JP6690776B2 - Photosensitive element, semiconductor device, and method for forming resist pattern - Google Patents

Description

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

  In manufacturing a semiconductor element or a printed wiring board on which the semiconductor element is mounted, for example, a negative photosensitive resin composition is used for forming 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, a substrate in the case of a printed wiring board) by applying a photosensitive resin composition and the like, and an actinic ray is irradiated through a predetermined pattern. By doing so, the exposed portion is cured. Further, a resist pattern, which is a cured film of the photosensitive resin composition, is formed on the base material by selectively removing the unexposed portion using a developing solution. Therefore, the photosensitive resin composition is required to have high sensitivity to actinic rays and to be capable of forming a fine pattern (resolution). Therefore, a photosensitive resin composition containing a novolak resin, an epoxy resin, a photoacid generator, etc., which is soluble in an alkaline aqueous solution, a photosensitive resin composition containing an alkali-soluble epoxy compound having a carboxyl group, a photocationic polymerization initiator, etc. The thing etc. are proposed (for example, refer patent documents 1-3).

  Further, the surface protection film and the interlayer insulating film used for the semiconductor element are required to have insulation reliability such as heat resistance, electrical characteristics and mechanical characteristics. Then, the photosensitive resin composition which the said photosensitive resin composition further contains a crosslinking monomer is proposed (for example, refer patent document 4).

  On the other hand, in recent years, semiconductor devices have become highly integrated and highly reliable along with higher performance of electronic devices. With the high integration of semiconductor elements, it is required to form finer patterns. Therefore, there is a continuous need for the photosensitive resin composition to improve the resolution even in units of 1 μm.

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

  In recent years, as the miniaturization of semiconductor devices has progressed and the number of pins has increased from tens of thousands to hundreds of thousands of pins, the vias formed in the interlayer insulating material of the printed wiring board can be formed according to the number of pins of the semiconductor device. It is required to reduce the diameter. Recently, development of a printed wiring board in which a via is provided by a laser using a thermosetting resin material has been advanced (for example, refer to Patent Document 5).

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

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

  By the way, in a structure in which an electrode is laminated on an insulating film having an opening, the conductor portion arranged in the opening may be electrically connected to the electrode, which is obtained by using a photosensitive resin composition. The resin pattern may be used as an insulating film. In this case, from the viewpoint of preventing disconnection of the electrodes arranged on the insulating film (improving connection reliability), the shape of the wall of the insulating film exposed in the opening is tapered (preferably, taper angle (gradient) Small angle) is required. FIG. 1 is a schematic view (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 arranged on the substrate 1. FIG. The taper angle is 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, which is an angle indicated by θ in FIG.

  Further, the photosensitive layer of the photosensitive element is transferred to the substrate by peeling off the protective layer, adhering the photosensitive layer to the substrate using a laminator, and peeling off the support. When a photosensitive element is manufactured, air may be mixed between the photosensitive layer and the protective layer in the step of attaching the photosensitive layer and the protective layer, and the protective layer may be wrinkled. If the protective layer is wrinkled, the wrinkle is transferred to the photosensitive layer, and that portion cannot be used, which reduces productivity during manufacturing. Therefore, from the viewpoint of productivity, there is a demand for laminating the photosensitive layer and the protective layer of the photosensitive element on the entire surface without a gap.

  An object of the present disclosure is to provide a photosensitive element having a photosensitive layer which is excellent in resolution, is capable of obtaining a resin pattern having a tapered opening, and has excellent sticking property to a protective layer. Especially. Another object of the present disclosure is to provide a semiconductor device using the photosensitive layer and a method for forming a resist pattern using the photosensitive layer.

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

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

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

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

  Further, the present disclosure provides a step of disposing the photosensitive layer of the photosensitive element on a substrate, a step of exposing the photosensitive layer to a predetermined pattern, and a step of developing the exposed photosensitive layer to obtain a resin pattern. Provided is a method for forming a resist pattern, which comprises a step and a step of heat-treating the resin pattern.

