TW201839509A - Photosensitive element, semiconductor device, and method for forming resist pattern - Google Patents

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 resist pattern forming method.

In the manufacture of semiconductor elements or printed wiring boards on which semiconductor elements are mounted, in order to form a fine pattern, for example, a negative photosensitive resin composition is used. In the above method, a photosensitive layer is formed on a substrate (for example, a wafer in the case of a semiconductor element and a substrate in the case of a printed wiring board) by coating of a photosensitive resin composition, etc., and a predetermined The pattern is irradiated with actinic rays, thereby hardening the exposed portion. Furthermore, the unexposed portion is selectively removed using a developing solution, thereby forming a resist pattern as a cured film of the photosensitive resin composition on the substrate. Therefore, the photosensitive resin composition is required to have excellent sensitivity to actinic rays, excellent properties (resolution) that can form fine patterns, and the like. Therefore, photosensitive resin compositions containing novolak resins, epoxy resins, photoacid generators, etc. soluble in alkaline aqueous solutions, those containing an alkali-soluble epoxy compound having a carboxyl group, a photocationic polymerization initiator, etc. have been proposed. Photosensitive resin composition, etc. (for example, refer to Patent Document 1 to Patent Document 3).

Furthermore, as surface protection films and interlayer insulating films used in semiconductor elements, insulation reliability such as heat resistance, electrical characteristics, and mechanical characteristics is required. Therefore, a photosensitive resin composition containing the above-mentioned photosensitive resin composition and further containing a crosslinkable monomer has been proposed (for example, refer to Patent Document 4).

On the other hand, in recent years, with the increase in performance of electronic devices, the increase in the integration of semiconductor elements and the increase in reliability have progressed year by year. Along with the increased integration of semiconductor elements, the formation of finer patterns is required. Therefore, there is a continuing demand for the photosensitive resin composition to improve the resolution even in the unit of 1 μm.

In addition, it is necessary to provide a via (opening) for electrically connecting the upper and lower wiring layers in the interlayer insulating material of the printed wiring board. If the number of pins of a flip chip mounted on a printed wiring board increases, it is necessary to provide through holes corresponding to the number of pins.

In recent years, with the development of miniaturization of semiconductor devices, the number of pins has increased from tens of thousands of pins to hundreds of thousands of pins, and it is required that the number of pins of the semiconductor device also corresponds to the through holes formed in the interlayer insulating material of the printed wiring board To reduce the diameter of the through hole. Recently, the development of printed wiring boards using thermosetting resin materials and using lasers to provide through holes has progressed (for example, refer to Patent Document 5). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 06-059444 [Patent Document 2] Japanese Patent Laid-Open No. 09-087366 [Patent Document 3] International Publication No. 2008/010521 [Patent Document 4] Japanese Patent Laid-Open 2003 -215802 [Patent Document 5] Japanese Patent Laid-Open No. 2001-217543

[Problems to be Solved by the Invention] However, the previous method of manufacturing a multilayer printed wiring board has the following problems: the introduction of novel equipment such as lasers is required, and it is difficult to provide a through hole with a large diameter or a minute through hole with a diameter of 60 μm or less It is necessary to use the lasers separately according to the opening diameter of the through hole, and it is difficult to set a special shape. In addition, in the case of using lasers to form the through holes, since each through hole must be formed one by one, it takes time to provide a large number of fine through holes. Furthermore, there is also a problem that the resin residues remain around the opening of the through hole, so unless the residues are removed, the reliability of the obtained multilayer printed wiring board will decrease. For example, in Patent Document 5, the interlayer insulating film is irradiated with a carbon dioxide gas laser to form a through hole, but the resolution of 60 μm in diameter makes it difficult to further reduce the diameter of the through hole.

In addition, in a structure in which an electrode is laminated on an insulating film having an opening, a conductor portion arranged in the opening may be electrically connected to the electrode, and a resin pattern obtained by using a photosensitive resin composition may be used as an insulation Film. In this case, from the viewpoint of preventing disconnection of the electrodes disposed on the insulating film (improving connection reliability), the shape of the wall portion of the insulating film exposed at the opening is required to be tapered (preferably tapered) Angle (tilt angle) is small). 1 is a schematic view (cross-sectional view) of an insulating film having an opening, and is an enlarged view of a boundary portion of the insulating film 2 disposed on the substrate 1 between the opening and the wall of the insulating film exposed by the opening . The taper angle refers to the angle formed between the surface of the substrate 1 and the wall (pattern side) of the insulating film 2 exposed at the opening, and in FIG. 1 refers to the angle indicated by θ.

Furthermore, the photosensitive layer of the photosensitive element is peeled off the protective layer, and the photosensitive layer is bonded to the substrate using a laminator, and the support is peeled off and transferred onto the substrate. 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 to wrinkle the protective layer. If the protective layer is wrinkled, the wrinkle is transferred to the photosensitive layer, and this part cannot be used, so the productivity at the time of manufacturing is lowered. Therefore, from the viewpoint of productivity, there is a demand for fully bonding 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 provided with a photosensitive layer that can obtain a resin pattern with excellent resolution, a tapered opening, and excellent adhesion to a protective layer. In addition, an 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. [Means to solve the problem]

The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found a photosensitive element having excellent characteristics. That is, the photosensitive element of one embodiment of the present disclosure includes a photosensitive layer and a protective layer, the photosensitive layer containing: (A) component: a resin having a phenolic hydroxyl group; (B) component: a photo-sensitive acid generator; ( C) Component: a compound having at least one selected from the group consisting of aromatic rings, heterocycles, and alicyclic rings, and having at least one of hydroxymethyl and alkoxyalkyl; and (D) component: having Two or more functional groups selected from the group consisting of acryloxy, methacryloxy, glycidoxy, oxetanyl alkyl ether, vinyl ether and hydroxyl The aliphatic compound, in the photosensitive layer, with respect to 100 parts by mass of the (A) component, the content of the (C) component is 20 parts by mass or less, and with respect to 100 parts by mass of the (A) component, the The total content of the components (C) and (D) is 65 parts by mass to 120 parts by mass.

The photosensitive element preferably further includes a support, and sequentially includes the support, the photosensitive layer, and the protective layer.

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

In addition, the present disclosure provides a semiconductor device including the cured product of the photosensitive layer in the photosensitive element.

Furthermore, the present disclosure provides a method for forming a resist pattern, which includes: a step of disposing the photosensitive layer of the photosensitive element on a substrate; a step of exposing the photosensitive layer into a predetermined pattern; The step of developing the photosensitive layer to obtain a resin pattern; and the step of performing heat treatment on the resin pattern. [Effect of invention]

According to the present disclosure, it is possible to provide a photosensitive element provided with a photosensitive layer which can obtain a resin pattern having excellent resolution, a tapered opening, and excellent adhesion to a protective layer. In addition, the present disclosure can provide a semiconductor device using a photosensitive layer and a method for forming a resist pattern using the photosensitive layer.

Hereinafter, an embodiment of the present disclosure will be specifically described, but the present disclosure is not limited thereto. In the following embodiments, the constituent elements (including the element steps, etc.) are not necessarily necessary except when specifically indicated and when it is considered that the principle must be clear. The situation is the same for the numerical value and the range, which should be interpreted as not unduly limiting the present disclosure.

