Photosensitive resin composition

Abstract

The present invention provides a photosensitive resin composition and the like, which is excellent in stability to a developing solution even if a developing time is extended. The present invention is a photosensitive resin composition containing (A) an alkali-soluble resin having a phenolic hydroxyl group in a molecule, (B) a compound containing at least two or more alkoxymethyl groups in a molecule, and (C) a photoacid generator, and the (A) component contains an alkali-soluble resin having a phenolic hydroxyl group in a molecule represented by Formula (A-1), Formula (A-2), and Formula (A-3).[Chemical Formula 1]

Description

Technical Field

[0001] This invention relates to photosensitive resin compositions. It further relates to methods for manufacturing photosensitive films with supports, printed wiring boards, semiconductor devices, and printed wiring boards obtained using the photosensitive resin compositions. Background Technology

[0002] Printed wiring boards, widely used in various electronic instruments, require thinness and fine wiring in order to achieve miniaturization and high functionality in electronic instruments.

[0003] As a manufacturing technology for printed circuit boards, a manufacturing method using a lamination method that alternately stacks insulating layers and conductor layers is known. In manufacturing methods using the lamination method, generally speaking, a thermosetting resin composition is used in the insulating layer, and a photosensitive resin composition is used in the solder resist layer.

[0004] In recent years, there has been a desire to use photosensitive resin compositions when forming interlayer insulating layers. For example, Patent Documents 1 to 3 disclose techniques for forming insulating layers or solder resists using photosensitive resin compositions.

[0005] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2002-139835 Patent Document 2: Japanese Patent Application Publication No. 2018-028690 Patent document 3: Japanese Patent Application Publication No. 2019-060960. Summary of the Invention

[0006] The problem that the invention aims to solve When forming an insulating layer using a photosensitive resin composition, the photosensitive resin composition is typically coated onto a circuit board, and patterning is performed through exposure and development to form multiple vias. The inventors' in-depth research has revealed that if the thickness of the coated photosensitive resin composition layer varies, vias sometimes fail to form in thicker areas. Therefore, if the development time is extended to form vias even in thicker areas, it is found that the bottom and sides of the vias in thinner areas are eroded by the developer, resulting in uneven diameters at the bottoms of multiple vias. Therefore, there is a need for a photosensitive resin composition that suppresses erosion by the developer even with extended development times, i.e., a photosensitive resin composition with excellent stability to the developer (development time dependence).

[0007] The objective of this invention is to provide a photosensitive resin composition with excellent development time dependence; and a method for manufacturing a photosensitive film with a support, a printed wiring board, a semiconductor device, and a printed wiring board obtained using the photosensitive resin composition.

[0008] means for solving problems Through in-depth research, the inventors discovered that by including a specific component in the resin as part of a photosensitive resin composition, the stability of the developing solution is excellent even with extended development time, thus completing the present invention.

[0009] That is, the present invention includes the following contents.

[0010] [1] A photosensitive resin composition comprising: (A) Alkali-soluble resins with phenolic hydroxyl groups within the molecule; (B) Compounds containing at least two alkoxymethyl groups in their molecules, and (C) Photoacid-producing agents (A) The ingredient contains: a compound having the structure shown in formula (A-1), a compound having the structure shown in formula (A-2), and a compound having the structure shown in formula (A-3).

[0011] [Chemistry 1] In equation (A-1), R 1 Each of the following independently represents the divalent group shown in formula (a), X 1 Each can independently represent an alkyl group, an aryl group, a halogen atom, or a monovalent heterocyclic group with optional substituents; n1 represents an integer from 0 to 4, m1 represents an integer from 1 to 200; * represents a bonding site; In equation (A-2), R 2 Each of the following can be independently represented as a divalent group shown in formula (b), a divalent group shown in formula (c), a divalent group formed by a combination of the divalent groups shown in formula (b) and (c), a divalent group formed by a combination of the divalent groups shown in formula (a) and (b), or a divalent group formed by a combination of the divalent groups shown in formula (a) and (c), X 2 Each can independently represent an alkyl group, an aryl group, a halogen atom, or a monovalent heterocyclic group with optional substituents; n2 represents an integer from 0 to 4, m2 represents an integer from 1 to 200; * represents a bonding site; In equation (A-3), R 3 X represents the divalent group shown in formula (a), the divalent group shown in formula (b), the divalent group shown in formula (c), or a divalent group formed by a combination of them. 3 and X 4Each of them independently represents an alkyl group with a substituent, an aryl group with a substituent, a halogen atom, or a monovalent heterocyclic group with a substituent; n3 and n4 each independently represent integers from 0 to 4; [Chemistry 2] In equation (a), R 11 and R 12 Each of the following groups independently represents a hydrogen atom, an alkyl group optionally with a substituent, an aryl group optionally with a substituent, a monovalent heterocyclic group optionally with a substituent, an amino group, a carbonyl group, a carboxyl group, or a group formed by a combination thereof, R 11 and R 12 They can bond together to form a ring; * indicates a bonding site; In equation (b), X 11 Each group independently represents an alkyl group with optional substituents; p1 represents an integer from 0 to 4; * represents a bond position; In equation (c), X 12 and X 13 Each of the above independently represents an alkyl group with optional substituents; p2 and p3 each independently represent integers from 0 to 4; * indicates a bond site.

[0012] [2] According to the photosensitive resin composition of [1], wherein the content of the compound containing the structure shown in formula (A-1) is 5% by mass or more and 85% by mass or less when the total amount of component (A) is 100 parts by mass.

[0013] [3] The photosensitive resin composition according to [1] or [2], wherein the content of the compound containing the structure shown in formula (A-2) is 6% by mass or more and 80% by mass or less when the total amount of component (A) is 100 parts by mass.

[0014] [4] The photosensitive resin composition according to any one of [1] to [3], wherein the content of the compound having the structure shown in formula (A-3) is 6% by mass or more and 80% by mass or less when the total amount of component (A) is 100 parts by mass.

[0015] [5] The photosensitive resin composition according to any one of [1] to [4] further comprises any one of (D) an organic filler and (E) an inorganic filler.

[0016] [6] The photosensitive resin composition according to any one of [1] to [5], wherein component (B) contains an amino resin having at least two alkoxymethyl groups in the molecule.

[0017] [7] The photosensitive resin composition according to any one of [1] to [6], wherein component (B) contains melamine resin.

[0018] [8] A photosensitive film with a support, comprising: a support, and a photosensitive resin composition layer comprising any one of [1] to [7] disposed on the support.

[0019] [9] A printed wiring board comprising an insulating layer formed from a cured product of any one of [1] to [7].

[0020]

[10] The printed wiring board according to [9], wherein the insulating layer is a solder resist.

[0021]

[11] A semiconductor device comprising the printed wiring board described in [9] or

[10] .

[0022]

[12] A method for manufacturing a printed wiring board, comprising: The step of forming a photosensitive resin composition layer comprising any one of the photosensitive resin compositions described in [1] to [7] on a circuit board, The step of curing the photosensitive resin composition layer by irradiating it with active light. The step of developing the cured photosensitive resin composition layer.

[0023] Invention Effects According to the present invention, a photosensitive resin composition with excellent development time dependence can be provided; and a method for manufacturing a photosensitive film with a support, a printed wiring board, a semiconductor device, and a printed wiring board obtained using the photosensitive resin composition can be provided. Detailed Implementation

[0024] The following provides a detailed description of the photosensitive resin composition, the photosensitive film with a support, the printed wiring board, and the semiconductor device of the present invention.

[0025] [Photosensitive Resin Composition] The photosensitive resin composition of the present invention is a photosensitive resin composition containing (A) an alkali-soluble resin having phenolic hydroxyl groups in the molecule, (B) a compound having at least two or more alkoxymethyl groups in the molecule, and (C) a photoacid-producing agent. The (A) component contains: a compound having the structure shown in formula (A-1), a compound having the structure shown in formula (A-2), and a compound having the structure shown in formula (A-3).

[0026] [Chemistry 3] In equation (A-1), R 1Each of the following independently represents the divalent group shown in formula (a), X 1 Each can independently represent an alkyl group, an aryl group, a halogen atom, or a monovalent heterocyclic group with optional substituents; n1 represents an integer from 0 to 4, m1 represents an integer from 1 to 200; * represents a bonding site; In equation (A-2), R 2 Each of the following can be independently represented as a divalent group shown in formula (b), a divalent group shown in formula (c), a divalent group formed by a combination of the divalent groups shown in formula (b) and (c), a divalent group formed by a combination of the divalent groups shown in formula (a) and (b), or a divalent group formed by a combination of the divalent groups shown in formula (a) and (c), X 2 Each can independently represent an alkyl group, an aryl group, a halogen atom, or a monovalent heterocyclic group with optional substituents; n2 represents an integer from 0 to 4, m2 represents an integer from 1 to 200; * represents a bonding site; In equation (A-3), R 3 X represents the divalent group shown in formula (a), the divalent group shown in formula (b), the divalent group shown in formula (c), or a divalent group formed by a combination of them. 3 and X 4 Each of them independently represents an alkyl group with a substituent, an aryl group with a substituent, a halogen atom, or a monovalent heterocyclic group with a substituent; n3 and n4 each independently represent integers from 0 to 4; [Chemistry 4] In equation (a), R 11 and R 12 Each of the following groups independently represents a hydrogen atom, an alkyl group optionally with a substituent, an aryl group optionally with a substituent, a monovalent heterocyclic group optionally with a substituent, an amino group, a carbonyl group, a carboxyl group, or a group formed by a combination thereof, R 11 and R 12 They can bond together to form a ring; * indicates a bonding site; In equation (b), X 11 Each group independently represents an alkyl group with optional substituents; p1 represents an integer from 0 to 4; * represents a bond position; In equation (c), X 12 and X 13 Each of the above independently represents an alkyl group with optional substituents; p2 and p3 each independently represent integers from 0 to 4; * indicates a bond site.

[0027] By incorporating components (A) to (C) into the photosensitive resin composition, excellent stability to the developer is achieved even with prolonged development time, resulting in stable developability. Furthermore, the present invention typically improves the crack resistance and insulation properties of the cured photosensitive resin composition.

[0028] The photosensitive resin composition may further comprise optional components in combination with components (A) to (C). Optional components include, for example, (D) organic fillers, (E) inorganic fillers, (F) solvents, and (G) other additives. The components included in the photosensitive resin composition will be described in detail below.

[0029] <(A) Alkali-soluble resins with phenolic hydroxyl groups within the molecule> The photosensitive resin composition, as component (A), contains an alkali-soluble resin having phenolic hydroxyl groups within the molecule. Component (A) contains: a compound having the structure shown in formula (A-1), a compound having the structure shown in formula (A-2), and a compound having the structure shown in formula (A-3).

[0030] [Chemistry 5] In equation (A-1), R 1 Each of the following independently represents the divalent group shown in formula (a), X 1 Each can independently represent an alkyl group, an aryl group, a halogen atom, or a monovalent heterocyclic group with optional substituents; n1 represents an integer from 0 to 4, m1 represents an integer from 1 to 200; * represents a bonding site; In equation (A-2), R 2 Each of the following can be independently represented as a divalent group shown in formula (b), a divalent group shown in formula (c), a divalent group formed by a combination of the divalent groups shown in formula (b) and (c), a divalent group formed by a combination of the divalent groups shown in formula (a) and (b), or a divalent group formed by a combination of the divalent groups shown in formula (a) and (c), X 2 Each can independently represent an alkyl group, an aryl group, a halogen atom, or a monovalent heterocyclic group with optional substituents; n2 represents an integer from 0 to 4, m2 represents an integer from 1 to 200; * represents a bonding site; In equation (A-3), R 3 X represents the divalent group shown in formula (a), the divalent group shown in formula (b), the divalent group shown in formula (c), or a divalent group formed by a combination of them. 3 and X 4Each of them independently represents an alkyl group with a substituent, an aryl group with a substituent, a halogen atom, or a monovalent heterocyclic group with a substituent; n3 and n4 each independently represent integers from 0 to 4; [Chemistry 6] In equation (a), R 11 and R 12 Each of the following groups independently represents a hydrogen atom, an alkyl group optionally with a substituent, an aryl group optionally with a substituent, a monovalent heterocyclic group optionally with a substituent, an amino group, a carbonyl group, a carboxyl group, or a group formed by a combination thereof, R 11 and R 12 They can bond together to form a ring; * indicates a bonding site; In equation (b), X 11 Each group independently represents an alkyl group with optional substituents; p1 represents an integer from 0 to 4; * represents a bond position; In equation (c), X 12 and X 13 Each of the above independently represents an alkyl group with optional substituents; p2 and p3 each independently represent integers from 0 to 4; * indicates a bond site.

[0031] -Compounds containing the structure shown in formula (A-1)- The photosensitive resin composition contains component (A) as component (A-1), which contains a compound having the structure shown in formula (A-1). Component (A-1) may be used alone or in combination of two or more.

[0032] [Chemistry 7] In equation (A-1), R 1 Each of the following independently represents the divalent group shown in formula (a), X 1 Each can independently represent an alkyl group, an aryl group, a halogen atom, or a monovalent heterocyclic group that is optionally substituented. n1 represents an integer from 0 to 4, and m1 represents an integer from 1 to 200. * indicates a bonding site.

