WO2018164233A1

WO2018164233A1 - Photosensitive element, semiconductor device, and method for forming resist pattern

Info

Publication number: WO2018164233A1
Application number: PCT/JP2018/009068
Authority: WO
Inventors: 加藤　哲也; 健一岩下; 鈴木　慶一
Original assignee: 日立化成株式会社
Priority date: 2017-03-09
Filing date: 2018-03-08
Publication date: 2018-09-13
Also published as: JPWO2018164233A1; TW201839509A; JP6690776B2

Abstract

Disclosed is a photosensitive element having a photosensitive layer and a protective layer, wherein the photosensitive layer contains: component (A), a resin having a phenolic hydroxyl group; component (B), a photosensitive acid generator; component (C), a compound having at least one selected from the group consisting of an aromatic ring, a heterocyclic ring, and an alicyclic ring, and having at least one among a methylol group and an alkoxyalkyl group; and component (D), an aliphatic compound having two or more of at least one functional group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanylalkyl ether group, a vinyl ether group, and a hydroxyl group, and the contents of component (C) and component (D) in the photosensitive layer are within specific ranges.

Description

Photosensitive element, semiconductor device, and resist pattern forming method

The present disclosure relates to a photosensitive element, a semiconductor device, and a method for forming a resist pattern.

In manufacturing a semiconductor element or a printed wiring board on which a semiconductor element is mounted, for example, a negative photosensitive resin composition is used to form a fine pattern. In this method, a photosensitive layer is formed on a base material (for example, a chip in the case of a semiconductor element or a substrate in the case of a printed wiring board) by application of a photosensitive resin composition, and irradiated with actinic rays through a predetermined pattern. By doing so, the exposed portion is cured. Furthermore, the resist pattern which is a cured film of the photosensitive resin composition is formed on a base material by selectively removing an unexposed part using a developing solution. Therefore, the photosensitive resin composition is required to have high sensitivity to actinic rays and to be able to form a fine pattern (resolution). Therefore, a photosensitive resin composition containing a novolak resin, an epoxy resin, a photoacid generator, etc. soluble in an alkaline aqueous solution, a photosensitive resin composition containing an alkali-soluble epoxy compound having a carboxyl group, a photocationic polymerization initiator, etc. Products have been proposed (see, for example, Patent Documents 1 to 3).

Furthermore, the surface protective film and the interlayer insulating film used in the semiconductor element are required to have insulation reliability such as heat resistance, electrical characteristics, and mechanical characteristics. Thus, a photosensitive resin composition in which the photosensitive resin composition further contains a crosslinkable monomer has been proposed (see, for example, Patent Document 4).

On the other hand, in recent years, with the improvement in performance of electronic devices, higher integration and higher reliability of semiconductor elements are progressing year by year. As semiconductor elements are highly integrated, it is required to form finer patterns. Therefore, there is a continuous need for the photosensitive resin composition to improve the resolution even in units of 1 μm.

Incidentally, it is necessary to provide vias (openings) for electrically connecting the upper and lower wiring layers in the interlayer insulating material of the printed wiring board. If the number of flip chip pins mounted on the printed wiring board increases, it is necessary to provide vias corresponding to the number of pins.

In recent years, as the miniaturization of semiconductor elements has progressed and the number of pins has increased from tens of thousands to hundreds of thousands of pins, vias formed in the interlayer insulating material of the printed circuit board have also been adjusted to the number of pins of the semiconductor elements. There is a need to reduce the diameter. Recently, development of a printed wiring board in which a via is provided by a laser using a thermosetting resin material has been advanced (for example, see Patent Document 5).

Japanese Patent Application Laid-Open No. 06-059444 Japanese Patent Laid-Open No. 09-087366 International Publication No. 2008/010521 JP 2003-215802 A JP 2001-217543 A

However, in the conventional method for manufacturing a multilayer printed wiring board, it is necessary to introduce new equipment such as a laser, it is difficult to provide a via having a relatively large diameter or a minute via having a diameter of 60 μm or less, There are problems that it is necessary to use different lasers according to the aperture diameter, and it is difficult to provide a special shape. In addition, when forming vias using a laser, each via must be formed one by one, which takes time when it is necessary to provide a large number of fine vias. Furthermore, since a resin residue remains around the via opening, there is a problem that the reliability of the obtained multilayer printed wiring board is lowered unless the residue is removed. For example, in Patent Document 5, vias are formed by irradiating a carbon dioxide laser to an interlayer insulating film, but the resolution is 60 μm in diameter, and it is difficult to further reduce the via diameter.

By the way, in a structure in which an electrode is laminated on an insulating film having an opening, there is a case where the conductor portion arranged in the opening and the electrode are electrically connected, and is obtained using a photosensitive resin composition. A resin pattern may be used as an insulating film. In this case, from the viewpoint of preventing disconnection of the electrode disposed on the insulating film (improvement of connection reliability), the shape of the wall of the insulating film exposed to the opening is tapered (preferably, the taper angle (inclination) The angle is small). FIG. 1 is a schematic diagram (cross-sectional view) of an insulating film having an opening, and a boundary portion between the opening and the wall of the insulating film exposed in the opening in the insulating film 2 disposed on the substrate 1. FIG. The taper angle refers to an angle formed by the surface of the substrate 1 and the wall portion (pattern side surface) of the insulating film 2 exposed in the opening, and is an angle indicated by θ in FIG.

Furthermore, the photosensitive layer of the photosensitive element is transferred to the substrate by peeling off the protective layer, laminating the photosensitive layer and the substrate using a laminator, and peeling off the support. When manufacturing the photosensitive element, in the step of bonding the photosensitive layer and the protective layer, air may be mixed between the photosensitive layer and the protective layer, and the protective layer may be wrinkled. If wrinkles approach the protective layer, the wrinkles are transferred to the photosensitive layer, and the portions cannot be used. Therefore, from the viewpoint of productivity, there is a demand for bonding the entire surface of the photosensitive layer and the protective layer of the photosensitive element without any gap.

An object of the present disclosure is to provide a photosensitive element including a photosensitive layer that is excellent in resolution, can obtain a resin pattern having a tapered opening, and has excellent adhesion to a protective layer. There is. Another object of the present disclosure is to provide a semiconductor device using the photosensitive layer and a method for forming a resist pattern using the photosensitive layer.

As a result of earnest research to solve the above problems, the present inventors have found a photosensitive element having excellent characteristics. That is, a photosensitive element according to an embodiment of the present disclosure includes a photosensitive layer and a protective layer, and the photosensitive layer includes (A) component: a resin having a phenolic hydroxyl group, and (B) component: a photosensitive acid. Generator, (C) component: a compound having at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and having at least one of a methylol group and an alkoxyalkyl group, and (D) component An acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, and an aliphatic compound having two or more functional groups selected from the group consisting of a hydroxyl group, The content of the component (C) in the photosensitive layer is 20 parts by mass or less with respect to 100 parts by mass of the component (A), and the components (C) and (D). The total content of is from 65 to 120 parts by mass parts with respect to the component (A) 100 parts by weight.

The photosensitive element further includes a support, and preferably includes the support, the photosensitive layer, and the protective layer in this order.

The photosensitive layer preferably further contains a component (G): a compound having a Si—O bond.

The present disclosure also provides a semiconductor device including a cured product of the photosensitive layer in the photosensitive element.

The present disclosure further includes a step of disposing the photosensitive layer of the photosensitive element on a substrate, a step of exposing the photosensitive layer to a predetermined pattern, and developing the exposed photosensitive layer to obtain a resin pattern. There is provided a resist pattern forming method including a step and a step of heat-treating the resin pattern.

According to the present disclosure, there is provided a photosensitive element including a photosensitive layer that is excellent in resolution, can obtain a resin pattern having a tapered opening, and has excellent adhesion to a protective layer. be able to. In addition, according to the present disclosure, it is possible to provide a semiconductor device using a photosensitive layer and a method for forming a resist pattern using the photosensitive layer.

