JP2017201346A - Photosensitive resin composition, photosensitive element, cured product, method for forming resist pattern, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which can provide a tapered resin pattern when providing a resin pattern having an opening.SOLUTION: The photosensitive resin composition contains a component (A): a resin having a phenolic hydroxyl group, a component (B): a compound having at least one selected from the group consisting of a methylol group and an alkoxyalkyl group, a component (C): an aliphatic compound having at least one selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, and a hydroxyl group, and a component (D): a photosensitive acid generator. The content of the component (B) is 20 pts.mass or less based on 100 pts.mass of the component (A).SELECTED DRAWING: None

Description

  The present disclosure relates to a photosensitive resin composition, a photosensitive element, a cured product, a resist pattern forming method, and a semiconductor device.

  In the production of a semiconductor element or a printed wiring board, for example, a negative photosensitive resin composition is used to form a fine pattern. In this method, a photosensitive layer is formed on a base material (for example, a chip in the case of a semiconductor element or a substrate in the case of a printed wiring board) by application of a photosensitive resin composition, and irradiated with actinic rays through a predetermined pattern. By doing so, the exposed portion is cured. Furthermore, the resist pattern which is a cured film of the photosensitive resin composition is formed on a base material by selectively removing an unexposed part using a developing solution. Therefore, the photosensitive resin composition is required to be excellent in that a fine pattern can be formed (resolution) (for example, see Patent Documents 1 and 2 below).

International Publication No. 2014/103516 International Publication No. 2015/046522

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

  However, in Patent Document 1 and Patent Document 2, the pattern shape of the resin pattern having openings is not studied, and the photosensitive resin composition is tapered when obtaining a resin pattern having openings. It is required to obtain a resin pattern.

  The present disclosure has been made in view of the above problems in the prior art, and an object thereof is to provide a photosensitive resin composition capable of obtaining a tapered resin pattern when obtaining a resin pattern having an opening. And Moreover, this indication aims at providing the photosensitive element and hardened | cured material which are obtained using the said photosensitive resin composition. Furthermore, this indication aims at providing the formation method of the resist pattern using the said photosensitive resin composition or the said photosensitive element. An object of this indication is to provide a semiconductor device provided with the above-mentioned hardened material.

  The present disclosure includes (A) component: a resin having a phenolic hydroxyl group, (B) component: a compound having at least one selected from the group consisting of a methylol group and an alkoxyalkyl group, and (C) component: an acryloyloxy group. , An aliphatic compound having at least one selected from the group consisting of a methacryloyloxy group, a glycidyloxy group and a hydroxyl group, and (D) component: a photosensitive acid generator, and containing the component (B) The photosensitive resin composition whose quantity is 20 mass parts or less with respect to 100 mass parts of said (A) component is provided.

  According to the photosensitive resin composition of the present disclosure, a tapered resin pattern can be obtained when a resin pattern having openings is obtained. According to the photosensitive resin composition of the present disclosure, when a resin pattern having an opening is obtained, a tapered resin pattern can be obtained while achieving excellent resolution.

  The component (B) preferably further has at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring.

The component (C) includes a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), and the following general formula (4) It is preferable that at least 1 sort (s) chosen from the group which consists of a compound represented by this is included.

[In General Formula (1), R ¹¹ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following General Formula (5), and R ¹² , R ^13, and R ¹⁴ are each represented by Independently, a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the following general formula (6), a group represented by the following general formula (7), or the following general formula (8) Represents a group. ]

[In General Formula (2), R ²¹ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following General Formula (5), and R ²² , R ^23, and R ²⁴ are each represented by Independently, a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the following general formula (6), a group represented by the following general formula (7), or the following general formula (8) Represents a group. ]

[In General Formula (3), R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ are each independently a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, the following general formula (6) A group represented by the following general formula (7), or a group represented by the following general formula (8). ]

[In General Formula (4), R ⁴¹ and R ⁴⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following General Formula (5), and R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ are each independently a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the following general formula (6), a group represented by the following general formula (7), or Represents a group represented by the following general formula (8). ]

[In General Formula (5), R ⁵ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group, or a methacryloyloxy group. ]

[In General Formula (6), R ⁶ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, and n represents an integer of 1 to 10. ]

[In General Formula (7), R ⁷ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group, or a methacryloyloxy group, and m represents an integer of 1 to 10. ]

[In General Formula (8), R ⁸ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, and l represents an integer of 1 to 10. ]

  Moreover, this indication provides the photosensitive element provided with the support body and the photosensitive layer provided on the said support body, and the said photosensitive layer contains the said photosensitive resin composition.

  Moreover, this indication provides the hardened | cured material of the said photosensitive resin composition. The cured product can be suitably used as a protective film (solder resist, surface protective film, etc.) or an interlayer insulating film.

  The present disclosure also includes a step of forming a photosensitive layer on a substrate using the photosensitive resin composition or the photosensitive element, and a step of performing a heat treatment after exposing the photosensitive layer to a predetermined pattern. And a step of heat-treating a resin pattern obtained by developing the photosensitive layer after the heat treatment.

  Moreover, this indication provides the semiconductor device provided with the hardened | cured material of the said photosensitive resin composition as a protective film or an interlayer insulation film.

