JP2021120703A - Photosensitive resin composition, cured relief pattern and method for producing the same - Google Patents

Abstract

To provide a photosensitive resin composition, a cured relief pattern and a method for producing the same that can improve in-plane uniformity of a cured relief pattern.SOLUTION: A photosensitive resin composition contains (A) at least one resin selected from the group consisting of a polyimide and a polyimide precursor, (B) a photosensitizer, and (C) a urea compound. When a cured film obtained by heating the photosensitive resin composition at 170°C for 2 hours is brought into contact with a dimethyl sulfoxide (DMSO) solution of tetramethylammonium hydroxide pentahydrate (TMAH) at a temperature of 50°C and a concentration of 2.38 mass% for 10 minutes, before and after the contact, IR peak intensities around 1778 cm-1 of the cured film when standardized by an IR peak intensity at 1500 cm-1 satisfy the following formula (1): 0.1≤(peak intensity after contact/peak intensity before contact)≤0.8 (1).SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin composition, a cured relief pattern, and a method for producing the same.

Conventionally, polyimide resins, polybenzoxazole resins, phenol resins, etc., which have excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic parts, passivation films, surface protective films, interlayer insulating films, etc. of semiconductor devices. It is used. Among these resins, those provided in the form of a photosensitive resin composition easily form a heat-resistant relief pattern film by applying, exposing, developing, and thermally imidizing the composition. be able to. Such a photosensitive resin composition has a feature that a process can be significantly shortened as compared with a conventional non-photosensitive material.

On the other hand, in recent years, the mounting method (packaging structure) of a semiconductor device on a printed wiring board has also changed from the viewpoint of improving the degree of integration and calculation function and reducing the chip size. The polyimide film comes into direct contact with the solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which enable higher density mounting from the conventional mounting method using metal pins and lead-tin eutectic solder. Structures are being used. Further, a structure having a plurality of rewiring layers having an area larger than the area of the semiconductor chip on the surface of the semiconductor chip, such as FO (fanout), has been proposed.

In the packaging structure that requires the formation of a multilayer film such as the above FO, the photosensitive resin composition is further applied on the interlayer insulating resin and the Cu wiring. Patent Document 1 discloses that a laminate having excellent adhesion between resins can be obtained by forming a multilayer film using a resin layer having specific physical characteristics. Further, Patent Document 2 discloses a photosensitive resin composition containing a polyimide precursor for an interlayer insulating film, a photopolymerization initiator, and a small molecule compound having a predetermined structure.

International Publication No. 2017/146152 Japanese Unexamined Patent Publication No. 2019-185031

However, when two or more layers of the cured relief pattern are laminated using the conventional photosensitive resin composition as described in Patent Document 2, the cured relief pattern is cured because the wettability of the cured relief pattern is low. It was found that the in-plane uniformity when the photosensitive resin composition was further applied onto the relief pattern was insufficient.

An object of the present invention is to provide a photosensitive resin composition, a cured relief pattern, and a method for producing the same, which can improve the in-plane uniformity of the cured relief pattern.

The present inventors specify the intensity ratio of the IR peaks of the cured film before and after the contact when the cured film of the photosensitive resin composition containing the urea compound is brought into contact with the DMSO solution of TMAH under specific conditions. We have found that the above problems can be solved by keeping the above range, and have completed the present invention. Examples of embodiments of the present invention are listed below.
[1]
(A) At least one resin selected from the group consisting of polyimide and polyimide precursors, and
(B) Photosensitizer and
(C) A photosensitive resin composition containing a urea compound.
A cured film cured by heating the photosensitive resin composition at 170 ° C. for 2 hours was prepared by dimethyl sulfoxide (TMAH) of tetramethylammonium hydroxide pentahydrate (TMAH) having a temperature of 50 ° C. and a concentration of 2.38% by mass. When contacted with a DMSO) solution for 10 minutes
^{The IR peak intensity near 1778 cm -1} when standardized with the IR peak intensity ^{of 1500 cm -1} of the cured film before and after contact is calculated by the following formula (1):
0.1 ≤ (Peak intensity after contact / Peak intensity before contact) ≤ 0.8 ... (1)
A photosensitive resin composition that meets the requirements.
[2]
The photosensitive resin composition according to item 1, wherein the amount of change in the film thickness of the cured film before and after contact is 1 nm or more and 1000 nm or less.
[3]
The photosensitive resin composition according to item 1 or 2, wherein the imidization rate of the cured film before contact is 70% or more and 100% or less.
[4]
The photosensitive resin composition according to any one of items 1 to 3, wherein the photosensitive resin composition is a photosensitive resin composition for forming an insulating member.
[5]
The photosensitive resin composition according to any one of items 1 to 4, wherein the photosensitive resin composition is a photosensitive resin composition for forming an interlayer insulating film.
[6]
The photosensitive resin composition according to any one of items 1 to 5, wherein the photosensitive resin composition is a photosensitive resin composition for forming two or more layers of an interlayer insulating film.
[7]
(1) A step of applying the photosensitive resin composition according to any one of items 1 to 6 onto a substrate to form a photosensitive resin layer on the substrate.
(2) The step of exposing the photosensitive resin layer and
(3) A step of developing the photosensitive resin layer after the exposure to form a relief pattern, and
(4) A step of heat-treating the relief pattern to form a cured relief pattern, and
(5) A step of bringing the cured relief pattern into contact with an alkaline solution, and
(6) A step of heat-treating the cured relief pattern in contact with the alkaline solution, and
A method for manufacturing a cured relief pattern, including.
[8]
The method for producing a cured relief pattern according to item 7, wherein the heat treatment is a heat treatment at 170 ° C. or lower.
[9]
^{The IR peak intensity near 1778 cm -1} when standardized with the IR peak intensity of ^{1500 cm -1} of the cured relief pattern obtained in the above step (4) and the cured relief pattern obtained in the above step (6) is the above step. The method for producing a cured relief pattern according to item 7 or 8, which is higher than the IR peak intensity near ^{1778 cm -1 of the} cured relief pattern obtained in (5).
[10]
The method for producing a cured relief pattern according to any one of items 7 to 9, wherein the step (5) of bringing the cured relief pattern into contact with the alkaline solution is a photoresist peeling step.
[11]
When the cured film was contacted with a DMSO solution of TMAH at a temperature of 50 ° C. and a concentration of 2.38% by mass for 10 minutes, the IR peak intensity ^{of 1500 cm -1 of the cured film was standardized before and after the contact.} The IR peak intensity near ^{1778 cm -1} is calculated by the following equation (1):
0.1 ≤ (Peak intensity after contact / Peak intensity before contact) ≤ 0.8 ... (1)
A cured film that meets the requirements.
[12]
The cured film according to item 11, wherein the amount of change in the film thickness of the cured film before and after contact is 1 nm or more and 1000 nm or less.
[13]
The cured film according to item 11 or 12, wherein the imidization rate of the cured film before contact is 70% or more and 100% or less.

According to the present invention, the photosensitive resin composition, the cured relief pattern, and the cured relief pattern thereof, which can improve the in-plane uniformity of the cured relief pattern when two or more layers of the cured relief pattern of the photosensitive resin composition are laminated. A manufacturing method can be provided.

Hereinafter, embodiments for carrying out the present invention (hereinafter, abbreviated as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof. In addition, throughout the present specification, the structures represented by the same reference numerals in the general formula may be the same or different from each other when a plurality of structures are present in the molecule.

<Photosensitive resin composition>
The photosensitive resin composition according to this embodiment is
(A) At least one resin selected from the group consisting of polyimide and polyimide precursors, and
(B) Photosensitizer and
(C) Includes urea compounds.

The photosensitive resin composition according to the present embodiment can be heated at 170 ° C. for 2 hours to obtain a cured film. This cured film is added to a dimethyl sulfoxide (DMSO) solution of tetramethylammonium hydroxide pentahydrate (TMAH) at a temperature of 50 ° C. and a concentration of 2.38% by mass (hereinafter, also referred to as “standard TMAH solution”) at 10 When contacted for 1 minute, ^{the IR peak intensity near 1778 cm -1} when standardized with the IR peak intensity ^{of 1500 cm -1} of the cured film before and after contact satisfies the following formula (1).
0.1 ≤ (Peak intensity after contact / Peak intensity before contact) ≤ 0.8 ... (1)

When the IR peak intensity of the cured film is within the above range, the hydrophilicity of the cured film is increased, and the cured film has a wettability suitable for further coating the photosensitive resin composition on the cured film. The value of the peak intensity after contact / peak intensity before contact is preferably 0.1 or more, more preferably 0.3 or more, and further preferably 0.5 or more from the viewpoint of chemical resistance. A cured film having a value of peak intensity after contact / peak intensity before contact of less than 0.1 has poor chemical resistance. The value of the peak intensity after contact / peak intensity before contact is preferably 0.8 or less, more preferably 0.7 or less, still more preferably 0.6 or less, from the viewpoint of wettability.

