JP2016188987A - Photosensitive resin composition, photosensitive element, semiconductor device and method for forming resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in resolution even when a coating film of the composition is formed to a thickness over 20 μm.SOLUTION: The photosensitive resin composition comprises the following components of: (A) a resin having a phenolic hydroxyl group; (B) a photosensitive acid generator; (C) a compound having at least one structure selected from a group consisting of an aromatic ring, heterocyclic and alicyclic structures, and having a methylol group or an alkoxyalkyl group; and (D) an aliphatic compound having two or more of at least one type of functional group selected from a group consisting of an acryloyloxy group, methacryloyloxy group, glycidyloxy group and hydroxyl group; and (E) at least one type of compound selected from a group consisting of an aliphatic amine and a nitrogen-containing heterocyclic compound.SELECTED DRAWING: None

Description

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

  In manufacturing a semiconductor device such as a semiconductor element or a printed wiring board on which the semiconductor element is mounted, for example, a negative photosensitive resin composition is used in order 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. To do. Furthermore, a resin pattern is formed on a base material by selectively removing unexposed portions using a developer. Therefore, the photosensitive resin composition is required to have high sensitivity to actinic rays and to be able to form a fine pattern (resolution). Accordingly, a photosensitive resin composition containing a novolak resin, an epoxy resin, a photoacid generator (photosensitive acid generator), etc. soluble in an alkaline aqueous solution, an alkali-soluble epoxy compound having a carboxyl group, and a photocationic polymerization initiator Etc. have been proposed (see, for example, Patent Documents 1 to 3).

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

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

  Further, by forming the interlayer insulating film thick, the insulation between the wirings in the thickness direction of the layers can be improved and the short circuit of the wiring can be prevented, so that the reliability regarding the insulation between the wirings is improved. In addition, when a chip is mounted, since the semiconductor element has a thick interlayer insulating film, the stress applied to the solder bump pad can be relieved, so that connection failure hardly occurs during mounting. Therefore, from the viewpoint of insulation reliability and productivity when mounting a chip, it is also required that a film of a thick photosensitive resin composition exceeding 20 μm can be formed.

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

  However, for example, in the photosensitive resin composition described in Patent Document 1 or 4, when the thickness of the coating film is 10 μm or less, good resolution with a space width of about 5 μm is obtained. When it is converted into a good resolution, good resolution cannot be obtained. Moreover, in the photosensitive resin composition of patent document 2 and 3, there exists room for improvement about the high resolution at the time of thickening.

  The object of the present disclosure is to solve the problems associated with the prior art as described above, and to provide a photosensitive resin composition having excellent resolution even when a coating film having a thickness exceeding 20 μm is formed. There is to do. Moreover, the objective of this indication is providing the formation method of the resist pattern using the photosensitive element and semiconductor device which are obtained using the said photosensitive resin composition, and the said photosensitive resin composition.

As a result of intensive studies to solve the above problems, the present inventors have found a photosensitive resin composition having excellent characteristics.
That is, the present disclosure is selected from the group consisting of (A) component: a resin having a phenolic hydroxyl group, (B) component: a photosensitive acid generator, and (C) component: an aromatic ring, a heterocyclic ring, and an alicyclic ring. A compound having at least one selected from the group having a methylol group or an alkoxyalkyl group, and component (D): an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanylalkyl ether group, a vinyl ether group, and a hydroxyl group An aliphatic compound having two or more functional groups selected from the group (E): at least one compound selected from the group consisting of aliphatic amines and nitrogen-containing heterocyclic compounds A photosensitive resin composition is provided.

  In the photosensitive resin composition of the present disclosure, the component (E) preferably includes a compound having at least one skeleton selected from the group consisting of a tetrazole skeleton and a benzotriazole skeleton, or a tertiary amine.

  Moreover, in the photosensitive resin composition of this indication, it is preferable that content of the said (D) component is 1-70 mass parts with respect to 100 mass parts of said (A) component.

  Moreover, in the photosensitive resin composition of this indication, it is preferable to contain further the compound which has (G) component: Si-O bond.

  The present disclosure also provides a photosensitive element comprising a support and a photosensitive layer formed using the photosensitive resin composition provided on the support.

  The present disclosure also provides a semiconductor device including a cured product of the photosensitive resin composition.

  The present disclosure also includes a step of applying the photosensitive resin composition onto a substrate, drying the photosensitive resin composition to form a photosensitive layer, exposing the photosensitive layer to a predetermined pattern, and A step of performing a heat treatment (hereinafter, this heat treatment is also referred to as “post-exposure bake”), a step of developing the photosensitive layer after the heat treatment (post-exposure bake), and a heat treatment of the resulting resin pattern And a method of forming a resist pattern.

  The present disclosure further includes a step of forming a photosensitive layer on the substrate using the photosensitive element, a step of exposing the photosensitive layer to a predetermined pattern, and performing a post-exposure heat treatment (post-exposure baking); And developing the photosensitive layer after heat treatment (post-exposure baking), and heat-treating the resulting resin pattern.

According to the present disclosure, even when a coating film having a thickness exceeding 20 μm is formed, a photosensitive resin composition having excellent resolution, a photosensitive element obtained using the photosensitive resin composition, and A semiconductor device and a method for forming a resist pattern using the photosensitive resin composition can be provided.
Further, the photosensitive resin composition of the present disclosure has a thickness exceeding 20 μm by containing at least one compound selected from the group consisting of component (E): aliphatic amine and nitrogen-containing heterocyclic compound. Even when a coating film is formed, the resolution is excellent and the tolerance of the exposure amount capable of forming a fine resist pattern can be improved. When manufacturing a mass-produced product using a photosensitive resin composition with a wide margin of exposure dose, it is not necessary to finely adjust the exposure dose to form a fine resist pattern, improving the throughput of mass-produced products can do.

It is a schematic diagram which shows the manufacturing method of the multilayer printed wiring board of this embodiment.

Hereinafter, although an embodiment of the present disclosure will be specifically described, the present disclosure is not limited thereto.
Note that in this specification, the term “layer” includes a structure formed in a part in addition to a structure formed in the entire surface when observed as a plan view. In this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used if the intended purpose of the process is achieved. included. In this specification, the numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In this specification, “Si—O bond” refers to a bond between a silicon atom and an oxygen atom.

