WO2020111086A1

WO2020111086A1 - (meth)acrylic compound and photosensitive insulation film composition

Info

Publication number: WO2020111086A1
Application number: PCT/JP2019/046257
Authority: WO
Inventors: 隼人服部; 雅久遠藤; 一樹平佐田
Original assignee: 日産化学株式会社
Priority date: 2018-11-29
Filing date: 2019-11-27
Publication date: 2020-06-04
Also published as: JP7327412B2; TW202028257A; JP2023156304A; JPWO2020111086A1

Abstract

The invention provides a photosensitive resin composition yielding a cured body having low permittivity and low dielectric tangent, a method using the photosensitive resin composition for producing a base board equipped with a cured relief pattern, and a semiconductor device equipped with the cured relief pattern.　The photosensitive resin composition contains (A) a resin and (B) a (meth)acrylic compound represented by formula [1a] (In formula [1a], R¹¹ represents an alkyl group having 2 to 30 carbon atoms, each R²¹ represents independently a hydrogen atom or a methyl group, L¹ represents a single bond or an oxymethylene group, L² represents an organic group represented by formula [2a] or formula [3a], and n represents an integer from 1 to 6.) (In formula [2a], * represents a terminal bonded to the carbonyl group, L³ and L⁴ each independently represent an alkylene group having 2 to 8 carbon atoms and optionally containing an ether bond.) (In formula [3a], * represents a terminal bonded to the carbonyl group, L⁵ represents a hydrocarbon group of valence (n+1) having 2 to 10 carbon atoms and optionally containing an ether bond.) and/or (B) a (meth)acrylic compound represented by formula [1a1] (In formula [1a1], R¹² represents an alkyl group having 2 to 30 carbon atoms, each R²² represents independently a hydrogen atom or a methyl group, and n represents an integer from 1 to 6.)

Description

(Meth)acrylic compound and photosensitive insulating film composition

The present invention relates to a (meth)acrylic compound, a photosensitive resin composition containing the compound, 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 The present invention relates to a semiconductor device having a cured relief pattern.

Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, and mechanical characteristics has been used for the insulating material of electronic parts, and the passivation film, surface protection film, and interlayer insulating film of semiconductor devices. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor easily form a heat-resistant relief pattern coating film by applying the precursor, exposing, developing, and thermally imidizing by curing. be able to. Such a photosensitive polyimide precursor has a feature that it can significantly reduce the process steps as compared with the conventional non-photosensitive polyimide resin.

On the other hand, in recent years, the method of mounting semiconductor devices on a printed wiring board has also changed from the viewpoint of improving the degree of integration and arithmetic functions, and reducing the chip size. From the conventional mounting method using metal pins and lead-tin eutectic solder, the polyimide coating directly contacts the solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which enables higher density mounting. 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 copper or copper alloy wiring having a lower resistance. Furthermore, a method of preventing wiring delay by increasing insulation between wirings is also adopted. In recent years, a low dielectric constant material often constitutes a semiconductor device as this highly insulating material, but on the other hand, a low dielectric constant material tends to be fragile and easily broken. There is a problem that the low dielectric constant material part is destroyed by the contraction due to the temperature change when mounted on the.
As a means for solving this problem, Patent Document 1 discloses that a photosensitive material containing a polyimide precursor is introduced by introducing an aliphatic group having an ethylene glycol structure and having 5 to 30 carbon atoms into a part of a side chain of the polyimide precursor. Disclosed is a photosensitive resin composition that improves the transparency when a photosensitive resin composition is formed and further improves the Young's modulus of a cured film after thermosetting.

Re-table 2013-168675

The photosensitive resin composition comprising the polyimide precursor described in Patent Document 1 has a high transparency and gives a cured product having a high Young's modulus after heat curing, but when used in the above-mentioned applications, the dielectric constant or There has been a demand for further reduction of the dielectric loss tangent.

Therefore, the present invention provides a photosensitive resin composition that gives a cured product having a further reduced dielectric constant or dielectric loss tangent, a method for producing a substrate with a cured relief pattern using the photosensitive resin composition, and the cured relief. An object is to provide a semiconductor device having a pattern.

As a result of intensive studies to achieve the above object, the present inventors have found that when a novel (meth)acrylic compound is added to form a photosensitive resin composition, the photosensitive resin composition gives a low relative dielectric constant and a low dielectric loss tangent. It was found that a functional resin composition can be obtained, and the present invention has been completed.

That is, the present invention includes the following.
<1> At least one selected from the group consisting of (A) resin, and (B) (meth)acrylic compound represented by the following formula [1a] and (meth)acrylic compound represented by the following formula [1a1]. A photosensitive resin composition containing a seed.

(In the formula [1a], R ¹¹ represents an alkyl group having 2 to 30 carbon atoms, R ²¹ independently represents a hydrogen atom or a methyl group, L ¹ represents a single bond or an oxymethylene group, and L ² Represents an organic group represented by the formula [2a] or the formula [3a], and n represents an integer of 1 to 6.)

(In the formula [2a], * represents an end bonded to a carbonyl group, and L ³ and L ⁴ each independently represent an alkylene group having 2 to 8 carbon atoms which may include an ether bond.)

(In the formula [3a], * represents an end bonded to a carbonyl group, and L ⁵ represents a (n+1)-valent hydrocarbon group having 2 to 10 carbon atoms which may include an ether bond).

(In the formula [1a1], R ¹² represents an alkyl group having 2 to 30 carbon atoms, R ²² independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6.)
<2> The resin (A) has the following general formula (1):

[In the formula, X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and R ¹ and R ² are each independently a monovalent organic group. ] The photosensitive resin composition as described in <1> which is a polyimide precursor which has a unit structure represented by these.
<3> The photosensitive resin composition according to <1>, wherein R ¹¹ or R ¹² represents an alkyl group having 6 to 26 carbon atoms.
<4> The photosensitive resin composition according to <1>, wherein R ¹¹ or R ¹² represents an alkyl group having 14 to 20 carbon atoms.
<5> The photosensitive resin composition according to <1>, wherein R ¹¹ or R ¹² is a branched chain alkyl group.
<6> The photosensitive resin composition according to <1>, wherein R ¹¹ or R ¹² is a group represented by the formula [4a].

(In the formula [4a], R ⁴³ and R ⁴⁴ each independently represent an alkyl group having 1 to 27 carbon atoms, and R ⁴⁵ represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, provided that The total number of carbon atoms in the CR ⁴³ R ⁴⁴ R ⁴⁵ group is 10 to 31.)
<7> A photosensitive resin film, which is a baked product of the coating film of the photosensitive resin composition according to any one of <1> to <6>.
<8> The following steps:
(1) A step of applying the photosensitive resin composition according to any one of <1> to <6> on a substrate to form a photosensitive resin layer on the substrate,
(2) a step of exposing the photosensitive resin layer,
(3) a step of developing the photosensitive resin layer after the exposure to form a relief pattern,
(4) A method for producing a substrate with a cured relief pattern, which comprises a step of heating the relief pattern to form a cured relief pattern.
<9> A substrate with a cured relief pattern produced by the method according to <8>.
<10> A semiconductor device comprising a semiconductor element and a cured film provided on the upper or lower part of the semiconductor element, wherein the cured film is the cured relief pattern according to <9>.
<11> A (meth)acrylic compound represented by the following formula [1a].

(In formula [2a], * represents an end bonded to a carbonyl group, and L ³ and L ⁴ each independently represent an alkylene group having 2 to 8 carbon atoms which may include an ether bond.)

(In formula [3a], * represents an end bonded to a carbonyl group, and L ⁵ represents a (n+1)-valent hydrocarbon group having 2 to 10 carbon atoms which may include an ether bond.)
<12> The (meth)acrylic compound according to <11>, wherein R ¹¹ represents an alkyl group having 6 to 26 carbon atoms.
<13> The (meth)acrylic compound according to <11>, wherein R ¹¹ represents an alkyl group having 14 to 20 carbon atoms.
<14> The (meth)acrylic compound according to <11>, wherein R ¹¹ is a branched chain alkyl group.
<15> The (meth)acrylic compound according to <11>, wherein R ¹¹ is a group represented by the formula [4a].

(In the formula [4a], R ⁴³ and R ⁴⁴ each independently represent an alkyl group having 2 to 27 carbon atoms, and R ⁴⁵ represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, The total number of carbon atoms in the CR ⁴³ R ⁴⁴ R ⁴⁵ group is 10 to 31.)
<16> L ³ and L ⁴ are each independently ethylene group, 3-oxypentane-1,5-diyl group, 3,6-dioxyoctane-1,8-diyl group, 3,6,9- The (meth)acrylic compound according to <11>, which is a group selected from the group consisting of trioxyundecane-1,11-diyl groups.
<17> L ⁵ is the following formula:

The (meth)acrylic compound according to <11>, which is a group selected from the group consisting of:
<18> (A) resin, and (B) <11> (meth) acrylic compound,
A resin composition comprising:

According to the present invention, a novel (meth)acrylic compound, a photosensitive resin composition containing the compound, which gives a cured product having a low dielectric constant and a low dielectric loss tangent, and a cured relief pattern with the photosensitive resin composition A method for manufacturing a substrate, a substrate with a cured relief pattern manufactured by the method, and a semiconductor device including the cured relief pattern can be provided.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention,
It contains (A) resin, (B) (meth)acrylic compound, and optionally (C) isocyanate compound, (D) carboxylic acid compound or its anhydride, and other components. Each component will be described below in order.

[(A) Resin]
The photosensitive resin composition according to the present invention contains a resin (A). Examples of the resin (A) include phenol resin, polyimide resin, bismaleimide resin, epoxy resin, urea (urea) resin, melamine resin, polyurethane resin, cyanate ester resin, silicone resin, oxetane resin, (meth)acrylate resin, Examples thereof include unsaturated polyester resins, diallyl phthalate resins, benzoxazine resins, and precursors of these resins. Among these, it is preferable to include a polyimide resin, and it is more preferable to include a polyimide precursor that gives a polyimide resin by performing a heat cyclization treatment.

[Polyimide precursor as resin (A)]
The polyimide precursor as the resin (A) is a resin component contained in the photosensitive resin composition and has a unit structure represented by the following general formula (1).

[In the formula, X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and R ¹ and R ² are each independently a monovalent organic group. ]

In the general formula (1), X ¹ is not particularly limited as long as it is a tetravalent organic group, but from the viewpoint of achieving both heat resistance and photosensitivity, it is preferably a tetravalent one having 6 to 40 carbon atoms. And more preferably an aromatic group in which the —COOR ¹ group or the —COOR ² group and the —CONH— group are in the ortho position with respect to each other, or an alicyclic aliphatic group. The tetravalent organic group represented by X ¹ is more preferably an aromatic ring-containing organic group having 6 to 40 carbon atoms.

More preferably, X ¹ is a tetravalent organic group represented by the following formula (5) or the following formulas (5-1) to (5-7).

The structure of X ¹ may be one kind or a combination of two or more kinds.

In the general formula (1), Y ¹ is not limited as long as it is a divalent organic group having 6 to 40 carbon atoms, but Y ¹ may be substituted from the viewpoint of achieving both heat resistance and photosensitivity. A cyclic organic group having 1 to 4 aromatic rings or aliphatic rings, or an aliphatic group having no cyclic structure or a siloxane group is preferable. More preferably, Y ¹ is a structure represented by the following general formula (6), the following general formula (7) or the following formula (8).