The temperature, concentration, and contact conditions of the standard TMAH solution are conditions for measuring the post-contact peak intensity / pre-contact peak intensity of the photosensitive resin composition, and the photosensitive resin composition of the present embodiment is used. Note that it does not limit the method or use. In the photosensitive resin composition of the present embodiment, the peak intensity after contact / the peak intensity before contact is within the range of the above formula (1) by further combining the component (A) and the component (B) with the urea compound (C). Tends to be able to adjust within.

The amount of change in the film thickness of the standard TMAH solution before and after contact is preferably 1 nm or more and 1000 nm or less. If the solubility in an alkaline solution in the method for producing a cured relief pattern is low, deterioration of the pattern (cracks, pattern shape collapse) can be effectively suppressed. Therefore, the cured film before and after contact with the standard TMAH solution. The amount of change in the film thickness of is more preferably 600 nm or less, and further preferably 300 nm or less. The amount of change in the film thickness of the cured film is measured by adjusting the film thickness of the cured film before contact to about 3 μm.

The cured film before being contacted with the standard TMAH solution preferably has an imidization ratio of 70% or more and 100% or less from the viewpoint of degassing property and curing shrinkage in the step of forming the multilayer body. When the imidization rate is 70% or more, degassing property and curing shrinkage can be suppressed in the step after the contact with the alkaline solution. The imidization ratio is more preferably 80% or more, and further preferably 90% or more.

｛式中、Ｘ_２は４価の有機基であり、Ｙ_２は２価の有機基であり、ｎ_１は２〜１５０の整数であり、そしてＲ_１及びＲ_２は、それぞれ独立に、水素原子、又は１価の有機基であり、Ｒ_１及びＲ_２の少なくともいずれかは、下記一般式（４）：

（式中、Ｌ_１、Ｌ_２及びＬ_３は、それぞれ独立に、水素原子又は炭素数１〜３の１価の有機基であり、そしてm₁は、２〜１０の整数である。）で表される１価の有機基である。｝ (A) Polyimide precursor The (A) polyimide precursor in the present embodiment is a resin component contained in a photosensitive resin composition, and is converted into polyimide by subjecting it to a heat cyclization treatment. The polyimide precursor is preferably a polyamide having a structure represented by the following general formula (3).

{In the formula, X ₂ is a tetravalent organic group, Y ₂ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are independently hydrogen. It is an atomic or monovalent organic group, and _{at least one of R 1} and R ₂ is the following general formula (4):

(In the formula, L ₁ , L ₂ and L ₃ are independently hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10). It is a monovalent organic group represented. }

_{The ratio of R 1} and R ₂ in the general formula (3) to be hydrogen atoms is more preferably 10% or less, more preferably 5% or less, based on the total number of moles of _{R 1} and R _2. It is more preferably 1% or less. _{The ratio of R 1} and R ₂ in the general formula (3) being monovalent organic groups represented by the general formula (4) is 70% or more based on the total number of moles of _{R 1} and R _2. It is preferably 80% or more, more preferably 90% or more. It is preferable that the ratio of hydrogen atoms and the ratio of organic groups of the general formula (4) are in the above range from the viewpoint of photosensitive characteristics and storage stability.

_{N 1} in the general formula (3) is not limited as long as it is an integer of 2 to 150, but an integer of 3 to 100 is preferable, and an integer of 5 to 70 is preferable from the viewpoint of the photosensitive characteristics and mechanical characteristics of the photosensitive resin composition. Is more preferable.

｛式中、Ｒ６は水素原子、フッ素原子、Ｃ_１〜Ｃ_１０の炭化水素基、及びＣ_１〜Ｃ_１０の含フッ素炭化水素基から成る群から選ばれる１価の基であり、ｌは０〜２から選ばれる整数であり、ｍは０〜３から選ばれる整数であり、そしてｎは０〜４から選ばれる整数である。｝で表される構造を有する基が挙げられるが、これらに限定されるものではない。また、Ｘ_１の構造は１種でも２種以上の組み合わせでもよい。上記式（２０）で表される構造を有するＸ_１基は、耐熱性と感光特性とを両立するという点で特に好ましい。 In the general formula (3), the _{tetravalent organic group represented by X 1} is preferably an organic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive characteristics, and more preferably. _One -COOR _{group, two} -COOR groups, and the -CONH- group are aromatic groups or alicyclic aliphatic groups in which they are in ortho positions with each other. As the _{tetravalent organic group represented by X 1} , specifically, an organic group having 6 to 40 carbon atoms containing an aromatic ring, for example, the following general formula (20):

{Wherein, R6 is a hydrogen atom, a fluorine _atom, a monovalent group selected from the group consisting of a fluorine-containing hydrocarbon group of a hydrocarbon group and a _C 1 _{-C 10,} of C 1 _{-C 10,} l is 0 It is an integer selected from ~ 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4. }, But the group is not limited thereto. Further, _{the structure of X 1} may be one kind or a combination of two or more kinds. X ₁ group having the structure represented by the above formula (20) are particularly preferred in that they both the photosensitive characteristic heat resistance.

｛式中、Ｒ６はフッ素原子、Ｃ_１〜Ｃ_１０の炭化水素基、及びＣ_１〜Ｃ_１０の含フッ素炭化水素基から成る群から選ばれる１価の基であり、ｍは０〜３から選ばれる整数である。｝で表される構造は、低温加熱時のイミド化率、脱ガス性、銅密着性、耐薬品性の観点から好ましい。 The group X _1, among other structure represented by the above formula (20), the following equation:

{Wherein, R6 is a monovalent radical fluorine _atom, selected from the group consisting of a fluorine-containing hydrocarbon group of a hydrocarbon group and a _C 1 _{-C 10,} of C 1 _{-C 10,} m is from 0 to 3 The integer chosen. } Is preferable from the viewpoint of imidization rate at low temperature heating, degassing property, copper adhesion, and chemical resistance.

｛式中、Ｒ６は水素原子、フッ素原子、Ｃ_１〜Ｃ_１０の炭化水素基、及びＣ_１〜Ｃ_１０の含フッ素炭化水素基から成る群から選ばれる１価の基であり、そしてｎは０〜４から選ばれる整数である。｝で表される構造が挙げられるが、これらに限定されるものではない。また、Ｙ_１の構造は１種でも２種以上の組み合わせでもよい。上記式（２１）で表される構造を有するＹ_１基は、耐熱性及び感光特性を両立するという点で特に好ましい。 In the general formula (3), the divalent organic group represented by Y ₁ in that they both heat resistance and sensitivity characteristics, is preferably an aromatic group having 6 to 40 carbon atoms, for example, The following formula (21):

{Wherein, R6 is a hydrogen atom, a fluorine _atom, a monovalent group selected from the group consisting of a fluorine-containing hydrocarbon group of a hydrocarbon group and a _C 1 _{-C 10,} of C 1 _{-C 10,} and n It is an integer selected from 0 to 4. }, But the structure is not limited to these. Further, _{the structure of Y 1} may be one kind or a combination of two or more kinds. _One Y group having a structure represented by the above formula (21) is particularly preferable in that it has both heat resistance and photosensitive characteristics.

｛式中、Ｒ６はフッ素原子、Ｃ_１〜Ｃ_１０の炭化水素基、及びＣ_１〜Ｃ_１０の含フッ素炭化水素基から成る群から選ばれる１価の基であり、そしてｎは０〜４から選ばれる整数である。｝で表される構造は、低温加熱時のイミド化率、脱ガス性、銅密着性、耐薬品性の観点から好ましい。 The Y ₁ group, among other structure represented by the above formula (21), the following equation:

{Wherein, R6 is a fluorine _atom, a monovalent group selected from the group consisting of a fluorine-containing hydrocarbon group of a hydrocarbon group and a _C 1 _{-C 10,} of C 1 _{-C 10,} and n is 0-4 It is an integer selected from. } Is preferable from the viewpoint of imidization rate at low temperature heating, degassing property, copper adhesion, and chemical resistance.

_{L 1} in the general formula (4) is preferably a hydrogen atom or a methyl group, and L ₂ and L ₃ are preferably hydrogen atoms from the viewpoint of photosensitive characteristics. Further, m ₁ is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less from the viewpoint of photosensitive characteristics.

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記に定義したものである。｝
で表される構造単位を有するポリイミド前駆体であることが好ましい。 In one embodiment, the (A) polyimide precursor is based on the following general formula (5):

{In the equation, R ₁ , R ₂ , and n ₁ are defined above. }
It is preferably a polyimide precursor having a structural unit represented by.