[Photosensitive resin composition]
The photosensitive resin composition of the present embodiment includes (A) component: a resin having a phenolic hydroxyl group, (B) component: a photosensitive acid generator, and (C) component: an aromatic ring, a heterocyclic ring, and an alicyclic ring. A compound having at least one selected from the group consisting of a methylol group or an alkoxyalkyl group, and component (D): an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanylalkyl ether group, a vinyl ether group And an aliphatic compound having two or more functional groups selected from the group consisting of hydroxyl groups and at least one selected from the group consisting of (E) component: aliphatic amine and nitrogen-containing heterocyclic compound And a compound. In the present specification, these components may be simply referred to as (A) component, (B) component, (C) component, (D) component, (E) component, and the like.

  The present inventors consider the reason why the photosensitive resin composition of the present embodiment is excellent in resolution as follows. In the unexposed area, the solubility of the component (A) in the developer is improved by the addition of the component (C). Next, in the exposed portion, due to the catalytic effect of the acid generated from the component (B), methylol groups or alkoxyalkyl groups in the component (C), or methylol groups or alkoxyalkyl groups in the component (C) and (A ) Component reacts with dealcoholization, so that the solubility of the composition in the developer is greatly reduced. Thereby, when developed, sufficient resolution can be obtained due to a remarkable difference in solubility in the unexposed and exposed portion of the developer.

  The photosensitive resin composition of this embodiment may contain (F) component: solvent, (G) component: compound having Si—O bond, (H) component: sensitizer, and the like, as necessary. it can.

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

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

  Specific examples of the novolak resin include phenol / formaldehyde condensed novolak resin, phenol-cresol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin, and the like. (A) A component can be used individually by 1 type or in mixture of 2 or more types.

  Examples of the component (A) other than the novolak resin include polyhydroxystyrene and copolymers thereof, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, and the like. It is done. (A) A component can be used individually by 1 type or in mixture of 2 or more types.

  The weight average molecular weight of the component (A) is preferably 100,000 or less, more preferably 1000 to 80000, and more preferably 2000 to 50000 from the viewpoint of further improving the resolution, developability, thermal shock resistance, heat resistance and the like of the resin pattern to be obtained. Is more preferable, 2000-20000 is particularly preferable, and 3000-15000 is very preferable.

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

  The content of the component (A) is preferably 10 to 90% by mass, based on the total amount of the photosensitive resin composition (however, when the component (F) is used, excluding the component (F)), and 30 to 80%. The mass% is more preferable, and 40 to 60 mass% is still more preferable. When the content of the component (A) is in the above range, a film formed using the resulting photosensitive resin composition tends to have better developability with an alkaline aqueous solution.

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

  The component (B) is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays or the like. For example, an onium salt compound, a halogen-containing compound, a diazoketone compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, a diazomethane compound Etc. Among them, it is preferable to use an onium salt compound or a sulfonimide compound from the viewpoint of availability. In particular, when a solvent is used, it is preferable to use an onium salt compound from the viewpoint of solubility in the solvent. Specific examples are shown below.

  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- Naphthalimide and N- (10-camphorsulfonyloxy) -1,8-naphthalimide are mentioned.

