WO2021187481A1

WO2021187481A1 - Photosensitive insulating film-forming composition

Info

Publication number: WO2021187481A1
Application number: PCT/JP2021/010607
Authority: WO
Inventors: 雅久遠藤; 和宏澤田; 高広岸岡
Original assignee: 日産化学株式会社
Priority date: 2020-03-18
Filing date: 2021-03-16
Publication date: 2021-09-23
Also published as: KR20220155258A; JPWO2021187481A1; CN115298616A; TW202204472A; JP7444239B2

Abstract

Provided are: a photosensitive insulating film composition that gives a cured body for which the initial dielectric tangent is low and changes over time therein are small; a method for producing a cured relief pattern-equipped substrate using the photosensitive insulating film composition; and a semiconductor device provided with the cured relief pattern. A photosensitive insulating film-forming composition containing a polymer having a repeating unit structure represented by formula (1): [in formula (1), group A¹ represents an aromatic heterocycle represented by (A¹); group A² represents an aromatic heterocycle represented by (A²); group A¹ and group A² may have crosslinkable substituents; group B¹ represents an organic group having a crosslinkable substituent; and group B² represents an organic group not having a crosslinkable substituent.] and a solvent.

Description

Photosensitive insulating film forming composition

The present invention relates to a photosensitive insulating film forming composition, a photosensitive resin film obtained from the composition, a photosensitive resin film obtained from the composition, a substrate with a cured relief pattern using the composition, and a method for producing the same. , And a semiconductor device having the cured relief pattern.

Conventionally, a polyimide resin having excellent heat resistance, electrical properties, and mechanical properties has been used as an insulating material for electronic components, a passivation film, a surface protective film, an interlayer insulating film, and the like of a semiconductor device. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor easily form a heat-resistant relief pattern film by coating, exposing, developing, and thermally imidizing the precursor. be able to. Such a photosensitive polyimide precursor has a feature that it enables a significant process shortening as compared with a conventional non-photosensitive polyimide resin.

On the other hand, in recent years, the method of mounting a semiconductor device on a printed wiring board has changed from the viewpoint of improving the degree of integration and calculation function and reducing the chip size. The polyimide film comes into direct contact with the solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which enable higher density mounting from the conventional mounting method using metal pins and lead-tin eutectic solder. Structures are being used. When forming such a bump structure, the coating is required to have high heat resistance and chemical resistance.

Further, with the progress of miniaturization of semiconductor devices, the problem of wiring delay has become apparent. As a means for improving the wiring resistance of a semiconductor device, the gold or aluminum wiring that has been used so far has been changed to a copper or copper alloy wiring having a lower resistance. Further, a method of preventing wiring delay by improving the insulation between wirings is also adopted. In recent years, low dielectric constant materials often constitute semiconductor devices as materials with high insulating properties, but on the other hand, low dielectric constant materials tend to be brittle and fragile, for example, on a substrate together with a semiconductor chip through a solder reflow process. When mounted on, there is a problem that the low dielectric constant material part is destroyed by shrinkage due to temperature change.
As a means for solving this problem, Patent Document 1 introduces an aliphatic group having an ethylene glycol structure and having 5 to 30 carbon atoms in a part of the side chain of the polyimide precursor, thereby containing the polyimide precursor. A photosensitive resin composition is disclosed in which the transparency when the sex resin composition is formed is improved, and the Young ratio of the cured film is further improved after heat curing.

Re-table 2013-168675

The photosensitive resin composition composed of the polyimide precursor described in Patent Document 1 gives a cured product having high transparency and a high Young's modulus after heat curing, but when used in the above-mentioned applications, it is dielectrically tangent. Further reduction and suppression of changes in dielectric loss tangent with time have been required.

Therefore, the present invention is a photosensitive resin composition, which not only reduces the dielectric loss tangent, but also provides a cured film in which the change over time of the dielectric loss tangent after being left for a certain period of time in a normal environment is suppressed to a small extent. It is an object of the present invention to provide a substrate with a cured relief pattern using the above, a method for manufacturing the same, and a semiconductor device provided with the cured relief pattern.

As a result of diligent studies to achieve the above problems, the present inventors have adopted a polymer having a repeating unit structure containing a specific aromatic heterocycle and a crosslinkable substituent, thereby achieving a low dielectric loss tangent. We have found that a photosensitive resin composition that provides a cured film that can be maintained even after long-term storage under normal circumstances can be obtained, and the present invention has been completed.

That is, the present invention includes the following.
[1] The following equation (1):

[In equation (1)
Group A ¹ is

Represents a 5- to 8-membered aromatic heterocycle represented by
The aromatic heterocycle may have a crosslinkable substituent and may have a crosslinkable substituent.
Group A ² is

Represents a 5- to 8-membered aromatic heterocycle represented by
The aromatic heterocycle may have a crosslinkable substituent and may have a crosslinkable substituent.
Group B ¹ represents an organic group having a crosslinkable substituent and having 6 to 40 carbon atoms, which may contain at least one heteroatom selected from N, S and O, and may contain a halogen atom.
Group B ² represents an organic group having 6 to 40 carbon atoms which does not have a crosslinkable substituent and may contain at least one heteroatom selected from N, S and O, and may contain a halogen atom. ,
n ¹ and n ² are independently numbers of 0 or more and 1 or less, respectively.
m ¹ and m ² are independently numbers of 0 or more and 1 or less, respectively.
n is a number greater than or equal to 1
m is a number greater than or equal to 0
10 ≦ n + m ≦ 500,
However, ^{when neither group A 1} nor group A ² has a crosslinkable substituent,
If m ≠ 0, then ^{at least one} ^{of n 1} and m 1 is 1.
If m = 0, n ¹ is 1. ]
A photosensitive insulating film-forming composition containing a polymer having a repeating unit structure represented by (1) and a solvent.
[2] group ^{A 1} is

Represents an aromatic heterocycle represented by, and the aromatic heterocycle may have a crosslinkable substituent.
The photosensitive insulating film forming composition according to [1].
[3] Group A ² is

as well as

Represents at least one aromatic heterocycle selected from the group consisting of aromatic heterocycles represented by, and any of these aromatic heterocycles may have a crosslinkable substituent.
The photosensitive insulating film forming composition according to [1] or [2].
[4] group ^{B 1} is at least one selected from the following,

(In the formula, G represents either a direct bond or one of the following formulas.