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記に定義したものである。｝
で表される構造単位を有するポリイミド前駆体であることが好ましい。 In the general formula (5), _{at least one of R 1} and R ₂ is more preferably a monovalent organic group represented by the general formula (4). When the polyimide precursor (A) contains the polyimide precursor represented by the general formula (5), the chemical resistance is particularly high.

{In the equation, R ₁ , R ₂ , and n ₁ are defined above. }
It is preferably a polyimide precursor having a structural unit represented by.

In the general formula (6), _{at least one of R 1} and R ₂ is more preferably a monovalent organic group represented by the general formula (4). The polyimide precursor (A) tends to have particularly high resolution by containing both the structural unit represented by the general formula (5) and the structural unit represented by the general formula (6). For example, the (A) polyimide precursor may contain a copolymer of a structural unit represented by the general formula (5) and a structural unit represented by the general formula (6), or may contain a copolymer of the general formula (5). ) May be a mixture of the polyimide precursor represented by the general formula (6) and the polyimide precursor represented by the general formula (6).

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記に定義したものである。｝
で表される構造単位を有するポリイミド前駆体であることが好ましい。 In one embodiment, the (A) polyimide precursor is represented by the following general formula (7):

{In the equation, R ₁ , R ₂ , and n ₁ are defined above. }
It is preferably a polyimide precursor having a structural unit represented by.

In the general formula (7), _{at least one of R 1} and R ₂ is more preferably a monovalent organic group represented by the general formula (4). The polyimide precursor (A) tends to have higher resolution in particular by containing both the structural unit represented by the general formula (5) and the structural unit represented by the general formula (7). .. For example, the (A) polyimide precursor may contain a copolymer of a structural unit represented by the general formula (5) and a structural unit represented by the general formula (7), or may contain a copolymer of the general formula (5). ) May be a mixture of the polyimide precursor represented by the general formula (7) and the polyimide precursor represented by the general formula (7).

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記に定義したものである。｝
で表される構造単位を有するポリイミド前駆体であることが好ましい。 In one embodiment, the (A) polyimide precursor is represented by the following general formula (9):

{In the equation, R ₁ , R ₂ , and n ₁ are defined above. }
It is preferably a polyimide precursor having a structural unit represented by.

In the general formula (9), _{it is more preferable that at least one of R 1} and R ₂ is a monovalent organic group represented by the general formula (4).

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は上記に定義したものである。｝
で表される構造単位を有するポリイミド前駆体であることが好ましい。一般式（１０）において、Ｒ_１及びＲ_２の少なくとも一方は、上記一般式（４）で表される１価の有機基であることがより好ましい。（Ａ）ポリイミド前駆体が、一般式（１０）で表される構造単位を有するポリイミド前駆体を含むことで、解像性、イミド化率、耐薬品性が良好となり、特に面内均一性が良好となる。 In one embodiment, the (A) polyimide precursor is represented by the following general formula (10):

{In the equation, R ₁ , R ₂ , and n ₁ are defined above. }
It is preferably a polyimide precursor having a structural unit represented by. In the general formula (10), _{it is more preferable that at least one of R 1} and R ₂ is a monovalent organic group represented by the general formula (4). When the polyimide precursor (A) contains a polyimide precursor having a structural unit represented by the general formula (10), the resolution, imidization ratio, and chemical resistance are improved, and in particular, in-plane uniformity is improved. It will be good.

(A) Method for preparing polyimide precursor (A) The polyimide precursor is first prepared from the above-mentioned _{tetracarboxylic acid dianhydride containing a tetravalent organic group X 1} and alcohols having a photopolymerizable unsaturated double bond. , And optionally an alcohol that does not have an unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester). Thereafter, a tetracarboxylic acid partially esterified, can be obtained by engagement amide polycondensation and diamines containing organic group Y ₁ of the divalent above.

(Preparation of acid / ester)
_{In the present embodiment, the tetracarboxylic acid dianhydride containing the tetravalent organic group X 1} preferably used for preparing the (A) polyimide precursor is the tetracarboxylic represented by the above general formula (20). Including acid dianhydride, for example, pyromellitic anhydride, diphenyl ether-3,3', 4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic acid dianhydride. Biphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride, diphenylsulfone-3,3', 4,4'-tetracarboxylic acid dianhydride, diphenylmethane-3,3', 4, 4'-Tetracarboxylic hydride, 2,2-bis (3,4-phthalic anhydride) propane, 2,2-bis (3,4-phthalic anhydride) -1,1,1,3,3 , 3-Hexafluoropropane and the like, preferably pyromellitic anhydride, diphenyl ether-3,3', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic acid. Dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic dianhydride can be mentioned, but is not limited thereto. In addition, these can be used alone or in combination of two or more.

Examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used for preparing the (A) polyimide precursor in the present embodiment include 2-acryloyloxyethyl alcohol and 1-acryloyloxy. -3-propyl alcohol, 2-acrylamide ethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxy Propyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3- Propyl alcohol, 2-methacrylamide ethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate , 2-Hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and the like.

The alcohols having a photopolymerizable unsaturated double bond include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol. , Neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl Alcohols having no unsaturated double bond such as ether, tetraethylene glycol monoethyl ether, and benzyl alcohol can also be partially mixed and used.

As the polyimide precursor, a non-photosensitive polyimide precursor prepared only with alcohols having no unsaturated double bond may be mixed with the photosensitive polyimide precursor and used. From the viewpoint of resolution, the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

The esterification reaction of the acid anhydride proceeds by dissolving and mixing the above-mentioned suitable tetracarboxylic acid dianhydride and the above-mentioned alcohols in a solvent as described later in the presence of a basic catalyst such as pyridine. The desired acid / ester compound can be obtained. Examples of the reaction conditions include stirring at a temperature of 20 to 50 ° C. for 4 to 24 hours.

(Preparation of polyimide precursor)
The acid / ester compound (typically, a solution in a solvent described later) is mixed with an appropriate dehydration condensate agent under ice-cooling to obtain an acid / ester compound as a polyacid anhydride. The desired polyimide precursor can be obtained by dropping and adding a diamine containing a divalent organic group Y1 preferably used in the embodiment separately dissolved or dispersed in a solvent and subjecting it to amide polycondensation. Examples of the dehydration condensing agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'. -Discusin imidyl carbonate and the like can be mentioned. Alternatively, the acid / ester compound is acid-chloride-ized with thionyl chloride or the like, and then reacted with a diamine compound in the presence of a base such as pyridine to obtain a desired polyimide precursor. be able to.

The diamines containing divalent organic group Y ₁ used suitably in the present embodiment, including the diamine having a structure represented by the general formula (21), 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'-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 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-amino) biphenyl Phenoxy) 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-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, ortho-trizine sulfone, 9,9-bis (4-Aminophenyl) Fluorene and some of the hydrogen atoms on these benzene rings are substituted with methyl group, ethyl group, hydroxymethyl group, hydroxyethyl group, halogen, etc., for example, 3,3'-. Dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4 , 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethitoxy-4,4'-diamino Examples thereof include, but are not limited to, biphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.

After completion of the amide polycondensation reaction, the water-absorbing by-products of the dehydration condensate coexisting in the reaction solution are filtered out as necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added. It can be added to the obtained polymer component to precipitate the polymer component. Further, by repeating the redissolving and reprecipitation operations, the polymer can be purified, vacuum dried, and the desired polyimide precursor can be isolated. In order to improve the degree of purification, a solution of this polymer may be passed through a column filled with anions and / or cation exchange resins swollen with an appropriate organic solvent to remove ionic impurities.

The molecular weight of the polyimide precursor (A) is preferably 8,000 to 150,000, preferably 9,000 to 50,000, as measured by the polystyrene-equivalent weight average molecular weight by gel permeation chromatography. Is more preferable. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developing solution is good, and the resolution performance of the relief pattern is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The weight average molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from Showa Denko's organic solvent-based standard sample STANDARD SM-105.

(B) Photosensitizer The (B) photosensitizer used in the present embodiment will be described. The photosensitizer is preferably a photoradical polymerization initiator, which is a benzophenone derivative such as benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, or fluorenone, 2,2'. -Acetophenone derivatives such as diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethyl Ketal, benzyl derivatives such as benzyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl-1,2-butandion-2- (o-methoxycarbonyl) oxime, 1-phenyl-1, 2-Propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- ( Oximes such as o-benzoyl) oxime, 1,3-diphenylpropanthrion-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropantrion-2- (o-benzoyl) oxime, N-phenyl Generation of photoacids such as N-arylglycines such as glycine, peroxides such as benzoylparkloride, aromatic biimidazoles, titanocenes, α- (n-octanesulfonyloxyimino) -4-methoxybenzyl cyanide, etc. Agents and the like are preferably mentioned, but are not limited thereto. Among the above-mentioned photopolymerization initiators, oximes are more preferable in terms of photosensitivity.

