reached 50°C. Polymerization was carried out for 20 hours to obtain polyamic acid.

[0329] Next, 9.5 g of 4-methoxyphenol (1% solution in cyclohexanone), 49.1 g of glycidyl methacrylate (GMA), and 3.8 g of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, yielding polyamic acid and / or polyamic acid ester (A2).

[0330] The molecular weight of (A2) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 5,700 in weight average molecular weight (Mw). 1H-NMR confirmed that the copolymer had the structural unit represented by formula (A-5-2) and the structural unit represented by formula (A-4-2), with a copolymerization ratio of m=59.6 (structural unit represented by formula (A-5-2)) and n=40.4 (structural unit represented by formula (A-4-2)). Furthermore, the modification rate u was 35.1%.

[0331] <Synthesis Example 3: Synthesis of polyamic acid and / or polyamic acid ester (A3)> A 3 L separable flask was charged with 59.9 g of 6-(2,5-dioxolan-3-yl)-4-methyl-3a,6,7,7a-tetrahydroisobenzofuran-1,3-dione (MCTC) and 490 g of cyclohexanone and stirred at room temperature. 97.4 g of KF-8010 (Shin-Etsu Chemical Co., Ltd.) and 30.2 g of 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (PIDA) were then added, and the separable flask was heated in an oil bath until the internal temperature reached 50°C. Polymerization was carried out for 20 hours to obtain polyamic acid.

[0332] Next, 9.4 g of 4-methoxyphenol (1% solution in cyclohexanone), 47.9 g of glycidyl methacrylate (GMA), and 3.8 g of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, yielding polyamic acid and / or polyamic acid ester (A3).

[0333] The molecular weight of (A3) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 5,200 in weight average molecular weight (Mw). 1 H-NMR analysis revealed that the copolymer had the structural unit represented by formula (A-5-2) and the structural unit represented by formula (A-4-2), with a copolymerization ratio of m = 50.1 (structural unit represented by formula (A-5-2)) and n = 49.9 (structural unit represented by formula (A-4-2)). The modification rate u was 35.6%.

[0334] <Synthesis Example 4: Synthesis of polyamic acid and / or polyamic acid ester (A4)> A 3 L separable flask was charged with 79.8 g of 6-(2,5-dioxolan-3-yl)-4-methyl-3a,6,7,7a-tetrahydroisobenzofuran-1,3-dione (MCTC) and 458 g of cyclohexanone and stirred at room temperature. 52.0 g of KF-8010 (Shin-Etsu Chemical Co., Ltd.) and 64.4 g of 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (PIDA) were then added, and the separable flask was heated in an oil bath until the internal temperature reached 50°C. Polymerization was carried out for 20 hours to obtain polyamic acid.

[0335] Next, 9.8 g of 4-methoxyphenol (1% solution in cyclohexanone), 51.4 g of glycidyl methacrylate (GMA), and 3.9 g of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, yielding polyamic acid and / or polyamic acid ester (A4).

[0336] The molecular weight of (A4) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 8,100 in weight average molecular weight (Mw). 1 H-NMR confirmed that the copolymer had the structural unit represented by formula (A-5-2) and the structural unit represented by formula (A-4-2), with a copolymerization ratio of m = 79.7 (structural unit represented by formula (A-5-2)) and n = 20.3 (structural unit represented by formula (A-4-2)). Furthermore, the modification rate u was 33.3%.

[0337] <Synthesis Example 5: Synthesis of polyamic acid and / or polyamic acid ester (A5)> A 3 L separable flask was charged with 50.9 g of 6-(2,5-dioxolan-3-yl)-4-methyl-3a,6,7,7a-tetrahydroisobenzofuran-1,3-dione (MCTC) and 475 g of cyclohexanone and stirred at room temperature. 103.2 g of X-22-9409 (Shin-Etsu Chemical Co., Ltd.) and 30.8 g of 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (PIDA) were then added, and the separable flask was heated in an oil bath until the internal temperature reached 50°C. Polymerization was carried out for 20 hours to obtain polyamic acid.

