Photosensitive resin composition, photosensitive element, semiconductor device, and method for forming resist pattern

Abstract

To provide a photosensitive resin composition capable of reducing a dielectric loss tangent.SOLUTION: The photosensitive resin composition according to the present disclosure contains: (A) a base resin containing a phenolic resin; (B) a crosslinking agent having at least one selected from the group consisting of a methylol group and an alkoxyalkyl group; (C) a dissolution accelerator; (D) a photoacid generator; and (G) a blocked isocyanate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a photosensitive element, a semiconductor device, and a method for forming a resist pattern. [Background technology]

[0002] In the manufacture of semiconductor devices or printed wiring boards, for example, negative-type photosensitive resin compositions are used to form fine patterns. In this method, a photosensitive layer is formed on a substrate (e.g., a chip in the case of a semiconductor device, or a substrate in the case of a printed wiring board) by coating the photosensitive resin composition, and the exposed areas are cured by irradiating the exposed areas with actinic rays through a predetermined pattern. Furthermore, a resist pattern, which is a cured product of the photosensitive resin composition, is formed on the substrate by selectively removing the unexposed areas using a developer. Known photosensitive resin compositions include photosensitive resin compositions containing a novolac resin, an epoxy resin, and a photoacid generator; photosensitive resin compositions containing an alkali-soluble epoxy compound having a carboxy group and a photocationic polymerization initiator; and photosensitive resin compositions containing a polyimide precursor (e.g., Patent Documents 1 to 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 09-087366 [Patent Document 2] International Publication No. 2008 / 010521 [Patent Document 3] Patent Publication No. 2021-196482 Summary of the Invention [Problem to be solved by the invention]

[0004] In semiconductor packages having a rewiring layer, as wiring becomes finer and denser, the photosensitive material used in the rewiring layer is required to have a low dielectric constant, and in particular, a low dielectric loss tangent. One aspect of the present disclosure aims to provide a photosensitive resin composition that can reduce the dielectric loss tangent. Another aspect of the present disclosure aims to provide a photosensitive element and a semiconductor device obtained using the photosensitive resin composition, and a method for forming a resist pattern using the photosensitive resin composition. [Means for solving the problem]

[0005] One aspect of the present disclosure relates to the following photosensitive resin composition, photosensitive element, semiconductor device, and method for forming a resist pattern. [1] A photosensitive resin composition comprising: (A) a base resin containing a phenolic resin; (B) a crosslinking agent having at least one selected from the group consisting of a methylol group and an alkoxyalkyl group; (C) a dissolution promoter; (D) a photoacid generator; and (G) a blocked isocyanate. [2] The photosensitive resin composition according to [1] above, wherein the blocked isocyanate has a block structure derived from at least one blocking agent selected from the group consisting of imidazole compounds, pyrazole compounds, lactam compounds, oxime compounds, alcohol compounds, and diester compounds. [3] The photosensitive resin composition according to the above [1] or [2], wherein the photoacid generator contains an onium salt compound. [4] The photosensitive resin composition according to any one of the above [1] to [3], wherein the dissolution promoter comprises at least one selected from the group consisting of a compound having a glycidyl ether group, a compound having an oxetanyl alkyl ether group, a compound having a vinyl ether group, a compound having an acryloyloxy group, a compound having a methacryloyloxy group, and a polyhydric alcohol compound. [5] A photosensitive element comprising a support and a photosensitive layer provided on the support, wherein the photosensitive layer contains the photosensitive resin composition according to any one of [1] to [4] above. [6] A semiconductor device comprising a cured product of the photosensitive resin composition according to any one of [1] to [4] above. [7] A method for forming a resist pattern, comprising the steps of: applying the photosensitive resin composition according to any one of [1] to [4] above onto a substrate; drying the photosensitive resin composition to form a photosensitive layer; exposing the photosensitive layer to a predetermined pattern and subjecting it to a post-exposure heat treatment; and developing the photosensitive layer after the heat treatment and subjecting the resulting resin pattern to a heat treatment. [8] A method for forming a resist pattern, comprising the steps of: placing the photosensitive layer of the photosensitive element described in [5] above on a substrate; exposing the photosensitive layer to a predetermined pattern and performing a post-exposure heat treatment; and developing the photosensitive layer after the heat treatment and heat treating the resulting resin pattern. [Effects of the Invention]

[0006] According to one aspect of the present disclosure, a photosensitive resin composition capable of reducing the dielectric loss tangent can be provided. According to another aspect of the present disclosure, a photosensitive element including a photosensitive layer containing the photosensitive resin composition can be provided. According to yet another aspect of the present disclosure, a method for producing a resist pattern using the above-described photosensitive resin composition or the above-described photosensitive element can be provided. [Brief explanation of the drawings]

[0007] [Figure 1] 1A to 1C are schematic diagrams illustrating an example of a method for manufacturing a multilayer printed wiring board. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present disclosure will be described in detail below. However, the present disclosure is not limited to the following embodiments. In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved. In this specification, the term "layer" includes a structure having a shape formed on the entire surface as well as a structure having a shape formed on a portion thereof when observed in a plan view.

[0009] In this specification, a numerical range indicated with "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. Furthermore, in the numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range may be replaced with the upper or lower limit of another numerical range. In the numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with a value shown in the Examples. When referring to the amount of each component in a composition in this specification, if multiple substances corresponding to each component are present in the composition, this refers to the total amount of those multiple substances present in the composition, unless otherwise specified. In this specification, the term "solid content" refers to the non-volatile content of a photosensitive resin composition excluding volatile substances such as water and solvents, and includes components that are liquid, syrup-like, or waxy at room temperature (around 25°C).