The blending amount of the (B) photosensitive agent is preferably 0.1 part by mass or more and 20 parts by mass, and more preferably 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor. .. The blending amount of the (B) photosensitive agent is 0.1 part by mass or more from the viewpoint of light sensitivity or patterning property, and 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition. Is preferable.

｛式（１１）中、Ｒ_７、Ｒ_８はそれぞれ独立にヘテロ原子を含んでも良い、炭素数１〜２０の１価の有機基であり、Ｒ_９，Ｒ_１０はそれぞれ独立に、水素原子、またはヘテロ原子を含んでも良い、炭素数１〜２０の１価の有機基である。｝

｛式（１２）中、Ｒ_１１、Ｒ_１２は、それぞれ独立に、ヘテロ原子を含んでも良い、炭素数１〜２０の１価の有機基であり、Ｒ_１３はヘテロ原子を含んでも良い、炭素数１〜２０の２価の有機基である。｝ (C) Urea compound The (C) urea compound used in the present embodiment is not limited to any other structure as long as it has a urea bond in its molecular structure. The urea compound (C) is represented by the following general formula (11) or (12) from the viewpoint of chemical resistance and from the viewpoint of easily adjusting the post-contact peak intensity / pre-contact peak intensity within the range of the present embodiment. It is preferable that the urea compound has a structure to be used.

{In formula (11), R ₇ and R ₈ are monovalent organic groups having 1 to 20 carbon atoms, which may independently contain heteroatoms, and R ₉ and R ₁₀ are independent hydrogen atoms, respectively. Alternatively, it is a monovalent organic group having 1 to 20 carbon atoms, which may contain a hetero atom. }

{In formula (12), R ₁₁ and R ₁₂ are monovalent organic groups having 1 to 20 carbon atoms, which may independently contain a heteroatom, and R ₁₃ may contain a heteroatom, carbon. It is a divalent organic group of numbers 1 to 20. }

Examples of the hetero atom according to the present embodiment include an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom.

In the formula (11), R ₇ and R ₈ are not limited as long as they are monovalent organic groups having 1 to 20 carbon atoms, which may contain heteroatoms, but more preferably contain oxygen atoms from the viewpoint of developability. .. The number of carbon atoms is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, the number of carbon atoms is preferably 1 to 10, and more preferably 3 to 10. _{R 9} and R ₁₀ in the formula (11) may be bonded to each other to have a cyclic structure, but from the viewpoint of chemical resistance, it is preferable not to have a cyclic structure. When R ₉ and R ₁₀ are bonded to each other to have a cyclic structure, the degree of freedom of the bond angle of the urea group is lost, and it becomes difficult to form a strong hydrogen bond.

In the formula (11), R ₉ and R ₁₀ are not limited as long as they are monovalent organic groups having 1 to 20 carbon atoms, which may contain a hydrogen atom or a hetero atom, but from the viewpoint of developability, a hydrogen atom or a hydrogen atom or It is more preferable to contain an oxygen atom. The number of carbon atoms is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, the number of carbon atoms is preferably 1 to 10, and more preferably 3 to 10.

In the formula (12), R ₁₁ and R ₁₂ are not limited as long as they are monovalent organic groups having 1 to 20 carbon atoms, which may contain heteroatoms, but more preferably contain oxygen atoms from the viewpoint of developability. .. The number of carbon atoms is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, the number of carbon atoms is preferably 1 to 10, and more preferably 3 to 10. _{R 11} and R ₁₂ in the formula (12) may be bonded to each other to have a cyclic structure, but from the viewpoint of chemical resistance, it is preferable not to have a cyclic structure. When R ₁₁ and R ₁₂ are bonded to each other to have a cyclic structure, the degree of freedom of the bond angle of the urea group is lost, and it becomes difficult to form a strong hydrogen bond.

In the present embodiment, the (C) urea compound preferably further has at least one functional group selected from the group consisting of a (meth) acrylic group, a hydroxyl group, and an amino group.

In the present embodiment, the molecular weight of the urea compound (C) is preferably 150 g / mol or more, and more preferably 250 g / mol or more. When the molecular weight of the urea compound is 250 g / mol or more, the urea compound is less likely to volatilize in the heat curing process, and the effect of promoting imidization becomes higher.

(C) The number of urea groups in the molecule of the urea compound is preferably 1 or 2. When the number of urea groups in the molecule is less than 3, the interaction between the urea compounds is small, the solubility is improved, and the filterability of the resin composition is improved.

The molecular weight (MW / number of urea groups) per urea group of the (C) urea compound is preferably 150 g / mol or more, and more preferably 200 g / mol or more. When the molecular weight per urea group is 200 g / mol or more, the interaction between the urea compounds is small, the solubility is improved, and the filterability of the resin composition is improved.

By containing the (C) urea compound in the present embodiment, it is easy to adjust the peak intensity before and after contact of the standard TMAH solution to the range of the present embodiment, and as a result, the wettability after the alkaline solution treatment tends to be improved. be. The reason is not clear, but the present inventors consider it as follows. First, in one embodiment, the photosensitive resin composition containing the polyimide precursor tends to have insufficient conversion of the polyimide precursor to polyimide when it is heat-cyclized at a low temperature of, for example, 170 ° C. On the other hand, in the photosensitive resin composition of the present embodiment, by containing the (C) urea compound, a part of the (C) urea compound is thermally decomposed to generate amines and the like, and the amines and the like are polyimide. It is believed to facilitate the conversion of precursors to polyimide. Then, in a preferred embodiment, the (C) urea compound further has a (meth) acrylic group, and particularly when the photosensitive resin composition is a negative type, the compound (B) is used as an initiator by light irradiation (C). ) The (meth) acrylic group of urea reacts with the side chain portion of the (A) polyimide precursor to crosslink. As a result, it is considered that the (C) urea compound is more likely to be present in the vicinity of the (A) polyimide precursor, and the conversion efficiency can be dramatically improved. As a result, the dissolution rate of the cured film when it comes into contact with the alkaline solution is suppressed, and the cured film can sufficiently remain even after the contact with the alkaline solution. Subsequently, the urea compound (C) is considered to have a strong hydrogen bond to a functional group such as an imide group. As a result, even when some of the imide groups are opened by the alkaline solution, it is considered that the membrane remains without being dissolved in the alkaline solution due to hydrogen bonds. As a result, it is considered that the imide ring is opened on the film surface to expose the highly hydrophilic functional groups, and the wettability is improved.

In the present embodiment, when the (C) urea compound further has a (meth) acrylic group, the (meth) acrylic equivalent of the (C) urea compound is preferably 150 to 400 g / mol. When the (meth) acrylic equivalent of the urea compound (C) is 150 g / mol or more, the chemical resistance of the negative photosensitive resin composition tends to be good, and when it is 400 g / mol or less, it is developed. The sex tends to be good. The lower limit of the (meth) acrylic equivalent of the urea compound (C) is more preferably 200 g / mol or more, 210 g / mol or more, 220 g / mol or more, 230 g / mol or more, still more preferably 240 g / mol or more, 250 g / mol or more. As described above, the lower limit is more preferably 350 g / mol or less, 330 g / mol or less, and further preferably 300 g / mol or less. The (meth) acrylic equivalent of the urea compound (C) is even more preferably 210-400 g / mol, particularly preferably 220-400 g / mol.

The method for producing the urea compound (C) is not particularly limited, but can be obtained, for example, by reacting an isocyanate compound with an amine-containing compound. When the amine-containing compound contains a functional group such as a hydroxyl group that can react with isocyanate, a part of the isocyanate compound may contain a compound that has reacted with a functional group such as a hydroxyl group.

As the urea compound (C) in the present embodiment, one type may be used alone, or two or more types may be used in combination.

The blending amount of the urea compound (C) is preferably 1 part by mass or more and 50 parts by mass or less, and more preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor. The blending amount of the urea compound is 1 part by mass or more from the viewpoint of chemical resistance, and 50 parts by mass or less from the viewpoint of film physical characteristics and photopatterning.

The photosensitive resin composition of the present embodiment may further contain components other than the above-mentioned components (A), (B) and (C). The components other than the components (A), (B) and (C) are not limited, but are not limited, but are a thermobase generator, a solvent, a nitrogen-containing heterocyclic compound, a hindered phenol compound, an organic titanium compound, an adhesion aid, and a sensitizer. Examples thereof include agents, photopolymerizable unsaturated monomers, and thermal polymerization inhibitors.

Thermal base generator The photosensitive resin composition of the present embodiment may contain a base generator. A base generator is a compound that generates a base when heated. By containing the thermal base generator, the imidization of the photosensitive resin composition can be further promoted.

The type of the thermobase generator is not particularly specified, and examples thereof include an amine compound protected by a tert-butoxycarbonyl group, a thermobase generator disclosed in International Publication No. 2017/0385898, and the like. .. However, the present invention is not limited to these, and other known thermobase generators can be used.

Amine compounds protected by the tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2 -Amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-amino Cyclohexaneethanol, 4- (2-aminoethyl) cyclohexanol, N-methylethanolamine, 3- (methylamino) -1-propanol, 3- (isopropylamino) propanol, N-cyclohexylethanolamine, α- [2- (Methylamino) ethyl] benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidin methanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidin, 4- (3-hydroxyphenyl) ) Piperidine, 4-piperidin methanol, 3-piperidin methanol, 2-piperidin methanol, 4-piperidin ethanol, 2-piperidin ethanol, 2- (4-piperidyl) -2-propanol, 1,4-butanolbis (3-amino) Propyl) ether, 1,2-bis (2-aminoethoxy) ethane, 2,2'-oxybis (ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15 -Crown 5-ether, diethylene glycol bis (3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, or amino groups of amino acids and derivatives thereof were protected by tert-butoxycarbonyl groups. Examples include, but are not limited to, compounds.

The blending amount of the thermobase generator is preferably 0.1 part by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor. .. The blending amount is preferably 0.1 part by mass or more from the viewpoint of the imidization promoting effect, and is preferably 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition.

Solvents Solvents include amides, dichloromethanes, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols and the like, and examples thereof include N-methyl-2. -Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, acetone, methylethylketone, methylisobutylketone, cyclopentanone, cyclohexanone, methylacetate, ethyl acetate, butylacetate, diethyl oxalate , Ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-Dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mecitylene and the like can be used. Among them, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene from the viewpoint of resin solubility, stability of resin composition, and adhesion to substrate. Glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

Among such solvents, those that completely dissolve the produced polymer are preferable, and for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethyl Examples include urea and gamma-butyrolactone. The solvent may be one kind, or two or more kinds of solvents may be mixed and used.

In the photosensitive resin composition of the present embodiment, the amount of the solvent used is preferably 100 to 1000 parts by mass, and more preferably 120 to 700 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. More preferably, it is in the range of 125 to 500 parts by mass.

Nitrogen-containing heterocyclic compound When a cured film is formed on a substrate made of copper or a copper alloy using the photosensitive resin composition of the present embodiment, the photosensitive resin composition is used to suppress discoloration on copper. May optionally contain a nitrogen-containing heterocyclic compound. Examples of the nitrogen-containing heterocyclic compound include an azole compound and a purine derivative.

Examples of azole compounds 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, hydroxyphenyl Triazole, 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, hydroxyphenyl Benzotriazole, triltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl- Examples thereof include 1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like.

Particularly preferred include triltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. Further, these azole compounds may be used alone or in a mixture of two or more kinds.

Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthin, xanthin, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-Methyladenine, N-methyladenine, N, N-dimethyladenine, 2-fluoroadenine, 9- (2-hydroxyethyl) adenine, guanine oxime, N- (2-hydroxyethyl) adenine, 8-aminoadenine, 6-Amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7- (2-hydroxyethyl) guanine, N- (3-chlorophenyl) Examples thereof include guanine, N- (3-ethylphenyl) guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthin, 8-azahipoxanthin and derivatives thereof.

When the photosensitive resin composition contains the azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and the light sensitivity characteristics are From the viewpoint, 0.5 to 5 parts by mass is more preferable. When the blending amount of the azole compound (A) with respect to 100 parts by mass of the polyimide precursor is 0.1 parts by mass or more, when the photosensitive resin composition of the present embodiment is formed on copper or a copper alloy, copper or Discoloration of the copper alloy surface is suppressed, while the light sensitivity is excellent when the amount is 20 parts by mass or less.

Further, in order to suppress discoloration on the copper surface, the photosensitive resin composition may optionally contain a hindered phenol compound. 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), triethylene glycol-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-hydrosin) Namamide), 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-dimethyl] Butyl] -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-dimethylbenzyl)- 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-3-3) 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- Examples include, but are not limited to, 3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione. 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 and the like are particularly preferable.

The blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and is 0.5 to 10 parts by mass from the viewpoint of light sensitivity characteristics. Is more preferable. When the blending amount of the hindered phenol compound with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, for example, when the photosensitive resin composition of the present embodiment is formed on copper or a copper alloy. , Discoloration and corrosion of copper or copper alloy are prevented, while the light sensitivity is excellent when the amount is 20 parts by mass or less.

Organic Titanium Compound The photosensitive resin composition of the present embodiment may contain an organic titanium compound. By containing the organic titanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

Examples of the organic titanium compound that can be used include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.

Specific examples of the organic titanium compound are shown in I) to VII) below:
I) Titanium chelate compound: Among them, a titanium chelate having two or more alkoxy groups is more preferable because storage stability and a good pattern of the photosensitive resin composition can be obtained. Specific examples are titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanionate, titanium diisopropoxyside bis (2,4-pentanionate)). , Titanium diisopropoxyside bis (tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
II) Titanium Alkoxy Titanium Compounds: For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide. , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis {2,2- (Aryloxymethyl) Butokiside}] etc.
III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compound: For example, titanium tris (dioctyl phosphate) isopropoxyside, titanium tris (dodecylbenzene sulfonate) isopropoxide, and the like.
V) Titanium oxide compound: For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetone compound: For example, titanium tetraacetylacetone.
VII) Titanate Coupling Agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.

Among them, the organic titanium compound is at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanosen compound, which exhibits better chemical resistance. It is preferable from the viewpoint. In particular, titanium diisopropoxyside bis (ethylacetacetate), titanium tetra (n-butoxide), and bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H)). -Pyrrole-1-yl) phenyl) titanium is preferred.

When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 10 parts by mass or less, storage stability is excellent.

Adhesive Aid The photosensitive resin composition may optionally contain an adhesive aid in order to improve the adhesiveness between the film and the substrate formed by using the photosensitive resin composition of the present embodiment. Adhesive aids 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-1, 4-Bis (N- [3-triethoxysilyl] propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propylsuccinic hydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyl Silane coupling agents such as trimethoxysilane, 3-ureidopropyltriethoxysilane, 3- (trialkoxysilyl) propylsuccinic acid anhydride, and aluminum tris (ethylacetacetate), aluminumtris (acetylacetonate), ethyl. Examples thereof include aluminum-based adhesive aids such as acetoacetate aluminum diisopropylate.

Among these adhesive aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. When the photosensitive resin composition contains an adhesion aid, the blending amount of the adhesion aid is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

As the silane coupling agent, 3-mercaptopropyltrimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd .: trade name KBM803, manufactured by Chisso Co., Ltd .: trade name Sila Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Asmax Co., Ltd .: Product name SIM6475.0), 3-Mercaptopropylmethyldimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd .: product name LS1375, manufactured by Asmax Co., Ltd .: product name SIM6474.0), Mercaptomethyltrimethoxysilane (manufactured by Asmax Co., Ltd .: product) Name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by ASMAX Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3 -Mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane , 2-Mercaptoethylethoxydimethoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethylethoxydipropoxysilane, 2-Mercaptoethyldimethoxypropoxysilane, 2-Mercaptoethylmethoxydipropoxysilane , 4-Mercaptobutyltrimethoxysilane, 4-Mercaptobutyltriethoxysilane, 4-Mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Industry Co., Ltd .: trade name LS3610, ASMAX stock) Company: Product name SIU9055.0), N- (3-trimethoxysilylpropyl) urea (Azmax Co., Ltd .: Product name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- ( 3-ethoxydimethoxysilylpropyl) urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N-( 3-Dimethoxypropoxysilylpropyl) urea, N -(3-methoxydipropoxysilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-Tripropoxysilylethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3-Trimethoxysilylbutyl) urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (Azmax Co., Ltd.) Manufactured by: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0599.1) aminophenyl Trimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0599.2), 2- (trimethoxysilylethyl) pyridine (manufactured by Azmax Co., Ltd .: trade name SIT8396.0), 2- (triethoxysilylethyl) pyridine, 2- (Dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, (3-triethoxysilylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetra Ethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis (methoxyethoxysilane), tetrakis (methoxy-n) -Propoxysilane), tetrakis (ethoxyethoxysilane), tetrakis (methoxyethoxyethoxysilane), bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) Ethan, bis (triethoxysilyl) ethylene, bis (triethoxysilyl) octane, bis (triethoxysilyl) octadiene, bis [3- (triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl] Tetrasulfide, di-t-butoxydiase Toxisilane, di-i-butoxyaluminoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilane Diol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenyl Silanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyl Examples thereof include, but are not limited to, diphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol. These may be used alone or in combination of two or more.

で表される構造を有するシランカップリング剤が好ましい。 Among the above-mentioned silane coupling agents, the silane coupling agent includes phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, and diethoxy from the viewpoint of storage stability. Diphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the following formula:

A silane coupling agent having a structure represented by is preferable.

When a silane coupling agent is used, the blending amount is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

Sensitizer The photosensitive resin composition of the present embodiment may optionally contain a sensitizer in order to improve the photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal). ) Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinna Millidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) Isonaftthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-Acetone-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, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2- Mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylamino) Examples thereof include styryl) naphtho (1,2-d) thiazole and 2- (p-dimethylaminobenzoyl) styrene. These can be used alone or, for example, in a combination of 2 to 5 types.

When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the blending amount is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

Photopolymerizable unsaturated monomer The photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond in order to improve the resolution of the relief pattern. As such a monomer, a (meth) acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and is not particularly limited to the following, but ethylene glycol or polyethylene such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Glycol mono or diacrylate and methacrylate, propylene glycol or polypropylene glycol mono or diacrylate and methacrylate, glycerol mono, di or triacrylate and methacrylate, cyclohexane diacrylate and dimethacrylate, diacrylate and 1,4-butanediol diacrylate and Dimethacrylate, diacrylate and dimethacrylate of 1,6-hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono or diacrylate and methacrylate of bisphenol A, benzenetrimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its Derivatives, methacrylicamides and derivatives thereof, trimethylolpropane triacrylates and methacrylates, di or triacrylates and methacrylates of glycerol, di, tri, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds, etc. Compounds can be mentioned.

When the photosensitive resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond for improving the resolution of the relief pattern, the blending amount of the monomer having a photopolymerizable unsaturated bond is ( A) It is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polyimide precursor.

Thermal polymerization inhibitor The photosensitive resin composition of the present embodiment is thermally polymerized in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition when stored in a solution containing a solvent. A banning agent may be optionally contained. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic 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.

<Manufacturing method of cured relief pattern and semiconductor device>
The method for producing the cured relief pattern of the present embodiment includes (1) a step of applying the photosensitive resin composition of the present embodiment described above onto a substrate to form a resin layer on the substrate, and (2) the step. 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, and (4) a step of heat-treating the relief pattern to obtain a cured relief pattern. It includes a step of forming, (5) a step of contacting the cured relief pattern with an alkaline solution, and (6) a step of heat-treating the cured relief pattern in contact with the alkaline solution.

(1) Resin layer forming step In this step, the photosensitive resin composition of the present embodiment is applied onto a base material, and if necessary, dried thereafter to form a resin layer. As a coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or the like, or spray coating with a spray coater. A method or the like can be used.

(2) Exposure step In this step, the resin layer formed above is exposed to an exposure device such as a contact aligner, a mirror projection, a stepper, etc., through a photomask or reticle having a pattern, or directly by an ultraviolet light source or the like. To expose.

(3) Relief pattern forming step In this step, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any of the conventionally known photoresist developing methods, for example, a rotary spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, and the like. The method can be selected and used. Further, after development, post-development baking may be performed at an arbitrary combination of temperature and time, if necessary, for the purpose of adjusting the shape of the relief pattern.

As the developing solution used for development, for example, a good solvent for the photosensitive resin composition or a combination of the good solvent and a poor solvent is preferable. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like are preferable. .. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the photosensitive resin composition. Further, two or more kinds of each solvent, for example, several kinds can be used in combination.

(4) Relief pattern heat treatment step In this step, the relief pattern obtained by the above development is heat-treated to dilute the photosensitive component, and (A) the polyimide precursor is imidized to cure the polyimide. Convert to relief pattern. As a method of heat treatment, various methods can be selected, for example, a method using a hot plate, a method using an oven, a method using a temperature-increasing oven in which a temperature program can be set, and the like. The heat treatment can be performed, for example, at 160 ° C. to 350 ° C. for 30 minutes to 5 hours. The temperature of the heat treatment is preferably 160 ° C. to 200 ° C., more preferably 160 ° C. to 180 ° C., and even more preferably 160 ° C. to 170 ° C. Air may be used as the atmospheric gas at the time of heat curing, or an inert gas such as nitrogen or argon may be used.

(5) Alkaline solution contact step of the cured relief pattern In this step, the in-plane uniformity of the cured relief pattern made of polyimide is improved by contacting the cured relief pattern obtained by the above heat treatment step with the alkaline solution. Can be made to. The alkaline source of the alkaline solution is not limited as long as it can improve the in-plane uniformity, and examples thereof include tetramethylammonium hydroxide pentahydrate (TMAH). Examples of the solvent for the alkaline solution include dimethyl sulfoxide (DMSO). Typically, a DMSO solution of TMAH, more specifically 2.38% by weight of TMAH DMSO solvent, can be used. The alkaline solution may contain an amine such as monoethanolamine or a solvent as other components. As the alkaline solution, a stripping solution used for stripping photoresists and dry film resists may be used. Contact with the alkaline solution can be carried out, for example, at room temperature to 100 ° C. for 5 to 120 minutes. The solution may be agitated upon contact with the alkaline solution. The cured film after contact with the alkaline solution may be washed with an organic solvent or water and then dried. The drying temperature is preferably 100 ° C. or lower. Air may be used as the atmospheric gas at the time of drying, or an inert gas such as nitrogen or argon may be used.

The alkaline solution contact step may be performed immediately after the cured relief pattern is formed, or may be performed in a state where Ti / Cu sputtering treatment is performed after the cured relief pattern is formed to form a photoresist pattern, and Cu wiring is formed by plating treatment. good. In this case, the alkaline solution can act on the cured relief pattern by peeling off the photoresist and further permeating through the edges of the wafer and the pinholes of the sputtering. That is, the contact step with the alkaline solution may be a photoresist stripping step.

(6) Reheating treatment of the cured relief pattern after contact with the alkaline solution In this step, the cured relief pattern after contact with the alkaline solution is reheated. This step may be performed immediately after the alkaline solution contacting step, or may be performed after forming an upper relief pattern on the cured relief pattern after the alkaline solution contacting step. That is, the reheat treatment step of the cured relief pattern after the contact with the alkaline solution may be performed at the same time as the heat treatment of the relief pattern of the upper layer after forming the interlayer insulating film of two or more layers. As a method of heat treatment, various methods can be selected, for example, a method using a hot plate, a method using an oven, a method using a temperature-increasing oven in which a temperature program can be set, and the like. The heat treatment can be performed, for example, at 160 ° C. to 350 ° C. for 30 minutes to 5 hours. The temperature of the heat treatment is preferably 160 ° C. to 200 ° C., more preferably 160 ° C. to 180 ° C., and even more preferably 160 ° C. to 170 ° C. Air may be used as the atmospheric gas at the time of heat curing, or an inert gas such as nitrogen or argon may be used.

In the method for producing a cured relief pattern of the present embodiment, when the cured relief pattern obtained in the above step (4) and the cured relief pattern obtained in the above step (6) are standardized with an IR peak intensity of ^{1500 cm -1.} IR peak intensity in the vicinity of 1778cm ^-1 is preferably higher than IR peak intensity around 1778cm ^-1 of the cured relief pattern obtained in the above step (5). ^{By temporarily lowering the IR peak intensity in the vicinity of 1778 cm -1 of the} cured relief pattern in the above step (5), wettability is imparted to the cured film, and a cured relief pattern having high in-plane uniformity can be obtained.

<Cured film>
The cured film of the present embodiment has an IR peak of ^{1500 cm -1} when contacted with a DMSO solution of TMAH having a temperature of 50 ° C. and 2.38% by mass (hereinafter, also simply referred to as "standard TMAH solution") for 10 minutes. ^{The IR peak intensity near 1778 cm -1} when standardized by intensity is within the range of the following formula (1) before and after contact.
0.1 ≤ (Peak intensity after contact / Peak intensity before contact) ≤ 0.8 ... (1)

When the IR peak intensity of the cured film is in the above range, the hydrophilicity of the cured film is increased, and the cured film has a wettability suitable for further coating the photosensitive resin composition on the cured film. The value of the peak intensity after contact / peak intensity before contact is preferably 0.1 or more, more preferably 0.3 or more, and further preferably 0.5 or more from the viewpoint of chemical resistance. A cured film having a value of peak intensity after contact / peak intensity before contact of less than 0.1 has poor chemical resistance. The value of the peak intensity after contact / peak intensity before contact is preferably 0.8 or less, more preferably 0.7 or less, still more preferably 0.6 or less, from the viewpoint of wettability.

The amount of change in film thickness before and after contact is preferably 1 nm or more and 1000 nm or less. If the solubility in an alkaline solution is high, pattern deterioration (cracks, pattern shape collapse) will occur. Therefore, the amount of change in the film thickness of the cured film when contacted with a standard TMAH solution is 600 nm or less. It is more preferably present, and more preferably 300 nm or less. The amount of change in the film thickness of the cured film is measured by adjusting the film thickness of the cured film before contact to about 3 μm.

The cured film before being contacted with the standard TMAH solution preferably has an imidization ratio of 70% or more and 100% or less from the viewpoint of degassing property and curing shrinkage in the step of forming the multilayer body. When the imidization rate is less than 70%, degassing property and curing shrinkage become problems in the process after contact with the chemical solution. The imidization ratio is more preferably 80% or more, and further preferably 90% or more.

<Semiconductor device>
In the present embodiment, a semiconductor device having a cured relief pattern obtained by the above-mentioned method for producing a cured relief pattern is also provided. The semiconductor device in the present embodiment has a base material which is a semiconductor element and a cured relief pattern of polyimide formed on the base material by the method for producing a cured relief pattern described above. Further, there is also provided a method for manufacturing a semiconductor device, which uses a semiconductor element as a base material and includes the above-described method for manufacturing a cured relief pattern of the present embodiment as a part of a process. More specifically, in the semiconductor device of the present embodiment, the cured relief pattern formed by the method for producing the cured relief pattern of the present embodiment is protected by a surface protective film, an interlayer insulating film, an insulating film for rewiring, and a flip chip device. It can be manufactured by forming it as a film, a protective film of a semiconductor device having a bump structure, or the like, and combining it with a known manufacturing method of a semiconductor device.

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

The photosensitive resin composition of the present embodiment is preferably a photosensitive resin composition for forming an insulating member or an interlayer insulating film. In addition to the application to semiconductor devices as described above, the photosensitive resin composition of the present embodiment has an interlayer insulating film for a multilayer circuit having two or more layers, a cover coat for a flexible copper-clad plate, a solder resist film, and a liquid crystal alignment film. It is also useful for applications such as.

Hereinafter, the present embodiment will be specifically described with reference to Examples, but the present embodiment is not limited thereto. In Examples, Comparative Examples, and Production Examples, the physical characteristics of the polyimide precursor or the photosensitive resin composition were measured and evaluated according to the following methods.

<Measurement and evaluation method>
(1) Weight Average Molecular Weight The weight average molecular weight (Mw) of each resin was measured under the following conditions using a gel permeation chromatography method (standard polystyrene conversion).
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Showa Denko Co., Ltd. Shodex KD-806M Two in series, or
Showa Denko Co., Ltd. Shodex 805M / 806M series standard monodisperse polystyrene: Showa Denko Co., Ltd. Shodex STANDARD SM-105
Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP)
Flow velocity: 1 mL / min.

(2) Preparation of cured relief pattern on Cu 200 nm on a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) using a sputtering device (L-440S-FHL type, manufactured by Canon Anerva). Thick Ti and 400 nm thick Cu were sputtered in this order. Subsequently, the photosensitive resin composition prepared by the method described below is spin-coated on this wafer using a coater developer (D-Spin 60A type, manufactured by SOKUDO), and prebaked on a hot plate at 110 ° C. for 180 seconds. This was performed to form a coating film having a thickness of about 4.5 μm. This coating film was irradiated with energy ^{of 100 to 1300 mJ / cm 2} by i-line by Prisma GHI (manufactured by Ultratech) using a mask with a test pattern. Next, using cyclopentanone as a developing solution for this coating film, the time until the unexposed portion was completely dissolved and disappeared was multiplied by 1.4, and the coater developer (D-Spin 60A type, manufactured by SOKUDO). The relief pattern on Cu was obtained by spray-developing with propylene glycol methyl ether acetate and rotating spray rinsing with propylene glycol methyl ether acetate for 10 seconds.

Wafers having the relief pattern formed on Cu are heat-treated for 2 hours at the temperatures shown in Table 1 under a nitrogen atmosphere using a heating program curing furnace (VF-2000 type, manufactured by Koyo Lindbergh Co., Ltd.). A cured relief pattern made of a resin having a thickness of about 3 μm was obtained on Cu.

(3) Contact with standard TMAH solution of cured relief pattern Standard TMAH solution dimethyl sulfoxide (DMSO): 97.62% by mass obtained by mixing the cured relief pattern prepared by the method of (2) above in the following weight ratio.
Tetramethylammonium hydroxide pentahydrate (TMAH): 2.38% by mass
Was immersed in a product heated to 50 ° C. for 10 minutes, washed with running water for 30 minutes, and air-dried. The film thickness before and after contact with the standard TMAH solution was measured, and the amount of change (dissolution amount) in the film thickness was calculated.

(4) Reheating treatment of the cured relief pattern after contact with the standard TMAH solution The cured relief pattern brought into contact with the standard TMAH solution by the method of (3) above is heated to a temperature-raising programmed cure furnace (VF-2000 type, Koyo Lindbergh). The product was heat-treated for 2 hours in a nitrogen atmosphere. The treatment temperature was the same as the first treatment temperature.

(5) IR measurement The cured relief pattern resin portion was measured with an ATR-FTIR measuring device (Nicolet Continuum, manufactured by Thermo Fisher Scientific) using a Si prism. The imidization index was obtained by dividing the peak intensity of 1380 cm ^{-1 by} the peak intensity of 1500 cm ^-1 , and the imidization index of the cured film of each Example and Comparative Example was obtained by curing the resin composition at 350 ° C. for 2 hours. The value divided by the imidization index of the membrane was calculated as the imid ratio. In addition, ^{the IR peak intensity near 1778 cm -1} when standardized with an IR peak intensity of ^{1500 cm -1} was also calculated. As for the peak intensity at each wavelength, the wavelength with the highest intensity was defined as the peak intensity of each wavelength ^{among 10 cm-1 before and after the indicated wavelength.} That is, for example, the peak intensity of 1500 cm ^-1 was the wavelength of the highest strength 1490～1510Cm ^-1 and the peak intensity of 1500 cm ^-1.

(6) Measurement of in-plane uniformity The photosensitive resin composition used in (2) above was rotationally applied onto the cured relief pattern using a coater developer (D-Spin 60A type, manufactured by SOKUDO). Prebaking was performed on a hot plate at 110 ° C. for 180 seconds. The rotation speed at the time of coating was adjusted so that the film thickness of the coating film portion formed on the resin of the cured relief pattern was about 6.0 μm. The film thickness of the coating film formed on the cured relief pattern was measured with a step meter (P-15: manufactured by KLA Tenko) with a width of 6000 μm centered on the boundary between the resin portion and the Cu portion formed in the lower layer. .. The in-plane uniformity was determined from the following formula.
In-plane uniformity = [(maximum film thickness)-(minimum film thickness) / (average film thickness of measuring part)]
The results were evaluated according to the following criteria.
A: In-plane uniformity less than 0.6 B: In-plane uniformity 0.6 or more and less than 0.8 C: In-plane uniformity 0.8 or more and less than 1.0 D: In-plane uniformity 1.0 or more

<Synthesis example of (A) polyimide precursor and (C) urea compound>
Production Example 1: (A) Synthesis of Polyimide Precursor A-1 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L volume separable flask, and 2-hydroxyethyl methacrylate (HEMA) 131 was placed. .2 g and 400 mL of γ-butyrolactone were added and stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the end of exotherm by the reaction, the reaction mixture was allowed to cool to room temperature and left for 16 hours.

Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture over 20 minutes with stirring, followed by 4,4'-oxydianiline (ODA). ) 93.0 g was suspended in 350 mL of γ-butyrolactone and added over 30 minutes with stirring. After further stirring at room temperature for 4 hours, 30 mL of ethyl alcohol was added and the mixture was stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 3 L of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polyimide precursor A-1). When the molecular weight of the polyimide precursor A-1 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 21,000.

Production Example 2: (A) Synthesis of Polyimide Precursor A-2 3,3', 4,4'-biphenyl instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1. The reaction was carried out in the same manner as in Production Example 1 described above except that 147.1 g of tetracarboxylic dianhydride (BPDA) was used to obtain a polymer (polyimide precursor A-2). When the molecular weight of the polyimide precursor A-2 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 24,000.

Production Example 3: Synthesis of (A) Polyimide Precursor A-3 124.0 g of ODPA and 29.4 g of BPDA are used in place of 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) of Production Example 1. The reaction was carried out in the same manner as in the above-mentioned production example 1 except that the polymer (polyimide precursor A-2) was obtained. When the molecular weight of the polyimide precursor A-2 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 24,000.

Production Example 4: (A) Synthesis of Polyimide Precursor A-4 In place of 93.0 g of 4,4'-oxydianiline (ODA) in Production Example 1, 2,2'-dimethylbiphenyl-4,4'- The reaction was carried out in the same manner as in Production Example 1 described above except that 98.6 g of diamine (m-TB) was used to obtain a polymer (A-2). When the molecular weight of the polymer (A-2) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 21,000.