[0338] Next, 9.2 g of 4-methoxyphenol (1% solution in cyclohexanone), 27.2 g of glycidyl methacrylate (GMA), and 3.7 g of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, yielding polyamic acid and / or polyamic acid ester (A5).

[0339] The molecular weight of (A5) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 5,900 in weight average molecular weight (Mw). 1 H-NMR analysis revealed that the copolymer had the structural units represented by the following formula (A-5-2) and the structural units represented by the following formula (A-4-3), with copolymerization ratios m = 59.8 (structural unit represented by formula (A-5-2)) and n = 40.2 (structural unit represented by formula (A-4-3)). Furthermore, the modification rate u was 30.9%. [ka]

[0340] <Synthesis Example 6: Synthesis of polyamic acid and / or polyamic acid ester (A6)> A 3 L separable flask was charged with 59.3 g of 6-(2,5-dioxolan-3-yl)-4-methyl-3a,6,7,7a-tetrahydroisobenzofuran-1,3-dione (MCTC) and 492 g of cyclohexanone and stirred at room temperature. 90.3 g of X-22-9409 (Shin-Etsu Chemical Co., Ltd.) and 41.9 g of 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (PIDA) were then added, and the separable flask was heated in an oil bath until the internal temperature reached 50°C. Polymerization was carried out for 20 hours to obtain polyamic acid.

[0341] Next, 9.6 g of 4-methoxyphenol (1% solution in cyclohexanone), 31.8 g of glycidyl methacrylate (GMA), and 3.8 g of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyamic acid and / or polyamic acid ester (A6).

[0342] The molecular weight of (A6) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 5,700 in weight average molecular weight (Mw). 1 H-NMR analysis revealed that the copolymer had the structural unit represented by formula (A-5-2) and the structural unit represented by formula (A-4-3), with a copolymerization ratio of m=69.5 (structural unit represented by formula (A-5-2)) and n=30.5 (structural unit represented by formula (A-4-3)). The modification rate u was 40.0%.

[0343] <Synthesis Example 7: Synthesis of polyamic acid and / or polyamic acid ester (A7)> A 3 L separable flask was charged with 50.9 g of 6-(2,5-dioxolan-3-yl)-4-methyl-3a,6,7,7a-tetrahydroisobenzofuran-1,3-dione (MCTC) and 475 g of cyclohexanone and stirred at room temperature. 51.6 g of X-22-9409 (Shin-Etsu Chemical Co., Ltd.) and 41.1 g of 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (PIDA) were then added, and the separable flask was heated in an oil bath until the internal temperature reached 50°C. Polymerization was carried out for 20 hours to obtain polyamic acid.

[0344] Next, 9.2 g of 4-methoxyphenol (1% solution in cyclohexanone), 54.5 g of glycidyl methacrylate (GMA), and 3.7 g of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyamic acid and / or polyamic acid ester (A7).

[0345] The molecular weight of (A7) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 5,900 in weight average molecular weight (Mw). 1 H-NMR confirmed that the copolymer had the structural unit represented by formula (A-5-2) and the structural unit represented by formula (A-4-3), with a copolymerization ratio of m = 80.0 (structural unit represented by formula (A-5-2)) and n = 20.0 (structural unit represented by formula (A-4-3)). Furthermore, the modification rate u was 41.2%.

[0346] <Synthesis Example 8: Synthesis of polyamic acid and / or polyamic acid ester (A8)> Polyamic acid was obtained in the same manner as in Synthesis Example 1. Next, 24.8 g of 4-methoxyphenol (1% solution in cyclohexanone), 64.6 g of glycidyl methacrylate (GMA), and 5.0 g of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyamic acid and / or polyamic acid ester (A8).

[0347] The molecular weight of (A8) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 6,100 in weight average molecular weight (Mw). 1 H-NMR analysis revealed that the copolymer had the structural unit represented by formula (A-5-2) and the structural unit represented by formula (A-4-2), with a copolymerization ratio of m=69.7 (structural unit represented by formula (A-5-2)) and n=30.3 (structural unit represented by formula (A-4-2)). The modification rate u was 37.8%.