L and M independently represent a hydrogen atom, a phenyl group, or a C1-3 alkyl group, respectively. )
The photosensitive insulating film forming composition according to any one of [1] to [3].
[5] Group B ¹

The photosensitive insulating film forming composition according to any one of [1] to [4] represented by.
[6] Group B ² is at least one selected from the following.

L and M independently represent a hydrogen atom, a phenyl group, or a C1-3 alkyl group, respectively. )
The photosensitive insulating film-forming composition according to any one of [1] to [5].
[7] Group B ²

The photosensitive insulating film forming composition according to any one of [1] to [6] represented by.
[8] The photosensitive insulating film-forming composition according to any one of [1] to [7], wherein the crosslinkable substituent contains a radical crosslinkable group.
[9] The photosensitive insulating film-forming composition according to any one of [1] to [8], wherein the crosslinkable substituent contains a (meth) acrylate group, a maleimide group, or an allyl group.
[10] The photosensitive insulating film-forming composition according to any one of [1] to [9], wherein m = 0.
[11] A photosensitive resin film, which is a fired product of a coating film of the photosensitive insulating film forming composition according to any one of [1] to [10].
[12] The photosensitive resin film according to [11], which has a dielectric loss tangent of 0.01 or less.
[13] The following steps:
(1) A step of applying the photosensitive insulating film forming composition according to any one of [1] to [10] onto a substrate to form a photosensitive resin layer on the substrate.
(2) A step of exposing the photosensitive resin layer and
(3) A step of developing the photosensitive resin layer after the exposure to form a relief pattern, and
(4) A method for manufacturing a substrate with a cured relief pattern, which comprises a step of heat-treating the relief pattern to form a cured relief pattern.
[14] A substrate with a cured relief pattern manufactured by the method according to [13].
[15] A semiconductor device comprising a semiconductor element and a cured film provided on the upper or lower portion of the semiconductor element, wherein the cured film has the cured relief pattern according to [14].

According to the present invention, a photosensitive resin composition that gives a cured product having a low dielectric loss tangent, a photosensitive resin film obtained from the composition, a photosensitive resin film obtained from the composition, and a cured relief using the composition. It is possible to provide a patterned substrate, a method for producing the same, and a semiconductor device having the cured relief pattern.

[Photosensitive insulating film forming composition]
The photosensitive insulating film forming composition of the present invention is
The following formula (1):

[In equation (1)
Group A ¹ is

Represents a 5- to 8-membered aromatic heterocycle represented by
The aromatic heterocycle may have a crosslinkable substituent and may have a crosslinkable substituent.
Group B ¹ represents an organic group having a crosslinkable substituent and having 6 to 40 carbon atoms, which may contain at least one heteroatom selected from N, S and O, and may contain a halogen atom.
Group B ² represents an organic group having 6 to 40 carbon atoms and which does not have a crosslinkable substituent, which may contain at least one heteroatom selected from N, S and O, and may contain a halogen atom.
n ¹ and n ² are independently numbers of 0 or more and 1 or less, respectively.
m ¹ and m ² are independently numbers of 0 or more and 1 or less, respectively.
n is a number greater than or equal to 1
m is a number greater than or equal to 0
10 ≦ n + m ≦ 500,
However, ^{when neither group A 1} nor group A ² has a crosslinkable substituent,
If m ≠ 0, then ^{at least one} ^{of n 1} and m 1 is 1.
If m = 0, n ¹ is 1. ]
Includes a polymer having a repeating unit structure represented by, and a solvent.
Each component will be described below in order.

<Polymer>
The polymer according to the present invention has a repeating unit structure represented by the above formula (1).

Group A ¹ represents a heteroatom-free 5- to 8-membered aromatic heterocycle in the shortest series of covalent bonds between two bonds, the aromatic heterocycle having a crosslinkable substituent. May be good.

Preferably, the group A ¹ is

Represents an aromatic heterocycle represented by, and the aromatic heterocycle may have a crosslinkable substituent.

The group A ¹ may be one kind or a combination of two or more kinds.

In the above formula (1), the group A ² represents a 5- to 8-membered aromatic heterocycle containing a nitrogen atom in the shortest series of covalent bonds between two bonds, and the aromatic heterocycle is crosslinkable. It may have a substituent.

Preferably, the group A ² is

as well as

Represents at least one aromatic heterocycle selected from the group consisting of aromatic heterocycles represented by, and any of these aromatic heterocycles may have a crosslinkable substituent.

The group A ² may be one kind or a combination of two or more kinds.

Preferably, the crosslinkable substituent contains a radical crosslinkable group.

Preferably, the crosslinkable substituent contains a (meth) acrylate group, a maleimide group, or an allyl group.

Examples of the crosslinkable substituent containing the (meth) acrylate group include the following general formula (2):

(In the formula, R ³ , R ⁴ and R ⁵ are independently hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms, and m is an integer of 1 to 10. * Is an integer of 1 to 10. Examples thereof include a group represented by ^{the group A 1} , the group A ² , or the group B ¹ of the general formula (1).

^{R 3} in the above general formula (2) is not limited as long as it is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but when the photosensitive insulating film forming composition is a negative type, it is not limited. From the viewpoint of photosensitive characteristics, it is preferably a hydrogen atom or a methyl group.

^{R 4} and R ⁵ in the above general formula (2) are not limited as long as they are independently hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms, but the photosensitive insulating film forming composition is negative. In the case of a mold, it is preferably a hydrogen atom from the viewpoint of its photosensitive characteristics.