  According to the present disclosure, it is possible to provide a photosensitive resin composition capable of obtaining a tapered resin pattern when obtaining a resin pattern having an opening. Moreover, according to this indication, the photosensitive element and hardened | cured material which are obtained using the said photosensitive resin composition can be provided. Furthermore, according to this indication, the formation method of the resist pattern using the said photosensitive resin composition or the said photosensitive element can be provided. According to the present disclosure, a semiconductor device including the cured product can be provided.

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

  Hereinafter, although embodiment of this indication is described concretely, this indication is not limited to this.

  The materials exemplified in the present specification can be used singly or in combination of two or more unless otherwise specified. In the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Means. Further, the term “layer” includes a structure formed in a part in addition to a structure formed over the entire surface when observed as a plan view. Moreover, the numerical value range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. In addition, in the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.

<Photosensitive resin composition and cured product>
The photosensitive resin composition of the present embodiment comprises (A) component: a resin having a phenolic hydroxyl group, and (B) component: a compound having at least one selected from the group consisting of a methylol group and an alkoxyalkyl group; C) component: an aliphatic compound having at least one selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group, and (D) component: a photo-sensitive acid generator, (B) Content of a component is 20 mass parts or less with respect to 100 mass parts of (A) component. Moreover, the photosensitive resin composition of this embodiment can also contain (E) component: solvent, (F) component: inorganic filler, (G) component: silane coupling agent, etc. as needed. The photosensitive resin composition of this embodiment can be used as a negative photosensitive resin composition. The photosensitive resin composition of this embodiment can have thermosetting properties. The cured product of the present embodiment is a cured product of the photosensitive resin composition of the present embodiment.

  According to the photosensitive resin composition of the present embodiment, when a resin pattern having openings is obtained, a tapered resin pattern can be obtained while achieving excellent resolution. The present inventors presume that the tapered resin pattern is obtained by the photosensitive resin composition of the present embodiment as follows. Due to the exposure and post-exposure heating, the component (B) reacts with the component (A) or the component (C) in the exposed area, and the solubility in the developer is greatly reduced. Therefore, a resin pattern having excellent resolution can be formed by development. Subsequently, by setting the content of the component (B) relative to the component (A) to a specific range by subsequent heating, a part of the exposed portion is melted, and a resin pattern having a tapered shape can be formed. Furthermore, a cured film can be obtained by heating while maintaining the tapered shape.

  The present inventors speculate that the reason why the photosensitive resin composition of the present embodiment is excellent in resolution is as follows. First, in the unexposed area, the solubility of the component (A) in the developer is greatly improved by the component (C). Next, in the exposed area, the methylol group or alkoxyalkyl group in the component (B) reacts with the component (C) by the acid generated from the component (D) and also reacts with the phenolic hydroxyl group of the component (A). In addition, the solubility of the photosensitive resin composition in the developer is greatly reduced. Thereby, when it develops, sufficient resolution is acquired by the remarkable difference of the solubility of the unexposed part with respect to a developing solution, and an exposed part.

((A) component)
Although it does not specifically limit as (A) component (resin which has a phenolic hydroxyl group), Resin soluble in alkaline aqueous solution is preferable, and novolak resin is more preferable. Such a novolak resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst.

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

  Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

  Specific examples of the novolak resin include phenol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin, and the like.

  Examples of the component (A) other than the novolak resin include polyhydroxystyrene and a copolymer thereof, a phenol-xylylene glycol condensation resin, a cresol-xylylene glycol condensation resin, and a phenol-dicyclopentadiene condensation resin.

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

  The weight average molecular weight of the component (A) is preferably 100000 or less, more preferably 1000 to 80000, from the viewpoint of further improving the resolution, thermal shock resistance, heat resistance and the like of the resulting cured product. More preferably, it is 2000-50000, It is especially preferable that it is 2000-20000, It is very preferable that it is 5000-15000. “Weight average molecular weight” refers to a value measured using a standard polystyrene calibration curve in accordance with a gel permeation chromatography (GPC) method. More specifically, a pump (manufactured by Hitachi, Ltd., L -6200 type), column (TSKgel-G5000HXL and TSKgel-G2000HXL, both manufactured by Tosoh Corporation, trade name) and a detector (Hitachi, Ltd., L-3300RI type) and tetrahydrofuran as an eluent And measured at a temperature of 30 ° C. and a flow rate of 1.0 mL / min. In addition, about the compound with a low molecular weight, when it is difficult to measure by the above-mentioned measuring method of the weight average molecular weight, the molecular weight can be measured by another method, and the average can be calculated.

  The content of the component (A) is preferably 30 to 90 parts by mass and more preferably 40 to 80 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition excluding the component (E). preferable. When the content of the component (A) is within this range, a photosensitive layer (film formed using a photosensitive resin composition) having sufficient resolution with an alkaline aqueous solution can be obtained.

((B) component)
The photosensitive resin composition of this embodiment contains the compound which has at least 1 sort (s) chosen from the group which consists of a methylol group and an alkoxyalkyl group as (B) component. (B) As a component, the component applicable to (A) component or (C) component is remove | excluded.

  When the photosensitive resin composition contains the component (B), when the photosensitive layer containing the photosensitive resin composition (such as a photosensitive layer (resin pattern) after pattern formation) is heated and cured, (B) The component reacts with the component (A) to form a bridge structure, and weakening and deformation of the photosensitive layer (resin pattern or the like) can be prevented.