[0348] <Synthesis Example 9: Synthesis of polyamic acid and / or polyamic acid ester (A9)> Polyamic acid was obtained in the same manner as in Synthesis Example 1. Next, 24.8 g of 4-methoxyphenol (1% solution in cyclohexanone), 193.7 g of glycidyl methacrylate (GMA), and 5.0 g of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyamic acid and / or polyamic acid ester (A9).

[0349] The molecular weight of (A9) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 6,000 in weight average molecular weight (Mw). 1 H-NMR analysis revealed that the copolymer had the structural unit represented by formula (A-5-2) and the structural unit represented by formula (A-4-2), with a copolymerization ratio of m=69.9 (structural unit represented by formula (A-5-2)) and n=30.1 (structural unit represented by formula (A-4-2)). The modification rate u was 52.2%.

[0350] Synthesis Example 10: Synthesis of polyamic acid and / or polyamic acid ester (A10) Polyamic acid was obtained in the same manner as in Synthesis Example 1. Next, 24.8 g of 4-methoxyphenol (1% solution in cyclohexanone), 258.3 g of glycidyl methacrylate (GMA), and 5.0 g of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyamic acid and / or polyamic acid ester (A10).

[0351] The molecular weight of (A10) was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was 6,300. 1 H-NMR confirmed that the copolymer had the structural unit represented by formula (A-5-2) and the structural unit represented by formula (A-4-2), with a copolymerization ratio of m=70.0 (structural unit represented by formula (A-5-2)) and n=30.0 (structural unit represented by formula (A-4-2)). Furthermore, the modification rate u was 67.8%.

[0352] <Synthesis Example 11: Synthesis of polyamic acid and / or polyamic acid ester (A11)> Polyamic acid was obtained in the same manner as in Synthesis Example 1. Next, 24.8 g of 4-methoxyphenol (1% solution in cyclohexanone), 322.9 g of glycidyl methacrylate (GMA), and 5.0 g of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyamic acid and / or polyamic acid ester (A11).

[0353] The molecular weight of (A11) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 6,500 in weight average molecular weight (Mw). 1H-NMR confirmed that the copolymer had the structural unit represented by formula (A-5-2) and the structural unit represented by formula (A-4-2), with a copolymerization ratio of m=69.7 (structural unit represented by formula (A-5-2)) and n=30.3 (structural unit represented by formula (A-4-2)). Furthermore, the modification rate u was 81.5%.

[0354] Comparative Synthesis Example 1: Synthesis of Polyamic Acid and / or Polyamic Acid Ester (A12) A 3 L separable flask was charged with 80.8 g of 6-(2,5-dioxolan-3-yl)-4-methyl-3a,6,7,7a-tetrahydroisobenzofuran-1,3-dione (MCTC) and 472.6 g of cyclohexanone and stirred at room temperature. 78.9 g of KF-8010 (Shin-Etsu Chemical Co., Ltd.) and 42.8 g of 4,4'-diaminodiphenyl ether (ODA) were then added, and the separable flask was heated in an oil bath until the internal temperature reached 50°C. Polymerization was carried out for 20 hours to obtain polyamic acid.

[0355] Next, 10.1 g of 4-methoxyphenol (1% solution in cyclohexanone), 115.0 g of glycidyl methacrylate (GMA), and 4.1 g of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyamic acid and / or polyamic acid ester (A12).

[0356] The molecular weight of (A12) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 7,100 in weight average molecular weight (Mw). 1 H-NMR confirmed that the copolymer had a structural unit represented by the following formula (A'-5-3) and a structural unit represented by the following formula (A-4-2), and the copolymerization ratio was 1 m = 71.1 (structural unit represented by formula (A'-5-3)), n = 28.9 (structural unit represented by formula (A-4-2)). Furthermore, the modification rate u was 39.0%. [ka]

[0357] Comparative Synthesis Example 2: Synthesis of Polyamic Acid and / or Polyamic Acid Ester (A13) A 3 L separable flask was charged with 208.1 g of 6-(2,5-dioxolan-3-yl)-4-methyl-3a,6,7,7a-tetrahydroisobenzofuran-1,3-dione (MCTC) and 1253.4 g of cyclohexanone and stirred at room temperature. 209.8 g of 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (PIDA) was then added, and the separable flask was heated in an oil bath until the internal temperature reached 50°C. Polymerization was carried out for 20 hours to obtain polyamic acid.