It is the schematic of the insulating film which has an opening part. It is a schematic cross section of the photosensitive element of this embodiment. It is a schematic diagram which shows the manufacturing method of the multilayer printed wiring board of this embodiment. 2 is a scanning electron micrograph of a via shape formed using the photosensitive element of Example 1. FIG. 3 is a scanning electron micrograph of a via shape formed using the photosensitive element of Example 2. FIG. 4 is a scanning electron micrograph of a via shape formed using the photosensitive element of Example 3. FIG. 2 is a scanning electron micrograph of a via shape formed using the photosensitive element of Comparative Example 1. 6 is a scanning electron micrograph of a via shape formed using the photosensitive element of Comparative Example 2. 6 is a scanning electron micrograph of a via shape formed using the photosensitive element of Comparative Example 2. 6 is a scanning electron micrograph of a via shape formed using the photosensitive element of Comparative Example 4.

Hereinafter, an embodiment of the present disclosure will be specifically described, but the present disclosure is not limited to this. In the following embodiments, it is needless to say that the constituent elements (including element steps and the like) are not necessarily indispensable unless otherwise specified or apparently essential in principle. This also applies to numerical values and ranges, and should not be construed to unduly limit the present disclosure.

In this specification, the terms “layer” and “film” include not only a structure formed on the entire surface but also a structure formed on a part when observed as a plan view. The The term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. “EO-modified” means a compound having a (poly) oxyethylene group, and “PO-modified” means a compound having a (poly) oxypropylene group. Here, “(poly) oxyethylene group” means at least one of an oxyethylene group and a polyoxyethylene group in which two or more ethylene groups are linked by an ether bond. The “(poly) oxypropylene group” means at least one of an oxypropylene group and a polyoxypropylene group in which two or more propylene groups are linked by an ether bond. The term “Si—O bond” refers to a bond between a silicon atom and an oxygen atom, and may be part of a siloxane bond (Si—O—Si bond). The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. “A or B” only needs to include either A or B, and may include both. The materials exemplified below can be used singly or in combination of two or more unless otherwise specified. The content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

[Photosensitive resin composition]
The photosensitive layer of this embodiment can be formed using the photosensitive resin composition demonstrated below, for example. The photosensitive resin composition used for forming the photosensitive layer of the present embodiment includes (A) component: a resin having a phenolic hydroxyl group, (B) component: a photosensitive acid generator, and (C) component: aroma. A compound having at least one selected from the group consisting of a ring, a heterocyclic ring and an alicyclic ring and having at least one of a methylol group and an alkoxyalkyl group; and component (D): an acryloyloxy group, a methacryloyloxy group, and glycidyl. And an aliphatic compound having two or more functional groups selected from the group consisting of an oxy group, an oxetanyl alkyl ether group, a vinyl ether group, and a hydroxyl group. In the present specification, these components may be simply referred to as (A) component, (B) component, (C) component and the like.

When the photosensitive layer of the present embodiment obtains a resin pattern having an opening, the present inventors consider that the reason why a tapered resin pattern can be obtained while achieving excellent resolution is as follows. ing. In the unexposed area, the solubility of the component (A) in the developer is improved by the addition of the component (C). Next, in the exposed area, due to the catalytic effect of the acid generated from the component (B), the methylol groups or alkoxyalkyl groups in the component (C) or the methylol groups or alkoxyalkyl groups in the component (C) When the component (A) reacts with dealcoholization, the solubility of the composition in the developer is greatly reduced. Thereby, when developed, sufficient resolution can be obtained due to a remarkable difference in solubility in the unexposed and exposed portion of the developer. When the content of the component (C) relative to the component (A) is in a specific range, a part of the exposed portion is melted by subsequent heating, and a resin pattern having a taper shape can be formed. Furthermore, a cured film can be obtained by heating while maintaining the tapered shape.

The photosensitive resin composition of the present embodiment comprises, as necessary, (E) component: benzophenone compound, (F) component: solvent, (G) component: compound having Si—O bond, (H) component: increased. Sensitizers and the like can be contained.

<(A) component>
The photosensitive resin composition of this embodiment contains resin which has a phenolic hydroxyl group. Although it does not specifically limit as resin which has a phenolic hydroxyl group, Resin soluble in alkaline aqueous solution is preferable, and a novolak resin is more preferable from a viewpoint of further improving resolution. The novolak resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a catalyst.

Phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3- Xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, Catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like can be mentioned. Phenols can be used alone or in combination of two or more.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like. Aldehydes can be used singly or in combination of two or more.

As the novolac resin, for example, a cresol novolac resin can be used. Specific examples of the novolak resin include phenol / formaldehyde condensed novolak resin, phenol-cresol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin, and the like.

Examples of the component (A) other than the novolak resin include hydroxystyrene homopolymers or copolymers, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, and the like.

(A) A component can be used individually by 1 type or in mixture of 2 or more types.

The weight average molecular weight of the component (A) is 100,000 or less, 1000 to 80000, 2000 to 50000, from the viewpoint of further improving the resolution, developability, thermal shock resistance, heat resistance and the like of the resulting resin pattern (cured film). It may be 2000-20000, 3000-15000, or 5000-15000.

In addition, in this embodiment, the weight average molecular weight of each component can be measured on condition of the following by the gel permeation chromatography method (GPC) using a standard polystyrene calibration curve, for example.
Equipment used: Hitachi L-6000 type (manufactured by Hitachi, Ltd.)
Column: Gel pack GL-R420 + Gel pack GL-R430 + Gel pack GL-R440 (manufactured by Hitachi Chemical Co., Ltd., trade name, total of 3)
Column specification: 10.7mmφ × 300mm
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 1.75 ml / min Detector: L-3300RI (manufactured by Hitachi, Ltd.)

The content of the component (A) is the total amount of the photosensitive resin composition (provided that (F)) from the viewpoint that the developability of the photosensitive layer formed using the photosensitive resin composition with respect to the alkaline aqueous solution tends to be further excellent. When the component is used, it is 10 to 90% by mass, 30 to 90% by mass, 30 to 80% by mass, 40 to 80% by mass, or 40 to 60% by mass on the basis of (except for the component (F)) May be.

<(B) component>
The photosensitive resin composition of this embodiment contains a photosensitive acid generator. The photosensitive acid generator is a compound that generates an acid upon irradiation with an actinic ray or the like. Due to the catalytic effect of the acid generated from the photosensitive acid generator, the methylol groups in the component (C) or the alkoxyalkyl groups, or the methylol group or the alkoxyalkyl group in the component (C) and the component (A) However, by reacting with dealcoholization, the solubility of the composition in the developer is greatly reduced, and a negative pattern can be formed.

The component (B) is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays or the like. Examples of the component (B) include onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds. Among these, from the viewpoint of excellent availability, the component (B) is preferably at least one selected from the group consisting of an onium salt compound and a sulfonimide compound. In particular, when a solvent is used, the component (B) is preferably an onium salt compound from the viewpoint of excellent solubility in the solvent.

Examples of the onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Specific examples of preferred onium salt compounds include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium heptadecafluorooctanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate Diaryl iodonium salts such as diphenyliodonium tris (pentafluoroethyl) trifluorophosphate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium tris [(trifluoromethyl) sulfonyl] methanide; Such as sulfonium salt and the like. Among these, a sulfonium salt is preferable from the viewpoint of further improving sensitivity and thermal stability, and a triarylsulfonium salt is more preferable from the viewpoint of further improving thermal stability. An onium salt compound can be used singly or in combination of two or more.