[0010] [Photosensitive resin composition] A photosensitive resin composition according to one embodiment contains (A) a base resin containing a phenolic resin (hereinafter sometimes referred to as "component (A)"); (B) a crosslinking agent having at least one selected from the group consisting of a methylol group and an alkoxyalkyl group (hereinafter sometimes referred to as "component (B)"); (C) a dissolution promoter (hereinafter sometimes referred to as "component (C)"); (D) a photoacid generator (hereinafter sometimes referred to as "component (D)"); and (G) a blocked isocyanate (hereinafter sometimes referred to as "component (G)"). The photosensitive resin composition according to this embodiment can be used as a negative-tone photosensitive resin composition. Each component contained in the photosensitive resin composition will be described in detail below.

[0011] (base resin) The photosensitive resin composition according to this embodiment contains a phenolic resin as component (A), which can improve the elongation of the cured product (cured film) of the photosensitive resin composition. Phenolic resins are polycondensation products of phenol or its derivatives with aldehydes. Polycondensation is usually carried out in the presence of a catalyst such as an acid or a base. Phenolic resins obtained using an acid catalyst are particularly called novolac-type phenolic resins. Component (A) can be used alone or in combination of two or more types.

[0012] Examples of novolac type phenolic resins include phenol / formaldehyde novolac resin, cresol / formaldehyde novolac resin, xylenol / formaldehyde novolac resin, resorcinol / formaldehyde novolac resin, and phenol-naphthol / formaldehyde novolac resin.

[0013] Examples of phenol derivatives constituting the phenolic resin include alkylphenols such as 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, and 3,4,5-trimethylphenol; alkoxyphenols such as methoxyphenol and 2-methoxy-4-methylphenol; alkenylphenols such as vinylphenol and allylphenol; aralkylphenols such as benzylphenol; alkoxycarbonylphenols such as methoxycarbonylphenol; arylcarbonylphenols such as benzoyloxyphenol; and halogenated phenols such as chlorophenol. Examples of suitable phenols include phenols; polyhydroxybenzenes such as catechol, resorcinol, and pyrogallol; bisphenols such as bisphenol A and bisphenol F; naphthol derivatives such as α-naphthol and β-naphthol; hydroxyalkylphenols such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol, and p-hydroxyphenyl-4-butanol; hydroxyalkyl cresols such as hydroxyethyl cresol; alcoholic hydroxyl group-containing phenol derivatives such as monoethylene oxide adducts of bisphenol and monopropylene oxide adducts of bisphenol; and carboxyl group-containing phenol derivatives such as p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylbutanoic acid, p-hydroxycinnamic acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxybenzoic acid, and diphenolic acid. These may be used alone or in combination of two or more.

[0014] Examples of aldehydes that constitute phenolic resins include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, glyceraldehyde, glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formylacetate, 2-formylpropionic acid, and methyl 2-formylpropionate. These may be used alone or in combination of two or more. Furthermore, formaldehyde precursors such as paraformaldehyde and trioxane, and ketone compounds such as acetone, pyruvic acid, levulinic acid, 4-acetylbutyric acid, acetonedicarboxylic acid, and 3,3'-4,4'-benzophenonetetracarboxylic acid may also be used in the reaction.

[0015] From the viewpoint of increasing the elongation of the cured film, the component (A) preferably contains a novolac phenolic resin having structural units based on m-cresol and structural units based on p-cresol, or the component (A) may be composed solely of a novolac phenolic resin.

[0016] Considering the balance between solubility in an alkaline aqueous solution, photosensitive properties, and mechanical properties of the cured film, the weight-average molecular weight (Mw) of component (A) may be 2,000 to 30,000, 4,000 to 20,000, or 6,000 to 15,000. In this specification, Mw is a value obtained by measuring by gel permeation chromatography (GPC) and converting from a standard polystyrene calibration curve.

[0017] (Crosslinking agent) The photosensitive resin composition according to this embodiment contains, as component (B), a crosslinking agent having at least one group selected from the group consisting of a methylol group and an alkoxyalkyl group. The crosslinking agent (component (B)) is a compound having a group capable of reacting with component (A) to form a bridged structure (crosslinked structure) when the resin film after pattern formation is heated and cured. This prevents the resin film from becoming brittle and melting.

[0018] When the photosensitive resin composition contains component (B), upon exposure and subsequent heat treatment to cure, the methylol groups in component (B) react with each other, or the alkoxyalkyl groups in component (B) react with each other, or the methylol groups or alkoxyalkyl groups in component (B) react with component (A), accompanied by dealcoholization, thereby significantly reducing the solubility of the composition in a developer and enabling the formation of a negative pattern. Component (B) can be used alone or in combination of two or more.

[0019] Component (B) may be a compound having an alkoxymethylamino group, such as hexakis(methoxymethyl)melamine, hexakis(butoxymethyl)melamine, tetrakis(methoxymethyl)glycoluril, tetrakis(butoxymethyl)glycoluril, and tetrakis(methoxymethyl)urea.

[0020] The content of component (B) may be 5 to 80 parts by mass, 10 to 70 parts by mass, 15 to 60 parts by mass, or 20 to 50 parts by mass, relative to 100 parts by mass of component (A). When the content of component (B) is 5 parts by mass or more, chemical resistance and heat resistance tend to be good, and when it is 80 parts by mass or less, resolution tends to be even better.