[0358] Next, 20.9 g of 4-methoxyphenol (1% solution in cyclohexanone), 104.5 g of glycidyl methacrylate (GMA), and 8.4 g of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was heated and stirred for 15 hours until the internal temperature reached 80°C, thereby carrying out an acrylic modification reaction and obtaining polyamic acid and / or polyamic acid ester (A13).

[0359] The molecular weight of (A13) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 7,700 in weight average molecular weight (Mw). 1 H-NMR analysis revealed that the polymer had a structural unit represented by the following formula (A-5-2), with a copolymerization ratio m of 100 (structural unit represented by formula (A-5-2)). Furthermore, the modification rate u was 35.1%. [ka]

[0360] Comparative Synthesis Example 3: Synthesis of polyamic acid and / or polyamic acid ester (A14) A 3 L separable flask was charged with 59.9 g of 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) (TAHQ) and 475 g of cyclohexanone and stirred at room temperature. 52.3 g of X-22-9409 (Shin-Etsu Chemical Co., Ltd.) and 24.4 g of 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (PIDA) were then added, and the separable flask was heated in an oil bath until the internal temperature reached 50°C. Polymerization was carried out for 20 hours to obtain a polyamic acid.

[0361] Next, 6.8 g of 4-methoxyphenol (1% solution in cyclohexanone), 18.6 g of glycidyl methacrylate (GMA), and 2.7 g of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyamic acid and / or polyamic acid ester (A14).

[0362] The molecular weight of (A14) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be a weight average molecular weight (Mw) of 8,800. 1 H-NMR confirmed that the copolymer had a structural unit represented by the following formula (A'-5-4) and a structural unit represented by the following formula (A'-4-4), and the copolymerization ratio was 1 m = 69.6 (structural unit represented by formula (A'-5-4)), l n =30.4 (structural unit represented by formula (A'-4-4)). Furthermore, the modification rate u was 27.0%. [ka]

[0363] The measurement results of the obtained polyamic acid and / or polyamic acid ester are shown in Table 1. [Table 1]

[0364] <Examples 1 to 15 and Comparative Examples 1 to 3: Preparation of Photosensitive Resin Compositions> (A1) to (A11) synthesized in Synthesis Examples 1 to 11, (A12) to (A14) synthesized in Comparative Synthesis Examples 1 to 3, (B) photopolymerization initiator, (C) crosslinking agent, (D) adhesion aid, (E) sensitizer, and (F) surfactant were mixed as shown in Table 2 below and stirred using a high-speed rotating mixer to prepare a photosensitive resin composition. Furthermore, the photosensitive resin composition was dissolved in cyclohexanone as an organic solvent (G) to prepare a varnish-like photosensitive resin composition. [Table 2]

[0365] The abbreviations in the table are as follows: (B) Photopolymerization initiator Irgacure OXE02: An oxime ester photoinitiator represented by the following structural formula (BASF's "Irgacure OXE02") [ka] Omnirad819: An acylphosphine photopolymerization initiator represented by the following structural formula (IGM's "Omnirad819") [ka]

[0366] (C) Crosslinker TMPT: A compound represented by the following structural formula ("TMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.) [ka] BANI-X: A compound represented by the following structural formula [ka]

[0367] (D) Adhesion aid DATA (3,5-diamino-1,2,4-triazole): A compound represented by the following structural formula [ka]

[0368] (E) Sensitizer N-phenyldiethanolamine: A compound represented by the following structural formula [ka]

[0369] (F) Surfactant KP-341: Polyether surfactant (Shin-Etsu Chemical Co., Ltd. "KP-341")

[0370] <Solubility test> The varnish-like photosensitive resin compositions prepared in the Examples and Comparative Examples were subjected to a storage test at 5° C. for one month, and the solubility was evaluated according to the following criteria. ◯: No precipitates after 1 month. △: No precipitates were observed after 10 hours, but precipitates were observed after one month. ×: Precipitation was observed after 10 hours.