As the triarylsulfonium salt of the component (B), for example, a compound represented by the following general formula (b1), a compound represented by the following general formula (b2), a compound represented by the following general formula (b3), And at least one cation selected from the group consisting of compounds represented by the following general formula (b4), a tetraphenylborate skeleton, an alkyl sulfonate skeleton having 1 to 20 carbon atoms, a phenyl sulfonate skeleton, and a 10-camphor sulfonate skeleton An anion having at least one skeleton selected from the group consisting of a trisalkylsulfonylmethanide skeleton having 1 to 20 carbon atoms, a tetrafluoroborate skeleton, a hexafluoroantimonate skeleton and a hexafluorophosphate skeleton, Can be mentioned.

The hydrogen atom of the phenyl group in the general formulas (b1), (b2), (b3) and (b4) is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 2 to 12 carbon atoms. And may be substituted with at least one selected from the group consisting of an alkylcarbonyl group having 2 to 12 carbon atoms, and when there are a plurality of substituents, they may be the same or different from each other. Also good.

The hydrogen atom of the phenyl group of the tetraphenylborate skeleton is a fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, It may be substituted with at least one selected from the group consisting of an alkylcarbonyl group having 2 to 12 carbon atoms and an alkoxycarbonyl group having 2 to 12 carbon atoms, and when there are a plurality of substituents, they are the same as each other. Or different.

The hydrogen atom of the alkyl sulfonate skeleton is at least one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, and an alkoxycarbonyl group. It may be substituted, and when there are a plurality of substituents, they may be the same or different.

The hydrogen atom of the phenyl group of the phenylsulfonate skeleton is a fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, carbon It may be substituted with at least one selected from the group consisting of an alkylcarbonyl group having 2 to 12 carbon atoms and an alkoxycarbonyl group having 2 to 12 carbon atoms. May be different.

The hydrogen atom of the trisalkylsulfonylmethanide skeleton is at least selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, and an alkoxycarbonyl group. It may be substituted with one kind, and when there are a plurality of substituents, they may be the same or different.

The fluorine atom of the hexafluorophosphate skeleton may be substituted with at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a perfluoroalkyl group having 1 to 12 carbon atoms, When there are a plurality of substituents, they may be the same or different.

The sulfonium salt used as the component (B) has, as a cation, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium, (2) from the viewpoint of further excellent sensitivity, resolution, and insulation. -Methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenylylsulfonium, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium, (2-ethoxy) At least one selected from the group consisting of phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium and tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium A compound is preferred.

The sulfonium salt used as component (B) includes trifluoromethanesulfonate, nonafluorobutanesulfonate, hexafluoroantimonate, tris [(trifluoromethyl) sulfonyl] methanide, 10-camphorsulfonate, tris (pentafluoroethyl) as anions. A compound having at least one selected from the group consisting of trifluorophosphate and tetrakis (pentafluorophenyl) borate is preferable.

Specific examples of the sulfonium salt include (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium nonafluorobutanesulfonate, [4- (4-biphenylylthio) Phenyl] -4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, and the like. A sulfonium salt can be used individually by 1 type or in mixture of 2 or more types.

Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl). Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) -1,8- And naphthalimide and N- (10-camphorsulfonyloxy) -1,8-naphthalimide. A sulfonimide compound can be used individually by 1 type or in mixture of 2 or more types.

(B) A component can be used individually by 1 type or in mixture of 2 or more types.

From the viewpoint of further improving the sensitivity, resolution, pattern shape and the like of the photosensitive resin composition of this embodiment, the content of the component (B) is 0.1 to It may be 15 parts by weight, 0.3 to 10 parts by weight, 1 to 10 parts by weight, 3 to 10 parts by weight, 5 to 10 parts by weight, or 6 to 10 parts by weight. In addition, in this specification, 100 mass parts of (A) component means that it is 100 mass parts of solid content of (A) component.

<(C) component>
The photosensitive resin composition of the present embodiment is at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and at least selected from the group consisting of a methylol group and an alkoxyalkyl group as the component (C). The compound which has 1 type is contained (however, (D) component, (E1) component, and (E2) component are not included). Here, the aromatic ring means an aromatic hydrocarbon group (for example, a hydrocarbon group having 6 to 10 carbon atoms), and examples thereof include a benzene ring and a naphthalene ring. The heterocyclic ring means a cyclic group having at least one hetero atom such as a nitrogen atom, oxygen atom, sulfur atom (for example, a cyclic group having 3 to 10 carbon atoms), such as a pyridine ring, an imidazole ring, Examples include a pyrrolidinone ring, an oxazolidinone ring, an imidazolidinone ring and a pyrimidinone ring. An alicyclic ring means a cyclic hydrocarbon group having no aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring and a cyclohexane ring. Is mentioned. An alkoxyalkyl group means a group in which an alkyl group is bonded to an alkyl group through an oxygen atom (a group in which one hydrogen atom of an alkyl group is substituted with an alkoxy group). The number of carbon atoms of the alkyl group and the alkoxy group in the alkoxyalkyl group is, for example, 1 to 10, and may be different from each other.

When the photosensitive resin composition contains the component (C), when exposed to light (or when cured by heat treatment after exposure and exposure), methylol groups or alkoxyalkyl groups in the component (C) Alternatively, the methylol group or alkoxyalkyl group in component (C) reacts with component (A) with dealcoholization to greatly reduce the solubility of the composition in the developer, resulting in a negative pattern. Can be formed. In addition, when the photosensitive layer after the resin pattern is formed is heated and cured, the (C) component reacts with the (A) component to form a bridge structure, thereby preventing the resin pattern from being weakened and melted. .

Specifically, the component (C) includes a compound having a phenolic hydroxyl group (however, the component (A) is not included), a compound having a hydroxymethylamino group, and a compound having an alkoxymethylamino group. At least one selected from the above is preferred. When the compound having a phenolic hydroxyl group has a methylol group or an alkoxyalkyl group, it is possible to further increase the dissolution rate of the unexposed area when developing with an alkaline aqueous solution, and to further improve the sensitivity of the photosensitive layer. (C) A component can be used individually by 1 type or in mixture of 2 or more types.

As the compound having a phenolic hydroxyl group, a conventionally known compound can be used. From the viewpoint of excellent balance between the effect of promoting the dissolution of the unexposed area and the effect of preventing the melting during curing of the photosensitive layer, The compound represented by the general formula (1) is preferable.

In the above general formula (1), Z represents a single bond or a divalent organic group, R ⁸¹ and R ⁸² each independently represent a hydrogen atom or a monovalent organic group, and R ⁸³ and R ⁸⁴ represent Each independently represents a monovalent organic group, a and b each independently represent an integer of 1 to 3, and c and d each independently represents an integer of 0 to 3. Here, as the monovalent organic group, for example, an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group or a propyl group; a carbon group such as a vinyl group having 2 to 10 carbon atoms. An alkenyl group; an aryl group having 6 to 30 carbon atoms, such as a phenyl group; and a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as a fluorine atom. When there are a plurality of R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ , they may be the same as or different from each other.

The compound represented by the general formula (1) is preferably a compound represented by the following general formula (2).

In the general formula (2), X ¹ represents a single bond or a divalent organic group, and a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). Several R may mutually be same or different.

Further, as the compound having a phenolic hydroxyl group, a compound represented by the following general formula (3) may be used.

In the general formula (3), a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). Several R may mutually be same or different.

In the above general formula (1), the compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent organic group represented by Z include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group; an ethylidene group and the like having 2 to 10 carbon atoms. An alkylidene group; an arylene group having 6 to 30 carbon atoms, such as a phenylene group; a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms; a sulfonyl group; a carbonyl group Ether bond; sulfide bond; amide bond and the like. Among these, Z is preferably a divalent organic group represented by the following general formula (4).

