Photosensitive resin composition

Abstract

To provide a photosensitive resin composition that can form an insulating layer having small marginal resolution and excellent adhesion to a conductor layer.SOLUTION: A photosensitive resin composition contains (A) an alkali-soluble novolac resin, (B) a melamine resin containing one or more alkoxymethyl groups, (C) a photoacid generator, and (D) an alkoxy oligomer-based coupling agent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a photosensitive film, a circuit board, and a semiconductor device using the same.

Background Art

[0002] As a manufacturing technique for printed wiring boards widely used in various electronic devices, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately stacked is known. In the manufacturing method by the build-up method, generally, a thermosetting resin composition is used for the insulating layer, and a photosensitive resin composition is used for the solder resist layer (Patent Document 1). In recent years, a photosensitive resin composition may be used for forming the insulating layer (Patent Document 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] In the insulating layer, openings such as holes and trenches may be formed by exposure and development of the photosensitive resin composition. Due to the recent progress in miniaturization of wiring, the above-mentioned openings are required to be small. Therefore, the photosensitive resin composition is required to have a small limit resolution. "Limit resolution" represents the limit of the size of the openings that can be formed in the photosensitive resin composition by exposure and development, and the smaller the better.

[0005] However, an insulating layer formed using a conventional photosensitive resin composition with low limit resolution tends to have poor adhesion to a conductor layer. Therefore, there is a demand for the development of a photosensitive resin composition capable of forming an insulating layer with low limit resolution and excellent adhesion to a conductor layer.

[0006] The present invention was devised in view of the above problems, and aims to provide a photosensitive resin composition capable of forming an insulating layer with low limit resolution and excellent adhesion to a conductor layer; a photosensitive film provided with a photosensitive resin composition layer containing the above photosensitive resin composition; a circuit board provided with an insulating layer containing a cured product of the above photosensitive resin composition and a method for manufacturing the same; and a semiconductor device provided with the circuit board.

Means for Solving the Problems

[0007] The present inventors intensively studied to solve the above problems. As a result, the present inventors found that a photosensitive resin composition containing (A) an alkali-soluble novolak resin, (B) a melamine resin containing one or more alkoxymethyl groups, (C) a photoacid generator, and (D) an alkoxy oligomer type coupling agent can solve the above problems, and completed the present invention. That is, the present invention includes the following.

[0008] 〔1〕 A photosensitive resin composition containing (A) an alkali-soluble novolak resin, (B) a melamine resin containing one or more alkoxymethyl groups, (C) a photoacid generator, and (D) an alkoxy oligomer type coupling agent. 〔2〕 The photosensitive resin composition according to 〔1〕, wherein the (A) alkali-soluble novolak resin contains a compound having a structure represented by formula (A-1).

Chemical formula

Chemical formula

[10] , [8] or [9]. 〔11〕 (I) A step of forming a photosensitive resin composition layer containing the photosensitive resin composition according to any one of [1] to [6] on a base substrate, (II) A step of exposing the photosensitive resin composition layer, and (III) A step of developing the photosensitive resin composition layer, A method for manufacturing a circuit board, comprising the steps in this order.

Advantages of the Invention

[0009] According to the present invention, there can be provided a photosensitive resin composition capable of forming an insulating layer having a small limit resolution and excellent adhesion to a conductor layer; a photosensitive film provided with a photosensitive resin composition layer containing the photosensitive resin composition; a circuit board provided with an insulating layer containing a cured product of the photosensitive resin composition and a method for manufacturing the same; and a semiconductor device provided with the circuit board.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and can be arbitrarily modified and implemented without departing from the scope of the claims and their equivalents.

[0011] [1. Overview of the Photosensitive Resin Composition] The photosensitive resin composition according to an embodiment of the present invention contains a combination of (A) an alkali-soluble novolak resin, (B) a melamine resin containing one or more alkoxymethyl groups, (C) a photoacid generator, and (D) an alkoxy oligomer type coupling agent. In the following description, the “(B) melamine resin containing one or more alkoxymethyl groups” may be referred to as “(B) melamine resin”.

[0012] This photosensitive resin composition can have a small limit resolution. Further, according to this photosensitive resin composition, an insulating layer having excellent adhesion to a conductor layer can be formed.

[0013] The photosensitive resin composition may further contain optional components in combination with components (A) to (D). Preferred optional components include, for example, (E) an organic filler.

[0014] [2. (A) Alkali-soluble novolak resin] The photosensitive resin composition contains (A) an alkali-soluble novolak resin as component (A). The (A) alkali-soluble novolak resin represents an alkali-soluble resin containing a structure in which benzene rings bonded to hydroxyl groups are linked by methylene groups which may have substituents. Since the hydroxyl groups of the (A) alkali-soluble novolak resin can undergo a crosslinking reaction with (B) a melamine resin, a latent image can be formed in the photosensitive resin composition layer by exposure. Further, since the (A) alkali-soluble novolak resin can be dissolved in an alkaline developer, the latent image can be developed. The (A) alkali-soluble novolak resin may be used alone or in combination of two or more.

[0015] Preferred examples of the (A) alkali-soluble novolak resin include compounds containing a structure represented by the following formula (A-1). Therefore, the (A) alkali-soluble novolak resin preferably contains a compound containing a structure represented by the following formula (A-1). A compound containing a structure represented by formula (A-1) may hereinafter be referred to as the “(A-1) component”.

[0016] [Chemical formula]

[0017] (In formula (A-1), R 1 each independently represents a divalent group represented by the following formula (a), and X 1 each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, or a monovalent heterocyclic group which may have a substituent, n1 represents an integer from 0 to 4, and m1 represents an integer from 2 to 200. * represents a bond.)

[0018]

Chem.

[0019] (In formula (a), R 11 and R 12 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, an amino group, a carbonyl group, a carboxyl group, or a group consisting of a combination thereof, and R 11 and R 12 may be bonded to each other to form a ring. * represents a bond.)

[0020] In formula (A-1), X 1 each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, or a monovalent heterocyclic group which may have a substituent. Among them, X 1 is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, or a halogen atom, more preferably an alkyl group which may have a substituent and an aryl group which may have a substituent, and even more preferably an alkyl group which may have a substituent.)

[0021] The alkyl group may be a straight-chain, branched-chain, or cyclic alkyl group. The cyclic alkyl group may be either monocyclic or polycyclic. As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is even more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an isopropyl group, an s-butyl group, a t-butyl group, a 2-methylpropyl group, a 3-heptyl group, etc. Among them, the methyl group is particularly preferable.)

[0022] As the aryl group, an aryl group having 6 to 30 carbon atoms is preferable, an aryl group having 6 to 20 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is even more preferable. Examples of the aryl group include a phenyl group and a naphthyl group.

[0023] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

[0024] As the monovalent heterocyclic group, a monovalent heterocyclic group having 3 to 21 carbon atoms is preferable, a monovalent heterocyclic group having 3 to 15 carbon atoms is more preferable, and a monovalent heterocyclic group having 3 to 9 carbon atoms is even more preferable. The monovalent heterocyclic group includes a monovalent aromatic heterocyclic group (heteroaryl group). Examples of the monovalent heterocyclic group include a thienyl group, a pyrrolyl group, a furanyl group, a furyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, a pyrrolidyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group. Among them, a pyrrolidyl group is preferable. The monovalent heterocyclic group means a group obtained by removing one hydrogen atom from the heterocyclic ring of a heterocyclic compound.

[0025] X 1 The alkyl group, aryl group, and monovalent heterocyclic group represented by may have a substituent. Examples of the substituent include a halogen atom, -OH, -O-C 1-6 alkyl group, -N(C 1-6 alkyl group)2, C 1-6 alkyl group, C 6-10 aryl group, -NH2, -NH(C 1-6 alkyl group), -CN, -C(O)O-C 1-6 alkyl group, -C(O)H, -NO2, etc.

[0026] In this specification, the expression "may have a substituent" means, unless otherwise specified, unsubstituted or having usually 1 to 5 (preferably 1, 2 or 3) substituents. When having a plurality of substituents, these substituents may be the same or different from each other. Also, in this specification, "Cp-q The term "(where p and q are positive integers and p < q)" indicates that the number of carbon atoms in the organic group described immediately after this term is from p to q. For example, " 1-6 the expression "alkyl group" indicates an alkyl group having 1 to 6 carbon atoms.

[0027] In formula (A-1), R 1 each independently represents a divalent group represented by formula (a). The bond in formula (a) is preferably bonded to the OH group at the phenolic site in formula (A-1) at any of the ortho, meta, and para positions, more preferably bonded to either the meta or para position, and even more preferably a mixture of those bonded to the meta and para positions. When the bonds in formula (a) are a mixture of those bonded to the meta and para positions of the OH group at the phenolic site in formula (A-1), let the mass of the bond in formula (a) bonded to the meta position be m, and the mass of the bond in formula (a) bonded to the para position be p. At this time, the mixing ratio (m:p) is preferably 1:0.1 to 1:10, more preferably 1:0.1 to 1:5, even more preferably 1:0.1 to 1:2, and particularly preferably 1:0.5 to 1:1.

[0028] In formula (a), R 11 and R 12 each independently represent a group consisting of a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, an amino group, a carbonyl group, a carboxyl group, or a combination thereof, and R 11 and R 12 may be bonded to each other to form a ring. Among them, R 11 and R 12 each independently are preferably a hydrogen atom or an alkyl group.