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

It is a schematic diagram of an insulating film which has an opening. It is a schematic cross section of the photosensitive element of this embodiment. It is a schematic diagram which shows the manufacturing method of the multilayer printed wiring board of this embodiment. 4 is a scanning electron micrograph of a via shape formed by using the photosensitive element of Example 1. 5 is a scanning electron micrograph of a via shape formed by using the photosensitive element of Example 2. 5 is a scanning electron micrograph of a via shape formed by using the photosensitive element of Example 3. 5 is a scanning electron micrograph of a via shape formed by using the photosensitive element of Comparative Example 1. 7 is a scanning electron micrograph of a via shape formed by using the photosensitive element of Comparative Example 2. 7 is a scanning electron micrograph of a via shape formed by using the photosensitive element of Comparative Example 2. 9 is a scanning electron micrograph of a via shape formed by using the photosensitive element of Comparative Example 4.

  Hereinafter, one embodiment of the present disclosure will be specifically described, but the present disclosure is not limited thereto. It goes without saying that, in the following embodiments, the constituent elements (including element steps, etc.) are not necessarily essential, unless otherwise specified or in principle considered to be essential. This is true for numerical values and ranges as well, and should not be interpreted as unduly limiting the present disclosure.

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

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

  The reason why the photosensitive layer of the present embodiment can obtain a tapered resin pattern while achieving excellent resolution in obtaining a resin pattern having openings is considered as follows. ing. In the unexposed area, the solubility of the component (A) in the developer is improved by adding the component (C). Next, in the exposed area, due to the catalytic effect of the acid generated from the component (B), the methylol groups or the alkoxyalkyl groups in the component (C), or the methylol groups or the alkoxyalkyl groups in the component (C) are combined. When the component (A) reacts with dealcoholization, the solubility of the composition in the developer is significantly reduced. As a result, when developed, sufficient resolution can be obtained due to the remarkable difference in solubility between the unexposed and exposed areas in the developing solution. When the content of the component (C) with respect to the component (A) is within a specific range, a part of the exposed portion is melted by subsequent heating, and a resin pattern having a taper shape can be formed. Further, by heating, a cured film can be obtained while maintaining the tapered shape.

  If necessary, the photosensitive resin composition of the present embodiment has a component (E): a benzophenone compound, a component (F): a solvent, a component (G): a compound having a Si—O bond, and a component (H): an additive. A sensitizer and the like can be contained.

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

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

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

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

  Examples of the component (A) other than the novolac resin include a homopolymer or copolymer of hydroxystyrene, a phenol-xylylene glycol condensation resin, a cresol-xylylene glycol condensation resin, and a phenol-dicyclopentadiene condensation resin.

  The component (A) may be used alone or in combination of two or more.

  The weight average molecular weight of the component (A) is 100,000 or less, 1,000 to 80,000, 2000 to 50,000, from the viewpoint of further excellent resolution, developability, thermal shock resistance, heat resistance and the like of the obtained resin pattern (cured film). It may be 2000 to 20000, 3000 to 15000, or 5000 to 15000.

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

  The content of the component (A) is such that the total amount of the photosensitive resin composition (provided that (F) When a component is used, it is 10 to 90% by mass, 30 to 90% by mass, 30 to 80% by mass, 40 to 80% by mass, or 40 to 60% by mass based on (excluding the component (F)). May be.

<(B) component>
The photosensitive resin composition of this embodiment contains a photosensitive acid generator. The photosensitive acid generator is a compound that generates an acid by irradiation with actinic rays or the like. Due to the catalytic effect of the acid generated from the photosensitive acid generator, the methylol groups or the alkoxyalkyl groups in the component (C), or the methylol group or the alkoxyalkyl group in the component (C) and the component (A). However, the reactivity of the composition with dealcohol significantly reduces the solubility of the composition in a developing solution, and a negative pattern can be formed.

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

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

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

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

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

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

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

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

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

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

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

  Specific examples of the sulfonium salt include (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium nonafluorobutanesulfonate and [4- (4-biphenylylthio). Examples thereof include phenyl] -4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate and tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tetrakis (pentafluorophenyl) borate. The sulfonium salt may be used alone or in combination of two or more.

  Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl). (Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) -1,8- Examples thereof include naphthalimide and N- (10-camphorsulfonyloxy) -1,8-naphthalimide. The sulfonimide compounds may be used alone or in combination of two or more.

  The component (B) can be used alone or in combination of two or more.