[0033] [Chemistry 8] In equation (a), R 11 and R 12 Each of the following groups independently represents a hydrogen atom, an alkyl group optionally with a substituent, an aryl group optionally with a substituent, a monovalent heterocyclic group optionally with a substituent, an amino group, a carbonyl group, a carboxyl group, or a group formed by a combination thereof, R 11 and R 12 They can bond together to form a ring. * indicates a bonding site.

[0034] X 1 Each of these groups independently represents an alkyl group optionally having a substituent, an aryl group optionally having a substituent, a halogen atom, or a monovalent heterocyclic group optionally having a substituent. From the viewpoint of achieving significant effects of the present invention, X is used as... 1 Preferably, the alkyl group has a substituent, the aryl group has a substituent, or the halogen atom is optional; more preferably, the alkyl group has a substituent, or the aryl group has a substituent; and even more preferably, the alkyl group has a substituent.

[0035] The alkyl group can be straight-chain, branched, or cyclic. Cyclic alkyl groups can be monocyclic or polycyclic. Preferably, the alkyl group has 1 to 10 carbon atoms; more preferably, it has 1 to 6 carbon atoms; and even more preferably, it has 1 to 3 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, sec-butyl, tert-butyl, 2-methylpropyl, and 3-heptyl. From the viewpoint of significantly obtaining the effects of the present invention, methyl is particularly preferred.

[0036] The preferred aryl group is an aryl group with 6 to 30 carbon atoms, more preferably an aryl group with 6 to 20 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms. Examples of aryl groups include phenyl and naphthyl groups.

[0037] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, with fluorine being the preferred choice.

[0038] The preferred monovalent heterocyclic group is one with 3 to 21 carbon atoms, more preferably one with 3 to 15 carbon atoms, and even more preferably one with 3 to 9 carbon atoms. The monovalent heterocyclic group also includes a monovalent aromatic heterocyclic group (heteroaryl). Examples of monovalent heterocyclic groups include thiophene, pyrrolith, furanyl, furanyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, pyrrolidinyl, piperidinyl, quinolinyl, and isoquinolinyl. Pyrrolidinyl is preferred. A monovalent heterocyclic group is a group obtained by removing one hydrogen atom from the heterocycle of a heterocyclic compound.

[0039] R 1Each of the two divalent groups represented by formula (a) is independently represented. The bonding sites in formula (a) are preferably bonded to the OH group of the phenolic site in formula (A-1) at any of the ortho, meta, and para positions, more preferably at either the meta or para position, and even more preferably in a mixture of meta and para bonded substances. When the bonding sites in formula (a) are present in a mixture of meta and para bonded substances to the OH group of the phenolic site in formula (A-1), and the meta bonded substance in formula (a) is denoted as m, and the para bonded substance in formula (a) is denoted as p, the mixing ratio (m:p) is preferably 1:0.1 to 10, more preferably 1:0.1 to 5, even more preferably 1:0.1 to 1, and particularly preferably 1:0.5 to 2.

[0040] In equation (a), R 11 and R 12 Each of the following groups independently represents a hydrogen atom, an alkyl group optionally with a substituent, an aryl group optionally with a substituent, a monovalent heterocyclic group optionally with a substituent, an amino group, a carbonyl group, a carboxyl group, or a group formed by a combination thereof, R 11 and R 12 They can bond together to form rings. From the viewpoint of achieving significant effects of the present invention, hydrogen atoms and alkyl groups are preferred.

[0041] As R 11 and R 12 The alkyl, aryl, and monovalent heterocyclic groups represented are the same as X in formula (A-1). 1 The alkyl, aryl, and monovalent heterocyclic groups are the same.

[0042] Examples of groups formed by combinations of these groups include groups formed by combinations of alkyl and carbonyl groups; groups formed by combinations of aryl and carbonyl groups; groups formed by combinations of alkyl, amino, and carbonyl groups; and groups formed by combinations of aryl, amino, and carbonyl groups.

[0043] R 11 and R 12 They can bond together to form rings; ring structures also include spiral rings and fused rings. In this case, R 11 and R 12 Preferably, the group forms a cyclopentane ring, a cyclohexane ring, a 2,2-dimethyl-4-methylcyclohexane ring, a fluorene ring, a pyrrolidine ring, or a γ-lactam ring.

[0044] As specific examples of the divalent group shown in formula (a), the following groups can be cited. In the formula, "*" indicates a bonding site.

[0045] [Chemistry 9] [Chemistry 10] X 1 The alkyl group and R are represented 11 and R 12 The alkyl and aryl groups represented may optionally have substituents. Examples of substituents in this invention, such as halogen atoms, -OH, and -OC, are examples of substituents where each group has substituents. 1-6 Alkyl, -N(C) 1-6 Alkyl)2, C 1-6 Alkyl, C 6-10 Aryl, -NH2, -NH(C 1-6 Alkyl groups, -CN, -C(O)OC 1-6 Alkyl groups, -C(O)H, -NO2, etc.

[0046] In this specification, the expression "optionally having substituents" means, unless otherwise specified, unsubstituted or having 1 to 5 (preferably 1, 2, or 3) substituents. It should be noted that in cases with multiple substituents, these substituents may be identical or different from each other. Furthermore, in this specification, "C"... p ~C q The term "(p and q are positive integers, satisfying p < q)" indicates that the number of carbon atoms in the organic group immediately following the term is p to q. For example, the expression "C1 to C6 alkyl" indicates an alkyl group with 1 to 6 carbon atoms.

[0047] n1 represents an integer from 0 to 4, preferably an integer from 0 to 3, more preferably 0 or 1, and especially preferably 1.

[0048] m1 represents an integer from 1 to 200, preferably an integer from 1 to 150, more preferably an integer from 1 to 100, and even more preferably an integer from 1 to 50.

[0049] Specific examples of component (A-1) include the following resins. It should be noted that in these specific examples, the resins are mixed in a ratio of 60% meta-position and 40% para-position relative to the OH groups at the phenolic site. In formula (1) below, n represents an integer from 1 to 200.

[0050] [Chemistry 11] (A-1) Components may be commercially available products, and two or more may be used together. Specific examples of commercially available (A-1) components that can be used include Asahi Organic Materials Co., Ltd.'s "TR4020G" (the resin shown in formula (1)); Asahi Organic Materials Co., Ltd.'s "TR4050G", "TR4080G", "TR5020G", "TR5050G", "TR6020G", "TR6050G", "TR6080G" and other AV Light series; Sumitomo Base Light Co., Ltd.'s photoresist resin series; Gunei Chemical Industry Co., Ltd.'s Retrap series; and DIC Co., Ltd.'s "PR-30" series. FENORIT series including “-40P”, “PR-100L”, “PR-100H”, “PR-50”, “PR-55”, “PR-56-1”, “PR-56-2”, “WR-101”, “WR-102”, “WR-103”, “WR-104”, etc.; LF-100”, “LF-110”, “LF-120”, “LF-200”, “LF-400”, “LF-500” manufactured by Reginay Co., Ltd.; and the base resin series for photoresists manufactured by Meiwa Kasei Co., Ltd., etc.

[0051] Component (A-1) is typically obtained by polycondensation of phenol or its derivatives with aldehydes and / or ketones. The polycondensation is carried out in the presence of a catalyst such as an acid or base. Therefore, the terminal groups of component (A-1) are optionally substituted hydroxyphenyl or aldehyde groups, preferably both terminals being optionally substituted hydroxyphenyl groups.

[0052] From the viewpoint of significantly obtaining the effects of the present invention, the weight-average molecular weight of component (A-1) is preferably 500 or more, more preferably 700 or more, even more preferably 1000 or more, preferably 150,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0053] The weight-average molecular weight of the resin can be determined by gel permeation chromatography (GPC) as a conversion value to polystyrene.

[0054] From the viewpoint of significantly obtaining the effects of the present invention, when the total content of component (A-1) is 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, preferably 85% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0055] Furthermore, regarding the content of component (A-1), from the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component of the photosensitive resin composition is 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, preferably 85% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less.

[0056] Furthermore, regarding the content of component (A-1), from the viewpoint of significantly achieving the effects of the present invention, when the resin component is 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less. Here, resin component refers to components other than components (D) and (E).

[0057] -Compounds containing the structure shown in formula (A-2)- The photosensitive resin composition contains component (A) as component (A-2), which contains a compound having the structure shown in formula (A-2). Component (A-2) can be used alone or in combination of two or more.

[0058] [Chemistry 12] In equation (A-2), R 2 Each of the following can be independently represented as a divalent group shown in formula (b), a divalent group shown in formula (c), a divalent group formed by a combination of the divalent groups shown in formula (b) and (c), a divalent group formed by a combination of the divalent groups shown in formula (a) and (b), or a divalent group formed by a combination of the divalent groups shown in formula (a) and (c), X 2 Each can independently represent an alkyl group, an aryl group, a halogen atom, or a monovalent heterocyclic group with optional substituents; n2 represents an integer from 0 to 4, m2 represents an integer from 1 to 200; * represents a bonding site; [Chemistry 13] In equation (a), R 11 and R 12 Each of the following groups independently represents a hydrogen atom, an alkyl group optionally with a substituent, an aryl group optionally with a substituent, a monovalent heterocyclic group optionally with a substituent, an amino group, a carbonyl group, a carboxyl group, or a group formed by a combination thereof, R 11 and R 12 They can bond together to form a ring; * indicates a bonding site; In equation (b), X11 Each group independently represents an alkyl group with optional substituents; p1 represents an integer from 0 to 4; * represents a bond position; In equation (c), X 12 and X 13 Each of the above independently represents an alkyl group with optional substituents; p2 and p3 each independently represent integers from 0 to 4; * indicates a bond site.

[0059] R 2 Each of the following can be independently represented: the divalent group shown in formula (b), the divalent group shown in formula (c), a divalent group formed by a combination of the divalent group shown in formula (b) and the divalent group shown in formula (c), a divalent group formed by a combination of the divalent group shown in formula (a) and the divalent group shown in formula (b), or a divalent group formed by a combination of the divalent group shown in formula (a) and the divalent group shown in formula (c). For the divalent group shown in formula (a), as described above, the bonding sites in formulas (a) to (c) are preferably bonded to the OH group of the phenolic site in formula (A-2) at any of the ortho, meta, and para positions, more preferably at either the meta or para positions, and even more preferably a mixture of meta and para bonded substances. The mixing ratio of substances in which the bonding sites in formulas (a) to (c) are bonded to the OH group of the phenolic site in formula (A-2) at the meta and para positions is the same as that for the group shown in formula (a).

[0060] X in equations (b) to (c) 11 X 12 and X 13 Each can be independently represented as an alkyl group with optional substituents. X 11 ~X 13 X in equation (A-1) 1 same.

[0061] In equations (b) to (c), p1, p2, and p3 each independently represent an integer from 0 to 4, preferably an integer from 0 to 3, and more preferably 0 or 1.

[0062] As specific examples of the divalent group shown in formula (b), the following groups can be cited. In the formula, "*" indicates a bonding site.

[0063] [Chemistry 14] As specific examples of the divalent group shown in formula (c), the following groups can be cited. In the formula, "*" indicates a bonding site.

[0064] [Chemistry 15] Specific examples of divalent groups formed by a combination of the divalent groups shown in formula (b) and formula (c), divalent groups formed by a combination of the divalent groups shown in formula (a) and formula (b), and divalent groups formed by a combination of the divalent groups shown in formula (a) and formula (c) can be given as follows. In the formulas, "*" indicates a bonding site.

[0065] [Chemistry 16] X 2 Each of these independently represents an alkyl group optionally having a substituent, an aryl group optionally having a substituent, a halogen atom, or a monovalent heterocyclic group optionally having a substituent, and X in formula (A-1). 1 same.

[0066] n2 represents an integer from 0 to 4, which is the same as n1 in equation (A-1). In addition, m2 represents an integer from 1 to 200, which is the same as m1 in equation (A-1).

[0067] Specific examples of component (A-2) include the following groups. It should be noted that in these specific examples, the OH groups at the phenolic sites are mixed in a ratio of 60% meta-position and 40% para-position. In formulas (2) and (3) below, n represents an integer from 1 to 200.

[0068] [Chemistry 17] (A-2) Components may be commercially available products, and two or more may be used together. Specific examples of commercially available (A-2) components that can be used include “MEHC-7851SS” (resin shown in formula (2)) and “MEHC-78004S” (resin shown in formula (3)) manufactured by Meiwa Chemical Co., Ltd., “MEHC-7851-SS”, “MEHC-7851-S”, “MEHC-7851-M”, “MEHC-7851-H”, “MEHC-7800-4S”, “MEHC-7800-SS”, “MEHC-7800-S”, “MEHC-7800-M”, “MEHC-7800-H” manufactured by Meiwa Chemical Co., Ltd., and “GPH-65”, “GPH-103”, and “MEHC-7841-4S” manufactured by Nippon Kayaku Co., Ltd.

[0069] Component (A-2) is typically obtained by polycondensation of phenol or its derivatives with compounds other than phenol. Polycondensation is carried out in the presence of a catalyst such as an acid or base. Therefore, the terminal portion of component (A-2) is preferably a hydroxyphenyl group optionally having substituents, and more preferably both terminals are hydroxyphenyl groups optionally having substituents.