M in the above general formula (2) is an integer of 1 or more and 10 or less, and is preferably an integer of 1 or more and 4 or less from the viewpoint of photosensitive characteristics.

Specific examples of the monovalent organic group having 1 to 3 carbon atoms include a linear alkyl group such as a methyl group, an ethyl group and a propyl group; a branched alkyl group such as an isopropyl group; and a fat such as a cyclopropyl group. Cyclic alkyl group; alkenyl group such as vinyl group and allyl group; alkynyl group such as ethynyl group; alkoxy group such as methoxy group, ethoxy group and propoxy group; acyl group such as acetyl group; ester group such as methoxycarbonyl group; Examples thereof include a heterocyclic group such as a formyl group; a haloformyl group; a carbamoyl group; a cyano group; an oxylanyl group, an aziridinyl group, a thietanyl group, a triazinyl group, an oxathiolanyl group, a dihydroazetyl group and a dihydrothiazolyl group.

In the above formula (1), the group B ¹ may contain at least one heteroatom selected from N, S and O, and may contain a halogen atom, and has 6 to 40 carbon atoms having a crosslinkable substituent. Represents an organic group of.

Preferably, the group B ¹ is at least one selected from the following:

L and M independently represent a hydrogen atom, a phenyl group, or a C1-3 alkyl group, respectively. )

Preferably, the group B ¹ is

It is represented by.

In the above formula (1), the group B ² may contain at least one hetero atom selected from N, S and O, may contain a halogen atom, and has 6 carbon atoms having no crosslinkable substituent. Represents 40 to 40 organic groups.

Preferably, the group B ² is at least one selected from the following:

Preferably, the group B ² is

It is represented by.

When neither the group A ¹ nor the group A ² ^{has a crosslinkable substituent, at least one} ^{of n 1} and m 1 is 1 if m ≠ 0, ^{and n 1} is 1 if m = 0. That is, in the polymer having a repeating unit structure of Formula (1), group A ^1, even when group A ² are both not having a crosslinkable substituent, a group B ¹ having a crosslinkable substituent exist.

In the polymer having the repeating unit structure represented by the formula (1), the group A ² does not necessarily have to be present. In that case, m = 0 in the equation (1).

[Method for preparing polymer having repeating unit structure represented by formula (1)]
The polymer having a repeating unit structure represented by the formula (1) can be prepared by a known method. For example, ^{a compound represented by HO-A 1-} OH, a compound represented by HO-A ^2- OH, a compound represented by X-B ^1- X, and a compound represented by X-B ^2- X. Can be prepared by appropriately selecting and condensing (in the formula, A ¹ , A ² , B ¹ and B ² are synonymous with the above, and X is a halogen atom). A compound represented by HO-A ^1- OH, a compound represented by HO-A ^2- OH, a compound represented by X-B ^1- X, and a compound represented by X-B ^2- X. May be used alone or in combination of two or more. In this condensation reaction, for a total of 1 mol of the compound represented by ^{HO-A 1-} OH and the compound represented by HO-A ^2- ^{OH, the compound represented by X-B 1-} X and X total 0.1 to 10 moles of -B compound represented by ² -X, it can be preferably used by setting the proportion of 0.1 to 2 moles.

As the catalyst used in the condensation reaction, a basic or acidic catalyst can be used, but it is preferable to use a basic catalyst.
Examples of the basic catalyst include a solid base catalyst, and examples thereof include calcium hydroxide, strontium hydroxide octahydrate, barium hydroxide octahydrate, magnesium hydroxide, sodium carbonate, potassium carbonate and the like.
Examples of acidic catalysts include mineral acids such as sulfuric acid, phosphoric acid and perchloric acid, organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate and methanesulfonic acid, formic acid and oxalic acid. The carboxylic acids of can be used.
The amount of the catalyst varies depending on the kind of the catalyst used, relative to total 100 parts by weight of ^HO-A 1 compound represented by -OH and ^HO-A compound represented by 2 -OH, usually 0. It is 001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.05 to 100 parts by mass.

The condensation reaction is carried out without a solvent, but usually it is carried out with a solvent. The solvent is not particularly limited as long as it can dissolve the reaction substrate and does not inhibit the reaction. For example, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, dioxane and the like can be mentioned. The condensation reaction temperature is usually 40 ° C. to 200 ° C., preferably 50 ° C. to 180 ° C. The reaction time varies depending on the reaction temperature, but is usually 5 minutes to 500 hours, preferably 5 minutes to 200 hours.

The weight average molecular weight of the polymer having the repeating unit structure represented by the formula (1) is usually 500 to 100,000, preferably 600 to 80,000, 800 to 60,000, or 1,000 to 50,000. be.

[solvent]
As the solvent, it is preferable to use an organic solvent from the viewpoint of solubility in a polymer having a repeating unit structure represented by the formula (1). Specifically, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butyrolactone. , Α-Acetyl-γ-butyrolactone, methyllactate, ethyllactate, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, N-methyl-2-pyrrolidinone and the like. These can be used alone or in combination of two or more.

The solvent is, for example, 30 parts by mass to 1500 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1), depending on the desired coating film thickness and viscosity of the photosensitive insulating film forming composition. It can be used in the range of parts by mass, preferably 40 parts by mass to 1000 parts by mass, and more preferably 50 parts by mass to 300 parts by mass.

[Other ingredients]
In the embodiment, the photosensitive insulating film forming composition may further contain components other than the polymer and the solvent having the repeating unit structure represented by the above formula (1). Examples of other components include resin components other than polymers having a repeating unit structure represented by the formula (1), photopolymerization initiators, adhesion aids, hindered phenol compounds, carboxylic acid compounds or anhydrides thereof, and crosslinks. Examples include sex compounds, sensitizers, thermal polymerization inhibitors, azole compounds, fillers and the like.