[0021] (solubility enhancer) By incorporating a dissolution promoter as component (C) into the photosensitive resin composition, the dissolution rate of the unexposed area during development with an alkaline aqueous solution can be increased. Conventionally known dissolution promoters can be used.

[0022] Examples of component (C) include compounds having a glycidyl ether group, compounds having an oxetanyl alkyl ether group, compounds having a vinyl ether group, compounds having an acryloyloxy group, compounds having a methacryloyloxy group, and polyhydric alcohol compounds. Component (C) can be used alone or in combination of two or more.

[0023] Examples of compounds having a glycidyl ether group include dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, and glycerin triglycidyl ether.

[0024] The compound having an oxetanyl alkyl ether group can be exemplified by a compound having a 3-alkyl-3-oxetanyl alkyl ether group, and a compound having a 3-ethyl-3-oxetanyl alkyl ether group is preferred. 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, trimethylolethane tris (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.

[0025] 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, ditrimethylolpropane 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 glycerin triacrylate, PO-modified glycerin triacrylate, and glycerin triacrylate.

[0026] Examples of compounds having a methacryloyloxy group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO-modified ditrimethylolpropane tetramethacrylate, PO-modified ditrimethylolpropane tetramethacrylate, ditrimethylolpropane 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 methacrylate, trimethylolpropane methacrylate, EO-modified glycerin trimethacrylate, PO-modified glycerin trimethacrylate, and glycerin trimethacrylate.

[0027] Examples of polyhydric alcohol compounds include dipentaerythritol, pentaerythritol, and glycerin.

[0028] Of the components (C), trimethylolethane triglycidyl ether and trimethylolpropane triglycidyl ether are preferred because they provide even better sensitivity and resolution.

[0029] The content of component (C) may be 10 to 70 parts by mass, 20 to 70 parts by mass, 25 to 65 parts by mass, or 30 to 50 parts by mass, relative to 100 parts by mass of component (A). When the content of component (C) is 10 parts by mass or more, flexibility is easily imparted to the coating film and the dissolution rate of the unexposed areas during development with an alkaline aqueous solution is easily increased, while when the content is 70 parts by mass or less, it is easy to form a film from the photosensitive resin composition on a desired support.

[0030] (Photoacid generator) The photoacid generator, component (D), is a compound that generates an acid when irradiated with actinic rays, etc. The action of the acid generated from the photoacid generator upon absorption of light selectively increases the solubility in an alkaline aqueous solution of the irradiated portion of the photosensitive layer.

[0031] Examples of photoacid generators include onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds. Of these, from the viewpoint of improving resolution and pattern shape, it is preferable that component (D) contains an onium salt compound. Examples of onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts. Component (D) can be used alone or in combination of two or more.

[0032] Among the onium salt compounds, sulfonium salts are preferred from the viewpoint of further improving sensitivity and thermal stability, and triarylsulfonium salts are more preferred from the viewpoint of further improving thermal stability.