[0070] From the viewpoint of significantly obtaining the effects of the present invention, the weight-average molecular weight of component (A-2) is preferably 100 or more, more preferably 300 or more, even more preferably 500 or more, preferably 50,000 or less, more preferably 10,000 or less, and even more preferably 5,000 or less.

[0071] From the viewpoint of significantly obtaining the effects of the present invention, when the total content of component (A-2) is 100% by mass, it is preferably 6% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0072] Furthermore, regarding the content of component (A-2), from the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component of the photosensitive resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.

[0073] Furthermore, regarding the content of component (A-2), from the viewpoint of significantly obtaining the effects of the present invention, when the resin component is 100% by mass, it is preferably 1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, preferably 70% by mass or less, more preferably 65% ​​by mass or less, and further preferably 60% by mass or less.

[0074] -Compounds having the structure shown in formula (A-3)- The photosensitive resin composition contains component (A) as component (A-3), which contains a compound having the structure shown in formula (A-3). Component (A-3) can be used alone or in combination of two or more.

[0075] [Chemistry 18] In equation (A-3), R 3 X represents the divalent group shown in formula (a), the divalent group shown in formula (b), the divalent group shown in formula (c), or a divalent group formed by a combination of them. 3 and X 4 Each of them independently represents an alkyl group with a substituent, an aryl group with a substituent, a halogen atom, or a monovalent heterocyclic group with a substituent; n3 and n4 each independently represent integers from 0 to 4; [Chemistry 19] In equation (a), R 11and R 12 Each of the following groups independently represents a hydrogen atom, an alkyl group optionally with a substituent, an aryl group optionally with a substituent, a monovalent heterocyclic group optionally with a substituent, an amino group, a carbonyl group, a carboxyl group, or a group formed by a combination thereof, R 11 and R 12 They can bond together to form a ring; * indicates a bonding site; In equation (b), X 11 Each group independently represents an alkyl group with optional substituents; p1 represents an integer from 0 to 4; * represents a bond position; In equation (c), X 12 and X 13 Each of the above independently represents an alkyl group with optional substituents; p2 and p3 each independently represent integers from 0 to 4; * indicates a bond site.

[0076] R 3 The divalent group represented by formula (a), formula (b), formula (c), or a combination thereof. The divalent groups represented by formulas (a) to (c) are as described above.

[0077] The bonding sites in formulas (a) to (c) are preferably bonded to the OH group of the phenolic site in formula (A-3) at any of the ortho, meta, and para positions, more preferably at either the meta or para positions, and even more preferably at the para position.

[0078] X 3 and X 4 Each of these independently represents an alkyl group optionally having a substituent, an aryl group optionally having a substituent, a halogen atom, or a monovalent heterocyclic group optionally having a substituent, and X in formula (A-1). 1 same.

[0079] n3 and n4 each independently represent integers from 0 to 4, the same as n1 in equation (A-1).

[0080] Specific examples of components (A-3) include the following groups.

[0081]

Chemistry 20

Chemistry 21

Chemistry 22

Chemistry 23

Chemistry 24

Chemistry 25

Chemistry 26

Chemistry 27

Chemistry 28

Chemistry 29

[0082] From the viewpoint of significantly obtaining the effects of the present invention, the molecular weight of component (A-3) is preferably 150 or more, more preferably 160 or more, even more preferably 170 or more, preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less.

[0083] From the viewpoint of significantly obtaining the effects of the present invention, when the total content of component (A-3) is 100% by mass, it is preferably 6% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0084] Furthermore, regarding the content of component (A-3), from the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component of the photosensitive resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.

[0085] Furthermore, regarding the content of component (A-3), from the viewpoint of significantly obtaining the effects of the present invention, when the resin component is 100% by mass, it is preferably 1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, preferably 60% by mass or less, more preferably 55% by mass or less, and further preferably 50% by mass or less.

[0086] When the content of component (A-1) is denoted as a1 when component (A) as a whole is 100% by mass, and the content of component (A-2) is denoted as a2 when component (A) as a whole is 100% by mass, the ratio a2 / a1 is preferably 0.01 or more, more preferably 0.05 or more, more preferably 0.1 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 1 or less.

[0087] When the content of component (A-3) is denoted as a3 when component (A) as a whole is 100% by mass, and a3 / a1 is taken as a3 / a1, from the viewpoint of significantly obtaining the effect of the present invention, it is preferably 0.01 or more, more preferably 0.05 or more, more preferably 0.1 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 1 or less.

[0088] Furthermore, from the viewpoint of significantly obtaining the effects of the present invention, a2 / a3 is preferably 0.2 or more, more preferably 0.25 or more, more preferably 0.3 or more, preferably 5 or less, more preferably 3 or less, and even more preferably 1.5 or less.

[0089] From the viewpoint of significantly obtaining the effects of the present invention, when the content of component (A) is 100% by mass, it is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 35% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less.

[0090] From the viewpoint of significantly obtaining the effects of the present invention, when the resin component of the photosensitive resin composition is 100% by mass, the content of component (A) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.

[0091] <(B) Compounds containing at least two alkoxymethyl groups in their molecules> The photosensitive resin composition, as component (B), contains a compound having at least two alkoxymethyl groups in its molecule. Component (B) has the function of reacting with component (A) to form a cross-linked structure. Component (B) can be used alone or in combination of two or more.

[0092] The alkoxymethyl group is the group shown in formula (B-1). In the formula, "*" indicates a bonding site.

[0093] [Chemistry 30] In equation (B-1), R 21 This indicates an alkyl group that may have a substituent.

[0094] R 21 The alkyl group can be a substituent. The alkyl group can be straight-chain, branched, or cyclic, and the cyclic alkyl group can be monocyclic or polycyclic. Preferably, the alkyl group has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, sec-butyl, and tert-butyl. From the viewpoint of significantly obtaining the effects of the present invention, methyl and butyl are preferred, and methyl is more preferred.

[0095] R 21 The alkyl group represented may optionally have substituents.

[0096] The alkoxymethyl group is preferably an alkoxymethyl amino group represented by the following formula (B-1'). In the formula, "*" indicates a bonding site.

[0097] [Chemistry 31] In formula (B-1'), R 22 R in equation (B-1) 21 Same. R represents a hydrogen atom or an alkoxymethyl group.

[0098] As component (B), a compound containing at least two alkoxymethyl groups in its molecule can be used. Examples of such compounds include amino resins containing at least two alkoxymethyl groups in their molecule and phenolic resins containing at least two alkoxymethyl groups in their molecule. From the viewpoint of obtaining a photosensitive resin composition with superior photosensitivity, an amino resin containing at least two alkoxymethyl groups in its molecule is preferred.

[0099] Examples of amino resins containing at least two alkoxymethyl groups in their molecules include melamine resin and urea resin, with melamine resin being preferred.

[0100] As a melamine resin, a melamine resin having, for example, the structural unit shown in formula (B-2) is preferred.

[0101] [Chemistry 32] In equation (B-2), X 21 X 22 X 23 and X 24 X 25 and X 26 Each can independently represent a hydrogen atom or an alkoxymethyl group. R 50 This represents a hydrogen atom, an amino group, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an alkoxymethylamino group as shown in formula (B-1'). However, in R... 50 In the case of a hydrogen atom, an alkyl group optionally having a substituent, or an aryl group optionally having a substituent, X 21 X 22 X 23 and X 24 At least two of them are alkoxymethyl groups.

[0102] X 21 ~X 24 The alkoxymethyl group represented is the same as that in formula (B-1). In R 50 In the case of a hydrogen atom, an alkyl group optionally having a substituent, or an aryl group optionally having a substituent, X 21 ~X 24 At least two of them are alkoxymethyl groups, preferably X. 21 ~X 24 At least three of them are alkoxymethyl groups, more preferably X. 21 ~X 24 At least four of them are alkoxymethyl groups.

[0103] R 50The term represents a hydrogen atom, an amino group, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an alkoxymethylamino group of formula (B-1'), preferably an aryl group optionally having a substituent, an alkoxymethylamino group of formula (B-1'), and more preferably an alkoxymethylamino group of formula (B-1'). The alkyl group optionally having a substituent and R in formula (a) 11 The alkyl groups represented are the same, and optionally the aryl group with substituents is the same as R in formula (a). 11 The aryl groups represented are the same.

[0104] Melamine resin having the structural unit shown in formula (B-2) is preferably melamine resin having the structural unit shown in formula (B-2').

[0105] [Chemistry 33] In equation (B-2'), X 25 X 26 X 27 X 28 X 29 and X 30 Each can independently represent a hydrogen atom or an alkoxymethyl group. However, X 25 X 26 X 27 X 28 X 29 and X 30 At least two of them are alkoxymethyl groups.

[0106] X 25 ~X 30 The alkoxymethyl group represented is the same as that in formula (B-1). X 25 ~X 30 At least two of them are alkoxymethyl groups, preferably X. 25 ~X 30 At least three of them are alkoxymethyl groups, more preferably X. 25 ~X 30 At least four of them are alkoxymethyl groups, with X being more preferred. 25 ~X 30 All are alkoxymethyl groups.

[0107] As specific examples of melamine resins, the following melamine resins can be cited.

[0108] [Chemistry 34] Commercially available melamine resins can be used. Examples of commercially available products include "MW-390", "MW-100LM", and "MX-750LM" manufactured by Sanwa Kemica Co., Ltd., and the Cymel series manufactured by Ornex Japan Co., Ltd.

[0109] Melamine resin can be prepared, for example, by the polycondensation of melamine and formaldehyde.

[0110] As a urea resin, a urea resin having, for example, either the structural unit shown in formula (B-3) or the structural unit shown in formula (B-4) is preferred.

[0111] [Chemistry 35] In equation (B-3), X 31 X 32 X 33 and X 34 Each can independently represent a hydrogen atom or an alkoxymethyl group. However, X 31 X 32 X 33 and X 34 At least two of them are alkoxymethyl groups.

[0112] In equation (B-4), X 35 and X 36 It represents an alkoxymethyl group.

[0113] X 31 ~X 38 The alkoxymethyl group represented is the same as that in formula (B-1). X 31 ~X 34 At least two of them are alkoxymethyl groups, preferably X. 31 ~X 34 At least three of them are alkoxymethyl groups, more preferably X. 31 ~X 34 At least four of them are alkoxymethyl groups.

[0114] Commercially available urea resins can be used. Examples of commercially available products include "MX-270", "MX-279", and "MX-280" manufactured by Sanwa Kemica Co., Ltd., and the Cymel series manufactured by Ornex Japan Co., Ltd.

[0115] Urea resin can be prepared, for example, by the polycondensation of urea and formaldehyde.

[0116] As a phenolic resin containing at least two alkoxymethyl groups in its molecule, a phenolic resin having, for example, the structural unit shown in formula (B-5) is preferred.

[0117] [Chemistry 36] In equation (B-5), X 39 R represents alkoxymethyl. 23 and R 24 Each independently represents an alkyl group optionally having a substituent, R 25 Represents a single bond or a divalent organic group. s and t each independently represent integers from 1 to 3, and u and v each independently represent integers from 0 to 4.

[0118] X 39 The alkoxymethyl group represented is the same as that in formula (B-1). R 23 and R 24 The optional alkyl group with substituents represented by X in formula (A-1) 1 The alkyl groups represented are the same as the optional alkyl groups.

[0119] R 25 This indicates a single bond or a divalent organic group. Examples of divalent organic groups include alkylene groups with 1 to 10 carbon atoms (such as methylene, ethylene, and propylene); alkylidene groups with 2 to 10 carbon atoms (such as ethoxyyl); aryl groups with 6 to 30 carbon atoms (such as phenylene); groups obtained by replacing some or all of the hydrogen atoms of these hydrocarbon groups with halogen atoms such as fluorine atoms; sulfonyl groups; carbonyl groups; ether bonds; thioether bonds; and amide bonds.

[0120] From the viewpoint of significantly obtaining the effects of the present invention, when the content of component (B) is 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 30% by mass or less, and more preferably 25% by mass or less.

[0121] From the viewpoint of significantly obtaining the effects of the present invention, when the content of component (B) is 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 30% by mass or less, and more preferably 25% by mass or less.

[0122] <(C) Photoacid-producing agents> The photosensitive resin composition, as component (C), contains a photoacid-generating agent. The photoacid-generating agent (C) generates acid upon irradiation by active light such as ultraviolet light. This acid promotes the reaction between component (A) and component (B), thereby favorably forming a negative pattern. Component (C) can be used alone or in combination of two or more.

[0123] As photoacid-producing agents, compounds that generate acid upon irradiation with active light can be used. Examples of such photoacid-producing agents include halogen-containing compounds, ononium salt compounds, diazonium ketone compounds, sulfone compounds, sulfonic acid compounds, sulfonylimide compounds, diazomethane compounds, and oxime ester compounds. Among these, halogen-containing compounds are preferred from the viewpoint of significantly obtaining the effects of the present invention.