[Resin components other than polymers having a repeating unit structure represented by the formula (1)]
In the embodiment, the photosensitive insulating film forming composition may further contain a resin component other than the polymer having the repeating unit structure represented by the formula (1). Examples of the resin component that can be contained in the photosensitive insulating film forming composition include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, and acrylic resin.
When such a resin is blended, the blending amount of the resin component is preferably in the range of 0.01 parts by mass to 20 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1). Is.

[Photopolymerization initiator]
The photosensitive insulating film-forming composition of the present invention may contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is a compound having absorption in the light source used during photocuring, but for example, tert-butylperoxy-iso-butyrate, 2,5-dimethyl-2,5-bis (benzoyl). Dioxy) hexane, 1,4-bis [α- (tert-butyldioxy) -iso-propoxy] benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butyldioxy) hexenehydro Peroxide, α- (iso-propylphenyl) -iso-propyl hydroperoxide, tert-butyl hydroperoxide, 1,1-bis (tert-butyldioxy) -3,3,5-trimethylcyclohexane, butyl-4,4-bis (Tart-butyldioxy) valerate, cyclohexanone peroxide, 2,2', 5,5'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert-amylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3'-bis (tert-butyl) Peroxycarbonyl) -4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldiperoxyisophthalate and other organic peroxides; 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone , Octamethylanthraquinone, 1,2-benzanthraquinone and other quinones; benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin and α-phenylbenzoin; 2,2-dimethoxy-1,2-diphenylethane- 1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy -2-Methyl-1-propane-1-one, 2-hydroxy-1- [4- {4- (2-hydroxy-2-methyl-propionyl) benzyl} -phenyl] -2-methyl-propane-1- On, phenylglioxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) ) -Alkylphenone compounds such as butane-1-one; acylphosphine oxide compounds such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazole-3-yl] Oxime ester compounds such as etanone can be mentioned.

The photopolymerization initiator is available as a commercially available product. For example, IRGACURE [registered trademark] 651, 184, 2959, 127, 907, 369, 379EG, 819, 819DW, and 819DW. 1800, 1870, 784, OXE01, OXE02, 250, 1173, MBF, TPO, 4265, TPO (above, manufactured by BASF), KAYACURE [registered trademark] DETX, MBP, same DMBI, EPA, OA (above, Nippon Kayaku Co., Ltd.), VICURE-10, 55 (above, STAUFFER Co. LTD), ESACURE KIP150, TZT, 1001, KTO46, KB1, KB1, KL200, KS300, EB3, Triazine-PMS, Triazine A, Triazine B (manufactured by Nippon Kayaku Hegner Co., Ltd.), ADEKA PUTMER N-1717, N-1414, N-1606 (manufactured by ADEKA Corporation) ). These photopolymerization initiators may be used alone or in combination of two or more.

The blending amount of the photopolymerization initiator is usually 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1), which is preferable from the viewpoint of photosensitivity characteristics. It is 0.5 parts by mass to 15 parts by mass. When 0.1 part by mass or more of the photopolymerization initiator is blended with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1), the photosensitivity of the photosensitive insulating film forming composition is likely to be improved. On the other hand, when 20 parts by mass or less is blended, the thick film curability of the photosensitive insulating film forming composition is likely to be improved.

[Crosslinking agent]
In the embodiment, a cross-linking agent can be added to the photosensitive insulating film forming composition in order to improve the resolution of the relief pattern. As such a cross-linking agent, a (meth) acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and is not particularly limited to the following, but ethylene such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Glycol or polyethylene glycol mono or diacrylate and methacrylate, propylene glycol or polypropylene glycol mono or diacrylate and methacrylate, glycerol mono, di or triacrylate and methacrylate, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol Diacrylate and dimethacrylate, diacrylate and dimethacrylate of 1,6-hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono or diacrylate and methacrylate of bisphenol A, benzenetrimethacrylate, isobornyl acrylate and methacrylate, Acrylamide and its derivatives, methacrylicamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di or triacrylate and methacrylate of glycerol, di, tri, or tetraacrylate and methacrylate of pentaerythritol, and ethylene oxide or propylene oxide of these compounds. Examples include compounds such as additives.

The blending amount of the cross-linking agent is preferably 1 part by mass to 100 parts by mass, and more preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1). be.

Examples of the thermal cross-linking agent include hexamethoxymethyl melamine, tetramethoxymethyl glycol uryl, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis (methoxymethyl) glycoluryl, 1,3,4,6-tetrakis (butoxymethyl). ) Glycoluryl, 1,3,4,6-tetrax (hydroxymethyl) glycoluryl, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrax (butoxymethyl) urea and 1,1, Examples thereof include 3,3-tetrakis (methoxymethyl) urea.

[Filler]
Examples of the filler include inorganic fillers, and specific examples thereof include sol such as silica, aluminum nitride, boron nitride, zirconia, and alumina.

[Adhesive aid]
In the embodiment, an adhesive auxiliary may be optionally added to the photosensitive insulating film forming composition in order to improve the adhesiveness between the film formed by using the photosensitive insulating film forming composition and the substrate. can. Examples of the adhesion aid include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and the like. 3-Methacryloxypropyldimethoxymethylsilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N -(3-Diethoxymethylsilylpropyl) succinimide, N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3'-bis (N- [3-triethoxysilyl] propylamide) -4 , 4'-Dicarboxylic acid, benzene-1,4-bis (N- [3-triethoxysilyl] propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propylsuccinic hydride, N- Examples thereof include silane coupling agents such as phenylaminopropyltrimethoxysilane, and aluminum-based adhesive aids such as aluminumtris (ethylacetacetate), aluminumtris (acetylacetonate), and ethylacetacetate aluminum diisopropyrate.

Among these adhesive aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. The blending amount of the adhesive aid is preferably in the range of 0.5 parts by mass to 25 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1).