In the general formula (4), X is a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylidene group (for example, an alkylidene group having 2 to 10 carbon atoms), A group in which part or all of the hydrogen atoms are substituted with a halogen atom, a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond, or an amide bond is shown. R ⁹ represents a hydrogen atom, a hydroxyl group, an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms) or a haloalkyl group, and e represents an integer of 1 to 10. A plurality of R ⁹ and X may be the same as or different from each other. Here, the haloalkyl group means an alkyl group substituted with a halogen atom.

Specifically, the compound having an alkoxymethylamino group is at least one selected from the group consisting of a compound represented by the following general formula (5) and a compound represented by the following general formula (6). preferable.

In the general formula (5), a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). Several R may mutually be same or different.

In the general formula (6), a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). Several R may mutually be same or different.

Examples of the compound having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) (N -Hydroxymethyl) urea and the like. Examples of the compound having an alkoxymethylamino group include nitrogen-containing compounds obtained by alkylating all or part of the methylol groups of the compound having a hydroxymethylamino group. Here, examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component that is partially self-condensed. Specific examples of the compound having an alkoxymethylamino group include hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, tetrakis (methoxymethyl). Examples include urea.

The content of the component (C) is 20 parts by mass or less with respect to 100 parts by mass of the component (A). When the component (C) is contained, the exposed portion is likely to react sufficiently, so that the resolution tends not to decrease. When the content of the component (C) is 20 parts by mass or less, a tapered resin pattern tends to be easily formed. From these viewpoints, the content of the component (C) is preferably more than 0 parts by weight and 18 parts by weight or less, more preferably 1 to 15 parts by weight, and more preferably 3 to 11 parts by weight. Further preferred.

<(D) component>
The photosensitive resin composition of the present embodiment includes at least one functional group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanylalkyl ether group, a vinyl ether group, and a hydroxyl group as the component (D). Containing an aliphatic compound having two or more. In addition, (D) component may have at least 1 type of 2 or more types of different functional groups, and may have 2 or more types of 1 type of functional groups. The compound is preferably an aliphatic compound having three or more functional groups. The upper limit of the number of functional groups is not particularly limited, but is 12 for example. The “aliphatic compound” refers to a compound in which the main skeleton is an aliphatic skeleton and does not contain an aromatic ring or an aromatic heterocyclic ring.

From the viewpoint of excellent workability when a photosensitive resin composition layer (photosensitive layer) is formed on a substrate, the photosensitive resin composition is also required to have excellent adhesion (tackiness) to the substrate. There is a case. When a photosensitive resin composition that does not have sufficient tackiness is used, the photosensitive resin composition in the exposed area is easily removed by the development process, and the adhesion between the substrate and the resin pattern (resist pattern) deteriorates. Tend. In this embodiment, when the photosensitive resin composition contains the component (D), there is a tendency that the adhesiveness (that is, tackiness) between the photosensitive resin composition and the substrate is improved. Furthermore, the photosensitive resin composition containing component (D) can impart flexibility to the photosensitive layer (coating film), and increase the dissolution rate of unexposed areas when developing with an alkaline aqueous solution. This tends to improve the resolution of the resin pattern. From the viewpoint of further improving tackiness and solubility in an aqueous alkali solution, the weight average molecular weight of the component (D) may be 92 to 2000, 106 to 1500, or 134 to 1300 in consideration of balance. . In addition, about the compound with a low molecular weight, when it is difficult to measure by the above-mentioned measuring method of the weight average molecular weight, the molecular weight can be measured by another method, and the average can be calculated.

Examples of the component (D) include compounds represented by the following general formulas (7), (8), (9) and (10). In the following general formulas (7), (8), (9), (10), (11), (12) and (13), examples of the alkyl group in the oxetanyl alkyl ether group include a methyl group, an ethyl group, and a propyl group. A methyl group is preferable.

In General Formula (7), R ¹ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following General Formula (11), and R ² , R ^3, and R ⁴ are each independently Are an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, a hydroxyl group, a group represented by the following general formula (12), or a group represented by the following general formula (13). .

In General Formula (8), R ⁵ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following General Formula (11), and R ⁶ , R ^7, and R ⁸ are each independently Are an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, a hydroxyl group, a group represented by the following general formula (12), or a group represented by the following general formula (13). .

In the general formula (9), R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently acryloyloxy group, methacryloyloxy group, glycidyloxy group, oxetanyl alkyl ether group, vinyl ether group, hydroxyl group , A group represented by the following general formula (12), or a group represented by the following general formula (13).

In the general formula (10), R ¹⁵ , R ¹⁷ , R ¹⁸ and R ²⁰ are each independently acryloyloxy group, methacryloyloxy group, glycidyloxy group, oxetanyl alkyl ether group, vinyl ether group, hydroxyl group, the following general formula (12 ) Or a group represented by the following general formula (13), R ¹⁶ and R ¹⁹ are each independently a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or the following general formula ( The group represented by 11) is shown.

In the general formula (11), R ²¹ represents an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group or a hydroxyl group.

In the general formula (12), R ²² represents an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group or a hydroxyl group, and n is an integer of 1 to 10.

In the general formula (13), R ²³ represents an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group or a hydroxyl group, and m is an integer of 1 to 10, respectively.

Specifically, as the component (D), at least selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, and a vinyl ether group from the viewpoint of further improving sensitivity and resolution. A compound having one kind is preferable, a compound having two or more glycidyloxy groups or two or more acryloyloxy groups is more preferable, and a compound having three or more glycidyloxy groups or three or more acryloyloxy groups is further included. preferable. (D) A component can be used individually by 1 type or in mixture of 2 or more types.

The component (D) includes a compound having an acryloyloxy group, a compound having a methacryloyloxy group, a compound having a glycidyloxy group, a compound having an oxetanyl alkyl ether group, a compound having a vinyl ether group, and a compound having a hydroxyl group. At least one selected from the group can be used. As the component (D), a compound having at least one group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group and a glycidyloxy group is preferable. From the viewpoint of improving the insulation reliability in a fine wiring, acryloyloxy A compound having at least one group selected from the group consisting of a group and a methacryloyloxy group is more preferable. From the viewpoint of further improving developability, the component (D) is preferably an aliphatic compound having two or more glycidyloxy groups, and preferably an aliphatic compound having three or more glycidyloxy groups. More preferably, it is more preferably an aliphatic compound having 3 or more glycidyloxy groups having a weight average molecular weight of 1000 or less.

Examples of the compound having an acryloyloxy group include EO-modified dipentaerythritol hexaacrylate, PO-modified dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, EO-modified ditrimethylolpropane tetraacrylate, PO-modified ditrimethylolpropane tetraacrylate, ditrile Methylolpropane tetraacrylate, EO-modified pentaerythritol tetraacrylate, PO-modified pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, EO-modified pentaerythritol triacrylate, PO-modified pentaerythritol triacrylate, pentaerythritol triacrylate, EO-modified trimethylolpropane acrylate, PO modified birds Chi triacrylate, trimethylolpropane acrylate, EO-modified glycerol tri acrylate, PO-modified glycerol triacrylate, glycerin triacrylate. The compounds having an acryloyloxy group can be used alone or in combination of two or more.

Examples of the compound having a methacryloyloxy group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO-modified ditrimethylolpropane tetramethacrylate, PO-modified ditrimethylolpropane tetramethacrylate, ditriethyl. Methylolpropane tetramethacrylate, EO-modified pentaerythritol tetramethacrylate, PO-modified pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, EO-modified pentaerythritol trimethacrylate, PO-modified pentaerythritol trimethacrylate, pentaerythritol trimethacrylate, EO-modified trimethylolpropane Methacrylate, PO-modified trimethylolpropane dimethacrylate, trimethylolpropane dimethacrylate, EO modified glycerol trimethacrylate, PO-modified glycerol trimethacrylate, glycerine trimethacrylate and the like. The compound which has a methacryloyloxy group can be used individually by 1 type or in mixture of 2 or more types.