In this specification, the terms "layer" and "film" include a structure formed on a part of the shape in addition to the structure formed on the entire surface when viewed in a plan view. The term "step" is not only an independent step. When it cannot be clearly distinguished from other steps, as long as the purpose required by the step is achieved, it is included in this term. The so-called "Ethylene Oxide (EO) modification" refers to a compound with (poly) oxyethylene group, and the so-called "Propylene Oxide (PO) modification" refers to having (poly) oxypropylene group compound of. Here, the "(poly) oxyethylene group" means at least one kind of polyoxyethylene group in which an oxyethylene group and two or more vinyl groups are connected by an ether bond. The "(poly) oxypropylene group" means at least one kind of polyoxypropylene group in which an oxypropylene group and two or more propylene groups are connected by an ether bond. The term "Si-O bond" means a bond between a silicon atom and an oxygen atom, and may also be part of a siloxane bond (Si-O-Si bond). The numerical range indicated by "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. In the numerical range described in stages in this specification, the upper limit value or the lower limit value of the numerical range of a certain stage may be replaced with the upper limit value or the lower limit value of the numerical range of another stage. In addition, in the numerical range 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. The term "A or B" may include any one of A and B, and may include both. Unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more. With regard to the content of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, it means the total amount of the plurality of substances present in the composition.

[Photosensitive resin composition] The photosensitive layer of this embodiment can be formed using the photosensitive resin composition described below, for example. The photosensitive resin composition used in the formation of the photosensitive layer of this embodiment contains: (A) component: a resin having a phenolic hydroxyl group; (B) component: a photosensitive acid generator; (C) component: A compound having at least one of the group consisting of an aromatic ring, a heterocyclic ring, and an alicyclic ring and having at least one of hydroxymethyl and alkoxyalkyl; and (D) component: having two or more selected from propylene amide An aliphatic compound of one or more functional groups in the group consisting of an oxy group, a methacryl oxy group, a glycidoxy group, an oxetanyl alkyl ether group, a vinyl ether group, and a hydroxyl group. In addition, in this specification, these components may be simply referred to as (A) component, (B) component, (C) component, and the like.

The reason why the photosensitive layer of the present embodiment can achieve excellent resolution and obtain a tapered resin pattern when obtaining a resin pattern having openings is considered as follows by the present inventors. In the unexposed part, the solubility of the component (A) in the developing solution is improved by the addition of the component (C). Next, in the exposed part, by the catalyst effect of the acid generated by the component (B), the methylol groups or the alkoxyalkyl groups in the component (C) or the methylol groups in the component (C) The group or the alkoxyalkyl group reacts with the component (A) along with the dealcoholization, whereby the solubility of the composition in the developer is greatly reduced. Thereby, at the time of development, sufficient resolution can be obtained by the significant difference in the solubility of the unexposed portion and the exposed portion in the developer. When the content of the component (C) relative to the component (A) is within a specific range, a part of the exposed portion is melted by subsequent heating, and a resin pattern having a tapered shape can be formed. Furthermore, by heating, a cured film can be obtained while maintaining a tapered shape.

The photosensitive resin composition of this embodiment may optionally contain (E) component: benzophenone compound, (F) component: solvent, (G) component: compound containing Si-O bond, (H) component: sensitizing Agent.

<(A) component> The photosensitive resin composition of this embodiment contains the resin which has a phenolic hydroxyl group. The resin having a phenolic hydroxyl group is not particularly limited, but it is preferably a resin soluble in an alkaline aqueous solution, and from the viewpoint of further improving the resolution, a novolak resin is more preferable. The novolak resin is obtained, for example, by condensing phenols and aldehydes in the presence of a catalyst.

Examples of 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, pyrogallic acid, α-naphthol, β-naphthol, etc. The phenols can be used alone or in combination of two or more.

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

As the novolak resin, for example, cresol novolak 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. Resin etc.

Examples of the (A) component other than the novolak resin include hydroxystyrene homopolymer or copolymer, phenol-benzenedimethanol condensation resin, cresol-benzenedimethanol condensation resin, and phenol-dicyclopentadiene condensation Resin etc.

(A) One component may be used alone or two or more types may be used in combination.

From the viewpoints of more excellent resolution, developability, thermal shock resistance, heat resistance, etc. of the obtained resin pattern (cured film), the weight average molecular weight of the component (A) may also be 100,000 or less, 1,000 to 80000, and 2000 to 50000, 2000 ～ 20000, 3000 ～ 15000 or 5000 ～ 15000.

In the present embodiment, the weight average molecular weight of each component can be measured by gel permeation chromatography (GPC) using the calibration curve of standard polystyrene under the following conditions, for example. Machine used: Hitachi L-6000 (manufactured by Hitachi, Ltd.) Column: Gel-Pak GL-R420 + Gel-Pak GL-R430 + Gel-Pak GL-R440 (manufactured by Hitachi Chemical Co., Ltd., trade name, 3 in total) Column specifications: 10.7 mmf × 300 mm Dissolution solution: Tetrahydrofuran Measurement temperature: 40 ° C Flow rate: 1.75 ml / min Detector: L-3300RI (manufactured by Hitachi, Ltd.)

From the viewpoint that the photosensitive layer formed using the photosensitive resin composition tends to be more excellent in the developability of the alkaline aqueous solution, the content of the (A) component is the total amount of the photosensitive resin composition (where F) In the case of a component, except (F) component as a reference, 10 mass%-90 mass%, 30 mass%-90 mass%, 30 mass%-80 mass%, 40 mass%-80 mass % Or 40% by mass to 60% by mass.

<(B) component> The photosensitive resin composition of this embodiment contains a photosensitive acid generator. The light-sensitive acid generator is a compound that generates an acid by irradiation with actinic rays or the like. By the catalyst effect of the acid generated from the light-sensitive acid generator, the methylol groups or alkoxyalkyl groups in (C) component or the methylol groups or alkoxy groups in (C) component The alkyl group and the (A) component react with the dealcoholization, whereby the solubility of the composition in the developer is greatly reduced, and a negative pattern can be formed.

(B) The component is not particularly limited as long as it is a compound that generates an acid by irradiation with actinic rays or the like. Examples of the component (B) include onium salt compounds, halogen-containing compounds, diazo ketone compounds, sulfone compounds, sulfonic acid compounds, sulfonylimide compounds, and diazomethane compounds. Among them, from the viewpoint of excellent availability, the component (B) is preferably at least one selected from the group consisting of onium salt compounds and sulfonylimide compounds. Especially in the case of using a solvent, the component (B) is preferably an onium salt compound from the viewpoint of excellent solubility in the solvent.

Examples of the onium salt compound include iodonium salt, osmium salt, phosphonium salt, diazonium salt, and pyridine salt. Specific examples of preferred onium salt compounds include diphenyliodotrifluoromethanesulfonate, diphenyliodononafluorobutanesulfonate, diphenyliodoheptadecafluorooctanesulfonate, Diphenyl iodine p-toluenesulfonate, diphenyl iodine hexafluoroantimonate, diphenyl iodine hexafluorophosphate, diphenyl iodine tris (pentafluoroethyl) trifluorophosphate, diphenyl iodide tetra Fluoroborate, diphenyl iodine tetrakis (pentafluorophenyl) borate, diphenyl iodide tri [(trifluoromethyl) sulfonyl] methanide and other diaryl iodonium salts; triaryl sulfonium salts, etc. Among them, from the viewpoint of further improving sensitivity and thermal stability, a samium salt is preferable, and from the viewpoint of further improving thermal stability, a triaryl samium salt is more preferable. One type of onium salt compound may be used alone or two or more types may be used in combination.