[0029] R 11 and R 12 The alkyl group which may have a substituent, the aryl group which may have a substituent, and the monovalent heterocyclic group which may have a substituent represented by are X in formula (A-1)1 It may be the same as an alkyl group which may have a substituent represented by, an aryl group which may have a substituent, and a monovalent heterocyclic group which may have a substituent.

[0030] Examples of the group composed of these combinations include a group composed of a combination of an alkyl group and a carbonyl group, a group composed of a combination of an aryl group and a carbonyl group, a group composed of a combination of an alkyl group, an amino group and a carbonyl group, a group composed of a combination of an aryl group, an amino group and a carbonyl group, and the like.

[0031] R 11 and R 12 may be bonded to each other to form a ring. R 11 and R 12 The ring structure that may be formed includes a spiro ring and a fused ring. In this case, R 11 and R 12 are preferably a group forming a cyclopentane ring, a group forming a cyclohexane ring, a group forming a 2,2-dimethyl-4-methylcyclohexane ring, a group forming a fluorene ring, a group forming a pyrrolidine ring, or a group forming a γ-lactam ring.

[0032] Specific examples of the divalent group represented by formula (a) include the following groups. In the formula, “*” represents a bond.

[0033]

Chemical formula

[0034]

Chemical formula

[0035] In formula (A-1), n1 represents an integer from 0 to 4, preferably represents an integer from 0 to 3, more preferably represents 0 or 1, and particularly preferably represents 1.

[0036] In formula (A-1), m1 represents an integer from 2 to 200, preferably represents an integer from 2 to 150, more preferably represents an integer from 2 to 100, and even more preferably represents an integer from 2 to 50.

[0037] Specific examples of the component (A-1) include the resin represented by the following formula (1). In the specific examples, the OH groups in the phenol moiety are mixed at a ratio of 60% in the meta position and 40% in the para position. In the following formula (1), n represents an integer from 1 to 200.

[0038] [Chemical formula]

[0039] As the (A) alkali-soluble novolak resin, commercially available products may be used. For example, as commercially available component (A-1), there are "TR4020G" (resin represented by formula (1)) manufactured by Asahi Organic Materials Co., Ltd.; "TR4050G", "TR4080G", "TR5020G", "TR5050G", "TR6020G", "TR6050G", "TR6080G", "OC4500", "TRM30B20G", "TRM30B35G", "EP16F30G", "EP16F50G", "TR4000B", "EP0090G", "EP3010A", "PAPS-PN2", "PAPS-PN4", "AYPN-3.5", etc. of the AV Light series; resin series for photoresists manufactured by Sumitomo Bakelite Co., Ltd.; Reditopp series manufactured by Gunei Chemical Industry Co., Ltd.; "PR-30-40P", "PR-100L", "PR-100H", "PR-50", "PR-55", "PR-56-1", "PR-56-2", "WR-101", "WR-102", "WR-103", "WR-104", etc. of the Phenolite series manufactured by DIC Corporation; "LF-100", "LF-110", "LF-120", "LF-200", "LF-400", "LF-500" manufactured by Lignite Co., Ltd.; base resin series for photoresists manufactured by Meiwafosis Co., Ltd., etc.

[0040] The (A) alkali-soluble novolak resin may be used alone or in combination of two or more.

[0041] (A) The method for producing the alkali-soluble novolak resin is not particularly limited. For example, the component (A-1) can be obtained by polycondensation of phenol or its derivative with an aldehyde and / or a ketone. The polycondensation can be carried out in the presence of a catalyst such as an acid or a base. Therefore, the terminal of the component (A-1) can usually be a hydroxyphenyl group or an aldehyde group which may have a substituent, and it is preferable that both terminals are hydroxyphenyl groups which may have a substituent.

[0042] (A) The weight-average molecular weight of the alkali-soluble novolak resin is preferably 500 or more, more preferably 700 or more, still more preferably 1000 or more, and preferably 150000 or less, more preferably 100000 or less, still more preferably 50000 or less. The weight-average molecular weight can be measured as a value in terms of polystyrene by the gel permeation chromatography (GPC) method.

[0043] (A) When the non-volatile components of the photosensitive resin composition are 100% by mass, the amount of the alkali-soluble novolak resin is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less. When the amount of the (A) alkali-soluble novolak resin is within the above range, both the ultimate resolution and the adhesion can be effectively improved.

[0044] (A) When the resin components of the photosensitive resin composition are 100% by mass, the amount of the alkali-soluble novolak resin is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less. The resin components of the photosensitive resin composition refer to the components excluding fillers such as (E) organic fillers and inorganic fillers among the non-volatile components of the photosensitive resin composition. When the amount of the (A) alkali-soluble novolak resin is within the above range, both the ultimate resolution and the adhesion can be effectively improved.

[0045] [3. (B) Melamine resin containing one or more alkoxymethyl groups] The photosensitive resin composition contains, as component (B), a melamine resin containing one or more alkoxymethyl groups. Since the alkoxymethyl groups contained in the (B) melamine resin can react and bond with the hydroxyl groups of the (A) alkali-soluble novolak resin, the photosensitive resin composition layer can be insolubilized in the developer or cured by exposure to form an insulating layer.

[0046] The alkoxymethyl groups contained in the (B) melamine resin are represented by the following formula (B-1). In the formula (B-1), "*" represents a bond.

[0047] [Chemical formula]

[0048] In the formula (B-1), R 21 represents an alkyl group which may have a substituent. The alkyl group may be a straight-chain, branched-chain, or cyclic alkyl group. Further, the cyclic alkyl group may be either a monocyclic or polycyclic group. As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is even more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an isopropyl group, an s-butyl group, a t-butyl group, etc. Among them, a methyl group and a butyl group are preferable, and a methyl group is more preferable.

[0049] R 21 The alkyl group represented may have a substituent.

[0050] The alkoxymethyl group is preferably contained in the alkoxymethylamino group represented by the following formula (B-1'). Therefore, the (B) melamine resin preferably contains an alkoxymethylamino group represented by the formula (B-1'). In the formula, "*" represents a bond.

[0051]

Chem.

[0052] In formula (B-1’), R 22 is the same as R 21 in formula (B-1). R represents a hydrogen atom or an alkoxymethyl group.

[0053] The (B) melamine resin contained in the photosensitive resin composition according to this embodiment usually contains 1 or more of the above alkoxymethyl groups per molecule. From the viewpoint of obtaining a photosensitive resin composition excellent in photosensitivity, the number of alkoxymethyl groups per molecule of the (B) melamine resin is preferably 2 or more.

[0054] As the (B) melamine resin, a melamine resin having a structure represented by the following formula (B-2) is preferable.

[0055]

Chem.

[0056] (In formula (B-2), X 21 , X 22 , X 23 and X 24 each independently represent a hydrogen atom or an alkoxymethyl group. R 50 represents a hydrogen atom, an amino group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxymethylamino group represented by formula (B-1’). However, when R 50 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, at least one of X 21 , X 22 , X 23 , and X 24 is an alkoxymethyl group.)

[0057] In formula (B-2), X 21 , X22 , X 23 and X 24 each independently represents a hydrogen atom or an alkoxymethyl group. The alkoxymethyl group represented by X 21 ~X 24 may be the same as the group represented by formula (B-1). R 50 When represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, at least one of X[[ID=]12] 21 ~X 24 is preferably an alkoxymethyl group, and more preferably two or more are alkoxymethyl groups. Preferably, when R 50 represents a hydrogen atom, an amino group, an alkyl group which may have a substituent, or an aryl group which may have a substituent, at least one of X 21 ~X 24 is preferably an alkoxymethyl group, and more preferably two or more are alkoxymethyl groups. It is more preferable that three or more of X 21 ~X 24 are alkoxymethyl groups, and particularly preferably four or more of X 21 ~X 24 are alkoxymethyl groups.

[0058] In formula (B-2), R 50 represents a hydrogen atom, an amino group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxymethylamino group represented by formula (B-1’). R 50 is preferably an aryl group which may have a substituent or an alkoxymethylamino group represented by formula (B-1’), and more preferably an alkoxymethylamino group represented by formula (B-1’). The alkyl group which may have a substituent and the aryl group which may have a substituent represented by R 50 may be the same as the alkyl group which may have a substituent and the aryl group which may have a substituent represented by X 1 in formula (A-1).

[0059] The melamine resin having the structure represented by formula (B-2) is preferably a melamine resin having the structure represented by formula (B-2’).

[0060] [Chemical formula]

[0061] (In formula (B-2’), X 25 , X 26 , X 27 , X 28 , X 29 and X 30 each independently represents a hydrogen atom or an alkoxymethyl group. However, at least one of X 25 , X 26 , X 27 , X 28 , X 29 and X 30 is an alkoxymethyl group.)

[0062] In formula (B-2’), X 25 , X 26 , X 27 , X 28 , X 29 and X 30 each independently represents a hydrogen atom or an alkoxymethyl group. The alkoxymethyl group represented by X 25 ~X 30 can be the same as the group represented by formula (B-1). At least one, preferably two or more, of X 25 ~X 30 is an alkoxymethyl group. It is more preferable that three or more of X 25 ~X 30 are alkoxymethyl groups, and it is even more preferable that four or more of X 25 ~X 30 are alkoxymethyl groups. It is particularly preferable that all of X 25 ~X 30 are alkoxymethyl groups.)

[0063] (B) Specific examples of the melamine resin include the following melamine resins.

[0064] [Chemical formula]

[0065] (B) Melamine resin may be a commercially available product. Examples of commercially available products include "MW-390", "MW-100LM", "MX-750LM" manufactured by Sanwa Chemical Co., Ltd.; "Cymel-300", "Cymel 370N", "Cymel 327" manufactured by Daicel Ornex Co., Ltd., etc.

