JP4899844B2 - Positive photosensitive resin composition, cured film, protective film, insulating film, and semiconductor device and display device using the same. - Google Patents

Description

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

Conventionally, polybenzoxazole resins and polyimide resins having excellent heat resistance and excellent electrical characteristics, mechanical characteristics, and the like have been used for protective films and insulating films of semiconductor elements.
However, circuit pattern formation on a semiconductor integrated circuit or printed circuit board is complicated and diverse, such as film formation of a resist material on the surface of a base material, exposure to a predetermined location, removal of unnecessary portions by etching, etc., and cleaning of the substrate surface. Since the pattern formation is performed through these processes, 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.

  As a material having such characteristics, Patent Document 1 proposes a positive photosensitive resin composition containing a polybenzoxazole precursor and a compound that generates an acid upon irradiation. Patent Document 2 proposes a positive photosensitive resin composition containing a polybenzoxazole precursor and a photosensitive diazonaphthoquinone compound. However, since the polybenzoxazole precursor used in the conventional positive photosensitive resin composition has high polarity and rigidity, it has poor solubility in general-purpose solvents. Therefore, since the polybenzoxazole precursor is dissolved in a solvent such as NMP (N-methyl-2pyrrolidone, hereinafter referred to as NMP), which is a nitrogen-containing solvent, scum (resin after development, hereinafter referred to as scum) is generated during development There was a problem that it would.

JP-A-2005-321466 JP-A-11-119426

  The present invention has been made in view of such circumstances, and an object of the present invention is to use a polybenzoxazole precursor excellent in solubility in a solvent not containing a nitrogen atom, and positively generating no scum during development. It is in providing a type photosensitive resin composition.

（式中、ａおよびｂはモル％を表し、ａ＝３０〜８０モル％、ｂ＝２０〜７０モル％であり、ａ＋ｂ＝１００モル％である。また、式中Ｒはアルキル基、アルコキシ基、ヒドロキシル基、アシルオキシ基、シクロアルキル基である。）
［３］活性ケイ素化合物（Ｃ）およびアルミニウム錯体（Ｄ）を含む、［１］または［２］に記載のポジ型感光性樹脂組成物。
［４］一分子中にオキセタニル基を２個以上含有する化合物（Ｅ）を含む、［１］ないし［３］のいずれかに記載のポジ型感光性樹脂組成物。
［５］一分子中にオキセタニル基を２個以上含有する化合物（Ｅ）の開環反応を促進する触媒（Ｆ）を含む、［４］に記載のポジ型感光性樹脂組成物。
［６］ポリベンゾオキサゾール前駆体（Ａ）の側鎖及び／又は少なくとも一方の末端が窒素含有環状化合物（Ｇ）を有するものである、［１］ないし［５］のいずれかに記載のポジ型感光性樹脂組成物。
［７］前記窒素含有化合物（Ｇ）は、テトラゾール基を含むものである［６］に記載のポジ型感光性樹脂組成物。
［８］前記テトラゾール基を有する窒素含有化合物は、式（２−１）および式（２−２）で示される化合物の少なくとも一方を含むものである［７］に記載のポジ型感光性樹脂組成物。

［９］［１］ないし［８］のいずれかに記載のポジ型感光性樹脂組成物の硬化物で構成されていることを特徴とする硬化膜。
［１０］［９］に記載の硬化膜で構成されていることを特徴とする保護膜。
［１１］［９］に記載の硬化膜で構成されていることを特徴とする絶縁膜
［１２］［９］に記載の硬化膜を有することを特徴とする半導体装置。
［１３］［９］に記載の硬化膜を有することを特徴とする表示体装置。 Such an object is achieved by the present invention described in the following [1] to [13].
[1] Polybenzoxazole precursor obtained by polymerizing bisaminophenol composed of 3,3-diamino-4,4-dihydroxydiphenyl ether and isophthalic acid or dicarboxylic acid composed of isophthalic acid and 4,4-dicarboxydiphenyl ether A positive photosensitive resin composition comprising a body (A) and a photosensitive agent (B).
[2] The positive photosensitive resin composition according to [1], wherein the polybenzoxazole precursor (A) is represented by the following general formula (1).

(In the formula, a and b represent mol%, a = 30 to 80 mol%, b = 20 to 70 mol%, and a + b = 100 mol%. In the formula, R represents an alkyl group or an alkoxy group. , Hydroxyl group, acyloxy group, and cycloalkyl group.)
[3] The positive photosensitive resin composition according to [1] or [2], comprising an active silicon compound (C) and an aluminum complex (D).
[4] The positive photosensitive resin composition according to any one of [1] to [3], including a compound (E) containing two or more oxetanyl groups in one molecule.
[5] The positive photosensitive resin composition according to [4], comprising a catalyst (F) that promotes a ring-opening reaction of the compound (E) containing two or more oxetanyl groups in one molecule.
[6] The positive type according to any one of [1] to [5], wherein the side chain and / or at least one end of the polybenzoxazole precursor (A) has a nitrogen-containing cyclic compound (G). Photosensitive resin composition.
[7] The positive photosensitive resin composition according to [6], wherein the nitrogen-containing compound (G) includes a tetrazole group.
[8] The positive photosensitive resin composition according to [7], wherein the nitrogen-containing compound having a tetrazole group includes at least one of the compounds represented by formula (2-1) and formula (2-2).