  As will be described later, when the photosensitive resin composition contains the component (D), an acid is generated by irradiation with actinic rays or the like. Due to the catalytic action of the generated acid, the methylol groups in component (B), or the methylol groups in component (B) react with components (A) with dealcoholization to form a negative pattern. can do. Moreover, the negative type is caused by the reaction between the alkoxyalkyl groups in the component (B) or the alkoxyalkyl groups in the component (B) and the component (A) with dealcoholization due to the catalytic action of the generated acid. The pattern can be formed.

  The component (B) preferably further has at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring from the viewpoint of excellent heat resistance.

  The component (B) preferably further has at least one selected from the group consisting of a phenolic hydroxyl group and a hydroxymethylamino group. When the component (B) has a phenolic hydroxyl group or a hydroxymethylamino group in addition to a methylol group or an alkoxyalkyl group (alkoxymethyl group, etc.), it is not only insolubilized by reaction with the component (A) but also an unexposed portion. Then, the dissolution rate at the time of developing with alkaline aqueous solution increases, and a sensitivity can be improved.

  The weight average molecular weight of the component (B) having a phenolic hydroxyl group is preferably 94 to 2000, and preferably 108 to 2000 in consideration of the balance of solubility in alkali aqueous solution, photosensitivity, mechanical properties, and the like. More preferably, it is 108-1500.

  As the component (B) having a phenolic hydroxyl group, a conventionally known component can be used, but it is excellent in the balance between the effect of promoting the dissolution of the unexposed area and the effect of preventing the melting of the photosensitive resin composition. From the viewpoint, a compound represented by the following general formula (9) is preferable.

[In General Formula (9), Z represents a single bond or a divalent organic group, R ⁹¹ and R ⁹² each independently represent a hydrogen atom or a monovalent organic group, and R ⁹³ and R ⁹⁴ represent Each independently represents a monovalent organic group, a and b each independently represent an integer of 1 to 3, and c and d each independently represent an integer of 0 to 3. ]

  In the general formula (9), the compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent organic group represented by Z include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group; an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group; Arylene groups having 6 to 30 carbon atoms such as phenylene groups; 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 bonds; Bond; Amide bond and the like can be mentioned. Among these, Z is preferably a divalent organic group represented by the following general formula (9a).

[In general formula (9a), X is a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylidene group (for example, an alkylidene group having 2 to 10 carbon atoms), or hydrogen thereof. A group in which part or all of the atoms are substituted with a halogen atom, a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond or an amide bond, and R ^9a represents a hydrogen atom, a hydroxyl group (hydroxy group), an alkyl group or a haloalkyl group. E represents an integer of 1 to 10. The plurality of R ₂₈ may be the same as or different from each other. ]

  As the component (B) having a hydroxymethylamino group, (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) (N-hydroxymethyl) urea and the like, and nitrogen-containing compounds obtained by alkylating all or part of the hydroxymethylamino group may be used. Here, examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, a butyl group, or a mixture thereof. The component (B) having a hydroxymethylamino group may be an oligomer component that is partially self-condensed, and specifically includes hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxy). And methyl) glycoluril, tetrakis (butoxymethyl) glycoluril, tetrakis (methoxymethyl) urea and the like.

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

  (B) Content of a component is 20 mass parts or less with respect to 100 mass parts of (A) component. When the content of the component (B) exceeds 0 parts by mass, the exposed portion tends to react sufficiently, and the resolution tends to be difficult to decrease. When the content of the component (B) is 20 parts by mass or less, a tapered resin pattern tends to be easily formed. From these viewpoints, the content of the component (B) is preferably more than 0 parts by mass and 15 parts by mass or less, more preferably 1 to 11 parts by mass, and 3 to 8 parts by mass. Further preferred.

((C) component)
The photosensitive resin composition of this embodiment contains an aliphatic compound having at least one functional group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, and a hydroxyl group as the component (C). . As the component (C), the component corresponding to the component (A) is excluded.

  The component (C) is solved by increasing the dissolution rate of the unexposed area when developing with an alkaline aqueous solution from the viewpoint of obtaining good tackiness (tackiness) between the photosensitive resin composition and the support. From the viewpoint of further improving image properties, a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), and the following general formula It is preferable to include at least one compound selected from the group consisting of compounds represented by (4).

[In General Formula (1), R ¹¹ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following General Formula (5), and R ¹² , R ^13, and R ¹⁴ are each represented by Independently, a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the following general formula (6), a group represented by the following general formula (7), or the following general formula (8) Represents a group. ]

[In General Formula (2), R ²¹ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following General Formula (5), and R ²² , R ^23, and R ²⁴ are each represented by Independently, a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the following general formula (6), a group represented by the following general formula (7), or the following general formula (8) Represents a group. ]

[In General Formula (3), R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ are each independently a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, the following general formula (6) A group represented by the following general formula (7), or a group represented by the following general formula (8). ]

[In General Formula (4), R ⁴¹ and R ⁴⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following General Formula (5), and R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ are each independently a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the following general formula (6), a group represented by the following general formula (7), or Represents a group represented by the following general formula (8). ]

[In General Formula (5), R ⁵ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group, or a methacryloyloxy group. ]

[In General Formula (6), R ⁶ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, and n represents an integer of 1 to 10. ]

[In General Formula (7), R ⁷ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group, or a methacryloyloxy group, and m represents an integer of 1 to 10. ]

[In General Formula (8), R ⁸ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, and l represents an integer of 1 to 10. ]

  As the component (C), it is preferable to use at least one selected from the group consisting of an acryloyl compound, a methacryloyl compound, an epoxy resin, and a polyhydric alcohol.