[0066] (B) Melamine resin may be used alone or in combination of two or more kinds.

[0067] When the non-volatile components of the photosensitive resin composition are 100% by mass, the amount of (B) melamine resin is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less. When the amount of (B) melamine resin is within the above range, both the limit resolution and the adhesion can be effectively improved.

[0068] When the resin components of the photosensitive resin composition are 100% by mass, the amount of (B) melamine resin is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less. When the amount of (B) melamine resin is within the above range, both the limit resolution and the adhesion can be effectively improved.

[0069] The ratio of the mass of (A) alkali-soluble novolak resin to the mass of (B) melamine resin ((B) melamine resin / (A) alkali-soluble novolak resin) contained in the photosensitive resin composition is preferably 0.01 or more, more preferably 0.1 or more, particularly preferably 0.2 or more, and preferably 0.5 or less, more preferably 0.4 or less, particularly preferably 0.3 or less.

[0070] [4. (C) Photoacid generator] The photosensitive resin composition contains a (C) photoacid generator as the component (C). The (C) photoacid generator generates an acid upon irradiation with actinic rays such as ultraviolet rays, and the generated acid can promote the reaction between the (A) alkali-soluble novolak resin and the (B) melamine resin. Therefore, the solubility of the photosensitive resin composition in the developer can be effectively reduced by exposure, so that the formation of a latent image by exposure can proceed smoothly. The (C) photoacid generator may be used alone or in combination of two or more kinds.

[0071] As the (C) photoacid generator, a compound that generates an acid upon irradiation with actinic rays can be used. Examples of the (C) photoacid generator include halogen-containing compounds, onium salt compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds, oxime ester compounds, and the like. Among them, halogen-containing compounds are preferred.

[0072] (C) Examples of the halogen-containing compounds that can be suitably used as photoacid generators include, for example, haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, and the like. Specific preferred examples of the halogen-containing compounds include 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 1,10-dibromo-n-decane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, phenyl-bis(trichloromethyl)-s-triazine, 4-methoxyphenyl-bis(trichloromethyl)-s-triazine, styryl-bis(trichloromethyl)-s-triazine, naphthyl-bis(trichloromethyl)-s-triazine, and other s-triazine derivatives. Commercially available products can be used as the halogen-containing compounds. Examples of commercially available products include "TFE-triazine", "TME-triazine", "MP-triazine", "MOP-triazine", "dimethoxytriazine" (halogen-containing compound-based photoacid generator having a triazine skeleton), etc. manufactured by Sanwa Chemical Co., Ltd.

[0073] (C) Examples of the onium salt compounds that can be suitably used as photoacid generators include, for example, iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Suitable specific examples of the onium salt compounds include tris(4-methylphenyl)sulfonium trifluoromethanesulfonate, tris(4-methylphenyl)sulfonium hexafluorophosphate, 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, 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate, and the like. Commercially available products can be used as the onium salt compounds. Examples of commercially available products include "TS-01" and "TS-91" manufactured by Sanwa Chemical Co., Ltd.; "CPI-110A", "CPI-210S", "HS-1", "LW-S1", "IK-1", "CPI-310B" manufactured by San-Apro Ltd.; "SI-110L", "SI-180L", "SI-100L" manufactured by Shin Shin Chemical Industry Co., Ltd., and the like.

[0074] (C) Examples of the diazoketone compounds that can be suitably used as photoacid generators include, for example, 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like. Suitable specific examples of the diazoketone compounds include 1,2-naphthoquinonediazide-4-sulfonic acid ester compounds of phenols, and the like.

[0075] (C) Examples of sulfone compounds that can be suitably used as photoacid generators include, for example, β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Preferable specific examples of the sulfone compound include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis(phenacylsulfonyl)methane, and the like.

[0076] (C) Examples of sulfonic acid compounds that can be suitably used as photoacid generators include, for example, alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, iminosulfonates, and the like. Preferable specific examples of the sulfonic acid compound include benzoin tosylate, pyrogallol tris(trifluoromethanesulfonate), o-nitrobenzyl trifluoromethanesulfonate, o-nitrobenzyl p-toluenesulfonate, and the like.

[0077] (C) Specific examples of sulfonimide compounds that can be suitably used as photoacid generators include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)naphthylimide, and the like.

[0078] (C) Specific examples of diazomethane compounds that can be suitably used as photoacid generators include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, and the like. Commercially available products can be used as the diazomethane compound.

[0079] (C) Specific examples of oxime ester compounds that can be suitably used as photoacid generators include benzenacetonitrile, 2-methyl-α-[2-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene], benzenacetonitrile, 2-methyl-α-[2-[[[(4-methylphenyl)sulfonyl]oxy]imino]-3(2H)-thienylidene], and the like. Commercially available products include, for example, "PAG103", "PAG121", "PAG169", "PAG203", etc. manufactured by BASF.

[0080] (C) When the non-volatile components in the photosensitive resin composition are 100% by mass, the amount of the photoacid generator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

[0081] [5. (D) Alkoxy Oligomer-Type Coupling Agent] The photosensitive resin composition contains a (D) alkoxy oligomer-type coupling agent as the component (D). The (D) alkoxy oligomer-type coupling agent usually has a plurality of repeating units containing both an alkoxy group and a functional group in the molecule. When this (D) alkoxy oligomer-type coupling agent is used in combination with the above-mentioned components (A) to (C), it is possible to improve both the ultimate resolution and the adhesion to the conductor layer.

[0082] Examples of the alkoxy group contained in the (D) alkoxy oligomer-type coupling agent include a methoxy group, an ethoxy group, a propoxy group, etc., and a methoxy group and an ethoxy group are preferred. Among them, from the viewpoint of enhancing the adhesion between the insulating layer and the GaAs substrate, a methoxy group is more preferred. In particular, from the viewpoint of particularly effectively enhancing the adhesion between the insulating layer and the GaAs substrate by utilizing the high reactivity of the methoxy group, it is particularly preferred that all of the alkoxy groups contained in the repeating unit of the (D) alkoxy oligomer-type coupling agent are methoxy groups.

[0083] (D) The functional groups contained in the alkoxy oligomer type coupling agent can usually react with appropriate organic compounds to form chemical bonds. Examples of such functional groups include an epoxy group, an acryloyl group, a methacryloyl group, a vinyl group, a mercapto group, etc. Also, the functional group may be one type or two or more types. Among them, from the viewpoint of effectively enhancing adhesion, a functional group capable of reacting with (A) an alkali-soluble novolak resin is preferable. Specifically, at least one functional group selected from the group consisting of an epoxy group, an acryloyl group, and a methacryloyl group is preferable.

[0084] (D) Examples of the alkoxy oligomer type coupling agent include a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent, and a silane coupling agent is preferable. The silane coupling agent usually contains a repeating unit containing a silicon atom, an alkoxy group directly bonded to the silicon atom, and a functional group bonded to the silicon atom directly or via a linking group. Usually, this repeating unit is linked via a bond extending from the silicon atom. Examples of the (D) alkoxy oligomer type coupling agent include, for example, a silane coupling agent containing a repeating unit represented by the following formula (D-1).

[0085]

Chemical formula

[0086] (In formula (D-1), X d represents a functional group, L d represents a divalent linking group, nd represents 0 or 1, R d represents an alkyl group, and Z d represents an oxygen atom or a divalent aliphatic hydrocarbon group.)

[0087] In formula (D-1), X d represents a functional group. The functional group is as described above.

[0088] In formula (D-1), L d represents a divalent linking group. Examples of the divalent linking group include alkylene groups such as methylene group, propylene group, and hexylene group; alkyleneoxyalkylene groups such as methyleneoxymethylene group, propyleneoxymethylene group, and octyleneoxymethylene group; and the like. Also, the number of carbon atoms in L d is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. As L d , an alkylene group is preferred, and a propylene group is more preferred.

[0089] In formula (D-1), nd represents 0 or 1.

[0090] In formula (D-1), R d represents an alkyl group. The number of carbon atoms in R d is usually 1 to 10, preferably 1 to 5, more preferably 1 to 2, and particularly preferably 1. Examples of R d include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc. Methyl group and ethyl group are preferred, and methyl group is more preferred.

[0091] In formula (D-1), Z d represents an oxygen atom or a divalent aliphatic hydrocarbon group. The divalent aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred. The number of carbon atoms in the divalent aliphatic hydrocarbon group is usually 1 or more, preferably 2 or more, more preferably 3 or more, preferably 6 or less, more preferably 5 or less, and particularly preferably 4 or less. Examples of the divalent aliphatic hydrocarbon group include alkylene groups such as methylene group, ethylene group, and propylene group. Among them, Z d is preferably an oxygen atom.

[0092] The number of repeating units per molecule of the (D) alkoxy oligomer type coupling agent is usually 3 or more, preferably 4 or more, preferably 20 or less, and more preferably 10 or less.

[0093] (D) The weight-average molecular weight of the alkoxy oligomer type coupling agent is preferably from 800 to 30,000, more preferably from 800 to 10,000.

[0094] (D) The viscosity of the alkoxy oligomer type coupling agent at 25 °C is preferably 5 mm 2 / s or more, more preferably 10 mm 2 / s or more, particularly preferably 15 mm 2 / s or more, and preferably 2000 mm 2 / s or less, more preferably 1000 mm 2 / s or less, particularly preferably 100 mm 2 / s or less. The viscosity can be measured using an E-type viscometer (RE-80 manufactured by Toki Sangyo Co., Ltd.) at a rotational speed set to 5 rpm to 20 rpm in an apparatus adjusted to 25 °C, by weighing approximately 0.2 ml of the sample using a syringe.