Examples of the triaryl alkoxide salt as component (B) include the following alkoxide salts selected from the group consisting of a compound represented by the following general formula (b1), a compound represented by the following general formula (b2), and the following At least one cation in the group consisting of the compound represented by the general formula (b3) and the compound represented by the following general formula (b4); and having a carbon number of 1-20 selected from the tetraphenylborate skeleton Alkylsulfonate skeleton, phenylsulfonate skeleton, 10-camphorsulfonate skeleton, trialkylsulfonyl methanate skeleton with 1 to 20 carbon atoms, tetrafluoroborate skeleton, hexafluoroantimonate Anion of at least one skeleton in the group consisting of a salt skeleton and a hexafluorophosphate skeleton.

[Chemical 1]

[Chem 2]

[Chemical 3]

[Chemical 4]

The hydrogen atom of the phenyl group of general formula (b1), general formula (b2), general formula (b3) and general formula (b4) may also be selected from the group consisting of hydroxyl group, alkyl group having 1 to 12 carbons, and carbon number 1 -12 alkoxy groups, C 2-12 alkyl carbonyl groups and C 2-12 alkoxy carbonyl groups at least one type of substitution, multiple substituents may be the same as each other It can be different.

The hydrogen atom of the phenyl group of the tetraphenylborate skeleton can be 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 hydroxy group, an alkyl group having 1 to 12 carbon atoms, and a carbon number of 1 -12 alkoxy groups, C 2-12 alkyl carbonyl groups and C 2-12 alkoxy carbonyl groups at least one type of substitution, multiple substituents may be the same as each other It can be different.

The hydrogen atom of the alkylsulfonate skeleton may be selected from the group consisting of fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, alkoxy group, alkylcarbonyl group and alkoxycarbonyl group At least one type of substitution may be the same or different when there are multiple substituents.

The hydrogen atom of the phenyl group of the phenylsulfonate skeleton may be -12 alkoxy groups, C 2-12 alkyl carbonyl groups and C 2-12 alkoxy carbonyl groups at least one type of substitution, multiple substituents may be the same as each other It can be different.

The hydrogen atom of the trialkylsulfonyl methanide skeleton may be selected from the group consisting of fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, alkoxy group, alkylcarbonyl group and alkoxycarbonyl group At least one substitution in the group of, when there are multiple substituents, they may be the same as or different from each other.

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, and the substituent is When there are many, they may be the same as or different from each other.

From the viewpoint of more excellent sensitivity, resolution, and insulation, the samium salt used as the component (B) preferably has a group selected from [4- (4-biphenylthio) phenyl] -4-linked Phenylphenyl alkene, (2-methyl) phenyl [4- (4-biphenylthio) phenyl] 4-biphenyl alkane, [4- (4-biphenylthio) -3 -Methylphenyl] 4-biphenylphenyl alkane, (2-ethoxy) phenyl [4- (4-biphenylthio) -3-ethoxyphenyl] 4-biphenyl At least one compound in the group consisting of cerium and tris [4- (4-acetylphenylthio) phenyl] cerium as a cation.

The samium salt used as the component (B) preferably has a compound selected from the group consisting of trifluoromethanesulfonate, nonafluorobutanesulfonate, hexafluoroantimonate, and tri [(trifluoromethyl) sulfonyl] methane At least one compound selected from the group consisting of compounds, 10-camphorsulfonate, tris (pentafluoroethyl) trifluorophosphate, and tetra (pentafluorophenyl) borate as anions.

As a specific example of the salicylate salt, (2-ethoxy) phenyl [4- (4-biphenylthio) -3-ethoxyphenyl] 4-biphenylaluminum nonafluorobutane Sulfonates, [4- (4-biphenylthio) phenyl] -4-biphenylphenylammonium tetrakis (pentafluorophenyl) borate, tris [4- (4-acetylphenylthio Group) phenyl] arylene tetrakis (pentafluorophenyl) borate, etc. Manganese salt can be used alone or in combination of two or more.

Specific examples of the sulfonylimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-di Formamide, N- (trifluoromethylsulfonyloxy) naphthaleneimide, N- (p-toluenesulfonyloxy) -1,8-naphthaleneimide, N- (10-camphorsulfonamide Oxy) -1,8-naphthalamide and the like. The sulfonylimide compound may be used alone or in combination of two or more.

(B) One component may be used alone or two or more components may be used in combination.

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

<(C) component> The photosensitive resin composition of this embodiment contains at least one selected from the group consisting of aromatic ring, heterocyclic ring, and alicyclic ring, and is selected from the group consisting of hydroxymethyl and alkoxyalkyl. At least one compound in the group of (C) component (which does not include (D) component, (E1) component and (E2) component). 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, an oxygen atom, a sulfur atom (for example, a cyclic group having 3 to 10 carbon atoms), and examples thereof include a pyridine ring, an imidazole ring, and pyrrolidine. Ketone ring, oxazolidinone ring, imidazolidinone ring and pyrimidinone ring. The alicyclic ring means a cyclic hydrocarbon group having no aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), and examples thereof include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and cyclohexane. ring. The alkoxyalkyl group refers to a group in which an alkyl group is bonded to an alkyl group via an oxygen atom (a group in which one hydrogen of the 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 (C) component, when exposure is performed (or heat treatment and hardening are performed after exposure and exposure), the hydroxymethyl groups or alkoxyalkyl groups in (C) component, Alternatively, the hydroxymethyl group or alkoxyalkyl group in the component (C) reacts with the component (A) along with the dealcoholization, whereby the solubility of the composition in the developer is greatly reduced, and a negative pattern can be formed. In addition, when the photosensitive layer after the formation of the resin pattern is heated and hardened, the component (C) and the component (A) react to form a cross-linked structure, which can prevent the resin pattern from becoming fragile and melted.

The component (C) is specifically preferably selected from a compound having a phenolic hydroxyl group (wherein (A) component is not included), a compound having a hydroxymethylamino group and a compound having an alkoxymethylamine group At least one of the group formed. When the compound having a phenolic hydroxyl group has a hydroxymethyl group or an alkoxyalkyl group, it is possible to further increase the dissolution rate of the unexposed portion when developing in an alkaline aqueous solution, and further improve the sensitivity of the photosensitive layer. (C) One component may be used alone or two or more components may be used in combination.

As the compound having a phenolic hydroxyl group, a previously known compound can be used, but from the viewpoint of excellent balance between the dissolution promoting effect of the unexposed portion and the effect of preventing melting when the photosensitive layer is hardened, the following general The compound represented by formula (1).

[Chem 5]

In the 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 each independently represent a monovalent organic group , A and b independently represent integers of 1 to 3, and c and d independently represent integers of 0 to 3. Here, examples of the monovalent organic group include alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, and propyl; alkenyl groups having 2 to 10 carbon atoms such as vinyl; and phenyl. Aryl groups having 6 to 30 carbon atoms; groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms. 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).

[化 6]

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

In addition, as the compound having the phenolic hydroxyl group, a compound represented by the following general formula (3) can also be used.

[化 7]

In the general formula (3), each of the plurality of R independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). The plurality of Rs may be the same as or different from each other.

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

[Chem 8]

In the general formula (4), X represents a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylene group (for example, an alkylene group having 2 to 10 carbon atoms) , A part or all of these hydrogen atoms are substituted with a halogen atom, a sulfonyl group, a carbonyl group, an ether bond, a thioether bond, or an amide bond. 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 halogenated alkyl 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 halogenated alkyl group refers to an alkyl group substituted with a halogen atom.

As the compound having an alkoxymethylamine group, specifically, it is preferably 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) At least one.

[化 9]

In the general formula (5), each of R independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). The plurality of Rs may be the same as or different from each other.

[化 10]

In the above general formula (6), each of R independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). The plurality of Rs may be the same as or different from each other.