  Examples of the acryloyl compound 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 acrylic Les DOO, trimethylolpropane acrylate, EO-modified glycerol tri acrylate, PO-modified glycerol triacrylate, glycerin triacrylate. An acryloyl compound can be used individually by 1 type or in combination of 2 or more types. EO represents an oxyethylene group, and PO represents an oxypropylene group.

  Examples of the methacryloyl compound 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 Trimethylol propane dimethacrylate, trimethylol propane dimethacrylate, EO modified glycerol trimethacrylate, PO-modified glycerol trimethacrylate, glycerine trimethacrylate and the like. A methacryloyl compound can be used individually by 1 type or in combination of 2 or more types. EO represents an oxyethylene group, and PO represents an oxypropylene group.

  Examples of epoxy resins include dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerin triglycidyl ether, and the like. It is done. An epoxy resin can be used individually by 1 type or in combination of 2 or more types.

  Examples of the polyhydric alcohol include dipentaerythritol, pentaerythritol, pentaerythritol, and glycerin. A polyhydric alcohol can be used individually by 1 type or in mixture of 2 or more types.

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

  The weight average molecular weight of the component (C) is preferably 92 to 2000, more preferably 106 to 1500, and more preferably 134 to 1300, from the viewpoint of excellent balance between tackiness and solubility in an aqueous alkali solution. More preferably it is.

  The content of component (C) is preferably 20 to 70 parts by mass, more preferably 25 to 65 parts by mass, and preferably 35 to 55 parts by mass with respect to 100 parts by mass of component (A). More preferably. When the content of the component (C) is 20 parts by mass or more, sufficient tackiness tends to be obtained, and when it is 70 parts by mass or less, the photosensitive layer containing the photosensitive resin composition is a desired support. It is easy to form (for example, film formation) on the top, and the resolution is not easily lowered.

((D) component)
The component (D) (photosensitive acid generator) is a compound that generates an acid upon irradiation with an actinic ray or the like. Due to the acid generated from the component (D), the methylol group or alkoxyalkyl group in the component (B) not only reacts with the component (C) but also reacts with the phenolic hydroxyl group of the component (A), and is photosensitive to the developer. The solubility of the resin composition is greatly reduced. A negative pattern can be formed by reducing the solubility of the photosensitive resin composition in the developing solution in the exposed portion. In the case where the component (C) is a compound having an acryloyloxy group or a methacryloyloxy group, radical polymerization of the acryloyloxy group or methacryloyloxy group also proceeds by irradiation with an actinic ray or the like.

  The component (D) is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays or the like, but it is an onium salt compound, a sulfonimide compound, a halogen-containing compound, a diazo ketone compound, a sulfone compound, a sulfonic acid compound, a diazomethane compound Etc. Among these, an onium salt compound or a sulfonimide compound is preferable from the viewpoint of excellent availability. In particular, when a solvent is used as the component (E), an onium salt compound is preferable from the viewpoint of excellent solubility in the solvent. Specific examples of the onium salt compound and the sulfonimide compound are shown below.

[Onium salt compound]
Examples of the onium salt compound include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Preferred examples of the onium salt compound include diaryl iodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diaryliodonium salts such as diphenyliodonium tetrafluoroborate; triphenylsulfonium Triarylsulfonium salts such as trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate; 4-t-butylphenyl-diphenylsulfonium trifluoromethanesulfonate; 4-t-butylphenyl-diphenylsulfonium p- Toluenesulfonate; 4, 7 And di -n- butoxy naphthyl tetrahydrothiophenium trifluoromethanesulfonate, and the like.

[Sulfonimide compound]
Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl). Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthalimide, N- (p-toluenesulfonyloxy) -1,8- And naphthalimide and N- (10-camphorsulfonyloxy) -1,8-naphthalimide.

  As the component (D), a compound having a trifluoromethanesulfonate group, a hexafluoroantimonate group, a hexafluorophosphate group, or a tetrafluoroborate group is preferable from the viewpoint of further excellent sensitivity and resolution.

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

  The content of the component (D) is 0.1 with respect to 100 parts by mass of the component (A) from the viewpoint that the sensitivity, resolution, pattern shape, and the like of the photosensitive resin composition of the present embodiment are even better. It is preferable that it is -15 mass parts, and it is more preferable that it is 0.3-10 mass parts.

((E) component)
The photosensitive resin composition of this embodiment can further contain a solvent as the component (E) in order to improve the handleability of the photosensitive resin composition or to adjust the viscosity and storage stability. . The component (E) is preferably an organic solvent.