[0033] Examples of triarylsulfonium salts include [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium trifluoromethanesulfonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium nonafluorobutanesulfonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium heptadecafluorooctanesulfonate, and [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium p-toluenesulfonate. nate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium hexafluoroantimonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium hexafluorophosphate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tetrafluoroborate, [4-(4-biphenylyl (4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl)borate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris[(trifluoromethyl)sulfonyl]methanide, (2-methyl)phenyl[4-(4-biphenylylthio)phenyl]4-biphenylylsulfonium trifluoromethanesulfonate, (2-methyl)phenyl[4-(4-biphenylylthio)phenyl]4-biphenylylsulfonium nonafluorobutanesulfonate, (2 -methyl)phenyl[4-(4-biphenylylthio)phenyl]4-biphenylylsulfonium heptadecafluorooctanesulfonate, (2-methyl)phenyl[4-(4-biphenylylthio)phenyl]4-biphenylylsulfonium p-toluenesulfonate, (2-methyl)phenyl[4-(4-biphenylylthio)phenyl]4-biphenylylsulfonium hexafluoroantimonate, (2-methyl)phenyl[4-(4-biphenylylthio)phenyl]4-biphenylylsulfonium hexafluorophosphate,(2-methyl)phenyl[4-(4-biphenylylthio)phenyl]4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate, (2-methyl)phenyl[4-(4-biphenylylthio)phenyl]4-biphenylylsulfonium tetrafluoroborate, (2-methyl)phenyl[4-(4-biphenylylthio)phenyl]4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate, (2-methyl)phenyl[4-(4-biphenylylthio)phenyl]4-biphenylylsulfonium 4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylphenylsulfonium trifluoromethanesulfonate, [4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylphenylsulfonium nonafluorobutanesulfonate, [4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylphenylsulfonium heptadecafluorooctanesulfonate, [4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylphenylsulfonium heptadecafluorooctanesulfonate, [4-(4-biphenylylthio)-3-methylphenyl] 4-Biphenylylphenylsulfonium p-toluenesulfonate, [4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylphenylsulfonium hexafluoroantimonate, [4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylphenylsulfonium hexafluorophosphate, [4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, [4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylphenylsulfonium [4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl)borate, [4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylphenylsulfonium tris[(trifluoromethyl)sulfonyl]methanide, (2-methyl)phenyl[4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylsulfonium trifluoromethanesulfonate,(2-methyl)phenyl[4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylsulfonium nonafluorobutanesulfonate, (2-methyl)phenyl[4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylsulfonium heptadecafluorooctanesulfonate, (2-methyl)phenyl[4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylsulfonium p-toluenesulfonate, (2-methyl)phenyl[4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylsulfonium Phenylylsulfonium hexafluoroantimonate, (2-methyl)phenyl[4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylsulfonium hexafluorophosphate, (2-methyl)phenyl[4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate, (2-methyl)phenyl[4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylsulfonium tetrafluoroborate, (2-methyl)phenyl phenyl[4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate, (2-methyl)phenyl[4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylsulfonium tris[(trifluoromethyl)sulfonyl]methanide, (2-methoxy)phenyl[4-(4-biphenylylthio)-3-methoxyphenyl]4-biphenylylsulfonium trifluoromethanesulfonate, (2-methoxy)phenyl[4-(4-biphenylylthio)-3-methoxyphenyl]4-biphenylylsulfonium tris[(trifluoromethyl)sulfonyl]methanide (2-methoxy)phenyl[4-(4-biphenylylthio)-3-methoxyphenyl]4-biphenylylsulfonium nonafluorobutanesulfonate, (2-methoxy)phenyl[4-(4-biphenylylthio)-3-methoxyphenyl]4-biphenylylsulfonium heptadecafluorooctanesulfonate, (2-methoxy)phenyl[4-(4-biphenylylthio)-3-methoxyphenyl]4-biphenylylsulfonium p-toluenesulfonate, (2-methoxy)phenyl[4-(4-biphenylylthio)-3-methoxyphenyl]4-biphenylylsulfonium hexafluoroantimonate,(2-Methoxy)phenyl[4-(4-biphenylylthio)-3-methoxyphenyl]4-biphenylylsulfonium hexafluorophosphate, (2-Methoxy)phenyl[4-(4-biphenylylthio)-3-methoxyphenyl]4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate, (2-Methoxy)phenyl[4-(4-biphenylylthio)-3-methoxyphenyl]4-biphenylylsulfonium tetrafluoroborate, (2-Methoxy)phenyl[4-(4- (2-ethoxy)phenyl[4-(4-biphenylylthio)-3-methoxyphenyl]4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate, (2-methoxy)phenyl[4-(4-biphenylylthio)-3-methoxyphenyl]4-biphenylylsulfonium tris[(trifluoromethyl)sulfonyl]methanide, (2-ethoxy)phenyl[4-(4-biphenylylthio)-3-ethoxyphenyl]4-biphenylylsulfonium trifluoromethanesulfonate, (2-ethoxy)phenyl[4-(4-biphenylylthio)-3-ethoxyphenyl]4-biphenylylsulfonium )-3-ethoxyphenyl]4-biphenylylsulfonium nonafluorobutanesulfonate, (2-ethoxy)phenyl[4-(4-biphenylylthio)-3-ethoxyphenyl]4-biphenylylsulfonium heptadecafluorooctanesulfonate, (2-ethoxy)phenyl[4-(4-biphenylylthio)-3-ethoxyphenyl]4-biphenylylsulfonium p-toluenesulfonate, (2-ethoxy)phenyl[4-(4-biphenylylthio)-3-ethoxyphenyl]4-biphenylylsulfonium phenyl hexafluoroantimonate, (2-ethoxy)phenyl[4-(4-biphenylylthio)-3-ethoxyphenyl]4-biphenylylsulfonium hexafluorophosphate, (2-ethoxy)phenyl[4-(4-biphenylylthio)-3-ethoxyphenyl]4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate, (2-ethoxy)phenyl[4-(4-biphenylylthio)-3-ethoxyphenyl]4-biphenylylsulfonium tetrafluoroborate,(2-ethoxy)phenyl[4-(4-biphenylylthio)-3-ethoxyphenyl]4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate, (2-ethoxy)phenyl[4-(4-biphenylylthio)-3-ethoxyphenyl]4-biphenylylsulfonium tris[(trifluoromethyl)sulfonyl]methanide, (2-butoxy)phenyl[4-(4-biphenylylthio)-3-butoxyphenyl]4-biphenylylsulfonium trifluoromethanesulfonate, (2-butoxy)phenyl[4-(4- (2-Butoxy)phenyl[4-(4-biphenylylthio)-3-butoxyphenyl]4-biphenylylsulfonium nonafluorobutanesulfonate, (2-Butoxy)phenyl[4-(4-biphenylylthio)-3-butoxyphenyl]4-biphenylylsulfonium heptadecafluorooctanesulfonate, (2-Butoxy)phenyl[4-(4-biphenylylthio)-3-butoxyphenyl]4-biphenylylsulfonium p-toluenesulfonate, (2-Butoxy)phenyl[4-(4-biphenylylthio)-3-butoxyphenyl]4-biphenylylsulfonium Hexafluoroantimonate, (2-butoxy)phenyl[4-(4-biphenylylthio)-3-butoxyphenyl]4-biphenylylsulfonium hexafluorophosphate, (2-butoxy)phenyl[4-(4-biphenylylthio)-3-butoxyphenyl]4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate, (2-butoxy)phenyl[4-(4-biphenylylthio)-3-butoxyphenyl]4-biphenylylsulfonium tetrafluoroborate, (2-butoxy)phenyl[4 -(4-biphenylylthio)-3-butoxyphenyl]4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate, (2-butoxy)phenyl[4-(4-biphenylylthio)-3-butoxyphenyl]4-biphenylylsulfonium tris[(trifluoromethyl)sulfonyl]methanide, tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium trifluoromethanesulfonate, tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium nonafluorobutanesulfonate,Tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium heptadecafluorooctanesulfonate, tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium p-toluenesulfonate, tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium hexafluoroantimonate, tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium hexafluorophosphate, tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate, tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium tetrafluoroborate, tris[4-(4-acetylphenylsulfanyl, )phenyl]sulfonium tetrakis(pentafluorophenyl)borate, tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium tris[(trifluoromethyl)sulfonyl]methanide, tris[4-(4-acetyl-3-methylphenylthio)phenyl]sulfonium trifluoromethanesulfonate, tris[4-(4-acetyl-3-methylphenylthio)phenyl]sulfonium nonafluorobutanesulfonate, tris[4-(4-acetyl-3-methylphenylthio)phenyl]sulfonium heptane Tadecafluorooctanesulfonate, tris[4-(4-acetyl-3-methylphenylthio)phenyl]sulfonium p-toluenesulfonate, tris[4-(4-acetyl-3-methylphenylthio)phenyl]sulfonium hexafluoroantimonate, tris[4-(4-acetyl-3-methylphenylthio)phenyl]sulfonium hexafluorophosphate, tris[4-(4-acetyl-3-methylphenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate, tris[4 -(4-acetyl-3-methylphenylthio)phenyl]sulfonium tetrafluoroborate, tris[4-(4-acetyl-3-methylphenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, tris[4-(4-acetyl-3-methylphenylthio)phenyl]sulfonium tris[(trifluoromethyl)sulfonyl]methanide, tris[4-(4-acetyl-3-ethylphenylthio)phenyl]sulfonium trifluoromethanesulfonate, tris[4-(4-acetyl-3-ethylphenylthio)phenyl]sulfonium tris[4-(4-acetyl-3-ethylphenylthio)phenyl]sulfonium nonafluorobutanesulfonate, tris[4-(4-acetyl-3-ethylphenylthio)phenyl]sulfonium heptadecafluorooctanesulfonate, tris[4-(4-acetyl-3-ethylphenylthio)phenyl]sulfonium p-toluenesulfonate, tris[4-(4-acetyl-3-ethylphenylthio)phenyl]sulfonium hexafluoroantimonate, tris[4-(4-acetyl-3-ethylphenylthio)phenyl]sulfonium hexafluorophosphate,Tris[4-(4-acetyl-3-ethylphenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate, tris[4-(4-acetyl-3-ethylphenylthio)phenyl]sulfonium tetrafluoroborate, tris[4-(4-acetyl-3-ethylphenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, tris[4-(4-acetyl-3-ethylphenylthio)phenyl]sulfonium tris[(trifluoromethyl)sulfonyl]methanide, tris[4-(4-acetyl-3-butylphenylthio)phenyl]sulfonium trifluoromethanesulfonate, tris[4-(4-acetyl-3-butylphenylthio)phenyl]sulfonium nonafluorobutanesulfonate, tris[4-(4-acetyl-3-butylphenylthio)phenyl]sulfonium heptadecafluorooctanesulfonate , tris[4-(4-acetyl-3-butylphenylthio)phenyl]sulfonium p-toluenesulfonate, tris[4-(4-acetyl-3-butylphenylthio)phenyl]sulfonium hexafluoroantimonate, tris[4-(4-acetyl-3-butylphenylthio)phenyl]sulfonium hexafluorophosphate, tris[4-(4-acetyl-3-butylphenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate, tris[4-(4-acetyl-3-butylphenylthio)phenyl]sulfonium tetrafluoroborate, tris[4-(4-acetyl-3-butylphenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, and tris[4-(4-acetyl-3-butylphenylthio)phenyl]sulfonium tris[(trifluoromethyl)sulfonyl]methanide.