[0095] (D) The functional group equivalent of the alkoxy oligomer type coupling agent is preferably 100 g / mol or more, more preferably 150 g / mol or more, still more preferably 200 g / mol or more, and preferably 2000 g / mol or less, more preferably 1500 g / mol or less, still more preferably 1000 g / mol or less. The functional group equivalent of the (D) alkoxy oligomer type coupling agent represents the mass of the (D) alkoxy oligomer type coupling agent having 1 mol of functional groups.

[0096] (D) Alkoxy oligomer type coupling agents may be commercially available products. Examples of commercially available products include "KR-513" manufactured by Shin-Etsu Chemical Co., Ltd. (an oligomer type silane coupling agent containing a methoxy group as an alkoxy group and an acryloyl group as a functional group), "KR-516" (an oligomer type silane coupling agent containing a methoxy group as an alkoxy group and an epoxy group as a functional group), "KR-517" (an oligomer type silane coupling agent containing a methoxy group and an ethoxy group as alkoxy groups and an epoxy group as a functional group), "X-40-9296" (an oligomer type silane coupling agent containing a methoxy group as an alkoxy group and a methacryloyl group as a functional group), "KR-511" (an oligomer type silane coupling agent containing a methoxy group as an alkoxy group and a vinyl group as a functional group), "KR-518" (an oligomer type silane coupling agent containing a methoxy group and an ethoxy group as alkoxy groups and a mercapto group as a functional group), "KR-519" (an oligomer type silane coupling agent containing a methoxy group as an alkoxy group and a mercapto group as a functional group), "X-40-9318" (an oligomer type silane coupling agent containing a methoxy group as an alkoxy group and an isocyanate group as a functional group), "X-12-981S" (an oligomer type silane coupling agent containing an ethoxy group as an alkoxy group and an epoxy group as a functional group), "X-12-984S" (an oligomer type silane coupling agent containing an ethoxy group as an alkoxy group and an epoxy group as a functional group), "X-12-1048" (an oligomer type silane coupling agent containing a methoxy group as an alkoxy group and an acryloyl group as a functional group), "X-12-1050" (an oligomer type silane coupling agent containing a methoxy group as an alkoxy group and an acryloyl group as a functional group), and "X-12-1159L" (an oligomer type silane coupling agent containing a methoxy group as an alkoxy group and an acryloyl group as a functional group). (D) The alkoxy oligomer type coupling agent may be used alone or in combination of two or more.

[0097] (D) The amount of the alkoxy oligomer type coupling agent is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, and preferably 20% by mass or less, more preferably 18% by mass or less, still more preferably 15% by mass or less when the nonvolatile components of the photosensitive resin composition are 100% by mass. When the amount of the (D) alkoxy oligomer type coupling agent is within the above range, both the ultimate resolution and the adhesion can be effectively improved.

[0098] (D) The amount of the alkoxy oligomer type coupling agent is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, and preferably 20% by mass or less, more preferably 18% by mass or less, still more preferably 15% by mass or less when the resin components of the photosensitive resin composition are 100% by mass. When the amount of the (D) alkoxy oligomer type coupling agent is within the above range, both the ultimate resolution and the adhesion can be effectively improved.

[0099] (D) The mass W of the alkoxy oligomer type coupling agent D and the mass W of the (A) alkali-soluble novolak resin A and the ratio (W D / W A ) is preferably 0.01 or more, more preferably 0.015 or more, still more preferably 0.02 or more, and preferably 0.5 or less, more preferably 0.3 or less, particularly preferably 0.2 or less.

[0100] [6. (E) Organic filler] The photosensitive resin composition may further contain a filler as an optional component in combination with the above-described components (A) to (D). The filler is usually incompatible with the resin component and can exist as particles in the photosensitive resin composition and its cured product. The photosensitive resin composition preferably contains an (E) organic filler as this filler.

[0101] (E) Since the organic filler is formed of an organic material, it generally has flexibility. Therefore, when using the (E) organic filler, it becomes possible to disperse stress in the insulating layer, and the crack resistance and insulation of the insulating layer can be improved. Examples of the (E) organic filler include urethane particles, rubber particles, polyamide particles, and silicone particles.

[0102] As urethane particles, commercially available products may be used. For example, "MM-101SW", "MM-101SWA", "MM-101SM", "MM-101SMA", "MM-110SMA" manufactured by Negami Kogyo Co., Ltd.; RKB series manufactured by Resinas Kasei Co., Ltd., etc. can be mentioned.

[0103] As rubber particles, resin particles that have been chemically cross-linked treated with a resin exhibiting rubber elasticity and are insoluble and infusible in an organic solvent can be used. Examples of rubber particles include acrylonitrile-butadiene rubber particles, butadiene rubber particles, acrylic rubber particles, methyl methacrylate-butadiene-styrene copolymer particles, etc. As rubber particles, commercially available products may be used. For example, "EXL-2655" manufactured by Dow Chemical Japan Co., Ltd.; "AC3816N", "AC3355", "AC3816", "AC3832", "AC4030", "AC3364", "IM101" manufactured by Gants Kasei Co., Ltd.; "Paraloid EXL2655", "EXL2602" manufactured by Kureha Chemical Co., Ltd.; "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", "M-210" manufactured by Kaneka Corporation; RKB series manufactured by Resinas Kasei Co., Ltd., etc. can be mentioned.

[0104] As the polyamide particles, particles of a resin having an amide bond can be used. Examples of the polyamide particles include particles of aliphatic polyamides such as nylon, particles of aromatic polyamides such as Kevlar, and polyamideimide particles. As the polyamide particles, commercially available products may be used, for example, "VESTOSINT 2070" manufactured by Daicel-Huels Co., Ltd.; "SP500" manufactured by Toray Industries, Inc., etc.

[0105] (E) The organic filler may be used alone or in combination of two or more.

[0106] (E) The average particle size of the organic filler is preferably 0.005 μm or more, more preferably 0.01 μm or more, still more preferably 0.05 μm or more, and preferably 5 μm or less, more preferably 2 μm or less, still more preferably 1 μm or less, particularly preferably 0.5 μm or less. The average particle size of the organic filler can be measured using the dynamic light scattering method. Specifically, the average particle size of the organic filler can be measured by uniformly dispersing the organic filler in a suitable organic solvent by ultrasonic waves, creating a particle size distribution of the organic filler based on mass using a concentrated system particle size analyzer (for example, "FPAR-1000" manufactured by Otsuka Electronics Co., Ltd.), and taking the median diameter as the average particle size.

[0107] (E) When the non-volatile components of the photosensitive resin composition are 100% by mass, the amount of the organic filler may be 0% by mass or more than 0% by mass, but is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less. When the amount of the organic filler is within the above range, both the limit resolution and the adhesion can be effectively improved.

[0108] [7.(F) Optional Additives] The photosensitive resin composition may further contain (F) an optional additive as an arbitrary non-volatile component in combination with the non-volatile components such as the above-described components (A) to (E). Examples of the (F) additive as the component (F) include, for example, thermoplastic resins; inorganic fillers such as silica particles and alumina particles; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black; polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; thickeners such as benton and montmorillonite; antifoaming agents of silicone-based, fluorine-based, and vinyl resin-based; flame retardants such as epoxy resins, antimony compounds, phosphorus-based compounds, aromatic condensed phosphoric acid esters, and halogen-containing condensed phosphoric acid esters; thermosetting resins such as phenolic curing agents and cyanate ester-based curing agents; and the like. The (F) additive may be used alone or in combination of two or more kinds.

[0109] [8. (G) Solvent] The photosensitive resin composition may contain (G) a solvent as a volatile component in combination with the non-volatile components such as the above-described components (A) to (F). According to the (G) solvent as this component (G), the viscosity of the photosensitive resin composition can be adjusted. Examples of the (G) solvent include, for example, organic solvents.

[0110] (G) As solvents, for example, ketone solvents such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbon solvents such as toluene, xylene, and tetramethylbenzene; glycol ether solvents 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; ester solvents such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, and ethyl diglycol acetate; aliphatic hydrocarbon solvents such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha can be mentioned. The solvent may be used alone or in combination of two or more.

[0111] (G) When the total amount of the photosensitive resin composition including the (G) solvent is 100% by mass, the amount of the (G) solvent may be 0% by mass, may be more than 0% by mass, preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less. In addition, the content of the (G) solvent in the photosensitive resin composition layer of the photosensitive film, when the total amount of the photosensitive resin composition including the (G) solvent is 100% by mass, is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.

[0112] [9. Method for Producing Photosensitive Resin Composition] The method for producing the photosensitive resin composition is not particularly limited. The photosensitive resin composition can be produced, for example, by mixing components (A) to (D) and, if necessary, components (E) to (G). When mixing, if necessary, kneading may be performed using a kneading device such as a three-roll mill, ball mill, bead mill, or sand mill, or stirring may be performed using a stirring device such as a super mixer or planetary mixer. There is no restriction on the order of mixing of each component. Also, cooling or heating may be performed during the process of mixing each component.

[0113] [10. Characteristics and Applications of Photosensitive Resin Compositions] The photosensitive resin composition according to this embodiment can have a small minimum resolution. Therefore, by using the photosensitive resin composition, an insulating layer having a small-sized opening can be formed. In one example, a photosensitive resin composition layer with a dry thickness of 20 μm is formed from the photosensitive resin composition, and an insulating layer having via holes is formed from the photosensitive resin composition layer by the method described in the examples. In this case, the minimum aperture diameter of the via holes that can be properly formed in the insulating layer can be reduced. Specifically, the above aperture diameter can be preferably 30 μm or less, more preferably 25 μm or less, and still more preferably 20 μm or less.