  The organic solvent is not particularly limited as long as it can exhibit the above performance. For example, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl Propylene glycol monoalkyl ethers such as ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; propylene glycol such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether Dialkyl ethers; propylene glycol Propylene glycol monoalkyl ether acetates such as methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; Lactic acid esters such as methyl, ethyl lactate, n-propyl lactate, isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, propionic acid aliphatic carboxylic acid esters such as n-butyl and isobutyl propionate; methyl 3-methoxypropionate and 3-methoxypropion Other esters such as ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; 2-butanone (methyl ethyl ketone), 2-heptanone, Examples include ketones such as 3-heptanone, 4-heptanone, and cyclohexanone; amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; and lactones such as γ-butyrolactone.

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

  The content of the component (E) is preferably 30 to 200 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition excluding the component (E), from the viewpoint of excellent storage stability. More preferably, it is 120 parts by mass.

((F) component)
The photosensitive resin composition of this embodiment can contain an inorganic filler as (F) component. Thereby, according to content of (F) component, the thermal expansion coefficient of the hardened | cured material obtained by heating a photosensitive layer (photosensitive layer etc. after pattern formation) can be reduced. (F) A component can be used individually by 1 type or in combination of 2 or more types. The component (F) is preferably dispersed in the resin composition with a maximum particle size of 2 μm or less.

  Examples of the inorganic filler include aluminum compounds such as aluminum oxide and aluminum hydroxide; alkali metal compounds; alkaline earth metal compounds such as calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide and magnesium hydroxide; talc And inorganic compounds derived from mineral products such as mica; particles containing fused spherical silica, fused ground silica, fumed silica, sol-gel silica and the like. These are pulverized by a pulverizer, classified according to circumstances, and can be dispersed in a state where the maximum particle diameter is 2 μm or less.

Any of the constituents of the inorganic filler can be used, but silica is preferred. Moreover, it is preferable that the thermal expansion coefficient of the inorganic filler containing silica is 5.0 × 10 ⁻⁶ / ° C. or less. As a constituent component of the inorganic filler, silica such as fused spherical silica, fumed silica, and sol-gel silica is preferable, and fumed silica or sol-gel silica is more preferable from the viewpoint that a suitable particle size can be easily obtained. It is preferable to use silica (nanosilica) having an average primary particle diameter in the range of 5 to 100 nm. These are preferably dispersed in the photosensitive resin composition with a maximum particle size of 2 μm or less. At that time, a silane coupling agent can be used in order to disperse the resin in the resin without aggregation.

  When measuring the particle diameter of each inorganic filler, it is preferable to use a known particle size distribution meter. For example, a laser diffraction scattering type particle size distribution meter that calculates particle size distribution from the intensity distribution pattern of diffracted / scattered light emitted from a particle group; particle size distribution using frequency analysis by dynamic light scattering method Examples thereof include a particle size distribution meter of nanoparticles for which distribution is obtained.

  The average primary particle diameter of the inorganic filler is preferably 100 nm or less, more preferably 80 nm or less, and further preferably 50 nm or less from the viewpoint of further improving the photosensitivity. When the average primary particle diameter is 100 nm or less, the resin composition is less likely to become cloudy, so that the exposure light is easily transmitted through the resin composition, so that unexposed portions are easily removed and resolution is not easily lowered. Tend. The average primary particle diameter can be a value obtained by conversion from the BET specific surface area.

  (F) As for content of a component, 1-70 mass parts is preferable with respect to 100 mass parts of whole quantity of the photosensitive resin composition except (E) component, and 3-65 mass parts is more preferable.

((G) component)
The photosensitive resin composition of this embodiment may contain a silane coupling agent as the component (G). When the photosensitive resin composition contains the component (G), the adhesion strength between the photosensitive layer (such as the photosensitive layer after the resin pattern is formed) and the substrate can be improved.

  As the component (G), generally available compounds can be used. Alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acryloyl silane, methacryloyl silane, mercapto silane, sulfide silane, isocyanate silane, sulfur silane , Styrylsilane, alkylchlorosilane, and the like can be used.

  Specific compound names include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxy. Silane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, phenyltrimethoxysilane, diphenyldimethoxy Silane, triphenylsilanol, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, n-octyldi Tylchlorosilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane , 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane Bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Lutriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3 -Mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane, aminosilane and the like.

  As the silane coupling agent, an epoxy silane having one or more glycidyloxy groups is preferable, and an epoxy silane having a trimethoxysilyl group or a triethoxysilyl group is more preferable. Further, acryloylsilane or methacryloylsilane may be used.

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

  The content of the component (G) is preferably 1 to 20 parts by mass and more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the component (A).

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

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

(Other ingredients)
The photosensitive resin composition of this embodiment may contain other components other than the above-mentioned components. Examples of other components include amines, organic peroxides, inhibitors for reactions accompanying irradiation with actinic rays, leveling agents, and sensitizers.

  In addition to the component (A), the photosensitive resin composition of the present embodiment may contain a phenolic low molecular compound having a molecular weight of less than 1000 (hereinafter referred to as “phenol compound (a)”). . As the phenolic compound (a), 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, Tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl ] Benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- {1 -(4-Hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1,2,2-tetra (4-hydroxyphenyl) Tan, and the like. Content of a phenol compound (a) can be 0-40 mass parts (especially 0-30 mass parts) with respect to 100 mass parts of (A) component.

<Photosensitive element>
Next, the photosensitive element of this embodiment will be described.