[0124] Examples of halogenated compounds suitable for use as photoacid-producing agents include, for example, alkyl-containing hydrocarbon compounds and heterocyclic compounds containing alkyl halogens. Specific examples of suitable halogenated compounds include 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-triazine, 2-(methoxyphenyl)-4,6-bis(trichloromethyl)-triazine, and 2-[2-(4-methoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-triazine. Triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-triazine, 1,10-dibromo-n-decane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, phenyl-bis(trichloromethyl)-triazine, 4-methoxyphenyl-bis(trichloromethyl)-triazine, styryl-bis(trichloromethyl)-triazine, naphthyl-bis(trichloromethyl)-triazine, and other triazine derivatives.

[0125] Halogen-containing compounds can be commercially available. Examples of commercially available products include "TFE-triazine", "TME-triazine", "MP-triazine", "MOP-triazine", and "dimethoxytriazine" (halogen-containing compounds with a triazine skeleton are photoacid-producing agents) manufactured by Sanwa Kemikal Co., Ltd.

[0126] Examples of onium salt compounds suitable for use as photoacid-producing agents include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts. Specific examples of suitable onium salt compounds include tris(4-methylphenyl)sulfonium trifluoromethanesulfonate, tris(4-methylphenyl)sulfonium hexafluorophosphonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-tert-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyl diphenylsulfonium p-toluenesulfonate, and 4,7-di-n-butoxynaphthiotetrahydrothiophenonium trifluoromethanesulfonate.

[0127] Onium salt compounds can be commercially available. Examples of commercially available products include "TS-01" and "TS-91" manufactured by Sanwa Kemica Co., Ltd.; "CPI-110A", "CPI-210S", "HS-1", "LW-S1", "IK-1", and "CPI-310B" manufactured by SunA Pro Co., Ltd.; and "SI-110L", "SI-180L", and "SI-100L" manufactured by Sanshin Chemical Industry Co., Ltd.

[0128] Examples of diazonone compounds suitable for use as photoacid-producing agents include 1,3-diketone-2-diazo compounds, diazonobenzoquinone compounds, and diazononaphthoquinone compounds. Specific examples of suitable diazonone compounds include phenolic 1,2-naphthoquinone diazono-4-sulfonate compounds.

[0129] Examples of sulfone compounds suitable for use as photoacid-producing agents include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples of suitable sulfone compounds include 4-tribenzoylmethyl sulfone, mesitylene benzoylmethyl sulfone, and bis(benzoylmethylsulfonyl)methane.

[0130] Examples of sulfonic acid compounds suitable for use as photo-induced acid-producing agents include alkyl sulfonates, haloalkyl sulfonates, aryl sulfonates, and imino sulfonates. Specific examples of suitable sulfonic acid compounds include benzoin toluene sulfonate, pyrogallol tris(trifluoromethanesulfonate), o-nitrobenzyl trifluoromethanesulfonate, and o-nitrobenzyl p-toluene sulfonate.

[0131] Specific examples of sulfonylimide compounds suitable for use as photoacid-producing agents include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, and N-(trifluoromethylsulfonyloxy)naphthylimide.

[0132] Specific examples of diazonium compounds suitable for use as photoacid-producing agents include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(phenylsulfonyl)diazomethane. Commercially available diazonium compounds are permitted.

[0133] Specific examples of oxime ester compounds suitable for use as photo-induced acid-producing agents include Benzeneacetonitrile, 2-methyl-α-[2-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene], Benzeneacetonitrile, 2-methyl-α-[2-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene], etc. As commercially available products, examples include BASF's Irgacure series such as "PAG103", "PAG121", "PAG169", and "PAG203".

[0134] (C) The content of the photoacid generator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, preferably 3% by mass or less, and more preferably 1.5% by mass or less, when the non-volatile component in the photosensitive resin composition is taken as 100% by mass.

[0135] <(D) Organic filler materials> The photosensitive resin composition may optionally further include (D) an organic filler material. The (D) organic filler material exhibits flexibility and is therefore able to disperse stress in the cured photosensitive resin composition, resulting in improved crack resistance and insulation.

[0136] Examples of components (D) include polyurethane microparticles, rubber particles, polyamide microparticles, silicone particles, etc.

[0137] As polyurethane microparticles, commercially available products can be used, such as "MM-101SW", "MM-101SWA", "MM-101SM", "MM-101SMA" and "MM-110SMA" manufactured by Genjo Kogyo Co., Ltd.; and the RKB series manufactured by Reginas Chemical Co., Ltd.

[0138] As rubber granules, any type of rubber granule can be made from microparticles of a resin that exhibits rubber elasticity and is chemically cross-linked to make it insoluble and infusible in organic solvents. Examples include acrylonitrile butadiene rubber granules, butadiene rubber granules, acrylic rubber granules, and methyl methacrylate-butadiene-styrene copolymer granules. Commercially available products can be used as rubber granules, such as "EXL-2655" manufactured by Dow Kemikar Nippon Co., Ltd.; "AC3816N", "AC3355", "AC3816", "AC3832", "AC4030", "AC3364", and "IM101" manufactured by Gunz Kasei Co., Ltd.; and "Pararoide EXL2655" and "EXL2602" manufactured by Kureha Chemical Co., Ltd. Models manufactured by Kanekka Co., Ltd., including "B-11A", "B513", "B22", "B-521", "B-561", "B-564", "FM-21", "FM-40", "FM-50", "M-701", "M-711", "M-732", "M-300", "FM-40", "M-570", and "M-210"; and the RKB series manufactured by Rejinas Chemical Co., Ltd., etc.

[0139] As polyamide microparticles, particles of resin with an amide bond of 50 μm or less can be used, such as aliphatic polyamides like nylon, aromatic polyamides like Kevlar, and polyamide-imide. Commercially available polyamide microparticles can be used, such as "VESTOSINT 2070" manufactured by Daiserhuis Co., Ltd., and "SP500" manufactured by Tore Co., Ltd.

[0140] (D) The average particle size of the organic filler material is preferably 0.005 μm or more, or 0.02 μm or more, more preferably 0.2 μm or more, preferably 1 μm or less, and more preferably 0.6 μm or less. (D) The average particle size of the organic filler material can be determined using a dynamic light scattering method. (D) The average particle size of the organic filler material can be determined, for example, by uniformly dispersing the organic filler material in a suitable organic solvent by ultrasonication, and then using a thick system particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.) to prepare the particle size distribution of the organic filler material on a mass basis, and recording the median diameter as the average particle size.

[0141] (D) From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component of the photosensitive resin composition is 100% by mass, the content of the organic filler material is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less.

[0142] <(E) Inorganic Filler Materials> The photosensitive resin composition may optionally contain (E) inorganic filler. By including (E) inorganic filler in the resin composition, a cured product with excellent insulating properties can be obtained.

[0143] Inorganic compounds are used as inorganic filler materials. Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Furthermore, spherical silica is preferred as silica. (E) One type of inorganic filler material may be used alone, or two or more may be used in combination.

[0144] Commercially available products as (E) inorganic filler materials include, for example, Denka's "UFP-30"; Nippon Steel & Sumitomo Metal Materials' "SP60-05" and "SP507-05"; and Admadex's "YC100C", "YA050C", "YA050C-MJE", and "YA010C". "UFP-30" manufactured by Tokuman Co., Ltd.; "シルフィルNSS-3N", "シルフィルNSS-4N", "シルフィルNSS-5" manufactured by Tokuman Co., Ltd. N"; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "SC2050-SXF", etc. manufactured by Atomtec Co., Ltd.

[0145] (E) From the viewpoint of significantly achieving the desired effect of the present invention, the average particle size of the inorganic filler material is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

[0146] (E) The average particle size of inorganic filler materials can be determined by laser diffraction and scattering based on Mie scattering theory. Specifically, a particle size distribution of the inorganic filler material is prepared on a volume basis using a laser diffraction and scattering particle size distribution measuring device, and the median diameter is recorded as the average particle size. The sample to be measured can be a substance obtained by weighing 100 mg of inorganic filler material and 10 g of methyl ethyl ketone in a vial and dispersing it ultrasonically for 10 minutes. For the sample to be measured, the volume-based particle size distribution of the inorganic filler material is measured using a laser diffraction and scattering particle size distribution measuring device with the light source wavelength set to blue and red in a flow cell manner. The average particle size is calculated from the obtained particle size distribution as the median diameter. Examples of laser diffraction and scattering particle size distribution measuring devices include, for example, the "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

[0147] (E) From the viewpoint of significantly achieving the desired effects of the present invention, the specific surface area of ​​the inorganic filler material is preferably 1m². 2 / g or more, preferably 2m 2 / g or more, preferably 3m 2 / g or more. There is no specific upper limit, but 60mg is preferred. 2 / g or less, 50m 2 / g or less or 40m 2 / g or less. The specific surface area is determined by using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Macsorb Corporation), which adsorbs nitrogen gas on the sample surface and calculates the specific surface area using the BET multi-point method. The specific surface area of ​​the inorganic filler material is thus determined.

[0148] (E) From the viewpoint of improving moisture resistance and dispersibility, inorganic filler materials are preferably treated with surface treatment agents. Examples of surface treatment agents include fluorinated silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. Furthermore, a single surface treatment agent can be used, or two or more can be used in combination.

[0149] Commercially available surface treatment agents include, for example, "KBM403" (3-epoxypropoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM-503" (3-methacryloylpropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM-4803" (long-chain epoxy silane coupling agent) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0150] From the viewpoint of improving the dispersibility of inorganic fillers by utilizing surface treatment agents, the degree of surface treatment is preferably within a specified range. Specifically, 0.2 to 5 parts by mass of surface treatment agent are preferably used to surface treat 100 parts by mass of inorganic filler, more preferably 0.2 to 3 parts by mass, and more preferably 0.3 to 2 parts by mass.

[0151] The degree of surface treatment using surface treatment agents can be evaluated by the carbon content per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area is preferably 0.02 mg / m³. 2 The above, and more preferably, is 0.1 mg / m³ 2 The above, and more preferably, is 0.2 mg / m³ 2 That's all. On the other hand, from the viewpoint of suppressing the increase in melt viscosity of the resin varnish and melt viscosity in flake form, 1 mg / m³ is preferred. 2 The following, more preferably, is 0.8 mg / m 2 The following, and more preferably, is 0.5 mg / m². 2 the following.

[0152] (E) The carbon content per unit surface area of ​​the inorganic filler material can be determined after washing the surface-treated inorganic filler material with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, as a solvent, a sufficient amount of MEK is added to the surface-treated inorganic filler material, and ultrasonic washing is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the carbon content per unit surface area of ​​the inorganic filler material can be determined using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. can be used.

[0153] From the viewpoint of significantly obtaining the effects of the present invention, when the content of the inorganic filler material (E) is 1% or more, more preferably 5% or more, further preferably 10% or more, more preferably 80% or less, more preferably 70% or less, and further preferably 60% or less, as 100% by mass, the content of the non-volatile component in the photosensitive resin composition is 100% by mass.

[0154] The total content of (E) inorganic filler and (D) organic filler, when the non-volatile component in the photosensitive resin composition is taken as 100% by mass, is denoted as β. The content of (A) component, when the non-volatile component in the photosensitive resin composition is taken as 100% by mass, is denoted as α. From the viewpoint of significantly obtaining the effects of the present invention, the ratio of β / α is preferably 0.05 or more, more preferably 0.08 or more, further preferably 0.1 or more, preferably 3 or less, more preferably 2.5 or less, further preferably 2 or less, or 1 or less.

[0155] <(F) Solvent> The photosensitive resin composition may optionally contain a solvent (F). The viscosity of the varnish can be adjusted by containing the solvent (F). Organic solvents can be cited as examples of the solvent (F).

[0156] Examples of solvents (F) include ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, and ethyl diethylene glycol acetate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha. One solvent may be used alone, or two or more may be used in combination. The amount of solvent used can be adjusted appropriately from the viewpoint of the coatability of the resin composition.

[0157] <(G) Other Additives> The photosensitive resin composition may further contain (G) other additives to the extent that it does not impair the purpose of the invention. As (G) other additives, for example, thermoplastic resins; vinyl silane coupling agents, epoxy silane coupling agents, styrene silane coupling agents, methacryloxysilane coupling agents, acryloyl silane coupling agents, amino silane coupling agents, isocyanurate silane coupling agents, urea silane coupling agents, mercaptosilane coupling agents, isocyanate silane coupling agents, anhydride silane coupling agents, etc.; triazine thiols (e.g., 2,4,6-trimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, N'-tert-butyl-N-cyclopropyl-6-(methylthio)-1,3,5-triazine-2,4-diamine), piperidines, pyrazoles (e.g., 3,5-dimethylpyrazole, 3-methyl... Compounds containing nitrogen and / or sulfur atoms, such as phenyl-5-pyrazolone, triazoles (e.g., 1,2,4-triazole, 3-mercapto-1,2,4-triazole), and benzotriazoles (e.g., 1,2,3-benzotriazole, 1-hydroxybenzotriazole); colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, carbon black, and naphthalene black; polymerization inhibitors such as hydroquinone, phenothiazine, methyl hydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; thickeners such as bentonite and montmorillonite; defoamers based on silicone, fluorine, and vinyl resins; flame retardants such as epoxy resins, antimony compounds, phosphorus compounds, aromatic condensed phosphates, and halogen-containing condensed phosphates; and various additives for thermosetting resins such as phenolic curing agents and cyanate ester curing agents.