[0371] <Preparation of photosensitive film> A PET film ("Lumirror T6AM" manufactured by Toray Industries, Inc., thickness 38 μm) was prepared as a support. The photosensitive resin compositions prepared in each example and comparative example were uniformly applied to the PET film using a die coater so that the dried photosensitive resin composition layer had a thickness of 10 μm or 100 μm. The film was then dried at 80°C to 120°C for 6 minutes to form a photosensitive resin composition layer on the PET. Next, a protective film (biaxially oriented polypropylene film, "MA-411" manufactured by Oji F-Tex Co., Ltd.) was placed on the surface of the photosensitive resin composition layer and laminated at 80°C to produce a photosensitive film with a three-layer structure of support / photosensitive resin composition layer / protective film.

[0372] <Evaluation of limiting resolution and film remaining (film thickness reduction rate during development)> A 5 μm thick copper plating was laminated on a silicon wafer and roughened with a 1% hydrochloric acid solution for 10 seconds to prepare a substrate. The protective film was removed from the 10 μm thick photosensitive film prepared by the above method, and the photosensitive resin composition layer of the photosensitive film was placed on the roughened substrate so that it was in contact with the surface of the copper layer. After lamination, the support was removed and the substrate was heated at 120°C for 1 minute using a hot plate to produce a photosensitive resin composition layer. This is called a laminate.

[0373] The laminate was then irradiated with ultraviolet light (wavelength 365 nm, intensity 40 mW / cm 2 The exposure was performed at a dose of 50 mJ / cm. 2 to 1000mJ / cm 2 The optimum value was set in the range of 1. For the exposure pattern, a quartz glass mask was used to draw round holes (vias) with opening diameters of 5 μm, 7 μm, 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm.

[0374] Next, the entire surface of the photosensitive resin composition layer of the laminate was spray-developed with cyclopentanone as a developer at a spray pressure of 0.1 MPa for an optimal time between 30 and 600 seconds, followed by rinsing with propylene glycol monomethyl ether acetate (PGMEA) at a spray pressure of 0.1 MPa for 30 seconds, and then heat-treated at 200°C for 120 minutes to cure the photosensitive resin composition layer.

[0375] The diameters of the bottoms of vias with openings of 5 μm, 7 μm, 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm in the exposure pattern were observed and measured using a scanning electron microscope (SEM) at a magnification of 1000x. The minimum size that can be opened is defined as the limiting resolution.

[0376] In addition, the film thickness of the photosensitive resin composition layer after development was measured in a via of the smallest size that could be opened, and the film remaining property was calculated as a film thickness reduction rate using the following calculation method and evaluated according to the following criteria. Film thickness reduction rate = Film thickness after development / Film thickness after application × 100 (%) ◎: Film thickness reduction rate is 90% or more ○: Film thickness reduction rate is 70% or more but less than 90% △: Film thickness reduction rate is 50% or more but less than 70% ×: Film thickness reduction rate is less than 50%

[0377] <Measurement of dielectric properties (dielectric constant, dielectric loss tangent)> The photosensitive resin composition was coated onto a release-treated PET film using a blade to a film thickness of 140 μm. The solution on the PET was heated at 80°C for 15 minutes using a heater to form a photosensitive film having a photosensitive resin composition layer. The photosensitive resin composition layer was peeled from the PET film, and the photosensitive resin composition layer was attached to a metal frame using heat-resistant tape. The photosensitive resin composition layer was then heated at 1000 mJ / cm. 2 The film was then cured at 180°C for 180 minutes to produce film 1 for measuring physical properties. Film 2 for measuring physical properties was also produced in the same manner as film 1 for measuring physical properties, except that the heat curing conditions were changed to 250°C for 120 minutes.