  The photosensitive element of this embodiment is equipped with the support body and the photosensitive layer provided on the said support body, and the said photosensitive layer contains the above-mentioned photosensitive resin composition. The photosensitive layer is formed on the support using the above-described photosensitive resin composition. The photosensitive element may be provided with a protective layer covering the photosensitive layer on the photosensitive layer.

  As the support, for example, a polymer film having heat resistance and solvent resistance such as a polyethylene terephthalate film, a polypropylene film, a polyethylene film, and a polyester film can be used. The thickness of the support (polymer film) is preferably 5 to 25 μm. In addition, a polymer film may be used by laminating on both sides of the photosensitive layer so as to sandwich the photosensitive layer, using one as a support and the other as a protective film.

  As the protective layer, for example, a polymer film having heat resistance and solvent resistance such as a polyethylene terephthalate film, a polypropylene film, a polyethylene film, and a polyester film can be used.

  The photosensitive layer can be formed by applying a photosensitive resin composition on a support or a protective layer. Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, and a spin coating method. Although the thickness of a photosensitive layer changes with uses, after drying a photosensitive layer, it is preferable that it is 5-100 micrometers, It is more preferable that it is 8-60 micrometers, It is still more preferable that it is 10-50 micrometers.

<Method for forming resist pattern>
The resist pattern forming method of the present embodiment includes a photosensitive layer forming step of forming a photosensitive layer on a substrate using the photosensitive resin composition or photosensitive element of the present embodiment, and the photosensitive layer having a predetermined pattern. A step of performing heat treatment after exposure to (hereinafter, this heat treatment is also referred to as “post-exposure baking”), a step of heat-treating a resin pattern obtained by developing the photosensitive layer after the heat treatment, Is provided. In the photosensitive layer forming step, after the photosensitive resin composition is applied on the substrate, the applied photosensitive resin composition may be dried to form the photosensitive layer. The photosensitive layer of the photosensitive element is used as the substrate. You may arrange on top.

  Next, the resist pattern forming method of this embodiment will be further described.

  First, a photosensitive layer containing the above-described photosensitive resin composition is formed on a substrate on which a resist is to be formed (a copper foil with resin, a copper clad laminate, a silicon wafer with a metal sputtered film, an alumina substrate, etc.). . As a method for forming the photosensitive layer, a method in which a photosensitive resin composition is applied to a substrate and dried to volatilize a solvent or the like to form a coating film (photosensitive layer); Examples thereof include a method of transferring onto a substrate.

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

Next, the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern. Examples of the actinic rays used for exposure include g-line stepper rays; ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and i-line steppers; electron beams; The exposure amount is appropriately selected depending on the light source to be used, the thickness of the coating film, and the like. For example, in the case of ultraviolet irradiation from a high pressure mercury lamp, the coating thickness is about 100 to 5000 mJ / cm ² when the coating thickness is 10 to 50 μm. is there.

  Further, a heat treatment (post exposure bake) is performed after the exposure. By performing post-exposure baking, the curing reaction of the component (A) and the component (B) by the generated acid can be promoted. The post-exposure baking conditions vary depending on the content of the photosensitive resin composition, the thickness of the coating film, etc., but it is usually preferable to heat at 70 to 150 ° C. for 1 to 60 minutes, and 1 to 70 to 120 ° C. It is more preferable to heat for 60 minutes.

  Next, the exposed and / or post-exposure baked coating film is developed with an alkaline developer, and a region other than the cured portion (unexposed portion) is dissolved and removed to obtain a desired resist pattern. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. The development conditions are usually 20 to 40 ° C. and 1 to 10 minutes.

  Examples of the alkaline developer include an alkaline aqueous solution obtained by dissolving an alkaline compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and choline in water so that the concentration is about 1 to 10% by mass; Can be mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline aqueous solution, for example. In addition, after developing with an alkaline developer, it can be washed with water and dried. As the alkaline developer, a tetramethylammonium hydroxide aqueous solution is preferable from the viewpoint of further excellent resolution.

  Furthermore, the cured film (resist pattern) of the photosensitive resin composition can be obtained by performing a heat treatment to develop the insulating film characteristics. The curing conditions of the photosensitive resin composition are not particularly limited, but the photosensitive resin composition may be cured by heating at 50 to 250 ° C. for 30 minutes to 10 hours depending on the use of the cured product. it can.

  Moreover, in order to fully advance hardening and to prevent the deformation | transformation of the obtained resin pattern shape, it can also heat in two steps. For example, it can be cured by heating at 50 to 120 ° C. for 5 minutes to 2 hours in the first stage and heating at 80 to 200 ° C. for 10 minutes to 10 hours in the second stage.

  In the above-described curing conditions, the heating equipment is not particularly limited, and a general oven, infrared furnace, or the like can be used.

<Semiconductor device>
The semiconductor device of this embodiment includes a cured product of the photosensitive resin composition as a protective film or an interlayer insulating film. Examples of the semiconductor device include a multilayer printed wiring board.

  The cured product of the photosensitive resin composition of the present embodiment can be suitably used as, for example, a protective film (solder resist or the like) and / or an interlayer insulating film in a multilayer printed wiring board. FIG. 2 is a view showing a method for producing a multilayer printed wiring board including a cured product of the photosensitive resin composition of the present embodiment as a solder resist and an interlayer insulating film. The multilayer printed wiring board 100 shown in FIG. 2F has a wiring pattern on the surface and inside. The multilayer printed wiring board 100 is obtained by laminating a copper clad laminate, an interlayer insulating film, a metal foil, and the like, and appropriately forming a wiring pattern by an etching method or a semi-additive method. Hereinafter, a method for manufacturing the multilayer printed wiring board 100 will be briefly described with reference to FIG.