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

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

  When the photosensitive resin composition contains the component (C), the methylol groups or the alkoxyalkyl groups in the component (C) are exposed to each other (or exposed and cured by heating after exposure). Alternatively, the methylol group or the alkoxyalkyl group in the component (C) and the component (A) react with dealcoholization, whereby the solubility of the composition in a developing solution is significantly lowered, and a negative pattern Can be formed. Further, when the photosensitive layer after forming the resin pattern is heated and cured, the component (C) reacts with the component (A) to form a crosslinked structure, which can prevent weakening and melting of the resin pattern. .

  Specific examples of the component (C) include a compound having a phenolic hydroxyl group (however, the component (A) is not included), a compound having a hydroxymethylamino group, and a compound having an alkoxymethylamino group. At least one selected from the above is preferable. When the compound having a phenolic hydroxyl group has a methylol group or an alkoxyalkyl group, it is possible to further increase the dissolution rate of the unexposed area at the time of developing with an alkaline aqueous solution and further improve the sensitivity of the photosensitive layer. The component (C) can be used alone or in combination of two or more.

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

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

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

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

  Moreover, you may use the compound represented by the following general formula (3) as a compound which has the said phenolic hydroxyl group.

  In the general formula (3), plural R's each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). A plurality of R may be the same or different from each other.

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

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

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

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

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

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

  The content of the component (C) is 20 parts by mass or less with respect to 100 parts by mass of the component (A). When the component (C) is contained, the exposed portion is likely to react sufficiently, and thus the resolution tends to be less likely to decrease. When the content of the component (C) is 20 parts by mass or less, a tapered resin pattern tends to be easily formed. From these viewpoints, the content of the component (C) is preferably more than 0 parts by mass and 18 parts by mass or less, more preferably 1 to 15 parts by mass, and 3 to 11 parts by mass. More preferable.

<(D) component>
The photosensitive resin composition of the present embodiment has, as the component (D), at least one functional group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanylalkyl ether group, a vinyl ether group and a hydroxyl group. It contains an aliphatic compound having two or more. In addition, the component (D) may have at least one of two or more different functional groups, or may have two or more of one functional group. The compound is preferably an aliphatic compound having three or more of the above functional groups. The upper limit of the number of functional groups is not particularly limited, but is 12 for example. The “aliphatic compound” means a compound whose main skeleton is an aliphatic skeleton and does not contain an aromatic ring or an aromatic heterocycle.

  From the viewpoint of excellent workability when forming a photosensitive resin composition layer (photosensitive layer) on a substrate, the photosensitive resin composition is also required to have excellent sticking property (tack property) to the substrate. There are cases. When a photosensitive resin composition that does not have sufficient tackiness is used, the photosensitive resin composition in the exposed area is easily removed by the development process, and the adhesion between the substrate and the resin pattern (resist pattern) deteriorates. Tend. In the present embodiment, the photosensitive resin composition containing the component (D) tends to improve the adhesiveness (that is, tackiness) between the photosensitive resin composition and the substrate. Furthermore, when the photosensitive resin composition contains the component (D), flexibility can be imparted to the photosensitive layer (coating film), and the dissolution rate of the unexposed portion when developing with an aqueous alkaline solution is increased. This tends to improve the resolution of the resin pattern. The weight average molecular weight of the component (D) may be 92 to 2000, 106 to 1500, or 134 to 1300 in consideration of the balance, from the viewpoint of more excellent tackiness and solubility in an alkaline aqueous solution. . When it is difficult to measure a compound having a low molecular weight by the above-mentioned weight average molecular weight measuring method, the molecular weight can be measured by another method and the average thereof can be calculated.

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

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

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

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

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

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

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

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

  The component (D) is specifically selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanylalkyl ether group and a vinyl ether group, from the viewpoint of further improving the sensitivity and resolution. A compound having one kind is preferable, a compound having two or more glycidyloxy groups or two or more acryloyloxy groups is more preferable, and a compound having three or more glycidyloxy groups or three or more acryloyloxy groups is further preferable. The component (D) can be used alone or in combination of two or more.