[9] A cured film comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [8].
[10] A protective film comprising the cured film according to [9].
[11] A semiconductor device comprising the cured film according to [9], which includes the cured film according to [9].
[13] A display device comprising the cured film according to [9].

  According to the present invention, since the polybenzoxazole precursor has appropriate solubility in a solvent that does not contain a nitrogen atom, a positive photosensitive resin composition in which scum hardly occurs during development is provided.

Hereinafter, preferred embodiments of the positive photosensitive resin composition, cured film, protective film, insulating film, semiconductor device, and display device of the present invention will be described in detail.
The present invention is a polybenzoxazole precursor obtained by reacting bisaminophenol and dicarboxylic acid, wherein the bisaminophenol is 3,3-diamino-4,4-dihydroxydiphenyl ether, A positive photosensitivity characterized in that the dicarboxylic acid contains isophthalic acid, or polybenzoxazole precursor (A) which is isophthalic acid and 4,4-dicarboxydiphenyl ether, and a diazoquinone compound (B) as a photosensitizer. The present invention relates to a conductive resin composition.
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.
Moreover, the protective film of this invention is comprised by the cured film as described above, It is characterized by the above-mentioned.
Moreover, the insulating film of the present invention is characterized by being composed of the cured film described above.

  The polybenzoxazole precursor (A) used in the present invention comprises 3,3-diamino-4,4-dihydroxydiphenyl ether as bisaminophenol and isophthalic acid or isophthalic acid and 4,4-dicarboxy as dicarboxylic acid. It is obtained by polymerizing diphenyl ether. By using isophthalic acid as the dicarboxylic acid, flexibility is developed in the polybenzoxazole precursor (A), so that the solubility in a solvent containing no nitrogen atom is improved. Further, by dissolving the polybenzoxazole precursor (A) in a solvent not containing a nitrogen atom, scum hardly occurs during development.

Usually, the positive photosensitive resin composition is developed with an etching solution for a portion irradiated with actinic radiation (exposed portion), and the resin is dissolved and removed to obtain a portion not exposed to actinic radiation (unexposed portion) as a relief pattern. I can do it. However, if NMP or the like, which is a nitrogen-containing solvent, is used when preparing a positive photosensitive resin composition, the developer is likely to penetrate due to the influence of the nitrogen-containing solvent remaining in the unexposed area during development. The resin in some unexposed areas is dissolved, which causes scum.
On the other hand, when a solvent that does not contain nitrogen atoms is used as the developer, the developer does not penetrate even if the solvent remains in the unexposed area during development, so that the resin in the unexposed area is less dissolved. Scum is unlikely to occur.
For the above reasons, the present invention provides a positive photosensitive resin composition in which scum hardly occurs during development.

  It is preferable that a which is a repeating unit of the polybenzoxazole precursor (A) represented by the general formula (1) of the present invention is 0 to 90 mol%, and the repeating unit b is 10 to 100 mol%. More preferably, the repeating unit a is 30 to 80 mol% and the repeating unit b is 20 to 70 mol%. When the molar ratio is within the above range, the obtained polybenzoxazole precursor (A) has appropriate solubility in a solvent containing no nitrogen atom, and the polybenzoxazole precursor (A) In the positive photosensitive resin composition containing scum, scum is unlikely to occur during development. When the repeating unit a using 4,4-dicarboxydiphenyl ether is 80 mol% or more, the flexibility of the polybenzoxazole precursor (A) is lowered and the solubility in a solvent containing no nitrogen atom is lowered. Therefore, since it is necessary to produce a positive photosensitive resin composition with NMP, which is a nitrogen-containing solvent, scum may be generated during development.

（式中、ａおよびｂはモル％を表し、ａ＝３０〜８０モル％、ｂ＝２０〜７０モル％であり、ａ＋ｂ＝１００モル％である。また、式中Ｒはアルキル基、アルコキシ基、ヒドロキシル基、アシルオキシ基、シクロアルキル基である。）

(In the formula, a and b represent mol%, a = 30 to 80 mol%, b = 20 to 70 mol%, and a + b = 100 mol%. In the formula, R represents an alkyl group or an alkoxy group. , Hydroxyl group, acyloxy group, and cycloalkyl group.)

  The polybenzoxazole precursor (A) of the present invention preferably has a weight average molecular weight (Mw) of 5,000 or more and 30,000 or less. The number average molecular weight (Mn) is preferably 5,000 or more and 20,000 or less. The molecular weight can be measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene. When the molecular weight is within the above range, moderate solubility in a solvent and good resolution can be obtained.

  The polybenzoxazole precursor (A) of the present invention comprises 3,3-diamino-4,4-dihydroxydiphenyl ether as bisaminophenol and isophthalic acid or isophthalic acid and 4,4-dicarboxydiphenyl ether as dicarboxylic acid. Can be obtained by an acid chloride method and a method such as condensation in the presence of a dehydration condensing agent such as polyphosphoric acid and dicyclohexylcarbodiimide.