(In the formula, each A independently represents a methyl group (—CH ₃ ), an ethyl group (—C ₂ H ₅ ), a propyl group (—C ₃ H ₇ ), or a butyl group (—C ₄ H ₉ ). .}

The structure of Y ¹ may be one kind or a combination of two or more kinds.

In the general formula (1), R ¹ and R ² are not particularly limited as long as they are independently monovalent organic groups. For example, R ¹ and R ² are each independently a monovalent aliphatic group having 1 to 30 carbon atoms or 5 to 22 carbon atoms, a cycloaliphatic group, an aromatic group and an aliphatic group bonded to each other. Or a group in which these groups are substituted with a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, an acetoxy group or the like. Typical halogen atoms are F, Cl, Br and I.

Preferably, R ¹ and R ² are each independently the following general formula (2):

(In the formula, R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m is an integer of 1 to 10. * is , Which is a binding site for a carboxylic acid present in the polyamic acid main chain of the general formula (1).)
It is preferable that

R ¹ and R ² are each independently the following general formula (3):

(In the formula, R ⁶ is a monovalent group selected from an alkyl group having 1 to 30 carbon atoms. * is the same as the above.)
A monovalent organic group represented by may be included.

Each of R ¹ and R ² in the general formula (1) may be one kind or a combination of two or more kinds, but is preferably a combination of three kinds or less, preferably a combination of two kinds or less, and most preferably a combination. It is one kind.

In the general formula (1), the monovalent organic group represented by the general formula (2) with respect to all of R ¹ and R ² and the general formula from the viewpoints of the photosensitivity and mechanical properties of the photosensitive resin composition. The total proportion of the monovalent organic groups represented by (3) is preferably 80 mol% or more, preferably 90 mol% or more, and preferably 100 mol%.

In the general formula (1), from the viewpoint of the photosensitivity and mechanical properties of the photosensitive resin composition, the ratio of the total of the monovalent organic groups represented by the general formula (2) to all R ¹ and R ^2. Is preferably 80 mol% or more, preferably 90 mol% or more, and preferably 100 mol%.

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 from the viewpoint of the photosensitive characteristics of the photosensitive resin composition, R ³ is a hydrogen atom or methyl. It is preferably a group.

R ⁴ and R ⁵ in the above general formula (2) are not limited as long as they are independently hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. From the viewpoint, it is preferably a hydrogen atom.

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

R ⁶ in the general formula (3) is not limited as long as it is a monovalent organic group selected from alkyl groups having 1 to 30 carbon atoms. An alkyl group having 5 to 30 carbon atoms is preferable, an alkyl group having 8 to 30 carbon atoms is preferable, an alkyl group having 9 to 30 carbon atoms is preferable, and an alkyl group having 10 to 30 carbon atoms is preferable. Preferably, an alkyl group having 11 to 30 carbon atoms is more preferable, and an alkyl group having 17 to 30 carbon atoms is further preferable. It may have a branched structure or a cyclic structure as well as a linear structure.

Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group (amyl group), hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group (lauryl group), tridecyl group Group, tetradecyl group (myristyl group), pentadecyl group, hexadecyl group (palmityl group), heptadecyl group (margaryl group), octadecyl group (stearyl group), nonadecyl group, icosyl group (arachil group), henicosyl group, docosyl group (behenyl) Group), tricosyl group, tetracosyl group (lignoceryl group), pentacosyl group, hexacosyl group, heptacosyl group, and other linear alkyl groups; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group , Tert-pentyl group, sec-isoamyl group, isohexyl group, neohexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group , 2-ethylpentyl group, heptan-3-yl group, heptan-4-yl group, 4-methylhexan-2-yl group, 3-methylhexan-3-yl group, 2,3-dimethylpentan-2- -Yl group, 2,4-dimethylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 6-methylheptyl group, 2-ethylhexyl group, octane-2-yl group, 6-methylheptane- 2-yl group, 6-methyloctyl group, 3,5,5-trimethylhexyl group, nonan-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group Group, 3-ethylheptan-3-yl group, 3,7-dimethyloctyl group, 8-methylnonyl group, 3-methylnonan-3-yl group, 4-ethyloctane-4-yl group, 9-methyldecyl group, undecane -5-yl group, 3-ethylnonan-3-yl group, 5-ethylnonan-5-yl group, 2,2,4,5,5-pentamethylhexane-4-yl group, 10-methylundecyl group, 11-methyldodecyl group, tridecan-6-yl group, tridecan-7-yl group, 7-ethylundecane-2-yl group, 3-ethylundecane-3-yl group, 5-ethylundecane-5-yl group, 12-methyltridecyl group, 13-methyltetradecyl group, pentadecane-7-yl group, pentadecane-8-yl group, 14-methylpentadecyl group, 15-methylhexadecyl group, hepta Decan-8-yl group, heptadecane-9-yl group, 3,13-dimethylpentadecan-7-yl group, 2,2,4,8,10,10-hexamethylundecane-5-yl group, 16-methyl Heptadecyl group, 17-methyloctadecyl group, nonadecane-9-yl group, nonadecane-10-yl group, 2,6,10,14-tetramethylpentadecane-7-yl group, 18-methylnonadecyl group, 19-methylicosyl group , Henicosan-10-yl group, 20-methylhenicosyl group, 21-methyldocosyl group, tricosane-11-yl group, 22-methyltricosyl group, 23-methyltetracosyl group, pentacosane-12-yl group, Pentacosan-13-yl group, 2,22-Dimethyltricosan-11-yl group, 3,21-Dimethyltricosan-11-yl group, 9,15-Dimethyltricosan-11-yl group, 24-Methylpen Branched chain alkyl groups such as tacosyl group, 25-methylhexacosyl group and heptacosan-13-yl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, 1 ,6-dimethylcyclohexyl group, menthyl group, cycloheptyl group, cyclooctyl group, bicyclo[2.2.1]heptan-2-yl group, bornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclo An alicyclic alkyl group such as a [5.2.1.0 ^2,6 ]decan-4-yl group, a tricyclo[5.2.1.0 ^2,6 ]decan-8-yl group, or a cyclododecyl group Can be mentioned.

R ⁶ in the above general formula (3) is preferably an alkyl group having 5 to 30 carbon atoms, an alkyl group having 8 to 30 carbon atoms, and an alkyl group having 9 to 30 carbon atoms, An alkyl group having 10 to 30 carbon atoms is preferable, an alkyl group having 11 to 30 carbon atoms is more preferable, and an alkyl group having 17 to 30 carbon atoms is further preferable.

Preferably, R ⁶ is represented by the following formula (4):

(Z ¹ is hydrogen or an alkyl group having 1 to 14 carbon atoms,
Z ² is an alkyl group having 1 to 14 carbon atoms,
Z ³ is an alkyl group having 1 to 14 carbon atoms,
However, Z ¹ , Z ² and Z ³ may be the same or different from each other,
The total number of carbon atoms of Z ¹ , Z ² and Z ³ is 4 or more. ) Is preferable.

It is preferred that Z ¹ is hydrogen.
Z ¹ , Z ² and Z ³ are preferably alkyl groups having 2 to 12 carbon atoms, and more preferably alkyl groups having 2 to 10 carbon atoms.
The total number of carbon atoms of Z ¹ , Z ² and Z ³ is preferably 5 or more, more preferably 6 or more, preferably 10 or more, preferably 12 or more, and 14 or more. Preferably, it is preferably 15 or more, more preferably 16 or more.
The total number of carbon atoms of Z ¹ , Z ² and Z ³ is preferably 6 or more and 20 or less.
The upper limit of the total number of carbon atoms of Z ¹ , Z ² and Z ³ is preferably 28.

Further, R ⁶ may be selected from the following formulas (3-1) to (3-7).

R ⁶ is preferably selected from the above formulas (3-1) to (3-7).

The polyimide precursor (A) is converted into polyimide by subjecting it to a heat cyclization treatment.
[(A) Method for Preparing Polyimide Precursor]
The polyimide precursor represented by the above general formula (1) in the present embodiment includes, for example, a tetracarboxylic acid dianhydride containing the above-mentioned tetravalent organic group X ¹ having 6 to 40 carbon atoms, and (a) the above An alcohol in which a monovalent organic group represented by the general formula (2) and a hydroxyl group are bonded, and (b) a monovalent organic group represented by the general formula (3) and a hydroxyl group are bonded. The partially formed esterified tetracarboxylic acid (hereinafter, also referred to as acid/ester form) is prepared by reacting the resulting alcohols, and then the above-mentioned divalent organic group Y ¹ having 6 to 40 carbon atoms is added. It is obtained by polycondensation with diamines containing it.

(Preparation of acid/ester form)
In the present embodiment, examples of the tetracarboxylic acid dianhydride containing a tetravalent organic group X ¹ having 6 to 40 carbon atoms include pyromellitic dianhydride and diphenyl ether-3,3′,4,4′-tetracarboxylic acid. Acid dianhydride (=4,4'-oxydiphthalic dianhydride), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetra Carboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis Examples thereof include (3,4-phthalic anhydride) propane and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane.
Further, tetracarboxylic dianhydrides represented by the following formulas (5-1-a) to (5-7-a) are also exemplified.

These can be used alone or in combination of two or more.

In the present embodiment, (a) alcohols having a structure represented by the above general formula (2) include, for example, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, methylol vinyl ketone and 2 -Hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3- Examples thereof include propyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxyethyl methacrylate and the like.

(B) As the aliphatic alcohol having 1 to 30 carbon atoms having the structure represented by the general formula (3), for example, the hydrogen atom of the alkyl group having 1 to 30 carbon atoms is substituted with a hydroxy group. Examples thereof include alcohols.

Further, alcohols having the structures of the above formulas (3-1) to (3-6) may be used.
The following commercial products may be used.
Alcohols containing the structure of formula (3-1): Fineoxochol (registered trademark) 180 (manufactured by Nissan Chemical Co., Ltd.),
Alcohols having the structure of formula (3-2): Fineoxochol (registered trademark) 2000 (manufactured by Nissan Chemical Co., Ltd.),
Alcohols containing the structure of formula (3-3): Fineoxochol (registered trademark) 180N (manufactured by Nissan Chemical Co., Ltd.),
Alcohols containing the structure of formula (3-4) or formula (3-5): Fineoxochol (registered trademark) 180T (manufactured by Nissan Chemical Co., Ltd.),
Alcohols containing the structure of formula (3-6): Fineoxochol (registered trademark) 1600K (manufactured by Nissan Chemical Co., Ltd.).
As these alcohols, it is preferable to use alcohols containing the structures of the above formulas (3-1) to (3-6).

The total content of the component (a) and the component (b) in the photosensitive resin composition is preferably 80 mol% or more with respect to the total content of R ¹ and R ² in the general formula (1). In order to lower the dielectric constant and lower the dielectric loss tangent, the content of the component (b) is preferably 1 mol% to 90 mol% with respect to the total content of R ¹ and R ² .

The above tetracarboxylic dianhydride and the above alcohols are stirred, dissolved and mixed in a reaction solvent at a reaction temperature of 0 to 100° C. for 10 to 40 hours in the presence of a basic catalyst such as pyridine. As a result, the half-esterification reaction of the acid dianhydride proceeds, and the desired acid/ester form can be obtained.

The reaction solvent is preferably one that dissolves the acid/ester form and a polyimide precursor which is a polycondensation product of the acid/ester form and diamines. For example, N-methyl-2-pyrrolidone, N , N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, gammabutyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methylethylketone, methyl Isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane , Heptane, benzene, toluene, xylene and the like. These may be used alone or in combination of two or more, if necessary.