Examples of the onium salt compound include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Specific examples of preferred onium salt compounds include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium heptadecafluorooctanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate Diaryl iodonium salts such as diphenyliodonium tris (pentafluoroethyl) trifluorophosphate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium tris [(trifluoromethyl) sulfonyl] methanide; Sulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium heptadecafluorooctanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium tris ( Pentafluoroethyl) trifluorophosphate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tris [(trifluoromethyl) sulfonyl] methanide, 4-t-butylphenyl-diphenylsulfonium trifluoro Lomethanesulfo 4-t-butylphenyl-diphenylsulfonium nonafluorobutane sulfonate, 4-t-butylphenyl-diphenylsulfonium heptadecafluorooctane sulfonate, 4-t-butylphenyl-diphenylsulfonium p-toluenesulfonate, 4-t- Butylphenyl-diphenylsulfonium hexafluoroantimonate, 4-t-butylphenyl-diphenylsulfonium hexafluorophosphate, 4-t-butylphenyl-diphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, 4-t-butylphenyl-diphenyl Sulfonium tetrafluoroborate, 4-t-butylphenyl-diphenylsulfonium tetrakis (pentafluorophenyl) borate, 4-t-butyl Tylphenyl-diphenylsulfonium tris [(trifluoromethyl) sulfonyl] methanide, diphenyl [4- (phenylthio) phenyl] sulfonium trifluoromethanesulfonate, diphenyl [4- (phenylthio) phenyl] sulfonium nonafluorobutanesulfonate, diphenyl [4- (phenylthio) ) Phenyl] sulfonium heptadecafluorooctanesulfonate, diphenyl [4- (phenylthio) phenyl] sulfonium p-toluenesulfonate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate, diphenyl [4- (phenylthio) phenyl] sulfonium Hexafluorophosphate, diphenyl [4- (phenylthio) phenyl] sulfonium tris (pen Fluoroethyl) trifluorophosphate, diphenyl [4- (phenylthio) phenyl] sulfonium tetrafluoroborate, diphenyl [4- (phenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium tris [(Trifluoromethyl) sulfonyl] methanide, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium trifluoromethanesulfonate, [4- (4-biphenylylthio) phenyl] -4-biphenylyl Phenylsulfonium nonafluorobutanesulfonate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium heptadecafluorooctanesulfonate, [4 -(4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium p-toluenesulfonate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium hexafluoroantimonate, [4- ( 4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium hexafluorophosphate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, [4 -(4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tetrafluoroborate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) bo [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tris [(trifluoromethyl) sulfonyl] methanide, (2-methyl) phenyl [4- (4-biphenylylthio) phenyl ] 4-biphenylylsulfonium trifluoromethanesulfonate, (2-methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenylylsulfonium nonafluorobutanesulfonate, (2-methyl) phenyl [4- (4- Biphenylylthio) phenyl] 4-biphenylylsulfonium heptadecafluorooctanesulfonate, (2-methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenylylsulfonium p-toluenesulfonate, (2-methyl) Phenyl [4- (4-Bif Nylylthio) phenyl] 4-biphenylylsulfonium hexafluoroantimonate, (2-methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenylylsulfonium hexafluorophosphate, (2-methyl) phenyl [4- (4-Biphenylylthio) phenyl] 4-biphenylylsulfonium tris (pentafluoroethyl) trifluorophosphate, (2-methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenylylsulfonium tetrafluoroborate , (2-methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenylylsulfonium tetrakis (pentafluorophenyl) borate, (2-methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-bife Nylylsulfonium tris [(trifluoromethyl) sulfonyl] methanide, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium trifluoromethanesulfonate, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium nonafluorobutanesulfonate, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium heptadecafluorooctanesulfonate, [4- (4 -Biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium p-toluenesulfonate, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium hexafluoroantimonate , [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium hexafluorophosphate, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium tris (Pentafluoroethyl) trifluorophosphate, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium tetrafluoroborate, [4- (4-biphenylylthio) -3-methylphenyl ] 4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium tris [(trifluoromethyl) sulfonyl] methanide, (2 -Methyl) Nyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium trifluoromethanesulfonate, (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4- Biphenylylsulfonium nonafluorobutanesulfonate, (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium heptadecafluorooctanesulfonate, (2-methyl) phenyl [4- (4-Biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium p-toluenesulfonate, (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium Hexafluoroantimonate, (2-methyl) Phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium hexafluorophosphate, (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4- Biphenylylsulfonium tris (pentafluoroethyl) trifluorophosphate, (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium tetrafluoroborate, (2-methyl) phenyl [4- (4-Biphenylylthio) -3-methylphenyl] 4-biphenylylsulfonium tetrakis (pentafluorophenyl) borate, (2-methyl) phenyl [4- (4-biphenylylthio) -3-methylphenyl ] 4-Biphenylylsulfonium tris [(Trif Olomethyl) sulfonyl] methanide, (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium trifluoromethanesulfonate, (2-methoxy) phenyl [4- (4-biphenyl) Rilthio) -3-methoxyphenyl] 4-biphenylylsulfonium nonafluorobutanesulfonate, (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium heptadecafluorooctane Sulfonate, (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium p-toluenesulfonate, (2-methoxy) phenyl [4- (4-biphenylylthio) -3-Methoxyphenyl 4-biphenylylsulfonium hexafluoroantimonate, (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium hexafluorophosphate, (2-methoxy) phenyl [4- (4-Biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium tris (pentafluoroethyl) trifluorophosphate, (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium tetrafluoroborate, (2-methoxy) phenyl [4- (4-biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium tetrakis (pentafluorophenyl) borate, (2-methoxy) phenyl [4- (4-Biphenylylthio) -3-methoxyphenyl] 4-biphenylylsulfonium tris [(trifluoromethyl) sulfonyl] methanide, (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl ] 4-biphenylylsulfonium trifluoromethanesulfonate, (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium nonafluorobutanesulfonate, (2-ethoxy) phenyl [4 -(4-Biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium heptadecafluorooctanesulfonate, (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenyl Rylsulfonium p-tolue Sulfonate, (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium hexafluoroantimonate, (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-Ethoxyphenyl] 4-biphenylylsulfonium hexafluorophosphate, (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium tris (pentafluoroethyl) trifluoro Phosphate, (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium tetrafluoroborate, (2-ethoxy) phenyl [4- (4-biphenylylthio)- 3-Ethoxyphenyl] 4-biphe Rylsulfonium tetrakis (pentafluorophenyl) borate, (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium tris [(trifluoromethyl) sulfonyl] methanide, (2 -Butoxy) phenyl [4- (4-biphenylylthio) -3-butoxyphenyl] 4-biphenylylsulfonium trifluoromethanesulfonate, (2-butoxy) phenyl [4- (4-biphenylylthio) -3-butoxyphenyl ] 4-Biphenylylsulfonium nonafluorobutanesulfonate, (2-butoxy) phenyl [4- (4-biphenylylthio) -3-butoxyphenyl] 4-biphenylylsulfonium heptadecafluorooctanesulfonate, (2-butoxy) phenyl [4- (4-Biphenylylthio) -3-butoxyphenyl] 4-biphenylylsulfonium p-toluenesulfonate, (2-butoxy) phenyl [4- (4-biphenylylthio) -3-butoxyphenyl] 4- Biphenylylsulfonium hexafluoroantimonate, (2-butoxy) phenyl [4- (4-biphenylylthio) -3-butoxyphenyl] 4-biphenylylsulfonium hexafluorophosphate, (2-butoxy) phenyl [4- (4 -Biphenylylthio) -3-butoxyphenyl] 4-biphenylylsulfonium tris (pentafluoroethyl) trifluorophosphate, (2-butoxy) phenyl [4- (4-biphenylylthio) -3-butoxyphenyl] 4- Biphenylylsulfonium tetrafluorovolley , (2-butoxy) phenyl [4- (4-biphenylylthio) -3-butoxyphenyl] 4-biphenylylsulfonium tetrakis (pentafluorophenyl) borate, (2-butoxy) phenyl [4- (4-biphenyl) Ruthio) -3-butoxyphenyl] 4-biphenylylsulfonium tris [(trifluoromethyl) sulfonyl] methanide, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium trifluoromethanesulfonate, tris [4- (4-acetyl) Phenylsulfanyl) phenyl] sulfonium nonafluorobutanesulfonate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium heptadecafluorooctanesulfonate, tris [4- (4-acetylphenylsulfate) Annyl) phenyl] sulfonium p-toluenesulfonate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium hexafluoroantimonate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium hexafluorophosphate, tris [4 -(4-acetylphenylsulfanyl) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tetrafluoroborate, tris [4- (4-acetylphenylsulfanyl) Phenyl] sulfonium tetrakis (pentafluorophenyl) borate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris [(Trifluoromethyl) sulfonyl] methanide, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium trifluoromethanesulfonate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium Nonafluorobutanesulfonate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium heptadecafluorooctanesulfonate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium p-toluene Sulfonate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium hexafluoroantimonate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium hexafluorophosphate Fate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium tetrafluoro Borate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, tris [4- (4-acetyl-3-methylphenylthio) phenyl] sulfonium tris [(tri Fluoromethyl) sulfonyl] methanide, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium trifluoromethanesulfonate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium Nafluorobutanesulfonate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium heptadecafluorooctanesulfonate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium p-toluene Sulfonate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium hexafluoroantimonate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium hexafluorophosphate, tris [4 -(4-acetyl-3-ethylphenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium tetrafluor Roborate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, tris [4- (4-acetyl-3-ethylphenylthio) phenyl] sulfonium tris [(tri Fluoromethyl) sulfonyl] methanide, tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium trifluoromethanesulfonate, tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium nonafluorobutane Sulfonate, tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium heptadecafluorooctane sulfonate, tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium p-toluene Sulfonate, tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium hexafluoroantimonate, tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium hexafluorophosphate, tris [ 4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium tetrafluoroborate, tris [ 4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, tris [4- (4-acetyl-3-butylphenylthio) phenyl] sulfonium tris [(trifluoro) Triarylsulfonium salts such as methyl) sulfonyl] methanide and the like.