[0034] The onium salt compound may be a compound having trifluoromethanesulfonate, nonafluorobutanesulfonate, hexafluoroantimonate, hexafluorophosphate, tetrafluoroborate, tris(pentafluoroethyl)trifluorophosphate, or tetrakis(pentafluorophenyl)borate, in terms of being even more excellent in sensitivity and resolution.

[0035] The content of the component (D) may be 0.1 to 15 parts by mass, 1 to 15 parts by mass, 2 to 12 parts by mass, or 3 to 10 parts by mass per 100 parts by mass of the component (A), from the viewpoints of the sensitivity, resolution, pattern formability, and the like of the photosensitive resin composition.

[0036] (Blocked isocyanate) The blocked isocyanate (component (G)) functions as a latent curing agent for component (A), thereby reducing the dielectric dissipation factor of the cured film. Blocked isocyanates are compounds in which the isocyanate groups of an isocyanate compound are protected with a blocking agent. When the blocked polyisocyanate is heated to a temperature at which the blocking agent dissociates, the isocyanate groups are regenerated. The isocyanate groups can react with phenolic hydroxyl groups derived from component (A) and alcoholic hydroxyl groups generated from component (C) to form urethane bonds. This reduces the number of hydroxyl groups remaining in the cured film, thereby reducing the dielectric dissipation factor. Component (G) can be used alone or in combination.

