JP4245077B1 - Photosensitive resin composition, cured film, protective film, insulating film, and semiconductor device using the same. - Google Patents

Abstract

A photosensitive resin composition having an excellent appearance after coating is provided.
A photosensitive resin composition includes an alkali-soluble resin (A), a photosensitive agent (B), one or more compounds (C) selected from unsaturated alcohols having a specific structure, and a solvent (D). Is included. Moreover, the cured film is comprised with the hardened | cured material of the said photosensitive resin composition. Further, the protective film and the insulating film are composed of the above-described cured film. Further, the content of the compound (C) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin, and the solvent (D) is γ-butyrolactone (D1).
[Selection figure] None

Description

  The present invention relates to a photosensitive resin composition, a cured film, a protective film, an insulating film, and a semiconductor device using the same.

Conventionally, a polyimide resin having excellent heat resistance and excellent electrical characteristics and mechanical characteristics has been used for a surface protective film and an interlayer insulating film which are semiconductor devices. Recently, however, polybenzoxazole resin, which is considered to have good moisture resistance reliability since there is no carbonyl group derived from a highly polar imide ring, has begun to be used. By providing photosensitivity to the resin itself, a relief pattern forming process A photosensitive resin composition that can simplify a part of the above has been developed.
At present, a positive photosensitive resin composition composed of a polybenzoxazole precursor that can be developed with an alkaline aqueous solution and a diazoquinone compound that is a photosensitizer has been developed by further improvement in terms of safety ( Patent Document 1). Here, the production of the relief pattern of the positive photosensitive resin composition will be described from the development mechanism. By exposing (exposing) actinic radiation to the coating film on the wafer from above the mask with an exposure device such as a stepper, the exposed portion (hereinafter exposed portion) and the unexposed portion (hereinafter unexposed portion) I can do it. The diazoquinone compound present in the unexposed area is insoluble in the alkaline aqueous solution, and further has resistance to the alkaline aqueous solution by interacting with the resin. On the other hand, the diazoquinone compound present in the exposed area undergoes a chemical change by the action of actinic radiation, becomes soluble in an alkaline aqueous solution, and promotes dissolution of the resin. By utilizing this difference in solubility between the exposed portion and the unexposed portion to dissolve and remove the exposed portion, a relief pattern of only the unexposed portion can be produced.

  Since these positive photosensitive resin compositions are wafer coating materials, applicability is an important performance. When this positive photosensitive resin composition is applied to a wafer, an uneven pattern may be seen on the coating film, and foundries sold in a wafer state may be regarded as a problem for cosmetic reasons. . In addition, in order to prevent contamination of the semiconductor manufacturing apparatus, the edge portion of the wafer is usually subjected to EBR (Edge Bead Remote) that removes the resin at the edge portion with a solvent or the like, but may not be removed depending on the device manufacturer. At that time, unevenness may become prominent at the wafer edge portion.

JP-A-56-27140

  The object of the present invention has been made in view of the above circumstances, and the object is to provide a photosensitive resin composition, a cured film, a protective film, an insulating film, and a semiconductor using the same, which are excellent in appearance after coating. To provide an apparatus.

Such an object is achieved by the present invention described in the following [1] to [11].
[1] A polyamide-based resin having a repeating unit represented by the general formula (2 ) which is an alkali-soluble resin (A) , a diazoquinone compound which is a photosensitive agent (B) , and a compound represented by the general formula (1) One or more types of compounds (C) and a solvent (D) are contained, The photosensitive resin composition characterized by the above-mentioned.

[2] The content of the compound (C) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the polyamide-based resin having the repeating unit represented by the general formula (2) . Photosensitive resin composition.
[3] The photosensitive resin composition according to [1] or [2], wherein the solvent (D) is γ-butyrolactone (D1).
[4] The photosensitive resin composition according to [3], wherein a combined ratio (C / D1) of the compound (C) and the γ-butyrolactone (D1) is 0.01 to 0.5.
[ 5 ] Any of [1] to [4], wherein X of the polyamide-based resin having the repeating unit represented by the general formula (2) includes one or more selected from the group consisting of the following formula (3) the photosensitive resin composition according to any.