  The component (D) includes a compound having an acryloyloxy group, a compound having a methacryloyloxy group, a compound having a glycidyloxy group, a compound having an oxetanylalkyl ether group, a compound having a vinyl ether group, and a compound having a hydroxyl group. At least one selected from the group can be used. As the component (D), a compound having at least one group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group and a glycidyloxy group is preferable, and acryloyloxy is preferable from the viewpoint of improving the insulation reliability in fine wiring. A compound having at least one group selected from the group consisting of a group and a methacryloyloxy group is more preferable. Further, from the viewpoint of further excellent developability, the component (D) is preferably an aliphatic compound having two or more glycidyloxy groups, and is preferably an aliphatic compound having three or more glycidyloxy groups. The aliphatic compound having a weight average molecular weight of 1,000 or less and having three or more glycidyloxy groups is more preferable.

  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, ditriethyl Methylolpropane tetraacrylate, EO modified pentaerythritol tetraacrylate, PO modified pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, EO modified pentaerythritol triacrylate, PO modified pentaerythritol triacrylate, pentaerythritol triacrylate, EO modified trimethylolpropane acrylate, PO modified trimmer Triacrylate, trimethylolpropane acrylate, EO-modified glycerol tri acrylate, PO-modified glycerol triacrylate, glycerin triacrylate. The compound having an acryloyloxy group may be used alone or in combination of two or more.

  Examples of the compound having a methacryloyloxy group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO-modified ditrimethylolpropane tetramethacrylate, PO-modified ditrimethylolpropane tetramethacrylate, and ditriethyl Methylol propane 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 Acrylate, PO-modified trimethylolpropane dimethacrylate, trimethylolpropane dimethacrylate, EO modified glycerol trimethacrylate, PO-modified glycerol trimethacrylate, glycerine trimethacrylate and the like. The compound having a methacryloyloxy group may be used alone or in combination of two or more.

  Examples of the compound having a glycidyloxy group include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl. Ether, glycerin diglycidyl ether, dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerin triglycidyl ether, Glycerol propoxyle Triglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, diglycidyl 1,2-cyclohexane dicarboxylate, and the like. The compound having a glycidyloxy group can be used alone or in combination of two or more.

  As the compound having a glycidyloxy group, in particular, dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, and At least one selected from the group consisting of glycerin triglycidyl ether is preferable.

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

  Examples of the compound having an oxetanyl alkyl ether group include a compound having a 3-alkyl-3-oxetanyl alkyl ether group, and a compound having a 3-ethyl-3-oxetanyl alkyl ether group is preferable. 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 , Glycerin tris (3-ethyl-3-oxetanylmethyl) ether and the like. The compound having an oxetanyl alkyl ether can be used alone or in combination of two or more.

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

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

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

  The content of the component (D) is such that the total content of the component (C) and the component (D) is 65 to 120 parts by mass with respect to 100 parts by mass of the component (A). When the total content of the component (C) and the component (D) is 65 parts by mass or more, the photosensitive layer formed of the photosensitive resin composition and the protective layer tend to stick to each other. When it exists, it becomes easy to form (for example, film-form) the photosensitive layer formed from a photosensitive resin composition on a desired support body, and resolution tends to be hard to fall. From these viewpoints, the total content of the component (C) and the component (D) is preferably more than 65 parts by mass and 110 parts by mass or less, more preferably 68 to 100 parts by mass, and 70 to 90 parts by mass. More preferably, it is parts by mass.

<(E) component>
The photosensitive resin composition of the present embodiment may contain a benzophenone compound as the component (E). By containing the benzophenone compound, the resolution of the photosensitive resin composition can be improved. Further, by containing the component (E), it is possible to improve the margin of the exposure amount capable of forming a fine resist pattern and further improve the productivity. Examples of the benzophenone compound include benzophenone, 4,4′-diaminobenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dibutylamino). Benzophenone, 4-ethylaminobenzophenone, 2,4-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetramethoxybenzophenone, 2,2', 4,4'-tetraethoxybenzophenone, 2,2 ', 4,4'-tetrabutoxybenzophenone , 2,2'-dihydroxy-4,4'-dimethoxybenzopheno , 2,2'-dihydroxy-4,4'-diethoxybenzophenone, 2,2'-dihydroxy-4,4'-dibutoxybenzophenone, 4,4'-dihydroxybenzophenone, 4,4'-dimethoxybenzophenone, 4 , 4'-dibutoxybenzophenone, 4,4'-diphenylbenzophenone and the like.