  The onium salt compound used as the component (B) is trifluoromethanesulfonate, nonafluorobutanesulfonate, hexafluoroantimonate, hexafluorophosphate, tetrafluoroborate, tris (pentafluoroethyl) in terms of further excellent sensitivity and resolution. ) A compound having trifluorophosphate or tetrakis (pentafluorophenyl) borate is preferred. Moreover, (B) component can be used individually by 1 type or in mixture of 2 or more types.

  (B) Content of component is 0.1-15 mass with respect to 100 mass parts of (A) component from a viewpoint which is excellent with the sensitivity of the photosensitive resin composition of this embodiment, resolution, a pattern shape, etc. Part is preferable, 0.3-10 mass parts is more preferable, 1-10 mass parts is still more preferable, and 3-10 mass parts is especially preferable. In addition, in this specification, 100 mass parts of (A) component means that it is 100 mass parts of solid content of (A) component.

<(C) component>
The photosensitive resin composition of the present embodiment includes, as the component (C), a compound having at least one selected from the group consisting of an aromatic ring, a heterocyclic ring, and an alicyclic ring, and having a methylol group or an alkoxyalkyl group. (However, (D) component or (E) component is not included). Here, the aromatic ring means an aromatic hydrocarbon group (for example, a hydrocarbon group having 6 to 10 carbon atoms), and examples thereof include a benzene ring and a naphthalene ring. The heterocyclic ring means a cyclic group (for example, a cyclic group having 3 to 10 carbon atoms) having at least one nitrogen atom, oxygen atom, sulfur atom, etc., for example, a pyridine ring, an imidazole ring, a pyrrolidinone ring, Examples include an oxazolidinone ring, an imidazolidinone ring, and a pyrimidinone ring. The alicyclic ring means a cyclic hydrocarbon group having no aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), for example, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and A cyclohexane ring is mentioned. An alkoxyalkyl group means a group in which an alkyl group is bonded to an alkyl group through an oxygen atom. Further, the two alkyl groups may be different from each other, for example, an alkyl group having 1 to 10 carbon atoms.

  By containing (C) component, when curing by exposure and post-exposure heat treatment, methylol groups or alkoxyalkyl groups in component (C), or methylol groups or alkoxy in component (C) By reacting the alkyl group and the component (A) with dealcoholization, the solubility of the composition in the developer is greatly reduced, and a negative pattern can be formed. In addition, when the photosensitive layer after the resin pattern is formed is heated and cured, the (C) component reacts with the (A) component to form a bridge structure, thereby preventing the resin pattern from being weakened and melted. . Specifically, a compound having a phenolic hydroxyl group (however, the component (A) is not included), a compound having a hydroxymethylamino group or a compound having an alkoxymethylamino group can be preferably used. . (C) A component can be used individually by 1 type or in mixture of 2 or more types.

As the compound having a phenolic hydroxyl group, a conventionally known compound can be used, and the compound represented by the following general formula (1) is effective in promoting the dissolution of unexposed portions and a photosensitive resin film (resin pattern). ) Is preferable because of its excellent balance with the effect of preventing melting during curing.

In the above general formula (1), Z represents a single bond or a divalent organic group, R ⁸¹ and R ⁸² each independently represent a hydrogen atom or a monovalent organic group, and R ⁸³ and R ⁸⁴ represent Each independently represents a monovalent organic group, a and b each independently represent an integer of 1 to 3, and c and d each independently 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; an alkenyl group having 2 to 10 carbon atoms such as a vinyl group. An aryl group having 6 to 30 carbon atoms such as a phenyl group; 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 to} R ⁸⁴ , they may be the same as or different from each other.

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

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

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

  In said general formula (3), several R shows an alkyl group (for example, a C1-C10 alkyl group) each independently.

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

In the above 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), or a hydrogen atom thereof. Or a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond or an amide bond in which a part or all of is substituted with a halogen atom. R ⁹ represents a hydrogen atom, a hydroxyl group (hydroxy group), an alkyl group 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.

Specifically, the compound having an alkoxymethylamino group is preferably a compound represented by the following general formula (5) or a compound represented by the following general formula (6).

In general formula (5), several R shows an alkyl group (for example, a C1-C10 alkyl group) each independently.

  In general formula (6), several R shows an alkyl group (for example, a C1-C10 alkyl group) each independently.

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

  (C) As for content of a component, 5-80 mass parts is preferable with respect to 100 mass parts of (A) component, 10-70 mass parts is more preferable, 15-55 mass parts is still more preferable, 20-40 mass parts Part is particularly preferred. When the content of component (C) is 5 parts by mass or more, chemical resistance and heat resistance tend to be good, and when it is 80 parts by mass or less, resolution tends to be further improved.

<(D) component>
The photosensitive resin composition of the present embodiment includes at least one functional group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, and a hydroxyl group as the component (D). Contains an aliphatic compound having two or more groups. In addition, (D) component may have 2 or more types of different functional groups one by one, and may have 2 or more of 1 type of functional groups. The compound is preferably an aliphatic compound having three or more functional groups. The upper limit of the number of functional groups is not particularly limited, but is 12 for example.

  From the viewpoint of workability when forming a photosensitive resin composition layer (photosensitive layer) on a substrate, the photosensitive resin composition may be required to have excellent adhesion (tackiness) to the substrate. . When using a photosensitive resin composition that does not have sufficient tackiness, the photosensitive resin composition layer in the exposed area is easily removed by the development process, and the adhesion between the substrate and the resist pattern tends to deteriorate. . When the photosensitive resin composition contains the component (D), the adhesiveness between the photosensitive resin composition layer and the substrate, that is, tackiness can be improved. Furthermore, the photosensitive resin composition contains the component (D), so that the coating film (photosensitive layer) can be given flexibility, and the dissolution rate of the unexposed area when developing with an alkaline aqueous solution can be increased. Can do. From the viewpoint of tackiness and solubility in an aqueous alkali solution, the molecular weight of component (D) is preferably 92 to 2000, more preferably 106 to 1500, and still more preferably 134 to 1300 in terms of weight average molecular weight in consideration of balance. In addition, about the compound with a low molecular weight, when it is difficult to measure by the above-mentioned measuring method of the weight average molecular weight, the molecular weight can be measured by another method, and the average can be calculated.