  First, an interlayer insulating film 103 is formed on both surfaces of a copper clad laminate 101 having a wiring pattern 102 on the surface (see FIG. 2A). The interlayer insulating film 103 may be formed by printing a photosensitive resin composition using a screen printer or a roll coater. The above-described photosensitive element is prepared in advance, and a laminator is used to form the photosensitive element in the photosensitive element. It can also be formed by attaching a photosensitive layer to the surface of a printed wiring board. Next, an opening 104 is formed using a YAG laser or a carbon dioxide gas laser in a place that needs to be electrically connected to the outside (see FIG. 2B). Smear (residue) around the opening 104 can be removed by desmear treatment. Next, a seed layer 105 is formed by an electroless plating method (see FIG. 2C). A photosensitive layer containing the above-described photosensitive resin composition is laminated on the seed layer 105, and a predetermined portion is exposed and developed to form a wiring pattern 106 (see FIG. 2D). After forming an adhesion layer (for example, a titanium layer having a thickness of about 30 nm) on the seed layer 105, a Cu layer having a thickness of about 100 nm may be formed. These adhesion layers can be formed by sputtering. Next, the wiring pattern 107 is formed by an electrolytic plating method, the cured product of the photosensitive resin composition is removed by a peeling solution, and then the seed layer 105 is removed by etching (see FIG. 2E). The multilayer printed wiring board 100 can be produced by repeating the above operations and forming the solder resist 108 made of the cured product of the above-described photosensitive resin composition on the outermost surface (see FIG. 2F).

  In the multilayer printed wiring board 100 obtained in this way, semiconductor elements are mounted at corresponding locations, and electrical connection can be ensured.

  Hereinafter, the present disclosure will be described in detail with reference to examples, but the present disclosure is not limited to the examples.

<Preparation of photosensitive resin composition>
50 parts by mass of cresol novolac resin (Asahi Organic Materials Co., Ltd., trade name: TR4020G), 50 parts by mass of cresol novolac resin (product of Asahi Organic Materials Co., Ltd., trade name: TR4080G), 1, 3, 4, 6-tetrakis (methoxymethyl) glycoluril (a compound having an alkoxyalkyl group, manufactured by Sanwa Chemical Co., Ltd., trade name: MX-270) and pentaerythritol triacrylate (acryloyl compound, manufactured by Nippon Kayaku Co., Ltd., trade name) : PET-30) 50 parts by mass, triarylsulfonium salt (photosensitive acid generator, manufactured by San Apro Co., Ltd., trade name: CPI-310B), and methyl ethyl ketone (solvent, manufactured by Wako Pure Chemical Industries, Ltd.) , Trade name: 2-butanone) and 100 parts by mass of Examples 1 to 3 and Comparative Example 1 To obtain a photosensitive resin composition. The content of 1,3,4,6-tetrakis (methoxymethyl) glycoluril is 7 parts by mass (Example 1), 10 parts by mass (Example 2), 14 parts by mass (Example 3), 28 parts by mass. Adjustment was made to (Comparative Example 1).

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

<Evaluation of minimum resolution (resolution)>
While peeling off the protective layer of the photosensitive element (photosensitive layer thickness: 10 μm), the photosensitive element was laminated on a 6-inch silicon wafer so that the photosensitive layer was in contact with the surface of the silicon wafer. Next, the support was peeled off to obtain uniform photosensitive layers having a thickness of 10 μm on the silicon wafer. Lamination is performed by using a continuous press type vacuum laminator (trade name: MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.), pressure bonding pressure 0.4 MPa, press hot plate temperature 90 ° C., vacuuming time 30 seconds, laminating press. The time was 30 seconds.

Subsequently, the i-line stepper (manufactured by Canon Inc., trade name: FPA-3000iW) was used to perform reduction projection exposure on the photosensitive layer with i-line (365 nm) through a mask. As the mask, a mask having a pattern in which an unexposed portion exists in a circular shape in an exposed portion and the diameter of a circle of the unexposed portion is in a range of 2 to 30 μm and used is 1 μm. The exposure amount is in the range of 100~3000mJ / cm ^2, was subjected to the reduction projection exposure while changing by 100 mJ / cm ^2.

Next, the exposed photosensitive layer was heated at 90 ° C. for 8 minutes (post-exposure baking), and then 2.38 mass% tetra in a time corresponding to twice the shortest development time (the shortest time for removing the unexposed portion). The development process was performed by removing unexposed portions by dipping in an aqueous solution of methylammonium hydroxide. After the development treatment, the formed resist pattern was observed using a metal microscope. Among the patterns in which the space portion (unexposed portion) was removed cleanly and vias were formed, the smallest via diameter value in the range of 100 to 3000 mJ / cm ² was evaluated as the minimum resolution. The evaluation results are shown in Table 1.