[0114] The photosensitive resin composition according to this embodiment can obtain a cured product that can adhere to a conductor layer such as a copper foil with high adhesiveness. Therefore, by using the photosensitive resin composition, an insulating layer that can adhere to the conductor layer with high adhesiveness can be formed. In one example, a photosensitive resin composition layer is formed on a copper foil by the method described in the examples and cured to form an insulating layer. In this case, the load (peel strength) required to peel the copper foil from the insulating layer can be made 0.4 kgf or more per 10 mm width.

[0115] The photosensitive resin composition according to this embodiment can preferably obtain a cured product that can adhere to a GaAs substrate (gallium arsenide substrate) such as a gallium arsenide wafer containing gallium arsenide with high adhesion. Therefore, by using the photosensitive resin composition, an insulating layer that can adhere to the GaAs substrate with high adhesion can be formed. In one example, a photosensitive resin composition layer is formed on a GaAs substrate by the method described in the examples and cured to form an insulating layer. When a cross-cut tape peel test is performed on this insulating layer in accordance with JIS K5600-5-6:1999 (ISO2409:1992), preferably, the results of classifications "0" to "2" in Table 1 of JIS K5600-5-6:1999 8.3 can be obtained, more preferably the results of classifications "0" to "1" can be obtained, and particularly preferably the result of classification "0" can be obtained. The above classifications indicate that the smaller the numerical value, the better the adhesion. Specifically, classification "0" indicates that the edge of the cut is completely smooth and there is no peeling in any grid. Also, classification "1" indicates that there are small peelings of the coating film at the intersections of the cuts, but the influence on the cross-cut part is clearly not more than 5%. Furthermore, classification "2" indicates that the coating film is peeled along the edge of the cut and / or at the intersections, but the influence on the cross-cut part is clearly more than 5% but not more than 15%.

[0116] The uses of the above-described photosensitive resin composition are not particularly limited. For example, it can be widely used in insulating resin sheets such as photosensitive films and prepregs; materials for forming insulating layers of circuit boards; solder resists, buffer coat films, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component embedding resins, etc.

[0117] Examples of the circuit board include semiconductor chip packages such as multi-chip packages, package-on-package, wafer-level packages, panel-level packages, and system-in-packages; package substrates including the semiconductor chip packages; printed wiring boards such as rigid boards, flexible boards, single-sided laminated boards, thin boards, and boards with built-in components; and the like. Among these, the photosensitive resin composition is suitable for semiconductor chip packages, and particularly suitable for wafer-level packages. Examples of the wafer-level package include, for example, a fan-in type wafer-level package and a fan-out type wafer-level package, and it may be applied to any of them.

[0118] In the circuit board, the insulating layer formed from the photosensitive resin composition may be an insulating layer for forming a wiring layer on the insulating layer. Further, the insulating layer formed from the photosensitive resin composition may be an interlayer insulating layer. Furthermore, the insulating layer formed from the photosensitive resin composition may be a solder resist. Also, the insulating layer formed from the photosensitive resin composition may be a buffer coat film.

[0119] [11. Photosensitive Film] The photosensitive film according to an embodiment of the present invention includes a support and a photosensitive resin composition layer formed on the support. Since the photosensitive resin composition layer is formed of the photosensitive resin composition, it contains the photosensitive resin composition and usually contains only the photosensitive resin composition.

[0120] Examples of the support include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, triacetyl acetate film, etc., and polyethylene terephthalate film is particularly preferable.

[0121] Examples of commercially available supports include polypropylene films such as the product names "Alpha MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., and polyethylene terephthalate films such as the PS series with product names like "PS-25" manufactured by Teijin Limited. To facilitate the peeling of the support, a release agent such as a silicone coating agent may be applied to the surface of the support. Examples of supports whose surfaces have been treated with a release agent include "AL-5" manufactured by Lintec Corporation. The thickness of the support is preferably in the range of 5 μm to 100 μm, and more preferably in the range of 10 μm to 50 μm.

[0122] The thickness of the photosensitive resin composition layer is not particularly limited and can be, for example, 1 μm or more and 100 μm or less. Among these, it is preferably 2 μm or more, more preferably 4 μm or more, preferably 50 μm or less, and more preferably 30 μm or less.

[0123] The photosensitive film may be provided with a protective film for protecting the photosensitive resin composition layer. Usually, the protective film is provided on the side opposite to the support of the photosensitive resin composition layer. As the protective film, for example, a film formed of the same material as the support can be used. The adhesion between the protective film and the photosensitive resin composition layer is preferably smaller than the adhesion between the support and the photosensitive resin composition layer. Usually, the photosensitive film is used after peeling off the protective film.

[0124] The photosensitive film can be produced, for example, by applying a photosensitive resin composition onto a support. From the viewpoint of performing the coating smoothly, a varnish-like photosensitive resin composition containing a solvent may be prepared and the varnish-like photosensitive resin composition may be applied. When a photosensitive resin composition containing a solvent is applied, drying may be performed after the coating if necessary.

[0125] The photosensitive resin composition layer included in the photosensitive film may or may not contain a solvent, but the amount of the solvent is preferably small. The preferable range of the amount of the solvent in the photosensitive resin composition layer is as described above.

[0126] [12. Circuit board] The circuit board according to an embodiment of the present invention includes an insulating layer containing a cured product of the above-described photosensitive resin composition. This insulating layer preferably contains only the cured product of the photosensitive resin composition. Since the insulating layer can preferably adhere to the GaAs substrate with high adhesiveness, it may be provided on the GaAs substrate. Therefore, the circuit board may include a GaAs substrate and an insulating layer formed on this GaAs substrate. Further, from the viewpoint of utilizing the advantage of small limiting resolution, it is preferable that openings are formed in the insulating layer by exposure and development.

[0127] The above-described photosensitive resin composition can be used as a negative photosensitive resin composition. Therefore, the circuit board is, for example, (I) A step of forming a photosensitive resin composition layer on a base substrate, (II) A step of exposing the photosensitive resin composition layer, and (III) A step of developing the photosensitive resin composition layer, can be manufactured by a manufacturing method including these steps in this order.

[0128] Further, the above manufacturing method may further include an arbitrary step. The above manufacturing method may include, for example, a step (IV) of heating the photosensitive resin composition layer between step (II) and step (III). Further, the above manufacturing method may include, for example, a step (V) of further exposing the photosensitive resin composition layer after step (III). Furthermore, the above manufacturing method may include, for example, a step (VI) of performing heat treatment on the photosensitive resin composition layer after step (III). The above manufacturing method may also include a step (VII) of forming a conductor layer on the insulating layer. Hereinafter, this manufacturing method will be described in detail.

[0129] [12.1. Step (I)] The manufacturing method of the circuit board according to the present embodiment includes a step (I) of forming a photosensitive resin composition layer on a base substrate. Since the photosensitive resin composition layer is formed by the photosensitive resin composition, it contains the photosensitive resin composition and usually contains only the photosensitive resin composition.

[0130] As the base substrate, an appropriate member to be provided on the circuit board can be used. For example, when manufacturing a printed wiring board as the circuit board, as the base substrate, an inner layer substrate that can be provided on the printed wiring board can be used. The inner layer substrate is a member that serves as the base material of the printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Further, the inner layer substrate may have a conductor layer on one or both sides thereof, and this conductor layer may be pattern-processed. Further, the inner layer substrate also includes an intermediate product on which an insulating layer and / or a conductor layer should be further formed when manufacturing the printed wiring board. Further, an inner layer substrate incorporating components may also be used.

[0131] For example, a wafer may be used as the base substrate. When a wafer is used as the base substrate, a wafer-level package can be manufactured as the circuit board. As the wafer, a semiconductor wafer or a dummy wafer may be used. Examples of the semiconductor wafer include a silicon wafer, a gallium arsenide (GaAs) wafer, an indium phosphide (InP) wafer, a gallium phosphide (GaP) wafer, a gallium nitride (GaN) wafer, a gallium telluride (GaTe) wafer, a zinc selenide (ZnSe) wafer, and a silicon carbide (SiC) wafer. Further, as the dummy wafer, for example, a plate-like member including a mold resin and electronic components embedded in the mold resin can be used. The dummy wafer can be manufactured, for example, by a method including arranging electronic components in a circular mold, filling the mold with the mold resin, and curing the mold resin. Usually, a wafer is prepared as a disk including a semiconductor, but the shape of the wafer is not limited to a disk shape. Further, the wafer may have a conductor layer on its surface or inside, and this conductor layer may be pattern-processed.

[0132] There is no particular limitation on the method for forming the photosensitive resin composition layer. For example, a photosensitive resin composition layer may be formed by applying a photosensitive resin composition onto a base substrate. From the viewpoint of performing the application smoothly, a varnish-like photosensitive resin composition containing a solvent may be prepared and the varnish-like photosensitive resin composition may be applied.

[0133] Examples of the coating method include, for example, gravure coating method, microgravure coating method, reverse coating method, kiss reverse coating method, die coating method, slot die method, lip coating method, comma coating method, blade coating method, roll coating method, knife coating method, curtain coating method, chamber gravure coating method, slot orifice method, spin coating method, slit coating method, spray coating method, dip coating method, hot melt coating method, bar coating method, applicator method, air knife coating method, curtain flow coating method, offset printing method, brush coating method, screen printing method, and the like.