The positive photosensitive resin composition of the present invention contains a photosensitive agent (B) together with the polybenzoxazole precursor (A).
Examples of the photosensitive agent (B) used in the present invention include diazoquinone compounds. This diazoquinone compound is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is a substance known from US Pat. Nos. 2,727,975, 2,797,213, and 3,669,658.
For example, the compound represented by the following formula is mentioned.

  In the formula, Q is selected from a hydrogen atom, formula (3), and formula (4). Here, at least one of Q of each compound is represented by formula (3) or formula (4).

  Among these, an ester of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid is particularly preferable. Specific examples thereof include the following formula. These may be used alone or in combination of two or more.

In the formula, Q is selected from a hydrogen atom, formula (3), and formula (4). Here, at least one of Q of each compound is represented by formula (3) or formula (4).
The preferable addition amount of the diazoquinone compound used in the present invention is 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the polybenzoxazole precursor (A). If the amount is less than 1 part by weight, a good pattern cannot be obtained, and if it exceeds 50 parts by weight, the sensitivity is greatly reduced.

The positive photosensitive resin composition of the present invention may contain an active silicon compound (C). Specifically, the active silicon compound means a compound in which a silanol group is generated by heating. A compound having a Si—O—C bond is preferable, and an alkoxysilane compound is more preferable. Among the alkoxysilane compounds, R′-Si— (O—R) ₃ (R
'Is an organic group, R is an alkyl group) An active silicon compound having a structure is preferably used because it has many reactive sites. Such compounds generate silanol groups by hydrolysis upon heating. It is preferable that the silanol group is not generated at the pre-baking temperature at the time of pattern processing, but is generated at the time of temperature increase in the curing process. In addition, the prebaking temperature generally used is 80 to 130 ° C.

Specific examples of active silicon compounds include diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldiacetoxysilane, diphenyldiphenoxysilane, triphenylmethoxysilane, triphenylethoxysilane, diphenylvinylethoxysilane, vinyltris. (Β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylme Dimethoxy silane, .gamma.-aminopropyltriethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, triethoxy (4- (trifluoromethyl) phenyl)
Alkoxysilane compounds such as silane and pentafluorophenyltrimethoxysilane, and active silicon compounds having the following structure can also be used. Of these, γ- (methacryloxypropyl) trimethoxysilane, an active silicon compound having the following structure, and the like are preferable. These may be used alone or in combination.

  It is preferable that the addition amount of an active silicon compound (C) is 0.1-50 weight part with respect to 100 weight part of polybenzoxazole precursor (A), More preferably, it is 1-30 weight part. If it exceeds the lower limit, it can react with the aluminum complex (D) to generate sufficient acid, and if it is lower than the upper limit, good preservability can be obtained.

The active silicon compound (C) is inactive to other resin compositions of the present invention at room temperature, but when heated to a certain temperature, a silanol group is generated, and the aluminum complex (D) and the resin composition It has the feature of reacting with. It is considered that a Bronsted acid is generated after the reaction and becomes a catalyst for promoting the cyclization of the alkali-soluble resin (A) of the present invention. The active silicon compound (C) and the aluminum complex (D) react to generate a Bronsted acid, and at the same time, an aluminum silicate compound is also generated. By making the active silicon compound and the aluminum complex (D) coexist in the resin composition, an acid is not generated at room temperature, but an acid is generated by heating, and a system that exhibits a cyclization promoting effect is constructed. .

  The positive photosensitive resin composition of the present invention may contain an aluminum complex (D). Specifically, an aluminum chelate complex is preferable. For example, aluminum ethyl acetoacetate diisopropylate, aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), alkyl acetoacetate aluminum diisopropylate, aluminum bisethyl Examples include acetoacetate monoacetylacetonate. Of these, aluminum tris (acetylacetonate) and aluminum ethylacetoacetate diisopropylate are preferable. These may be used alone or in combination.

  It is preferable that the addition amount of an aluminum complex (D) is 0.1-20 weight part with respect to 100 weight part of polybenzoxazole precursor (A), More preferably, it is 0.5-10 weight part. If it exceeds the lower limit, it acts more effectively on cyclization, and if it is less than the upper limit, problems such as precipitation during frozen storage are reduced.

  The positive photosensitive resin composition of the present invention may contain a compound (E) containing two or more oxetanyl groups in one molecule. Specifically, it is a compound having two or more 4-membered cyclic ether structures in one molecule, and capable of cationic ring-opening polymerization reaction or addition reaction with carboxylic acid, thiol and phenol. For example, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis [1-ethyl (3-oxetanyl)] methyl ether, 4,4′-bis [(3-ethyl-3- Oxetanyl) methoxymethyl] biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis (3-ethyl-3-oxetanyl) Methyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenoate, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, poly [ [3-[(3-Ethyl-3-io Setaniru) methoxy] propyl] silasesquioxane] derivatives, oxetanyl silicate, phenol novolak type oxetane, 1,3-bis [(3-ethyl oxetane over 3-yl) methoxy] Although benzene, and the like, without limitation. These may be used alone or in combination.

  The compound (E) containing two or more oxetanyl groups in one molecule is preferably used in an amount of 1 part by weight or more based on 100 parts by weight of the polybenzoxazole precursor (A). When used in an amount of 1 part by weight or more, sufficient reflow resistance and chemical resistance can be obtained.