[ 6 ] Any one of [1] to [5], wherein Y of the polyamide-based resin having the repeating unit represented by the general formula (2) includes one or more selected from the group consisting of the following formula (4). the photosensitive resin composition according to any.

[ 7 ] A cured film comprising a cured product of the photosensitive resin composition according to any one of [1] to [ 6 ].
[ 8 ] A protective film comprising the cured film according to [ 7 ].
[ 9 ] An insulating film comprising the cured film according to [ 7 ].
[ 10 ] A semiconductor device comprising the cured film according to [ 7 ].
[ 11 ] A display device comprising the cured film according to [ 7 ].

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition excellent in the external appearance after application | coating, a cured film, a protective film, an insulating film, and a semiconductor device using the same can be obtained.

  Hereinafter, preferred embodiments of the photosensitive resin composition, the cured film, the protective film, the insulating film, and the semiconductor device of the present invention will be described in detail.

  The photosensitive resin composition of the present invention includes an alkali-soluble resin (A), a photosensitive agent (B), and one or more compounds selected from the compound (C) represented by the following general formula (1). Features.

  Moreover, the cured film of this invention is comprised by the hardened | cured material of the photosensitive resin composition as described above, It is characterized by the above-mentioned.

  In addition, the protective film and the insulating film of the present invention are configured by the cured film described above.

  In addition, a semiconductor device and a display device of the present invention have the cured film described above.

First, the photosensitive resin composition (particularly preferably, the positive photosensitive resin composition) will be described.
The photosensitive resin composition of this invention contains alkali-soluble resin (A).
Examples of the alkali-soluble resin include acrylic resins such as cresol-type novolak resins, hydroxystyrene resins, methacrylic acid resins, and methacrylic ester resins, cyclic olefin resins containing hydroxyl groups, carboxyl groups, and polyamide resins. . Among these, polyamide resins are preferred from the viewpoint of excellent heat resistance and good mechanical properties. Specifically, they have at least one of a polybenzoxazole structure and a polyimide structure, and have hydroxyl groups or carboxyl groups in the main chain or side chain. , A resin having an ether group or an ester group, a resin having a polybenzoxazole precursor structure, a resin having a polyimide precursor structure, a resin having a polyamic acid ester structure, and the like. As such a polyamide-type resin, the polyamide-type resin which has a repeating unit shown by following General formula (2) can be mentioned, for example.

In the polyamide resin represented by the general formula (2), O— R ₃ as a substituent of X
, O-R ₃ as a substituent of Y, COO- R ₃ represents a hydroxyl group, for the purpose of adjusting the solubility in an alkali aqueous solution of the carboxyl groups, protected by R ₃ is an organic group having 1 to 15 carbon atoms It is a group, and if necessary, a hydroxyl group and a carboxyl group may be protected. Examples of R ₃ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. It is done.

  The polyamide resin having the structure represented by the general formula (2) is, for example, a compound selected from diamine containing X or bis (aminophenol), 2,4-diaminophenol, and the like, and tetracarboxylic dianhydride containing Y , Trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, and a compound selected from dicarboxylic acid derivatives and the like. In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.

  Examples of X of the polyamide-based resin represented by the general formula (2) include aromatic compounds such as a benzene ring and a naphthalene ring, heterocyclic compounds such as bisphenols, pyrroles and furans, and siloxane compounds. More specifically, what is shown by following formula (5) can be mentioned preferably. By using these, good patterning properties can be obtained. These may be used alone or in combination of two or more.

As shown in the general formula (2), 0 to 8 R ₁ are bonded to X (in the formula (5), R ₁
Is omitted).

  Preferred examples of the formula (5) include those represented by the following formula (6; 6-1 to 6-18), which are particularly excellent in heat resistance.

（式中、＊はＮＨ基に結合することを示す。式中Ｄは、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、又は単結合である。Ｒ_８は、アルキル基、アルコキシ基、アシルオキシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。Ｒ_１６は、アルキル基、アルキルエステル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。ｓ＝１〜３、ｔ＝０〜４の整数である。）

(In the formula, * indicates bonding to an NH group. In the formula, D represents —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —O—, —S—, And —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or a single bond, R ₈ is any one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, R ₁₆ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and may be the same or different, s = 1-3, t = 0 It is an integer of 4.)