[0134] The photosensitive resin composition may be applied once or may be applied in multiple portions. Further, different coating methods may be combined and implemented. In order to avoid foreign matter contamination, it is preferable to perform the application in an environment with less generation of foreign matter such as a clean room.

[0135] After the application of the photosensitive resin composition, drying of the photosensitive resin composition layer may be performed as necessary. Drying can be performed by a drying device such as a hot air furnace or a far-infrared furnace. The drying conditions are preferably set appropriately according to the composition of the photosensitive resin composition. As a specific example, the drying temperature is preferably 50°C or higher, more preferably 70°C or higher, particularly preferably 80°C or higher, and preferably 150°C or lower, more preferably 130°C or lower, particularly preferably 120°C or lower. Also, the drying time is preferably 30 seconds or longer, more preferably 60 seconds or longer, particularly preferably 120 seconds or longer, and preferably 60 minutes or shorter, more preferably 20 minutes or shorter, particularly preferably 5 minutes or shorter.

[0136] The formation of the photosensitive resin composition layer may be performed, for example, using a photosensitive film. To give a specific example, by laminating the photosensitive resin composition layer of the photosensitive film onto the base substrate, a photosensitive resin composition layer can be formed on the base substrate. Lamination is usually performed by pressing the photosensitive resin composition layer of the photosensitive film onto the base substrate while heating. This lamination is preferably performed under reduced pressure by the vacuum lamination method. Also, before lamination, a preheating process for heating the photosensitive film and the base substrate may be performed as necessary.

[0137] The conditions for lamination can be, for example, performed under the conditions of a crimping temperature (lamination temperature) of 70°C to 140°C, a crimping pressure of 1 kgf / cm 2 ~11 kgf / cm 2 (9.8×10 4 N / m 2 ~107.9×10 4 N / m 2 ), and a crimping time of 5 seconds to 300 seconds. Also, lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. Lamination may be performed batchwise or continuously using a roll.

[0138] The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include the Vacuum Applicator manufactured by Nippon Materials Co., Ltd., the Vacuum Pressure Laminator manufactured by Meiki Seisakusho Co., Ltd., the Roll-Type Dry Coater manufactured by Hitachi Industries Co., Ltd., the Vacuum Laminator manufactured by Hitachi AIC Inc., and the like.

[0139] When a photosensitive resin composition layer is formed using a photosensitive film, usually, the support is peeled off at an appropriate time before step (III).

[0140] [12.2. Step (II)] The method for manufacturing a circuit board according to this embodiment includes a step (II) of exposing the photosensitive resin composition layer after step (I). In this step (II), usually, the photosensitive resin composition layer is irradiated with actinic light to form a latent image in the photosensitive resin composition layer. Specifically, in step (II), the actinic light is selectively irradiated to a specific portion of the photosensitive resin composition layer. Therefore, in the photosensitive resin composition layer, an exposed portion irradiated with the actinic light and an unexposed portion not irradiated with the actinic light are formed. And a latent image corresponding to the opening is formed by the unexposed portion.

[0141] As the actinic light, it is preferable to use an appropriate light ray according to the composition of the photosensitive resin composition. The wavelength of the actinic light is usually 190 nm to 1000 nm, preferably 240 nm to 550 nm, but light rays with other wavelengths may also be used. Specific examples of the actinic light source include ultraviolet rays, visible light rays, electron beams, X-rays, etc., and ultraviolet rays are particularly preferable.

[0142] The irradiation amount of the actinic light is preferably set so that a desired opening can be formed after development. In one example, the specific range of the irradiation amount is preferably 10 mJ / cm 2 or more, more preferably 50 mJ / cm 2 or more, particularly preferably 200 mJ / cm 2 or more, and preferably 10,000 mJ / cm 2 or less, more preferably 8,000 mJ / cm 2 or less, particularly preferably 1,000 mJ / cm 2 or less.

[0143] The irradiation of the actinic light is usually performed using a mask. Specifically, the actinic light is irradiated to the photosensitive resin composition layer through a mask having a light-transmitting portion and a light-shielding portion. The actinic light passes through the light-transmitting portion and enters the exposed portion, but cannot pass through the light-shielding portion, so it cannot enter the unexposed portion. Therefore, the exposed portion and the unexposed portion corresponding to the light-transmitting portion and the light-shielding portion can be provided in the photosensitive resin composition layer. The mask may be brought into close contact with the photosensitive resin composition layer (contact exposure method), or exposure may be performed using parallel light rays without bringing it into close contact (non-contact exposure method).

[0144] Generally, the light-shielding portion of the mask is formed to have a planar shape corresponding to the opening to be formed in the insulating layer. The "planar shape" represents the shape as viewed from the thickness direction, unless otherwise specified. Also, the light-shielding portion having a planar shape corresponding to the opening of the insulating layer may be hereinafter referred to as a "mask pattern". In one example, a via pattern such as a round hole pattern may be adopted 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 may be 0.1 μm or more, 0.5 μm or more, etc.

[0145] When a support is present on the photosensitive resin composition layer, exposure may be performed through the support, or exposure may be performed after peeling off the support.

[0146] [12.3. Step (IV)] The method for manufacturing a circuit board according to this embodiment may include a step (IV) of heating the photosensitive resin composition layer after step (II) and before step (III). According to the heating in step (IV), the crosslinking reaction between (A) an alkali-soluble novolak resin and (B) a melamine resin can be promoted, so that the solubility of the exposed portion in the developer can be rapidly reduced.

[0147] The heating temperature in step (IV) may be performed on a hot plate or in an oven. The heating temperature can be, for example, 40°C or more and 115°C or less. Also, the heating time can be, for example, 30 seconds or more and 60 minutes or less. In particular, when heating is performed on a hot plate, the heating temperature is preferably 50°C or more, more preferably 60°C or more, particularly preferably 70°C or more, preferably 115°C or less, more preferably 110°C or less, particularly preferably 105°C or less. Also, the heating time is preferably 30 seconds or more, more preferably 60 seconds or more, particularly preferably 120 seconds or more, preferably 30 minutes or less, more preferably 20 minutes or less, particularly preferably 10 minutes or less. When heating is performed in an oven, the heating temperature is preferably 40°C or higher, more preferably 50°C or higher, and preferably 100°C or lower, more preferably 90°C or lower. Also, the heating time is preferably 3 minutes or longer, more preferably 10 minutes or longer, particularly preferably 15 minutes or longer, and preferably 60 minutes or shorter, more preferably 50 minutes or shorter, particularly preferably 40 minutes or shorter.

[0148] [12.4. Step (III)] The method for manufacturing a circuit board according to this embodiment includes a step (III) of developing the photosensitive resin composition layer after step (II). According to development, non-exposed portions that were not exposed in step (II) can be removed to form openings. Development is usually performed by a wet development method in which the photosensitive resin composition layer is brought into contact with a developer. Examples of the developer include alkaline aqueous solutions, aqueous developers, organic solvents, and the like.

[0149] Examples of the alkaline aqueous solution as the developer include aqueous solutions of alkali metal compounds. Examples of the alkali metal compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal 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 the like. Also, examples of the alkaline aqueous solution include aqueous solutions of organic bases that do not contain metal ions, such as tetraalkylammonium hydroxide. The alkaline aqueous solution may be used alone or in combination of two or more. Among them, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferable in that it does not contain metal ions and has little influence on semiconductor chips. The pH of the alkaline aqueous solution is preferably in the range of 8 to 14, for example. Also, the base concentration of the above alkaline aqueous solution is preferably 0.1 mass% to 10 mass%.

[0150] Examples of the organic solvent as the developer include acetone, ethyl acetate, alkoxyethanol having an alkoxy group with 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like. The organic solvent may be used alone or in combination of two or more. The concentration of the organic solvent is usually 2% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more based on the total amount of the developer. The developer may be 100% by mass of the organic solvent. Examples of the organic solvent-based developer that can be used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0151] If necessary, the developer may contain additives such as a surfactant and an antifoaming agent to improve the developing action.

[0152] The developing time is preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly defined, but is preferably 20°C or higher, preferably 50°C or lower, and more preferably 40°C or lower.

[0153] Examples of the developing method include a paddle method, a spray method, a dipping method, a brushing method, a slapping method, an ultrasonic method, and the like.

[0154] After development using the developer, rinsing of the photosensitive resin composition layer may be further performed. The rinsing is preferably performed with a solvent different from the developer. For example, rinsing may be performed using the same type of solvent as contained in the photosensitive resin composition. The rinsing time is preferably 5 seconds to 1 minute.

[0155] [12.5. Step (V)] Although an insulating layer may be obtained by curing the photosensitive resin composition layer through the above-described steps, from the perspective of further advancing the curing of the photosensitive resin composition layer to obtain an insulating layer with excellent mechanical strength, the method for manufacturing a circuit board according to this embodiment may include a step (V) of further exposing the photosensitive resin composition layer after step (III). In this step (V), the photosensitive resin composition layer is irradiated with actinic rays. As the actinic rays used for exposure in step (V), the same actinic rays as those used for exposure in step (II) may be used.

[0156] The irradiation amount of the actinic rays in step (V) is preferably set so that a desired opening can be formed after development. In one example, the specific range of the irradiation amount is preferably 500 mJ / cm 2 or more, more preferably 800 mJ / cm 2 or more, particularly preferably 1000 mJ / cm 2 or more, and preferably 10,000 mJ / cm 2 or less, more preferably 8,000 mJ / cm 2 or less, particularly preferably 6,000 mJ / cm 2 or less.