[0378] Test pieces measuring 2 mm in width and 80 mm in length were cut out from the physical property measurement film 1 and the physical property measurement film 2. The dielectric constant Dk and dielectric loss tangent Df of the cut test pieces were measured by the cavity resonance perturbation method using an Agilent Technologies HP8362B measuring device at a measurement frequency of 2.8 GHz and a measurement temperature of 23°C.

[0379] <Measurement of glass transition temperature> The physical property measurement films 1 and 2 prepared for measuring the dielectric properties were cut into test pieces approximately 5 mm wide and 15 mm long, and thermomechanical analysis was performed using a thermomechanical analyzer (Rigaku Corporation, "Thermo Plus TMA8310") by the tensile load method. Specifically, the test pieces were mounted in the thermomechanical analyzer and subjected to two consecutive measurements under the conditions of a 1 g load and a heating rate of 5°C / min (the first measurement was performed at 200°C, and the second measurement was performed at 260°C). The glass transition temperature Tg (°C) was calculated from the results of the second measurement.

[0380] <Warp evaluation> A 100 μm-thick photosensitive film was laminated onto an 8-inch silicon wafer using a laminator, and then heated on a hot plate at 120°C for 5 minutes. The photosensitive resin composition layer was then thermally cured by heating at 200°C for 120 minutes. This resulted in a sample substrate comprising a silicon wafer and a cured layer of the photosensitive resin composition. The amount of warpage of the sample substrate at 25°C was measured using a shadow moiré measurement device ("Thermoire AXP" 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 for all data on the substrate surface in the measurement area was used as the reference plane, and the difference between the minimum and maximum values ​​in the vertical direction from this reference plane was calculated as the amount of warpage (μm).

[0381] In Examples 1 to 15, which contained the component (A) having the specified structure of the present invention, the photosensitive resin composition exhibited excellent solubility in organic solvents, suppressed warpage, and produced cured products with excellent dielectric properties. On the other hand, Comparative Example 1, which did not contain a structure derived from a diamine compound having an indane structure, and Comparative Example 3, which did not contain a structure derived from a tetracarboxylic dianhydride having an alicyclic structure, exhibited poor solubility in cyclohexanone, making it impossible to produce a photosensitive film and perform various evaluations. Furthermore, Comparative Example 2, which did not contain a structure derived from a diamine compound having a siloxane structure, did not exhibit satisfactory dielectric properties or warpage values ​​after curing. It was confirmed that, even in Examples 1 to 15, even when the sensitizer (E) was not contained, increasing the exposure dose resulted in similar results to those of the above examples, although to varying degrees.

Claims

1. (1A) A polyamic acid and / or a polyamic acid ester having a structure derived from a diamine compound having a siloxane structure, a structure derived from a diamine compound having an indane structure, and a structure derived from a tetracarboxylic dianhydride having an alicyclic structure, wherein the polyamic acid ester has an ester residue derived from an epoxy compound having an ethylenically unsaturated bond; (B) a photopolymerization initiator, and (C) a crosslinking agent, A photosensitive resin composition comprising:

2. 2. The photosensitive resin composition according to claim 1, wherein, in the component (1A), the diamine compound having a siloxane structure is a compound represented by the following formula (1a), and the diamine compound having an indane structure is a compound represented by the following formula (2a): 【Chemical 1】 (In formula (1a), R ａ１ , R ａ２ , R ａ３ and R ａ４ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 4 to 20 carbon atoms. １ and X ２ each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and p represents an integer of 1 to 100. 【Chemistry 2】 (In formula (2a), Xa and Xb each independently represent a single bond, a group represented by formula (X-1) below, a group represented by formula (X-2) below, or a group represented by formula (X-3) below, and x represents an integer of 0 to 5.) 【Chemistry 3】 (In the formula, * represents a bond.)

3. 2. The photosensitive resin composition according to claim 1, wherein in component (1A), the tetracarboxylic acid dianhydride having an alicyclic structure has 10 to 30 carbon atoms and a 6-membered alicyclic structure.