(Preparation of polyimide precursor)
A known dehydrating condensing agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, to the above acid/ester form (typically a solution in the above reaction solvent) under ice cooling. 1,1-Carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, N,N'-diisopropylcarbodiimide, etc. are added and mixed to form an acid/ester compound as a polyacid. After being made into an anhydride, a diamine containing a divalent organic group Y ¹ having 6 to 40 carbon atoms, which is separately dissolved or dispersed in a solvent, is added dropwise to the mixture, and polycondensation is carried out. It is possible to obtain a polyimide precursor that can be used in.

Examples of the diamine containing a divalent organic group Y ¹ having 6 to 40 carbon atoms include, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3 '-Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3 ,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis( 4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4, 4'-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl ] Ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4- Aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-amino) Phenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and hydrogen atoms on these benzene rings Partially substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen or the like, for example, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodi Phenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethylmethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and the like A mixture etc. are mentioned.
Further, diamines represented by the following formula (8-1) are also included.

The diamines used in the present application are not limited to these.

In the embodiment, in order to improve the adhesion between the photosensitive resin layer formed on the substrate and various substrates by applying the photosensitive resin composition onto the substrate, (A) Preparation of polyimide precursor At the same time, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can be copolymerized.

After the completion of the polycondensation reaction, the water absorption by-product of the dehydration condensation agent coexisting in the reaction solution is filtered off if necessary, and then water, an aliphatic lower alcohol, or a poor solvent such as a mixed solution thereof is used. , A polymer precursor that can be used in the embodiment by pouring into a reaction solution to precipitate a polymer component, and further repeating redissolution, reprecipitation and precipitation operations to purify the polymer and perform vacuum drying. Isolate the body. In order to improve the degree of purification, a solution of this polymer may be passed through a column packed by swelling an anion and/or cation exchange resin with a suitable organic solvent to remove ionic impurities.

The molecular weight of the (A) polyimide precursor is preferably 5,000 to 150,000, and preferably 7,000 to 50,000, as measured by polystyrene conversion weight average molecular weight by gel permeation chromatography. Is more preferable. When the weight average molecular weight is 5,000 or more, mechanical properties are good, which is preferable. On the other hand, when the weight average molecular weight is 150,000 or less, dispersibility in a developing solution and resolution performance of a relief pattern are good. It is preferable because it is good.

[(B) (meth)acrylic compound]
The (B) (meth)acrylic compound is represented by the following general formula [1a].

(In the formula [1a], R ¹¹ represents an alkyl group having 2 to 30 carbon atoms, R ²¹ independently represents a hydrogen atom or a methyl group, L ¹ represents a single bond or an oxymethylene group, and L ² Represents an organic group represented by the formula [2a] or the formula [3a], and n represents an integer of 1 to 6.)
n represents an integer of 1 to 6, n is an integer of 1 to 5, n is an integer of 1 to 4, n is an integer of 1 to 3, and n is 1 or 2.

(In the formula [3a], * represents an end bonded to a carbonyl group, and L ⁵ represents a (n+1)-valent hydrocarbon group having 2 to 10 carbon atoms which may include an ether bond).
A (meth)acrylic compound represented by.

The (B) (meth)acrylic compound may be represented by the following formula [1a1].

(In the formula [1a1], R ¹² represents an alkyl group having 2 to 30 carbon atoms, R ²² independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6.)

In formula [1a], R ¹¹ is preferably an alkyl group having 2 to 30 carbon atoms, preferably an alkyl group having 6 to 26 carbon atoms, and preferably an alkyl group having 14 to 20 carbon atoms. It is preferred that R ¹¹ is a branched chain alkyl group. It is also preferable that R ¹¹ is a group represented by the formula [4a].

(In the formula [4a], R ⁴³ and R ⁴⁴ each independently represent an alkyl group having 1 to 27 carbon atoms, and R ⁴⁵ represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, provided that The total number of carbon atoms of the CR ⁴³ R ⁴⁴ R ⁴⁵ group is 10 to 31, but it is preferable that each of R ⁴³ and R ⁴⁴ is independently an alkyl group having 2 to 27 carbon atoms.)

In formula [1a1], R ¹² is preferably an alkyl group having 6 to 26 carbon atoms, and preferably an alkyl group having 14 to 20 carbon atoms. It is preferred that R ¹² is a branched chain alkyl group. It is also preferable that R ¹² is a group represented by the formula [4a].

Examples of the alkyl group for R ¹¹ , R ¹² , R ⁴³ , R ⁴⁴ , and R ⁴⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group (amyl group), a hexyl group, a heptyl group, and an octyl group. , Linear alkyl groups such as nonyl group and decyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, sec-isoamyl group, isohexyl group, neo Hexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 2-ethylpentyl group, heptan-3-yl group, heptane -4-yl group, 4-methylhexan-2-yl group, 3-methylhexan-3-yl group, 2,3-dimethylpentan-2-yl group, 2,4-dimethylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 6-methylheptyl group, 2-ethylhexyl group, octan-2-yl group, 6-methylheptan-2-yl group, 6-methyloctyl group, 3,5 5-trimethylhexyl group, nonan-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group, 3-ethylheptan-3-yl group, 3,7 -Branched alkyl groups such as dimethyloctyl group, 8-methylnonyl group, 3-methylnonan-3-yl group, 4-ethyloctane-4-yl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group , 4-tert-butylcyclohexyl group, 1,6-dimethylcyclohexyl group, menthyl group, cycloheptyl group, cyclooctyl group, bicyclo[2.2.1]heptan-2-yl group, bornyl group, isobornyl group, 1 -Adamantyl group, 2-adamantyl group, tricyclo[5.2.1.0 ^2,6 ]decan-4-yl group, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl group, etc. Examples thereof include alicyclic alkyl groups.

When L ¹ is an oxymethylene group, the bonding direction is not particularly limited. In particular,
^**- CH ₂ O-
Even
^** -OCH _2-
( ^** indicates a bond with R ¹¹ or R ¹² ).

Examples of L ³ and L ⁴ include a substituted or unsubstituted ethylene group, a propylene group, and a butylene group. Examples of the alkylene group which may have an ether bond include, for example, —CH ₂ —O—CH ₂ —, —C ₂ H ₄ —O—CH ₂ —, and —CH ₂ —O—C ₂ H ₄ —. Etc.

L ³ and L ⁴ are each independently ethylene group, 3-oxypentane-1,5-diyl group, 3,6-dioxyoctane-1,8-diyl group, 3,6,9-trioxyundecane It is preferably a group selected from the group consisting of -1,11-diyl groups.

L ⁵ is preferably a (n+1)-valent saturated hydrocarbon group having 2 to 10 carbon atoms, which may contain an ether bond.

L ⁵ is preferably a group derived by removing a hydroxy group from a primary to 6th alcohol. However, this expression serves only for the purpose of explaining the chemical structure of the group, and does not limit the method for producing the (meth)acrylic compound according to the present invention. Specific examples of alcohol include
Primary alcohols such as ethanol, methanol, isopropyl alcohol, 2-ethylhexyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol and decyl alcohol,
Secondary alcohols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, propanediol, butanediol, pentanediol, hexanediol and heptanediol,
Propanetriol (glycerin), butanetriol (eg 2-hydroxy-1,4-butanediol, trimethylolmethane), 2-methylpropane-1,2,3-triol, pentanetriol (eg 1,1,1 -Trimethylolethane), hexanetriol (eg 1,1,1-trimethylolpropane), tertiary alcohols such as heptanetriol,
Quaternary alcohols such as propanetetraol, butanetetraol, pentanetetraol, hexanetetraol, heptanetetraol, ditrimethylolpropane and pentaerythritol,
Quaternary alcohols such as pentane pentaol and hexane pentaol,
A sixth alcohol such as dipentaerythritol may be mentioned.

L ⁵ is 2-methylpropane-1,2,3-triol, glycerin, 2-hydroxy-1,4-butanediol, trimethylolmethane, 1,1,1-trimethylolethane, 1,1,1- A group derived from a polyol selected from the group consisting of trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol by removing a hydroxy group is particularly preferable.

The chemical formula is as follows.

The amount of the (B) (meth)acrylic compound in the photosensitive resin composition according to the present invention is usually 1 part by mass or more, preferably 100 parts by mass with respect to 100 parts by mass of the resin (A) (for example, the polyimide precursor). It is 5 parts by mass or more, more preferably 10 parts by mass or more, usually 80 parts by mass or less, preferably 60 parts by mass or less, more preferably 40 parts by mass or less.

Some specific examples of the (B) (meth)acrylic compound in the photosensitive resin composition according to the present invention are as follows. After reacting an aliphatic carboxylic acid chloride with a dialkanolamine, a method of reacting with an alcohol group and a (meth)acrylic acid chloride, or reacting a di(meth)acrylate compound containing an isocyanate group with an aliphatic alcohol It can be synthesized. A specific synthesis method will be described in the section of Examples below.

((2-(4,4-Dimethylpentan-2-yl)-5,7,7-trimethyloctanoyl)azanediyl)bis(ethane-2,1-diyl)diacrylate

2-(((((2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctyl)oxy)carbonyl)amino)-2-methylpropane-1,3-diyldiacrylate

Isostearyl acrylate

(For example, S-1800A manufactured by Shin Nakamura Chemical Co., Ltd.)

[(C) Isocyanate Compound]
The photosensitive resin composition of the present invention may further contain (C) an isocyanate compound represented by the following general formula (20), if desired.

[In the formula, R ²³ represents a hydrogen atom or a methyl group, R ²⁴ represents an alkylene group having 1 to 5 carbon atoms, which may have a substituent and may be interrupted by an oxygen atom; ²⁵ represents an isocyanate group or a blocked isocyanate group. ]

R ²⁴ is not particularly limited as long as it has a substituent and is an alkylene group having 1 to 5 carbon atoms which may be interrupted by an oxygen atom. Examples of the alkylene group having 1 to 5 carbon atoms include a substituted or unsubstituted methylene group, ethylene group, propylene group, butylene group and the like. Examples of the alkylene group interrupted by an oxygen atom include —CH ₂ —O—CH ₂ —, —C ₂ H ₄ —O—CH ₂ —, and —CH ₂ —O—C ₂ H ₄ —. . Examples of the substituent include a halogen atom, an acryloyl group, a methacryloyl group, a nitro group, an amino group, a cyano group, a methoxy group and an acetoxy group, and an acryloyl group and a methacryloyl group are preferable.

R ²⁵ represents an isocyanate group or a blocked isocyanate group. The isocyanate group means a group represented by —NCO, and the blocked isocyanate group means a group in which an isocyanate group is blocked by a heat-eliminating protective group, that is, a compound for isocyanate blocking (blocking agent) is added to the isocyanate group. The reacted group.

An isocyanate group blocking agent generally reacts with an isocyanate group to prevent a reaction with a functional group in another molecule (for example, an acid functional group) at room temperature, but is released at a high temperature to release an isocyanate group. Regenerated and allows subsequent reactions (eg with acid functional groups).
Examples of the blocking agent include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol, phenol and o-nitrophenol. , Phenols such as p-chlorophenol, o-cresol, m-cresol, p-cresol, lactams such as ε-caprolactam, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, etc. Oximes, amines, amides, nitrogen-containing heteroaryl compounds such as pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, thiols such as dodecanethiol, benzenethiol, malonic acid diester, acetoacetic acid ester, malon Examples thereof include active methylene compounds such as acid dinitrile, acetylacetone, methylenedisulfone, dibenzoylmethane, dipivaloylmethane, and acetonedicarboxylic acid diester, and hydroxamic acid ester.
The blocking agent is volatile and advantageously evaporates from the composition after desorption.