The present invention may include a catalyst (F) that promotes ring opening of the compound (E) containing two or more oxetanyl groups in one molecule. Examples of the catalyst (F) for promoting the ring opening of the compound (E) containing two or more oxetanyl groups in one molecule include onium salts, halogenated organic compounds, quinonediazide compounds, and sulfone compounds. Specific examples of the onium salt include a diazonium salt having an unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group, aromatic group, heterocyclic group, ammonium salt, iodonium salt, Examples include sulfonium salts, phosphonium salts, arsonium salts, oxonium salts, and the like. Specific examples of the counter anion of these onium salts are not particularly limited as long as they are compounds capable of forming a counter anion, but boronic acid, arsenic acid, phosphoric acid, antimonic acid, sulfonic acid, carboxylic acid, or these Of the halides. The halogenated organic compound is not particularly limited as long as it is a halide of an organic compound, and various known compounds can be used. Specific examples include halogen-containing oxadiazol compounds, halogen-containing triazine compounds, halogen compounds. -Containing acetophenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds, halogen-containing thiazole compounds, halogen-containing oxazole compounds, halogen-containing triazole compounds, halogen-containing 2 -Various compounds such as pyrone compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, other halogen-containing heterocyclic compounds, and sulfenyl halide compounds. Further, as halogenated organic compounds, tris (pentafluorophenyl) borane, pentafluorophenylboronic acid, tris (2,3-dibromopropyl) phosphate, tris (2,3-dibromo-3-chloropropyl) phosphate , Chlorotetrabromoethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis (bromoethyl ether) -Ter) tetrabromobisphenol A, bis (chloroethyl ether) tetrachlorobisphenol A, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxy-3, 5-dibromophenyl) propyl Bread, 2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, dichlorodiphenyltrichloroethane, benzene hexachloride, pentachlorophenol, 2,4,6-trichlorophenyl-4-nitrophenyl ether -Ter, 2,4-dichlorophenyl-3'-methoxy-4'-nitrophenyl ether, 2,4-dichlorophenoxyacetic acid, 4,5,6,7-tetrachlorofusalide, 1,1-bis (4 -Chlorophenyl) ethanol, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethanol, ethyl-4,4-dichlorobenzylate, 2,4,5,4'- Tetrachlorodiphenyl sulfide, 2,4,5,4'-tetrachlorodiphenyl sulfone and the like are also included. Specific examples of the quinonediazide compound include 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,2 -Naphthoquinonediazide-6-sulfonic acid ester, 2,1-naphthoquinonediazide-4-sulfonic acid ester, 2,1-naphthoquinonediazide-5-sulfonic acid ester, 2,1-naphthoquinonediazide-6-sulfonic acid ester, etc. Sulfonic acid esters of quinonediazide derivatives, 1,2-benzoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2 -Naphthoquinonediazide-6 Sulfonic acid chloride, 2,1-naphthoquinonediazide-4-sulfonic acid chloride, 2,1-naphthoquinonediazide-5-sulfonic acid chloride, 2,1-naphthoquinonediazide-6-sulfonic acid chloride, sulfonic acid of other quinone azide derivatives Examples include o-quinone azide compounds such as chloride. It is also known that an acid is generated when an active silicon compound (C) and an aluminum complex (D) are used in combination. Among these, since an acid is generated in the cyclization step, the acid is not deactivated during alkali development, and the compound (E) containing two or more oxetanyl groups in one molecule only in the cyclization step. The combined use of the active silicon compound (C) and the aluminum complex (D), which acts as a catalyst for promoting ring opening, is preferred. These compounds acting as catalysts may be used alone or in combination of two or more.

  The polybenzoxazole precursor (A) used in the present invention has an organic group having an unsaturated group at one end, and a nitrogen-containing cyclic compound (G) at least one of a side chain and the other end. Also good.

Examples of the nitrogen-containing cyclic compound (G) include 5- (1-amino) methyl-1H-triazole, 3-amino-1H-pyrazole, 4-amino-1H-pyrazole, 5-amino-1H-pyrazole, 3- (1-amino) methyl-1H-pyrazole, 4- (1-amino) methyl-1H-pyrazole, 5- (1-amino) methyl-1H-pyrazole, 5-amino-1H-tetrazole, 5- (1- Amino) methyl-1H-tetrazole, 3- (1H-tetrazol-5-yl) aniline and the like. Among these, a tetrazole compound represented by the formula (1) is preferable. Thereby, especially adhesiveness with the metal wiring of copper and a copper alloy can be improved more.

As described above, the polybenzoxazole precursor (A) of the present invention is an organic group having an unsaturated group at one end, and a nitrogen-containing cyclic compound at least one of the side chain and the other end. The cured film has excellent mechanical properties and the like, and has excellent adhesion to metal wiring.
The reason for this is that when one end of the polybenzoxazole precursor (A) is an organic group having an unsaturated group, the resin reacts, so mechanical properties such as elongation are excellent, and the side chain and the other end This is because when at least one of the nitrogen-containing cyclic compounds has a nitrogen-containing cyclic compound, the nitrogen-containing cyclic compound reacts with the metal wiring of copper and copper alloy, so that the adhesion is excellent.
On the other hand, in the method of simply adding a nitrogen-containing compound, it is difficult to obtain sufficient adhesion because the alkali-soluble resin itself does not react with copper and copper alloy metal wiring. In other words, when a nitrogen-containing compound is added, in order to obtain sufficient adhesion with copper and copper alloy metal wiring, the reaction between the nitrogen-containing compound copper and copper alloy metal wiring, the nitrogen-containing compound and alkali-soluble Although both reactions with the resin must be sufficiently performed, the method of simply adding a nitrogen-containing compound usually results in an insufficient reaction between the nitrogen-containing compound and the alkali-soluble resin.