Examples of the compound having a hydroxymethylamine group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, and (poly) (N-hydroxymethyl) Benzoguanamine, (poly) (N-hydroxymethyl) urea, etc. Examples of the compound having an alkoxymethylamine group include nitrogen-containing compounds in which all or part of the hydroxymethyl groups of the compound having a hydroxymethylamine group are etherified with an alkyl group. Here, as the alkyl group of the alkyl ether, a methyl group, an ethyl group, a butyl group, or a mixture of these groups may be mentioned, and an oligomer component partially condensed may be contained. Specific examples of the compound having an alkoxymethylamine group include hexa (methoxymethyl) melamine, hexa (butoxymethyl) melamine, tetra (methoxymethyl) glycoluril, tetra (Butoxymethyl) glycoluril, tetra (methoxymethyl) urea, etc.

The content of the component (C) is 20 parts by mass or less with respect to 100 parts by mass of the component (A). If the component (C) is included, the exposed portion is likely to react sufficiently, and therefore the resolution tends not to decrease easily. If the content of the component (C) is 20 parts by mass or less, there is a tendency for a tapered resin pattern to be easily formed. From these viewpoints, the content of the component (C) is preferably more than 0 parts by mass and 18 parts by mass or less, more preferably 1 part by mass to 15 parts by mass, and still more preferably 3 parts by mass to 11 parts by mass.

<(D) component> The photosensitive resin composition of this embodiment contains two or more members selected from the group consisting of acryloxy, methacryloxy, glycidoxy, oxetanyl alkyl ether groups, An aliphatic compound having at least one functional group in the group consisting of a vinyl ether group and a hydroxyl group is used as the component (D). Furthermore, the component (D) may have at least one different two or more kinds of functional groups, or may have two or more kinds of one kind of functional groups. The compound is preferably an aliphatic compound having three or more functional groups. The upper limit of the number of the functional groups is not particularly limited, for example, 12. In addition, the "aliphatic compound" refers to a compound whose 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 forming a photosensitive resin composition layer (photosensitive layer) on a substrate, the photosensitive resin composition may also require excellent adhesion (viscosity) to the substrate. When a photosensitive resin composition that does not have sufficient viscosity is used, the photosensitive resin composition of the exposed portion is easily removed by development processing, and there is adhesion between the substrate and the resin pattern (resist pattern) The tendency to get worse. In the present embodiment, since the photosensitive resin composition contains the component (D), there is a tendency that the adhesiveness (ie, viscosity) of the photosensitive resin composition and the substrate increases. Furthermore, by containing the component (D), the photosensitive resin composition can impart flexibility to the photosensitive layer (coating film), and the dissolution rate of the unexposed portion during development with an alkaline aqueous solution increases, and there is analysis of the resin pattern The tendency to improve sex. From the viewpoint of more excellent viscosity and solubility in an alkaline aqueous 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, when it is difficult to measure the compound with a low molecular weight by the weight average molecular weight measurement method, the molecular weight may be measured by other methods to calculate the average.

Examples of the component (D) include compounds represented by the following general formula (7), general formula (8), general formula (9), and general formula (10). In the following general formula (7), general formula (8), general formula (9), general formula (10), general formula (11), general formula (12) and general formula (13), as oxygen heterocycle Examples of the alkyl group in the butyl alkyl ether group include a methyl group, an ethyl group, a propyl group, and the like, and a methyl group is preferred.

[Chem 11]

In the 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 each independently represent an acryloxy group , Methacryloyloxy, glycidoxy, oxetanyl alkyl ether group, vinyl ether group, hydroxyl group, the group represented by the following general formula (12) or the following general formula (13) Represented base.

[化 12]

In the 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 each independently represent an acryloxy , Methacryloyloxy, glycidoxy, oxetanyl alkyl ether group, vinyl ether group, hydroxyl group, the group represented by the following general formula (12) or the following general formula (13) Represented base.

[Chem 13]

In the general formula (9), R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent acryloxy, methacryloxy, glycidoxy, oxetane An alkyl 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).

[化 14]

In the general formula (10), R ¹⁵ , R ¹⁷ , R ¹⁸ and R ²⁰ independently represent acryloxy, methacryloxy, glycidoxy, oxetanyl alkyl ether groups , Vinyl ether group, hydroxyl group, the group represented by the following general formula (12) or the group represented by the following general formula (13), R ¹⁶ and R ¹⁹ independently represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group Or a group represented by the following general formula (11).

[化 15]

In the general formula (11), R ²¹ represents acryloxy, methacryloxy, glycidoxy, oxetanyl alkyl ether group, vinyl ether group or hydroxyl group.

[Chem 16]

In the general formula (12), R ²² represents acryloxy, methacryloxy, glycidoxy, oxetanyl alkyl ether group, vinyl ether group or hydroxyl group, n is 1-10 Integer.

[化 17]

In the general formula (13), R ²³ represents acryloxy, methacryloxy, glycidoxy, oxetanyl alkyl ether group, vinyl ether group or hydroxyl group, and m is 1 to 1 An integer of 10.

As the component (D), specifically, from the viewpoint of further improvement in sensitivity and resolution, it is preferable to have a member selected from the group consisting of acryloxy, methacryloxy, glycidoxy, and oxetane The compound of at least one of the group consisting of an alkyl alkyl ether group and a vinyl ether group is more preferably a compound having two or more glycidyloxy groups or two or more acryloxy groups, and more preferably three or more A compound of glycidyloxy or three or more acryloxy groups. (D) One component may be used alone or two or more components may be used in combination.

As component (D), a compound selected from the group consisting of a compound having an acryloxy group, a compound having a methacryloxy group, a compound having a glycidyloxy group, a compound having an oxetanyl alkyl ether group, At least one of the group consisting of a compound having a vinyl ether group and a compound having a hydroxyl group. The component (D) is preferably a compound having at least one group selected from the group consisting of acryloxy, methacryloxy and glycidoxy, which improves the insulation reliability of fine wiring From a viewpoint, a compound having at least one group selected from the group consisting of acryloxy and methacryloxy is more preferable. From the viewpoint of more excellent developability, the component (D) is preferably an aliphatic compound having two or more glycidoxy groups, more preferably an aliphatic compound having three or more glycidoxy groups, and further preferably It is an aliphatic compound having a weight average molecular weight of 1,000 or less and having three or more glycidyloxy groups.

Examples of the compound having an acrylic oxy group include: EO modified dipentaerythritol hexaacrylate, PO modified dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, EO modified di-trimethylolpropane tetraacrylate , PO modified di-trimethylolpropane tetraacrylate, di-trimethylolpropane 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 trimethylolpropane acrylate, trimethylolpropane acrylate, EO modified Quality glycerin triacrylate, PO modified glycerin triacrylate, glycerin triacrylate, etc. The compound having an acrylic oxy 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 di- Trimethylolpropane tetramethacrylate, PO modified di-trimethylolpropane tetramethacrylate, di-trimethylolpropane tetramethacrylate, EO modified pentaerythritol tetramethacrylate, PO modified pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, EO modified pentaerythritol trimethacrylate, PO modified pentaerythritol trimethacrylate, pentaerythritol trimethacrylate, EO modified trimethylol Propane methacrylate, PO modified trimethylolpropane methacrylate, trimethylolpropane methacrylate, EO modified glycerol trimethacrylate, PO modified glycerol trimethacrylate, Glycerin trimethacrylate, etc. The compound having a methacryloyloxy group may be used alone or in combination of two or more.