[0158] Examples of commercially available silane coupling agents include “KBM-1003”, “KBE-1003”, “KBM-303”, “KBM-402”, “KBM-403”, “KBE-402”, “KBE-403”, “KBM-1403”, “KBM-502”, “KBM-503”, “KBE-502”, “KBE-503”, “KBM-5103”, “KBM-602”, “KBM-603”, “KBM-903”, “KBE-903”, “KBE-9103P”, “KBM-573”, “KBM-575”, “KBM-9659”, “KBE-585A”, “KBM-802”, “KBM-803”, “KBE-9007N”, and “X-12-967C” manufactured by Shin-Etsu Chemical Co., Ltd. Preferred examples of these commercially available products include “KBM-303”, “KBM-402”, “KBM-403”, “KBE-402”, and “KBE-403”, with “KBM-403” being more preferred. The silane coupling agent used as (G) other additives is preferably used separately from the surface treatment agent used for (E) inorganic filler materials.

[0159] Examples of commercially produced atomic sums / compounds containing sulfur atoms, available from the three-part chemical company system “Gisnet F (TTCA)”, “Gisnet DB”, “SanAlga 1907”; Actor (registered trademark) series manufactured by Kawaguchi Chemical Co., Ltd.: “BSH”, “IBSH”, “ASH”, “IPSH”, “ESH”, “VBATDT” (6-(4-methylmethyl-positive-methyl)amino-1,3,5-trimethyl-2,4-disulfur) manufactured by Kawaguchi Chemical Co., Ltd.; Noxellar TCA, Noxellar H, Noxellar 8, Noxellar 8-N, Noxellar TMU, Noxellar EUR, Noxellar D, Noxellar DT, Noxellar PR, Noxellar M-P, Noxellar DM-P, Noxellar MZ, Noxellar PR -M-60-OT", "Noxellar MDB-P", "Noxellar CZ-G", "Noxellar MSA-G", "Noxellar TT-P", "Noxellar TET-G", "Noxellar TBT. TBT-N", "Noxellar TOT-N", "Noxellar TS", "Noxellar TRA", "Noxellar PZ", "Noxellar EZ", "Noxellar BZ-P", "Noxellar PX", "Noxellar ZP", "Noxellar ZTC", "Noxellar TP", "Noxellar TTCU", "Noxellar TTTE", "Noxellar ZIX-O", "Noxellar F", "Noxellar MIX No. 2", "Noxellar MIX No. 3, Noxellar EP-55, Noxellar EP-60, Noxellar EP-90, Nocrack 224, Nocrack AW, Nocrack AW-N, Nocrack B, Nocrack B-N, Nocrack PA, Nocrack ODA, Nocrack ODA-N, Nocrack AD-F, Nocrack CD, Nocrack TD, Nocrack White, Nocrack 810-NA, "Nocrac 6C", "Nocrac G-1", "Nocrac 300", "Nocrac MB", "Nocrac MMB", "Nocrac MBZ", "Nocrac NBC", "Nocrac TNP", "Nocrac 400", "Sconock", "Retarder CTP", "Balnock GM-P", "Balnock DGM", "Balnock R", "Balnock DNB", "Balnock AB-S", "Balnock PM", "Noctizer SS";The following are chemical products manufactured by Chengbei Chemical Co., Ltd.: “BT-120”, “BT-120SG”, “BT-LX”, “CBT-1”, “CBT-SG”, “TT-LX”, “TT-LYK”, “JCL-400”, “TT-130F”, “JF-77”, “JF-79”, “JF-80”, “JF-83”, “JF-832”, “JAST-500”, “JF-90G”, and “JF-95”; 3,5-dimethylpyrazole, 3-methyl-5-pyrazolinone, 1,2,4-triazole, 3-mercapto-1,2,4-triazole, and 1- Hydroxybenzotriazole; the "VERZONE" series manufactured by Daiwa Chemical Co., Ltd., including "Crystal#120" (1,2,3-benzotriazole), "TTA" (tolyltriazole), "VT-120M" (5-methyl-1H-benzotriazole), "C-BTA" (carboxybenzotriazole), "N-BTA" (nitro-1H-benzotriazole), "TT-250A" (benzotriazole derivative), "OA-386" (benzotriazole derivative), "OA-372" (N,N-bis(2-ethylhexyl)(1H-benzotriazole-1-yl)methylamine), and "NEW DAIN SILVER OIL RD" manufactured by Daiwa Chemical Co., Ltd. Preferred examples of these commercially available products include: Kawaguchi Chemical's Actor (registered trademark) series of "BSH", "IBSH", "ASH", "IPSH", and "ESH"; Kawaguchi Chemical's "VBATDT" (6-(4-vinylbenzyl-n-propyl)amino-1,3,5-triazine-2,4-dithiol); Sankyo Chemical's "Jsnet F(TTCA)" (triazine trithiol), "Jsnet DB" (2-butylamino-4,6-dimercapto-s-triazine); Ouchi Shinsei Chemical's "Nocuser TCA" (triazine trithiol); Johoku Chemical's "BT-120" (1,2,3-benzotriazole), "BT-120SG" (1,2,3-benzotriazole); and Yamato Chemical's "VERZONE Crystal#120" (1,2,3-benzotriazole).

[0160] The photosensitive resin composition can be manufactured by mixing the above-mentioned components (A) to (C) as essential components, and appropriately mixing the above-mentioned components (D) to (G) as optional components. In addition, it can be manufactured by mixing or stirring by mixing means such as a three-roll mill, ball mill, bead mill, sand mill, or a stirring means such as a super mixer or planetary mixer, as needed.

[0161] <Properties and Uses of Photosensitive Resin Compositions> The photosensitive resin composition exhibits excellent stability to the developer (development time dependence) even with prolonged development time. The evaluation of development time dependence is based on the bottom diameter of the 20 μm aperture of the exposure pattern for development times of 30 seconds, 60 seconds, 90 seconds, and 120 seconds. In these cases, the more development times with a bottom aperture diameter of 15 μm or more and 20 μm or less, the better the development time dependence evaluation. Preferably, the number of development times with a bottom aperture diameter of 15 μm or more and 20 μm or less is 1 or more, more preferably 2 or more, and even more preferably 3 or more. The evaluation of development time dependence can be determined by the method described in the examples below.

[0162] Cured products obtained by photocuring photosensitive resin compositions typically exhibit excellent crack resistance. Therefore, the aforementioned cured products provide an insulating layer with excellent crack resistance. Crack resistance is evaluated by the following test: exposure to -40°C atmosphere for 15 minutes, followed by heating at a rate of 180°C / min, then exposure to 160°C atmosphere for 15 minutes, followed by cooling at a rate of 180°C / min; this thermal cycling process is repeated 1000 times. Preferably, no cracks or peeling are observed after 200 cycles, more preferably after 500 cycles. Crack resistance can be determined by the method described in the examples below.

[0163] Cured products obtained by photocuring photosensitive resin compositions typically exhibit excellent insulation properties after HAST testing (100 hours or 200 hours at 130°C and 85% relative humidity). Therefore, the aforementioned cured products provide an insulating layer with excellent insulation properties. For insulation performance, an insulation resistance value of less than 1 × 10⁻⁶ after 100 hours is preferred. 7 The insulation resistance of Ω is less than 1 in 6 locations, and more preferably less than 1×10 after 200 hours. 7 The Ω wiring is present in one or fewer of the six locations. Insulation performance can be evaluated using the methods described in the examples below.

[0164] The applications of the photosensitive resin composition of the present invention are not particularly limited, and can be used in a wide range of applications requiring a photosensitive resin composition, such as photosensitive films with supports, insulating resin sheets such as prepregs, circuit boards (for laminates, multilayer printed circuit boards, etc.), solder resists, underfill materials, chip materials, semiconductor sealing materials, through-hole filling resins, and component embedding resins. Specifically, it is suitable for use as a photosensitive resin composition for insulating layers of printed circuit boards (printed circuit boards with a cured photosensitive resin composition as the insulating layer), a photosensitive resin composition for interlayer insulating layers (printed circuit boards with a cured photosensitive resin composition as the interlayer insulating layer), a photosensitive resin composition for plating formation (printed circuit boards with a plating formed on a cured photosensitive resin composition), a photosensitive resin composition for solder resist (printed circuit boards with a cured photosensitive resin composition as the solder resist), and a photosensitive resin composition for rewiring layers in wafer-level packaging (photosensitive resin...). Photosensitive resin compositions for rewiring layers of fan-out chip-level packages (using the cured form of the photosensitive resin composition as the rewiring layer), photosensitive resin compositions for rewiring layers of fan-out panel-level packages (using the cured form of the photosensitive resin composition as the rewiring layer), photosensitive resin compositions for buffer coatings (semiconductor devices using the cured form of the photosensitive resin composition as the buffer coating), and photosensitive resin compositions for insulating layers of displays (displays using the cured form of the photosensitive resin composition as the insulating layer).

[0165] [Photosensitive film with support] The photosensitive resin composition of the present invention can be suitably used in the form of a photosensitive film with a support, wherein a photosensitive resin composition layer is formed on a support. That is, the photosensitive film with a support comprises: a support, and a photosensitive resin composition layer formed of the photosensitive resin composition of the present invention disposed on the support.

[0166] Examples of supports include polyethylene terephthalate films, polyethylene naphthalate films, polypropylene films, polyethylene films, polyvinyl alcohol films, triacetyl acetate films, etc., with polyethylene terephthalate films being particularly preferred.

[0167] Commercially available supports include, but are not limited to, products such as "Alpha MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and polyethylene terephthalate films such as "PP-25" and other PS series products manufactured by Teijin Co., Ltd. To facilitate removal, these supports can be coated with a release agent such as a silicone coating agent. The thickness of the support is preferably in the range of 5μm to 50μm, more preferably in the range of 10μm to 25μm. By setting the thickness to 5μm or more, support breakage during support peeling before development can be suppressed; by setting the thickness to 50μm or less, the resolution during exposure from the support can be improved. Furthermore, a support with low fisheye spots is preferred. Here, fisheye spots are obtained when foreign matter, undissolved substances, oxidative deterioration products, etc., are incorporated into the film during the manufacturing process of a film by hot melting of the material and mixing, extrusion, biaxial stretching, casting, etc.

[0168] Furthermore, the photosensitive resin composition layer can be protected by a protective film. By protecting the photosensitive resin composition layer side of the photosensitive film with the support with a protective film, it is possible to prevent the adhesion of dirt or scratches on the surface of the photosensitive resin composition layer. As the protective film, a film made of the same material as the support described above can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and even more preferably in the range of 10 μm to 30 μm. By setting the thickness to 1 μm or more, the processability of the protective film can be improved, and by setting it to 40 μm or less, there is a tendency for it to be inexpensive. It should be noted that the protective film preferably has a smaller adhesion strength between the photosensitive resin composition layer and the protective film compared to the adhesion strength between the photosensitive resin composition layer and the support.

[0169] A photosensitive film with a support can be manufactured according to methods known to those skilled in the art, for example, by coating a photosensitive resin composition onto a support and drying the (F) component by heating or hot air blowing. The photosensitive resin composition can be manufactured, for example, using a resin varnish containing a non-volatile component of the photosensitive resin composition and an excess of the (F) component. Specifically, firstly, after completely removing bubbles from the resin varnish by a vacuum degassing method, the resin varnish is coated onto a support, and the amount of the (F) component is adjusted by drying in a hot air furnace or a far-infrared furnace. This allows for the manufacture of a photosensitive film with a support comprising a layer of the photosensitive resin composition. As one embodiment of the method for manufacturing a photosensitive film with a support, the resin varnish is dried by setting a maximum temperature of 105°C or higher and 135°C or lower, and a drying time of 6 minutes or higher and 20 minutes or lower.

[0170] The drying temperature varies depending on the curability of the photosensitive resin composition and the amount of (F) component in the resin varnish, and can be carried out at 50°C to 120°C. However, from the viewpoint of obtaining a cured product with excellent lateral corrosion resistance, the maximum drying temperature is preferably 60°C or higher, more preferably 80°C or higher. The lower limit of the maximum temperature is not particularly limited, but is preferably 135°C or lower, more preferably 130°C or lower.

[0171] The drying time varies depending on the curability of the photosensitive resin composition and the amount of (F) component in the resin varnish, and is preferably 6 minutes or more, preferably 30 minutes or less, and more preferably 20 minutes or less. Here, the drying time refers to the time taken from when the drying temperature reaches 60°C.

[0172] The residual amount of component (F) in the photosensitive resin composition layer relative to the total amount of the photosensitive resin composition layer is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less. Those skilled in the art can appropriately set suitable drying conditions through simple experiments.

[0173] The thickness of the photosensitive resin composition layer can be set in the range of 1 μm or more and 100 μm or less, depending on the purpose, from the viewpoint of improving processability and suppressing the reduction of sensitivity and resolution within the photosensitive resin composition layer. For example, the thickness of the photosensitive resin composition layer is preferably 10 μm or more, more preferably 15 μm or more, further preferably 20 μm or more, preferably 30 μm or less, more preferably 28 μm or less, and further preferably 25 μm or less.