  Further, among the formulas (6), those represented by the following formula (3) are particularly preferable. By using these, good mechanical properties can be obtained.

  In addition, Y of the polyamide-based resin represented by the general formula (2) is an organic group, and examples thereof include those similar to X. Examples thereof include aromatic compounds such as a benzene ring and a naphthalene ring, bisphenols, pyrroles, Examples thereof include heterocyclic compounds such as pyridines and furans, siloxane compounds, and the like, and more specifically, those represented by the following formula (7) can be preferably exemplified. By using these, good patterning properties can be obtained. These may be used alone or in combination of two or more.

As shown in the general formula (2), 0 to 8 R ₂ are bonded to Y (in the formula (7), R ₂
Is omitted).

As a preferable thing in Formula (7), what is shown by following formula (8; 8-1-21) and Formula (9) is mentioned. By using these, good heat resistance can be obtained.
As for the structure derived from tetracarboxylic dianhydride in the following formula (8), the position where both C═O groups are bonded to the meta position, and both the para positions are listed. A structure including each of the para positions may be used.

Further, among the formulas (8) and (9), those represented by the following formula (4) are particularly preferable. By using these, good mechanical properties can be obtained.

Further, the polyamide resin represented by the general formula (2) is an aliphatic group having a terminal amino group and at least one alkenyl group or alkynyl group, or a cyclic compound. It is preferred to cap as an amide with an acid anhydride containing a group. Thereby, preservability can be improved.
Examples of such a group derived from an acid anhydride containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group include formula (10) and formula (11). ) And the like. These may be used alone or in combination of two or more.
In the case of a group derived from an acid anhydride, it may be cyclized to have an imide structure.

  Among these, a group selected from the formula (12) is particularly preferable. Thereby, especially storability can be improved.

  The method is not limited to this method, and the terminal acid contained in the polyamide-based resin is converted into an amide using an amine derivative containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group. It can also be capped.

The photosensitive resin composition of this invention contains a photosensitive agent (B).
Examples of the photosensitive agent (B) include esters of phenol compounds and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. . Specific examples include ester compounds represented by formula (13) to formula (16). These may be used alone or in combination of two or more.

  In the formula, Q is selected from a hydrogen atom, formula (17), and formula (18). Here, at least one of Q of each compound is the formula (17) or the formula (18).

  Although content of the said photosensitizer (B) is not specifically limited, 1-50 weight part is preferable with respect to 100 weight part of alkali-soluble resin (A), and 10-40 weight part is more preferable. When the content is within the above range, the sensitivity is particularly excellent.

  The photosensitive resin composition of this invention contains 1 or more types of compounds chosen from the compound (C) shown by following General formula (1). Thereby, it is excellent in the external appearance after apply | coating the photosensitive resin composition.

  Thus, the reason why the appearance after application of the photosensitive resin composition is excellent by using the compound (C) is not clear, but the dynamic viscosity and volatility of the composition with respect to the substrate at the time of application are affected. It is expected that

  Although content of the said compound (C) is not specifically limited, It is preferable that it is 0.1-50 weight part with respect to 100 weight part of alkali-soluble resin (A), Especially 0.1-0.1 weight part. 30 parts by weight is preferred. If the content is within the above range, a photosensitive resin composition having a particularly excellent appearance after coating can be obtained.

The photosensitive resin composition of the present invention contains a solvent (D). Thereby, a photosensitive resin composition can be made into the state of a varnish, and, thereby, applicability | paintability can be improved.
Examples of the solvent (D) include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, and dipropylene glycol. Monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl- 3-methoxypropionate etc. are mentioned, You may use individually or in mixture. Among these, γ-butyrolactone (D1) is preferable. Thereby, the external appearance after application can be further improved.

  Although content of the said solvent is not specifically limited, 100-400 weight part is preferable with respect to 100 weight part of said alkali-soluble resin, and 120-300 weight part is especially preferable. When the content is within the above range, a practical viscosity capable of coating can be obtained even for various film thicknesses.