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, and neopentyl glycol diglycidyl ether. Ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, Trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerol triglycidyl ether, glycerol propoxylate triglycidyl ether, 1,4-cyclohexane dimethanol diglycidyl ether, Diglycidyl-1,2-cyclohexane dicarboxylic acid ester and so on. The compound having a glycidyloxy group can be used alone or in combination of two or more.

The compound having a glycidyloxy group is particularly preferably selected from the group consisting of dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane At least one of the group consisting of triglycidyl ether, glycerin polyglycidyl ether, and glycerin triglycidyl ether.

The compound having a glycidyloxy group can be used as, for example, Epolight 40E, Epolight 100E, Epolight 70P, Epolight 200P, Epolight 1500NP, Epolight 1600, Epolight 80MF, Epolight 100MF (the above is manufactured by Kyoeisha Chemical Co., Ltd., trade name), alkyl epoxy resin ZX-1542 (new Nippon Steel & Sumitomo Chemical Co., Ltd., trade name), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Danacole (Denacol) EX-321L and Denacol EX-850L (above are manufactured by Nagase chemtex Co., Ltd., trade name, and "Denacol" is a registered trademark). Obtained commercially.

Examples of the compound having an oxetanyl alkyl ether group include a compound having a 3-alkyl-3-oxetanyl alkyl ether group, preferably 3-ethyl-3- Oxycyclobutane alkyl ether group compounds. Examples of the oxetane compound include dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether and pentaerythritol tetra (3-ethyl-3-oxetane Methyl) ether, pentaerythritol tris (3-ethyl-3-oxetanyl methyl) ether, trimethylolethane tris (3-ethyl-3-oxetanyl methyl ) Ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, glycerin poly (3-ethyl-3-oxetanylmethyl) ether , Glycerin tris (3-ethyl-3-oxetanylmethyl) ether, etc. The compound having an oxetanyl alkyl ether group may be used alone or in combination of two or more.

Examples of the compound having a hydroxyl group include polyhydric alcohols such as dipentaerythritol, pentaerythritol, and glycerin. The compound having a hydroxyl group may be used alone or in combination of two or more.

In the component (D), from the viewpoint of more excellent sensitivity and resolution, it is preferably selected from the group consisting of trimethylolethane triglycidyl ether and trimethylolpropane triglycidyl ether At least one.

(D) The component can be used as an alkyl epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name ZX-1542), an alkyl acrylic resin (manufactured by Nippon Chemical Co., Ltd., trade name PET-30) Wait for it to be obtained commercially.

(D) The content of a component is 65 mass parts-120 mass parts of total content of (C) component and (D) component with respect to 100 mass parts of (A) component. If the total content of the component (C) and the component (D) is 65 parts by mass or more, there is a tendency for the photosensitive layer formed of the photosensitive resin composition and the protective layer to be easily attached, and if it is 120 parts by mass or less, there is The photosensitive layer formed from the photosensitive resin composition is easily formed (for example, formed into a film) on the required support, and the resolution tends not to deteriorate. From these viewpoints, the total content of the component (C) and the component (D) is preferably more than 65 parts by mass and 110 parts by mass or less, more preferably 68 parts by mass to 100 parts by mass, and still more preferably 70 parts by mass ~ 90 parts by mass.

<(E) component> The photosensitive resin composition of this embodiment may contain a benzophenone compound as (E) component. By containing a benzophenone compound, the resolution of the photosensitive resin composition can be improved. In addition, by containing the (E) component, the margin of the exposure amount capable of forming a fine resist pattern can be increased, and the productivity can be further improved. 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-dihydroxy Benzophenone, 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'-dimethoxybenzophenone, 2,2'-dihydroxy-4 , 4'-diethoxybenzophenone, 2,2'-dihydroxy-4,4'-dibutoxybenzophenone, 4,4'-dihydroxybenzophenone, 4,4 '-Dimethoxybenzophenone, 4,4'-dibutoxybenzophenone, 4,4'-diphenylbenzophenone, etc.

In the component (E), in terms of more excellent resolution, it is preferable to have one or more selected from the group consisting of an amine group, a dimethylamino group, a diethylamino group, a dibutylamino group, a hydroxyl group, and a methoxy group The benzophenone compound of the group consisting of a group, an ethoxy group, a butoxy group and a phenyl group preferably has two or more selected from the group consisting of an amine group, a dimethylamino group and a diethylamino group , Dibutylamine group, hydroxyl group, methoxy group, ethoxy group, butoxy group and phenyl group of benzophenone compounds, and more preferably having two or more diethylamine groups Or hydroxybenzophenone compounds, particularly preferred are 4,4'-bis (dimethylamino) benzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone. (E) One component may be used alone or two or more components may be used in combination.

(E) The content of the component is preferably 0.001 to 10 parts by mass relative to 100 parts by mass of the (A) component, more preferably 0.01 to 1 part by mass, further preferably 0.01 to 0.8 part by mass, particularly preferably It is 0.05 to 0.1 parts by mass. If the content of the (E) component is in the range of 0.001 parts by mass to 10 parts by mass, the resolution of the photosensitive resin composition can be improved, and the margin of the exposure amount capable of forming a fine resist pattern can be increased, further Improve productivity.

By including the (E) component, the resolution is further improved, and it becomes easy to form, for example, a fine resist pattern, that is, a fine resist pattern with a via opening diameter of 20 (unit: μm) or less. Moreover, for example, when forming a fine resist pattern with a through-hole opening diameter of 20 (unit: μm) or less, it is necessary to adjust the exposure amount appropriately, but by including the (E) component, a fine resist can be formed The width of the exposure amount of the etchant pattern becomes wider to increase the margin of exposure (allowable range). Therefore, when manufacturing a mass product, etc., it is not necessary to finely adjust the exposure amount in order to form a fine resist pattern, and productivity is improved.

<(F) component> In order to improve the handleability of a photosensitive resin composition or to adjust viscosity and storage stability, the photosensitive resin composition of this embodiment may further contain a solvent as (F) component. (F) The component is preferably an organic solvent. The organic solvent is not particularly limited as long as it can exert the above-mentioned properties, and examples thereof include ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate. ; Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and other propylene glycol monoalkyl ethers; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether and other propylene glycol dialkyl ethers ; Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc. Propylene glycol monoalkyl ether acetate; ethyl cellosolve, butyl cellosolve Cellosolve; carbitol such as butyl carbitol; lactate such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate , N-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate and other aliphatic carboxylic acid esters; 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl ester, methyl pyruvate, ethyl pyruvate and other esters; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone (alias 2-butanone), 2-heptanone, 3-heptanone, 4-heptanone Ketones such as ketones and cyclohexanone; N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc .; -Lactones such as butyrolactone. (F) One component may be used alone or two or more components may be used in combination.

The content of the (F) component may be 30 parts by mass to 200 parts by mass relative to 100 parts by mass of the total amount of the photosensitive resin composition (excluding the (F) component when the (F) component is used) Or 40 parts by mass to 120 parts by mass.

<(G) component> The photosensitive resin composition of this embodiment may contain the compound which has Si-O bond (except the compound corresponding to (A) component-(F) component) as (G) component. 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 silicon dioxide (silica filler) and silane compounds (silane coupling agents, etc.). (G) One component may be used alone or two or more components may be used in combination.

Since the photosensitive resin composition of this embodiment contains an inorganic filler, the coefficient of thermal expansion of the resin pattern can be reduced. In the case where 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, sol-gel silica, and the like. In addition, by treating the inorganic filler with a silane compound, the inorganic filler may also have a Si-O bond. Among the inorganic fillers treated with silane compounds, examples of inorganic fillers other than silica include alumina, aluminum hydroxide, calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide, or Inorganic fillers derived from mineral products such as talc and mica.