Blocked isocyanate groups, for example,

[In the formula, A represents a residue of an isocyanate blocking compound selected from the group consisting of alcohol, amine, amide, active methylene compound, nitrogen-containing heteroaryl compound, oxime, ketoxime, and hydroxamic acid ester. ]
It is represented by.

Specific examples of the isocyanate compound represented by the formula (20) include isocyanate-containing (meth)acrylates such as 2-isocyanate ethyl methacrylate and 2-isocyanate ethyl acrylate, and methyl ethyl ketone oxime, ε-caprolactam, γ-caprolactam. , 3,5-dimethylpyrazole, diethyl malonate, ethanol, isopropanol, n-butanol, 1-methoxy-2-propanol and the like. In addition, these compounds may be used individually or may be used in combination of 2 or more type.

The isocyanate compound (C) can be synthesized by a known method, or the following commercially available products can be used.
Vestanat (registered trademark) B 1358 A (manufactured by EVONIK)
Karens AOI (2-Isocyanatoethyl acrylate, a registered trademark of Showa Denko KK),
Karenz AOI-BM (2-(O-[1'-methylpropylideneamino]carboxamino)ethyl acrylate, registered trademark manufactured by Showa Denko KK)
Karens AOI-VM (2-Isocyanatoethyl acrylate, a registered trademark of Showa Denko KK),
Karenz MOI (2-isocyanatoethyl methacrylate, a registered trademark of Showa Denko KK),
Karenz MOI-BM (2-(O-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate, registered trademark, manufactured by Showa Denko KK),
Karens MOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, a registered trademark, manufactured by Showa Denko KK),
Karenz MOI-EG (registered trademark of Showa Denko KK),
Karens BEI (Showa Denko KK 1,1-(bisacryloyloxymethyl)ethyl isocyanate, registered trademark).
Among these, 2-(O-[1′-methylpropylideneamino]carboxyamino)ethyl acrylate (eg Karenz AOI-BM) and 1,1-(bisacryloyloxymethyl)ethylisocyanate (eg Karenz) Preference is given to using BEI).

Further, an isocyanate compound having a blocked isocyanate group having the following structure can be used.

When the (C) isocyanate compound is added to the photosensitive resin composition according to the present invention, the amount thereof is usually 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the resin (A) (for example, the polyimide precursor). It is a mass part.

[(D) Carboxylic acid compound or anhydride thereof]
The photosensitive resin composition of the present invention may further contain (D) a carboxylic acid compound represented by the following general formula (30) or an anhydride thereof, if desired.

[Wherein Z ¹ and Z ² are each independently
Hydrogen atom, halogen atom, hydroxy group, mercapto group, carboxy group, cyano group, formyl group, haloformyl group, sulfo group, nitro group, nitroso group, oxo group, thioxy group,
An optionally substituted alkyl, alkoxy, or alkylsulfanyl group having 1 to 10 carbon atoms,
Represents an optionally substituted alkenyl, alkynyl, or alkoxycarbonyl group having 2 to 10 carbon atoms, or an optionally substituted amino, imino, or carbamoyl group,
Z ¹ and Z ² may be bonded to each other to form a ring which may contain a hetero atom, may have a substituent or may be condensed, and the ring is an aromatic ring. When

Is a conjugated double bond in which HOOC is in an ortho position with respect to COOH, and when the ring is an aromatic ring,

Indicates a cis double bond for HOOC and COOH. ]

Preferably, the carboxylic acid compound or its anhydride (D) is a carboxylic acid compound represented by the following general formula (31) or its anhydride.

[In the formula, R ³³ to R ³⁶ are each independently
Hydrogen atom, halogen atom, hydroxy group, mercapto group, carboxy group, cyano group, formyl group, haloformyl group,
Sulfo group, nitro group, nitroso group, oxo group, thioxy group,
An optionally substituted alkyl, alkoxy, or alkylsulfanyl group having 1 to 6 carbon atoms,
Represents an optionally substituted alkenyl, alkynyl, or alkoxycarbonyl group having 2 to 6 carbon atoms, or an optionally substituted amino, imino, or carbamoyl group,
R ³³ and R ³⁴ , R ³⁴ and R ³⁵ , or R ³⁵ and R ³⁶ may be bonded to each other to contain a hetero atom, may have a substituent, or may be a condensed ring. May be formed. ]

Specific examples of the alkyl group include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group (amyl group), a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, sec-isoamyl group, isohexyl group, neohexyl group, 4-methylhexyl group, 5-methyl Hexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 2-ethylpentyl group, heptan-3-yl group, heptan-4-yl group, 4-methylhexane-2- Group, 3-methylhexan-3-yl group, 2,3-dimethylpentan-2-yl group, 2,4-dimethylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 6 -Methylheptyl group, 2-ethylhexyl group, octan-2-yl group, 6-methylheptan-2-yl group, 6-methyloctyl group, 3,5,5-trimethylhexyl group, nonan-4-yl group, 2,6-Dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group, 3-ethylheptan-3-yl group, 3,7-dimethyloctyl group, 8-methylnonyl group, 3-methylnonane Branched-chain alkyl groups such as -3-yl group and 4-ethyloctane-4-yl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, 1,6- Dimethylcyclohexyl group, menthyl group, cycloheptyl group, cyclooctyl group, bicyclo[2.2.1]heptan-2-yl group, bornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclo[5. Examples thereof include alicyclic alkyl groups such as 2.1.0 ^2,6 ]decan-4-yl group and tricyclo[5.2.1.0 ^2,6 ]decan-8-yl group.

Specific examples of the alkoxy, alkylsulfanyl group, and alkoxycarbonyl group include groups in which -O-, -S-, and -COO- are respectively bonded to the above alkyl group.

Specific examples of the alkenyl group include ethenyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group and 3- Examples include a pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 1-heptenyl group, 2-heptenyl group, 5-heptenyl group, 1-octenyl group, 3-octenyl group, and 5-octenyl group. ..

Specific examples of the alkynyl group include an acetylenyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-pentethyl group, a 2-pentethyl group, and a 3-pentynyl group. Pentethyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 1-heptynyl group, 2-heptynyl group, 5-heptynyl group, 1-octynyl group, 3-octynyl group, 5-octynyl group and the like. ..

Specific examples of the ring in which Z ¹ and Z ² are bonded to each other to form a ring which may contain a hetero atom, may have a substituent, and may be condensed, and R ³³ In the case where R ³⁴ , R ³⁴ and R ³⁵ , or R ³⁵ and R ³⁶ are bonded to each other to form a ring which may contain a hetero atom, may have a substituent, or may be condensed. Specific examples of the ring of benzene, naphthalene, anthracene, pyrrole, furan, thiophene, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, pyridine, piperidine, tetrahydropyran, tetrahydrothiopyran, imidazole, pyrazole, oxazole, thiazole, imidazoline, dioxane, Morpholine, thiazine, triazole, dioxolane, pyridazine, pyrimidine, pyrazine, indole, isoindole, benzimidazole, purine, benzotriazole, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, pteridine, chromene, isochromene, acridine, xanthene, carbazole, etc. Can be mentioned.

Examples of the substituent include a halogen atom, hydroxy group, mercapto group, carboxy group, cyano group, formyl group, haloformyl group, sulfo group, amino group, nitro group, nitroso group, oxo group, thioxy group, and 1 carbon atom. Examples thereof include an alkyl or haloalkyl group having 1 to 10 carbon atoms and an alkoxy or haloalkoxy group having 1 to 10 carbon atoms.

Preferably, Z ¹ and Z ^{2 in} the general formula (2) are a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.

Some of the suitable carboxylic acid compounds or their anhydrides (D) are shown below.

The carboxylic acid compound exemplified above may be an acid anhydride.

When the carboxylic acid compound or its anhydride (D) in the photosensitive resin composition according to the present invention is blended, the amount thereof is usually 100 parts by mass with respect to 100 parts by mass of the resin (A) (for example, the polyimide precursor). It is from 0.1 to 10 parts by weight.

[Other ingredients]
In the embodiment, the photosensitive resin composition may further contain components other than the above components (A) to (D). Examples of other components include a photopolymerization initiator, a crosslinkable compound, a solvent, a resin, a sensitizer, an adhesion aid, a thermal polymerization inhibitor, an azole compound, a hindered phenol compound, and a filler.

[Photopolymerization initiator]
The photosensitive resin 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, and examples thereof include tert-butylperoxy-iso-butyrate and 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 (Tert-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 , Quinones such as octamethylanthraquinone and 1,2-benzanthraquinone; benzoin derivatives such as benzoinmethyl, 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-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy -2-Methyl-1-propan-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propionyl)benzyl}-phenyl]-2-methyl-propan-1- On, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl )-Butan-1-one and other alkylphenone compounds; bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and other acylphosphine oxide compounds 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methyl Examples thereof include oxime ester compounds such as benzoyl)-9H-carbazol-3-yl]ethanone.
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 (manufactured by BASF), KAYACURE [registered trademark] DETX, MBP, and the like. DMBI, same EPA, same OA (above, manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, same 55 (above, manufactured by STAUFFER Co. LTD), ESACURE KIP150, same TZT, same 1001, same KTO46, same KB1, same. KL200, KS300, EB3, triazine-PMS, triazine A, triazine B (above, manufactured by Japan Siber Hegner Co., Ltd.), ADEKA OPTOMER N-1717, N-1414, N-1606 (above, manufactured by ADEKA Co., Ltd.) ) Is mentioned. These photopolymerization initiators may be used alone or in combination of two or more kinds.
When the photopolymerization initiator is blended, the amount thereof is usually 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the resin (A) (for example, the polyimide precursor), and it is preferable in terms of photosensitivity. It is preferably from 0.5 to 15 parts by mass. When 0.1 part by mass or more of the photopolymerization initiator is added to 100 parts by mass of the resin (A), the photosensitivity of the photosensitive resin composition is likely to be improved, while when 20 parts by mass or less is mixed. Is likely to improve the thick film curability of the photosensitive resin composition.

[Crosslinkable compound]
In the embodiment, in order to improve the resolution of the relief pattern, the (meth)acrylic compound (B) represented by the general formula [1a] and the isocyanate compound (C represented by the general formula (20) are represented. Monomers (crosslinking compounds) other than the above) can be arbitrarily added to the photosensitive resin composition. As such a crosslinkable compound, 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 includes diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Ethylene glycol or polyethylene glycol mono- or diacrylates and methacrylates, propylene glycol or polypropylene glycol mono- or diacrylates and methacrylates, glycerol mono-, di- or triacrylates and methacrylates, cyclohexane diacrylates and dimethacrylates, 1,4-butanediol Diacrylates and dimethacrylates, 1,6-hexanediol diacrylates and dimethacrylates, neopentyl glycol diacrylates and dimethacrylates, bisphenol A mono- or diacrylates and methacrylates, benzenetrimethacrylate, isobornyl acrylates and methacrylates , Acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, glycerol di- or triacrylates and methacrylates, pentaerythritol di-, tri- or tetra-acrylates and methacrylates, and ethylene oxide or propylene of these compounds. Examples thereof include compounds such as oxide adducts.

When the above optional crosslinkable compound is added, the amount thereof is preferably 1 part by mass to 100 parts by mass, more preferably 100 parts by mass of the resin (A) (for example, the polyimide precursor). Is 1 to 50 parts by mass.