  When γ-butyrolactone (D1) is used as the solvent (D), the combined ratio (C / D1) of the compound (C) and γ-butyrolactone (D1) is not particularly limited, but 0.01 ~ 0.5 is preferred. When the combined use ratio is less than the lower limit, the effect of improving applicability may be reduced, and when the upper limit is exceeded, the storage stability of the resin composition may be reduced. Furthermore, the combination ratio (C / D1), particularly 0.05 to 0.2 is preferable. When the combined use ratio is within the above range, in addition to the above-described effects, storability can be improved when a photosensitizer or additive having poor solubility is used together.

  Furthermore, the photosensitive resin composition of the present invention can be used in combination with a compound having a phenolic hydroxyl group for the purpose of improving the scum at the time of patterning with high sensitivity.

  As a specific structure, one represented by the formula (19) can be given. These may be used alone or in combination of two or more.

  Although content of the compound which has the said phenolic hydroxyl group is not specifically limited, 1-30 weight part is preferable with respect to 100 weight part of alkali-soluble resin (A), More preferably, it is 1-20 weight part. When the content is within the above range, the occurrence of scum is further suppressed during development, and the sensitivity is improved by promoting the solubility of the exposed area.

  The photosensitive resin composition may contain an additive such as an acrylic, silicone, fluorine or vinyl leveling agent or a silane coupling agent other than the compound (C), if necessary.

  Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacrylate. Loxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) ) -3-Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimetho Sisilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, 3-isocyanate Examples thereof include, but are not limited to, propyltriethoxysilane, and a silane coupling agent obtained by reacting a silicon compound having an amino group with an acid dianhydride or acid anhydride.

  The silicon compound having an amino group is not particularly limited, and examples thereof include 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropylmethyl. Examples include dimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, and 3-aminopropyltriethoxysilane.

  The acid anhydride is not particularly limited, and examples thereof include maleic anhydride, chloromaleic anhydride, cyanomaleic anhydride, cytoconic acid, and phthalic anhydride. Moreover, in using, it can be used individually or in combination of 2 or more types.

  The acid dianhydride is not particularly limited. For example, pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3 ′, 4,4 '-Benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2 , 5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1, 2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5 6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloro Naphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5, 8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyl Tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyltetracarboxylic dianhydride, 3,3 ″, 4,4 ″ -p-terphenyltetracarboxylic dianhydride, 2,2 ″ , 3,3 "-p-terphenyltetracarboxylic dianhydride, 2,3 3 ", 4" -p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) ) -Propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride Bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1 -Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-tetracarboxylic acid bis Water, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic acid Dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,9,10- Tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5 -Tetracarboxylic dianhydride, 4,4'-hexafluoroisopropylidene diphthalic dianhydride, etc. are mentioned. Moreover, in using, it can be used individually or in combination of 2 or more types.

  As a silane coupling agent obtained by reacting the silicon compound having an amino group with an acid dianhydride or an acid anhydride, the silicon wafer after preserving and developing the photosensitive resin composition or after heat treatment Bis (3,4-dicarboxyphenyl) ether dianhydride and 3-aminopropyltriethoxysilane, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, which have good adhesion to substrates such as And a combination of 3-aminopropyltriethoxysilane, bis (3,4-dicarboxyphenyl) sulfone dianhydride and 3-aminopropyltriethoxysilane, maleic anhydride and 3-aminopropyltriethoxysilane.

  In the method of using the photosensitive resin composition of the present invention, first, the composition is applied to a suitable support (substrate), for example, a silicon wafer, a ceramic substrate, an aluminum substrate or the like. When applied on a semiconductor element, the applied amount is applied so that the final film thickness after curing is 0.1 to 30 μm. If the film thickness is below the lower limit value, it will be difficult to fully function as a protective surface film of the semiconductor element. If the film thickness exceeds the upper limit value, it will be difficult to obtain a fine processing pattern. Takes a long time to reduce throughput. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Next, after prebaking at 60 to 130 ° C. to dry the coating film, actinic radiation is applied to the desired pattern shape. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable.

  Next, a relief pattern is obtained by dissolving and removing the irradiated portion with a developer. Developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and di-n. Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution of an alkali such as a salt and an aqueous solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added can be preferably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.

Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinse liquid. Next, heat treatment is performed to form an oxazole ring, an imide ring, or an oxazole ring and an imide ring, thereby obtaining a final pattern rich in heat resistance.
The heat treatment temperature is preferably 180 ° C to 380 ° C, more preferably 200 ° C to 350 ° C. The heat treatment performed here is the heat treatment step described above.

  Next, the cured film of the present invention will be described. The cured film, which is a cured product of the photosensitive resin composition, is used not only for semiconductor devices such as semiconductor elements, but also for display device devices such as TFT-type liquid crystals and organic EL, interlayer insulation films for multilayer circuits, and flexible copper-clad plates. It is also useful as a cover coat, solder resist film or liquid crystal alignment film.

Examples of semiconductor device applications include a passivation film formed by forming a cured film of the above-described photosensitive resin composition on a semiconductor element, and a buffer formed by forming a cured film of the above-described photosensitive resin composition on the passivation film. Protective film such as a coating film, an insulating film such as an interlayer insulating film formed by forming a cured film of the above-mentioned positive photosensitive resin composition on a circuit formed on a semiconductor element, and an α-ray blocking film , Flattening films, protrusions (resin posts), partition walls, and the like.
In addition, since the wafer having these cured films is excellent in the coating property around the wafer, the yield of the semiconductor device can be improved.

Examples of display device applications include a protective film formed by forming a cured film of the above-described photosensitive resin composition on a display element, an insulating film or a planarizing film for TFT elements and color filters, MVA type liquid crystal, etc. Examples thereof include protrusions for display devices, partition walls for organic EL element cathodes, and the like. The use method is based on forming the photosensitive resin composition layer patterned on the substrate on which the display element and the color filter are formed according to the semiconductor device application by the above method. High transparency is required for display device applications, especially for insulating films and flattening films. By introducing a post-exposure step before curing of the photosensitive resin composition layer, excellent transparency is achieved. A resin layer can be obtained, which is more preferable in practical use.
In addition, since the display substrate having these cured films is excellent in applicability around the substrate, the yield of the display device can be improved.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited to this.
Example 1
[Synthesis of Alkali-soluble Resin (A-1)]
443.21 g of dicarboxylic acid derivative (active ester) obtained by reacting 0.900 mol of diphenyl ether-4,4′-dicarboxylic acid with 1.800 mol of 1-hydroxy-1,2,3-benzotriazole 900 mol) and 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 366.26 g (1.000 mol) equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube Into a four-necked separable flask, 3200 g of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath.
Next, 32.8 g (0.200 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 100 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction. After the reaction mixture is filtered, the reaction mixture is put into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate is collected by filtration, washed thoroughly with water, dried under vacuum, and the desired alkali-soluble resin. (A-1) was obtained.

[Synthesis of photosensitive diazoquinone compound]
A thermometer containing 15.82 g (0.025 mol) of 2,2-bis [4,4-bis (4-hydroxy-3-methylphenyl) cyclohexyl] -propane and 8.60 g (0.085 mol) of triethylamine. Into a four-necked separable flask equipped with a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 135 g of tetrahydrofuran was added and dissolved. After cooling this reaction solution to 10 ° C. or lower, 22.84 g (0.085 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride was gradually added dropwise with 100 g of tetrahydrofuran so as not to exceed 10 ° C. . Thereafter, the mixture was stirred at 10 ° C. or lower for 5 minutes and then stirred at room temperature for 5 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the formula (B-1 The photosensitive diazoquinone compound shown by this was obtained.

[Preparation of positive photosensitive resin composition]
10. 100.00 g of the synthesized alkali-soluble resin represented by the formula (A-1), 15.00 g of a photosensitive diazoquinone compound having the structure of the formula (B-1), and a compound having the structure of the following formula (C-1) 00 g was dissolved in 150.00 g of γ-butyrolactone, and then filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm to obtain a positive photosensitive resin composition.

[Evaluation of coating unevenness]
The positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then prebaked on a hot plate at 120 ° C. for 4 minutes to obtain a coating film having a thickness of about 7.0 μm.
Next, when a clean oven was next irradiated with an interference fringe inspection lamp (manufactured by Funatech, model FNA-35), the periphery of the wafer was observed, and the appearance was good with no unevenness.