  Among the component (E), it is selected from the group consisting of amino group, dimethylamino group, diethylamino group, dibutylamino group, hydroxy group, methoxy group, ethoxy group, butoxy group and phenyl group in view of further excellent resolution. A benzophenone compound having one or more groups is preferable, and two or more groups selected from the group consisting of amino group, dimethylamino group, diethylamino group, dibutylamino group, hydroxy group, methoxy group, ethoxy group, butoxy group and phenyl group. The benzophenone compound having is more preferable, the benzophenone compound having two or more diethylamino groups or hydroxy groups is further preferable, and 4,4′-bis (dimethylamino) benzophenone and 2,2 ′, 4,4′-tetrahydroxybenzophenone are particularly preferable. preferable. The component (E) can be used alone or in combination of two or more.

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

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

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

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

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

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

  The average primary particle size 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 excellent photosensitivity of the photosensitive layer. When the average primary particle size is 100 nm or less, the photosensitive resin composition is less likely to become cloudy, and light for exposure easily passes through the photosensitive layer. As a result, the unexposed portion is easily removed, and the resolution of the resin pattern tends not to be lowered. The average primary particle size is a value obtained by conversion from the BET specific surface area.

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

  When measuring the particle diameter of the inorganic filler, a known particle size distribution meter can be used. As a particle size distribution meter, a laser diffraction / scattering type particle size distribution meter that irradiates a particle group with a laser beam and obtains a particle size distribution by calculating an intensity distribution pattern of diffracted light and scattered light emitted from the particle group; by a dynamic light scattering method Examples include a particle size distribution analyzer for nanoparticles that determines the particle size distribution using frequency analysis.

  When the photosensitive resin composition of the present embodiment contains a silane compound, it is possible to improve the adhesion strength between the photosensitive layer after pattern formation and the substrate. When a silane compound is used as the component (G), the silane compound is not particularly limited as long as the silane compound has a Si—O bond. Examples of the silane compound include alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acryl silane, methacryl silane, mercapto silane, sulfide silane, isocyanate silane, sulfur silane, styryl silane, and alkyl chloro silane.

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

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

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

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

<(H) component>
The photosensitive resin composition of the present embodiment may further contain a sensitizer as the component (H). When the photosensitive resin composition contains the component (H), the sensitivity of the photosensitive resin composition can be further improved. Examples of the sensitizer include 9,10-dibutoxyanthracene. As the component (H), one type may be used on its own or two or more types may be used in combination.

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

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

  Further, the photosensitive resin composition of the present embodiment may contain other components than the above components. Examples of other components include a colorant, an adhesion aid, a leveling agent, and an inorganic filler having no Si—O bond. The inorganic filler is not particularly limited, but examples thereof include aluminum compounds such as aluminum oxide and aluminum hydroxide; alkali metal compounds; alkali carbonates such as calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide and magnesium hydroxide. Earth metal compounds; inorganic compounds derived from mines and the like. These can be pulverized with a pulverizer, and classified according to the case, and can be dispersed with a maximum particle diameter of 2 μm or less. The inorganic fillers may be used alone or in combination of two or more. It is preferable that any of the inorganic fillers has a maximum particle size of 2 μm or less when dispersed in the photosensitive resin composition. At this time, a silane coupling agent can be used in order to disperse the resin in the resin without aggregating. The content of the inorganic filler is preferably 1 to 70% by mass based on the total amount of the photosensitive resin composition (however, when the component (F) is used, the component (F) is excluded). It is more preferable that the content is ˜65% by mass.

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

  As the support 4, for example, a polymer film having heat resistance and solvent resistance, such as polyethylene terephthalate, polypropylene, polyethylene, or polyester, can be used. The thickness of the support (polymer film) 4 is preferably 5 to 100 μm. In addition, one of the above-mentioned polymer films may be laminated on both surfaces of the photosensitive layer 5 as the support 4 and the other one as the protective layer 6.

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

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

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

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

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

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

  The photosensitive layer preparation step may be a step of applying the above-mentioned photosensitive resin composition onto a base material (for example, a substrate) and drying the photosensitive resin composition to form a photosensitive layer. Examples of the method for forming the photosensitive layer include a method in which the photosensitive resin composition is applied (for example, applied) to a substrate, dried, and a solvent or the like is volatilized to form a photosensitive layer (coating). .