Examples of thermal crosslinking agents include hexamethoxymethylmelamine, tetramethoxymethylglycoluril, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl). ) Glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea and 1,1,1. Examples thereof include 3,3-tetrakis(methoxymethyl)urea.
Examples of the filler include inorganic fillers, and specific examples thereof include sols such as silica, aluminum nitride, boron nitride, zirconia, and alumina.

As the solvent, it is preferable to use an organic solvent from the viewpoint of solubility in the resin (A) (for example, the polyimide precursor). 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, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, etc., which may 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 resin (A) (for example, the polyimide precursor) depending on a desired coating film thickness and viscosity of the photosensitive resin composition. It can be used in a range, preferably in a range of 100 parts by mass to 1000 parts by mass.

In the embodiment, the photosensitive resin composition may further contain a resin component other than the resin (A). Examples of the resin component that can be contained in the photosensitive resin composition include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, acrylic resin and the like.
When these resin components are blended, the amount thereof 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 resin (A) (for example, the polyimide precursor).

In the embodiment, the photosensitive resin composition may optionally contain a sensitizer in order to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4′-bis(diethylamino)benzophenone, 2,5-bis(4′-diethylaminobenzal)cyclopentane, 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 Millideneindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene) Isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7- Diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, dimethylaminobenzoic acid isoamyl, diethylaminobenzoic acid isoamyl, 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.

When the sensitizer is added, the amount thereof is preferably 0.1 part by mass to 25 parts by mass with respect to 100 parts by mass of the resin (A) (for example, the polyimide precursor).

In the embodiment, in order to improve the adhesiveness between the film formed using the photosensitive resin composition and the substrate, an adhesion aid can be optionally blended with the photosensitive resin composition. Examples of the adhesion aid include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 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- Silanes such as 1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic hydride, N-phenylaminopropyltrimethoxysilane Examples include coupling agents and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. When the adhesion aid is blended, the amount thereof 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 resin (A) (for example, the polyimide precursor).

In the embodiment, a thermal polymerization inhibitor may be optionally added in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition, particularly when stored in a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 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-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt and the like are used.

When the thermal polymerization inhibitor is blended, the amount thereof 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 resin (A) (for example, the polyimide precursor).

For example, when a substrate made of copper or a copper alloy is used, an azole compound can be optionally added to the photosensitive resin 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, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5- Methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like can be mentioned. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. Moreover, these azole compounds may be used alone or in a mixture of two or more kinds.

When the azole compound is blended, the amount thereof is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the resin (A) (for example, the polyimide precursor), and in view of photosensitivity characteristics. To 0.5 parts by mass to 5 parts by mass is more preferable. When the compounding amount of the azole compound with respect to 100 parts by mass of the resin (A) is 0.1 part by mass or more, when the photosensitive resin composition is formed on copper or a copper alloy, the surface of the copper or copper alloy is Discoloration is suppressed, and on the other hand, when it is 20 parts by mass or less, the photosensitivity is excellent, which is preferable.

In the embodiment, a hindered phenol compound can be optionally added to the photosensitive resin composition in order to suppress discoloration on copper. 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 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.

When the hindered phenol compound is blended, the amount thereof is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the resin (A) (for example, the polyimide precursor), and the photosensitivity characteristics From the viewpoint of the above, it is more preferably 0.5 parts by mass to 10 parts by mass. When the compounding amount of the hindered phenol compound with respect to 100 parts by mass of the resin (A) is 0.1 parts by mass or more, for example, when the photosensitive resin composition is formed on copper or copper alloy, copper or copper alloy It is preferable that the discoloration and corrosion are prevented, while the content of 20 parts by mass or less is excellent in photosensitivity.

[Method for producing cured relief pattern]
In the embodiment, the following steps are performed:
(1) a step of applying a photosensitive resin 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,
(3) a step of developing the photosensitive resin layer after the exposure to form a relief pattern,
(4) It is possible to provide a method for producing a substrate with a cured relief pattern, which includes a step of heating the relief pattern to form a cured relief pattern.

Each step will be described below by taking a polyimide precursor as an example of the resin (A).

(1) Step of applying a photosensitive resin composition according to the present invention onto a substrate to form a photosensitive resin layer on the substrate In this step, the photosensitive resin composition according to the present invention is applied onto a substrate. The photosensitive resin layer is formed by applying and then drying it if necessary. As a coating method, a method conventionally used for coating a photosensitive resin composition, for example, a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine or the like, spray coating with a spray coater. A method etc. can be used.

If necessary, the coating film made of the photosensitive resin composition can be dried, and as the drying method, for example, methods such as air drying, heat drying using an oven or a hot plate, and vacuum drying can be used. Further, it is desirable to dry the coating film under the condition that imidization of the polyimide precursor in the photosensitive resin composition does not occur. Specifically, when air drying or heat drying is performed, the drying can be performed at 20° C. to 200° C. for 1 minute to 1 hour. As described above, the photosensitive resin layer 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 subjected to a photomask having a pattern by using an exposure device such as a contact aligner, a mirror projection, and a stepper. Alternatively, exposure is performed by an ultraviolet light source or the like via a reticle or directly.
Examples of the light source used for the exposure include g-line, h-line, i-line, ghi-line broadband, and KrF excimer laser. The exposure dose is preferably 25 mJ/cm ² to 1000 mJ/cm ² .

After that, for the purpose of improving the photosensitivity, a post-exposure bake (PEB) and/or a pre-development bake may be performed at any combination of temperature and time, if necessary. The baking conditions are preferably such that the temperature is from 50° C. to 200° C. and the time is preferably from 10 seconds to 600 seconds, as long as the characteristics of the photosensitive resin composition are not impaired. Not limited to

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

(4) Step of heating 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 to volatilize the photosensitive component and imidize the polyimide precursor. By doing so, it is converted into a cured relief pattern made of polyimide. As the method for heat curing, various methods such as a method using a hot plate, a method using an oven, and a method using a temperature rising oven capable of setting a temperature program can be selected. 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, and an inert gas such as nitrogen or argon may be used.

[Semiconductor device]
In the embodiment, there is also provided a semiconductor device having a cured relief pattern obtained by the method for producing a cured relief pattern described above. Therefore, it is possible to provide a semiconductor device having a base material which is a semiconductor element and a cured relief pattern of polyimide formed on the base material by the above-described cured relief pattern manufacturing method. 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 method for manufacturing a cured relief pattern described above as a part of the process. The semiconductor device of the present invention is a semiconductor device having a cured relief pattern formed by the above-mentioned method for producing a cured relief pattern, 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. Can be manufactured by combining it with a known semiconductor device manufacturing method.

[Display unit]
In the embodiment, there is provided a display device including a display element and a cured film provided on the display element, wherein the cured film has the above-described 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 interposed therebetween. For example, examples of the cured film include a surface protective film of a TFT liquid crystal display element and a color filter element, an insulating film, and a flattening film, a protrusion for an MVA type liquid crystal display device, and a partition wall for an organic EL element cathode. .

INDUSTRIAL APPLICABILITY The photosensitive resin composition of the present invention is useful not only for application to the semiconductor device as described above but also for applications such as interlayer insulation of multilayer circuits, cover coat of flexible copper clad board, solder resist film, and liquid crystal alignment film. Is.

The weight average molecular weights shown in the following synthesis examples of the present specification are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in the present specification). A GPC device (HLC-8320GPC) manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions and the like are as follows.
GPC column: KD-803, KD-805 (manufactured by Shodex)
Column temperature: 50°C
Solvent: N,N-dimethylformamide (Kanto Chemical, special grade), lithium bromide monohydrate (Kanto Chemical, deer special grade) (30 mM)/phosphoric acid (Aldrich) (30 mM)/tetrahydrofuran (Kanto Chemical, special grade) ( 1%)
Flow rate: 1.0 mL/min Standard sample: Polystyrene (GL Science)

<Synthesis example 1>
Isostearic acid (Nissan Chemical Co., Ltd., 200 g, 702 mmol), dimethylformamide (1.5 g, 20 mmol), dichloromethane (800 g) were mixed, and thionyl chloride (100 g, 844 mmol) was added at 5° C. or lower after cooling to 0° C. Dropped. After reacting for 16 hours at room temperature, volatile components were distilled off with an evaporator, and the distillation residue was diluted with dichloromethane (800 g) to prepare a dichloromethane solution of isostearyl chloride. Diethanolamine (294 g, 2800 mmol) and dichloromethane (1200 g) were mixed, cooled to 0° C., and a dichloromethane solution of isostearic acid was added dropwise at 5° C. or lower, and the mixture was reacted at room temperature for 15 hours. After the reaction, unreacted diethanolamine was separated and removed from the solution. The obtained organic layer was separated and washed with 1 L of water three times, and then concentrated to obtain diethanolamine isostearate (234 g, purity 98%). Diethanolamine isostearate (100 g, 269 mmol), hydroquinone (500 mg, 5 mmol), triethylamine (60 g, 592 mmol), dichloromethane (400 g) were mixed, and after cooling to 0° C., acrylic acid chloride (51 g, 565 mmol) was added at 10° C. or lower. Dropped. After reacting at room temperature for 1 hour, 5% saline (400 g) was added to separate the layers. The organic layer was separated and washed with 1N hydrochloric acid water (400 g) and then with 5% aqueous sodium hydrogen carbonate solution (400 g). After magnesium sulfate was added to the obtained organic layer for dehydration, the inorganic salt was filtered off. By concentrating the filtrate with an evaporator, ((2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoyl)azandiyl)bis(ethane-2,1-diyl)diacrylate was obtained. (110 g, purity 98%) was obtained.
¹ H-NMR (500 MHz, CDCl ₃ ): δ=0.9 to 1.7 (m, 34H), 2.3 to 2.4 (m, 1H), 3.6 to 3.8 (m, 4H) ), 4.3 to 4.4 (m, 4H), 5.8 to 5.9 (m, 2H), 6.1 to 6.2 (m, 2H), 6.4 to 6.5 (m , 2H)

<Synthesis example 2>
Isostearyl alcohol (manufactured by Nissan Chemical Co., Ltd., product name: Fineoxocol 180, grade: FO-180, 113 g, 418 mmol), 1,1-(bisacryloyloxymethyl)ethyl isocyanate (manufactured by Showa Denko KK, product name Karenz BEI (105 g, 418 mmol) and hydroquinone (2 g, 18 mmol) were mixed, heated to 100° C. and reacted for 45 hours. As a result, 2-((((2-(4,4-dimethylpentan-2-yl) -5,7,7-Trimethyloctyl)oxy)carbonyl)amino)-2-methylpropane-1,3-diyldiacrylate (220 g, purity 97%) was obtained.
¹ H-NMR (500 MHz, CDCl ₃ ): δ=0.9 to 1.7 (m, 38H), 3.6 to 4.0 (m, 2H), 4.3 to 4.4 (m, 4H) ), 5.0 (m, 1H), 5.9 (m, 2H), 6.1 to 6.2 (m, 2H), 6.2 to 6.4 (m, 2H)

<Production Example 1> Synthesis of dicarboxylic acid diester (1) 280.00 g (0.903 mol) of 4,4'-oxydiphthalic dianhydride (Tokyo Kasei Kogyo Co., Ltd.) was placed in a 2-liter four-necked flask, and 2 -Hydroxyethyl methacrylate (Aldrich) 232.50 g (0.181 mol), hydroquinone (Tokyo Kasei Kogyo Co., Ltd.) 0.98 g (0.009 mol) and γ-butyrolactone (Kanto Chemical Industry Co., Ltd. Deer grade) 840 g After stirring at 23° C. and adding 142.78 g (1.805 mol) of pyridine (Kanto Chemical Co., Inc., dehydration), the temperature was raised to 50° C. and the mixture was stirred at 50° C. for 2 hours to obtain the following formula (1). A solution containing the compound represented by

<Production Example 2> Synthesis of Polymer (2) as Polyimide Precursor 43.68 g (0.026 mol) of the solution prepared in Production Example 1 and 34.57 g of γ-butyrolactone were placed in a 200 ml four-necked flask, and 5 A solution prepared by dissolving 6.43 g (0.053 mol) of N,N'-diisopropylcarbodiimide (DIC, Tokyo Chemical Industry Co., Ltd.) in 15 g of γ-butyrolactone was added dropwise to the reaction solution at 20° C. or below with stirring over 20 minutes. Subsequently, 8.74 g (0.03 mol) of 4,4′-bis(4-aminophenoxy)biphenyl (Seika Co., Ltd.) was dissolved in 15 g of N-methyl-2-pyrrolidinone (Kanto Chemical Co., Inc., Shika Special Grade). The resulting mixture was added dropwise with stirring over 20 minutes. After that, the temperature was raised to 23° C., and the mixture was stirred for 26.5 hours, then 2.25 g of ethanol (Kanto Chemical Co., Inc., special grade) was added and stirred for 1 hour.