[Hindered phenol compound]
In the embodiment, a hindered phenol compound can be optionally added to the photosensitive insulating film-forming composition in order to suppress discoloration on copper or as a polymerization inhibitor at a radical cross-linking site. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and octadecyl-3- (3,5-di-t-butyl). -4-Hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-thio-bis (3-methyl-6-t-butylphenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), triethyleneglycol-bis [3- (3) -T-Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2 -Thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro) Cinnamamide), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2,2'-methylene-bis (4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3-hydroxy-2,6-dimethyl-4-isopropylbenzyl) )-1,3,5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) )-1,3,5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-s-butyl-3-hydroxy-2,6-dimethylbenzyl) )-1,3,5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris [4- (1-ethylpropyl) -3-hydroxy-2,6 -Dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris [4-triethylmethyl-3-hydroxy-2,6- Dimethylbenzyl] -1 , 3,5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (3-hydroxy-2,6-dimethyl-4-phenylbenzyl) -1,3 , 5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl) -1 , 3,5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethyl) Benzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2) -Methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy) -2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5,6) -Diethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl) -3-Hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3) -Hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5) -Ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione and the like, but are not limited thereto. .. Among these, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) ) -Trione is particularly preferred.

The blending amount of the hindered phenol compound is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1), from the viewpoint of light sensitivity characteristics. More preferably, it is 0.5 parts by mass to 10 parts by mass. When the blending amount of the hindered phenol compound with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1) is 0.1 parts by mass or more, for example, a photosensitive insulating film forming composition on copper or a copper alloy. When an object is formed, discoloration and corrosion of copper or a copper alloy are prevented, while when the amount is 20 parts by mass or less, the light sensitivity is excellent, which is preferable.

[Sensitizer]
In the embodiment, a sensitizer can be optionally added to the photosensitive insulating film forming composition in order to improve the photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal). ) Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinna Millidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) Isonaphthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocumine), 3-Acetyl-7-dimethylaminocumine, 3-ethoxycarbonyl-7-dimethylaminocumarin, 3-benzyloxycarbonyl-7-dimethylaminocumarin, 3-methoxycarbonyl-7-diethylaminocumine, 3-ethoxycarbonyl-7- Diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2- Mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylamino) Examples thereof include styryl) naphtho (1,2-d) thiazole and 2- (p-dimethylaminobenzoyl) styrene. These can be used alone or in combination of two or more.

The blending amount of the sensitizer is preferably 0.1 part by mass to 25 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1).

[Thermal polymerization inhibitor]
In the embodiment, a thermal polymerization inhibitor can be optionally added in order to improve the stability of the viscosity and photosensitivity of the photosensitive insulating film-forming composition, especially when stored in a solution containing a solvent. .. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, and 2 , 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-) N-Sulphopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.

The blending amount of the thermal polymerization inhibitor is preferably in the range of 0.005 parts by mass to 12 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1).

[Azole compound]
For example, when a substrate made of copper or a copper alloy is used, an azole compound can be optionally added to the photosensitive insulating film forming composition in order to suppress discoloration of the substrate. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, and 4-t-butyl. -5-Phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, Hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3, 5-bis (α, α-dimethylbenzyl) phenyl] -benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl) -2-Hydroxyphenyl) -benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, Hydroxyphenylbenzotriazole, triltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5- Examples thereof include methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like. Particularly preferred include tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. Further, these azole compounds may be used alone or in a mixture of two or more kinds.

The blending amount of the azole compound is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1), and is 0. It is more preferably 5 parts by mass to 5 parts by mass. When the blending amount of the azole compound with respect to 100 parts by mass of the polymer having the repeating unit structure represented by the formula (1) is 0.1 part by mass or more, the photosensitive insulating film forming composition is placed on copper or a copper alloy. When it is formed in, discoloration of the surface of copper or a copper alloy is suppressed, while when it is 20 parts by mass or less, it is preferable because it has excellent light sensitivity.

[Manufacturing method of substrate with cured relief pattern]
In the embodiment, the following steps:
(1) A step of applying the photosensitive insulating film forming composition according to the present invention onto a substrate to form a photosensitive resin layer on the substrate.
(2) A step of exposing the photosensitive resin layer and
(3) A step of developing the photosensitive resin layer after the exposure to form a relief pattern, and
(4) It is possible to provide a method for manufacturing a substrate with a cured relief pattern, which includes a step of heat-treating the relief pattern to form a cured relief pattern.

Hereinafter, each step will be described.
(1) Step of applying the photosensitive insulating film forming composition according to the present invention on a substrate and forming a photosensitive resin layer on the substrate In this step, the photosensitive insulating film forming composition according to the present invention is used. It is applied onto a substrate and, if necessary, dried thereafter to form a photosensitive resin layer. As a coating method, a method conventionally used for coating a photosensitive insulating film forming composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or the like, or spraying with a spray coater. A coating method or the like can be used.
If necessary, the coating film composed of the photosensitive insulating film-forming composition can be dried, and as the drying method, for example, air drying, heat drying in an oven or a hot plate, vacuum drying and the like are used. When the coating film is dried by air drying or heat drying, it can be dried at 20 ° C. to 200 ° C. for 1 minute to 1 hour. Further, after applying the photosensitive insulating film forming composition by a predetermined method, the film is formed by prebaking in a relatively low temperature range of the above temperature range, baking in a medium temperature range, and further baking in a high temperature range. You can also do it. As described above, the photosensitive resin layer (film) can be formed on the substrate.