As described above, when the polybenzoxazole precursor (A) of the present invention is an organic group having an unsaturated group at one end and a nitrogen-containing cyclic compound at the other end (first form), When the terminal is an organic group having an unsaturated group and the side chain is a nitrogen-containing cyclic compound (second form, the other terminal is not particularly limited), one terminal is an organic group having an unsaturated group. Yes, and the other end is a nitrogen-containing cyclic compound and the side chain has a nitrogen-containing cyclic compound (third form).
Within the scope of the object of the present invention, a polybenzoxazole precursor (A) whose both ends are nitrogen-containing cyclic compounds, and a polybenzoxazole precursor (A) whose both ends are organic groups having an unsaturated group, It may be included.

  As the organic group having an unsaturated group for sealing the terminal of the polybenzoxazole (A), a derivative having an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group is used. It can be introduced as an acid derivative or an amine derivative at the terminal of the polybenzoxazole precursor (A). By introducing an organic group having an unsaturated group, the preservability of the positive photosensitive resin composition can be improved.

  Specifically, for example, after a first and second diamine and a carboxylic acid are reacted to obtain a polybenzoxazole precursor, the terminal amino group contained in the polybenzoxazole precursor is converted to an alkenyl group or It is preferable to seal as an amide using an acid anhydride or acid derivative containing an aliphatic group having at least one alkynyl group or a cyclic compound group.

Examples of the end-capping functional group include those represented by the following formula.

  Among these, a functional group represented by the following formula is particularly preferable. These may be used alone or in combination of two or more. Further, the present invention is not limited to this method, and the terminal acid contained in the polyamide resin is sealed as an amide using an amine derivative containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group. You can also.

The positive photosensitive resin composition in the present invention may contain additives such as a leveling agent and a silane coupling agent as necessary.

Solvents used in the positive photosensitive resin composition in the present invention include γ-butyrolactone, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, 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. May be used alone or in combination.
Among these, γ-butyrolactone, which is inexpensive and hardly generates scum during development, is preferably used.

  Next, the usage method of the positive photosensitive resin composition of this invention is demonstrated. First, the positive photosensitive resin composition is applied to an appropriate support such as a silicon wafer, a ceramic substrate, an aluminum substrate, or the like. In the case of a semiconductor device, the coating 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 actinic radiation 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, and a final pattern with high heat resistance is obtained.

  As for the development mechanism of this positive photosensitive resin composition, the diazoquinone compound acts with the polybenzoxazole resin in the unexposed area, exhibits a dissolution inhibiting effect, and becomes hardly soluble in an alkaline aqueous solution. On the other hand, in the exposed area, the diazoquinone compound undergoes a chemical change and becomes soluble in an alkaline aqueous solution. By utilizing the difference in solubility between the exposed portion and the unexposed portion to dissolve and remove the exposed portion, a coating film pattern of only the unexposed portion can be created.

  Next, the cured film of the positive photosensitive resin composition according to the present invention will be described. The cured film, which is a cured product of the positive photosensitive resin composition, is used not only for semiconductor devices such as semiconductor elements, but also for display devices such as TFT liquid crystal and organic EL, interlayer insulating films for multilayer circuits, and flexible copper-clad It is also useful as a plate 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 positive photosensitive resin composition on a semiconductor element, and a cured film of the above-described positive photosensitive resin composition formed on the passivation film. A protective film such as a buffer 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, Examples include an α-ray blocking film, a planarizing film, a protrusion (resin post), and a partition wall.

  Examples of display device applications include a protective film formed by forming a cured film of the above-described positive photosensitive resin composition on a display element, an insulating film or a planarizing film for TFT elements and color filters, MVA, and the like. Protrusions for a liquid crystal display device, partition walls for an organic EL element cathode, and the like. The use method is based on forming a cured film of the positive photosensitive resin composition 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. Transparency can be achieved by introducing a post-exposure step before curing the positive photosensitive resin composition layer. It is also possible to obtain a resin layer that is excellent in practical use, which is more preferable in practical use.