Specific examples of the component (D) include compounds represented by the following general formulas (7) to (10). The “aliphatic compound” refers to a compound in which the main skeleton is an aliphatic skeleton and does not contain an aromatic ring or an aromatic heterocyclic ring.

In general formulas (7) to (10), R ₁ , R ₅ , R ₁₆ and R ₁₉ each independently represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group or a group represented by general formula (11). , R ₂₁ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, and R ₂ , R ₃ , R ₄ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₇ , R ₁₈ and R ₂₀ are each represented by a hydroxyl group, a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, an acryloyloxy group, a methacryloyloxy group, and the general formula (12). that a group represented by the group or the general formula (13), a hydroxyl group, respectively R ₂₂ and R ₂₃ independently, glycidyloxy group, oxetanyl alkyl ether group Vinyl ether group, an acryloyloxy group or a methacryloyloxy group, n and m is an integer of from 1 to 10, respectively. Examples of the alkyl group in the oxetanyl alkyl ether group include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable.

  As the component (D), specifically, a compound having a glycidyloxy group, an oxetanyl alkyl ether group, a vinyl ether group, an acryloyloxy group or a methacryloyloxy group is preferable, and two or more glycidyloxy groups or two or more acryloyl groups are preferred. A compound having an oxy group is more preferable, and a compound having three or more glycidyloxy groups or three or more acryloyloxy groups is more preferable. (D) A component can be used individually by 1 type or in mixture of 2 or more types.

  (D) As a functional group of a component, a glycidyloxy group, an acryloyloxy group, or a methacryloyloxy group is preferable, a glycidyloxy group or an acryloyl group is more preferable, and an acryloyloxy group is still more preferable. From the viewpoint of developability, the component (D) is preferably an aliphatic compound having two or more glycidyloxy groups, and more preferably an aliphatic compound having three or more glycidyloxy groups. More preferably, it is an aliphatic compound having a glycidyloxy group having a weight average molecular weight of 1000 or less.

  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, 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 propoxylay Triglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, diglycidyl 1,2-cyclohexane dicarboxylate.

  Particularly preferred are dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, and glycerin triglycidyl ether. These compounds having a glycidyloxy group can be used singly or in combination of two or more.

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

  Examples of the compound having an oxetanyl alkyl ether include a compound having a 3-alkyl-3-oxetanyl alkyl ether group, and a compound having a 3-ethyl-3-oxetanyl alkyl ether group is preferable. Examples of such oxetane compounds include dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris (3-ethyl-3- Oxetanylmethyl) ether, trimethylolethane tris (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, glycerol poly (3-ethyl-3-oxetanylmethyl) ether And glycerin tris (3-ethyl-3-oxetanylmethyl) ether. These compounds having oxetanyl alkyl ether can be used singly or in combination of two or more.

  Examples of the compound having an acryloyloxy group include EO-modified dipentaerythritol hexaacrylate, PO-modified dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, EO-modified ditrimethylolpropane tetraacrylate, PO-modified ditrimethylolpropane tetraacrylate, ditrile Methylolpropane tetraacrylate, EO-modified pentaerythritol tetraacrylate, PO-modified pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, EO-modified pentaerythritol triacrylate, PO-modified pentaerythritol triacrylate, pentaerythritol triacrylate, EO-modified trimethylolpropane acrylate, PO modified trim Triacrylate, trimethylolpropane acrylate, EO-modified glycerol tri acrylate, PO-modified glycerol triacrylate, glycerin triacrylate. These compounds having an acryloyloxy group can be used singly or in combination of two or more. EO represents an oxyethylene group, and PO represents an oxypropylene group.

  Examples of the compound having a methacryloyloxy group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO-modified ditrimethylolpropane tetramethacrylate, PO-modified ditrimethylolpropane tetramethacrylate, ditriethyl. Methylolpropane tetramethacrylate, EO modified pentaerythritol tetramethacrylate, PO modified pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, EO modified pentaerythritol trimethacrylate, PO modified pentaerythritol trimethacrylate, pentaerythritol trimethacrylate, EO modified trimethylolpropane methacrylate Acrylate, PO-modified trimethylolpropane dimethacrylate, trimethylolpropane dimethacrylate, EO modified glycerol trimethacrylate, PO-modified glycerol trimethacrylate, glycerine trimethacrylate and the like. These compounds having a methacryloyloxy group can be used singly or in combination of two or more. EO represents an oxyethylene group, and PO represents an oxypropylene group.

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

  Among the components (D), pentaerythritol triacrylate, trimethylolethane triglycidyl ether, and trimethylolpropane triglycidyl ether are preferable because they are further excellent in sensitivity and resolution.

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

  (D) As for content of component, 1-70 mass parts is preferred to 100 mass parts of (A) component, 10-70 mass parts is more preferred, 20-70 mass parts is still more preferred, 25-65 mass. Part is particularly preferable, and 30 to 50 parts by mass is extremely preferable. When the content of the component (D) is 1 part by mass or more, the coating film can be further provided with flexibility, and the dissolution rate of the unexposed part when developing with an alkaline aqueous solution is further easily increased. There is a tendency that the photosensitive resin composition is easily formed on a desired support.

<(E) component>
The photosensitive resin composition of the present embodiment contains at least one compound selected from the group consisting of aliphatic amines and nitrogen-containing heterocyclic compounds as the component (E), so that the solution of the photosensitive resin composition can be obtained. The image quality can be improved. Moreover, the tolerance of the exposure amount which can form a fine resist pattern can be improved by containing (E) component, and productivity can be improved more. Here, the aliphatic amine means an amine whose main skeleton is an aliphatic skeleton and does not contain an aromatic ring or a heterocyclic ring. The nitrogen-containing heterocyclic compound means a compound having an optionally substituted aromatic heterocyclic ring or an optionally substituted alicyclic heterocyclic ring and having nitrogen as a hetero atom, such as a piperidine compound. , Piperidone compounds, pyrrolidine compounds, tetrazole compounds, benzotriazole compounds, and the like. In addition, the nitrogen-containing heterocyclic compound of (E) component shall exclude the compound which has a methylol group or an alkoxyalkyl group.