[0037] The isocyanate compound is not particularly limited as long as it has an isocyanate group, and may be a monomer, oligomer, or polymer. Examples of blocking agents include imidazole compounds, pyrazole compounds, lactam compounds, oxime compounds, alcohol compounds, and diester compounds. From the viewpoint of further reducing the dielectric loss tangent, component (G) preferably has a block structure derived from a pyrazole compound, lactam compound, oxime compound, or alcohol compound, and more preferably has a block structure derived from a pyrazole compound or oxime compound.

[0038] The content of the component (G) in the photosensitive resin composition may be 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, or 4 parts by mass or more per 100 parts by mass of the component (A) from the viewpoint of further reducing the dielectric loss tangent of the cured film. The content of the component (G) in the photosensitive resin composition may be 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, or 8 parts by mass or less per 100 parts by mass of the component (A) from the viewpoint of adhesion of the cured film.

[0039] (coupling agent) The photosensitive resin composition according to this embodiment may further contain a coupling agent as component (E). The coupling agent may include an organic silane compound (silane coupling agent), an aluminum chelate compound, or a combination thereof.

[0040] Examples of silane coupling agents include alkylsilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, and tetraethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, N-(1,3-dimethylbutylidene) aminosilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane; sulfide silanes such as bis(3-(triethoxysilyl)propyl)disulfide and bis(3-(triethoxysilyl)propyl)tetrasulfide; vinyltriacetoxysilane, vinyltrimethicone vinylsilanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropyltriethoxysilane; and mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltriethoxysilane.

[0041] From the viewpoint of adhesion, the content of the (E) component may be 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, or 4 parts by mass or more, and may be 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, or 8 parts by mass or less, per 100 parts by mass of the (A) component.

[0042] (solvent) The photosensitive resin composition according to this embodiment may further contain a solvent as component (F) in order to improve the handleability of the photosensitive resin composition and to adjust the viscosity and storage stability.

[0043] Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; ethyl acetate Cellsolves such as butyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, and isopropyl lactate; aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, and isobutyl propionate; methyl 3-methoxypropionate, 3-methoxypropionate Examples of the (F) component include esters such as ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and lactones such as γ-butyrolactone. Component (F) can be used alone or in combination of two or more.

[0044] The content of the component (F) may be 30 to 200 parts by mass, 60 to 180 parts by mass, 80 to 170 parts by mass, or 100 to 160 parts by mass relative to 100 parts by mass of the total amount of the photosensitive resin composition excluding the component (F).

[0045] The photosensitive resin composition according to this embodiment may contain other components in addition to the components described above. Examples of other components include a filler, an adhesion aid, and a leveling agent.

[0046] [Photosensitive element] The photosensitive element according to the present embodiment includes a support and a photosensitive layer provided on the support, the photosensitive layer containing the photosensitive resin composition according to the present embodiment. The photosensitive element may further include a protective film on the photosensitive layer that covers the photosensitive layer.

[0047] The support and / or protective film may be a polymer film having heat resistance and solvent resistance, such as polyethylene terephthalate, polypropylene, polyethylene, or polyester. By disposing the polymer film on both sides of the photosensitive layer, one polymer film can be used as the support and the other polymer film can be used as the protective film. The thickness of the support and / or protective film may be, for example, 5 to 25 μm.

[0048] The photosensitive layer is a layer formed using the photosensitive resin composition according to this embodiment, and can be formed by applying the photosensitive resin composition onto a support or a protective film. Examples of application methods include dipping, spraying, bar coating, roll coating, and spin coating. The thickness of the photosensitive layer (after drying) may be, for example, 1 to 100 μm, 2 to 60 μm, 3 to 50 μm, 3 to 20 μm, or 3 to 10 μm.

[0049] [Method for forming resist pattern] A resist pattern can be formed using the photosensitive resin composition or photosensitive element according to this embodiment. The resist pattern forming method of the first embodiment includes the steps of applying the photosensitive resin composition to a base material (e.g., a substrate) and drying the photosensitive resin composition to form a photosensitive layer; exposing the photosensitive layer to a predetermined pattern and performing a post-exposure bake; developing the photosensitive layer after the heat treatment (post-exposure bake); and heat-treating the resulting resin pattern. The resist pattern forming method of the second embodiment includes the steps of placing the photosensitive layer of the photosensitive element on a base material (e.g., a substrate); exposing the photosensitive layer to a predetermined pattern and performing a post-exposure bake; and developing the photosensitive layer after the heat treatment (post-exposure bake); and heat-treating the resulting resin pattern. An example of the resist pattern forming method according to this embodiment will be further described below.

[0050] First, a photosensitive layer containing the above-mentioned photosensitive resin composition is formed on a substrate on which a resist is to be formed (such as a resin-coated copper foil, a copper-clad laminate, a silicon wafer with a metal sputtered film, or an alumina substrate). Methods for forming the photosensitive layer include a method in which the photosensitive resin composition is applied (for example, coated) to the substrate and dried to volatilize the solvent, etc., to form a coating film (photosensitive layer), and a method in which the photosensitive layer of the above-mentioned photosensitive element is transferred onto the substrate.

[0051] Examples of methods for applying the photosensitive resin composition to a substrate include dipping, spraying, bar coating, roll coating, spin coating, etc. The thickness of the photosensitive layer (coating film) can be appropriately controlled by adjusting the application means and the solids concentration and viscosity of the photosensitive resin composition.

[0052] Next, the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern. Examples of actinic rays used for exposure include rays from a g-line stepper; ultraviolet rays from a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an i-line stepper, etc.; electron beams; and laser beams. The exposure dose is appropriately selected depending on the light source used and the thickness of the coating film. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the dose is 100 to 5000 mJ / cm for a coating film thickness of 10 to 50 μm. 2 That's about it.