Examples of the compound having a glycidyloxy group include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl. Ether, glycerin diglycidyl ether, dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerin triglycidyl ether, Glycerol propoxyle Totori glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, diglycidyl 1,2-cyclohexane dicarboxylate, and the like. The compound which has a glycidyloxy group can be used individually by 1 type or in mixture of 2 or more types.

Examples of the compound having a glycidyloxy group include dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, and And at least one selected from the group consisting of glycerin triglycidyl ether is preferred.

The compound having a glycidyloxy group includes, for example, Epolite 40E, Epolite 100E, Epolite 70P, Epolite 200P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), alkyl epoxy resin ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L and Denacol EX-850L (above, manufactured by Nagase ChemteX Corporation, product) The name “Denacol” is a commercially available trademark).

Examples of the compound having an oxetanyl alkyl ether group include a compound having a 3-alkyl-3-oxetanyl alkyl ether group, and a compound having a 3-ethyl-3-oxetanyl alkyl ether group is preferable. Examples of such oxetane compounds include dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris (3-ethyl-3- Oxetanylmethyl) ether, trimethylolethanetris (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, glycerol poly (3-ethyl-3-oxetanylmethyl) ether And glycerin tris (3-ethyl-3-oxetanylmethyl) ether. The compound which has oxetanyl alkyl ether can be used individually by 1 type or in mixture of 2 or more types.

Examples of the compound having a hydroxyl group include polyhydric alcohols such as dipentaerythritol, pentaerythritol, and glycerin. The compound which has a hydroxyl group can be used individually by 1 type or in mixture of 2 or more types.

Among the components (D), at least one selected from the group consisting of trimethylolethane triglycidyl ether and trimethylolpropane triglycidyl ether is preferable from the viewpoint of further excellent sensitivity and resolution.

Component (D) is commercially available as an alkyl type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name ZX-1542), an alkyl type acrylic resin (manufactured by Nippon Kayaku Co., Ltd., trade name: PET-30), and the like. .

The content of the component (D) is a mass part in which the total content of the component (C) and the component (D) is 65 to 120 parts by mass with respect to 100 parts by mass of the component (A). When the total content of the component (C) and the component (D) is 65 parts by mass or more, the photosensitive layer formed from the photosensitive resin composition and the protective layer tend to stick, and 120 parts by mass or less. If it exists, it will become easy to form the photosensitive layer formed from the photosensitive resin composition on a desired support body (for example, film-forming), and there exists a tendency for resolution to fall easily. From these viewpoints, the total content of the component (C) and the component (D) is preferably more than 65 parts by weight and 110 parts by weight or less, more preferably 68 to 100 parts by weight, and more preferably 70 to 90 parts by weight. More preferably, it is part by mass.

<(E) component>
The photosensitive resin composition of this embodiment may contain a benzophenone compound as the component (E). By containing a benzophenone compound, the resolution of the photosensitive resin composition can be improved. Moreover, the tolerance of the exposure amount which can form a fine resist pattern can be improved by containing (E) component, and productivity can be improved more. Examples of the benzophenone compound include benzophenone, 4,4′-diaminobenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dibutylamino) Benzophenone, 4-ethylaminobenzophenone, 2,4-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetramethoxybenzophenone, 2,2', 4,4'-tetraethoxybenzophenone, 2,2 ', 4,4'-tetrabutoxybenzophenone 2,2'-dihydroxy-4,4'-

dimethoxybenzopheno

2,2′-dihydroxy-4,4′-diethoxybenzophenone, 2,2′-dihydroxy-4,4′-dibutoxybenzophenone, 4,4′-dihydroxybenzophenone, 4,4′-dimethoxybenzophenone, 4, 4,4′-dibutoxybenzophenone, 4,4′-diphenylbenzophenone, and the like.

Among the components (E), the compound is selected from the group consisting of an amino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a hydroxy group, a methoxy group, an ethoxy group, a butoxy group, and a phenyl group in that the resolution is further improved. A benzophenone compound having one or more groups is preferred, and two or more groups selected from the group consisting of amino group, dimethylamino group, diethylamino group, dibutylamino group, hydroxy group, methoxy group, ethoxy group, butoxy group and phenyl group Benzophenone compounds having 2 or more diethylamino groups or hydroxy groups are more preferable, and 4,4′-bis (dimethylamino) benzophenone and 2,2 ′, 4,4′-tetrahydroxybenzophenone are particularly preferable. preferable. (E) A component can be used individually by 1 type or in mixture of 2 or more types.

The content of component (E) is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 1 part by weight, and 0.01 to 0.8 parts by weight with respect to 100 parts by weight of component (A). Is more preferable, and 0.05 to 0.1 part by mass is particularly preferable. When the content of the component (E) is in the range of 0.001 to 10 parts by mass, the resolution of the photosensitive resin composition can be improved, and the exposure amount that can form a fine resist pattern is high. The degree can be improved, and the productivity is further improved.

By including the component (E), the resolution is further improved. For example, it is easy to form a fine resist pattern (that is, a fine resist pattern having a via opening diameter of 20 (unit: μm) or less). For example, in the case of forming a fine resist pattern having a via opening diameter of 20 (unit: μm) or less, it is necessary to adjust the exposure amount appropriately. The width of the exposure amount that can form a simple resist pattern can be widened, that is, the tolerance (allowable range) of the exposure amount can be improved, so that when a mass-produced product or the like is manufactured, a fine resist pattern is formed. In addition, it is not necessary to finely adjust the exposure amount, and productivity is improved.

<(F) component>
The photosensitive resin composition of the present embodiment may further contain a solvent as the component (F) in order to improve the handleability of the photosensitive resin composition or to adjust the viscosity and storage stability. it can. The component (F) is preferably an organic solvent. The organic solvent is not particularly limited as long as it can exhibit the above performance, but ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl Propylene glycol monoalkyl ethers such as ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; Propylene glycol monomethyl ether acetate Propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; methyl lactate, ethyl lactate, Lactic acid esters such as n-propyl lactate and isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, propion Aliphatic carboxylic acid esters such as isobutyl acid; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate Esters such as methyl nitrate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; methyl ethyl ketone (also known as 2-butanone), 2-heptanone, 3-heptanone, 4- Ketones such as heptanone and cyclohexanone; amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; and lactones such as γ-butyrolactone. (F) A component can be used individually by 1 type or in mixture of 2 or more types.

The content of the component (F) is 30 to 200 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition (however, when the component (F) is used, excluding the component (F)), or It may be 40 to 120 parts by mass.

<(G) component>
The photosensitive resin composition of the present embodiment may contain a compound having an Si—O bond (excluding compounds corresponding to the components (A) to (F)) as the component (G). The compound having a Si—O bond may be a compound having a siloxane bond. The component (G) is not particularly limited as long as it has a Si—O bond, and examples thereof include silica (silica filler) and silane compounds (silane coupling agent and the like). (G) A component can be used individually by 1 type or in mixture of 2 or more types.

When the photosensitive resin composition of this embodiment contains an inorganic filler, the thermal expansion coefficient of the resin pattern can be reduced. When an inorganic filler is used as the component (G), the inorganic filler is preferably silica such as fused spherical silica, fused pulverized silica, fumed silica, or sol-gel silica. Alternatively, an inorganic filler having a Si—O bond may be used by treating the inorganic filler with a silane compound. Among inorganic fillers treated with a silane compound, as inorganic fillers other than silica, aluminum oxide, aluminum hydroxide, calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide, or talc, Examples include inorganic fillers derived from mineral products such as mica.

The average primary particle diameter of the inorganic filler is preferably 100 nm or less, more preferably 80 nm or less, and further preferably 50 nm or less from the viewpoint of further improving the photosensitivity of the photosensitive layer. When the average primary particle size is 100 nm or less, the photosensitive resin composition is less likely to become cloudy, and light for exposure is easily transmitted through the photosensitive layer. As a result, since the unexposed part is easily removed, the resolution of the resin pattern tends to be difficult to decrease. The average primary particle diameter is a value obtained by converting from the BET specific surface area.