4. 2. The photosensitive resin composition according to claim 1, wherein in the component (1A), the tetracarboxylic acid dianhydride having an alicyclic structure is a compound represented by the following formula (3a): 【Chemistry 4】

5. 2. The photosensitive resin composition according to claim 1, wherein the epoxy compound having an ethylenically unsaturated bond in component (1A) is glycidyl (meth)acrylate.

6. In the component (1A), the number of structures derived from a diamine compound having an indane structure is M １ , the number of structures derived from the diamine compound having a siloxane structure is N １ When the compound has a structure derived from another diamine compound, the number of the structures derived from the other diamine compound is represented by L １ When this is the case, m defined by the following formula (1) １ and n defined by the following formula (2) １ The sum of (m １ +n １ 2. The photosensitive resin composition according to claim 1, wherein the molecular weight of the polymer is 90 to 100. [Equation 1] [Equation 2]

7. m １ The photosensitive resin composition according to claim 6, wherein β is 40 to 90.

8. n １ The photosensitive resin composition according to claim 6, wherein β is 10 to 60.

9. In the component (1A), the total number of polyamic acid moieties and polyamic acid ester moieties is T １ , the number of polyamic acid ester moieties having an ester residue derived from an epoxy compound having an ethylenically unsaturated bond is S １ When the above formula is used, the modification rate u is defined by the following formula (3): １ 2. The photosensitive resin composition according to claim 1, wherein (%) is 20 to 100%. [Equation 3]

10. In the diamine compound represented by formula (1a) of component (1A), R ａ１ , R ａ２ , R ａ３ and R ａ４ The photosensitive resin composition according to claim 2 , wherein is a methyl group.

11. In the diamine compound represented by formula (1a) of component (1A), R ａ１ , R ａ２ , R ａ３ and R ａ４ The photosensitive resin composition according to claim 2 , wherein is a phenyl group.

12. In the diamine compound represented by formula (1a) of component (1A), X １ and X ２ The photosensitive resin composition according to claim 2, wherein is a 1,3-propylene group.

13. 3. The photosensitive resin composition according to claim 2, wherein in the component (1A), the diamine compound represented by formula (2a) is a compound represented by the following formula (2a-1): 【Chemistry 5】

14. The photosensitive resin composition according to claim 1 , further comprising (D) an adhesion aid.

15. The photosensitive resin composition according to claim 1 , further comprising (E) a sensitizer.

16. The photosensitive resin composition according to claim 1 , further comprising (F) a surfactant.

17. The photosensitive resin composition according to claim 1 , which is a negative-working photosensitive resin composition.

18. (2A) A polyamic acid and / or a polyamic acid ester having a structural unit represented by the following formula (A-1), a structural unit represented by the following formula (A-2), and a structural unit represented by the following formula (A-3): (B) a photopolymerization initiator, and (C) a crosslinking agent, A photosensitive resin composition comprising: 【Chemistry 6】 (In formula (A-1), each A independently represents a tetravalent organic group having an alicyclic structure. R １ and R ２ each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms and an ethylenically unsaturated group. 【Chemistry 7】 (In formula (A-2), R ａ１ , R ａ２ , R ａ３ and R ａ４ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 4 to 20 carbon atoms. １ and X ２ each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and p represents an integer of 1 to 100. 【Chemistry 8】 (In formula (A-3), Xa and Xb each independently represent a single bond, a group represented by formula (X-1) below, a group represented by formula (X-2) below, or a group represented by formula (X-3) below, and x represents an integer of 0 to 5.) 【Chemistry 9】 (In the formula, * represents a bond.)

19. The photosensitive resin composition according to claim 18, wherein the component (2A) is a polyamic acid and / or a polyamic acid ester having a structural unit represented by the following formula (A-4) and a structural unit represented by the following formula (A-5): 【Chemistry 10】 【Chemistry 11】 (In formula (A-4) and formula (A-5), each A independently represents a tetravalent organic group having an alicyclic structure. R １ and R ２ R each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms and an ethylenically unsaturated group. ａ１ , R ａ２ , R ａ３ and R ａ４ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 4 to 20 carbon atoms. １ and X ２ each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms. p represents an integer of 1 to 100. Xa and Xb each independently represent a single bond, a group represented by the above formula (X-1), a group represented by the above formula (X-2), or a group represented by the above formula (X-3). x represents an integer of 0 to 5.