  The component (E) is not particularly limited as long as it is a compound selected from the group consisting of an aliphatic amine and a nitrogen-containing heterocyclic compound, but at least one selected from the group consisting of a tetrazole skeleton and a benzotriazole skeleton from the viewpoint of resolution. A compound having a seed skeleton or a tertiary amine is preferred. (E) A component can be used individually by 1 type or in mixture of 2 or more types. Specific examples are shown below.

  Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, triisobutylamine, N , N-diisopropylethylamine, N, N-diethylmethylamine, N, N-diethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, 1-methylpiperidine, 1- (2- Aminoethyl) piperidine, 4-amino-1-isopropylpiperidine, 1-methyl-4-piperidone, 4-hydroxy-1-methylpiperidine, 1-piperidineethanol, 1-ethylpyrrolidine, tris [2- (dimethylamino) ethyl Amine, N- Chill diethanolamine, N, N- dibutyl ethanolamine, 2-diethylaminoethanol, N- methyldiethanolamine and the like. These tertiary amines can be used singly or in combination of two or more.

  Examples of the tetrazole compounds include 1H-tetrazole, 5-amino-1H-tetrazole, 5-mercapto-1H-tetrazole, 5-methyl-1H-tetrazole, 5-ethyl-1H-tetrazole, 5-propyl-1H- Tetrazole, 5-butyl-1H-tetrazole, 5-benzyl-1H-tetrazole, 5-amino-1-methyltetrazole, 5-amino-1-ethyltetrazole, 5-amino-1-propyltetrazole, 5-amino-1 -Butyltetrazole, 5-mercapto-1-methyltetrazole, 5-mercapto-1-ethyltetrazole, 5-mercapto-1-propyltetrazole, 5-mercapto-1-butyltetrazole, 1H-tetrazol-1-acetic acid, 1H- Tetrazole-5-acetic acid, 1H-te Razole-1-ethyl acetate, 1H-tetrazole-5-ethyl acetate, 1- (4-carboxyphenyl) -1-mercapto-1H-tetrazole, 1- (2-dimethylaminoethyl) -1-mercaptotetrazole, 5- And mercapto-1- (4-methoxyphenyl) -1H-tetrazole. These tetrazole compounds can be used singly or in combination of two or more.

  Examples of the benzotriazole compounds include 1,2,3-benzotriazole, 1-aminobenzotriazole, 2-aminobenzotriazole, 5-carboxybenzotriazole, and 2- (2′-hydroxy-5′-methylphenyl). Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2,2 ′-[[(methyl-1H-benzotriazol-1-yl) methyl] imino] Bisethanol, 1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole and the like can be mentioned. These benzotriazole compounds can be used singly or in combination of two or more.

  Among the components (E), a compound having a tertiary amine, a tetrazole skeleton and an amino group, and a compound having a benzotriazole skeleton and an amino group are more preferable, and a tertiary amine is more preferable, in terms of further excellent resolution. Triamylamine is particularly preferred. (E) 0.01-1.5 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of a component, 0.10-1.0 mass part is more preferable. When the content of the component (E) is 0.01 parts by mass or more, the resolution of the photosensitive resin composition is easily improved, and when it is 1.5 parts by mass or less, the sensitivity of the photosensitive resin composition tends to be maintained. There is.

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

  The content of the component (F) is preferably 30 to 200 parts by mass and more preferably 55 to 120 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition excluding the component (F).

<(G) component>
The photosensitive resin composition of this embodiment may contain the compound which has a Si-O bond as (G) component. The component (G) is not particularly limited as long as it has a Si—O bond, and examples thereof include an inorganic filler and a silane compound having a Si—O bond, and an alkoxy oligomer having a Si—O bond. It is done. (G) A component can be used individually by 1 type or in mixture of 2 or more types.

  When an inorganic filler is used as the component (G), the inorganic filler is preferably silica such as fused spherical silica, fused pulverized silica, fumed silica, or sol-gel silica. Moreover, the inorganic filler may have a Si-O bond by processing an inorganic filler with a silane compound. Among inorganic fillers treated with silane compounds, inorganic fillers other than silica include aluminum oxide, aluminum hydroxide, calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide, talc, mica Inorganic fillers derived from mineral products such as

  When a silane compound is used as the component (G), the silane compound is not particularly limited as long as the silane compound has a Si—O bond. Examples of the silane compound include alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acrylic silane, methacryl silane, mercapto silane, sulfide silane, isocyanate silane, sulfur silane, styryl silane, alkyl chlorosilane, and the like.

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

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

  Specific examples of the silane compound as component (G) include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, and diisopropyl. Dimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, Phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrieth Sisilane, 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- (triethoxy Silyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Tacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylidene ) -3-aminopropyltriethoxysilane and the like.

  As for content of (G) component, 1.8-420 mass parts is preferable with respect to 100 mass parts of (A) component, and 1.8-270 mass parts is more preferable.

<Other ingredients>
In addition to the component (A), the photosensitive resin composition of the present embodiment may contain a phenolic low molecular compound having a molecular weight of less than 1000 (hereinafter referred to as “phenol compound (a)”). 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) ethane Emissions, and the like. The content of these phenol compounds (a) may be, for example, in the range of 0 to 40 parts by mass, particularly 0 to 30 parts by mass with respect to 100 parts by mass of the component (A).

  Moreover, the photosensitive resin composition of this embodiment may contain other components other than the above-mentioned component. Examples of other components include colorants, adhesion assistants, and leveling agents.

[Photosensitive element]
Next, the photosensitive element of this embodiment will be described.
The photosensitive element of this embodiment includes a support and a photosensitive layer provided on the support, and the photosensitive layer includes the above-described photosensitive resin composition. The photosensitive element of this embodiment may further include a protective layer that covers the photosensitive layer on the photosensitive layer.

  As the support, for example, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used. As for the thickness of the said support body (polymer film), 5-25 micrometers is preferable. In addition, the said polymer film may be laminated | stacked and used for both surfaces of a photosensitive layer by using one as a support body and another as a protective layer.

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

  The photosensitive layer can be formed by applying the 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 the photosensitive layer varies depending on the application, it is preferably 1 to 100 μm, more preferably 3 to 60 μm, still more preferably 5 to 40 μm after the photosensitive layer is dried. Further, from the viewpoint of insulation reliability and productivity in mounting a chip, the thickness of the photosensitive layer is preferably more than 20 μm, but may be 20 μm or less.