The average primary particle diameter of the inorganic filler is preferably 100 nm or less, more preferably 80 nm or less, and from the viewpoint of more excellent sensitivity of the photosensitive layer, further preferably 50 nm or less. If the average primary particle size is 100 nm or less, the photosensitive resin composition hardly becomes cloudy, and light used for exposure easily transmits through the photosensitive layer. As a result, it is easy to remove the unexposed portion, so there is a tendency that the resolution of the resin pattern hardly decreases. Furthermore, the average primary particle size is a value obtained by converting from the specific surface area of Brunauer-Emmett-Teller (BET).

The thermal expansion coefficient of silicon dioxide is preferably 5.0 × 10 ⁻⁶ / ° C. or less. As the silica, from the viewpoint of easily obtaining a suitable particle size, fused spherical silica, fumed silica, sol-gel silica and other silica are preferred, and fumed is more preferred Silica or sol-gel silica. In addition, the silicon dioxide is preferably silicon dioxide (nanometer silicon dioxide) having an average primary particle size of 5 nm to 100 nm.

When measuring the particle size of the inorganic filler, a known particle size distribution meter can be used. Examples of the particle size distribution meter include: a laser diffraction scattering particle size distribution meter that irradiates a particle group with laser light, obtains a particle size distribution by calculation based on the intensity distribution pattern of diffracted light and scattered light emitted from the particle group; A frequency analysis by dynamic light scattering method is used to obtain a particle size distribution meter of nanoparticles with a particle size distribution.

Since 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. In the case of using a silane compound as the (G) component, 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, methacrylic silane, mercapto silane, sulfide silane, isocyanate silane, sulfur silane, Styrene silane, alkyl chlorosilane, etc.

The silane compound as the component (G) is preferably a compound represented by the following general formula (14). (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 methyl, ethyl, and propyl, R ¹⁰² represents a monovalent organic group, and f represents an integer of 0 to 3. When f is 0, 1, or 2, a 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. From the viewpoint of more excellent resolution, R ^{101 is} preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. In the case of treating with a silane compound (a compound represented by the general formula (14), etc.) 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 , More preferably 0 to 1.

Specific examples of the silane compound as the component (G) include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, and methyltribenzene Oxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyl Triethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, Phenyltrimethoxysilane, diphenyldimethoxysilane, triphenylsilanol, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-phenylaminopropyl Trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- Glycidoxypropylmethyl diethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide Ether, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3-methacrylonitrile Propylpropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxy Silane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylene) -3-aminopropyltriethoxy Silane, etc. (G) The component is preferably an epoxy silane having one or more glycidyloxy groups, and more preferably an epoxy silane having at least one selected from the group consisting of trimethoxysilane and triethoxysilane .

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

<(H) component> The photosensitive resin composition of this embodiment may further contain a sensitizer as (H) component. By containing the (H) component in the photosensitive resin composition, the sensitivity of the photosensitive resin composition can be further improved. Examples of the sensitizer include 9,10-dibutoxyanthracene. (H) One component may be used alone or two or more components may be used in combination.

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

<Other Components> The photosensitive resin composition of this embodiment may contain a phenolic low-molecular compound having a molecular weight of less than 1,000 (hereinafter, referred to as "phenol compound (a)") in addition to the component (A). As the phenol compound (a), 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylmethane, tris (4-hydroxyphenyl) methane, 1,1-bis ( 4-hydroxyphenyl) -1-phenylethane, tri (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, etc. The content of these phenol compounds (a) is, for example, in the range of 0 to 40 parts by mass (particularly 0 to 30 parts by mass) relative to 100 parts by mass of the component (A).

Moreover, the photosensitive resin composition of this embodiment may contain components other than the above-mentioned components. Examples of other components include colorants, adhesion aids, leveling agents, and inorganic fillers that do not contain Si-O bonds. The inorganic filler is not particularly limited, and examples thereof include aluminum compounds such as aluminum oxide and aluminum hydroxide; alkali metal compounds; alkaline earths such as calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, and magnesium hydroxide Metalloid compounds; inorganic compounds derived from mineral products, etc. These compounds can be crushed by a pulverizer, classified according to the situation, and 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 of the inorganic fillers is preferably dispersed with a maximum particle diameter of 2 μm or less when dispersed in the photosensitive resin composition. At this time, in order to disperse it in the resin without aggregation, a silane coupling agent may be used. The content of the inorganic filler is based on the total amount of the photosensitive resin composition (excluding the (F) component when the (F) component is used), and is preferably 1% by mass to 70% by mass, more preferably It is 3% by mass to 65% by mass.

[Photosensitive Element] Next, the photosensitive element of this embodiment will be described with reference to FIG. 2. 2 is a schematic cross-sectional view of the photosensitive element 10 of 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 may be formed of the photosensitive resin composition. The photosensitive element 10 can be used in the manufacturing method of the semiconductor device of this embodiment, for example, a circuit substrate. 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 μm to 100 μm. In addition, regarding the polymer film, one of them may be used as a support 4 and the other as a protective layer 6, and stacked on both sides of the photosensitive layer 5.

As the protective layer 6, 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 protective layer 6 is preferably 5 μm to 100 μm.

The photosensitive layer 5 can be formed by applying the photosensitive resin composition on the support 4 or the protective layer 6 and drying 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. The thickness of the photosensitive layer 5 varies depending on the application, and after drying is preferably 1 μm to 100 μm, more preferably 3 μm to 60 μm, further preferably 5 μm to 60 μm, particularly preferably 5 μm to 40 μm. It is preferably 5 μm to 25 μm. In addition, from the viewpoint of excellent insulation reliability (insulation between wirings in the thickness direction of the layer, etc.) and productivity when mounting a wafer, the thickness of the photosensitive layer 5 is preferably more than 20 μm, but may also be 20 μm the following.

[Method of forming resist pattern] The method of forming a resist pattern of this embodiment includes the steps of arranging a photosensitive layer of the photosensitive element on a substrate (photosensitive layer preparation step); exposing the photosensitive layer The step of forming a predetermined pattern; the step of developing the exposed photosensitive layer to obtain a resin pattern; and the step of heating the resin pattern.

The method for forming a resist pattern of this embodiment may further include a step of subjecting the photosensitive layer to heat treatment (post-exposure baking) between the exposure step and the development step. In this case, the method for forming a resist pattern of this embodiment includes the steps of arranging a photosensitive layer of a photosensitive element on a substrate; exposing the photosensitive layer into a predetermined pattern; and exposing the exposed photosensitive layer A step of performing post-exposure heat treatment (post-exposure baking); a step of developing the photosensitive layer after the heat treatment (post-exposure baking) to obtain a resin pattern; and a step of subjecting the resulting resin pattern to heat treatment.

In the method for forming a resist pattern of this embodiment, for example, the photosensitive layer is first formed on the substrate on which the resist pattern is to be formed. The step of forming the photosensitive layer can be performed by arranging the photosensitive layer of the photosensitive element on the substrate, for example. The photosensitive layer preparation step may also be referred to as a step of obtaining a substrate (eg, substrate) provided with a photosensitive layer. The formation of the photosensitive layer can be performed by, for example, transferring (laminating) the photosensitive layer in the photosensitive element onto the substrate.

Examples of the base material include substrates. As the base material, for example, copper foil with resin, copper-clad laminate, silicon wafer with metal sputtering film, silicon wafer with copper plating film, aluminum oxide substrate, or the like can be used. The surface on the substrate on which the photosensitive layer is formed may be a hardened resin layer formed using a photosensitive resin composition. In this case, the adhesion to the base material tends to be improved.