[Evaluation of applicability]
The positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then prebaked on a hot plate at 120 ° C. for 4 minutes to obtain a coating film having a thickness of about 7.0 μm. As a result of measuring this coating film with a light interference type film thickness measuring device VM-8000J (manufactured by Dainippon Screen Mfg. Co., Ltd.) at a pitch of 10 mm in the X axis direction, the average film thickness was 148,784 mm. Met. The film thickness range (maximum value-minimum value) at this time was 1,552 mm and the standard deviation was 496 mm, and there was no problem with the coating film of the entire film.

[Developability evaluation]
This positive photosensitive resin composition was applied to an 8-inch silicon wafer using a spin coater and then prebaked at 120 ° C. for 4 minutes on a hot plate to obtain a coating film having a thickness of about 7 μm. Through the resulting coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a left pattern and a blank pattern having a width of 0.88 to 50 μm are drawn), Nikon Corporation i-line stepper NSR- Using 4425i, the exposure amount was increased in steps of 100 mJ / cm ² to 10 mJ / cm ² to perform exposure. Next, the development time was adjusted in a 2.38% tetramethylammonium hydroxide aqueous solution so that the film slip during development was 0.5 μm, and the exposed portion was dissolved and removed, followed by rinsing with pure water for 30 seconds. When the pattern was observed, it was confirmed that the pattern was well opened with no scum at an exposure amount of 400 mJ / cm ² .

[Tensile elongation evaluation]
The positive photosensitive resin composition was applied to an 8-inch silicon wafer so that the thickness after curing was about 10 μm, and in a nitrogen atmosphere with a Koyo Thermo System (clean oven (CLH-21CDL) manufactured by Curing was performed in a nitrogen atmosphere at 150/30 minutes + 320 ° C./30 minutes to obtain a cured film.
The obtained cured film was immersed in 2% hydrogen fluoride water, and the cured film was peeled off from the silicon wafer. The obtained cured film was sufficiently washed with pure water and then dried in an oven at 60 ° C. for 5 hours. Then, the cured film was cut into a strip shape having a width of 10 mm to obtain a sample for a tensile test. Next, when the tensile elongation was measured with a tensile tester at a sample shape of 10 mm width × 120 mm length and a tensile speed of 5 mm / min, a good elongation of 36% was shown.
<< Example 2 >>
In place of C-1 used in Example 1, 15.00 g of the following formula (C-2) was used, and the formula (B-1) was increased to 18.00 g. A photosensitive resin composition was prepared and evaluated in the same manner.

Example 3
In place of C-1 used in Example 1, 8.00 g of the following formula (C-3) was used, and the formula (B-1) was reduced to 13.00 g. A photosensitive resin composition was prepared and evaluated in the same manner.

Example 4
[Synthesis of alkali-soluble resin (A-2)]
In the synthesis of the alkali-soluble resin of Example 1, instead of 366.26 g (1.000 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3- (Amino-4-hydroxyphenyl) propane (258.33 g (1.000 mol)) was used, and the alkali-soluble resin (A-2) was synthesized in the same manner as in Example 1 except that Similarly, after producing a positive photosensitive resin composition, the same evaluation was performed.

Example 5
[Synthesis of alkali-soluble resin (A-3)]
17.06 g (0.055 mol) of 4,4′-oxydiphthalic anhydride, 5.07 g (0.110 mol) of ethanol, and 10.92 g (0.138 mol) of pyridine were added to a thermometer, a stirrer, and a raw material inlet. Into a four-necked separable flask equipped with a dry nitrogen gas inlet tube, 150 g of N-methyl-2-pyrrolidone was added and dissolved. To this reaction solution, 14.86 g (0.110 mol) of 1-hydroxy-1,2,3-benzotriazole was added dropwise together with 30 g of N-methyl-2-pyrrolidone, and then 22.70 g (0.110 mol) of dicyclohexylcarbodiimide. Was added dropwise together with 50 g of N-methyl-2-pyrrolidone and allowed to react overnight at room temperature. Thereafter, a dicarboxylic acid derivative (active ester) 27 obtained by reacting 1.0 mol of diphenyl ether-4,4′-dicarboxylic acid and 2 mol of 1-hydroxy-1,2,3-benzotriazole with this reaction solution. 0.09 g (0.055 mol) and 44.68 g (0.122 mol) hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane with 70 g N-methyl-2-pyrrolidone, Stir at room temperature for 2 hours. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath.