The thermal expansion coefficient of silica is preferably 5.0 × 10 ⁻⁶ / ° C. or less. Silica is preferably silica such as fused spherical silica, fumed silica, sol-gel silica, and more preferably fumed silica or sol-gel silica from the viewpoint of easily obtaining a suitable particle size. The silica is preferably silica (nanosilica) having an average primary particle diameter of 5 to 100 nm.

When measuring the particle size of the inorganic filler, a known particle size distribution meter can be used. The particle size distribution meter is a laser diffraction / scattering type particle size distribution meter that calculates the particle size distribution by irradiating the particle group with laser light and calculating from the intensity distribution pattern of the diffracted light and scattered light emitted from the particle group; Examples thereof include a particle size distribution meter of nanoparticles for obtaining a particle size distribution using frequency analysis.

When the photosensitive resin composition of this embodiment contains a silane compound, the adhesion strength between the photosensitive layer and the substrate after pattern formation can be improved. When a silane compound is used as the component (G), the silane compound is not particularly limited as long as the silane compound has a Si—O bond. Examples of the silane compound include alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acrylic silane, methacryl silane, mercapto silane, sulfide silane, isocyanate silane, sulfur silane, styryl silane, alkyl chlorosilane, and the like.

As the silane compound as component (G), a compound represented by the following general formula (14) is preferable.
(R ¹⁰¹ O) _4-f -Si- (R ¹⁰² ) _f (14)

In the general formula (14), R ¹⁰¹ represents an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, or a propyl group, R ¹⁰² represents a monovalent organic group, and f is An integer from 0 to 3 is shown. When f is 0, 1 or 2, the plurality of R ¹⁰¹ may be the same as or different from each other. When f is 2 or 3, the plurality of R ¹⁰² may be the same as or different from each other. R ¹⁰¹ is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, from the viewpoint of further improving resolution. In the case of treating with a silane compound (such as a compound represented by the general formula (14)) in order to improve the dispersibility of the inorganic filler, f is preferably 0 to 2 from the viewpoint of further improving the dispersibility of the inorganic filler. 0 to 1 are more preferable.

Specific examples of the silane compound as component (G) include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, and diisopropyl. Dimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, Phenyltrimethoxysilane, diphenyldimethoxysilane, triphenylsilanol, tetraethoxysilane, 3-aminopropyltrimethoxysilane, -Aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis ( 3- (triethoxysilyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3-methacryloyloxy Propyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane and the like. The component (G) is preferably an epoxy silane having at least one glycidyloxy group, more preferably an epoxy silane having at least one selected from the group consisting of a trimethoxysilyl group and a triethoxysilyl group. .

The content of the component (G) is preferably 1.8 to 420 parts by mass, more preferably 1.8 to 270 parts by mass with respect to 100 parts by mass of the component (A). The content of component (G) may be 1 to 20 parts by mass or 3 to 10 parts by mass with respect to 100 parts by mass of component (A).

<(H) component>
The photosensitive resin composition of the present embodiment may further contain a sensitizer as the component (H). When the photosensitive resin composition contains the component (H), the sensitivity of the photosensitive resin composition can be further improved. Examples of the sensitizer include 9,10-dibutoxyanthracene. (H) component can be used individually by 1 type or in mixture of 2 or more types.

The content of the component (H) is preferably 0.01 to 1.5 parts by mass, more preferably 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the component (A).

<Other ingredients>
In addition to the component (A), the photosensitive resin composition of the present embodiment may contain a phenolic low molecular compound having a molecular weight of less than 1000 (hereinafter referred to as “phenol compound (a)”). Examples of the phenol compound (a) include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, Tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl ] Benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- {1 -(4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane Emissions, and the like. The content of these phenol compounds (a) is, for example, in the range of 0 to 40 parts by weight (particularly 0 to 30 parts by weight) with respect to 100 parts by weight of component (A).

Moreover, the photosensitive resin composition of this embodiment may contain other components other than the above-mentioned components. Examples of other components include a colorant, an adhesion aid, a leveling agent, and an inorganic filler having no Si—O bond. Examples of the inorganic filler include, but are not limited to, aluminum compounds such as aluminum oxide and aluminum hydroxide; alkali metal compounds; alkalis such as calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, and magnesium hydroxide. Earth metal compounds; inorganic compounds derived from mines. These are pulverized by a pulverizer, classified according to circumstances, and can be dispersed with a maximum particle size of 2 μm or less. The inorganic filler may be used alone or in combination of two or more. Any inorganic filler is preferably dispersed with a maximum particle size of 2 μm or less when dispersed in the photosensitive resin composition. At that time, a silane coupling agent can be used in order to disperse the resin in the resin without aggregation. The content of the inorganic filler is preferably 1 to 70% by mass based on the total amount of the photosensitive resin composition (however, when the component (F) is used, excluding the component (F)). More preferably, it is ˜65 mass%.

[Photosensitive element]
Next, the photosensitive element of this embodiment will be described with reference to FIG. FIG. 2 is a schematic cross-sectional view of the photosensitive element 10 according to this embodiment. As shown in FIG. 2, the photosensitive element 10 includes a support 4, a photosensitive layer 5, and a protective layer 6 in this order. That is, in the photosensitive element 10, the support 4 is provided on one surface of the photosensitive layer 5, and the protective layer 6 is provided on the other surface of the photosensitive layer 5. The photosensitive layer 5 can be formed from the above-mentioned photosensitive resin composition. The photosensitive element 10 can be used for the manufacturing method of the semiconductor device of this embodiment, for example, a circuit base material. The photosensitive element 10 may not include the support 4.

As the support 4, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used. The thickness of the support (polymer film) 4 is preferably 5 to 100 μm. In addition, you may use the said polymer film by laminating | stacking on the both surfaces of the photosensitive layer 5 by making the other one the support body 4 into the support body 4, and the other.

As the protective layer 6, for example, a polymer film having heat resistance and solvent resistance, such as polyethylene terephthalate, polypropylene, polyethylene, polyester, or the like can be used. The thickness of the protective layer 6 is preferably 5 to 100 μm.

The photosensitive layer 5 can be formed by applying the above-described photosensitive resin composition on the support 4 or the protective layer 6 and drying it as necessary. Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, and a spin coating method. Although the thickness of the photosensitive layer 5 varies depending on the use, it is preferably 1 to 100 μm after drying, more preferably 3 to 60 μm, still more preferably 5 to 60 μm, and further preferably 5 to 40 μm. Particularly preferred is 5 to 25 μm. In addition, from the viewpoint of excellent insulation reliability (insulation between wirings in the thickness direction of the layer) and productivity when mounting a chip, the thickness of the photosensitive layer 5 is preferably over 20 μm. 20 μm or less.

[Method of forming resist pattern]
The resist pattern forming method according to the present embodiment includes a step of placing the photosensitive layer of the photosensitive element on a substrate (photosensitive layer preparation step), a step of exposing the photosensitive layer to a predetermined pattern, and a post-exposure step. A step of developing the photosensitive layer to obtain a resin pattern, and a step of heat-treating the resin pattern.

The resist pattern forming method of this embodiment may further include a step of heat-treating (post-exposure baking) the photosensitive layer between the exposure step and the development step. In this case, the resist pattern forming method of the present embodiment includes a step of placing the photosensitive layer of the photosensitive element on the substrate, a step of exposing the photosensitive layer to a predetermined pattern, and exposing the exposed photosensitive layer to the photosensitive layer. A step of performing post-heat treatment (post-exposure bake), a step of developing the photosensitive layer after the heat treatment (post-exposure bake) to obtain a resin pattern, and a step of heat-treating the obtained resin pattern .