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

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

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

  Then, the exposed and / or post-exposure baked photosensitive layer (coating film) is developed with an alkaline developing solution to dissolve and remove the unexposed area (area other than the hardened area) to form a desired resist pattern. To get Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. The developing conditions are, for example, 20 to 40 ° C. and 10 to 300 seconds in the spray developing method.

  Examples of the alkaline developer include an alkaline aqueous solution prepared by dissolving an alkaline compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and choline in water to a concentration of 1 to 10% by mass; ammonia water and the like. Is mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant may be added to the alkaline developer. After developing with the alkaline developing solution, it is washed with water and dried. The alkaline developer is preferably tetramethylammonium hydroxide from the viewpoint of further excellent resolution.

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

  Further, heating can be carried out in two steps in order to sufficiently proceed the curing and / or to prevent deformation of the obtained resin pattern. For example, in the first step, it is possible to heat at 50 to 120 ° C. for 5 minutes to 2 hours, and in the second step to heat at 80 to 200 ° C. for 10 minutes to 10 hours to cure. When the heat treatment is performed under the above-mentioned curing conditions, the heating equipment is not particularly limited, and a general oven, an infrared furnace or the like can be used.

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

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

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

  First, interlayer insulating films 103 are formed on both surfaces of a base material (copper clad laminate, etc.) 101 having a wiring pattern 102 on the surface (see FIG. 3A). The interlayer insulating film 103 may be formed by printing a photosensitive resin composition using a screen printer or a roll coater, and preparing the above-mentioned photosensitive element in advance and using the laminator to detect the photosensitive element. It can also be formed by adhering the photosensitive layer in 1 to the surface of the printed wiring board.

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

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

  Next, the wiring pattern 107 is formed on the portion of the seed layer 105 where the resin pattern 106 is not formed by electrolytic plating, and the resin pattern 106 is removed by stripping, and then the wiring pattern 107 of the seed layer 105 is formed. The non-existing portion is removed by etching (see FIG. 3E).

  By repeating the above operation and forming the solder resist 108 containing the cured product of the above-described photosensitive resin composition on the outermost surface, the multilayer printed wiring board 100A can be manufactured (see FIG. 3 (f)). The interlayer insulating film 103 and / or the solder resist 108 can be formed using the above-described resist pattern forming method. Further, it can be formed using a method including a step of forming a photosensitive layer and a step of heat treatment. In the multilayer printed wiring board 100A thus obtained, the semiconductor element is mounted at the corresponding location, and electrical connection can be secured.

  Hereinafter, the objects and advantages of the present disclosure will be described in detail with reference to Examples, but the present disclosure is not limited to these Examples.

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

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

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

<Evaluation of sticking property of protective layer>
Observing the appearance of the above-mentioned photosensitive element, "A" indicates that the photosensitive layer and the protective layer are bonded together without any gap, and air is introduced between the photosensitive layer and the protective layer to bond part or the entire surface. The adhesiveness of the protective layer was evaluated by setting "B" as the non-existent one. The evaluation results are shown in Table 1.

<Evaluation of resolution and taper shape>
The photosensitive element was laminated on the copper-clad laminate so that the photosensitive layer was in contact with the surface of the copper-clad laminate while the protective layer of the photosensitive element was peeled off to obtain a laminate. For the laminate, a vacuum pressure laminator (trade name: MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.) was used, and a heater at 60 ° C. (upper), a heater at 60 ° C. (lower), a vacuuming time of 20 seconds, 20 The pressing time was 2 seconds and the pressure was 0.4 MPa. Then, the support of the laminated body was peeled off, and a projection exposure machine (manufactured by Ushio Inc., trade name: UX-2240SM-XJ-0) was used for i-line (365 nm) to form a photosensitive layer through a mask. The same size projection exposure was performed. As the mask, a negative pattern having a via opening portion (unexposed portion) with a via diameter of 5 to 100 μm in steps of 5 μm was used. The exposure amount was 400 mJ / cm ² .

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

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

  4, 5, 6, 7, 8, 9 and 10 are the same as the above evaluation of the tapered shape using the photosensitive elements of Examples 1, 2, 3 and Comparative Examples 1, 2, 3 and 4, respectively, in order. 3 is a scanning electron microscope photograph when a via opening is formed in the. These photographs showed that using the photosensitive elements of Examples 1 to 3 formed openings with tapered walls.