Hereinafter, the present invention will be described specifically by way of examples.
«Reference Example 1 >>
[Synthesis of Polyamide Resin (A-1)]
Diphenyl ether-4,4'-dicarboxylic acid 10.6 g (41.0 mmol), iso off Tal acid 1.69 g (10.2 mmol) and 1-hydroxy-1,2,3-benzotriazole 13.8 g (102 24.3 g (51.2 mmol) and 3,3-diamino-4,4-dihydroxydiphenyl ether (13.2 g, 56.8 mmol) were thermometers. Into a four-necked separable flask equipped with a stirrer, raw material inlet, and dry nitrogen gas inlet tube, 145 g of NMP was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath. Next , 2.50 g (14.5 mmol) of 5-ethynyl-isobenzofuran-1,3-dione and 15 g of N-methyl-2-pyrrolidone were added, and the mixture was further stirred for 3 hours to complete the reaction. After the reaction mixture is filtered, the reaction mixture is put into a solution of water / methanol = 3/1 (volume ratio), the precipitate is collected by filtration, thoroughly washed with water, and dried under vacuum to obtain the target polyamide. Resin (A-1) was obtained.
[Preparation of positive photosensitive resin composition]
10 g of the synthesized polyamide resin (A-1) and 2 g of photosensitive diazoquinone (B-1) having the following structure are dissolved in 20 g of γ-butyrolactone, and then filtered through a 0.2 μm fluororesin filter, and positive photosensitive property is obtained. A resin composition (P-1) was obtained.
[Gamma-Butyrolactone Solubility Evaluation]
0.5 g of the above polyamide resin is weighed into a 10 ml sample bottle, 1.5 g of GBL is added, and ultrasonic waves are applied for 2 hours. Thereafter, the sample bottle is allowed to stand at room temperature for 2 days, and the solubility in GBL is judged. Each code is as follows.
○: dissolved, ×: not dissolved [Evaluation of cyclization rate]
The positive photosensitive resin composition was applied onto two silicon wafers using a spin coater and then pre-baked at 120 ° C. for 4 minutes on a hot plate to obtain a coating film having a thickness of about 1 μm. Next, one film-coated silicon wafer was immersed in 2% hydrofluoric acid to obtain a film. This film was measured using a Fourier transform infrared spectrophotometer PARAGON 1000 (manufactured by Perkin Elmer), and the ratio (A) of peaks associated with an amide group of 1650 cm −1 and a total aromatic of 1490 cm −1 was calculated. Next, after another silicon wafer with a coating film was heated at 250 ° C./90 minutes using an oven, a cured film was obtained in the same manner, and measured by a Fourier transform infrared spectrophotometer at 1650 cm −1. The ratio (B) of the peak associated with the amide group of 1490 cm −1 and the total aromatic of 1490 cm −1 was calculated. The cyclization rate was a value obtained by multiplying (1- (B / A)) by 100. The cyclization rate thus determined was 61%.
[Scum evaluation]
The positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, and then dried on a hot plate at 120 ° C. for 4 minutes to obtain a protective film having a thickness of about 5 μm. Through this protective film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a left pattern and a blank pattern with a width of 0.88 to 50 μm are drawn) is irradiated with ultraviolet light using a high-pressure mercury lamp, and the exposure amount is changed. And irradiated.
Next, the development time was adjusted so that the film slip during development was 2.0 μm in a 2.38% tetramethylammonium hydroxide aqueous solution, the exposed area was dissolved and removed, and then rinsed with pure water for 30 seconds. The presence or absence of scum in the 50 μm wide punch pattern was observed.
[Peeling evaluation after PCT 500 hr]
The positive photosensitive resin composition was applied onto a sputtered Cu film having a thickness of 3,000 mm prepared by sputtering using a spin coater so as to have a thickness of 5 μm, and then heated on a hot plate at 120 ° C. for 4 minutes. It was dried and then cured using a clean oven at an oxygen concentration of 1,000 ppm or less at 250 ° C./90 minutes to obtain a cured film (protective film). A 1 × 1 (mm) sized square was formed on this cured film with a cutter knife so that a total of 100 grids were formed in 10 rows. This sample was subjected to a PCT (pressure cooker) test; continuously treated at 125 ° C., 100%, 0.2 MPa for 500 hours, and then the previous grid was brought into close contact with cello tape (registered trademark), and the number of peeled pieces was counted at once. .

（式中、Ｑ１、Ｑ２、Ｑ３の７５％は式（１）であり、２５％は水素原子である。）

(In the formula, 75% of Q1, Q2 and Q3 are the formula (1), and 25% are hydrogen atoms.)

«Reference Example 2 >>
[Preparation of positive photosensitive resin composition]
10 g of the synthesized polyamide resin (A-1), 2 g of photosensitive diazoquinone (B-1) having the above structure, 0.8 g of a silicon compound having the structure of the following formula (C-1), and the following formula (D-1) 0.1 g of the aluminum complex having a structure was dissolved in 20 g of γ-butyrolactone, and then filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition (P-2).

<< Reference Example 3 >>
[Preparation of positive photosensitive resin composition]
10 g of synthesized polyamide resin (A-1), 2 g of photosensitive diazoquinone (B-1) having the above structure, 0.8 g of silicon compound (C-1) having the above structure, aluminum complex having the above structure (D-1 ) 0.1 g, 3 g of a compound having an oxetanyl group having the structure of the following formula (E-1) was dissolved in 20 g of γ-butyrolactone, and then filtered through a 0.2 μm fluororesin filter to form a positive photosensitive resin A composition (P-3) was obtained.