The obtained reaction mixture was added to 375 g of methanol (Kanto Chemical Co., Inc., special grade) to produce a precipitate composed of a crude polymer. The supernatant was decanted to separate the crude polymer, which was dissolved in 60.0 g of tetrahydrofuran and 15.0 g of N-methyl-2-pyrrolidinone to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 750 g of water to precipitate a polymer, and the obtained precipitate was separated by filtration, washed twice with 75 g of methanol, and vacuum dried to obtain a fibrous polymer (2). Obtained. When the molecular weight of the polymer (2) was measured by GPC (standard polystyrene conversion), the weight average molecular weight (Mw) was 12,059. The yield was 74.7%. This reaction product has a repeating unit structure represented by the following formula (2).

<Production Example 3> (Synthesis of Polymer (3) as Polyimide Precursor)
40.00 g (0.129 mol) of 4,4′-oxydiphthalic acid dianhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was placed in a 4-liter flask having a capacity of 1 liter, and 26.43 g (0 of 2-hydroxyethyl methacrylate (Aldrich) was added. .206 mol), fine oxo call 180 (manufactured by Nissan Chemical Co., Ltd.) 13.67 g (0.052 mol) and γ-butyrolactone (Kanto Chemical Co., Ltd., Shika Special Grade) 116 g, and cooled to 10°C or lower and stirred. , Pyridine (Kanto Chemical Industry Co., Ltd., dehydrated), 20.89 g (0.264 mol) were added, the temperature was raised to 23° C., and the mixture was stirred for 24 hours.

Next, at 5° C. or lower, a solution prepared by dissolving 32.88 g (0.258 mol) of N,N′-diisopropylcarbodiimide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) in 80 g of γ-butyrolactone was stirred for 50 minutes to obtain a reaction solution. Then, 44.46 g (0.122 mol) of 4,4′-bis(4-aminophenoxy)biphenyl (manufactured by Seika Co., Ltd.) was added to 120 g of N-methyl-2-pyrrolidinone (Kanto Kagaku Kogyo Co., Ltd., Shika Special Grade). The solution dissolved in was added dropwise over 80 minutes. After the dropping, the temperature was raised to 23° C. and the mixture was stirred for 2 hours, then 6.0 g of ethanol (Kanto Chemical Co., Inc., special grade) was added and stirred for 1 hour. The precipitate generated in the reaction solution was removed by filtration to obtain a reaction mixture.

The obtained reaction mixture was added to 600 g of ethanol (Kanto Chemical Co., Inc., special grade) to form a precipitate composed of a crude polymer. The precipitate was filtered and dissolved in 340 g of tetrahydrofuran (THF, Kanto Chemical Co., Inc., special grade) to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 7.2 kg of water to precipitate a polymer, and the obtained precipitate was filtered off and dried in a vacuum 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 15,457. The yield was 63.3%. This polymer has a repeating unit structure represented by the following formula (3).

<Production Example 4> (Synthesis of Polymer (4) as Polyimide Precursor)
40.00 g (0.136 mol) of 4,4′-biphthalic acid dianhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was placed in a 4-liter flask having a capacity of 1 liter, and 2-hydroxyethyl methacrylate (Aldrich) 17.60 g (0 .136 mol), Fineoxocol 180 (manufactured by Nissan Chemical Co., Ltd.), 36.41 g (0.136 mol) and 116 g of γ-butyrolactone (Kanto Chemical Industry Co., Ltd., Shika Special Grade) were added, and the mixture was cooled to 10°C or lower and stirred. , 22.28 g (0.279 mol) of pyridine (Kanto Chemical Industry Co., Ltd., dehydration) was added, the temperature was raised to 23° C., and the mixture was stirred for 47 hours.

Next, at 5° C. or lower, a solution of 35.03 g (0.272 mol) of N,N′-diisopropylcarbodiimide (manufactured by Tokyo Chemical Industry Co., Ltd.) in 80.1 g of γ-butyrolactone was stirred for 90 minutes. To the reaction solution was dropped, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane (manufactured by Tokyo Chemical Industry Co., Ltd.) (53.57 g, 0.129 mol) was added to N-methyl-2-pyrrolidinone (Kanto Kagaku). A solution dissolved in 120 g of Kogyo Co., Ltd., Shika Special Grade) was added dropwise over 60 minutes. After the dropping, the temperature was raised to 23° C. and the mixture was stirred for 2 hours, then 6.0 g of ethanol (Kanto Chemical Co., Inc., special grade) was added and stirred for 1 hour. The precipitate generated in the reaction solution was removed by filtration to obtain a reaction mixture.

The obtained reaction mixture was added to 600 g of ethanol (Kanto Chemical Co., Inc., special grade) to form a precipitate composed of a crude polymer. The precipitate was filtered and dissolved in 340 g of tetrahydrofuran (THF, Kanto Chemical Co., Inc., special grade) to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 7.2 kg of water to precipitate a polymer, and the obtained precipitate was filtered off and then 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 8,903. The yield was 64.3%. This polymer has a repeating unit structure represented by the following formula (4).

<Production Example 5> Synthesis of dicarboxylic acid diester (5) 4,4'-biphthalic dianhydride (Tokyo Kasei Kogyo Co., Ltd.) 40.00 g (0.14 mol) was placed in a four-necked flask, and 2-hydroxyethyl methacrylate was added. (Aldrich) 10.46 g (0.082 mol) and 1-butanol (Tokyo Kasei Kogyo Co., Ltd.) 10.08 g (0.14 mol) and isostearyl alcohol (Nissan Chemical Co., Ltd., product name: Fine Oxocole 180, grade) : FO-180, 14.42 g, 0.054 mol) and 120 g of γ-butyrolactone (Kanto Chemical Co., Ltd., Shika Special Grade) were added and stirred at 23° C., cooled to 10° C., and then pyridine (Kanto Chemical Co., Ltd. 22.05 g (0.28 mol) was added dropwise. By raising the temperature to 25° C. and stirring for 88 hours, a solution containing a compound represented by the following formula (5) was obtained.

<Production Example 6> Synthesis of Polymer (6) as Polyimide Precursor The solution prepared in Production Example 5 was cooled to 5°C, and N,N'-dicyclohexylcarbodiimide (DCC, FUJIFILM Wako Pure Chemical Industries, Ltd.) 57. A solution prepared by dissolving 87 g (0.27 mol) in 80 g of γ-butyrolactone was added dropwise to the reaction solution over 0.5 hours with stirring, and after the addition, the mixture was stirred for 0.5 hours. Subsequently, 53.02 g (0.13 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (Tokyo Kasei Kogyo Co., Ltd.) was added to N-methyl-2-pyrrolidinone (Kanto Chemical Co., Inc. What was melt|dissolved in 80 g of (special grade) was dripped over 0.5 hour, stirring. Then, the temperature was raised to about 25° C., the mixture was stirred for 2 hours, then 6.0 g of ethanol (Kanto Chemical Co., Inc., special grade) was added, and the mixture was stirred for 1 hour.

To the obtained reaction mixture, 60 g of N-methyl-2-pyrrolidinone (Kanto Chemical Co., Inc., Shika Special Grade) and 140 g of tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.) were added and filtered. The filtrate was added dropwise to 4000 g of isopropanol to precipitate a polymer, the resulting precipitate was filtered off, washed twice with 1000 g of methanol, and vacuum dried to obtain a powdery polymer (6). When the molecular weight of the polymer (6) was measured by GPC (standard polyethylene glycol conversion), the weight average molecular weight (Mw) was 13,749. The yield was 48.0%. This reaction product has a repeating unit structure represented by the following formula (6).

<Production Example 7> Synthesis of dicarboxylic acid diester (7) 40.00 g (0.14 mol) of 4,4'-biphthalic acid dianhydride (Tokyo Kasei Kogyo Co., Ltd.) was placed in a four-necked flask, and 2-hydroxyethyl methacrylate was added. (Aldrich) 17.43 g (0.14 mol) and 2-methoxyethanol (Tokyo Kasei Kogyo Co., Ltd.) 6.15 g (0.082 mol) and isostearyl alcohol (Nissan Chemical Co., Ltd., product name: Fine Oxocole 180, Grade: FO-180, 14.42 g, 0.054 mol) and 120 g of γ-butyrolactone (Kanto Chemical Industry Co., Ltd., Shika Special Grade) were added, stirred at 23° C., cooled to 10° C., and then pyridine (Kanto Chemical Industrial). 22.05 g (0.28 mol) was added dropwise. By raising the temperature to 25° C. and stirring for 18 hours, a solution containing a compound represented by the following formula (7) was obtained.

<Production Example 8> Synthesis of polymer (8) as polyimide precursor The solution prepared in Production Example 7 was cooled to 5°C, and N,N'-dicyclohexylcarbodiimide (DCC, FUJIFILM Wako Pure Chemical Industries, Ltd.) 57. A solution prepared by dissolving 87 g (0.27 mol) in 80 g of γ-butyrolactone was added dropwise to the reaction solution over 0.5 hour with stirring, and after the addition, the solution was stirred for 0.5 hour. Subsequently, 53.02 g (0.13 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (Tokyo Kasei Kogyo Co., Ltd.) was added to N-methyl-2-pyrrolidinone (Kanto Chemical Co., Inc. What was melt|dissolved in 80 g of (special grade) was dripped over 0.5 hour, stirring. Then, the temperature was raised to about 25° C., the mixture was stirred for 2 hours, then 6.0 g of ethanol (Kanto Chemical Co., Inc., special grade) was added, and the mixture was stirred for 1 hour.

To the obtained reaction mixture, 60 g of N-methyl-2-pyrrolidinone (Kanto Chemical Co., Inc., Shika Special Grade) and 140 g of tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.) were added and filtered. The filtrate was added dropwise to 4000 g of isopropanol to precipitate a polymer, the resulting precipitate was filtered off, washed twice with 1000 g of methanol, and vacuum dried to obtain a powdery polymer (8). When the molecular weight of the polymer (8) was measured by GPC (standard polyethylene glycol conversion), the weight average molecular weight (Mw) was 12,894. The yield was 56.0%. This reaction product has a repeating unit structure represented by the following formula (8).