[0053] Subsequently, after exposure, a heat treatment (post-exposure bake) is performed. By performing post-exposure bake, the curing reaction of components (A) and (B) due to the generated acid can be promoted. The conditions for post-exposure bake vary depending on the content of the photosensitive resin composition, the thickness of the photosensitive layer (coating film), etc. For example, heating at 50 to 150°C for 1 to 60 minutes is preferred, and heating at 60 to 100°C for 1 to 15 minutes is more preferred.

[0054] The photosensitive layer that has been exposed and / or post-exposure baked is then developed with a developer to dissolve and remove the areas other than the cured areas (unexposed areas), thereby obtaining the desired resist pattern. Examples of development methods include shower development, spray development, immersion development, and puddle development. Development conditions for spray development are, for example, 20 to 40°C for 10 to 300 seconds.

[0055] The developer is not particularly limited, but may contain a component that dissolves the unexposed areas of the photosensitive layer. Examples of the developer include organic solvents and alkaline developers. Examples of organic solvents include solvents that dissolve the photosensitive resin composition without damaging the substrate (e.g., the above-mentioned component (F)). Examples of alkaline developers include alkaline aqueous solutions in which alkaline compounds such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and choline are dissolved in water to a concentration of 1 to 10% by mass, and alkaline aqueous solutions such as ammonia water. The alkaline developer may also contain an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, etc. After development with the alkaline developer, the film is washed with water and dried. Tetramethylammonium hydroxide is preferred as the alkaline developer because it provides even better resolution.

[0056] A cured film (resist pattern) of the photosensitive resin composition can be obtained by performing a heat treatment to develop insulating film properties. The curing conditions for the photosensitive resin composition are not particularly limited. Depending on the application of the cured film, the photosensitive resin composition can be cured, for example, by heating at 50 to 250°C for 30 minutes to 10 hours.

[0057] To ensure sufficient curing and prevent deformation of the resulting resin pattern, heating can be performed in two stages. For example, the resin can be cured by heating at 50 to 120°C for 5 minutes to 2 hours in the first stage, and then heating at 80 to 200°C for 10 minutes to 10 hours in the second stage. There are no particular limitations on the heating equipment, and a general oven, infrared furnace, etc. can be used.

[0058] [Semiconductor Devices] The semiconductor device according to this embodiment includes a cured product of the photosensitive resin composition according to this embodiment. The cured product of the photosensitive resin composition according to this embodiment can be suitably used, for example, as a surface protective film or an interlayer insulating film for a semiconductor element, or as a solder resist and / or an interlayer insulating film for a multilayer printed wiring board.

[0059] FIG. 1 is a schematic cross-sectional view showing an example of a method for manufacturing a multilayer printed wiring board containing a cured product of the photosensitive resin composition according to this embodiment as a solder resist and / or an interlayer insulating film. Multilayer printed wiring board 100A shown in FIG. 1(f) has wiring patterns on its surface and inside. Multilayer printed wiring board 100A is obtained by laminating a copper clad laminate, an interlayer insulating film, a metal foil, etc., and then appropriately forming a wiring pattern by an etching method or a semi-additive method. The method for manufacturing multilayer printed wiring board 100A will be briefly described below with reference to FIG. 1.

[0060] First, interlayer insulating films 103 are formed on both sides of a copper clad laminate 101 having a wiring pattern 102 on its surface (see FIG. 1(a)). The interlayer insulating film 103 may be formed by printing a photosensitive resin composition using a screen printer or a roll coater, or by preparing the above-mentioned photosensitive element in advance and using a laminator to attach the photosensitive layer of the photosensitive element to the surface of a printed wiring board.

[0061] Next, openings 104 are formed using a YAG laser or a carbon dioxide laser at locations that require electrical connection to the outside (see FIG. 1(b)). Smears (residues) around the openings 104 are removed by desmearing.

[0062] Next, a seed layer 105 is formed by electroless plating (see FIG. 1(c)). A photosensitive layer containing the above-mentioned photosensitive resin composition is formed on the seed layer 105, and predetermined portions are exposed and developed to form a wiring pattern 106 (see FIG. 1(d)).

[0063] Next, a wiring pattern 107 is formed by electrolytic plating, and the cured photosensitive resin composition is removed with a stripping solution, and then the seed layer 105 is removed by etching (see FIG. 1(e)).

[0064] The above operations are repeated to form a solder resist 108 containing the cured product of the above-mentioned photosensitive resin composition on the outermost surface, thereby producing a multilayer printed wiring board 100A (see (f) of Figure 1).The multilayer printed wiring board 100A obtained in this manner can have, for example, semiconductor elements mounted in corresponding locations, ensuring electrical connections. [Example]

[0065] The present disclosure will be described in detail below using examples, but the present disclosure is not limited to these examples.

[0066] [Photosensitive resin composition] The components were mixed in the amounts (parts by mass) shown in Table 1 to prepare photosensitive resin compositions of Examples and Comparative Examples.