[0174] Printed wiring board The printed wiring board of the present invention comprises an insulating layer formed from a cured product of the photosensitive resin composition of the present invention. This insulating layer is preferably used as a solder resist.

[0175] In detail, the printed wiring board of the present invention can be manufactured using the above-mentioned photosensitive film with a support. Specifically, the method for manufacturing the printed wiring board includes: (I) The step of forming a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention on a circuit board. (II) The step of curing the photosensitive resin composition layer by irradiating it with active light, and (III) The step of developing the cured photosensitive resin composition layer.

[0176] The following is an example illustrating the case where the insulating layer is a solder resist.

[0177] <Step (I)> Examples of methods for forming a photosensitive resin composition layer include directly applying a resin varnish containing a photosensitive resin composition onto a circuit board and using the aforementioned photosensitive film with a support.

[0178] When a resin varnish containing a photosensitive resin composition is directly applied to a circuit board, a photosensitive resin composition layer is formed on the circuit board by drying and evaporating component (F).

[0179] Examples of resin varnish coating methods include gravure coating, microgravure coating, reverse coating, contact reverse coating, die coating, slit coating, lip coating, comma coating, doctor blade coating, roller coating, knife coating, curtain coating, chamber gravure coating, slot coating, spin coating, slit coating, spray coating, dip coating, hot melt coating, rod coating, applicator coating, air knife coating, curtain flow coating, offset printing, brush coating, and full-surface printing using screen printing.

[0180] Resin varnish can be applied in multiple coats, or in a single coat, or a combination of different methods. Die-casting, which provides excellent uniformity, is preferred. Furthermore, to avoid contamination by foreign matter, the coating process is preferably performed in an environment with minimal foreign matter generation, such as a cleanroom.

[0181] After applying the resin varnish, it is dried using a hot air oven or far-infrared oven as needed. The drying time is preferably set to 3 to 13 minutes at 80°C to 120°C. In this way, a photosensitive resin composition layer is formed on the circuit board.

[0182] Examples of circuit boards include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. It should be noted that, here, a circuit board refers to a substrate, as described above, on one or both sides of a supporting substrate where a patterned conductor layer (circuit) is formed. Furthermore, in multilayer printed circuit boards obtained by alternating layers of conductor and insulating layers, the outermost layer of the multilayer printed circuit board with a patterned conductor layer (circuit) is also included in the circuit boards described herein. It should be noted that the surface of the conductor layer can be pre-treated by blackening, copper etching, etc.

[0183] On the other hand, when using a photosensitive film with a support, the photosensitive resin composition layer is laminated onto one or both sides of the circuit board using a vacuum laminator. In the lamination step, if the photosensitive film with the support has a protective film, the protective film is removed, and the photosensitive film with the support and the circuit board are preheated as needed. The photosensitive resin composition layer is then pressed onto the circuit board while being pressurized and heated. For photosensitive films with supports, a method of laminating them onto the circuit board under reduced pressure using vacuum lamination is suitable.

[0184] There are no particular limitations on the lamination conditions, but preferably, the lamination temperature is set to 70℃~140℃, and the lamination pressure is set to 1 kgf / cm². 2 ~11kgf / cm 2 (9.8×10 4 N / m 2 ~107.9×10 4 N / m 2 The lamination time is preferably set to 5 to 300 seconds, and lamination is performed under reduced pressure of 20 mmHg (26.7 hPa) or less. Furthermore, the lamination process can be intermittent or continuous using rollers. Vacuum lamination can be performed using commercially available vacuum laminators. Examples of commercially available vacuum laminators include vacuum applicators manufactured by Nikon Materias, vacuum pressure laminators manufactured by Meiki Seisakusho, roller dry coating machines manufactured by Hitachi Industrie, and vacuum laminators manufactured by Hitachi Airisie.

[0185] <Step (II)> The exposure step involves depositing a photosensitive resin composition layer on a circuit board through coating and drying or lamination. Then, a predetermined portion of the photosensitive resin composition layer is irradiated with active light through a mask pattern, causing the irradiated portion of the photosensitive resin composition layer to photocur. Examples of active light include ultraviolet light, visible light, electron beams, and X-rays, with ultraviolet light being particularly preferred. The irradiation dose of ultraviolet light is approximately 10 mJ / cm². 2 ~1000mJ / cm 2 Among the exposure methods, there are contact exposure methods where the mask pattern is in close contact with the printed circuit board, and non-contact exposure methods where parallel light is used for exposure without close contact; either method can be used. Furthermore, if a support is present on the photosensitive resin composition layer, exposure can be performed on the support or after the support has been peeled off.

[0186] In step (II), a via can be formed using a via pattern, such as a circular hole pattern, as the mask pattern. The via diameter (opening diameter) is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. The lower limit is not particularly limited and can be set to 1 μm or more, 5 μm or more, etc.

[0187] <Step (III)> After the exposure step, if a support is present on the photosensitive resin composition layer, the support is removed and development is performed. The uncured portions (unexposed areas) are removed, thereby forming a pattern. Development is usually performed by wet development.

[0188] In the case of wet development described above, safe, stable, and easy-to-handle developers such as alkaline aqueous solutions, aqueous developers, and organic solvents are used as the developer, with the development step using an alkaline aqueous solution being preferred. Furthermore, known methods such as spraying, shaking immersion, brushing, and scraping can be appropriately employed as the development method.

[0189] Examples of alkaline aqueous solutions used as developing solutions 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; 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. In terms of not containing metal ions and not affecting semiconductor chips, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred.

[0190] These alkaline aqueous solutions may contain surfactants, defoamers, etc., to improve the developing effect. The pH of the alkaline aqueous solution is preferably in the range of 8 to 12, more preferably in the range of 9 to 11. Furthermore, the alkali concentration of the alkaline aqueous solution is preferably set to 0.1% to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected according to the developability of the photosensitive resin composition layer, and is preferably set to 20°C to 50°C.

[0191] Organic solvents used as developing solutions include, for example, acetone, ethyl acetate, alkoxyethanol having alkoxy groups with 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

[0192] The concentration of such organic solvent relative to the total amount of developer is preferably 2% to 90% by mass. Furthermore, the temperature of such organic solvent can be adjusted according to the developability. Moreover, such organic solvent can be used alone or in combination of two or more. Examples of organic solvent-based developers used alone include, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0193] During pattern formation, two or more of the above-mentioned developing methods can be used simultaneously as needed. Developing methods include immersion, water pit development, spraying, high-pressure spraying, brushing, and scraping. High-pressure spraying is suitable for improving resolution. When using the spraying method, the preferred spray pressure is 0.05 MPa to 0.3 MPa.

[0194] <Thermosetting (Post-baking) Steps> After step (III) above is completed, a heat-curing (post-baking) step is performed as needed to form the solder resist. Examples of post-baking steps include ultraviolet irradiation using a high-pressure mercury lamp or heating using a clean oven. When irradiating with ultraviolet light, the irradiation intensity can be adjusted as needed, for example, to 0.05 J / cm². 2 ~10J / cm 2 Irradiation is performed at approximately the same irradiation level. Furthermore, the heating conditions can be appropriately selected based on the type and content of the resin components in the photosensitive resin composition, preferably within the range of 150°C to 250°C for 20 to 180 minutes, and more preferably within the range of 160°C to 230°C for 30 to 120 minutes.

[0195] <Other Steps> After the solder resist is formed, the printed wiring board may further include an opening step and a desmearing step. These steps can be performed according to various methods known to those skilled in the art in the manufacture of the printed wiring board.

[0196] After the solder resist is formed, an opening step is performed on the solder resist formed on the circuit board to form vias or through holes, as desired. The opening step can be performed by known methods such as drilling, lasers, or plasma, and these methods can be combined as needed. The opening step using lasers such as carbon dioxide lasers or YAG lasers is preferred.

[0197] The desmearing step is a process that removes drill smear material. The opening formed during the drilling process typically contains resin residue (drill smear). This drill smear can cause poor electrical connections, therefore this step involves removing it.

[0198] Desmearing can be carried out through dry desmearing, wet desmearing, or a combination thereof.

[0199] As a dry desmearing process, examples include desmearing using plasma. Plasma desmearing can be performed using commercially available plasma desmearing equipment. Among commercially available plasma desmearing equipment suitable for printed circuit board manufacturing, examples include microwave plasma equipment manufactured by Nissin Corporation and atmospheric pressure plasma etching equipment manufactured by Sekisui Chemicals Co., Ltd.

[0200] As a wet desmearing process, desmearing treatment using an oxidizing solution can be used, for example. When using an oxidizing solution for desmearing, it is preferable to perform swelling treatment using a swelling solution, oxidation treatment using an oxidizing solution, and neutralization treatment using a neutralizing solution in that order. Examples of swelling solutions include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing the substrate with vias, etc., in a swelling solution heated to 60°C to 80°C for 5 to 10 minutes. The oxidizing solution is preferably an alkaline permanganate aqueous solution; examples include solutions containing potassium permanganate and sodium permanganate dissolved in an aqueous sodium hydroxide solution. The oxidation treatment using the oxidizing solution can be performed by immersing the swollen substrate in an oxidizing 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 "Dating Solution Securitization P" manufactured by Atotech Japan. The neutralization treatment using the neutralizing solution is preferably performed by immersing the oxidized substrate in a neutralizing solution at 30°C to 50°C for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and commercially available examples include, for example, "Reducing Solution Securitization P" manufactured by Atotech Japan.

[0201] When combining dry and wet desmearing treatments, either the dry or wet desmearing treatment can be performed first.

[0202] When the insulating layer is used as an interlayer insulating layer, it can be done in the same way as the solder resist, and the drilling step, descaling step and plating step can be performed after the thermosetting step.

[0203] The plating step is the step of forming a conductor layer on an insulating layer. The conductor layer can be formed by sputtering after the insulating layer is formed, or it can be formed by a combination of electroless plating and electrolytic plating. Furthermore, a resist agent with a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed solely by electroless plating. As for the subsequent patterning method, methods such as subtractive plating and semi-additive plating, which are well known to those skilled in the art, can be used.

[0204] [Semiconductor Devices] The semiconductor device of the present invention includes a printed wiring board. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0205] Examples of semiconductor devices include various semiconductor devices used in electrical appliances (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as autonomous vehicles, automobiles, trains, ships, and aircraft).

[0206] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. "Conductive portion" refers to "a portion in the printed wiring board that transmits electrical signals," and this portion can be either surface-mounted or embedded. Furthermore, the semiconductor chip is not particularly limited to any electrical circuit element that uses semiconductors as its material.

[0207] The method for mounting the semiconductor chip in the semiconductor device of the present invention is not particularly limited as long as it effectively performs the function of the semiconductor chip. Specifically, examples include wire bonding mounting, flip chip mounting, mounting using bumpless multilayer (BBUL), mounting using anisotropic conductive film (ACF), and mounting using non-conductive film (NCF). Here, "mounting using bumpless multilayer (BBUL)" refers to "a mounting method in which the semiconductor chip is directly embedded in a recess of a printed circuit board, and the semiconductor chip is connected to the wiring on the printed circuit board." Example

[0208] The present invention will now be described in detail with reference to specific embodiments, but the present invention is not limited to these embodiments. It should be noted that, in the following description, the terms "parts" and "%" to indicate quantity refer to "parts by mass" and "% by mass," respectively, unless otherwise expressly stated.

[0209] <Example 1> 10 parts by mass of component (A-1) ("TR4020G", manufactured by Asahi Organic Materials Co., Ltd.), 5 parts by mass of component (A-2) ("MEHC-7851SS", manufactured by Meiwa Kasei Co., Ltd.), 5 parts by mass of component (A-3) ("BisE", manufactured by Honshu Chemical Co., Ltd.), 5 parts by mass of a compound containing at least two alkoxymethyl groups in its molecule ("MW-390", manufactured by Sanwa Kemikal Co., Ltd.), 0.05 parts by mass of a photoacid-producing agent ("MP-triazine", manufactured by Sanwa Kemikal Co., Ltd.), 6 parts by mass of an organic filler ("MM-101SM", manufactured by Negami Kogyo Co., Ltd.), and 12 parts by mass of MEK (manufactured by Pure Chemical Co., Ltd.) were mixed to obtain resin composition 1.

[0210] MP-triazine has the following structure.

[0211] [Chemistry 37] <Example 2> In Example 1, the amount of organic filler material ("MM-101SM", manufactured by Kenjo Industrial Co., Ltd.) was changed from 6 parts by mass to 2 parts by mass.

[0212] Apart from the above, resin composition 2 was obtained in the same manner as in Example 1.

[0213] <Example 3> In Example 2, 2 parts by weight of organic filler material ("MM-101SM", manufactured by Genjo Industries) were not used.

[0214] Apart from the above, resin composition 3 was obtained in the same manner as in Example 2.

[0215] <Example 4> In Example 2, 5 parts by mass of component (A-3) ("BisE", manufactured by Honshu Chemical Co., Ltd.) were changed to 5 parts by mass of component (A-3) ("BisA", manufactured by Mitsui Chemicals Fin Co., Ltd.).