[0157] [12.6. Step (VI)] Although an insulating layer may be obtained by curing the photosensitive resin composition layer through the above-described steps, from the perspective of further advancing the curing of the photosensitive resin composition layer to obtain an insulating layer with excellent mechanical strength, the method for manufacturing a circuit board according to this embodiment preferably includes a step (VI) of subjecting the photosensitive resin composition layer to heat treatment after step (III). When the method for manufacturing a circuit board includes step (V), step (VI) is preferably performed after step (V).

[0158] The heat treatment can be performed using a heating device such as a clean oven. The atmosphere during the heat treatment may be air or an inert gas atmosphere such as nitrogen. Further, the heat treatment conditions may be selected according to the type and amount of the resin component in the photosensitive resin composition, preferably in the range of 150 °C to 250 °C for 20 minutes to 180 minutes, more preferably in the range of 160 °C to 230 °C for 30 minutes to 120 minutes.

[0159] [12.7. Step (VII)] The method for manufacturing a circuit board according to this embodiment may include a step (VII) of forming a conductor layer on an insulating layer. The conductor material used for the conductor layer is not particularly limited. For example, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of versatility, cost, and ease of patterning of conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferable, and a single metal layer of copper is even more preferable.

[0160] The conductor layer may have a single-layer structure or a multilayer structure including two or more single metal layers or alloy layers made of different types of metals or alloys. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0161] The thickness of the conductor layer depends on the design of the circuit board, but is usually 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0162] There is no limitation on the method for forming the conductor layer. The conductor layer may be formed, for example, by sputtering. Also, the conductor layer may be formed, for example, by combining electroless plating and electroplating. Further, the conductor layer may be formed only by electroless plating after forming a plating resist having a pattern opposite to that of the conductor layer.

[0163] Among them, it is preferable to form the conductor layer by sputtering. When forming the conductor layer by sputtering, usually, a conductor seed layer is formed on the insulating layer by sputtering, and then a conductor sputter layer is further formed on the conductor seed layer by sputtering. Also, before forming the conductor seed layer by sputtering, the surface of the insulating layer may be cleaned by reverse sputtering. As the gas used for reverse sputtering, Ar gas, O2 gas, and N2 gas are preferable. Sputtering can be performed using various sputtering apparatuses such as magnetron sputtering and mirrortron sputtering. Examples of the metal for forming the conductor seed layer include Cr, Ni, Ti, nichrome, etc. In particular, Cr and Ti are preferable. The thickness of the conductor seed layer is preferably 5 nm or more, more preferably 10 nm or more, preferably 1000 nm or less, and more preferably 500 nm or less. Examples of the metal for forming the conductor sputter layer include Cu, Pt, Au, Pd, etc. In particular, Cu is preferable. The thickness of the conductor sputter layer is preferably 50 nm or more, more preferably 100 nm or more, preferably 3000 nm or less, and more preferably 1000 nm or less.

[0164] A copper plating layer may be further formed by electroplating copper on the layer formed by sputtering. The thickness of the copper plating layer is preferably formed to be 5 μm or more, more preferably 8 μm or more, preferably 75 μm or less, and more preferably 35 μm or less.

[0165] Pattern formation may be performed on the conductor layer. As the method for pattern formation, for example, methods such as subtractive method and semi-additive method can be used.

[0166] [12.8. Optional Process] The method for manufacturing a circuit board according to this embodiment may further include an optional process in combination with the above-described processes. For example, the method for manufacturing a circuit board may include a process of drilling holes in the insulating layer. The holes to be formed may be trenches that do not penetrate the insulating layer, via holes that penetrate only the insulating layer, or through holes that penetrate the entire circuit board. Drilling can be performed by methods such as drilling, laser, and plasma.

[0167] Also, the method for manufacturing a circuit board may include a process of performing desmear treatment on the insulating layer. When a hole is drilled in the insulating layer, resin residues (smear) may adhere to the formed hole. In desmear treatment, this smear is removed. Desmear treatment may be performed by dry desmear treatment, wet desmear treatment, or a combination thereof.

[0168] Furthermore, the method for manufacturing a circuit board may include a process of dicing the manufactured circuit board.

[0169] The method for manufacturing a circuit board may repeat the above-described processes. For example, processes (I) to (VII) may be repeated to manufacture a circuit board having a multilayer structure including insulating layers and conductor layers alternately.

[0170] [13. Semiconductor Device] The above circuit board can be used in the manufacture of semiconductor devices. A semiconductor device includes a circuit board and, for example, various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trains, ships, and airplanes).

Example

[0171] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "mass%" respectively, unless otherwise specified. Further, the operations described below were carried out in the air at normal temperature and pressure (23°C, 1 atm) unless otherwise specified.

[0172] [Examples 1 to 9 and Comparative Examples 1 to 5] Reagents ((A) component, (A’) component, (B) component, (B’) component, (C) component, (D) component, and (E) component) and 2-butanone (MEK) in the amounts (parts by mass) shown in Tables 1 and 2 below were mixed to produce a photosensitive resin composition. In the following table, the meanings of the abbreviations of the reagents are as follows.

[0173] (A) component: ·TR4020G: Cresol novolak resin "TR4020G" manufactured by Asahi Organic Materials Co., Ltd.

[0174]

Chemical formula

[0175] (A’) component: ·BisA: "BisA" manufactured by Mitsui Chemicals Fine Co., Ltd.

[0176]

Chemical formula

[0177] (B) component: ·Cymel-300: "Cymel-300" manufactured by Daicel Ornex Co., Ltd. A compound in which R represents a methyl group in the following formula (B-X). [·Cymel-370N: "Cymel-370N" manufactured by Daicel Ornex Co., Ltd. A compound in which R represents a methyl group or a hydrogen atom in the following formula (B-X). · Cymel-327: "Cymel-327" manufactured by Daicel Ornex Co., Ltd. In the following formula (B-X), R represents a methyl group, and a reaction product in which some of the groups -CH2OR are replaced by hydrogen atoms. Therefore, some of the -N(CH2OR)2 bonded to the triazine ring are replaced by the groups represented by the following formula (b-1). In the formula (b-1), * represents a bond.

[0178]

Chemical formula

[0179] (Component (B’)): · MX-270: "Niclac MX-270" manufactured by Sanwa Chemical Co., Ltd. · TML-BPA: "TML-BPA" manufactured by Honshu Chemical Co., Ltd.

[0180]

Chemical formula

[0181] (Component (C)): · MP-Triazine: "MP-Triazine" manufactured by Sanwa Chemical Co., Ltd.

[0182]

Chemical formula

[0183] (Component (D)): · KR-513: Acrylic-containing oligomer silane coupling agent "KR-513" manufactured by Shin-Etsu Chemical Co., Ltd. It contains a methoxysilyl group as an alkoxysilyl group and an acryloyl group as a functional group. Acryloyl group equivalent : 210 g / mol, viscosity at 25 °C : 35 mm 2 / s. · KR-516: An epoxy-containing oligomer silane coupling agent "KR-516" manufactured by Shin-Etsu Chemical Co., Ltd. It contains a methoxysilyl group as an alkoxysilyl group and an epoxy group as a functional group. Methyl groups are bonded to some silicon atoms. Epoxy equivalent 280 g / mol, viscosity at 25 °C 50 mm 2 / s. · X-40-9296: A methacryl-containing oligomer silane coupling agent "X-40-9296" manufactured by Shin-Etsu Chemical Co., Ltd. It contains a methoxysilyl group as an alkoxysilyl group and a methacryloyl group as a functional group. Methacryloyl equivalent 230 g / mol, viscosity at 25 °C 20 mm 2 / s. · KR-517: An epoxy-containing oligomer silane coupling agent "KR-517" manufactured by Shin-Etsu Chemical Co., Ltd. It contains a methoxysilyl group and an ethoxysilyl group as alkoxysilyl groups and an epoxy group as a functional group. Epoxy equivalent 830 g / mol, viscosity at 25 °C 12 mm 2 / s.

[0184] (E) component: · MM-101SM: Urethane fine particles "MM-101SM" manufactured by Negami Kogyo Co., Ltd. Average particle size 0.07 - 0.1 μm.

[0185] [Manufacture of photosensitive film] As a support, a polyethylene terephthalate film (Toray Industries, Inc.'s "Lumirror T60", thickness 38 μm) with a release treatment on the surface was prepared. The photosensitive resin compositions prepared in each example and comparative example were uniformly coated on such a support with a die coater so that the thickness of the photosensitive resin composition layer after drying would be 20 μm, and dried at 80 °C to 110 °C for 6 minutes to obtain a photosensitive film. This photosensitive film was provided with a support and a photosensitive resin composition layer formed on this support.

[0186] [Evaluation of limiting resolution] A copper-plated laminate was prepared by plating copper on a silicon wafer to form a copper layer with a thickness of 5 μm and subjecting it to a roughening treatment with a 1% hydrochloric acid aqueous solution for 60 seconds. A photosensitive film was placed on this copper-plated laminate such that the photosensitive resin composition layer was in contact with the surface of the copper layer, and it was laminated using a vacuum laminator (manufactured by Nikkō Materials Co., Ltd., VP160). The lamination conditions were a vacuum evacuation time of 30 seconds, a crimping temperature of 80°C, a crimping pressure of 0.7 MPa, and a pressurization time of 30 seconds. After standing at room temperature for 10 minutes, the support was peeled off to obtain an intermediate laminate comprising a copper-clad laminate and a photosensitive resin composition layer.