≪参考例４≫
ポリアミド樹脂として以下のものを用いた以外は、参考例３と同様にポジ型感光性樹脂組成物を得た。
［ポリアミド樹脂（Ａ−２）の合成］
参考例１のポリアミド樹脂の合成において、ジフェニルエーテル−４，４’−ジカルボン酸１０．６ｇ（４１．０ミリモル）をジフェニルエーテル−４，４’−ジカルボン酸６．８４ｇ（２６．５ミリモル）、イソフタル酸１．６９ｇ（１０．２ミリモル）をイソフタル酸４．４０ｇ（２６．５ミリモル）、１−ヒドロキシ−１，２，３−ベンゾトリアゾール１３．８ｇ（１０２．４モル）を１−ヒドロキシ−１，２，３−ベンゾトリアゾール１４．３ｇ（１０６．０モル）、３，３−ジアミノ−４，４−ジヒドロキシジフェニルエーテル１３．２ｇ（５６．８ミリモル）を３，３−ジアミノ−４，４−ジヒドロキシジフェニルエーテル１３．７ｇ（５９．０ミリモル）とした以外は参考例１と同様にしてポリアミド樹脂（Ａ−２）を得た。

<< Reference Example 4 >>
A positive photosensitive resin composition was obtained in the same manner as in Reference Example 3 except that the following polyamide resin was used.
[Synthesis of Polyamide Resin (A-2)]
In the synthesis of the polyamide resin of Reference Example 1, diphenyl ether 4,4'-dicarboxylic acid 10.6g of (41.0 mmol) diphenyl ether 4,4'-dicarboxylic acid 6.84 g (26.5 mmol), iso off 1.69g Tal acid (10.2 mmol) of 4.40g iso full barrel acid (26.5 mmol), 1-hydroxy-1,2,3-benzotriazole 13.8g of (102.4 moles) of 1- Hydroxy-1,2,3-benzotriazole (14.3 g, 106.0 mol), 3,3-diamino-4,4-dihydroxydiphenyl ether (13.2 g, 56.8 mmol), 3,3-diamino-4, A polyamide resin (A-2) was obtained in the same manner as in Reference Example 1 except that 13.7 g (59.0 mmol) of 4-dihydroxydiphenyl ether was used.

Reference Example 5
A positive photosensitive resin composition was obtained in the same manner as in Reference Example 3 except that the following polyamide resin was used.
[Synthesis of Polyamide Resin (A-3)]
Iso off Tal acid 9.42 g (56.7 mmol) and 1-hydroxy-1,2,3-benzotriazole 15.3 g (113.5 moles) is reacted with a dicarboxylic acid derivative obtained 22.7 g ( 56.7 mmol), 14.6 g (63.3 mmol) of 3,3-diamino-4,4-dihydroxydiphenyl ether, and a 4-neck equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube In a separable flask, 145 g of NMP was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath. Next, 2.70 g (14.5 mmol) of 5-ethynyl-isobenzofuran-1,3-dione and 15 g of N-methyl-2-pyrrolidone were added, and the mixture was further stirred for 3 hours to complete the reaction. After the reaction mixture is filtered, the reaction mixture is put into a solution of water / methanol = 3/1 (volume ratio), the precipitate is collected by filtration, thoroughly washed with water, and dried under vacuum to obtain the target polyamide. Resin (A-3) was obtained.

Example 6
A positive photosensitive resin composition was obtained in the same manner as in Reference Example 3 except that the following polyamide resin was used.
[Synthesis of Polyamide Resin (A-4)]
35.2 g (136.3 mmol) of diphenyl ether-4,4′-dicarboxylic acid, 5.7 g (34.5 mmol) of isophthalic acid, and 1-hydroxy-1,2,3-benzotriazole 46. 80.7 g (170.3 mmol) of a mixture of dicarboxylic acid derivatives obtained by reacting 0 g (340.8 mmol) with 41.6 g (179.3) of 3,3-diamino-4,4-dihydroxydiphenyl ether Mmol) and 3.3 g (31.4 mmol) of 5-amino-1H-tetrazole monohydrate were added to a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube. Then, 363.5 g of NMP was added and dissolved, and the mixture was stirred at room temperature for 2 hours. Then, it was made to react at 75 degreeC for 12 hours using the oil bath. Next, 2.3 g (13.4 mmol) of 5-ethynyl-isobenzofuran-1,3-dione dissolved in 11.5 g of NMP was added and stirred for 2 hours to complete the reaction. After the reaction mixture was filtered, 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 polyamide resin ( A-4) was obtained (content of nitrogen-containing cyclic compound 3.2% by weight).

Example 7
A positive photosensitive resin composition was obtained in the same manner as in Reference Example 3 except that the following polyamide resin was used.
[Synthesis of Polyamide Resin (A-5)]
6.5 g (34.1 mmol) of trimellitic anhydride and 4.3 g (41.3 mmol) of 5-amino-1H-tetrazole monohydrate were added to a thermometer, stirrer, raw material inlet, and dry nitrogen gas introduced. Into a four-necked separable flask equipped with a tube, 37.8 g of NMP was added and dissolved, and the mixture was stirred overnight at 20 ° C. or lower. Next, 31.6 g (136.2 mmol) of diphenyl ether-4,4′-dicarboxylic acid was added, and 46.0 g (340.6 mmol) of 1-hydroxy-1,2,3-benzotriazole was obtained. A mixture of 76.0 g (170.3 mmol) of the dicarboxylic acid derivative obtained by the reaction and 41.6 g (179.0 mmol) of 3,3-diamino-4,4-dihydroxydiphenyl ether was added to 363.5 g of NMP. The mixture was dissolved and stirred at room temperature for 2 hours. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath. Then dissolved 5-ethynyl NMP11.5G - After stirred for 2 hours was added isobenzofuran-1,3-dione 3.7 g (19.3 mmol) and the reaction was completed, the the same manner as in Reference Example 1 Treatment was performed to obtain a polyamide resin (A-5). (Content of nitrogen-containing cyclic compound is 4.5% by weight).