Furthermore, the photosensitive layer preparation step may be a step of coating the photosensitive resin composition on a base material (for example, a substrate) and drying the photosensitive resin composition to form a photosensitive layer. Examples of the method for forming the photosensitive layer include a method of coating (eg, coating) the photosensitive resin composition on a substrate, drying, and evaporating a solvent or the like to form a photosensitive layer (coating film).

As a method of coating the photosensitive resin composition on a substrate, for example, coating methods such as a dipping method, a spray method, a bar coating method, a roll coating method, and a spin coating method can be used. The thickness of the coating film can be appropriately controlled by adjusting the solid concentration and viscosity of the coating mechanism and the photosensitive resin composition.

Next, the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern. Examples of actinic rays used in exposure include light using a g-ray stepper as a light source; low-pressure mercury lamps, high-pressure mercury lamps, metal halogen lamps, and ultraviolet rays using an i-ray stepper as a light source; electron beams; Light, etc. The exposure amount is appropriately selected according to 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, when the thickness of the photosensitive layer is 5 μm to 50 μm, the exposure amount may be about 100 mJ / cm ² to 3000 mJ / cm ² .

Furthermore, heat treatment (post-exposure baking) may be performed after exposure and before development. By performing post-exposure baking, the hardening reaction of the component (A) and the component (C) caused by the acid generated from the light-sensitive acid generator can be promoted. The conditions of baking after exposure vary depending on the composition of the photosensitive resin composition, the content of each component, the thickness of the photosensitive layer, etc., for example, it is preferably heated at 50 ° C to 150 ° C for 1 minute to 60 minutes, more preferably 60 ° C to Heat at 100 ° C for 1 to 15 minutes. In addition, it may be heated at 70 ° C to 150 ° C for 1 minute to 60 minutes, or at 80 ° C to 120 ° C for 1 minute to 60 minutes.

Then, the exposed and / or post-exposure baked photosensitive layer (coating film) is developed with an alkaline developer to dissolve and remove the unexposed area (the area other than the hardened area), thereby obtaining the desired Resist pattern. Examples of the development method in this case include a shower development method, a spray development method, a immersion development method, and a coating solution development method. As the development conditions, for example, in the spray development method, it is 10 seconds to 300 seconds at 20 ° C to 40 ° C.

Examples of the alkaline developing solution include: dissolving alkaline compounds such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and choline in water so that the concentration reaches 1% by mass to 10% by mass. The obtained alkaline aqueous solution; ammonia water and so on. For example, an appropriate amount of water-soluble organic solvents such as methanol and ethanol, surfactants, etc. may be added to the alkaline developer. In addition, after developing with this alkaline developer, it was washed with water and dried. From the viewpoint of more excellent resolution, the alkaline developer is preferably tetramethylammonium hydroxide.

Furthermore, heat treatment is performed in order to exhibit the characteristics of the insulating film, thereby obtaining a cured film (resist pattern) of the photosensitive layer. The curing conditions of the photosensitive layer are not particularly limited, and can be adjusted according to the application of the cured product. For example, heating at 50 ° C to 250 ° C for 30 minutes to 10 hours can harden the photosensitive layer.

In addition, in order to sufficiently cure and / or prevent deformation of the resulting resin pattern, heating may be performed in two stages. For example, it may be heated at 50 ° C to 120 ° C for 5 minutes to 2 hours in the first stage, and further heated at 80 ° C to 200 ° C for 10 minutes to 10 hours in the second stage to harden it. In the case of performing heat treatment under the above-mentioned curing conditions, the heating equipment is not particularly limited, and a general oven, infrared oven, 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 °.

<Cured 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 the 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 of 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.

FIGS. 3 (a) to (f) are diagrams showing a method of manufacturing a multilayer printed wiring board including the cured product of the photosensitive layer of the present embodiment as a solder resist and / or an interlayer insulating film. The multilayer printed wiring board 100A shown in (f) of FIG. 3 has wiring patterns 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, etc., and suitably 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 based on (a) to (f) of FIG. 3.

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

Then, an opening 104 is formed using a yttrium aluminum garnet (YAG) laser or a carbon dioxide gas laser at a position where electrical connection to the outside is required (see FIG. 3 (b)). The plastic residue (residue) around the opening 104 is removed by the plastic residue removal process.

Then, the seed layer 105 is formed by an electroless plating method (see (c) of FIG. 3). A photosensitive layer containing a photosensitive resin composition (a photosensitive resin composition for semi-addition) is formed on the seed layer 105, and exposure and development processing are performed at predetermined positions to form a resin pattern 106 (see FIG. 3 ( d)).

Then, 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 after removing the resin pattern 106 with a stripping solution, the wiring pattern 107 where the seed layer 105 is not formed is etched Part of the removal (see (e) of Figure 3).

By repeating the above operation, the solder resist 108 containing the cured product of the photosensitive resin composition is formed on the outermost surface, whereby a multilayer printed wiring board 100A can be produced (see FIG. 3 (f)). In addition, the interlayer insulating film 103 and / or the solder resist 108 can be formed using the method of forming the resist pattern. In addition, it can be formed by a method including a step of forming a photosensitive layer and a step of performing heat treatment. The multilayer printed wiring board 100A thus obtained is mounted with semiconductor elements at corresponding positions, which can ensure electrical connection. [Example]

Hereinafter, the purpose and advantages of the present disclosure will be described in detail through the embodiments, but the present disclosure is not limited by these embodiments.

[Examples 1 to 3 and Comparative Examples 1 to 4] <Preparation of photosensitive resin composition> Based on 100 parts by mass of the resin components (A-1 and A-2), the formulation shown in Table 1 Amount (unit: parts by mass) of light-sensitive acid generator (B-1), alkoxyalkyl compound (C-1), compound with acryloxy group (D-1), benzophenone compound (E-1), a solvent (F-1) and a compound (G-1) having a Si—O bond to obtain a photosensitive resin composition.

In addition, the abbreviation of Table 1 is as follows. A-1: Novolak resin (manufactured by Asahi Organic Materials Co., Ltd., trade name: TR4020G, weight average molecular weight: 13000) A-2: Novolak resin (manufactured by Asahi Organic Materials Co., Ltd., trade name: TR4080G, weight average Molecular weight: 5000) B-1: Triaryl alkane salt (made by San-apro Co., Ltd., trade name: CPI-310B, anion: tetrakis (pentafluorophenyl) borate) C-1: 1, 3,4,6-Tetra (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: NIKALAC MX-270) D-1: pentaerythritol triacrylate (Japanese chemical Co., Ltd., trade name: PET-30) E-1: 4,4'-bis (diethylamino) benzophenone (manufactured by Hodogaya Chemical Industry 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 Industry Co., Ltd., Product name: KBM-403)

<Preparation of photosensitive element> The photosensitive resin composition is applied to a polyethylene terephthalate film (made by Teijin Dupont Film Co., Ltd., commercial product) so that the thickness of the photosensitive resin composition is uniform. Name: Purex (Purex A53), and then dried with a 90 ° C hot air convection dryer for 10 minutes, thereby forming a photosensitive layer with a thickness of 10 μm after drying. A polyethylene film (manufactured by Tamapoly Co., Ltd., product name: NF-15) is laminated on the photosensitive layer as a protective layer, and polyethylene terephthalate films laminated in sequence are obtained respectively (Support), photosensitive element of photosensitive layer and protective layer.