[Method of forming resist pattern]
Next, a resist pattern forming method of this embodiment will be described. The resist pattern forming method of the first embodiment includes a step of applying the photosensitive resin composition on a substrate (for example, a substrate), drying the photosensitive resin composition to form a photosensitive layer, and the photosensitive layer. A step of exposing the layer to a predetermined pattern, performing a post-exposure heat treatment (post-exposure bake), a step of developing the photosensitive layer after the heat treatment (post-exposure bake), and subjecting the resulting resin pattern to a heat treatment And including. The resist pattern forming method of the second embodiment includes a step of placing the photosensitive layer of the photosensitive element on a substrate (for example, a substrate), exposing the photosensitive layer to a predetermined pattern, and post-exposure heat treatment ( A step of performing post-exposure baking, and a step of developing the photosensitive layer after the heat treatment (post-exposure baking) and heat-treating the obtained resin pattern.

  In the resist pattern forming method of the present embodiment, for example, first, a substrate on which a resist pattern is to be formed (resin-coated copper foil, copper-clad laminate, silicon wafer with a metal sputtered film, silicon with a copper plating film) A photosensitive layer containing the above-described photosensitive resin composition is formed on a wafer, an alumina substrate, or the like. As the method for forming the photosensitive layer, the photosensitive resin composition is applied to a substrate (for example, coating), dried, and the solvent is volatilized to form a coating film (photosensitive layer). And a method of transferring the photosensitive layer in the conductive element onto the 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. Moreover, the thickness of the coating film can be appropriately controlled by adjusting the coating means, the solid content concentration and the viscosity of the photosensitive resin composition.

Next, the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern. Examples of actinic rays used for exposure include g-line stepper rays; UV rays such as low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and i-line steppers; electron beams; laser rays. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the thickness is about 100 to 3000 mJ / cm ² when the thickness of the photosensitive layer is 5 to 50 μm.

  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 (C) by the acid generated from the photosensitive acid generator can be promoted. The post-exposure baking conditions vary depending on the composition of the photosensitive resin composition, the content of each component, the thickness of the photosensitive layer, and the like, but for example, heating at 50 to 150 ° C. for 1 to 60 minutes is preferable, and 60 to 100 It is more preferable to heat at a temperature of 1 to 15 minutes.

  Next, the photosensitive layer that has been subjected to exposure and / or post-exposure baking is developed with an alkaline developer, and the unexposed areas are 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, for example, 20 to 40 ° C. and 10 to 300 seconds in the spray development method.

  Examples of the alkaline developer include an alkaline aqueous solution obtained by dissolving an alkaline compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and choline in water so that the concentration becomes 1 to 10% by mass, and alkaline such as aqueous ammonia. An aqueous solution etc. are mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, after developing with this alkaline developing solution, it wash | cleans with water and dries. The alkaline developer is preferably tetramethylammonium hydroxide in terms of further excellent resolution.

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

  Moreover, in order to fully advance hardening and to prevent a deformation | transformation of the obtained resin pattern, 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 further heating at 80 to 200 ° C. for 10 minutes to 10 hours in the second stage. If it is the above-mentioned hardening conditions, there will be no restriction | limiting in particular as heating equipment, A general oven, an infrared furnace, etc. can be used.

[Semiconductor device]
The semiconductor device according to the present embodiment includes a cured product of the photosensitive resin composition according to the present embodiment. The cured product of the photosensitive resin composition of the present embodiment can be suitably used as, for example, a surface protective film 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.

  FIG. 1 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 / or an interlayer insulating film. A multilayer printed wiring board 100A shown in FIG. 1 (f) has a wiring pattern on its surface and inside. Hereinafter, a method of manufacturing the multilayer printed wiring board 100A according to an embodiment of the present disclosure will be briefly described with reference to FIG.

  First, the interlayer insulating film 103 is formed on both surfaces of the base material 101 having the wiring pattern 102 on the surface (see FIG. 1A). The interlayer insulating film 103 may be formed by printing a photosensitive resin composition using a screen printing machine or a roll coater. Alternatively, the photosensitive element described above is prepared in advance, and the photosensitive resin composition is prepared using a laminator. The photosensitive layer in the element can also be formed on the surface of the 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. 1B). Smear (residue) around the opening 104 is removed by desmear treatment.

  Next, a seed layer 105 is formed by an electroless plating method (see FIG. 1C). A photosensitive layer containing a semi-additive photosensitive resin composition is formed on the seed layer 105, and a predetermined portion is exposed and developed to form a resin pattern 106 (see FIG. 1D).

  Next, a wiring pattern 107 is formed on the portion of the seed layer 105 where the resin pattern 106 is not formed by electrolytic plating, and the resin pattern 106 is removed by a peeling solution, and then the wiring pattern 107 of the seed layer 105 is formed. Unexposed portions are removed by etching (see FIG. 1E).

  By repeating the above operation and forming a solder resist 108 containing a cured product of the above-described photosensitive resin composition on the outermost surface, the multilayer printed wiring board 100A can be produced (see FIG. 1 (f)). In the multilayer printed wiring board 100A thus obtained, 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.

<Examples 1 to 9 and Comparative Example 1>
Photosensitive acid generator (B-1), alkoxyalkyl compound (C-1), and compound having an acryloyloxy group (D-1) with respect to 100 parts by mass of the resin components (A-1 and A-2) ), A compound (E-1 to E-9) selected from the group consisting of an aliphatic amine and a nitrogen-containing heterocyclic compound, a solvent (F-1), and a compound (G-1) having a Si-O bond Were blended in the blending amount (unit: part by mass) shown in Table 1 below to obtain a photosensitive resin composition.

Abbreviations in Table 1 are as follows.
A-1: Novolac resin (made by Asahi Organic Materials Co., Ltd., trade name: TR4020G, weight average molecular weight: 13000)
A-2: Novolac resin (Asahi Organic Materials Co., Ltd., trade name: TR4080G, weight average molecular weight: 5000)
B-1: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-310B)
C-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicalak MX-270)
D-1: Pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: PET-30)
E-1: N, N-diisopropylethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-2: Tripropylamine (Wako Pure Chemical Industries, Ltd.)
E-3: Triethylamine (Wako Pure Chemical Industries, Ltd.)
E-4: Trihexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-5: 1,2,3-benzotriazole (manufactured by Wako Pure Chemical Industries, Ltd.)
E-6: 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole (manufactured by ADEKA, trade name: LA-29)
E-7: 1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-8: 5-amino-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
E-9: Triamylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
F-1: Methyl ethyl ketone (made by Wako Pure Chemical Industries, Ltd., trade name: 2-butanone)
G-1: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-403)

  The above photosensitive resin composition is formed on a polyethylene terephthalate film (manufactured by Teijin DuPont Films, trade name: Purex A53, "Purex" is a registered trademark) (support), and the thickness of the photosensitive resin composition is uniform. And dried for 10 minutes with a hot air convection dryer at 90 ° C. After drying, it was coated with a polyethylene film (trade name: NF-15, manufactured by Tamapoly Co., Ltd.) (protective layer) to obtain a photosensitive element having a photosensitive layer thickness of 25 μm.