20. The number of repetitions of the structural unit represented by formula (A-5) is M ２ , the number of repetitions of the structural unit represented by formula (A-4) is N ２ , when other structural units are present, the number of repetitions of the other structural units is L ２ Then, m defined by the following formula (4) ２ and n defined by the following formula (5): ２ The sum of (m ２ +n ２ 20. The photosensitive resin composition according to claim 19, wherein the molecular weight of the polymer is 90 to 100. [Equation 4] [Equation 5]

21. m ２ The photosensitive resin composition according to claim 20, wherein β is 40 to 90.

22. n ２ The photosensitive resin composition according to claim 20, wherein:

23. 20. The photosensitive resin composition according to claim 19, wherein in formulas (A-4) and (A-5), A is a tetravalent organic group having 6 to 26 carbon atoms and a 6-membered alicyclic structure.

24. The photosensitive resin composition according to claim 19, wherein in formula (A-4) and formula (A-5), A is a group represented by the following formula (X-6): 【Chemistry 12】 (In the formula, * represents a bond.)

25. In formula (A-4) and formula (A-5), R １ and R ２ are each independently a hydrogen atom, a group represented by the following formula (X-4), or a group represented by the following formula (X-5): 【Chemistry 13】 (In formula (X-4), R ２４ , R ２５ and R ２６ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; p ２ represents an integer of 0 to 10. * represents a bond. 【Chemistry 14】 In formula (X-5), ring Z represents an aliphatic hydrocarbon ring having 3 to 20 carbon atoms, which may have a substituent. ３４ , R ３５ and R ３６ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; p ３ represents an integer of 0 to 10. * represents a bond.

26. In formula (A-4) and formula (A-5), R １ and R ２ are each independently a hydrogen atom or a group represented by formula (X-4), In formula (X-4), R ２４ is a hydrogen atom or a methyl group, and R ２５ is a hydrogen atom, and R ２６ is a hydrogen atom, and p ２ The photosensitive resin composition according to claim 25, wherein

27. In the component (2A), the structural unit represented by formula (A-1) has R １ and R ２ The total number of ２ , R contained in the structural unit represented by formula (A-1) １ and R ２ The total number of monovalent groups having 1 to 20 carbon atoms and having an ethylenically unsaturated group is S ２ When the modification rate is u ２ The photosensitive resin composition according to claim 18, wherein (%) is 20 to 100%. [Equation 6]

28. In formula (A-4), R ａ１ , R ａ２ , R ａ３ and R ａ４ The photosensitive resin composition according to claim 19, wherein is a methyl group.

29. In formula (A-4), R ａ１ , R ａ２ , R ａ３ and R ａ４ The photosensitive resin composition according to claim 19, wherein is a phenyl group.

30. In formula (A-4), X １ and X ２ The photosensitive resin composition according to claim 19, wherein is a 1,3-propylene group.

31. The photosensitive resin composition according to claim 19, wherein the structural unit represented by formula (A-5) is a structural unit represented by the following formula (A-5-1): 【Chemistry 15】 (In formula (A-5-1), A represents a tetravalent organic group having an alicyclic structure. R １ and R ２ each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms and an ethylenically unsaturated group.

32. The photosensitive resin composition according to claim 18, further comprising (D) an adhesion aid.

33. The photosensitive resin composition according to claim 18, further comprising (E) a sensitizer.

34. The photosensitive resin composition according to claim 18, further comprising (F) a surfactant.

35. The photosensitive resin composition according to claim 18, which is a negative type.

36. 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 35.

37. 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 35.

38. A semiconductor device comprising the semiconductor package substrate of claim 37.

39. A step of forming a photosensitive resin composition layer containing the photosensitive resin composition according to any one of claims 1 to 35 on a circuit board; and a step of irradiating the photosensitive resin composition layer with actinic rays to perform development; A method for manufacturing a semiconductor package substrate, comprising:

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