In the method for forming a resist pattern according to this embodiment, for example, first, the above-described photosensitive layer is formed on a substrate on which a resist pattern is to be formed. The process of forming a photosensitive layer can be performed by arrange | positioning the photosensitive layer of the said photosensitive element on a base material, for example. The photosensitive layer preparation step can also be referred to as a step of obtaining a base material (for example, a substrate) provided with a photosensitive layer. The photosensitive layer can be formed, for example, by transferring (laminating) the photosensitive layer in the photosensitive element onto a substrate.

The substrate may be a substrate. As the substrate, for example, a copper foil with resin, a copper clad laminate, a silicon wafer with a metal sputtered film, a silicon wafer with a copper plating film, an alumina substrate, or the like can be used. The surface on which the photosensitive layer is formed on the substrate may be a cured resin layer formed using the photosensitive resin composition. In that case, there exists a tendency for adhesiveness with a base material to improve.

The photosensitive layer preparation step may be a step of forming the photosensitive layer by applying the above-described photosensitive resin composition onto a substrate (for example, a substrate) and drying the photosensitive resin composition. Examples of the method for forming the photosensitive layer include a method of forming the photosensitive layer (coating film) by applying (for example, coating) the photosensitive resin composition to a substrate and drying it to evaporate the solvent. .

As a method for applying the photosensitive resin composition to the substrate, for example, a coating method such as a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, or the like can be used. The thickness of the coating film can be appropriately controlled by adjusting the coating means and the solid content concentration and viscosity of the photosensitive resin composition.

Next, the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern. Examples of actinic rays used for exposure include rays using a g-line stepper as a light source; ultraviolet rays using a low-pressure mercury lamp, high-pressure mercury lamp, metal halide lamp, i-line stepper and the like as a light source; electron beams; The exposure amount is appropriately selected depending on the light source used, the thickness of the photosensitive layer, and the like. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the exposure dose may be about 100 to 3000 mJ / cm ² when the photosensitive layer thickness is 5 to 50 μm.

Further, a heat treatment (post-exposure baking) may be performed after the exposure and before the development. By performing post-exposure baking, the curing reaction between the component (A) and the component (C) by the acid generated from the photosensitive acid generator can be promoted. The post-exposure baking conditions vary depending on the composition of the photosensitive resin composition, the content of each component, the thickness of the photosensitive layer, and the like, but for example, heating at 50 to 150 ° C. for 1 to 60 minutes is preferable. It is more preferable to heat at 100 ° C. for 1 to 15 minutes. Further, it may be heated at 70 to 150 ° C. for 1 to 60 minutes, or at 80 to 120 ° C. for 1 to 60 minutes.

Next, the photosensitive layer (coating film) that has been subjected to exposure and / or post-exposure baking is developed with an alkaline developer, and the unexposed areas (areas other than the cured areas) are dissolved and removed to obtain a desired resist pattern. Get. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. The development conditions are, for example, 20 to 40 ° C. and 10 to 300 seconds in the spray development method.

Examples of the alkaline developer include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and choline is dissolved in water so as to have a concentration of 1 to 10% by mass; Is mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, after developing with the said alkaline developing solution, it wash | cleans with water and dries. The alkaline developer is preferably tetramethylammonium hydroxide from the viewpoint of further excellent resolution.

Further, a cured film (resist pattern) of the photosensitive layer is obtained by performing a heat treatment in order to develop the insulating film characteristics. The curing conditions for the photosensitive layer are not particularly limited, but can be adjusted according to the use of the cured product. For example, the photosensitive layer can be cured by heating at 50 to 250 ° C. for 30 minutes to 10 hours.

Also, heating can be performed in two stages in order to sufficiently advance the curing and / or to prevent deformation of the obtained resin pattern. For example, it can be cured by heating at 50 to 120 ° C. for 5 minutes to 2 hours in the first stage and further heating at 80 to 200 ° C. for 10 minutes to 10 hours in the second stage. When the heat treatment is performed under the above-described curing conditions, the heating equipment is not particularly limited, and a general oven, infrared furnace, or the like can be used.

By using the photosensitive layer, the openings of the obtained resin pattern and resist pattern can be tapered. The taper angle of the tapered opening may be, for example, 20 to 90 °, preferably 30 to 85 °, and more preferably 45 to 75 °.

<Hardened product and semiconductor device>
The cured product of this embodiment is a cured product of the photosensitive layer of this embodiment. The semiconductor device of this embodiment includes a cured product of the photosensitive layer of this embodiment. The cured product of the photosensitive layer of this embodiment can be suitably used as, for example, a surface protective film and / or an interlayer insulating film of a semiconductor element, or a solder resist and / or an interlayer insulating film in a multilayer printed wiring board. The semiconductor device of this embodiment includes a circuit substrate (for example, a circuit board) having a cured product of the photosensitive layer of this embodiment.

FIG. 3 is a view showing a method for producing a multilayer printed wiring board including the cured product of the photosensitive layer according to the present embodiment as a solder resist and / or an interlayer insulating film. The multilayer printed wiring board 100A shown in FIG. 3F has a wiring pattern on the surface and inside. The multilayer printed wiring board 100A is obtained by laminating a copper clad laminate, an interlayer insulating film, a metal foil, and the like and appropriately forming a wiring pattern by an etching method or a semi-additive method. Hereinafter, a method of manufacturing the multilayer printed wiring board 100A according to an embodiment of the present disclosure will be briefly described with reference to FIG.

First, an interlayer insulating film 103 is formed on both surfaces of a substrate 101 (such as a copper clad laminate) having a wiring pattern 102 on the surface (see FIG. 3A). The interlayer insulating film 103 may be formed by printing a photosensitive resin composition using a screen printer or a roll coater. The above photosensitive element is prepared in advance, and the photosensitive element is prepared using a laminator. The photosensitive layer in can be formed by affixing to the surface of the printed wiring board.

Next, an opening 104 is formed by using a YAG laser or a carbon dioxide gas laser in a place that needs to be electrically connected to the outside (see FIG. 3B). Smear (residue) around the opening 104 is removed by desmear treatment.

Next, a seed layer 105 is formed by an electroless plating method (see FIG. 3C). A photosensitive layer containing a photosensitive resin composition (a semi-additive photosensitive resin composition) is formed on the seed layer 105, and a predetermined pattern is exposed and developed to form a resin pattern 106 (FIG. 3 ( d)).

Next, a wiring pattern 107 is formed on the portion of the seed layer 105 where the resin pattern 106 is not formed by electrolytic plating, and the resin pattern 106 is removed by a peeling solution, and then the wiring pattern 107 of the seed layer 105 is formed. The part which is not removed is removed by etching (see FIG. 3E).

The multilayer printed wiring board 100A can be manufactured by repeating the above operation and forming the solder resist 108 containing the cured product of the above-described photosensitive resin composition on the outermost surface (see FIG. 3 (f)). The interlayer insulating film 103 and / or the solder resist 108 can be formed by using the resist pattern forming method described above. Moreover, it can form using the method provided with the process of forming a photosensitive layer, and the process of heat-processing. In the multilayer printed wiring board 100A thus obtained, semiconductor elements are mounted at corresponding locations, and electrical connection can be ensured.

Hereinafter, the objects and advantages of the present disclosure will be described in detail by way of examples, but the present disclosure is not limited to these examples.

[Examples 1 to 3 and Comparative Examples 1 to 4]
<Preparation of photosensitive resin composition>
The photosensitive acid generator (B-1), the alkoxyalkyl compound (C-1), and the compound having an acryloyloxy group (D-1) with respect to 100 parts by mass of the resin components (A-1 and A-2) ), A benzophenone compound (E-1), a solvent (F-1), and a compound (G-1) having a Si—O bond at the blending amounts (unit: parts by mass) shown in Table 1. The photosensitive resin composition was obtained by blending.