<Evaluation of resolution and sensitivity>
The protective layer of the photosensitive element was peeled off from a 6-inch diameter silicon wafer, and the photosensitive element was laminated to obtain a laminate including a support, a photosensitive layer, and a silicon wafer in this order. Lamination was performed using a 100 ° C. heat roll at a pressure of 0.4 MPa and a roll speed of 1.0 m / min. Next, the support of the laminate is peeled off, and reduced projection exposure is performed on the photosensitive layer through a mask with i-line (365 nm) using an i-line stepper (trade name: FPA-3000iW, manufactured by Canon Inc.). Went. As the mask, a mask having a pattern in which the width of the exposed part and the unexposed part is 1: 1 is from 2 μm: 2 μm to 30 μm: 30 μm in 1 μm increments. Further, the reduced projection exposure was performed while changing the exposure amount by 150 mJ / cm ^{2 in} the range of 150 to 1650 mJ / cm ² .

  The exposed photosensitive layer was heated at 65 ° C. for 1 minute and then at 75 ° C. for 8 minutes (post exposure bake). Next, a 2.38 mass% tetramethylammonium hydroxide aqueous solution (manufactured by Tama Chemical Co., Ltd., trade name: TMAH 2.38%) and a developing machine (manufactured by Takizawa Sangyo Co., Ltd., trade name: AD-1200) are used as a developer. The developer is sprayed onto the photosensitive layer for a time corresponding to four times the shortest development time (the shortest time for removing the unexposed area) (pump discharge pressure [developer]: 0.16 MPa), and unexposed. Part was removed. Subsequently, purified water (manufactured by Wako Pure Chemical Industries, Ltd.) is sprayed as a rinsing liquid for 30 seconds (pump discharge pressure [rinsing liquid]: 0.12 to 0.14 MPa), the developer is washed away, and the resin is dried. A pattern was formed. The formed resin pattern was observed by enlarging the magnification to 1000 times using a metal microscope. Among the patterns in which the space portion (unexposed portion) is removed cleanly and the line portion (exposed portion) is formed without meandering or chipping, the smallest space width value is set as the resolution, and the exposure at that time Quantity was assessed as sensitivity. Moreover, the range of the exposure amount in which a via (resin pattern) having a resolution of 10 μm or less could be formed was evaluated as the exposure dose margin. The evaluation results are shown in Table 2 below.

As is clear from Table 2, Examples 1 to 9 using an aliphatic amine or a nitrogen-containing heterocyclic compound have a resolution higher than that of Comparative Example 1 using no aliphatic amine and a nitrogen-containing heterocyclic compound. It was found that the resolution was extremely good as compared with Comparative Example 1 in which the resolution was 7 μm or less and the resolution was 10 μm. Further, in Comparative Example 1, the exposure amount (sensitivity) that can form a via with a resolution of 10 μm or less was only one point of 300 mJ / cm ² . On the other hand, in Examples 1 to 9, there was a width of 150 to 1050 mJ / cm ^{2 in} the margin of exposure (sensitivity) that can form a via with a resolution of 10 μm or less (allowable range). Therefore, it was found that Examples 1 to 9 had a wide exposure dose and excellent productivity compared to Comparative Example 1.

  The photosensitive resin composition of this indication is applied as a material used for the surface protection film or interlayer insulation film of a semiconductor element. Moreover, it is applied as a material used for a solder resist of a wiring board material or an interlayer insulating film. In particular, since the photosensitive resin composition has good resolution and heat resistance after curing, it is suitably used for highly integrated package substrates that are thinned and densified.

  DESCRIPTION OF SYMBOLS 100A ... Multilayer printed wiring board, 101 ... Base material, 102, 107 ... Wiring pattern, 103 ... Interlayer insulation film, 104 ... Opening part, 105 ... Seed layer, 106 ... Resin pattern, 108 ... Solder resist.

Claims (8)

(A) component: a resin having a phenolic hydroxyl group;
(B) component: a photosensitive acid generator;
(C) component: a compound having at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and having a methylol group or an alkoxyalkyl group;
(D) component: an aliphatic compound having two or more functional groups selected from the group consisting of acryloyloxy group, methacryloyloxy group, glycidyloxy group, oxetanyl alkyl ether group, vinyl ether group and hydroxyl group;
(E) component: The photosensitive resin composition containing the at least 1 sort (s) of compound chosen from the group which consists of an aliphatic amine and a nitrogen-containing heterocyclic compound.   The photosensitive resin composition according to claim 1, wherein the component (E) includes a compound having at least one skeleton selected from the group consisting of a tetrazole skeleton and a benzotriazole skeleton, or a tertiary amine.   The photosensitive resin composition of Claim 1 or 2 whose content of the said (D) component is 1-70 mass parts with respect to 100 mass parts of said (A) component.   (G) The photosensitive resin composition as described in any one of Claims 1-3 which further contains the compound which has Si: O bond.   A photosensitive element provided with a support body and the photosensitive layer formed using the photosensitive resin composition as described in any one of Claims 1-4 provided on this support body.   A semiconductor device provided with the hardened | cured material of the photosensitive resin composition as described in any one of Claims 1-4. Applying the photosensitive resin composition according to any one of claims 1 to 4 on a substrate, and drying the photosensitive resin composition to form a photosensitive layer;
Exposing the photosensitive layer to a predetermined pattern and performing a post-exposure heat treatment;
Developing the photosensitive layer after the heat treatment, and heat-treating the obtained resin pattern. Forming a photosensitive layer on the substrate using the photosensitive element according to claim 5;
Exposing the photosensitive layer to a predetermined pattern and performing a post-exposure heat treatment;
Developing the photosensitive layer after the heat treatment, and heat-treating the obtained resin pattern.

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