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

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

Claims (5)

With a photosensitive layer and a protective layer,
The photosensitive layer is
(A) component: a resin having a phenolic hydroxyl group,
Component (B): a photosensitive acid generator,
Component (C): a compound having at least one selected from the group consisting of an aromatic ring, a heterocycle and an alicycle, and having at least one of a methylol group and an alkoxyalkyl group,
Component (D): an aliphatic compound having two or more functional groups selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanylalkyl ether group, a vinyl ether group and a hydroxyl group,
Contains
The component (C) is (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) (N-hydroxymethyl). Urea, or a compound obtained by alkyletherifying all or a part of the methylol groups of these compounds, selected from the group consisting of compounds represented by the following general formula (1), (3), (5) or (6) At least one,
The component (D) is at least one selected from the group consisting of compounds represented by the following general formulas (7), (8), (9) or (10),
The content of the (C) component in the photosensitive layer is 20 parts by mass or less relative to 100 parts by mass of the (A) component, and the total content of the (C) component and the (D) component is the above ( is 70-120 parts by weight with respect to a) 100 parts by weight of component, the photosensitive element.

[In general formula (1), Z represents a single bond or a divalent organic group, R ⁸¹ and R ⁸² each independently represent a hydrogen atom or a monovalent organic group, and R ⁸³ and R ⁸⁴ represent Each independently represents a monovalent organic group, a and b each independently represent an integer of 1 to 3, and c and d each independently represent an integer of 0 to 3. The monovalent organic group is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms. The divalent organic group is an alkylene group having 1 to 10 carbon atoms, an alkylidene group having 2 to 10 carbon atoms, an arylene group having 6 to 30 carbon atoms, a sulfonyl group, a carbonyl group, An ether bond, a sulfide bond, an amide bond, or a group represented by the following general formula (4). When there are a plurality of R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ , they may be the same or different from each other. ]

[In general formula (3), several R shows an alkyl group each independently. A plurality of R may be the same or different from each other. ]

[In the general formula (4), X represents a single bond, an alkylene group, an alkylidene group, a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond or an amide bond. R ⁹ represents a hydrogen atom, a hydroxyl group, or an alkyl group, and e represents an integer of 1 to 10. A plurality of R ⁹ and X may be the same or different from each other. ]

[In general formula (5), several R shows an alkyl group each independently. A plurality of R may be the same or different from each other. ]

[In general formula (6), several R shows an alkyl group each independently. A plurality of R may be the same or different from each other. ]

[In the general formula (7), R ¹ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following general formula (11), and R ² , R ³ and R ⁴ are respectively An acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanylalkyl ether group, a vinyl ether group, a hydroxyl group, a group represented by the following general formula (12), or a group represented by the following general formula (13) Show. ]

[In the general formula (8), R ⁵ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, or a group represented by the following general formula (11), and R ⁶ , R ^7, and R ⁸ are respectively An acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanylalkyl ether group, a vinyl ether group, a hydroxyl group, a group represented by the following general formula (12), or a group represented by the following general formula (13) Show. ]

[In the general formula (9), R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanylalkyl ether group, a vinyl ether group, A hydroxyl group, a group represented by the following general formula (12), or a group represented by the following general formula (13) is shown. ]

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

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

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

[In the general formula (13), R ²³ represents an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanylalkyl ether group, a vinyl ether group, or a hydroxyl group, and m is an integer of 1 to 10, respectively. ]   The photosensitive element according to claim 1, further comprising a support, and the support, the photosensitive layer, and the protective layer in this order.   The photosensitive element according to claim 1, wherein the photosensitive layer further contains a component (G): a compound having a Si—O bond. In any one of claims 1 to 3 comprising placing a cured product of the photosensitive layer in the photosensitive element according method of semi-conductor devices Ru comprising a cured product. The step of disposing the photosensitive layer of the photosensitive element according to any one of claims 1 to 3 on a substrate, the step of exposing the photosensitive layer to a predetermined pattern, and the step of developing the exposed photosensitive layer. To obtain a resin pattern, and a step of heat-treating the resin pattern.