Abbreviations in Table 1 are as follows.
A-1: Novolac resin (Asahi Organic Materials Co., Ltd., trade name: TR4020G, weight average molecular weight: 13000)
A-2: Novolak resin (Asahi Organic Materials Co., Ltd., trade name: TR4080G, weight average molecular weight: 5000)
B-1: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-310B, anion: tetrakis (pentafluorophenyl) borate)
C-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicalak MX-270)
D-1: Pentaerythritol triacrylate (Nippon Kayaku Co., Ltd., trade name: PET-30)
E-1: 4,4′-bis (diethylamino) benzophenone (made by Hodogaya Chemical Co., Ltd., trade name: EAB)
F-1: Methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd., trade name: 2-butanone)
G-1: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-403)

<Production of photosensitive element>
After applying the photosensitive resin composition on a polyethylene terephthalate film (trade name: Purex A53, manufactured by Teijin DuPont Films Ltd.) so that the thickness of the photosensitive resin composition becomes uniform, a hot air convection type at 90 ° C. By drying with a dryer for 10 minutes, a photosensitive layer having a thickness of 10 μm after drying was formed. On this photosensitive layer, a polyethylene film (trade name: NF-15, manufactured by Tamapoly Co., Ltd.) is bonded as a protective layer, and a polyethylene terephthalate film (support), a photosensitive layer, and a protective layer are sequentially laminated. Each sex element was obtained.

<Evaluation of adhesiveness of protective layer>
Observe the appearance of the above photosensitive element, “A” when the photosensitive layer and the protective layer are bonded together without any gaps, air enters between the photosensitive layer and the protective layer, and a part or the entire surface is bonded. The sticking property of the protective layer was evaluated as “B”. The evaluation results are shown in Table 1.

<Evaluation of resolution and taper shape>
On the copper-clad laminate, the photosensitive element was laminated so that the photosensitive layer was in contact with the surface of the copper-clad laminate while peeling off the protective layer of the photosensitive element to obtain a laminate. Lamination was performed using a vacuum pressure laminator (trade name: MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.), a heater at 60 ° C. (upper), a heater at 60 ° C. (lower), a vacuum drawing time of 20 seconds, 20 The pressurization time was 1 second, and the pressure was 0.4 MPa. Next, the support of the above laminate is peeled off, and is applied to the photosensitive layer through a mask with i-line (365 nm) using a projection exposure machine (trade name: UX-2240SM-XJ-0, manufactured by USHIO INC.). The same magnification projection exposure was performed. As the mask, a negative pattern having via openings (unexposed portions) in 5 μm increments with a via diameter of 5 to 100 μm was used. The exposure amount was 400 mJ / cm ² .

The exposed photosensitive layer (coating film) was heated at 95 ° C. for 8 minutes (post exposure bake). Then, a 2.38 mass% tetramethylammonium hydroxide aqueous solution (manufactured by Tama Chemical Industry Co., Ltd., trade name: TMAH 2.38%) is used as a developer, and a developing machine (trade name: AD- manufactured by Takizawa Sangyo Co., Ltd.) is used. 1200) and spray the developer at 23 ° C. on the photosensitive layer (pump discharge pressure [developer]: 0. 0) for the shortest development time (a time corresponding to four times the minimum time for removing the unexposed portion). 16 MPa) to remove the unexposed area. Next, 23 ° C. purified water (trade name: purified water, manufactured by Wako Pure Chemical Industries, Ltd.) is sprayed as a rinsing solution for 60 seconds (pump discharge pressure [rinsing solution]: 0.12 to 0.14 MPa) to develop the developer. Washed away. And it was made to dry and the resin pattern was formed. Next, using an inert oven (trade name: INH-21CD, manufactured by Koyo Thermo System Co., Ltd.), the temperature was raised from 30 ° C. to 5 ° C./min under a nitrogen stream (oxygen concentration of 20 ppm or less) and reached 200 ° C. Then, heat treatment was performed for 1 hour to prepare a cured film. The formed resin pattern was observed by enlarging the magnification to 1000 times using a metal microscope. Evaluate the diameter of the smallest via opening as a resolution among the patterns formed in the insulating resin part (exposed part) without removing the film and roughening the via opening (unexposed part). did. Further, the cross section of the via opening of the obtained cured film was observed with a scanning electron microscope (manufactured by Keyence Corporation, trade name: VE-8800) at an acceleration voltage of 5 kV and an inclination of 80 °, and the taper angle was measured. . The evaluation results are shown in Table 1.

As can be seen from Table 1, in Examples 1 to 3, in which the content of the component (C) is 20 parts by mass or less with respect to 100 parts by mass of the component (A), the taper angle is 70 ° or less. As compared with Comparative Example 1 in which the content of component C) was 20 parts by mass or more, the via opening was improved to a tapered shape. Examples 1 to 3, in which the total content of the component (C) and the component (D) is 65 to 120 parts by mass with respect to 100 parts by mass of the component (A), are the sum of the components (C) and (D). Compared with Comparative Examples 2 to 4 having a content of less than 65 parts by mass, the sticking property of the protective layer was improved from B to A. In addition, in Examples 1 to 3, it was found that the resolution was 20 μm and the resolution was extremely good.

4, 5, 6, 7, 8, 9, and 10 are similar to the evaluation of the tapered shape using the photosensitive elements of Examples 1, 2, 3, and Comparative Examples 1, 2, 3, and 4, respectively. It is a scanning electron micrograph at the time of forming a via opening. From these photographs, it was shown that when the photosensitive elements of Examples 1 to 3 were used, openings having tapered walls were formed.

The photosensitive layer in the photosensitive element of the present disclosure can be applied as a material used for a surface protective film or an interlayer insulating film of a semiconductor element, for example. The photosensitive layer can also be applied as a material used for a solder resist of a wiring board material or an interlayer insulating film. In particular, the photosensitive layer in the photosensitive element of the present disclosure has good resolution, via opening shape (tapered shape), and sticking property between the photosensitive layer and the protective layer. It is preferably used for a highly integrated package substrate having a higher density.

DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Insulating film, 4 ... Support body, 5 ... Photosensitive layer, 6 ... Protective layer, 100A ... Multilayer printed wiring board, 101 ... Base material, 102, 107 ... Wiring pattern, 103 ... Interlayer insulating film, 104 ... Opening, 105 ... Seed layer, 106 ... Resin pattern, 108 ... Solder resist.

Claims

A photosensitive layer and a protective layer;
The photosensitive layer is
(A) component: a resin having a phenolic hydroxyl group;
(B) component: a photosensitive acid generator;
(C) component: a compound having at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and having at least one of a methylol group and an alkoxyalkyl group;
(D) component: an aliphatic compound having two or more functional groups selected from the group consisting of acryloyloxy group, methacryloyloxy group, glycidyloxy group, oxetanyl alkyl ether group, vinyl ether group and hydroxyl group;
Containing
The content of the component (C) in the photosensitive layer is 20 parts by mass or less with respect to 100 parts by mass of the component (A), and the total content of the component (C) and the component (D) A) A photosensitive element that is 65 to 120 parts by mass with respect to 100 parts by mass of the component.
The photosensitive element according to claim 1, further comprising a support, and further comprising the support, the photosensitive layer, and the protective layer in this order.
3. The photosensitive element according to claim 1, wherein the photosensitive layer further contains a compound having component (G): Si—O bond.
A semiconductor device comprising a cured product of the photosensitive layer in the photosensitive element according to any one of claims 1 to 3.
A step of disposing the photosensitive layer of the photosensitive element according to any one of claims 1 to 3 on a substrate, a step of exposing the photosensitive layer to a predetermined pattern, and developing the exposed photosensitive layer And forming a resin pattern, and a step of heat-treating the resin pattern.