[0216] Apart from the above, resin composition 4 was obtained in the same manner as in Example 2.

[0217] <Example 5> In Example 2, 5 parts by mass of component (A-3) (“BisE” manufactured by Honshu Chemical Co., Ltd.) were changed to 5 parts by mass of component (A-3) (“BisF” manufactured by Mitsui Chemicals Fin Co., Ltd.).

[0218] Apart from the above, resin composition 5 was obtained in the same manner as in Example 2.

[0219] <Example 6> In Example 2, 5 parts by mass of component (A-3) (“BisE” manufactured by Honshu Chemical Co., Ltd.) were changed to 5 parts by mass of component (A-3) (“BisP-TMC” manufactured by Honshu Chemical Co., Ltd.).

[0220] Apart from the above, resin composition 6 was obtained in the same manner as in Example 2.

[0221] <Example 7> In Example 2, 5 parts by mass of component (A-3) (“BisE” manufactured by Honshu Chemical Co., Ltd.) were changed to 5 parts by mass of component (A-3) (“BisP-M” manufactured by Mitsui Chemicals Fin Co., Ltd.).

[0222] Apart from the above, resin composition 7 was obtained in the same manner as in Example 2.

[0223] <Example 8> In Example 2, 5 parts by mass of component (A-2) (“MEHC-7851SS” manufactured by Meiwa Kasei Corporation) were changed to 5 parts by mass of component (A-2) (“MEHC-78004S” manufactured by Meiwa Kasei Corporation).

[0224] Apart from the above, resin composition 8 was obtained in the same manner as in Example 2.

[0225] <Example 9> In Example 2, 30 parts by weight of inorganic filler material (“UFP-30” with an average particle size of 0.3 μm, manufactured by Denka Corporation) were further used.

[0226] Apart from the above, resin composition 9 was obtained in the same manner as in Example 2.

[0227] <Example 10> In Example 2, 30 parts by weight of inorganic filler material ("SO-C2", average particle size 0.5 μm, manufactured by Admadex Corporation) were further used.

[0228] Apart from the above, resin composition 10 was obtained in the same manner as in Example 2.

[0229] <Example 11> In Example 2, The amount of component (A-1) ("TR4020G", manufactured by Asahi Organic Materials Co., Ltd.) was changed from 10 parts by mass to 4 parts by mass. The amount of component (A-2) (“MEHC-7851SS” manufactured by Meiwa Chemical Co., Ltd.) was changed from 5 parts by mass to 12 parts by mass, and The amount of component (A-3) (“BisE” manufactured by Honshu Chemical Company) was changed from 5 parts by mass to 4 parts by mass.

[0230] Apart from the above, resin composition 11 was obtained in the same manner as in Example 2.

[0231] <Example 12> In Example 2, The amount of component (A-1) ("TR4020G", manufactured by Asahi Organic Materials Co., Ltd.) was changed from 10 parts by mass to 4 parts by mass. The amount of component (A-2) (“MEHC-7851SS” manufactured by Meiwa Chemical Co., Ltd.) was changed from 5 parts by mass to 4 parts by mass, and The amount of component (A-3) (“BisE” manufactured by Honshu Chemical Company) was changed from 5 parts by mass to 12 parts by mass.

[0232] Apart from the above, resin composition 12 was obtained in the same manner as in Example 2.

[0233] <Example 13> In Example 2, The amount of component (A-1) ("TR4020G", manufactured by Asahi Organic Materials Co., Ltd.) was changed from 10 parts by mass to 16 parts by mass. The amount of component (A-2) (“MEHC-7851SS” manufactured by Meiwa Chemical Co., Ltd.) was changed from 5 parts by mass to 2 parts by mass, and The amount of component (A-3) (“BisE” manufactured by Honshu Chemical Co., Ltd.) was changed from 5 parts by mass to 2 parts by mass.

[0234] Apart from the above, resin composition 13 was obtained in the same manner as in Example 2.

[0235] <Example 14> In Example 2, The amount of component (A-1) ("TR4020G", manufactured by Asahi Organic Materials Co., Ltd.) was changed from 10 parts by mass to 18 parts by mass. The amount of component (A-2) (“MEHC-7851SS” manufactured by Meiwa Chemical Co., Ltd.) was changed from 5 parts by mass to 1 part by mass, and The amount of component (A-3) (“BisE” manufactured by Honshu Chemical Co., Ltd.) was changed from 5 parts by mass to 1 part by mass.

[0236] Apart from the above, resin composition 14 was obtained in the same manner as in Example 2.

[0237] <Example 15> In Example 2, The amount of component (A-1) ("TR4020G", manufactured by Asahi Organic Materials Co., Ltd.) was changed from 10 parts by mass to 2 parts by mass. The amount of component (A-2) (“MEHC-7851SS” manufactured by Meiwa Chemical Co., Ltd.) was changed from 5 parts by mass to 4 parts by mass, and The amount of component (A-3) (“BisE” manufactured by Honshu Chemical Company) was changed from 5 parts by mass to 14 parts by mass.

[0238] Apart from the above, resin composition 15 was obtained in the same manner as in Example 2.

[0239] <Example 16> In Example 2, The amount of component (A-1) ("TR4020G", manufactured by Asahi Organic Materials Co., Ltd.) was changed from 10 parts by mass to 2 parts by mass. The amount of component (A-2) (“MEHC-7851SS” manufactured by Meiwa Chemical Co., Ltd.) was changed from 5 parts by mass to 14 parts by mass, and The amount of component (A-3) (“BisE” manufactured by Honshu Chemical Company) was changed from 5 parts by mass to 4 parts by mass.

[0240] Apart from the above, resin composition 16 was obtained in the same manner as in Example 2.

[0241] <Comparative Example 1> In Example 2, The amount of component (A-1) ("TR4020G", manufactured by Asahi Organic Materials Co., Ltd.) was changed from 10 parts by mass to 20 parts by mass. It does not use 5 parts by weight of ingredient (A-2) ("MEHC-7851SS", manufactured by Meiwa Chemical Co., Ltd.), and 5 parts by weight of component (A-3) (“BisE” manufactured by Honshu Chemical Company) are not used.

[0242] Apart from the above, resin composition 17 was obtained in the same manner as in Example 2.

[0243] <Comparative Example 2> In Example 2, The amount of component (A-2) (“MEHC-7851SS” manufactured by Meiwa Chemical Co., Ltd.) was changed from 5 parts by mass to 10 parts by mass, and 5 parts by weight of component (A-3) (“BisE” manufactured by Honshu Chemical Company) are not used.

[0244] Apart from the above, resin composition 18 was obtained in the same manner as in Example 2.

[0245] <Comparative Example 3> In Example 2, It does not use 5 parts by weight of ingredient (A-2) ("MEHC-7851SS", manufactured by Meiwa Chemical Co., Ltd.), and The amount of component (A-3) (“BisE” manufactured by Honshu Chemical Co., Ltd.) was changed from 5 parts by mass to 10 parts by mass.

[0246] Apart from the above, resin composition 19 was obtained in the same manner as in Example 2.

[0247] <Comparative Example 4> In Example 2, Do not use 10 parts by weight of ingredient (A-1) ("TR4020G", manufactured by Asahi Organic Materials Co., Ltd.) The amount of component (A-2) (“MEHC-7851SS” manufactured by Meiwa Chemical Co., Ltd.) was changed from 5 parts by mass to 10 parts by mass, and The amount of component (A-3) (“BisE” manufactured by Honshu Chemical Co., Ltd.) was changed from 5 parts by mass to 10 parts by mass.

[0248] Apart from the above, resin composition 20 was obtained in the same manner as in Example 2.

[0249] <Comparative Example 5> In Example 2, 5 parts by mass of component (A-3) (“BisE” manufactured by Honshu Chemical Co., Ltd.) were replaced with 5 parts by mass of alkali-soluble resin (“TrisP-PA” manufactured by Honshu Chemical Co., Ltd.) as shown in the following structural formula.

[0250] Apart from the above, resin composition 21 was obtained in the same manner as in Example 2.

[0251] [Chemistry 38] <Comparative Example 6> In Example 2, The amount of component (A-1) ("TR4020G", manufactured by Asahi Organic Materials Co., Ltd.) was changed from 10 parts by mass to 15 parts by mass. It does not use 5 parts by weight of ingredient (A-2) ("MEHC-7851SS", manufactured by Meiwa Chemical Co., Ltd.), and The 5 parts by weight of component (A-3) (“BisE” manufactured by Honshu Chemical Co., Ltd.) were replaced with 5 parts by weight of alkali-soluble resin (“TrisP-PA” manufactured by Honshu Chemical Co., Ltd.).

[0252] Apart from the above, resin composition 22 was obtained in the same manner as in Example 2.

[0253] <Comparative Example 7> In Example 2, The amount of component (A-1) ("TR4020G", manufactured by Asahi Organic Materials Co., Ltd.) was changed from 10 parts by mass to 14 parts by mass. The 5 parts by weight of component (A-2) ("MEHC-7851SS", manufactured by Meiwa Kasei Corporation) are changed to 6 parts by weight of component (A-2) ("MEHC-78004S", manufactured by Meiwa Kasei Corporation). Do not use 5 parts by weight of ingredient (A-3) ("BisE", manufactured by Honshu Chemical Company). The amount of organic filler material ("MM-101SM", manufactured by Genjo Kogyo Co., Ltd.) was changed from 2 parts by mass to 3 parts by mass, and The amount of the compound containing at least two alkoxymethyl groups in the molecule (“MW-390” manufactured by Sanwa Kemika Co., Ltd.) was changed from 5 parts by mass to 6 parts by mass.

[0254] Apart from the above, resin composition 23 was obtained in the same manner as in Example 2.

[0255] <Comparative Example 8> In Example 2, The amount of component (A-1) ("TR4020G", manufactured by Asahi Organic Materials Co., Ltd.) was changed from 10 parts by mass to 16 parts by mass. Do not use 5 parts by weight of ingredient (A-2) ("MEHC-7851SS", manufactured by Meiwa Chemical Co., Ltd.) The 5 parts by weight of component (A-3) ("BisE", manufactured by Honshu Chemical Co., Ltd.) were changed to 4 parts by weight of alkali-soluble resin ("TrisP-PA", manufactured by Honshu Chemical Co., Ltd.), and The amount of organic filler material ("MM-101SM", manufactured by Genjo Kogyo Co., Ltd.) was changed from 2 parts by mass to 3 parts by mass.

[0256] Apart from the above, resin composition 24 was obtained in the same manner as in Example 2.

[0257] <Fabrication of Photosensitive Film with Support> As a support, a PET film (Lumira T60 manufactured by Tore Co., Ltd., with a thickness of 38 μm) was prepared. The resin composition (photosensitive resin composition) prepared in each example and comparative example was uniformly coated on the PET film using a die coater to achieve a thickness of 20 μm after drying. The film was then dried at 80°C to 110°C for 6 minutes, thereby obtaining a photosensitive film with a support having a photosensitive resin composition layer on the demolded PET.

[0258] <Evaluation of Development Time Dependence> The copper layer of the glass epoxy board (copper-clad laminate) is treated with 5% sulfuric acid. A photosensitive resin composition layer with a support is placed in contact with the copper layer surface and laminated using a vacuum laminator (manufactured by Nikolai Materias, VP160) to form a laminate in which the aforementioned copper-clad laminate, the aforementioned photosensitive resin composition layer, and the aforementioned support are sequentially stacked. The lamination conditions are set as follows: vacuum time 30 seconds, lamination temperature 80°C, lamination pressure 0.7 MPa, and lamination time 30 seconds.

[0259] After allowing the laminate to stand at room temperature for at least 30 minutes, and then peeling off the support structure, a circular hole pattern is created using a pattern forming apparatus and ultraviolet light (wavelength 365nm, intensity 40mW / cm²). 2 Expose the sample. Set the development time to 30 seconds and the exposure dose to 50 mJ / cm². 2 Up to 1000mJ / cm 2 The range is set appropriately. A quartz glass mask with a 20μm opening (via) is used to depict the exposure pattern. After standing at room temperature for 5 minutes, the support is peeled off from the aforementioned laminate. The process is the same as for the case with a 30-second development time, where the development times are set to 60 seconds, 90 seconds, and 120 seconds respectively.

[0260] Next, after heat treatment at 80°C for 10 minutes, a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 23°C was sprayed onto the entire surface of the photosensitive resin composition layer on the laminate, and sprayed at a pressure of 0.1 MPa for 30 seconds, 60 seconds, 90 seconds, and 120 seconds. After spray development, a 1 J / cm² spray was applied. 2 The photosensitive resin composition layer is cured by irradiation with ultraviolet light and further heat treatment at 190°C for 60 minutes.

[0261] The bottom diameter of the 20μm aperture of the exposed pattern was measured using SEM (1000x magnification) at development times of 30, 60, 90, and 120 seconds. It should be noted that the bottom of the aperture is larger than the opening (inverted conical shape). When the bottom of the via cannot be observed using SEM, it is represented as "inverted cone".

[0262] In addition, for four development times of 30 seconds, 60 seconds, 90 seconds and 120 seconds, the number of development times in which the bottom diameter of the via with an opening of 20 μm in the exposure pattern reaches more than 15 μm and less than 20 μm is shown (the four of 30 seconds, 60 seconds, 90 seconds and 120 seconds are the maximum values).