<Evaluation of the adhesion of the protective layer> Observe the appearance of the photosensitive element, and set the photosensitive layer and the protective layer to be fully bonded without any gap as "A", and let air enter between the photosensitive layer and the protective layer to If a part or the entire surface is not bonded, it is set to "B", and the adhesion of the protective layer is evaluated. Table 1 shows the evaluation results.

<Evaluation of Analysability and Cone Shape> On the copper-clad laminate, while peeling off the protective layer of the photosensitive element, the photosensitive element was laminated so that the photosensitive layer was in contact with the surface of the copper-clad laminate, And the laminate is obtained. Lamination is performed using a vacuum press laminator (made by Mingji Manufacturing Co., Ltd., trade name: MVLP-500), with a heater at 60 ° C (upper), a heater at 60 ° C (lower), for 20 seconds The evacuation time, the pressurization time of 20 seconds, and the crimping pressure of 0.4 MPa were performed. Then, the support of the laminated body was peeled off, and a projection exposure machine (manufactured by Niuwei Electric Co., Ltd., trade name: UX-2240SM-XJ-0) was used, and the photosensitive layer was shielded by i-ray (365 nm) through the mask Perform equal-exposure projection exposure. As the mask, a negative pattern having a through hole opening (unexposed portion) at a 5 μm scale until the through hole diameter is 5 μm to 100 μm is used. In addition, exposure was performed at an exposure amount of 400 mJ / cm ² .

The exposed photosensitive layer (coating film) was heated at 95 ° C. for 8 minutes (baking after exposure). Then, a 2.38% by mass tetramethylammonium hydroxide aqueous solution (made by Tama Chemical Industry Co., Ltd., trade name: TMAH 2.38%) was used as a developing solution, and a developing machine (made by Takizawa Industry Co., Ltd., trade name: AD) was used -1200) Spray the photosensitive layer (pump discharge pressure [developer]: 0.16 MPa) at 23 ° C with a time equivalent to 4 times the shortest development time (the shortest time to remove the unexposed part) to remove the unexposed part . Then, as the eluent, spray (pump discharge pressure [eluent]: 0.12 MPa to 0.14 MPa) purified water at 23 ° C. (made by Wako Pure Chemical Industries, Ltd., trade name: purified water) for 60 seconds, and develop Wash away. Moreover, a resin pattern is formed by drying it. Then, using an inert oven (manufactured by Koyo Thermo Systems Co., Ltd., trade name: INH-21CD), under a nitrogen flow (oxygen concentration of 20 ppm or less), the temperature was raised from 30 ° C at 5 ° C / min, After reaching 200 ° C, heat treatment was performed for 1 hour to produce a cured film. Use a metal microscope to magnify to a magnification of 1,000 times and observe the resin pattern formed. In the pattern formed when the via opening (unexposed portion) is cleanly removed and the insulating resin portion (exposed portion) does not cause film reduction or roughness, the diameter of the smallest via opening is used as an analysis Evaluation. In addition, the cross section of the through-hole opening of the obtained cured film was observed at an acceleration voltage of 5 kV and an inclination of 80 ° using a scanning electron microscope (manufactured by Keyencec Corporation, trade name: VE-8800), and the taper angle was measured. . Table 1 shows the evaluation results.

[Table 1]

As is clear from Table 1, 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 of Examples 1 to 3 is 70 ° or less, and that of the component (C) Compared with Comparative Example 1 having a content of 20 parts by mass or more, the opening of the through hole is improved to be tapered. The total content of (C) component and (D) component is 65 mass parts-120 mass parts with respect to 100 mass parts of (A) component, Examples 1 to 3, and (C) component and (D) component Compared with Comparative Examples 2 to 4 in which the total content is less than 65 parts by mass, the adhesion of the protective layer is improved from B to A. In addition, it can be seen that the resolution of Examples 1 to 3 is 20 μm, and the resolution is extremely good.

Fig. 4, Fig. 5, Fig. 6, Fig. 7, Fig. 8, Fig. 9 and Fig. 10 are respectively the use of Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example A scanning electron microscope photograph of the photosensitive element of 4 when a through hole opening is formed in the same manner as the evaluation of the tapered shape. According to these photographs, if the photosensitive elements of Examples 1 to 3 are used, an opening having a tapered wall portion is formed. [Industry availability]

The photosensitive layer in the photosensitive element of the present disclosure can be applied as a material that can be used as a surface protection film or an interlayer insulating film of a semiconductor element, for example. In addition, the photosensitive layer can also be applied as a solder resist for a wiring board material or a material usable in an interlayer insulating film. In particular, regarding the photosensitive layer in the photosensitive element of the present disclosure, the resolution, the shape of the opening of the through hole (taper shape), and the adhesion between the photosensitive layer and the protective layer are all good, and therefore it can be preferably used for fine lines High-density packaging substrates for high-density and high-density packaging.

1‧‧‧ substrate

2‧‧‧Insulation film

4‧‧‧Support

5‧‧‧Photosensitive layer

6‧‧‧Protection layer

10‧‧‧Photosensitive element

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

θ‧‧‧Cone angle

FIG. 1 is a schematic view of an insulating film having openings. 2 is a schematic cross-sectional view of the photosensitive element of this embodiment. FIGS. 3 (a) to (f) are schematic diagrams showing the method of manufacturing the multilayer printed wiring board of this embodiment. 4 is a scanning electron microscope photograph of a through-hole shape formed using the photosensitive element of Example 1. FIG. 5 is a scanning electron microscope photograph of a through hole formed using the photosensitive element of Example 2. FIG. 6 is a scanning electron microscope photograph of a through hole formed using the photosensitive element of Example 3. FIG. 7 is a scanning electron microscope photograph of a through-hole shape formed using the photosensitive element of Comparative Example 1. FIG. FIG. 8 is a scanning electron microscope photograph of a through-hole shape formed using the photosensitive element of Comparative Example 2. FIG. 9 is a scanning electron microscope photograph of a through-hole shape formed using the photosensitive element of Comparative Example 3. FIG. FIG. 10 is a scanning electron microscope photograph of a through-hole shape formed using the photosensitive element of Comparative Example 4. FIG.

Claims (5)

A photosensitive element comprising a photosensitive layer and a protective layer, the photosensitive layer containing: (A) component: a resin having a phenolic hydroxyl group; (B) component: a light-sensitive acid generator; (C) component: having optional A compound having at least one of the group consisting of a free aromatic ring, a heterocyclic ring and an alicyclic ring and having at least one of hydroxymethyl and alkoxyalkyl; and (D) component: having two or more selected from propylene An aliphatic compound of one or more functional groups in the group consisting of acetyloxy, methacryloyloxy, glycidoxy, oxetanyl alkyl ether group, vinyl ether group and hydroxyl group, In the photosensitive layer, with respect to 100 parts by mass of the (A) component, the content of the (C) component is 20 parts by mass or less, and with respect to 100 parts by mass of the (A) component, the (C) component and (D) The total content of the components is 65 parts by mass to 120 parts by mass. The photosensitive element according to item 1 of the patent application scope further includes a support, and the support, the photosensitive layer, and the protective layer are sequentially provided. The photosensitive element according to item 1 or 2 of the patent application range, wherein the photosensitive layer further contains (G) component: a compound having a Si—O bond. A semiconductor device including the cured product of the photosensitive layer in the photosensitive element according to any one of the first to third patent application ranges. A method for forming a resist pattern, comprising: a step of arranging the photosensitive layer of the photosensitive element according to any one of claims 1 to 3 on a substrate; The step of exposing the layer into a predetermined pattern; the step of developing the exposed photosensitive layer to obtain a resin pattern; and the step of subjecting the resin pattern to heat treatment.