≪Comparative example 1≫
[Synthesis of Polyamide Resin (a-1)]
13.0 g (50.2 mmol) of diphenyl ether-4,4′-dicarboxylic acid and 1
-24.7 g (50.2 mmol) of a dicarboxylic acid derivative obtained by reacting 13.6 g (100.4 mmol) of hydroxy-1,2,3-benzotriazole with 3,3-diamino-4,4 -12.9 g (55.5 mmol) of dihydroxydiphenyl ether was placed in a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, and 145 g of NMP was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath. Next, 5-ethynyl-isobenzofuran-1,3-dione.
4 g (13.9 mmol) and 15 g of NMP were added, and the mixture was further stirred for 3 hours to complete the reaction. After the reaction mixture is filtered, the reaction mixture is put into a solution of water / methanol = 3/1 (volume ratio), the precipitate is collected by filtration, thoroughly washed with water, and dried under vacuum to obtain the target polyamide. Resin (a-1) was obtained.
[Preparation of positive photosensitive resin composition]
10 g of the synthesized polyamide resin (a-1) and 2 g of the photosensitive diazoquinone (B-1) having the above structure are dissolved in 20 g of NMP, and then filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition. (P-1) was obtained.

≪Comparative example 2≫
A positive photosensitive resin composition was obtained in the same manner as in Comparative Example 1 except that the following polyamide resin was used.
[Synthesis of Polyamide Resin (a-2)]
Diphenyl ether-4,4'-dicarboxylic acid 12.4 g (47.9 mmol), iso off Tal acid 0.41 g (2.5 mmol) and 1-hydroxy-1,2,3-benzotriazole 13.6 g (100 Dicarboxylic acid derivative 24.6 g (50.4 mmol) and 3,3-diamino-4,4-dihydroxydiphenyl ether 13.1 g (56.4 mmol) obtained by reacting with. Into a four-necked separable flask equipped with a stirrer, raw material inlet, and dry nitrogen gas inlet tube, 145 g of NMP was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath. Next , 2.4 g (13.9 mmol) of 5-ethynylisophthalic anhydride and 15 g of NMP were added, and the mixture was further stirred for 3 hours to complete the reaction. After the reaction mixture is filtered, the reaction mixture is put into a solution of water / methanol = 3/1 (volume ratio), the precipitate is collected by filtration, thoroughly washed with water, and dried under vacuum to obtain the target polyamide. Resin (a-2) was obtained.

The positive photosensitive resin composition of the present invention can be produced with a solvent containing no nitrogen atom,
It has a characteristic that scum hardly occurs during development, and is suitably used for a protective film, an insulating film, and the like of a semiconductor device or a display device.

Claims (12)

Polybenzoxazole precursor (A) obtained by polymerizing bisaminophenol composed of 3,3-diamino-4,4-dihydroxydiphenyl ether and isophthalic acid or dicarboxylic acid composed of isophthalic acid and 4,4-dicarboxydiphenyl ether and), characterized in a photosensitive agent (B), seen containing a side chain and / or at least one end of the polybenzoxazole precursor (a) is one having a nitrogen-containing cyclic compound (G), it A positive photosensitive resin composition. The positive photosensitive resin composition according to claim 1, wherein the polybenzoxazole precursor (A) is represented by the following general formula (1).

(In the formula, a and b represent mol%, a = 30 to 80 mol%, b = 20 to 70 mol%, and a + b = 100 mol%. In the formula, R represents an alkyl group or an alkoxy group. , Hydroxyl group, acyloxy group, and cycloalkyl group.)   The positive photosensitive resin composition of Claim 1 or 2 containing an active silicon compound (C) and an aluminum complex (D).   The positive photosensitive resin composition according to any one of claims 1 to 3, comprising a compound (E) containing two or more oxetanyl groups in one molecule.   The positive photosensitive resin composition according to claim 4, comprising a catalyst (F) that promotes a ring-opening reaction of the compound (E) containing two or more oxetanyl groups in one molecule. The positive photosensitive resin composition according to claim 1, wherein the nitrogen-containing compound (G) contains a tetrazole group. The positive photosensitive resin composition according to any one of claims 1 to 6, wherein the nitrogen-containing compound having a tetrazole group contains at least one of the compounds represented by formula (2-1) and formula (2-2). object.

It claims 1 to cured film, which is composed of a cured product of the positive photosensitive resin composition according to any one of 7. A protective film comprising the cured film according to claim 8 . An insulating film comprising the cured film according to claim 8. A semiconductor device comprising the cured film according to claim 8 . A display device comprising the cured film according to claim 8 .