[0067] The components shown in Table 1 are as follows: A-1: Novolac phenolic resin (manufactured by Asahi Organic Chemicals Co., Ltd., product name "TR4020G") B-1: Trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Corporation, product name "Denacol EX-321L") C-1: 1,3,4,6-tetrakis(methoxymethyl)glycoluril (manufactured by Sanwa Chemical Co., Ltd., product name "MX-270") D-1: Triarylsulfonium salt-based photoacid generator (Sanapro Co., Ltd., product name "CPI-310B") E-1: 3-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-403") F-1: Propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.) G-1: Oxime-based blocked polyisocyanate of the following formula (G-1) (manufactured by Daiei Sangyo Co., Ltd., product name "1605V") [ka] G-2: Pyrazole-based blocked polyisocyanate of the following formula (G-2) (manufactured by GSI Creos Co., Ltd., product name "BI7982") [ka] G-3: Pyrazole-based blocked polyisocyanate of the following formula (G-3) (manufactured by GSI Creos Co., Ltd., product name "BI7960") [ka]

[0068] (Dielectric properties) The dielectric properties of the photosensitive resin compositions of the Examples and Comparative Examples were evaluated by the following procedures.

[0069] A photosensitive resin composition was spin-coated onto a 6-inch silicon wafer using a coating device (Mikasa Co., Ltd., MS-A200) so that the film thickness after curing would be approximately 10 μm, and the wafer was pre-baked on a hot plate at 120 °C for 3 minutes. An exposure dose of 400 mJ / cm was then applied using an exposure device (Mikasa Co., Ltd., ML-320FSAT). 2 After broadband (BB) exposure, the film was post-exposure baked on a hot plate at 85°C for 3 minutes, and then heated at 180°C for 1 hour in a nitrogen atmosphere using a high-temperature clean oven CLH-35CD (manufactured by JTEKT Corporation) to obtain a cured film.

[0070] The silicon wafer with the cured film formed on it was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and the cured film was peeled off from the silicon wafer to obtain a test piece for dielectric properties. The test piece was dried in an oven at 100°C for 1 hour, and then the relative permittivity (Dk) and dielectric loss tangent (Df) of the test piece at 10 GHz were measured at an air temperature of 25°C and a humidity of 45% using a cavity resonator perturbation method using a split cylinder resonator. A network analyzer (MS46122B, manufactured by Anritsu Corporation) was used as the measuring device. The results are shown in Table 1.

[0071] [Table 1]

[0072] It was confirmed that the cured films formed from the photosensitive resin compositions of Examples 1 to 6 were able to further reduce the dielectric loss tangent.

[0073] (resolution) The photosensitive resin composition of Comparative Example 1 and the photosensitive resin compositions of Examples 1, 3 and 5 were evaluated for resolution under the following conditions.

[0074] Using a coating device (MS-A200), the photosensitive resin composition was spin-coated onto a 6-inch silicon wafer so that the film thickness after curing would be approximately 5 μm, and the wafer was pre-baked on a hot plate at 120°C for 3 minutes. Using an exposure device (ML-320FSAT), the 6-inch silicon wafer was brought into contact with a quartz glass mask on which a fine pattern had been formed, and the exposure dose was 500 mJ / cm. 2 After broadband (BB) exposure, the film was post-exposure baked on a hot plate at 85°C for 3 minutes, developed using a 2.38% TMAH aqueous solution in a developing device (AD-3000), and washed with pure water.Then, it was heated at 180°C for 1 hour in a nitrogen atmosphere using a high-temperature clean oven CLH-35CD (manufactured by JTEKT Corporation) to obtain a cured film with a fine pattern formed.

[0075] It was confirmed that the photosensitive resin compositions of Examples 1, 3 and 5 had resolution equivalent to that of the photosensitive resin composition of Comparative Example 1. [Explanation of symbols]

[0076] 100A... multilayer printed wiring board, 101... copper clad laminate, 102, 106, 107... wiring pattern, 103... interlayer insulating film, 104... opening, 105... seed layer, 108... solder resist.

Claims

1. (A) a base resin containing a phenolic resin; (B) a crosslinking agent having at least one selected from the group consisting of a methylol group and an alkoxyalkyl group; (C) a solubility enhancer; (D) a photoacid generator; (G) a blocked isocyanate.

2. 2. The photosensitive resin composition according to claim 1, wherein the blocked isocyanate has a block structure derived from at least one blocking agent selected from the group consisting of imidazole compounds, pyrazole compounds, lactam compounds, oxime compounds, alcohol compounds, and diester compounds.

3. The photosensitive resin composition according to claim 1 , wherein the photoacid generator comprises an onium salt compound.

4. 2. The photosensitive resin composition according to claim 1, wherein the dissolution promoter comprises at least one selected from the group consisting of a compound having a glycidyl ether group, a compound having an oxetanyl alkyl ether group, a compound having a vinyl ether group, a compound having an acryloyloxy group, a compound having a methacryloyloxy group, and a polyhydric alcohol compound.

5. A support and a photosensitive layer provided on the support, A photosensitive element, wherein the photosensitive layer comprises the photosensitive resin composition according to any one of claims 1 to 4.

6. A semiconductor device comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 4.

7. A step of applying the photosensitive resin composition according to any one of claims 1 to 4 onto a substrate and drying the photosensitive resin composition to form a photosensitive layer; a step of exposing the photosensitive layer to a predetermined pattern and performing a post-exposure heat treatment; developing the photosensitive layer after the heat treatment, and heat-treating the resulting resin pattern.

8. disposing the photosensitive layer of the photosensitive element of claim 5 on a substrate; a step of exposing the photosensitive layer to a predetermined pattern and performing a post-exposure heat treatment; developing the photosensitive layer after the heat treatment, and heat-treating the resulting resin pattern.

Images