[0263] <Evaluation of Crack Resistance (TCT Resistance)> The copper layer of a glass epoxy board (copper-clad laminate) with a patterned 18 μm thick copper layer was treated with 5% sulfuric acid. A pre-fabricated photosensitive film with a support was prepared by contacting the copper circuit surface with a photosensitive resin composition layer, and then laminated using a vacuum laminator (Niko Materias, VP160) to form a laminate in which the aforementioned copper-clad laminate, the aforementioned photosensitive resin composition layer, and the aforementioned support were sequentially stacked. The lamination conditions were set as follows: vacuum time 30 seconds, lamination temperature 80°C, lamination pressure 0.7 MPa, and lamination time 30 seconds. The laminate was allowed to stand at room temperature for at least 30 minutes, and then a circular hole pattern was created on the support of the laminate using a patterning apparatus and exposed to ultraviolet light. The exposure pattern was created using a quartz glass mask with circular openings of 10μm / 20μm / 30μm / 40μm / 50μm / 60μm / 70μm / 80μm / 90μm / 100μm. After standing at room temperature for 5 minutes, the support was peeled off from the aforementioned laminate. Next, a heat treatment at 80°C for 10 minutes was performed. Then, on the entire surface of the photosensitive resin composition layer on the laminate, a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 23°C was spray-developed at a spray pressure of 0.1 MPa for 1 minute. After spray development, an exposure was performed at 1 J / cm². 2 The photosensitive resin composition layer is cured by ultraviolet irradiation and further heat treatment at 190°C for 60 minutes, forming an insulating layer with openings on the laminate. This laminate is used for crack resistance evaluation.

[0264] The following test was conducted: The laminate used for crack resistance evaluation was exposed to atmospheric temperature at -40°C for 15 minutes, then heated at a rate of 180°C / min, followed by exposure to atmospheric temperature at 160°C for 15 minutes, and then cooled at a rate of 180°C / min. This thermal cycling process was repeated 1000 times. After 200 and 500 cycles, the degree of cracking and spalling in the laminate was observed using an optical microscope (Nikon, "LV-100ND"), and the evaluation was based on the following criteria. ◎: No cracks or peeling were detected after 500 cycles.

[0265] ○: Cracks and peeling were confirmed after 500 cycles, but not after 200 cycles.

[0266] ×: Cracks and peeling were confirmed after 200 tests.

[0267] <Evaluation of Insulation (HAST Resistance)> A comb-shaped copper circuit with six wiring locations was prepared on a polyimide substrate, with a line width of 15 μm and a spacing of 15 μm. Next, a pre-fabricated photosensitive resin composition layer with a support was placed in contact with the surface of the copper circuit and laminated using a vacuum laminator (Niko Materias, VP160) to form a laminate in which the aforementioned copper-clad laminate, the aforementioned photosensitive resin composition layer, and the aforementioned support were sequentially stacked. The lamination conditions were set as follows: vacuum time 30 seconds, lamination temperature 80°C, lamination pressure 0.7 MPa, and lamination time 30 seconds. The laminate was allowed to stand at room temperature for at least 30 minutes, and then the entire surface of the laminate was exposed to ultraviolet light from the support. The exposure amount was set to the exposure amount with the best resolution. After standing at room temperature for 5 minutes, the support was peeled off from the laminate. Then, a heat treatment at 80°C for 10 minutes was performed. On the entire surface of the photosensitive resin composition layer on the laminate, a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 23°C was spray-developed at a spray pressure of 0.1 MPa for 1 minute. After spray development, a 1 J / cm² spray was applied. 2 The photosensitive resin composition layer is cured by ultraviolet irradiation and further heat treatment at 190°C for 60 minutes, forming an insulating layer with openings on the laminate. This laminate is used for insulation evaluation.

[0268] The insulation resistance value of the insulation evaluation laminate was measured using a resistance measuring machine (J-RAS ECM-100). Subsequently, the insulation evaluation laminate was subjected to an environment of 130°C and 85% relative humidity using a HAST testing machine (Kusumoto Kasei Corporation PM422), with a voltage of 3.3V applied across the electrodes. After 100 hours and 200 hours, the insulation resistance value was measured, and the evaluation was conducted based on the following evaluation criteria. ◎: The insulation resistance value is less than 1×10 after 200 hours. 7 The wiring of Ω is less than 1 out of 6 locations. 〇: The insulation resistance value is less than 1×10 after 100 hours. 7 The wiring of Ω is less than 1 out of 6 locations. ×: The insulation resistance value is less than 1×10 after 100 hours. 7 The Ω wiring is present in more than 2 out of 6 locations. *In the table, the content of component (A-1) refers to the content of component (A-1) when component (A) as a whole is taken as 100% by mass. The content of component (A-2) refers to the content of component (A-2) when component (A) as a whole is taken as 100% by mass. The content of component (A-3) refers to the content of component (A-3) when component (A) as a whole is taken as 100% by mass.

[0269] As shown in the table above, the number of development times (30 seconds, 60 seconds, 90 seconds, and 120 seconds) with a bottom diameter of 15 μm or more but less than 20 μm in Examples 1-16 is greater than that in Comparative Examples 1-8. This indicates that Examples 1-16 maintain excellent stability with the developer even with extended development times. Therefore, Examples 1-16 can achieve uniform bottom diameter of the vias even with variations in the thickness of the photosensitive resin composition layer.

[0270] Furthermore, it is known that Examples 1-16 also exhibit superior crack resistance and insulation compared to Comparative Examples 1-8.

[0271] In each embodiment, even without components (D) and (E), despite some differences, the results were confirmed to be the same as those in the embodiments described above.

Claims

1. A photosensitive resin composition comprising: (A) Alkali-soluble resins with phenolic hydroxyl groups within the molecule; (B) Compounds containing at least two alkoxymethyl groups in their molecules, and (C) Photoacid-producing agents (A) The component contains: a compound having the structure shown in formula (A-1) and two ends, a compound having the structure shown in formula (A-2) and two ends, and a compound having the structure shown in formula (A-3). Component (A-1) is terminated by an optional hydroxyphenyl or aldehyde group with substituents, and component (A-2) is terminated by an optional hydroxyphenyl group with substituents. [Chemistry 1] In equation (A-1), R 1 Each of the following independently represents the divalent group shown in formula (a), X 1 Each can independently represent an alkyl group, an aryl group, a halogen atom, or a monovalent heterocyclic group with optional substituents; n1 represents an integer from 0 to 4, m1 represents an integer from 1 to 200; * represents a bonding site; In equation (A-2), R 2 Each of the following can be independently represented as a divalent group shown in formula (b), a divalent group shown in formula (c), a divalent group formed by a combination of the divalent groups shown in formula (b) and (c), a divalent group formed by a combination of the divalent groups shown in formula (a) and (b), or a divalent group formed by a combination of the divalent groups shown in formula (a) and (c), X 2 Each can independently represent an alkyl group, an aryl group, a halogen atom, or a monovalent heterocyclic group with optional substituents; n2 represents an integer from 0 to 4, m2 represents an integer from 1 to 200; * represents a bonding site; In equation (A-3), R 3 X represents the divalent group shown in formula (a), the divalent group shown in formula (b), the divalent group shown in formula (c), or a divalent group formed by a combination of them. 3 and X 4 Each of them independently represents an alkyl group with a substituent, an aryl group with a substituent, a halogen atom, or a monovalent heterocyclic group with a substituent; n3 and n4 each independently represent integers from 0 to 4; [Chemistry 2] In equation (a), R 11 and R 12 Each of the following groups independently represents a hydrogen atom, an alkyl group optionally with a substituent, an aryl group optionally with a substituent, a monovalent heterocyclic group optionally with a substituent, an amino group, a carbonyl group, a carboxyl group, or a group formed by a combination thereof, R 11 and R 12 They can bond together to form a ring; * indicates a bonding site; In equation (b), X 11 Each group independently represents an alkyl group with optional substituents; p1 represents an integer from 0 to 4; * represents a bond position; In equation (c), X 12 and X 13 Each of the above independently represents an alkyl group with optional substituents; p2 and p3 each independently represent integers from 0 to 4; * indicates a bond site.

2. The photosensitive resin composition according to claim 1, wherein, The content of the compound containing the structure shown in formula (A-1) is 5% by mass or more and 85% by mass or less when the total mass of component (A) is 100 parts by mass.

3. The photosensitive resin composition according to claim 1, wherein, The content of the compound containing the structure shown in formula (A-1) is 20% by mass or more when the total mass of component (A) is 100 parts by mass.

4. The photosensitive resin composition according to claim 1, wherein, The content of the compound containing the structure shown in formula (A-1) is 60% by mass or less when the total mass of component (A) is 100 parts by mass.

5. The photosensitive resin composition according to claim 1, wherein, The content of the compound containing the structure shown in formula (A-2) is 6% by mass or more and 80% by mass or less when the total mass of component (A) is 100 parts by mass.

6. The photosensitive resin composition according to claim 1, wherein, The content of the compound containing the structure shown in formula (A-2) is 10% by mass or more when the total mass of component (A) is 100 parts by mass.

7. The photosensitive resin composition according to claim 1, wherein, The content of the compound containing the structure shown in formula (A-2) is 60% by mass or less when the total mass of component (A) is 100 parts by mass.

8. The photosensitive resin composition according to claim 1, wherein, The content of the compound having the structure shown in formula (A-3) is 6% by mass or more and 80% by mass or less when the total amount of component (A) is 100 parts by mass.

9. The photosensitive resin composition according to claim 1, wherein, The content of the compound having the structure shown in formula (A-3) is 10% by mass or more when the total mass of component (A) is 100 parts by mass.

10. The photosensitive resin composition according to claim 1, wherein, The content of the compound having the structure shown in formula (A-3) is 60% by mass or less when the total mass of component (A) is 100 parts by mass.

11. The photosensitive resin composition according to claim 1, wherein, (A) The content of the component is 20% by mass or more when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

12. The photosensitive resin composition according to claim 1, wherein, (A) The content of the component is 35% by mass or more when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

13. The photosensitive resin composition according to claim 1, wherein, (A) The content of the component is 90% by mass or less when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

14. The photosensitive resin composition according to claim 1, wherein, (A) The content of the component is 80% by mass or less when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

15. The photosensitive resin composition according to claim 1, wherein, (B) The content of component is 1% by mass or more when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

16. The photosensitive resin composition according to claim 1, wherein, (B) The content of component is 5% by mass or more when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

17. The photosensitive resin composition according to claim 1, wherein, (B) The content of component is 30% by mass or less when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

18. The photosensitive resin composition according to claim 1, wherein, (B) The content of component is 25% by mass or less when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

19. The photosensitive resin composition according to claim 1, wherein, (C) The content of component (C) is 0.01% by mass or more when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

20. The photosensitive resin composition according to claim 1, wherein, (C) The content of component (C) is 0.1% by mass or more when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

21. The photosensitive resin composition according to claim 1, wherein, (C) The content of component (C) is 3% by mass or less when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

22. The photosensitive resin composition according to claim 1, wherein, (C) The content of component (C) is 1.5% by mass or less when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

23. The photosensitive resin composition according to claim 1, further comprising any one of (D) an organic filler and (E) an inorganic filler.

24. The photosensitive resin composition according to claim 23, wherein, (D) The content of component (D) is 1% by mass or more when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

25. The photosensitive resin composition according to claim 23, wherein, (D) The content of component (D) is 5% by mass or more when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

26. The photosensitive resin composition according to claim 23, wherein, (D) The content of component (D) is 40% by mass or less when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

27. The photosensitive resin composition according to claim 23, wherein, (D) The content of component (D) is 20% by mass or less when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

28. The photosensitive resin composition according to claim 23, wherein, (E) The content of component (E) is 1% by mass or more when the non-volatile component of the photosensitive resin composition is 100% by mass.

29. The photosensitive resin composition according to claim 23, wherein, (E) The content of component (E) is 10% by mass or more when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

30. The photosensitive resin composition according to claim 23, wherein, (E) The content of component (E) is 80% by mass or less when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

31. The photosensitive resin composition according to claim 23, wherein, (E) The content of component (E) is 60% by mass or less when the non-volatile component of the photosensitive resin composition is taken as 100% by mass.

32. The photosensitive resin composition according to claim 1, wherein, (B) The component contains an amino resin that contains at least two alkoxymethyl groups in the molecule.

33. The photosensitive resin composition according to claim 1, wherein, (B) contains melamine resin.

34. A photosensitive film with a support, comprising: a support, and a photosensitive resin composition layer comprising any one of claims 1 to 33 disposed on the support.

35. A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of claims 1 to 33.

36. The printed wiring board according to claim 35, wherein, The insulating layer is a solder resist.

37. A semiconductor device comprising the printed wiring board of claim 35 or 36.

38. A method for manufacturing a printed wiring board, comprising: The step of forming a photosensitive resin composition layer comprising any one of the photosensitive resin compositions according to claims 1 to 33 on a circuit board. The step of curing the photosensitive resin composition layer by irradiating it with active light. The step of developing the cured photosensitive resin composition layer.

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