(2) Step of exposing the photosensitive resin layer In this step, the photosensitive resin layer formed in the above step (1) is exposed to a photomask having a pattern using an exposure device such as a contact aligner, a mirror projection, or a stepper. Alternatively, it is exposed through a reticle or directly with an ultraviolet light source or the like.
Light sources used for exposure include, for example, g-line, h-line, i-line, ghi-line broadband, and KrF excimer laser. The exposure amount is preferably 25 mJ / cm ² to 1000 mJ / cm ² .
After that, post-exposure bake (PEB) and / or pre-development bake at any combination of temperature and time may be applied, if necessary, for the purpose of improving light sensitivity and the like. The range of the baking conditions is preferably a temperature of 50 ° C. to 200 ° C. and a time of preferably 10 seconds to 600 seconds, but as long as it does not interfere with various properties of the photosensitive insulating film forming composition. Not limited to this range.

(3) Step of developing the photosensitive resin layer after exposure to form a relief pattern In this step, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any of conventionally known photoresist developing methods, for example, a rotary spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, etc. The method can be selected and used. Further, after development, post-development baking may be performed at an arbitrary combination of temperature and time, if necessary, for the purpose of adjusting the shape of the relief pattern. Examples of the developing solution used for development include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ. -Butyrolactone and the like are preferable. Further, two or more kinds of each solvent, for example, several kinds can be used in combination.

(4) Step of heat-treating the relief pattern to form a substrate with a cured relief pattern In this step, the relief pattern obtained by the above development is heated and converted into a cured relief pattern. As a method of heat curing, various methods can be selected, for example, a method using a hot plate, a method using an oven, a method using a temperature-increasing oven in which a temperature program can be set, and the like. The heating can be performed, for example, at 130 ° C. to 250 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas at the time of heat curing, or an inert gas such as nitrogen or argon may be used. From the above, a substrate with a cured relief pattern can be manufactured.

The cured relief pattern according to the present invention thus obtained has a dielectric loss tangent of 0.01 or less immediately after formation, and an increase in dielectric loss tangent is formed after exposure to a 23 ° C. and 50% RH environment for 24 hours. It is less than 0.004, preferably 0.003 or less, as compared with immediately after.
The relative ratio of the dielectric loss tangent of the cured relief pattern to the dielectric loss tangent of the cured relief pattern immediately after formation after exposure to 23 ° C. and 50% RH environment for 24 hours is usually within ± 80%, preferably within ± 70%. Yes, more preferably within ± 60%.

[Semiconductor device]
In the embodiment, a semiconductor device having a cured relief pattern obtained by the above-mentioned method for producing a cured relief pattern is also provided. Therefore, a semiconductor device having a base material which is a semiconductor element and a cured relief pattern (cured film) formed on the base material by the above-described cured relief pattern manufacturing method on the upper or lower part of the semiconductor element is provided. be able to. The present invention can also be applied to a method for manufacturing a semiconductor device, which uses a semiconductor element as a base material and includes the above-mentioned method for manufacturing a cured relief pattern as a part of a process. The semiconductor device of the present invention is a semiconductor device having a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a bump structure of a cured relief pattern formed by the above-mentioned cured relief pattern manufacturing method. It can be manufactured by forming it as a protective film or the like and combining it with a known manufacturing method of a semiconductor device.

[Display device]
In the embodiment, a display body device including a display body element and a cured film provided on the upper portion of the display body element is provided, and the cured film is a display body device having the above-mentioned cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched between them. For example, examples of the cured film include a surface protective film, an insulating film, and a flattening film of a TFT liquid crystal display element and a color filter element, a protrusion for an MVA type liquid crystal display device, and a partition wall for an organic EL element cathode. ..

The photosensitive insulating film-forming composition of the present invention is applied to semiconductor devices as described above, as well as applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad plates, solder resist films, and liquid crystal alignment films. Is also useful.

Hereinafter, specific examples of the photosensitive insulating film forming composition of the present invention will be described with reference to the following examples, but the present invention is not limited thereto.

The weight average molecular weight shown in the following synthetic example of the present specification is a measurement result by gel permeation chromatography (hereinafter, abbreviated as GPC in the present specification). A GPC device (HLC-8320GPC) manufactured by Tosoh Corporation is used for the measurement, and the measurement conditions and the like are as follows.
GPC column: TSKgelSuperH-RC, TSKgelSuperMultipore HZ-N, TSKgelSuperMultipore HZ-N (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Solvent: Tetrahydrofuran (Kanto Chemical Co., Inc., for high performance liquid chromatography)
Standard sample: Polystyrene (manufactured by Shodex)

<Synthesis Example 1> (Synthesis of Polymer (1))
4,6-Dichloropyrimidine (Tokyo Chemical Industry Co., Ltd.) 15.00 g (0.101 mol), 2,2-bis (3-allyl-4-hydroxyphenyl) propane (Konishi Chemical Industry Co., Ltd.) in a four-necked flask with a capacity of 500 ml 32.07g (0.099mol), potassium carbonate (Kanto Chemical Co., Inc., special grade) 32.80g (0.252mol), N-methyl-2-pyrrolidinone (Kanto Chemical Co., Ltd., dehydrated) 155.47g The temperature was raised to 70 ° C., and the mixture was stirred at 70 ° C. for 5 hours and at 90 ° C. for 23 hours. After the temperature was lowered to 30 ° C. or lower, 268.14 g of tetrahydrofuran (Kanto Chemical Co., Inc., special grade) was added and diluted, and the precipitate formed in the reaction solution was removed by filtration to obtain a reaction mixture. The obtained reaction mixture was added dropwise to 405.10 g of methanol (Kanto Chemical Co., Inc., special grade) and 202.55 g of pure water to precipitate a polymer. The obtained precipitate was filtered off, the filtrate was washed twice with 302.55 g of methanol, and vacuum dried to obtain a polymer. When the molecular weight of this polymer was measured by GPC (standard polystyrene conversion), the weight average molecular weight (Mw) was 33,367, and the yield was 77.84%. This polymer has a repeating unit structure represented by the following formula (2).