<Production Example 9> Synthesis of dicarboxylic acid diester (9) 40.00 g (0.13 mol) of 4,4'-oxydiphthalic anhydride (Tokyo Kasei Kogyo Co., Ltd.) was placed in a four-necked flask, and 2-hydroxyethyl methacrylate ( 16.53 g (0.13 mol) of Aldrich) and 5.83 g (0.077 mol) of 2-methoxyethanol (Tokyo Kasei Kogyo Co., Ltd.) and isostearyl alcohol (manufactured by Nissan Chemical Co., Ltd., product name: Fine Oxocole 180, grade) : FO-180, 13.67 g, 0.052 mol) and 120 g of γ-butyrolactone (Kanto Chemical Co., Ltd., Shika Special Grade) were added and stirred at 23° C., cooled to 10° C., and then pyridine (Kanto Chemical Co., Ltd. stock) (Company, dehydrated) 20.91 g (0.26 mol) was added dropwise. By raising the temperature to 25° C. and stirring for 15 hours, a solution containing a compound represented by the following formula (9) was obtained.

<Production Example 10> Synthesis of polymer (10) as polyimide precursor The solution prepared in Production Example 9 was cooled to 5°C, and N,N'-dicyclohexylcarbodiimide (DCC, FUJIFILM Wako Pure Chemical Industries, Ltd.) 54. A solution prepared by dissolving 89 g (0.26 mol) in 80 g of γ-butyrolactone was added dropwise to the reaction solution over 0.5 hour with stirring, and after the addition, the solution was stirred for 0.5 hour. Subsequently, 44.68 g (0.12 mol) of 4,4′-bis(4-aminophenoxy)biphenyl (Seika Co., Ltd.) was dissolved in 80 g of N-methyl-2-pyrrolidinone (Kanto Chemical Co., Inc., Shika Special Grade). The product was added dropwise with stirring over 0.5 hours. After that, the temperature was raised to about 25° C., the mixture was stirred for 2 hours, 6.0 g of ethanol (Kanto Chemical Co., Inc., special grade) was added, and the mixture was stirred for 1 hour.

To the obtained reaction mixture, 60 g of N-methyl-2-pyrrolidinone (Kanto Chemical Co., Inc., Shika Special Grade) and 140 g of tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.) were added and filtered. The filtrate was added dropwise to 4000 g of isopropanol to precipitate the polymer, the resulting precipitate was filtered off, washed twice with 1000 g of methanol, and vacuum dried to obtain a powdery polymer (10). When the molecular weight of the polymer (10) was measured by GPC (standard polyethylene glycol conversion), the weight average molecular weight (Mw) was 19,690. The yield was 65.1%. This reaction product has a repeating unit structure represented by the following formula (10).

<Production Example 11> Synthesis of dicarboxylic acid diester (11) 4,4'-oxydiphthalic anhydride (Tokyo Chemical Industry Co., Ltd.) 40.00 g (0.13 mol) was placed in a four-necked flask, and 2-hydroxyethyl methacrylate ( 16.53 g (0.13 mol) of Aldrich), 1-butanol (Tokyo Kasei Kogyo Co., Ltd.) 5.73 g (0.077 mol) and isostearyl alcohol (manufactured by Nissan Kagaku Co., Ltd., product name: Fine Oxocole 180, grade: FO-180, 13.67 g, 0.052 mol) and 120 g of γ-butyrolactone (Kanto Chemical Co., Ltd., Shika Special Grade) were added, stirred at 23° C., cooled to 10° C., and then pyridine (Kanto Chemical Co., Ltd.). , Dehydration) 20.91 g (0.26 mol) was added dropwise. By raising the temperature to 25° C. and stirring for 24 hours, a solution containing a compound represented by the following formula (11) was obtained.

<Production Example 12> Synthesis of polymer (12) as polyimide precursor The solution prepared in Production Example 11 was cooled to 5°C, and N,N'-dicyclohexylcarbodiimide (DCC, FUJIFILM Wako Pure Chemical Industries, Ltd.) 54. A solution prepared by dissolving 89 g (0.26 mol) in 80 g of γ-butyrolactone was added dropwise to the reaction solution over 0.5 hour with stirring, and after the addition, the solution was stirred for 0.5 hour. Subsequently, 44.68 g (0.12 mol) of 4,4′-bis(4-aminophenoxy)biphenyl (Seika Co., Ltd.) was dissolved in 80 g of N-methyl-2-pyrrolidinone (Kanto Chemical Co., Inc., Shika Special Grade). The product was added dropwise with stirring over 0.5 hours. Then, the temperature was raised to about 25° C., the mixture was stirred for 2 hours, then 6.0 g of ethanol (Kanto Chemical Co., Inc., special grade) was added, and the mixture was stirred for 1 hour.

To the obtained reaction mixture, 60 g of N-methyl-2-pyrrolidinone (Kanto Chemical Co., Inc., Shika Special Grade) and 140 g of tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.) were added and filtered. The filtrate was added dropwise to 4000 g of isopropanol to precipitate a polymer, the obtained precipitate was filtered off, washed twice with 1000 g of methanol, and vacuum dried to obtain a powdery polymer (12). When the molecular weight of the polymer (12) was measured by GPC (standard polyethylene glycol conversion), the weight average molecular weight (Mw) was 13,422. The yield was 69.8%. This reaction product has a repeating unit structure represented by the following formula (12).

<Production Example 13> Synthesis of dicarboxylic acid diester (13) 4,4'-biphthalic acid dianhydride (Tokyo Chemical Industry Co., Ltd.) 40.00 g (0.14 mol) was placed in a four-necked flask, and 2-hydroxyethyl methacrylate was added. (Aldrich) 17.43 g (0.14 mol) and 1-butanol (Tokyo Kasei Kogyo Co., Ltd.) 6.05 g (0.082 mol) and isostearyl alcohol (Nissan Chemical Co., Ltd., product name: Fine Oxocole 180, grade) : FO-180, 14.42 g, 0.054 mol) and 120 g of γ-butyrolactone (Kanto Chemical Co., Ltd., Shika Special Grade) were added and stirred at 23° C., cooled to 10° C., and then pyridine (Kanto Chemical Co., Ltd. 22.05 g (0.28 mol) was added dropwise. By raising the temperature to 25° C. and stirring for 92 hours, a solution containing a compound represented by the following formula (13) was obtained.

<Production Example 14> Synthesis of polymer (14) as polyimide precursor The solution prepared in Production Example 13 was cooled to 5°C, and N,N'-dicyclohexylcarbodiimide (DCC, FUJIFILM Wako Pure Chemical Industries, Ltd.) 57. A solution prepared by dissolving 87 g (0.27 mol) in 80 g of γ-butyrolactone was added dropwise to the reaction solution over 0.5 hour with stirring, and after the addition, the solution was stirred for 0.5 hour. Subsequently, 53.02 g (0.13 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (Tokyo Kasei Kogyo Co., Ltd.) was added to N-methyl-2-pyrrolidinone (Kanto Chemical Co., Inc. What was melt|dissolved in 80 g of (special grade) was dripped over 0.5 hour, stirring. Then, the temperature was raised to about 25° C., the mixture was stirred for 2 hours, then 6.0 g of ethanol (Kanto Chemical Co., Inc., special grade) was added, and the mixture was stirred for 1 hour.

To the obtained reaction mixture, 60 g of N-methyl-2-pyrrolidinone (Kanto Chemical Co., Inc., Kaka Special Grade) and 140 g of tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.) were added and filtered. The filtrate was added dropwise to 4000 g of isopropanol to precipitate a polymer, the resulting precipitate was filtered off, washed twice with 1000 g of methanol, and vacuum dried to obtain a powdery polymer (14). When the molecular weight of the polymer (14) was measured by GPC (standard polyethylene glycol conversion), the weight average molecular weight (Mw) was 10,637. The yield was 67.7%. This reaction product has a repeating unit structure represented by the following formula (14).

<Production Example 15> (Synthesis of Polymer (15) as Polyimide Precursor)
40.00 g (0.136 mol) of 4,4′-biphthalic acid dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a 4-liter flask having a capacity of 1 liter, and 28.16 g (0 of 2-hydroxyethyl methacrylate (Aldrich) was added. .218 mol), Fineoxocall 180 (manufactured by Nissan Chemical Co., Ltd.) 14.56 g (0.054 mol) and γ-butyrolactone (Kanto Chemical Co., Ltd., Shika Special Grade) 116 g, and the mixture is cooled to 10°C or lower and stirred. After adding 22.28 g (0.279 mol) of pyridine (Kanto Chemical Co., Inc., dehydration), the temperature was raised to 23° C. and the mixture was stirred for 48 hours.

Next, at 5° C. or lower, a solution of 35.02 g (0.272 mol) of N,N′-diisopropylcarbodiimide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) in 80 g of γ-butyrolactone was stirred for 60 minutes to obtain a reaction solution. Then, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (manufactured by Tokyo Chemical Industry Co., Ltd.) 53.56 g (0.129 mol) was added to N-methyl-2-pyrrolidinone (Kanto Chemical Co., Inc.). A solution prepared by dissolving 120 g of the company (deer special grade) was added dropwise over 60 minutes. After the dropping, the temperature was raised to 23° C. and the mixture was stirred for 2 hours, then 6.0 g of ethanol (Kanto Chemical Co., Inc., special grade) was added and stirred for 1 hour. The precipitate generated in the reaction solution was removed by filtration to obtain a reaction mixture.

The obtained reaction mixture was added to 600 g of ethanol (Kanto Chemical Co., Inc., special grade) to form a precipitate composed of a crude polymer. The precipitate was filtered and dissolved in 340 g of tetrahydrofuran (THF, Kanto Chemical Co., Inc., special grade) to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 7.2 kg of water to precipitate a polymer, and the obtained precipitate was filtered off and dried in a vacuum 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 10,779. The yield was 63.3%. This polymer has a repeating unit structure represented by the following formula (15).

<Example 1>
32.00 g of the polymer obtained from the polymer obtained in Production Example 2, 0.64 g of IRGACURE [registered trademark] OXE01 (manufactured by BASF), 6.40 g of the compound obtained in Synthesis Example 1, KBM-5103 (Shin-Etsu) 0.48 g manufactured by Kagaku Kogyo Co., Ltd. and 0.48 g of IRGANOX3114 (manufactured by BASF) were dissolved in 48.00 g of cyclohexanone and 12.00 g of ethyl lactate to prepare a composition. Then, the negative photosensitive resin composition 1 was prepared by filtering using a polypropylene microfilter having a pore size of 5 μm.

<Example 2>
Negative-type photosensitive resin composition 2 was prepared in the same procedure as in Example 1 except that the compound obtained in Synthesis Example 1 of Example 1 was changed to the compound obtained in Synthesis Example 2.

<Example 3>
Negative-type photosensitive resin composition 3 was prepared in the same procedure as in Example 1 except that the compound obtained in Synthesis Example 1 of Example 1 was changed to S-1800A (manufactured by Shin-Nakamura Chemical Co., Ltd.). ..

<Example 4>
29.63 g of the polymer obtained in Production Example 3, 0.59 g of IRGACURE [registered trademark] OXE01 (manufactured by BASF), 5.93 g of the compound obtained in Synthesis Example 1, KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.44 g, IRGANOX3114 (manufactured by BASF) 0.44 g, and Vestanat (registered trademark) B 1358 A (manufactured by EVONIK) 2.96 g are dissolved in cyclohexanone 48.00 g and ethyl lactate 12.00 g to form a composition. Prepared. Then, the negative photosensitive resin composition 4 was prepared by filtering using a polypropylene microfilter having a pore size of 5 μm.