  Next, 4.80 g (0.049 mol) of maleic anhydride dissolved in 40 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction. After the reaction mixture is filtered, the reaction mixture is put into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate is collected by filtration, washed thoroughly with water, dried under vacuum, and the desired alkali-soluble resin. (A-3) was obtained.

[Synthesis of photosensitive diazoquinone compound]
1,1,1-tris (4-hydroxyphenyl) ethane (manufactured by Honshu Chemical Co., Ltd.) 18.38 g (0.060 mol) and triethylamine 13.66 g (0.135 mol) were thermometer, stirrer, Into a four-necked separable flask equipped with a raw material inlet and a dry nitrogen gas inlet tube, 135 g of tetrahydrofuran was added and dissolved. After cooling the reaction solution to 10 ° C. or lower, 36.27 g (0.135 mol) of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride was gradually added dropwise with 100 g of tetrahydrofuran so as not to exceed 10 ° C. . Thereafter, the mixture was stirred at 10 ° C. or lower for 5 minutes and then stirred at room temperature for 5 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum to obtain the formula (B-2 The photosensitive diazoquinone compound shown by this was obtained.

<Preparation of positive photosensitive resin composition>
100.00 g of the alkali-soluble resin represented by the formula (A-3) synthesized, 20.00 g of the photosensitive diazoquinone compound having the structure of the formula (B-2), and the compound 20 having the structure of the formula (C-1) 0.000 g was dissolved in 140.00 g of γ-butyrolactone, and then filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm to obtain a positive photosensitive resin composition.

[Evaluation of applicability]
The positive photosensitive resin composition was evaluated in the same manner as in Example 1.

≪Comparative example 1≫
In the production of the positive photosensitive resin composition of Example 1, 100.00 g of the synthesized alkali-soluble resin represented by the formula (A-1) and the photosensitive diazoquinone compound having the structure of the formula (B-1) 15. 00 g, dissolved in 160.00 g of γ-butyrolactone, and then filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm to obtain a positive photosensitive resin composition not containing the compound (C). Went.

The obtained results are shown in Table 1. Here, the numbers of alkali-soluble resins, photosensitizers, and compounds in Table 1 represent parts by weight.

  As shown in Table 1, in Examples 1, 2, 3, 4 and 5, it was found that the coating unevenness of the edge portion was not observed and the coating property was good. Furthermore, it was found that the sensitivity and tensile elongation were better than those of the comparative example.

The present invention is suitably used for a photosensitive resin composition having excellent appearance after coating, a cured film, a protective film, an insulating film, and a semiconductor device using the same.

Claims (11)

A polyamide-based resin having a repeating unit represented by the general formula (2 ) which is an alkali-soluble resin (A);
A diazoquinone compound which is a photosensitive agent (B);
One or more compounds (C) selected from the compounds represented by the general formula (1);
A photosensitive resin composition comprising a solvent (D).

2. The photosensitive resin according to claim 1, wherein the content of the compound (C) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the polyamide-based resin having the repeating unit represented by the general formula (2). Composition.   The photosensitive resin composition according to claim 1, wherein the solvent (D) is γ-butyrolactone (D1).   The photosensitive resin composition according to claim 3, wherein a combined ratio (C / D1) of the compound (C) and the γ-butyrolactone (D1) is 0.01 to 0.5. The photosensitive resin according to any one of claims 1 to 4, wherein X of the polyamide-based resin having a repeating unit represented by the general formula (2) contains at least one selected from the group consisting of the following formula (3). Resin composition.

The photosensitive resin according to any one of claims 1 to 5, wherein Y of the polyamide-based resin having a repeating unit represented by the general formula (2) includes at least one selected from the group consisting of the following formula (4). Resin composition.

It claims 1 to cured film, which is composed of a cured product of the photosensitive resin composition according to any one of 6. A protective film comprising the cured film according to claim 7 . An insulating film comprising the cured film according to claim 7 . A semiconductor device comprising the cured film according to claim 7 . A display device comprising the cured film according to claim 7 .