<Evaluation of taper shape>
Similarly to the evaluation of the minimum resolution (resolution), uniform photosensitive layers having a thickness of 10 μm were obtained on a silicon wafer. Subsequently, the i-line stepper (manufactured by Canon Inc., trade name: FPA-3000iW) was used to perform reduction projection exposure on the photosensitive layer with i-line (365 nm) through a mask. As the mask, a mask having a pattern in which the unexposed portion exists in a circular shape in the exposed portion and the diameter of the circle of the unexposed portion is 20 μm was used. Moreover, the exposure amount was set to the minimum exposure amount in the range of 100 to 3000 mJ / cm ² .

  Next, the exposed photosensitive layer was heated at 90 ° C. for 8 minutes (post-exposure baking), and then 2.38 mass% tetra in a time corresponding to twice the shortest development time (the shortest time for removing the unexposed portion). The development process was performed by removing unexposed portions by dipping in an aqueous solution of methylammonium hydroxide. After the development treatment, heat treatment was performed at 180 ° C. for 1 hour under a nitrogen stream (oxygen concentration of 20 ppm or less) using an inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd., to prepare a cured film.

  The cross section of the obtained cured film was observed with a digital microscope VHX-2000 manufactured by Keyence Corporation, and the taper angle was measured. The evaluation results are shown in Table 1.

  As is clear from Table 1, in Comparative Example 1, the taper angle was 90 °, and the taper was not tapered. On the other hand, in Examples 1 to 3, the taper angle was 80 ° or less, and a taper was formed. In addition, excellent resolution (pattern property) of a minimum resolution (resolution) of 8 μm or less was exhibited.

  FIG. 3 is a scanning electron micrograph when a resin pattern is formed using the photosensitive resin composition of Example 1 in the same manner as in the evaluation of the tapered shape. FIG. 4 is a scanning electron micrograph when a resin pattern is formed using the photosensitive resin composition of Example 3 in the same manner as in the evaluation of the tapered shape. FIG. 5 is a scanning electron micrograph when a resin pattern is formed using the photosensitive resin composition of Comparative Example 1 in the same manner as in the evaluation of the tapered shape. From these drawings, it can be seen that when the photosensitive resin compositions of Examples 1 and 3 are used, a taper is formed. Moreover, when the scanning electron micrograph (not shown) when forming the resin pattern similarly to the said taper-shaped evaluation using the photosensitive resin composition of Example 2, taper is formed. Was confirmed.

  The photosensitive resin composition of the present disclosure is applied to a protective film (such as a solder resist) or an interlayer insulating film such as a printed wiring board, or a surface protective film (overcoat film) or an interlayer insulating film (passivation film) such as a semiconductor element. It can be applied as a material to be used. In particular, since the photosensitive resin composition of the present disclosure has good resolution, it can be suitably used for a high-density package substrate that is thinned and densified.

  DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Insulating film, 100 ... 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 (7)

(A) component: a resin having a phenolic hydroxyl group;
(B) component: a compound having at least one selected from the group consisting of a methylol group and an alkoxyalkyl group;
(C) component: an aliphatic compound having at least one selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group;
(D) component: a photosensitive acid generator,
The photosensitive resin composition whose content of the said (B) component is 20 mass parts or less with respect to 100 mass parts of said (A) component.   The photosensitive resin composition of Claim 1 in which the said (B) component further has at least 1 sort (s) chosen from the group which consists of an aromatic ring, a heterocyclic ring, and an alicyclic ring. The component (C) is a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), and the following general formula (4) The photosensitive resin composition of Claim 1 or 2 containing at least 1 sort (s) chosen from the group which consists of a compound represented by this.

[In General Formula (1), R ¹¹ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following General Formula (5), and R ¹² , R ^13, and R ¹⁴ are each represented by Independently, a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the following general formula (6), a group represented by the following general formula (7), or the following general formula (8) Represents a group. ]

[In General Formula (2), R ²¹ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following General Formula (5), and R ²² , R ^23, and R ²⁴ are each represented by Independently, a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the following general formula (6), a group represented by the following general formula (7), or the following general formula (8) Represents a group. ]

[In General Formula (3), R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ are each independently a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, the following general formula (6) A group represented by the following general formula (7), or a group represented by the following general formula (8). ]

[In General Formula (4), R ⁴¹ and R ⁴⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following General Formula (5), and R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ are each independently a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the following general formula (6), a group represented by the following general formula (7), or Represents a group represented by the following general formula (8). ]

[In General Formula (5), R ⁵ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group, or a methacryloyloxy group. ]

[In General Formula (6), R ⁶ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, and n represents an integer of 1 to 10. ]

[In General Formula (7), R ⁷ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group, or a methacryloyloxy group, and m represents an integer of 1 to 10. ]

[In General Formula (8), R ⁸ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, and l represents an integer of 1 to 10. ] A support, and a photosensitive layer provided on the support,
The photosensitive element in which the said photosensitive layer contains the photosensitive resin composition as described in any one of Claims 1-3.   Hardened | cured material of the photosensitive resin composition as described in any one of Claims 1-3. A step of forming a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 3 or the photosensitive element according to claim 4, and
Performing a heat treatment after exposing the photosensitive layer to a predetermined pattern;
And a step of heat-treating a resin pattern obtained by developing the photosensitive layer after the heat treatment.   A semiconductor device comprising the cured product of the photosensitive resin composition according to claim 5 as a protective film or an interlayer insulating film.