[0187] This intermediate laminate was heat-treated at 100°C for 3 minutes. Thereafter, ultraviolet light (wavelength 365 nm, intensity 40 mW / cm 2 ) was used to expose the photosensitive resin composition layer of the intermediate laminate through a quartz glass mask. The exposure dose was set to an optimal value in the range of 50 mJ / cm 2 to 1000 mJ / cm 2 . Here, the optimal value represents the value that can minimize the limit resolution. Also, as the glass mask, one having a plurality of mask patterns with different dimensions was used so that a plurality of round holes (via holes) with different design aperture diameters could be drawn. After standing at room temperature for 5 minutes, a heat treatment was performed at 100°C for 3 minutes. A 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23°C was sprayed onto the entire surface of the photosensitive resin composition layer of the intermediate laminate at a spray pressure of 0.1 MPa for 1 minute for spray development. After spray development, ultraviolet irradiation at 1 J / cm 2 was performed, and further heat treatment at 190°C for 60 minutes was performed to cure the photosensitive resin composition layer. By the above operations, an insulating layer was formed on the copper-clad laminate by the cured product of the photosensitive resin composition.

[0188] The diameter of the bottom of the via hole formed in the insulating layer was observed (1000x magnification) and measured using a scanning electron microscope (SEM). If the diameter of the bottom of the via hole was within the range of 60% to 120% of the design value of the via hole, the via hole was determined to have been properly formed. Of the properly formed via holes, the via hole with the smallest design value was selected, and the design value of the selected via hole was taken as the limiting resolution.

[0189] [GaAs adhesion evaluation] A photosensitive film was placed on a 6-inch gallium arsenide wafer as a GaAs substrate, with the photosensitive resin composition layer in contact with the gallium arsenide wafer. Lamination was performed using a vacuum laminator (VP160, manufactured by Nikko Materials Co., Ltd.) to obtain a laminate comprising the gallium arsenide wafer, the photosensitive resin composition layer, and the support, in that order. The lamination conditions were a vacuum time of 30 seconds, a pressure bonding temperature of 80°C, a pressure of 0.7 MPa, and a pressure time of 30 seconds. The laminate was left at room temperature for 30 minutes or more, and the entire surface of the photosensitive resin composition layer was exposed to ultraviolet light through the support. The exposure dose was set to the optimal value described above. After leaving the laminate at room temperature for 5 minutes, the support was peeled off. Next, a heat treatment was performed at 80°C for 10 minutes. Spray development was performed by spraying a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C as a developer onto the entire surface of the photosensitive resin composition layer at a spray pressure of 0.1 MPa for 1 minute. After spray development, 1J / cm 2 The photosensitive resin composition layer was cured by irradiating the wafer with ultraviolet light for 100 seconds at 190°C and then by heating the wafer for 60 minutes at 190°C. Through the above operations, a sample substrate was obtained that included a gallium arsenide wafer and an insulating layer formed of the cured product of the photosensitive resin composition.

[0190] The insulating layer of the obtained sample substrate was subjected to a cross-cut tape peel test in accordance with JIS K5600-5-6:1999 (ISO2409:1992). The adhesion to the gallium arsenide wafer was evaluated according to the following criteria. "A": Corresponds to classification 0 in Table 1 of JIS K5600-5-6:1999 8.3. "B": Corresponds to classification 1 in Table 1 of JIS K5600-5-6:1999 8.3. "C": Corresponds to classification 2 in Table 1 of JIS K5600-5-6:1999 8.3. "D": Corresponds to classification 3 in Table 1 of JIS K5600―5-6:1999 8.3. "E": Corresponds to category 4 or 5 in Table 1 of JIS K5600―5-6:1999 8.3.

[0191] [Cu adhesion measurement] A rolled copper foil (JX Nippon Mining & Metals Corporation, "BHY-22B-T," thickness 18 μm) was prepared by washing with 10% sulfuric acid and drying. A photosensitive film was placed on the shiny side of the rolled copper foil so that the photosensitive resin composition layer was in contact with the surface of the copper layer. Lamination was performed using a vacuum laminator (Nikko Materials Co., Ltd., VP160) to obtain a laminate comprising, in this order, the rolled copper foil, the photosensitive resin composition layer, and the support. The lamination conditions were a vacuum time of 30 seconds, a pressure bonding temperature of 80°C, a pressure of 0.7 MPa, and a pressure time of 30 seconds. The laminate was left at room temperature for 30 minutes or more, and the entire surface of the photosensitive resin composition layer was exposed to ultraviolet light through the support. The exposure dose was set to the optimum value described above. The laminate was left at room temperature for 5 minutes, and then the support was peeled off. Next, a heat treatment was performed at 80°C for 10 minutes. A 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C was sprayed as a developer onto the entire surface of the photosensitive resin composition layer at a spray pressure of 0.1 MPa for 1 minute to perform spray development. 2 The photosensitive resin composition layer was cured by irradiating the substrate with ultraviolet light for 10 minutes at 190°C and then by heating the substrate for 60 minutes at 190°C. By the above operations, a sample substrate was obtained which included a rolled copper foil and an insulating layer formed of a cured product of the photosensitive resin composition.

[0192] The insulating layer side of the obtained material substrate and the glass epoxy substrate were joined, and the peel strength of the copper foil was measured using a tensile testing machine (manufactured by TSE, "AC-50C-SL") conforming to Japanese Industrial Standard (JIS C6481). Specifically, a cut was made around a portion with a width of 10 mm and a length of 100 mm on the rolled copper foil of the sample substrate, one end of this portion was peeled off, grasped with the gripper of the tensile testing machine, and the load when peeling 35 mm vertically at a speed of 50 mm / min was measured as the peel strength. Based on the measured peel strength, the adhesion to the copper foil was evaluated according to the following criteria. "○": The peel strength is 0.4 kgf or more. "×": The peel strength is less than 0.4 kgf.

[0193] [Results] The compositions and evaluation results of the photosensitive resin compositions of the above-described examples and comparative examples are shown in the following table. In the following table, the numerical values in the reagent column represent parts by mass. Also, in the following table, the meanings of the abbreviations are as follows. (E) component concentration: The ratio of the (E) component to 100% by mass of the non-volatile components of the photosensitive resin composition. Type of alkoxy group: The type of alkoxy group contained in the alkoxysilyl group of the silane coupling agent. "M" in the "Type of alkoxy group" column: Methoxy group. "E" in the "Type of alkoxy group" column: Ethoxy group. "NG" in the "Limit resolution" column: A via hole with an aperture diameter of 100 μm or less could not be formed. GaAs adhesion: Adhesion to the GaAs substrate. Cu adhesion: Adhesion to the copper foil.

[0194] [Table 1]

[0195] [Table 2]

Claims

1. (A) An alkali-soluble novolak resin, (B) A melamine resin containing one or more alkoxymethyl groups, (C) A photoacid generator, and (D) An alkoxy oligomer type coupling agent, comprising, (D) The alkoxy oligomer type coupling agent is a silane coupling agent having a plurality of repeating units containing both an alkoxy group and at least one functional group selected from the group consisting of an epoxy group, an acryloyl group, a methacryloyl group, a vinyl group, and a mercapto group in the molecule, a photosensitive resin composition.

2. The photosensitive resin composition according to claim 1, wherein (A) the alkali-soluble novolak resin contains a compound having a structure represented by formula (A-1). 【Chemical 1】 (In formula (A-1), R １ each independently represents a divalent group represented by the following formula (a): X １ each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, a halogen atom, or an optionally substituted monovalent heterocyclic group, n1 represents an integer of 0 to 4, m1 represents an integer of 2 to 200. * represents a bond. 【Chemical 2】 In formula (a), R １１ and R １２ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted monovalent heterocyclic group, an amino group, a carbonyl group, a carboxyl group, or a group consisting of a combination thereof; R １１ and R １２ may be bonded to each other to form a ring. * represents a bond.)

3. The photosensitive resin composition according to claim 1 or 2, comprising (E) an organic filler.

4. The photosensitive resin composition according to claim 3, wherein the amount of (E) the organic filler is 7% by mass or more and 30% by mass or less when the non-volatile components of the photosensitive resin composition are 100% by mass.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein (D) the alkoxy oligomer type coupling agent contains a methoxy group.

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein (D) the alkoxy oligomer type coupling agent contains at least one functional group selected from the group consisting of an epoxy group, an acryloyl group, and a methacryloyl group.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the repeating unit contained in (D) the alkoxy oligomer type coupling agent is represented by the following formula (D-1). [Chemical Formula 3] (In formula (D-1), Xd represents at least one functional group selected from the group consisting of an epoxy group, an acryloyl group, a methacryloyl group, a vinyl group, and a mercapto group, Ld represents a divalent linking group, nd represents 0 or 1, Rd represents an alkyl group, and Zd represents an oxygen atom or a divalent aliphatic hydrocarbon group.)

8. A photosensitive film comprising a support and a photosensitive resin composition layer provided on the support and containing the photosensitive resin composition according to any one of claims 1 to 7.

9. A circuit board comprising an insulating layer containing a cured product of the photosensitive resin composition according to any one of claims 1 to 7.

10. The circuit board according to claim 9 , wherein the insulating layer is a solder resist.

11. A semiconductor device comprising the circuit board according to claim 9 or 10.

12. (I) forming a photosensitive resin composition layer containing the photosensitive resin composition according to any one of claims 1 to 7 on a base substrate; (II) a step of exposing the photosensitive resin composition layer to light; and (III) developing the photosensitive resin composition layer; A method for manufacturing a circuit board, comprising the steps of:

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