<Synthesis Example 2> (Synthesis of Polymer (2))
4,6-Dichloropyrimidine (Tokyo Chemical Industry Co., Ltd.) 25.00 g (0.164 mol), 2,2-bis (3-allyl-4-hydroxyphenyl) propane (Konishi Chemical Industry Co., Ltd.) in a 1000 ml capacity four-necked flask (Co., Ltd.) 26.554 g (0.081 mol), 2,2-bis (4-hydroxyphenyl) propane (Tokyo Chemical Industry Co., Ltd.) 18.58 g (0.081 mol), potassium carbonate (Kanto Chemical Co., Inc., special grade) 54.66 g (0.420 mol) and 225.89 g of N-ethyl-2-pyrrolidinone (BASF) were added, the temperature was raised to 100 ° C., and the mixture was stirred at 100 ° C. for 24 hours. After the temperature was lowered to 30 ° C. or lower, 171.55 g of tetrahydrofuran (Kanto Chemical Co., Inc., special grade) was added and diluted, and the precipitate formed in the reaction solution was removed by filtration to obtain a reaction mixture. The obtained reaction mixture was added dropwise to 1418.95 g of methanol (Kanto Chemical Co., Inc., special grade) and 283.79 g of pure water to precipitate a polymer. The obtained precipitate was filtered off, and the filtrate was washed twice with 227.03 g of methanol and vacuum dried to obtain a polymer. When the molecular weight of this polymer was measured by GPC (standard polystyrene conversion), the weight average molecular weight (Mw) was 48,683, and the yield was 74.49%. This polymer has a repeating unit structure represented by the following formula (2).

<Synthesis Example 3> (Synthesis of Polymer (3))
4,6-Dichloropyrimidine (Tokyo Chemical Industry Co., Ltd.) 15.00 g (0.101 mol), 2,2-bis (4-hydroxyphenyl) propane (Tokyo Chemical Industry Co., Ltd.) 22 in a four-necked flask with a capacity of 500 ml. Add .52 g (0.099 mol), 32.79 g (0.252 mol) of potassium carbonate (Kanto Chemical Co., Inc., special grade), and 117.31 g of N-methyl-2-pyrrolidinone (Kanto Chemical Co., Inc., dehydrated) at 70 ° C. The temperature was raised to 70 ° C. for 51 hours and 90 ° C. for 3 hours. After the temperature was lowered to 30 ° C. or lower, 199.33 g of tetrahydrofuran (Kanto Chemical Co., Inc., special grade) was added and diluted, and the precipitate formed in the reaction solution was removed by filtration to obtain a reaction mixture. The obtained reaction mixture was added dropwise to 309.68 g of methanol (Kanto Chemical Co., Inc., special grade) and 154.84 g of pure water to precipitate a polymer. The obtained precipitate was filtered off, and the filtrate was washed twice with 154.84 g of methanol and vacuum dried to obtain a polymer. When the molecular weight of this polymer was measured by GPC (standard polystyrene conversion), the weight average molecular weight (Mw) was 34,536, and the yield was 50.37%. This polymer has a repeating unit structure represented by the following formula (5).

<Example 1>
6.557 g of the polymer obtained in Synthesis Example 1, IRGACURE [registered trademark] OXE01 (manufactured by BASF, photopolymerization initiator) 0.1311 g, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane ( A composition was prepared by dissolving 1.3115 g of (manufactured by Tokyo Chemical Industry Co., Ltd.) in 12.00 g of N-methyl-2-pyrrolidinone. Then, it was filtered using a microfilter made of PTFE having a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Example 2>
The polymer obtained in Synthesis Example 1 was dissolved in 10.00 g and 14.99 g of N-methyl-2-pyrrolidinone, and then filtered using a microfilter made of PTFE having a pore size of 5 μm to prepare a resin composition.

<Example 3>
5.6609 g of the polymer obtained in Synthesis Example 1, IRGACURE [registered trademark] OXE01 (manufactured by BASF, photopolymerization initiator) 0.1311 g, trisocyanurate (2-acryloyloxyethyl) (manufactured by Tokyo Chemical Industry Co., Ltd.) A composition was prepared by dissolving 1.1202 g in 10.2496 g of N-methyl-2-pyrrolidinone. Then, it was filtered using a microfilter made of PTFE having a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Example 4>
N2.6984 g of the polymer obtained in Synthesis Example 1, 0.7619 g of IRGACURE [registered trademark] OXE01 (manufactured by BASF, a photopolymerization initiator), and 2.5397 g of trimethylolpropane triacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.). The composition was prepared by dissolving in 24.00 g of -methyl-2-pyrrolidinone. Then, it was filtered using a microfilter made of PTFE having a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Example 5>
N-DCP (tricyclodecanedimethanol diacrylate) 2.5397 g, IRGACURE® OXE01 (manufactured by BASF, photopolymerization initiator) 0.7619 g, the polymer obtained in Synthesis Example 1 The composition was prepared by dissolving in 24.00 g of methyl-2-pyrrolidinone. Then, it was filtered using a microfilter made of PTFE having a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Example 6>
6.355 g of the polymer obtained in Synthesis Example 2, IRGACURE [registered trademark] OXE01 (manufactured by BASF, photopolymerization initiator) 0.3810 g, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane ( 1.270 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 2.394 g of N-ethyl-2-pyrrolidinone and 9.600 g of cyclohexanone to prepare a composition. Then, it was filtered using a microfilter made of PTFE having a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Comparative example 1>
6.557 g of the polymer obtained in Synthesis Example 3, IRGACURE [registered trademark] OXE01 (manufactured by BASF, photopolymerization initiator) 0.1311 g, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane ( A composition was prepared by dissolving 1.3115 g of (manufactured by Tokyo Chemical Industry Co., Ltd.) in 12.00 g of N-methyl-2-pyrrolidinone. Then, it was filtered using a microfilter made of PTFE having a pore size of 5 μm to prepare a negative photosensitive resin composition.