<Example 5>
Negative photosensitive resin composition 5 was prepared in the same procedure as in Example 4 except that the compound obtained in Synthesis Example 1 of Example 4 was changed to the compound obtained in Synthesis Example 2.

<Example 6>
29.41 g of the polymer obtained in Production Example 3, 0.59 g of IRGACURE [registered trademark] OXE01 (manufactured by BASF), 5.88 g of the compound obtained in Synthesis Example 1, KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.44 g, IRGANOX3114 (manufactured by BASF) 0.44 g, Vestanat (registered trademark) B 1358 A (manufactured by EVONIK) 2.94 g, and phthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.29 g, and cyclohexanone 48. A composition was prepared by dissolving it in 0.000 g and ethyl lactate 12.00 g. Then, the negative photosensitive resin composition 6 was prepared by filtering using a polypropylene microfilter having a pore size of 5 μm.

<Example 7>
Negative photosensitive resin composition 7 was prepared in the same procedure as in Example 6 except that the compound obtained in Synthesis Example 1 of Example 6 was changed to the compound obtained in Synthesis Example 2.

<Example 8>
23.53 g of the polymer obtained in Production Example 4, 1.41 g of IRGACURE [registered trademark] OXE01 (manufactured by BASF), 4.71 g of the compound obtained in Synthesis Example 2, KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.35 g, IRGANOX3114 (manufactured by BASF) 0.35 g, AOI-BM (manufactured by Showa Denko KK) 9.41 g, and phthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.24 g, cyclohexanone 48.00 g, A composition was prepared by dissolving it in 12.00 g of ethyl lactate. Then, the negative photosensitive resin composition 8 was prepared by filtering using a polypropylene microfilter having a pore size of 5 μm.

<Example 9>
25.00 g of the polymer obtained in Production Example 6, 1.50 g of IRGACURE [registered trademark] OXE01 (manufactured by BASF), 7.50 g of the compound obtained in Synthesis Example 1, KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.38 g, IRGANOX3114 (manufactured by BASF) 0.38 g, AOI-BM (manufactured by Showa Denko KK) 5.00 g, and phthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.25 g, cyclohexanone 48.00 g, A composition was prepared by dissolving it in 12.00 g of ethyl lactate. Then, the negative photosensitive resin composition 9 was prepared by filtering using a polypropylene microfilter having a pore size of 5 μm.

<Example 10>
Negative photosensitive resin composition 10 was prepared in the same procedure as in Example 9 except that the polymer obtained in Production Example 6 of Example 9 was changed to the polymer obtained in Production Example 8.

<Example 11>
26.67 g of the polymer obtained in Production Example 10, 1.60 g of IRGACURE [registered trademark] OXE01 (manufactured by BASF), 5.33 g of the compound obtained in Synthesis Example 1, KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.40 g, IRGANOX3114 (manufactured by BASF) 0.40 g, AOI-BM (manufactured by Showa Denko KK) 5.33 g, and phthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.27 g, cyclohexanone 48.00 g, A composition was prepared by dissolving it in 12.00 g of ethyl lactate. Then, the negative photosensitive resin composition 11 was prepared by filtering using a polypropylene microfilter having a pore size of 5 μm.

<Example 12>
A negative photosensitive resin composition 12 was prepared in the same procedure as in Example 11 except that the polymer obtained in Production Example 10 of Example 11 was changed to the polymer obtained in Production Example 12.

<Example 13>
Negative photosensitive resin composition 13 was prepared in the same procedure as in Example 11 except that the polymer obtained in Production Example 10 of Example 11 was changed to the polymer obtained in Production Example 14.

<Example 14>
Negative photosensitive resin composition 14 was prepared in the same procedure as in Example 11 except that the polymer obtained in Production Example 10 of Example 11 was changed to the polymer obtained in Production Example 15.

<Example 15>
Same as Example 11 except that the polymer obtained in Production Example 10 of Example 11 was changed to the polymer obtained in Production Example 15 and the compound obtained in Synthesis Example 1 was changed to the compound obtained in Synthesis Example 2. Negative photosensitive resin composition 15 was prepared by the procedure of.

<Comparative Example 1>
29.63 g of the polymer obtained in Production Example 2, 0.59 g of IRGACURE [registered trademark] OXE01 (manufactured by BASF), tricyclodecane dimethanol diacrylate (trade name A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 .93 g, KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.44 g, IRGANOX 3114 (manufactured by BASF) 0.44 g, and Nicarak MX-280 (Sanwa Chemical Co., Ltd.) 2.96 g, cyclohexanone 48.00 g, A composition was prepared by dissolving it in 12.00 g of ethyl lactate. Then, the negative photosensitive resin composition 16 was prepared by filtering using a polypropylene microfilter having a pore size of 5 μm.

<Comparative example 2>
29.63 g of the polymer obtained in Production Example 3, 0.59 g of IRGACURE [registered trademark] OXE01 (manufactured by BASF), A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.) 5.93 g, KBM-5103 (Shin-Etsu Chemical Co., Ltd.) 0.44 g (made by corporation), IRGANOX3114 (made by BASF) 0.44 g, and Vestanat (registered trademark) B 1358 A (made by EVONIK) 2.96 g are dissolved in 48.00 g of cyclohexanone and 12.00 g of ethyl lactate. A composition was prepared. Then, the negative photosensitive resin composition 17 was prepared by filtering using a polypropylene microfilter having a pore size of 5 μm.

[Electrical property test]
The negative photosensitive resin compositions prepared in Examples and Comparative Examples were applied on a silicon wafer on which aluminum was laminated using a spin coater, prebaked at 100° C., and aligned (PLA-501, manufactured by Canon Inc.). (I-line, exposure amount: 500 mJ/cm ² ), bake at 115° C., and bake at 230° C. to form a film having a thickness of 10 μm. Then, it was immersed in 6N hydrochloric acid. The part where the aluminum was dissolved and the film was lifted was collected and cut into a length of 3 cm and a width of 9 cm to obtain a free-standing film. Using this free-standing film, the relative permittivity and dielectric loss tangent at 1 GHz were calculated by a perturbation type cavity resonator method (apparatus: TMR-1A, manufactured by Keycom Co., Ltd.). Details of the measuring method are as follows.

(Measuring method)
Perturbation type cavity resonator 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: 1192822mm ³
Measurement frequency: Approximately 1 GHz (depends on sample resonance frequency)
Sample tube: Made of PTFE Inner diameter: 3mm Length: About 30mm
The measurement results are shown in Table 1 below.

Compared with Comparative Examples 1 and 2, Examples 1 to 11 using the (meth)acrylic compound according to the present invention have the same relative dielectric constant, but the dielectric loss tangent is significantly reduced.

The photosensitive resin composition according to the present invention provides a cured product having high transparency, high Young's modulus after thermosetting, and reduced dielectric constant and dielectric loss tangent.

Claims

At least one selected from the group consisting of (A) a resin, and (B) a (meth)acrylic compound represented by the following formula [1a] and a (meth)acrylic compound represented by the following formula [1a1]. Photosensitive resin composition.

(In the formula [1a], R 11 represents an alkyl group having 2 to 30 carbon atoms, R 21 independently represents a hydrogen atom or a methyl group, L 1 represents a single bond or an oxymethylene group, and L 2 Represents an organic group represented by the formula [2a] or the formula [3a], and n represents an integer of 1 to 6.)

(In formula [2a], * represents an end bonded to a carbonyl group, and L 3 and L 4 each independently represent an alkylene group having 2 to 8 carbon atoms which may include an ether bond.)

(In the formula [3a], * represents an end bonded to a carbonyl group, and L 5 represents a (n+1)-valent hydrocarbon group having 2 to 10 carbon atoms which may include an ether bond).

(In the formula [1a1], R 12 represents an alkyl group having 2 to 30 carbon atoms, R 22 independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6.)
The resin (A) has the following general formula (1):

[In the formula, X 1 is a tetravalent organic group, Y 1 is a divalent organic group, and R 1 and R 2 are each independently a monovalent organic group. ] The photosensitive resin composition of Claim 1 which is a polyimide precursor which has a unit structure represented by these.
The photosensitive resin composition according to claim 1, wherein R 11 or R 12 represents an alkyl group having 6 to 26 carbon atoms.
The photosensitive resin composition according to claim 1, wherein R 11 or R 12 represents an alkyl group having 14 to 20 carbon atoms.
The photosensitive resin composition according to claim 1, wherein R 11 or R 12 is a branched alkyl group.
The photosensitive resin composition according to claim 1, wherein R 11 or R 12 is a group represented by the formula [4a].

(In the formula [4a], R 43 and R 44 each independently represent an alkyl group having 1 to 27 carbon atoms, and R 45 represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, provided that The total number of carbon atoms in the CR 43 R 44 R 45 group is 10 to 31.)
A photosensitive resin film, which is a fired product of a coated film of the photosensitive resin composition according to any one of claims 1 to 6.
The following steps:
(1) A step of applying the photosensitive resin composition according to any one of claims 1 to 6 onto a substrate to form a photosensitive resin layer on the substrate,
(2) a step of exposing the photosensitive resin layer,
(3) a step of developing the photosensitive resin layer after the exposure to form a relief pattern,
(4) A method for producing a substrate with a cured relief pattern, which comprises a step of heating the relief pattern to form a cured relief pattern.
A substrate with a cured relief pattern manufactured by the method according to claim 8.
A semiconductor device comprising a semiconductor element and a cured film provided above or below the semiconductor element, wherein the cured film is the cured relief pattern according to claim 9.
A (meth)acrylic compound represented by the following formula [1a].

(In the formula [1a], R 11 represents an alkyl group having 2 to 30 carbon atoms, R 21 independently represents a hydrogen atom or a methyl group, L 1 represents a single bond or an oxymethylene group, and L 2 Represents an organic group represented by the formula [2a] or the formula [3a], and n represents an integer of 1 to 6.)

(In formula [2a], * represents an end bonded to a carbonyl group, and L 3 and L 4 each independently represent an alkylene group having 2 to 8 carbon atoms which may include an ether bond.)

(In formula [3a], * represents an end bonded to a carbonyl group, and L 5 represents a (n+1)-valent hydrocarbon group having 2 to 10 carbon atoms which may include an ether bond.)
The (meth)acrylic compound according to claim 11, wherein R 11 represents an alkyl group having 6 to 26 carbon atoms.
The (meth)acrylic compound according to claim 11, wherein R 11 represents an alkyl group having 14 to 20 carbon atoms.
The (meth)acrylic compound according to claim 11, wherein R 11 is a branched alkyl group.
The (meth)acrylic compound according to claim 11, wherein R 11 is a group represented by the formula [4a].

(In the formula [4a], R 43 and R 44 each independently represent an alkyl group having 2 to 27 carbon atoms, and R 45 represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, The total number of carbon atoms in the CR 43 R 44 R 45 group is 10 to 31.)
L 3 and L 4 are each independently ethylene group, 3-oxypentane-1,5-diyl group, 3,6-dioxyoctane-1,8-diyl group, 3,6,9-trioxyundecane The (meth)acrylic compound according to claim 11, which is a group selected from the group consisting of -1,11-diyl groups.
L 5 is the following formula:

The (meth)acrylic compound according to claim 11, which is a group selected from the group consisting of:
(A) a resin, and (B) a (meth)acrylic compound according to claim 11,
A resin composition comprising: