JP4411936B2 - Photosensitive resin composition, pattern forming method using the photosensitive resin composition, and semiconductor device - Google Patents

Description

  The present invention relates to a heat-resistant photosensitive resin composition and a pattern forming method using the same, and further to a semiconductor device having a pattern film such as a buffer coat film and an interlayer insulating film formed using the composition. Is.

  Conventionally, in the semiconductor industry, an inorganic material has been used for an interlayer insulating film. However, in recent years, an organic material having excellent heat resistance such as a polyimide resin has been utilized as an interlayer insulating material. Has been used.

  As is well known, circuit pattern formation on a semiconductor integrated circuit or a printed circuit board involves forming a resist material on the surface of the base material, removing unnecessary portions by exposure, etching, etc., cleaning the substrate surface, etc. Pattern formation is performed through complicated and diverse processes. Therefore, in such a field, it is desired to develop a heat-resistant photosensitive material that can be used by leaving a necessary portion of the resist as an insulating material even after pattern formation by exposure and development. In response to such demands, recently, in order to shorten the semiconductor manufacturing process, it is possible to easily form a pattern by coating, exposing, and developing by imparting photosensitivity to the resin itself. As such resins, photosensitive polyimide and polybenzoxazole are becoming mainstream.

  Conventionally, the negative type of the photosensitive polyimide that uses an organic solvent as a developer and insolubilizes the exposed portion is mainly used. For example, a compound having a photosensitive group is added to or mixed with the acid functional group of the polyimide precursor. A method (Patent Document 1) or the like has been proposed as a negative photosensitive polyimide that produces contrast by a photocrosslinking reaction.

  On the other hand, the use of the polybenzoxazole is due to the recent growing demand for alkaline aqueous solution development from the viewpoint of material cost and environmental conservation. As a conventional technique, a naphthoquinonediazide compound as a photosensitizer and a polybenzoxazole precursor having an acid functional group as a base resin (Patent Document 2) has been proposed.

  However, in such a photosensitive resin, in order to improve the development characteristics, it is necessary to prepare a polymer with a low molecular weight in order to increase the solubility. Such a low molecular weight polymer cannot obtain sufficient mechanical properties even when cured, and loses desirable properties as a resin. Moreover, it is necessary to add many compounds to the photosensitive resin in order to impart photosensitivity. In order to maintain sufficient cured resin properties, it is necessary to pay attention as a heat-resistant photosensitive material even in these blends, and the added composition is a compound that can impart good photosensitive properties and cured resin properties. It is hoped that. In this case, the conventional technology, for example, the above-mentioned polybenzoxazole precursor as a base resin (Patent Document 2) contains a considerable amount of a photosensitive agent having an aromatic phenol skeleton, and thus has an effect on the cured resin characteristics. As a skeleton structure, there are many rigid structures composed only of aromatic and quaternary carbons, and the types are limited.

JP-A-54-109828 Japanese Examined Patent Publication No. 1-46862

The present invention has been made in view of the above-described conventional circumstances, and the problem is to provide a photosensitive resin composition having good photosensitive characteristics and excellent cured resin characteristics rich in flexibility that has not been conventionally available. It is to provide.
Another object of the present invention is to provide a pattern forming method in which a layer having a pattern having good cured resin properties can be formed by inexpensive alkaline aqueous solution development instead of conventional organic solvent development.
Furthermore, another object of the present invention is to provide a semiconductor device having the good cured resin characteristics as a buffer coat film, an interlayer insulating film or the like.

（式中、Ｒ ₄ およびＲ ₅ は２価の有機基であり、Ｒ ₆ は水素または１価の有機基である。Ｘ ₂ はｌ＋ｍ＋ｎ価の有機基であり、ｌ＋ｍは１以上であり、ｌ＋ｍ＋ｎは１〜１０、ｌは０〜６、ｍは０〜６、ｎは０〜６の整数である。Ａは酸素原子または窒素原子であり、Ｄは光により酸を発生する官能基を示す。）で表される、主骨格部にアミド結合を有し、かつ光反応により酸を発生する光反応性化合物（Ｂ）と、溶媒（Ｃ）とを含有してなる感光性樹脂組成物。
［２］ 前記光反応性化合物（Ｂ）が、光反応によりカルボキシル基を発生させる化合物であることを特徴とする［１］記載の感光性樹脂組成物。
［３］ 前記ポリマー成分（Ａ）を構成する重合体における酸性官能基が、カルボキシル基またはフェノール性水酸基であることを特徴とする［１］または［２］記載の感光性樹脂組成物。
［４］ 前記ポリマー成分（Ａ）が、ポリイミド前駆体、ポリベンゾオキサゾール前駆体もしくはそれらの共重合体、またはそれらの混合物であるであることを特徴とする［１］から［３］のいずれか１項に記載の感光性樹脂組成物。
［５］ 前記［１］から［４］のいずれかに１項に記載の感光性樹脂組成物を支持基板上に塗布し乾燥する工程と、前記乾燥後の感光性樹脂膜を露光する工程と、前記露光後の感光性樹脂膜をアルカリ水溶液を用いて現像する工程と、前記現像によって得られたパターンを加熱処理する工程とを含むことを特徴とするパターン形成方法。
［６］ 前記［５］に記載の製造法により得られたパターンの層を有してなることを特徴とする電子デバイス。 The present invention has been made to solve the above-mentioned problems, and the features thereof can be summarized in the following items.
[1] A polymer component (A) comprising a heat-resistant polymer having an acidic functional group or a derivative substituent thereof or a precursor thereof, and the following general formula (3):

Wherein R ₄ and R ₅ are divalent organic groups, R ₆ is hydrogen or a monovalent organic group, X ₂ is an l + m + n valent organic group, l + m is 1 or more, and l + m + n 1 to 10, l is 0 to 6, m is an integer of 0 to 6, and n is an integer of 0 to 6. A is an oxygen atom or a nitrogen atom, and D is a functional group that generates an acid by light. A photosensitive resin composition comprising a photoreactive compound (B) having an amide bond in the main skeleton and generating an acid by a photoreaction and a solvent (C).
[2] The photosensitive resin composition according to [1], wherein the photoreactive compound (B) is a compound that generates a carboxyl group by a photoreaction.
[3] The photosensitive resin composition according to [1] or [2], wherein the acidic functional group in the polymer constituting the polymer component (A) is a carboxyl group or a phenolic hydroxyl group.
[4] Any one of [1] to [3], wherein the polymer component (A) is a polyimide precursor, a polybenzoxazole precursor or a copolymer thereof, or a mixture thereof. 2. The photosensitive resin composition according to item 1.
[5] A step of applying and drying the photosensitive resin composition according to any one of [1] to [4] on a support substrate, and a step of exposing the photosensitive resin film after drying. A pattern forming method comprising: developing the exposed photosensitive resin film with an alkaline aqueous solution; and heating the pattern obtained by the development.
[6] An electronic device comprising a layer having a pattern obtained by the production method according to [5].

Hereinafter, the present invention will be described in more detail.
As described above, the photosensitive resin composition of the present invention has a polymer component (A) composed of a heat-resistant polymer having an acidic functional group or a derivative substituent thereof or a precursor thereof, and an amide bond in the main skeleton. In addition, the photoreactive compound (B) that generates an acid by photoreaction and the solvent (C) are essential components. As the component (B) having an amide bond in the main skeleton and generating an acid by a photoreaction, a compound represented by the following general formula (3) is used.

  The polymer component (A) in the present invention is, for example, a tetracarboxylic dianhydride, a dicarboxylic acid, or those further having an acid functional group, and diamine or those further having an acid functional group as the main raw material of the polymer. And a polyimide precursor, a polybenzoxazole precursor, a copolymer thereof, or a mixture thereof.

（式中、Ｘ₁は２〜８価の有機基、Ｙ₁は２〜８の有機基、ｐおよびｑは０〜４の整数、Ｒ _１ は水素原子または炭素数１〜２０の有機基、ｌおよびｍは０〜２の整数、ｎは２〜１０００の整数、Ｒ _２ は水素または１価の有機基）で示される繰り返し単位を有するものを挙げることができる。 Examples of the structure of the polymer component (A) include:

(In the formula, X ₁ is a divalent to octavalent organic group, Y ₁ is an organic group of 2 to 8, p and q are integers of 0 to 4, R ₁ is a hydrogen atom or an organic group of 1 to 20 carbon atoms, and l and m are integers of 0 to 2, n is an integer of _{2 to} 1000, and R ₂ is hydrogen or a monovalent organic group).

The divalent to octavalent organic group constituting X ₁ in the general formula (1) is tetracarboxylic dianhydride, dicarboxylic acid, or further has an acid functional group.

  Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid. Acid dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3 ′ -Benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1 -Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, Screw (2,3 Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,3,4-cyclopentanetetra Carboxylic dianhydride, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetra Carboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenyl Silane tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, and the like can be mentioned, but are not limited thereto. These can be used alone or in combination of two or more.

  Among the specific tetracarboxylic dianhydrides described above, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetra Carboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3 '-Benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, N- (tri Mellitic acid dianhydride) -2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is preferred for obtaining good film properties with high heat resistance.

  Examples of the dicarboxylic acid include 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 3-fluorophthalic acid, 2-fluorophthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 3,4,5. , 6-tetrafluorophthalic acid, 4,4'-hexafluoroisopropylidenediphenyl-1,1'-dicarboxylic acid, perfluorosuberic acid, 2,2'-bis (trifluoromethyl) -4,4'-biphenylene Examples thereof include, but are not limited to, dicarboxylic acid, terephthalic acid, isophthalic acid, 4,4′-oxydiphenyl-1,1′-dicarboxylic acid, and the like. These can be used alone or in combination of two or more.

  Of the above-mentioned specific dicarboxylic acids, terephthalic acid, isophthalic acid, and 4,4′-oxydiphenyl-1,1′-dicarboxylic acid are preferable for obtaining good film properties with high heat resistance.

  Moreover, in order to adjust alkali solubility, the dicarboxylic acid which has an acid functional group which shows alkali solubility can be used. Examples of the dicarboxylic acid having an acid functional group include N- (trimellitic dianhydride) -2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, N- (trimellitic acid di-acid). Anhydride) -2,2'-bis (3-amino-4-hydroxyphenyl) propane, N- (trimellitic dianhydride) -4,4'-diamino-3,3'-dihydroxybiphenyl, N- (Trimellitic dianhydride) -2,2′-bis (3-amino-4-hydroxyphenyl) sulfone, N- (trimellitic dianhydride) -2,2′-bis (3-amino-4) -Hydroxyphenyl) ether, N- (trimellitic dianhydride) -2,2'-bis (3-amino-4-hydroxyphenyl) propane, N- (trimellitic dianhydride) -2,4- Diaminoph Nol, N- (trimellitic dianhydride) -2,5-diaminophenol, N- (trimellitic dianhydride) -1,4-diamino-2,5-dihydroxybenzene, and the like. However, it is not limited to these. These can be used alone or in combination of two or more.

  Among the dicarboxylic acids having the acid functional groups described above, N- (trimellitic dianhydride) -2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, N- (trimellitic acid 2 Anhydride) -2,2'-bis (3-amino-4-hydroxyphenyl) propane, N- (trimellitic dianhydride) -4,4'-diamino-3,3'-dihydroxybiphenyl, N- (Trimellitic dianhydride) -2,2′-bis (3-amino-4-hydroxyphenyl) sulfone, N- (trimellitic dianhydride) -2,2′-bis (3-amino-4) -Hydroxyphenyl) ether and N- (trimellitic dianhydride) -2,2'-bis (3-amino-4-hydroxyphenyl) propane are preferred for obtaining good film properties with high heat resistance.

The divalent to octavalent organic group constituting Y ₁ of the general formula (1) is a diamine having a diamine and / or an acid functional group.

  Examples of the diamine include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, m-phenylenediamine, and p-phenylenediamine. 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4 -Aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl 3,3′-dimethyl-4,4′-diaminobipheny 3,3′-diethyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetramethyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetraethyl-4 , 4'-diaminobiphenyl, 2,2'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dihydroxy-4,4'-diamino Biphenyl, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl, and the like can be mentioned, but are not limited thereto. These can be used alone or in combination of two or more.

  Among the specific diamines, 4,4′-diaminodiphenyl ether, m-phenylenediamine, p-phenylenediamine, bis (4-aminophenoxy) biphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3 , 3′-dimethyl-4,4′-diaminobiphenyl is preferred for obtaining good film properties with high heat resistance.

Moreover, in order to adjust alkali solubility, the diamine which has an acid functional group which shows alkali solubility can be used.
Examples of the diamine having an acid functional group include 2,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,3′-diaminobiphenyl-5,5′-dicarboxylic acid, and 4,4 ′. -Diaminodiphenyl ether-5,5'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-5,5'-dicarboxylic acid, 4,4'-diaminodiphenylsulfone-5,5'-dicarboxylic acid, 4,4'- Diaminodiphenyl sulfide, which has one or more carboxyl groups such as 5,5′-dicarboxylic acid or isomers thereof, or 4,4′-diamino-3,3′-dihydroxybiphenyl, 2,2′-bis (3-amino-4-hydroxyphenyl) propane, 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, oxybis (3- Mino-4-hydroxyphenyl), bis (3-amino-4-hydroxyphenyl) sulfone, 2,4-diaminophenol, 1,4-diamino-2,5-dihydroxybenzene, N, N ′-(4-amino Phenylcarbonyl) -3,3'-dihydroxybiphenyl, N, N '-(3-aminophenylcarbonyl) -3,3'-dihydroxybiphenyl, N, N'-(4-aminophenylcarbonyl) 2,2'- Bis (3-amino-4-hydroxyphenyl) hexafluoropropane, N, N ′-(3-aminophenylcarbonyl) 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, N, N '-(4-aminophenylcarbonyl) 2,2'-bis (3-amino-4-hydroxyphenyl) propane, N, N'-(3-aminophenyl Nylcarbonyl) 2,2′-bis (3-amino-4-hydroxyphenyl) propane, N, N ′-(4-aminophenylcarbonyl) -oxybis (3-amino-4-hydroxyphenyl), N, N ′ -(3-aminophenylcarbonyl) -oxybis (3-amino-4-hydroxyphenyl), N, N '-(4-aminophenylcarbonyl) -bis (3-amino-4-hydroxyphenyl) sulfone, N, N '- (3-aminophenyl-carbonyl) - bis (3-amino-4-hydroxyphenyl) sulfone, N, N' - (4-aminophenyl carbonyl) - 2,4-aminophenol, N, N '- (3 - aminophenyl carbonyl) - 2,4-aminophenol, N, N '- (4- aminophenyl carbonyl) - 1,4-diamino-2,5 Dihydroxybenzene, N, N '- those having a phenolic group, such as (3-aminophenyl-carbonyl) -1,4-diamino-2,5-dihydroxybenzene, but like can be exemplified, without limitation. These can be used alone or in combination of two or more.

Among the diamines having specific acid functional groups, 3,5-diaminobenzoic acid and 4,4′-diamino-3,3′-dihydroxybiphenyl having a phenol group, 2,2′-bis (3-amino) -4-hydroxyphenyl) propane, 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, oxybis (3-amino-4-hydroxyphenyl), bis (3-amino-4-hydroxyphenyl) ) Sulfone, 2,4-diaminophenol, 1,4-diamino-2,5-dihydroxybenzene, N, N ′-(4-aminophenylcarbonyl) -3,3′-dihydroxybiphenyl, N, N ′-( 3-aminophenylcarbonyl) -3,3′-dihydroxybiphenyl, N, N ′-(4-aminophenylcarbonyl) 2,2′-bis (3 -Amino-4-hydroxyphenyl) hexafluoropropane, N, N '-(3-aminophenylcarbonyl) 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, N, N'-( 4-aminophenylcarbonyl) 2,2′-bis (3-amino-4-hydroxyphenyl) propane, N, N ′-(3-aminophenylcarbonyl) 2,2′-bis (3-amino-4-hydroxy) phenyl) propane, N, N '- (4- aminophenyl carbonyl) - oxybis (3-amino-4-hydroxyphenyl), N, N' - (3-aminophenyl-carbonyl) - oxybis (3-amino-4 hydroxyphenyl), N, N '- (4-aminophenyl carbonyl) - bis (3-amino-4-hydroxyphenyl) sulfone, N, N' (3-aminophenyl-carbonyl) - bis (3-amino-4-hydroxyphenyl) sulfone is preferred for obtaining good alkali developing properties.

  By polymerizing these tetracarboxylic dianhydrides, dicarboxylic acids and / or dicarboxylic acids having acid functional groups and diamines and / or diamines having acid functional groups, the acidic functional groups of the polymer component (A) and In addition, a heat-resistant polymer having a derivative substituent or a precursor thereof can be obtained. For example, a polyimide precursor can be obtained by polymerizing tetracarboxylic dianhydride and a diamine and / or a diamine having an acid functional group. Further, a polybenzoxazole precursor can be obtained by polymerizing an activated esterified dicarboxylic acid and / or a dicarboxylic acid having an acid functional group and a diamine having a phenolic acid functional group. Further, polyimide / polybenzoxazole is prepared by copolymerizing tetracarboxylic dianhydride, dicarboxylic acid and / or dicarboxylic acid having an active esterified acid functional group and diamine and / or diamine having an acid functional group. A precursor copolymer can be obtained.

By partially introducing a functional group such as an organic group represented by R ₁ in the general formula (1), it is possible to control solubility during development and / or pattern processing utilizing photoreaction. Examples of such functional groups include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, cyclopropenyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cyclohexenyl, norbornyl, norbornenyl, Adamantyl, benzyl, p-nitrobenzyl, trifluoromethyl, methoxyethyl, ethoxyethyl, methoxymethyl, ethoxymethyl, methoxyethoxymethyl, benzoxymethyl, tetrahydropyranyl, ethoxytetrahydropyranyl, tetrahydrofuranyl, 2-trimethylsilylethoxymethyl , Groups such as trimethylsilyl, t-butyldimethylsilyl, 3-oxocyclohexyl, 9-fluorenylmethyl, methylthiomethyl, allyl alcohol, 2- Tyl-2-propen-1-ol, crotyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-butene- 1-ol, 3-methyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-penten-1-ol, 4-penten-1-ol, 3-penten-2- Ol, 4-penten-2-ol, 1-penten-3-ol, 4-methyl-3-penten-1-ol, 3-methyl-1-penten-3-ol, 2-hexen-1-ol 3-hexen-1-ol, 4-hexen-1-ol, 5-hexen-1-ol, 1-hexen-3-ol, 1-heptane-3-ol, 6-methyl-5-heptane-2 -Ol, 1-octane-3-ol, citronellol, 3-nonen-1-ol, -Decan-1-ol, 9-decan-1-ol, 7-decan-1-ol, 1,4-pentadien-3-ol, 2,4-hexadien-1-ol, 1,5-hexadiene-3 -Ol, 1,6-heptadiene-4-ol, 2,4-dimethyl-2,6-heptadiene-1-ol, nerol, geraniol, linalool, 2-cyclohexen-1-ol, 3-cyclohexene-1-methanol , Isopulegol, 5-norbornen-2-ol, 5-norbornene-2-methanol, ethylene glycol vinyl ether, 1,4-butanediol vinyl ether, 1,6-hexanediol vinyl ether, diethylene glycol vinyl ether, 2-hydroxyethyl acrylate, 3- Hydroxypropyl acrylate, 2-hydroxyethyl methacrylate Lilate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, dicaprolactone 2- (methacrylic) And compounds such as leuoxy) ethyl ester, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate. Furthermore, a functional group obtained by reacting with a carboxyl group bonded to X ₁ or Y ₁ can also be used. However, it is not necessarily limited to those listed here. Alkali solubility can also be controlled by partially introducing these functional groups. Moreover, when the terminal of a polymer has an acidic functional group, it is also possible to introduce these functional groups into the polymer.

  Among the specific functional groups described above, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, methoxyethyl, ethoxyethyl, methoxymethyl, ethoxymethyl, methoxyethoxymethyl, tetrahydropyranyl, ethoxy Tetrahydropyranyl and tetrahydrofuranyl are preferred for controlling the solubility well.

Also, R ₂ in the general formula (1), R ₁ and control of the development time of solubility by introducing the functional group of the same type and / or patterned using optical reaction is possible in the general formula (1) . Moreover, alkali solubility can also be controlled by partially introducing these functional groups. Furthermore, when the terminal of a polymer has an acidic functional group, it is also possible to introduce these functional groups.

  In the polymer component (A), both ends are amine functional groups and / or derived derivatives thereof, or acidic functional groups and / or derived substituents, or both functional groups at one end. Either one or a mixture of them. When the amine functional group at the terminal is a primary amine, the stability of the photosensitive resin composition deteriorates due to side reactions, so at least one of the two hydrogen atoms on the amine functional group is another atom or other atom. Substitution with a functional group is preferred for obtaining stability as a photosensitive resin composition. The substitution ratio is more preferably in the range of 30% to 100% in order to obtain sufficient stability.

Substituents on nitrogen derived from amine functional groups include amide, imide, carbamate, sulfonyl, sulfenyl, phosphinyl, alkylsilyl and the like. Of these, amide, imide, carbamate, and sulfonyl are preferable in terms of obtaining more excellent cured resin properties.
These substituents are represented by hydrogen or general formula (2).

In the general formula (2), R ₃ is a monovalent or divalent organic group, preferably having 1 to 20 carbon atoms. X ₃ is an oxygen, sulfur, or nitrogen atom. When X ₃ is an oxygen atom or a sulfur atom, n = 1, and when X ₃ is a nitrogen atom, n = 2.

In the case of monovalent R ₃ , for example, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, cyclopropenyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cyclohexenyl, Norbornyl, norbornenyl, adamantyl, benzyl, p-nitrobenzyl, trifluoromethyl, methoxyethyl, ethoxyethyl, methoxymethyl, ethoxymethyl, methoxyethoxymethyl, benzoxymethyl, ethoxytetrahydropyranyl, tetrahydrofuranyl, 2-trimethylsilylethoxymethyl , Trimethylsilyl, t-butyldimethylsilyl, 3-oxocyclohexyl, 9-fluorenylmethyl, phenyl, toluyl, xylyl, 9,10-dihydroanthranyl, Methylphenyl, pentamethylphenyl, biphenyl, terphenyl, quarterphenyl, dimethylbiphenyl, naphthalenyl, methylnaphthalenyl, fluorenyl, fluorophenyl, fluorobiphenyl, isopropylidenebiphenyl, tetrafluoroisopropylidenebiphenyl, benzylphenyl ether, phenyl ether, Phenoxytoluyl, methoxybiphenyl, dimethoxybiphenyl, methoxynaphthalenyl, dimethoxynaphthalenyl, nitrophenyl, etc. In the case of divalent, methane, ethane, propane, isopropane, dimethylmethane, butane, cyclopropane, cyclobutane , Cyclopentane, cyclohexane, methylcyclohexane, norbornane, adamantane, isopropylidenedicyclohexane, Toximethane, methoxyethane, ethoxyethane, methoxyethoxymethane, benzoxymethane, tetrahydrofuran, benzene, toluene, cumene, diphenylmethane, xylene, 9,10-dihydroanthracene, mesitylene, hexamethylbenzene, biphenyl, terphenyl, triphenylbenzene , Quarterphenyl, dimethylbiphenyl, azulene, naphthalene, methylnaphthalene, anthracene, fluorene, fluorobenzene, fluorobiphenyl, isopropylidenebiphenyl, tetrafluoroisopropylidenebiphenyl, anisole, benzylphenyl ether, phenyl ether, phenoxytoluene, tolyl ether, methoxy Biphenyl, dimethoxybiphenyl, methoxynaphthalene, dimethoxynaphthalene Such as nitrobenzene, those two hydrogen atoms sites in its structure is a linking group instead of hydrogen atoms, there may be mentioned, but not limited to necessarily listed herein.

As the acidic functional group and / or its derived substituent at the terminal portion, those represented by R ₁ and R ₂ in the general formula (1) are used.

  The molecular weight of the polymer component (A) in the present invention is not particularly limited, but is preferably 5000 to 80000 in terms of weight average molecular weight. The molecular weight is measured by gel permeation chromatography and can be calculated using a standard polystyrene calibration curve.

  The photoreactive compound (B) used in the present invention, which has an amide bond in the main skeleton and generates an acid by a photoreaction, is a photosensitizer, generates an acid, and generates an alkali in the light-irradiated part. It has a function of increasing the solubility in an aqueous solution. Examples of the type include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, and the like. The compounds are not limited to those listed here, and any compound that generates an acid by light can be used.

  The o-quinonediazide compound can be obtained, for example, by subjecting o-quinonediazidesulfonyl chlorides to a condensation reaction with a hydroxy compound, an amino compound, or the like. In the present invention, the hydroxy compound, amino compound and the like to be subjected to the reaction are those having an amide bond in the main skeleton part in order to obtain good cured resin properties. More specifically, the general formula (3 ).

（式中、Ｒ₄およびＲ₅は２価の有機基であり、Ｒ₆は水素または１価の有機基である。Ｘ₂はｌ＋ｍ＋ｎ価の有機基であり、ｌ＋ｍは１以上であり、ｌ＋ｍ＋ｎは１〜１０、ｌは０〜６、ｍは０〜６、ｎは０〜６の整数である。Ａは酸素原子または窒素原子であり、Ｄは光により酸を発生する官能基を示す。）

Wherein R ₄ and R ₅ are divalent organic groups, R ₆ is hydrogen or a monovalent organic group, X ₂ is an l + m + n valent organic group, l + m is 1 or more, and l + m + n 1 to 10, l is 0 to 6, m is an integer of 0 to 6, and n is an integer of 0 to 6. A is an oxygen atom or a nitrogen atom, and D is a functional group that generates an acid by light. )

X ₂ in the general formula (3) includes an alkyl chain, a cyclopentyl ring, a cyclohexyl ring, a cyclooctyl ring, and other bicyclo rings in the aliphatic group, and these may contain heteroatoms composed of oxygen, sulfur and the like. Good. For example, methane, ethane, propane, isopropane, dimethylmethane, butane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, methylcyclohexane, norbornane, adamantane, isopropylidenedicyclohexane, methoxymethane, methoxyethane, ethoxyethane, methoxyethoxymethane , Benzoxymethane, tetrahydrofuran, and the like, in which 1 + m + n hydrogen atom sites are bonded groups instead of hydrogen atoms.

Moreover, as X < ₂ > in the said General formula (3), a benzene ring, a naphthalene ring, etc. can be mentioned in aromatic. Of these, aromatics are preferred from the viewpoint of heat resistance. For example, benzene, toluene, cumene, diphenylmethane, xylene, 9,10-dihydroanthracene, mesitylene, hexamethylbenzene, biphenyl, terphenyl, triphenylbenzene, quarterphenyl, dimethylbiphenyl, azulene, naphthalene, methylnaphthalene, anthracene, Fluorene, fluorobenzene, fluorobiphenyl, isopropylidenebiphenyl, tetrafluoroisopropylidenebiphenyl, anisole, benzylphenyl ether, phenyl ether, phenoxytoluene, tolyl ether, methoxybiphenyl, dimethoxybiphenyl, methoxynaphthalene, dimethoxynaphthalene, nitrobenzene, acetophenone, benzophenone , Benzanilide, phenylsulfone, furan, thiophene , Benzyl, may be a group having a structure such as nitrobenzyl, not limited to those necessarily listed herein. Of these, benzene, toluene, biphenyl, dimethylbiphenyl, phenyl ether, benzophenone, isopropylidenebiphenyl, and tetrafluoroisopropylidenebiphenyl are preferable for obtaining good film properties with higher heat resistance.

R ₄ and R ₅ are each a divalent organic group, and R ₆ is hydrogen or a monovalent organic group.

Examples of R ₄ and R ₅ include aliphatic alkyl chains, cyclopentyl rings, cyclohexyl rings, cyclooctyl rings, and other bicyclo rings, which may contain heteroatoms composed of oxygen, sulfur, and the like. For example, methane, ethane, propane, isopropane, dimethylmethane, butane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, methylcyclohexane, norbornane, adamantane, isopropylidenedicyclohexane, methoxymethane, methoxyethane, ethoxyethane, methoxyethoxymethane, Mention may be made of those in which two hydrogen atom sites are bonded groups instead of hydrogen atoms, such as benzoxymethane and tetrahydrofuran.

Furthermore, examples of R ₄ and R ₅ include aromatic groups such as a benzene ring and a naphthalene ring. Of these, aromatics are preferred from the viewpoint of heat resistance. Examples of such aromatics include benzene, toluene, cumene, diphenylmethane, xylene, 9,10-dihydroanthracene, mesitylene, hexamethylbenzene, biphenyl, terphenyl, triphenylbenzene, quarterphenyl, dimethylbiphenyl, and azulene. , Naphthalene, methylnaphthalene, anthracene, fluorene, fluorobenzene, fluorobiphenyl, isopropylidenebiphenyl, tetrafluoroisopropylidenebiphenyl, anisole, benzylphenyl ether, phenyl ether, phenoxytoluene, tolyl ether, methoxybiphenyl, dimethoxybiphenyl, methoxynaphthalene, Dimethoxynaphthalene, nitrobenzene, acetophenone, benzophenone, benzanilide, phenyl Sulfone, furan, thiophene, benzyl, etc. nitrobenzyl, it can be mentioned.

R ₆ is hydrogen or a monovalent organic group, and the organic group may further contain a functional group such as a carboxyl group, a hydroxy group, an ester group, an ether group, or an amide group. Examples of such functional groups include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, cyclopropenyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cyclohexenyl, norbornyl, norbornenyl, Adamantyl, benzyl, p-nitrobenzyl, trifluoromethyl, methoxyethyl, ethoxyethyl, methoxymethyl, ethoxymethyl, methoxyethoxymethyl, benzoxymethyl, ethoxytetrahydropyranyl, tetrahydrofuranyl, 2-trimethylsilylethoxymethyl, trimethylsilyl, t -Butyldimethylsilyl, 3-oxocyclohexyl, 9-fluorenylmethyl, phenyl, toluyl, xylyl, 9,10-dihydroanthranyl, trimethyl Phenyl, pentamethylphenyl, biphenyl, terphenyl, quarterphenyl, dimethylbiphenyl, naphthalenyl, methylnaphthalenyl, fluorenyl, fluorophenyl, fluorobiphenyl, isopropylidenebiphenyl, tetrafluoroisopropylidenebiphenyl, benzylphenyl ether, phenyl ether, phenoxy Examples include tolueil, methoxybiphenyl, dimethoxybiphenyl, methoxynaphthalenyl, dimethoxynaphthalenyl, nitrophenyl and the like.

  A is an oxygen atom and / or an NH group. The D represents a functional group that generates an acid by light. Examples of D include groups having a structure such as o-quinonediazide, aryldiazonium salt, diaryliodonium salt, and triarylsulfonium salt.

  Examples of the o-quinonediazides include benzoquinone-1,2-diazide-4-sulfonyl, naphthoquinone-1,2-diazide-5-sulfonyl, naphthoquinone-1,2-diazide-4-sulfonyl, and the like. However, it is not necessarily limited to those listed here.

  Examples of the aryldiazonium salt, diaryliodonium salt, and triarylsulfonium salt include benzenediazonium-p-toluenesulfonate, diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate, and tris (4-t-butylphenyl). ) Sulfonium trifluoromethanesulfonate, N-naphthalimide trifluoromethanesulfonate, p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate, 4-methoxy-α-[[[(4-methylphenyl) sulfonyl] oxy] Imino] benzeneacetonitrile, 2- (2′-furylethenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, etc. can be used in combination, but are not limited to those listed here. But it is not limited to.

  The functional group D can be introduced, for example, by a condensation reaction between the corresponding A ester and an active ester such as a carbonyl chloride or a sulfonium chloride compound. In this case, the A site is, for example, a hydroxyl group or amino group having active hydrogen. Such introduction of the D functional group may be partial, and the introduction rate is preferably in the range of 50 to 100% with respect to the A site. These photosensitizers are used alone or in combination of two or more.

  The amount of the photoreactive compound (B) used is preferably 0.1 to 40 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the polymer component (A). preferable. In addition, the “photoreactive compound (B) having an amide bond in the main skeleton and generating an acid by photoreaction” can be used in combination with other photoreactive compounds. is there. In that case, the amount of (B) is preferably at least 5% by weight or more of the total amount of the photosensitive agent, more preferably 20% by weight or more.

  As the solvent (C) in the present invention, gamma-butyrolactone, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylsulfoxide, hexamethylphosphortriamide, dimethyl Polar solvents such as imidazolidinone and N-acetyl-ε-caprolactam are preferred. Besides this polar solvent, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, for example, Acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydride Furan, dichloromethane, 1,2-dichloroethane, 1,4-dichloro butane, trichloroethane, chlorobenzene, o- dichlorobenzene, hexane, heptane, octane, benzene, toluene, and xylene can be used. These organic solvents are used alone or in combination of two or more. However, the type is not particularly limited as long as it can dissolve the photosensitive resin composition of this report. Generally, the solvent is used in an amount of 40 to 90% by weight in the photosensitive resin composition.

In the photosensitive resin composition of the present invention, in addition to the above essential components, a silane coupling agent is used for the purpose of enhancing adhesion to a silicon substrate, or diaminosiloxane is used as Y ₁ part in the general formula (1). It is also possible to modify and use the base polymer by having residues derived from.

  As such a silane coupling agent, alkoxysilanes are preferable from the viewpoint of reactivity. For example, vinyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltrimethoxy Silane, N-methylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N, N-bis (3- (trimethoxysilyl) propyl) ethylenediamine, N- (3- Trimethoxysilylpropyl) pyrrole, urea Dopropyltrimethoxysilane, (3-triethoxysilylpropyl) -t-butylcarbamate, N-phenylaminopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, (furfuryloxymethyl) triethoxysilane, etc. Can be mentioned.

  In the resin composition of the present invention, a dissolution accelerator can be used for the purpose of increasing contrast. Examples of the dissolution accelerator include compounds containing an acidic functional group. As such an acidic functional group, a phenolic hydroxyl group, a carboxylic acid group, and a sulfonic acid group are preferable. Specific examples of the compound include methylene bisphenol, 2,2-methylene bis (4-methylphenol), 4,4-oxybisphenol, 4,4- (1-methylethylidene) bis (2-methylphenol), 4, 4- (1-phenylethylidene) bisphenol, 5,5- (1-methylethylidene) bis (1,1- (biphenyl) -2-ol), 4,4,4-ethylidinetrisphenol, 2,6- Bis ((2-hydroxy-5-methylphenyl) methyl) -4-methylphenol, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol 4,4-sulfonyldiphenol, (2-hydroxy-5-methyl) -1,3-benzenedimethylol, 3,3-methylenebis ( -Hydroxy-5-methylbenzenemethanol), salicylic acid, malonic acid, glutaric acid, 2,2-dimethylglutaric acid, maleic acid, diglycolic acid, 1,1-cyclobutanedicarboxylic acid, 3,3-tetramethyleneglutaric acid, 1 , 3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,2-phenylenedioxydiacetic acid, 1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid, terephthalate Examples include acid, isophthalic acid, 4,4′-oxydiphenyldicarboxylic acid, 4,4-biphenyldicarboxylic acid, 4-hydroxybenzenesulfonic acid, and the like. These dissolution promoters are used alone or in combination of two or more.

  Moreover, you may mix | blend an addition polymerizable compound, a dissolution inhibitor, a stabilizer, etc. with the resin composition of this invention according to the objective.

  The photosensitive resin composition of the present invention is applied onto a support substrate such as a silicon wafer, a metal substrate, or a ceramic substrate by a dipping method, a spray method, a screen printing method, a spin coating method, or the like, and the solvent is appropriately heated and dried. Thus, a non-adhesive coating film (photosensitive resin film) can be obtained. The coating film can be exposed by irradiation with actinic rays or actinic rays through a mask on which a desired pattern is drawn. Actinic rays or actinic rays to be irradiated include actinic rays from contact / proximity exposure machines using an ultra-high pressure mercury lamp, mirror projection exposure machines, i-line steppers, g-line steppers, other ultraviolet rays, visible light sources, X-rays and electron beams can be used. Thereafter, post-exposure bake (PEB) treatment may be performed as necessary to perform development. A desired pattern can be obtained by dissolving and removing the irradiated portion with a developer after irradiation with actinic rays.

  As the developer, an organic solvent or an alkaline aqueous solution is used. In the present invention, development using an alkaline aqueous solution is preferable in terms of material cost and environmental conservation.

  Examples of the organic solvent developer include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, water, or Alcohols, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons such as methanol, ethanol, isopropyl alcohol, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, Ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloro Examples include loethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, and the like. These may be used alone or in combination of two or more. Is done.

  Examples of the alkaline aqueous solution include aqueous solutions of alkali metal hydroxides such as caustic potash and caustic soda, and aqueous amine solutions such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline and other quaternary ammonium hydroxides, ethanolamine, propylamine, and ethylenediamine Is used. After development, rinsing is performed with water or a poor solvent as necessary. As the rinsing liquid, for example, methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, methyl cellosolve, water, or the like is used. By heating the pattern thus obtained, a stable high heat-resistant resin pattern from which the photosensitive agent and the solvent have been removed is obtained.

  The heating temperature of the pattern is preferably 150 to 500 ° C, and more preferably 200 to 400 ° C. If the heating temperature is less than 150 ° C., the mechanical properties and thermal properties of the film tend to deteriorate, and if it exceeds 500 ° C., the mechanical properties and thermal properties of the film tend to decrease. Moreover, it is preferable that the heating time at this time shall be 0.05 to 10 hours. If this heating time is less than 0.05 hours, the mechanical properties and thermal properties of the film tend to deteriorate, and if it exceeds 10 hours, the mechanical properties and thermal properties of the film tend to deteriorate.

  The photosensitive resin composition of the present invention has an unprecedented good cured resin characteristic that the photosensitive characteristic is not impaired and the elongation characteristic is excellent. In addition, the pattern manufacturing method of the present invention can be used to process polyimide patterns such as interlayer insulating films for multilayer wiring boards, α-ray shielding films for semiconductor memory devices, buffer coat films, etc., instead of conventional organic solvent development, It can be carried out by aqueous solution development. Therefore, the electronic device of the present invention has a characteristic that it is excellent in reliability.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, a following example is only the illustration which illustrates this invention suitably, and does not limit this invention at all.

(Synthesis Example 1: Polymer Component (A) Synthesis Example)
100 g dry N-methylpyrrolidone and 21.18 g (0.072 mol) 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride in a closed reaction vessel equipped with stirrer, thermometer and nitrogen inlet tube To the stirred solution, 1.1 g (0.018 mol) of isopropyl alcohol was added and stirred at 45 ° C. overnight. This solution is referred to as reaction solution (a).

  On the other hand, in a closed reaction vessel equipped with a stirrer, thermometer and nitrogen inlet tube, 6.49 g (0.06 mol) metaphenylenediamine and 0.25 g (0.001 mol) in 80 ml dry N-methylpyrrolidone. A solution to which 1,3-bis (3-aminopropyl) tetramethyldisiloxane was added was prepared. This prepared solution is referred to as solution (b).

  The solution (b) was added dropwise to the reaction solution (a) over 1 hour and stirred at room temperature overnight. This solution is referred to as reaction solution (c).

  A solution prepared by dissolving 20.6 g (0.1 mol) of N, N-dicyclohexylcarbodiimide in 100 g of dry N-methylpyrrolidone was added dropwise to the reaction solution (c) with stirring over 1 hour. . This reaction solution is referred to as reaction solution (d). To this reaction solution (d), 18 g (0.30 mol) of isopropyl alcohol was added, followed by stirring at 50 ° C. for 5 hours and at room temperature overnight. The reaction mixture was diluted with 50 g of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was treated with 2.0 L of ion exchange water with vigorous stirring.

  The precipitated solid was further washed with ion-exchanged water, then with methanol, suction dried on a filtration filter, and dried under reduced pressure at room temperature until the water content was less than 1.0% by weight. A polymer (P-1) was obtained. This polymer (P-1) was a polyimide precursor, the weight average molecular weight was 20,600, and the degree of dispersion was 1.59.

(Synthesis Example 2: Polymer Component (A) Synthesis Example)
A solution consisting of 100 g dry N-methylpyrrolidone and 25.8 g (0.1 mol) 4,4′-oxybis (carboxyphenyl) in a closed reaction vessel equipped with a stirrer, thermometer and nitrogen inlet tube Then, 23.8 g (0.2 mol) of thionyl chloride was added dropwise to the solution, followed by stirring for 30 minutes to obtain a reaction solution (A-1).

  Then, in a closed reaction vessel equipped with another stirrer, thermometer and nitrogen inlet tube, 100 g dry N-methylpyrrolidone and 40.3 g (0.11 mol) 2,2-bis (3-amino-4) A solution consisting of -hydroxyphenyl) hexafluoropropane and 1.58 g (0.02 mol) of pyridine was prepared. The solution was cooled to 0 ° C., and 2.09 g (0.02 mol) of cyclopropanecarbonyl chloride was added dropwise to the solution. After the addition, the mixture was stirred at room temperature for 30 minutes. To this stirring solution, 15.82 g (0.2 mol) of pyridine was further added and cooled to 0 ° C., and then the reaction solution (A-1) obtained above was added dropwise over 30 minutes, and at room temperature for 30 minutes. Stir.

  The reaction mixture obtained after the stirring was treated with 2.0 L of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, suction-dried on a filtration filter, and dried under reduced pressure at room temperature until the water content was less than 1.0% by weight, whereby polymer (P-2 ) This polymer (P-2) was a polyimide precursor, and the weight average molecular weight was 23,900 and the dispersity was 1.71.

(Synthesis example 3: Polymer component (A) synthesis example)
In a closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen inlet tube, 100 g of dry N-methylpyrrolidone and 14.8 g (0.2 mol) of n-butanol were added, and an additional 31.0 g (0.1 mol). Of bis (3,4-dicarboxyphenyl) ether dianhydride was added and stirred at 70 ° C. for 24 hours to obtain an ester.

  The ester solution was cooled to 0 ° C., and 23.8 g (0.2 mol) of thionyl chloride was added dropwise, followed by stirring for 30 minutes to obtain a reaction solution (A-2).

  Then, in a closed reaction vessel equipped with another stirrer, thermometer and nitrogen inlet tube, 100 g dry N-methylpyrrolidone and 33.0 g (0.09 mol) 2,2-bis (3-amino-4) -Hydroxyphenyl) hexafluoropropane and 15.82 g (0.2 mol) of pyridine were added and dissolved by stirring. This solution was cooled to 0 ° C., and the reaction solution (A-2) obtained earlier was dropped into this solution over 30 minutes, and then stirred at room temperature for 30 minutes.

  The reaction mixture obtained after the stirring was treated with 2.0 L of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, sucked and dried on a filtration filter, and dried under reduced pressure at room temperature until the water content was less than 1.0% by weight, whereby polymer (P-3) Got. This polymer (P-3) was a polyimide precursor, and the weight average molecular weight was 24,100 and the dispersity was 1.69.

(Synthesis Example 4: Polymer Component (A) Synthesis Example)
Agitation consisting of 100 g dry N-methylpyrrolidone and 22.3 g (0.072 mol) bis (3,4-dicarboxyphenyl) ether dianhydride in a closed reaction vessel equipped with stirrer, thermometer and nitrogen inlet tube To solution (a) was added 1.2 g (0.008 mol) 3,5-diaminobenzoic acid and 26.4 g (0.072 mol) 2,2-bis (3-amino) in 80 g dry N-methylpyrrolidone. A solution (b) formed by adding -4-hydroxyphenyl) hexafluoropropane was added and stirred at room temperature overnight to obtain a reaction solution (c). Thereafter, 2.4 g (0.015 mol) of phenylchloroformate and 1.2 g (0.015 mol) of pyridine were added to the reaction solution (c), and the mixture was stirred at room temperature for 30 minutes.

  The reaction mixture obtained after the stirring was diluted with 50 g of acetone, and unnecessary filtrate was removed by suction filtration to obtain a filtrate. This filtrate was treated with 2.0 L of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, then with methanol, suction dried on a filtration filter, and dried under reduced pressure at room temperature until the water content was less than 1.0% by weight. A polymer (P-4) was obtained. This polymer (P-4) was a polyimide precursor, and the weight average molecular weight was 22,200 and the dispersity was 1.60.

(Synthesis Example 5: Photoreactive Compound (B) Synthesis Example)
A solution consisting of 300 g dry N-methylpyrrolidone and 25.8 g (0.1 mol) 4,4′-oxybis (carboxyphenyl) in a closed reaction vessel equipped with a stirrer, thermometer and nitrogen inlet tube was The solution was cooled to 0 ° C., and 23.8 g (0.2 mol) of thionyl chloride was added dropwise to this solution, followed by stirring for 30 minutes to obtain a reaction solution (i).

  Then, a solution consisting of 100 g of dry N-methylpyrrolidone and 21.8 g (0.2 mol) of 3-aminophenol in a closed reaction vessel equipped with another stirrer, thermometer and nitrogen inlet tube was cooled to 0 ° C., Thereafter, the reaction solution (i) obtained earlier was added dropwise to this solution, and 15.82 g (0.2 mol) of pyridine was further added, followed by stirring at room temperature for 30 minutes.

  The reaction mixture obtained after the stirring was treated with 2.0 L of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, sucked and dried on a filtration filter, and dried under reduced pressure at room temperature until the water content was less than 1.0% by weight, whereby compound (ii) was obtained. It was.

  In a closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen inlet tube, 22.0 g (0.05 mol) of the compound (ii) and 48.4 g (0. 4 g) of naphthoquinone-1,2-diazide-5-sulfonyl chloride. 09 mol) and 200 g of dry N-methylpyrrolidone. To this solution, 9.1 g (0.09 mol) of triethylamine was dropped and reacted under cooling. The reaction mixture was filtered and the filtrate was treated with 2.0 l of ion exchange water with vigorous stirring. The solid matter precipitated by this treatment is further washed with ion-exchanged water, sucked and dried on a filtration filter, and dried under reduced pressure at room temperature until the water content is less than 1.0% by weight. An orthoquinonediazide compound (B-1: photoreactive compound) having an amide bond was obtained.

(Synthesis Example 6: Photoreactive Compound (B) Synthesis Example)
A solution consisting of 10.9 g (0.1 mol) of dry N-methylpyrrolidone and 3-aminophenol was prepared in 100 g in a closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube. After cooling this solution to 0 ° C., 10.1 g (0.05 mol) of isophthalic acid chloride was added to this solution, and 4.0 g (0.05 mol) of pyridine was further added, followed by stirring at room temperature for 30 minutes. .

  The reaction mixture obtained by the stirring was treated with 1.0 l of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, sucked and dried on a filtration filter, and dried under reduced pressure at room temperature until the water content was less than 1.0% by weight, whereby compound (iii) was obtained. Obtained.

  In a closed reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 17.4 g (0.05 mol) of the compound (iii) and 24.2 g (0. 2 g) of naphthoquinone-1,2-diazide-4-sulfonyl chloride. 09 mol) and 200 g of dry N-methylpyrrolidone. To this solution, 9.1 g (0.09 mol) of triethylamine was dropped and reacted under cooling. The resulting reaction mixture was filtered, and the filtrate was treated with 2.0 l of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, suction-dried on a filtration filter, and dried under reduced pressure at room temperature until the water content was less than 1.0% by weight. An orthoquinonediazide compound (B-2: photoreactive compound) having a bond was obtained.

(Synthesis Example 7: Photoreactive Compound (B) Synthesis Example)
In a closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube, a solution consisting of 100 g of dry N-methylpyrrolidone and 21.8 g (0.2 mol) of 4-aminophenol was prepared. After cooling this solution to 0 ° C., 21.3 g (0.1 mol) of 1,4-cyclohexyldicarboxylic acid chloride was added to this solution, and then 15.82 g (0.2 mol) of pyridine was added, Stir overnight at room temperature.

  The reaction mixture obtained by the stirring was treated with 2.0 L of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, sucked and dried on a filtration filter, and dried under reduced pressure at room temperature until the water content was less than 1.0% by weight, thereby obtaining compound (iii). It was.

  In a closed reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 17.7 g (0.05 mol) of the compound (iii) and 24.2 g (0. 2 g) of naphthoquinone-1,2-diazide-5-sulfonyl chloride. 09 mol) and 150 g of dry N-methylpyrrolidone. To this solution, 9.1 g (0.09 mol) of triethylamine was dropped and reacted under cooling. The resulting reaction mixture was filtered, and the filtrate was treated with 2.0 l of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, sucked and dried on a filtration filter, and dried at room temperature under reduced pressure until the water content was less than 1.0% by weight, whereby an amide bond was formed on the main skeleton. An orthoquinonediazide compound (B-3: photoreactive compound) was obtained.

(Synthesis Example 8: Synthesis Example of Photoreactive Compound (B))
In a sealed reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube, a solution consisting of 100 g of dry N-methylpyrrolidone and 21.8 g (0.2 mol) of 3-aminophenol was prepared. After cooling this solution to 0 ° C., 18.6 g (0.07 mol) of 1,3,5-benzenetricarbonyltrichloride was added to this solution, and 15.82 g (0.2 mol) of pyridine was added. Add and stir overnight at room temperature.

  The reaction mixture obtained by the stirring was treated with 2.0 L of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, suction-dried on a filtration filter, and dried under reduced pressure at room temperature until the water content was less than 1.0% by weight, whereby reactant (iv) Got.

  In a closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube, 24.2 g (0.05 mol) of the reactant (iv) and 37.6 g of naphthoquinone-1,2-diazide-5-sulfonyl chloride (0 .14 mol) and 200 g of dry N-methylpyrrolidone. To this solution, 14.2 g (0.14 mol) of triethylamine was reacted dropwise while cooling. The obtained reaction mixture was filtered, and the obtained filtrate was treated with 2.0 l of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, sucked and dried on a filtration filter, and dried at room temperature under reduced pressure until the water content was less than 1.0% by weight, whereby an amide bond was formed on the main skeleton. An orthoquinonediazide compound (B-4: photoreactive compound) was obtained.

(Synthesis Example 9: Comparative Photoreactive Compound Synthesis Example)
In a closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube, 14.6 g (0.05 mol) of tris (4-hydroxyphenyl) methane and 37.6 g of naphthoquinone-1,2-diazide-5-sulfonyl chloride. A solution consisting of (0.14 mol) and 200 g of dry N-methylpyrrolidone was prepared. To this solution, 14.2 g (0.14 mol) of triethylamine was reacted dropwise while cooling. The obtained reaction mixture was filtered, and the obtained filtrate was treated with 2.0 L of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, sucked and dried on a filtration filter, and dried at room temperature under reduced pressure until the water content was less than 1.0% by weight, whereby an amide bond was formed on the main skeleton. An orthoquinonediazide compound (B-5: comparative photoreactive compound) was obtained.

(Synthesis Example 10: Comparative Photoreactive Compound Synthesis Example)
In a closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube, 21.1 g (0.05 mol) of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene and naphthoquinone-1,2-diazide A solution consisting of 37.6 g (0.14 mol) of -5-sulfonyl chloride and 200 g of dry N-methylpyrrolidone was prepared. To this solution, 14.2 g (0.14 mol) of triethylamine was reacted dropwise while cooling. The obtained reaction mixture was filtered, and the obtained filtrate was treated with 2.0 l of ion exchange water with vigorous stirring. The precipitated solid was further washed with ion-exchanged water, sucked and dried on a filtration filter, and dried at room temperature under reduced pressure until the water content was less than 1.0% by weight, whereby an amide bond was formed on the main skeleton. An orthoquinonediazide compound (B-6: comparative photoreactive compound) was obtained.

Example 1
In a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 10 g of the polymer (P-1) obtained in Synthesis Example 1 and 15 g of γ-butyrolactone were stirred and mixed, and further dissolved in Synthesis Example 5. 2.0 g of the photoreactive compound (B-1) obtained in 1 above was added, and dissolved by stirring overnight at room temperature, and then filtered to obtain a photosensitive resin composition solution. This solution was spin-coated on a 5-inch silicon wafer and then dried to form a 5.0 ± 1.0 μm coating film. Thereafter, this coating film was subjected to pattern masking using an I-line stepper, and the exposure amount was set to 200 to 1000 mJ / cm ² and exposed. This was left in a light-shielding box for 1 hour, and then developed with a paddle using a 2.38% tetramethylammonium hydroxide aqueous solution. As a result, the resolution reached 10 μm (minimum line width) at an exposure amount of 780 mJ / cm ² , and a good relief pattern was obtained.

The photosensitive resin composition solution was spin-coated on a 5-inch silicon wafer and then dried to form a 15.0 ± 1.0 μm coating film. Thereafter, a pattern mask was used using a contact aligner, and exposure was performed at an exposure amount of 1000 mJ / cm ² . This was left in a light-shielding box for 1 hour, and then paddle-developed using a 2.38% tetramethylammonium hydroxide aqueous solution to obtain a strip-shaped pattern of 10 mm × 80 mm. This wafer was baked at 300 ° C. for 1 hour in an oven purged with nitrogen to obtain a cured film. Using a hydrofluoric acid aqueous solution, the strip-shaped thin film was peeled from the silicon wafer and dried, and then the elongation was measured using an autograph. As a result, the elongation was 26%.

(Example 2)
As a blend, 10 g of the polymer (P-2) obtained in Synthesis Example 2, 15 g of γ-butyrolactone, and 1.0 g of the photoreactive compound (B-1) obtained in Synthesis Example 5 were used. Other than that, a relief pattern was formed in the same manner as in Example 1. As a result, the resolution of the obtained pattern reached 10 μm (minimum line width) at an exposure amount of 480 mJ / cm ² , and a good relief pattern was obtained. Moreover, the elongation rate of the strip-shaped thin film obtained by processing similar to Example 1 was measured using the autograph. As a result, the elongation was 34%.

(Example 3)
As a blend, 10 g of the polymer (P-2) obtained in Synthesis Example 2, 15 g of γ-butyrolactone, and 1.0 g of the photoreactive compound (B-2) obtained in Synthesis Example 6 were used. Other than that, a relief pattern was formed in the same manner as in Example 1. As a result, the resolution of the obtained pattern reached 10 μm (minimum line width) at an exposure amount of 550 mJ / cm ² , and a good relief pattern was obtained. Moreover, the elongation rate of the strip-shaped thin film obtained by processing similar to Example 1 was measured using the autograph. As a result, the elongation was 32%.

Example 4
As a blend, 10 g of the polymer (P-2) obtained in Synthesis Example 2, 15 g of γ-butyrolactone, and 1.0 g of the photoreactive compound (B-4) obtained in Synthesis Example 8 were used. Other than that, a relief pattern was formed in the same manner as in Example 1. As a result, the resolution of the obtained pattern reached 10 μm (minimum line width) at an exposure amount of 440 mJ / cm ² , and a good relief pattern was obtained. Moreover, the elongation rate of the strip-shaped thin film obtained by processing similar to Example 1 was measured using the autograph. As a result, the elongation was 38%.

(Example 5)
As a blend, 10 g of the polymer (P-2) obtained in Synthesis Example 2, 15 g of γ-butyrolactone, 0.75 g of the photoreactive compound (B-1) obtained in Synthesis Example 5, and the synthesis A relief pattern was formed in the same manner as in Example 1 except that 0.25 g of the photoreactive compound (B-6) obtained in Example 10 was used. As a result, the resolution of the obtained pattern reached 10 μm (minimum line width) at an exposure amount of 510 mJ / cm ² , and a good relief pattern was obtained. Moreover, the elongation rate of the strip-shaped thin film obtained by processing similar to Example 1 was measured using the autograph. As a result, the elongation was 26%.

(Example 6)
As a blend, 10 g of the polymer (P-3) obtained in the synthesis example 3, 15 g of γ-butyrolactone, and 1.0 g of the photoreactive compound (B-1) obtained in the synthesis example 5, Otherwise, a relief pattern was formed in the same manner as in Example 1. As a result, the resolution of the obtained pattern reached 10 μm (minimum line width) at an exposure amount of 500 mJ / cm ² , and a good relief pattern was obtained. Moreover, the elongation rate of the strip-shaped thin film obtained by processing similar to Example 1 was measured using the autograph. As a result, the elongation was 30%.

(Example 7)
As a blend, using 10 g of the polymer (P-3) obtained in Synthesis Example 3, 15 g of γ-butyrolactone, and 1.0 g of the photoreactive compound (B-3) obtained in Synthesis Example 7, Otherwise, a relief pattern was formed in the same manner as in Example 1. As a result, the resolution of the obtained pattern reached 10 μm (minimum line width) at an exposure amount of 480 mJ / cm ² , and a good relief pattern was obtained. Moreover, the elongation rate of the strip-shaped thin film obtained by processing similar to Example 1 was measured using the autograph. As a result, the elongation was 24%.

(Example 8)
As a blend, 10 g of the polymer (P-3) obtained in Synthesis Example 3, 15 g of γ-butyrolactone, 0.50 g of the photoreactive compound (B-2) obtained in Synthesis Example 6, and the above A relief pattern was formed in the same manner as in Example 1 except that 0.50 g of the comparative photoreactive compound (B-6) obtained in Synthesis Example 9 was used. As a result, the resolution of the obtained pattern reached 10 μm (minimum line width) at an exposure amount of 540 mJ / cm ² , and a good relief pattern was obtained. Moreover, the elongation rate of the strip-shaped thin film obtained by processing similar to Example 1 was measured using the autograph. As a result, the elongation was 29%.

Example 9
As a blend, 10 g of the polymer (P-4) obtained in Synthesis Example 4, 15 g of γ-butyrolactone, and 1.0 g of the photoreactive compound (B-1) obtained in Synthesis Example 5 were used. Other than that, a relief pattern was formed in the same manner as in Example 1. As a result, the resolution of the obtained pattern reached 15 μm (minimum line width) at an exposure amount of 600 mJ / cm ² , and a good relief pattern was obtained. Moreover, the elongation rate of the strip-shaped thin film obtained by processing similar to Example 1 was measured using the autograph. As a result, the elongation was 27%.

(Example 10)
As a blend, 10 g of the polymer (P-4) obtained in Synthesis Example 4, 15 g of γ-butyrolactone, and 1.0 g of the photoreactive compound (B-2) obtained in Synthesis Example 6 were used. Other than that, a relief pattern was formed in the same manner as in Example 1. As a result, the resolution of the obtained pattern reached 15 μm (minimum line width) at an exposure amount of 600 mJ / cm ² , and a good relief pattern was obtained. Moreover, the elongation rate of the strip-shaped thin film obtained by processing similar to Example 1 was measured using the autograph. As a result, the elongation was 31%.

(Comparative Example 1)
As a blend, 10 g of the polymer (P-1) obtained in Synthesis Example 1, 15 g of γ-butyrolactone, and 2.0 g of the comparative photoreactive compound (B-5) obtained in Synthesis Example 9 were used. Otherwise, a relief pattern was formed in the same manner as in Example 1. As a result, the resolution of the obtained pattern reached 10 μm (minimum line width) at an exposure amount of 800 mJ / cm ² , and a good relief pattern was obtained. However, when the elongation percentage of the strip-shaped thin film obtained by the same treatment as in Example 1 was measured using an autograph, the elongation percentage was 10%.

(Comparative Example 2)
As a blend, 10 g of the polymer (P-2) obtained in Synthesis Example 2, 15 g of γ-butyrolactone, and 1.0 g of the comparative photoreactive compound (B-6) obtained in Synthesis Example 10 were used. Otherwise, a relief pattern was formed in the same manner as in Example 1. As a result, the resolution of the obtained pattern reached 10 μm (minimum line width) at an exposure amount of 570 mJ / cm ² , and a good relief pattern was obtained. However, when the elongation rate of the strip-shaped thin film obtained by the same treatment as in Example 1 was measured using an autograph, the elongation rate was 15%.

(Comparative Example 3)
As a blend, 10 g of the polymer (P-3) obtained in Synthesis Example 3, 15 g of γ-butyrolactone, and 1.0 g of the comparative photoreactive compound (B-5) obtained in Synthesis Example 9 were used. Otherwise, a relief pattern was formed in the same manner as in Example 1. As a result, the resolution of the obtained pattern reached 10 μm (minimum line width) at an exposure amount of 550 mJ / cm ² , and a good relief pattern was obtained. However, when the elongation percentage of the strip-shaped thin film obtained by the same treatment as in Example 1 was measured using an autograph, the elongation percentage was 8%.

(Comparative Example 4)
As a blend, 10 g of the polymer (P-3) obtained in Synthesis Example 3, 15 g of γ-butyrolactone, and 1.0 g of the comparative photoreactive compound (B-6) obtained in Synthesis Example 10 were used. Otherwise, a relief pattern was formed in the same manner as in Example 1. As a result, the resolution of the obtained pattern reached 10 μm (minimum line width) at an exposure amount of 570 mJ / cm ² , and a good relief pattern was obtained. However, when the elongation percentage of the strip-shaped thin film obtained by the same treatment as in Example 1 was measured using an autograph, the elongation percentage was 7%.

(Comparative Example 5)
As a blend, 10 g of the polymer (P-4) obtained in Synthesis Example 4, 15 g of γ-butyrolactone, and 1.0 g of the comparative photoreactive compound (B-6) obtained in Synthesis Example 10 were used. Otherwise, a relief pattern was formed in the same manner as in Example 1. As a result, the resolution of the obtained pattern reached 15 μm (minimum line width) at an exposure amount of 650 mJ / cm ² , and a good relief pattern was obtained. However, when the elongation percentage of the strip-shaped thin film obtained by the same treatment as in Example 1 was measured using an autograph, the elongation percentage was 12%.

  The combination structure of the photosensitive polymer (polymer component) and the photosensitive agent (photoreactive compound) in the above examples and comparative examples, and the photosensitive characteristics of the obtained photosensitive resin composition, the measurement results of elongation, Table 1 shows.

  As described above, the photosensitive resin composition of the present invention has an unprecedented good cured resin characteristic that has good photosensitive characteristics and excellent elongation characteristics. Further, by using this photosensitive resin composition, the relief pattern forming method of the present invention forms a pattern layer having excellent elongation characteristics by inexpensive alkaline aqueous solution development instead of conventional organic solvent development. Can do. By these photosensitive resin composition and relief pattern forming method, the semiconductor device of the present invention can have a pattern film such as a buffer coat film and an interlayer insulating film having a good pattern shape and excellent elongation characteristics, and is high. Reliability can be demonstrated.

Claims (6)

A polymer component (A) comprising a heat-resistant polymer having an acidic functional group or a derivative substituent thereof or a precursor thereof; and
The following general formula (3):

Wherein R ₄ and R ₅ are divalent organic groups, R ₆ is hydrogen or a monovalent organic group, X ₂ is an l + m + n valent organic group, l + m is 1 or more, and l + m + n 1 to 10, l is 0 to 6, m is an integer of 0 to 6, and n is an integer of 0 to 6. A is an oxygen atom or a nitrogen atom, and D is a functional group that generates an acid by light. And a photoreactive compound (B) having an amide bond in the main skeleton and generating an acid by a photoreaction represented by:
A photosensitive resin composition comprising a solvent (C).   The photosensitive resin composition according to claim 1, wherein the photoreactive compound (B) is a compound that generates a carboxyl group by a photoreaction.   The photosensitive resin composition according to claim 1 or 2, wherein the acidic functional group in the polymer constituting the polymer component (A) is a carboxyl group or a phenolic hydroxyl group.   The said polymer component (A) is a polyimide precursor, a polybenzoxazole precursor, those copolymers, or those mixtures, The photosensitive property of any one of Claim 1 to 3 characterized by the above-mentioned. Resin composition.   The process of apply | coating the photosensitive resin composition of any one of Claims 1-4 on a support substrate, and drying, the process of exposing the photosensitive resin film after the said drying, and the photosensitive property after the said exposure The pattern formation method characterized by including the process of developing a resin film using aqueous alkali solution, and the process of heat-processing the pattern obtained by the said image development.   An electronic device comprising a layer having a pattern obtained by the manufacturing method according to claim 5.