[Photosensitivity test]
The prepared resin composition was applied onto a silicon wafer using a spin coater, prebaked at 115 ° C. for 270 seconds ^{, and exposed at 500 mJ / cm 2} to form a film having a film thickness of about 10 μm. Then, after immersing the film in cyclohexanone for 1 minute for development, the film thickness after spin-drying and drying at 115 ° C. for 270 seconds was measured, and the film thickness before and after development with cyclohexanone was compared, and the residual film ratio was 50% or more. Was allowed, and less than that was not allowed.

[Electrical property test]
The resin compositions prepared in Examples 1 to 6 were applied onto a silicon wafer laminated on aluminum using a spin coater, prebaked at 115 ° C. for 270 seconds, exposed to ^{500 mJ / cm 2, and further subjected to nitrogen.} After baking at 160 ° C. for 1 hour, the film was further baked at 230 ° C. for 1 hour to form a film having a film thickness of about 20 μm. Then, it was immersed in 6N hydrochloric acid. The place where the aluminum was melted and the film was lifted was collected and cut into a length of 3 cm and a width of 9 cm to obtain a self-supporting film. Relative permittivity at 1 GHz immediately after acquisition of the self-supporting membrane and after storage for 24 hours in a 23 ° C. 50% RH environment by the perturbation type cavity resonance method (device: TMR-1A, manufactured by Keycom Co., Ltd.) using this self-supporting membrane. The rate and dielectric loss tangent were calculated. The details of the measurement method are as follows.
(Measuring method)
Perturbation method Cavity resonance method (device configuration)
Vector Network Analyzer: FieldFox N9926A (manufactured by Keysight Technologies, Inc.)
Cavity resonator: Model TMR-1A (manufactured by Keycom Co., Ltd.)
Cavity volume: 1192822 mm ³
Measurement frequency: Approximately 1 GHz (depending on the resonance frequency of the sample)
Sample tube: Made of PTFE Inner diameter: 3 mm Length: Approximately 30 mm

The measurement results are shown in Table 1 below.

According to the negative photosensitive insulating film composition according to the present invention, a cured product having a low initial dielectric loss tangent and a small change with time is provided.

Claims

The following formula (1):

[In equation (1)
Group A 1 is

Represents a 5- to 8-membered aromatic heterocycle represented by
The aromatic heterocycle may have a crosslinkable substituent and may have a crosslinkable substituent.
Group A 2 is

Represents a 5- to 8-membered aromatic heterocycle represented by
The aromatic heterocycle may have a crosslinkable substituent and may have a crosslinkable substituent.
Group B 1 represents an organic group having a crosslinkable substituent and having 6 to 40 carbon atoms, which may contain at least one heteroatom selected from N, S and O, and may contain a halogen atom.
Group B 2 represents an organic group having 6 to 40 carbon atoms which does not have a crosslinkable substituent and may contain at least one heteroatom selected from N, S and O, and may contain a halogen atom. ,
n 1 and n 2 are independently numbers of 0 or more and 1 or less, respectively.
m 1 and m 2 are independently numbers of 0 or more and 1 or less, respectively.
n is a number greater than or equal to 1
m is a number greater than or equal to 0
10 ≦ n + m ≦ 500,
However, when neither group A 1 nor group A 2 has a crosslinkable substituent,
If m ≠ 0, then at least one of n 1 and m 1 is 1.
If m = 0, n 1 is 1. ]
A photosensitive insulating film-forming composition containing a polymer having a repeating unit structure represented by (1) and a solvent.
Group A 1

Represents an aromatic heterocycle represented by, and the aromatic heterocycle may have a crosslinkable substituent.
The photosensitive insulating film forming composition according to claim 1.
Group A 2

as well as

Represents at least one aromatic heterocycle selected from the group consisting of aromatic heterocycles represented by, and any of these aromatic heterocycles may have a crosslinkable substituent.
The photosensitive insulating film forming composition according to claim 1 or 2.
Group B 1 is at least one selected from the following,

(In the formula, G represents either a direct bond or one of the following formulas.

L and M independently represent a hydrogen atom, a phenyl group, or a C1-3 alkyl group, respectively. )
The photosensitive insulating film-forming composition according to any one of claims 1 to 3.
Group B 1

The photosensitive insulating film forming composition according to any one of claims 1 to 4, which is represented by.
Group B 2 is at least one selected from the following,

(In the formula, G represents either a direct bond or one of the following formulas.

L and M independently represent a hydrogen atom, a phenyl group, or a C1-3 alkyl group, respectively. )
The photosensitive insulating film-forming composition according to any one of claims 1 to 5.
Group B 2

The photosensitive insulating film forming composition according to any one of claims 1 to 6, which is represented by.
The photosensitive insulating film-forming composition according to any one of claims 1 to 7, wherein the crosslinkable substituent contains a radical crosslinkable group.
The photosensitive insulating film-forming composition according to any one of claims 1 to 8, wherein the crosslinkable substituent contains a (meth) acrylate group, a maleimide group, or an allyl group.
The photosensitive insulating film forming composition according to any one of claims 1 to 9, wherein m = 0.
A photosensitive resin film, which is a fired product of a coating film of the photosensitive insulating film forming composition according to any one of claims 1 to 10.
The photosensitive resin film according to claim 11, which has a dielectric loss tangent of 0.01 or less.
The following steps:
(1) A step of applying the photosensitive insulating film forming composition according to any one of claims 1 to 10 onto a substrate to form a photosensitive resin layer on the substrate.
(2) A step of exposing the photosensitive resin layer and
(3) A step of developing the photosensitive resin layer after the exposure to form a relief pattern, and
(4) A method for manufacturing a substrate with a cured relief pattern, which comprises a step of heat-treating the relief pattern to form a cured relief pattern.
A substrate with a cured relief pattern manufactured by the method according to claim 13.
A semiconductor device including a semiconductor element and a cured film provided on the upper or lower portion of the semiconductor element, wherein the cured film is the cured relief pattern according to claim 14.