Production Example 5: Synthesis of (C) Urea Compound C-1 55.1 g (0.25 mol) of diethylene glycol bis (3-aminopropyl) ether is placed in a separable flask having a capacity of 500 mL, 150 mL of tetrahydrofuran is added, and the mixture is stirred at room temperature. bottom.

Next, under ice-cooling, a solution of 77.6 g (0.50 mol) of 2-methacryloyloxyethyl isocyanate (product name: Karens MOI) plus 150 mL of tetrahydrofuran was placed in the flask over 30 minutes. The mixture was added dropwise, and the mixture was stirred at room temperature for 5 hours. Then, tetrahydrofuran was distilled off using a rotary evaporator to obtain compound C-1.

Production Example 6: Synthesis of (C) Urea Compound C-2 In Production Example 5, 55.1 g of diethylene glycol bis (3-aminopropyl) ether was replaced with 26.3 g (0.25 mol) of diethanolamine, and 2-methacryloyloxyethyl was used. Compound C-2 was obtained by synthesizing in the same manner as in Production Example 5 except that 77.6 g of isocyanate (Product of Showa Denko Co., Ltd., product name: Karens MOI) was replaced with 38.8 g (0.25 mol).

Production Example 7: Synthesis of (C) Urea Compound C-3 In Production Example 5, 55.1 g of diethylene glycol bis (3-aminopropyl) ether was replaced with 60.4 g (0.25 mol) of di-n-octylamine. Synthesis was carried out in the same manner as in Production Example 5 except that 77.6 g of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko, product name: Karens MOI) was replaced with 38.8 g (0.25 mol), and compound C- I got 3.

Production Example 8: Synthesis of (C) Urea Compound C-4 26.3 g (0.25 mol) of diethanolamine was placed in a separable flask having a capacity of 500 mL, 150 mL of tetrahydrofuran was added, and the mixture was stirred at room temperature.

Next, under ice-cooling, add 150 mL of tetrahydrofuran to 59.8 g (0.25 mol) of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (Showa Denko, product name: Karenz BEI) for 30 minutes. It was added dropwise to the flask and stirred at room temperature for 5 hours. Then, tetrahydrofuran was distilled off using a rotary evaporator to obtain compound C-4.

Production Example 9: Synthesis of (C) Urea Compound C-5 In Production Example 6, 38.8 g (0.25 mol) of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko, product name: Karens MOI) was added with isocyanic acid. Compound C-5 was obtained by synthesizing in the same manner as in Production Example 6 except that hexyl (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 31.8 g (0.25 mol).

<Example 1>
A photosensitive resin composition was prepared by the following method using the polyimide precursor A-1, and the prepared composition was evaluated. (A) A-1: 100 g as a polyimide precursor, (B) B-1: 2 g as a photosensitizer, (C) C-1: 15 g as a urea compound, γ-butyl lactone (hereinafter referred to as GBL): It was dissolved in 100 g. The viscosity of the obtained solution was adjusted to about 40 poise by further adding a small amount of GBL to obtain a photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 1.

<Examples 2 to 13, Comparative Examples 1 to 3>
The same photosensitive resin composition as in Example 1 was prepared except that the compounding ratio was prepared as shown in Table 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 1. (B) Photosensitizers B-1, B-2, (C) Urea compounds C-1 to C-6, and (D) Photopolymerizable unsaturated monomers D-1, (E) shown in Tables 1 and 2. ) The thermobase generator E-1 is as follows.

B-1: PBG305 (manufactured by Changzhou Power Co., Ltd.)
B-2: PBG3057 (manufactured by Changzhou Power Co., Ltd.)

C-1: The compound according to Production Example 5.

C-2: The compound according to Production Example 6.

C-3: The compound according to Production Example 7.

C-4: The compound according to Production Example 8.

C-5: The compound according to Production Example 9.

C-6: 1,3-Dimethylurea (manufactured by Tokyo Chemical Industry Co., Ltd.)

D-1: NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.)
E-1: 1- (tert-butoxycarbonyl) -4-hydroxypiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.)

As shown in Table 1, in the photosensitive resin composition of Example 1, ^{the post-} contact peak intensity / pre-contact peak intensity ratio of the IR peak intensity near 1778 cm -1 when standardized with an IR peak intensity of ^{1500 cm -1 is 0.} It was .45, and the in-plane uniformity evaluation was B. The photosensitive resin compositions of Examples 2 to 13 all had an intensity ratio in the range of 0.1 to 0.8, and the evaluation of in-plane uniformity was C or higher. The imidization rate was 70% or more, and the peak intensity before contact with the chemical solution and the peak intensity after reheating were higher than the peak intensity after contact with the chemical solution. The amount of change in film thickness (dissolution amount) at the time of contact with the chemical solution was 1000 nm or less.

In Comparative Example 1, the amount of dissolution at the time of contact with the chemical solution was large, and the membrane disappeared. In Comparative Example 2, the amount of dissolution at the time of contact with the chemical solution was large, and the value exceeded 1000 nm. The peak intensity ratio was 1.20, and the in-plane uniformity evaluation was D. In Comparative Example 3, the IR peak intensity hardly changed before and after the chemical contact, the intensity ratio exceeded 0.9, and the evaluation result of in-plane uniformity was D.

By using the photosensitive resin composition according to the present invention, a cured relief pattern having excellent in-plane uniformity can be obtained by contact with a chemical solution. The present invention can be suitably used in the field of photosensitive materials useful for manufacturing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (13)

(A) At least one resin selected from the group consisting of polyimide and polyimide precursors, and
(B) Photosensitizer and
(C) A photosensitive resin composition containing a urea compound.
A cured film cured by heating the photosensitive resin composition at 170 ° C. for 2 hours was prepared by dimethyl sulfoxide (TMAH) of tetramethylammonium hydroxide pentahydrate (TMAH) having a temperature of 50 ° C. and a concentration of 2.38% by mass. When contacted with a DMSO) solution for 10 minutes
^{The IR peak intensity near 1778 cm -1} when standardized with the IR peak intensity ^{of 1500 cm -1} of the cured film before and after contact is calculated by the following formula (1):
0.1 ≤ (Peak intensity after contact / Peak intensity before contact) ≤ 0.8 ... (1)
A photosensitive resin composition that meets the requirements. The photosensitive resin composition according to claim 1, wherein the amount of change in the film thickness of the cured film before and after contact is 1 nm or more and 1000 nm or less. The photosensitive resin composition according to claim 1 or 2, wherein the imidization rate of the cured film before contact is 70% or more and 100% or less. The photosensitive resin composition according to any one of claims 1 to 3, wherein the photosensitive resin composition is a photosensitive resin composition for forming an insulating member. The photosensitive resin composition according to any one of claims 1 to 4, wherein the photosensitive resin composition is a photosensitive resin composition for forming an interlayer insulating film. The photosensitive resin composition according to any one of claims 1 to 5, wherein the photosensitive resin composition is a photosensitive resin composition for forming two or more layers of an interlayer insulating film. (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) The step of exposing the photosensitive resin layer and
(3) A step of developing the photosensitive resin layer after the exposure to form a relief pattern, and
(4) A step of heat-treating the relief pattern to form a cured relief pattern, and
(5) A step of bringing the cured relief pattern into contact with an alkaline solution,
(6) A step of heat-treating the cured relief pattern in contact with the alkaline solution, and
A method for manufacturing a cured relief pattern, including. The method for producing a cured relief pattern according to claim 7, wherein the heat treatment is a heat treatment at 170 ° C. or lower. ^{The IR peak intensity near 1778 cm -1} when standardized with the IR peak intensity of ^{1500 cm -1} of the cured relief pattern obtained in the step (4) and the cured relief pattern obtained in the step (6) is the step. The method for producing a cured relief pattern according to claim 7 or 8, which is higher than the IR peak intensity near ^{1778 cm -1 of the} cured relief pattern obtained in (5). The method for producing a cured relief pattern according to any one of claims 7 to 9, wherein the step (5) of bringing the cured relief pattern into contact with the alkaline solution is a photoresist peeling step. When the cured film was brought into contact with a DMSO solution of TMAH at a temperature of 50 ° C. and a concentration of 2.38% by mass for 10 minutes, the IR peak intensity ^{of 1500 cm -1 of the cured film was standardized before and after the contact.} The IR peak intensity near ^{1778 cm -1} is calculated by the following equation (1):
0.1 ≤ (Peak intensity after contact / Peak intensity before contact) ≤ 0.8 ... (1)
A cured film that meets the requirements. The cured film according to claim 11, wherein the amount of change in the film thickness of the cured film before and after contact is 1 nm or more and 1000 nm or less. The cured film according to claim 11 or 12, wherein the imidization rate of the cured film before contact is 70% or more and 100% or less.