JP2009079028A - Amidophenol compound and naphthoquinonediazide compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a halogen-free naphthoquinonediazide compound which exhibits a high sensitivity and a high resolution when used in a positive photosensitive resin composition and has good storage stability and to provide an amidophenol compound as an intermediate useful for the production of the same. <P>SOLUTION: The compound is represented by formula (1) (wherein R<SB>1</SB>and R<SB>4</SB>are each independently a monovalent phenyl-containing organic group; R<SB>2</SB>, R<SB>3</SB>, R<SB>5</SB>, and R<SB>6</SB>are each independently a hydrogen atom or a monovalent organic group; Q<SB>1</SB>and Q<SB>2</SB>are independent of each other, and at least either of them is a 4-or 5-naphthoquinonediazidosulfonyl group; and X is a divalent halogen-free group or a single bond). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel naphthoquinone diazide compound that can be suitably used as a photoactive agent, and an amidophenol compound that is an intermediate useful in the production thereof.

  Conventionally, polyimide resins and polybenzoxazole resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been used as surface protective films and interlayer insulating films of semiconductor elements. These resins are usually formed by imidation or oxazolation by applying a heat treatment after applying the precursor composition. When this resin needs to be patterned, a photosensitive precursor composition is generally used. The reason is that if it is a photosensitive precursor composition, it can be easily exposed to actinic rays after being applied, and then subjected to development, thermal imidization, and the like to easily form a polyimide pattern. This is because the process can be greatly shortened compared to the case where non-photosensitive polyimide is used.

These photosensitive performances include positive type and negative type, and alkali development type and solvent development type, depending on the choice of photosensitive agent to be added. Recently, alkali development type that can be developed with dilute alkaline aqueous solution like photoresist. Various proposals of heat-resistant photosensitive resin materials have been made.
Among them, a method in which an alkali development type hydroxy polyamide, for example, a polybenzoxazole (hereinafter also referred to as “PBO”) precursor is mixed with a photoactive component (hereinafter also referred to as “PAC”) such as naphthoquinone diazide has recently been used. It is attracting attention (for example, see Patent Documents 1 and 2).
These resins can easily form a positive pattern by exposure and development with an aqueous alkali solution, have good developability and storage stability, can be polybenzoxazole by thermosetting after patterning, and are heat resistant. A film having film characteristics such as mechanical characteristics and electrical characteristics can be obtained.

Originally, in the case of a photosensitive resin composition using naphthoquinone diazide, by adding naphthoquinone diazide to an alkali-soluble polymer, the ability to reduce the alkali solubility of the composition (dissolution inhibition) is expressed, Resistance to dissolution in the developer occurs. On the other hand, naphthoquinonediazide is converted into indenecarboxylic acid in the exposed portion, so that the dissolution inhibiting ability disappears and dissolves in the developer.
Patterning is performed using the difference in alkali solubility between the exposed and unexposed areas. To obtain high sensitivity and high residual film rate (high contrast) patterning performance, the exposed and unexposed areas can be obtained. It is important to select a PAC that can sufficiently take the difference in solubility between the parts.
That is, by adding PAC, the solubility of the alkali-soluble polymer in the alkaline aqueous solution is extremely reduced in the unexposed area, thereby providing sufficient resistance to dissolution in an alkaline developer, while in the exposed area, a slight amount of light is used. Therefore, it is necessary to use a highly sensitive PAC that decomposes efficiently and exhibits sufficient alkali solubility.

Among them, a positive photosensitive resin composition that achieves high sensitivity by using a PAC having a specific structure has been proposed (see, for example, Patent Document 3). This PAC has a high sensitivity that can achieve sufficient alkali solubility even when exposed to light in a short time, while maintaining a high level of resistance to dissolution of the unexposed area in the developer even under thick film conditions. PAC. However, the PAC disclosed here also has problems and concerns and needs to be improved.
For example, when the positive photosensitive resin composition disclosed in Patent Document 3 is used as a semiconductor application, the remaining halogen element may cause corrosion of metal parts such as substrates and circuits. A type in which halogen elements are reduced is desired. In particular, in the additive component, a type containing no halogen element is desired. Therefore, it can be said that the PAC is preferably a compound containing no halogen element.
Therefore, in order to solve the above problems, a PAC having a naphthoquinonediazide structure that has high sensitivity and does not contain a halogen element has been required.

Japanese Examined Patent Publication No. 01-046862 JP 63-096162 A JP 2003-131368 A

  An object is to provide a photoactivator for realizing a positive photosensitive resin composition having high sensitivity, high resolution, and good storage stability. More specifically, the present invention provides a naphthoquinonediazide compound that does not contain a halogen element and an amidephenol compound that is an intermediate useful for the production thereof.

（式中、Ｒ_１およびＲ_４はフェニル基を有する１価の有機基であり、Ｒ_２、Ｒ_３、Ｒ_５およびＲ_６は互いに独立に、水素原子または１価の有機基である。Ｑ_１およびＱ_２は、互いに独立であり、少なくとも１つは下記式（２）で示される二つの基のどちらかである。また、Ｘはハロゲン元素を含まない２価の基または単結合である。）

２．Ｒ_１、Ｒ_２、Ｒ_４、及びＲ_５はフェニル基を有する１価の有機基であり、Ｒ_３およびＲ_６は互いに独立に水素原子または１価の有機基であることを特徴とする上記１に記載のナフトキノンジアジド化合物。
３．Ｘが−ＳＯ_２−または、−ＣＲ_７Ｒ_８−、（ここで、Ｒ_７およびＲ_８は互いに独立に炭素数が１〜４の１価の有機基である。）であることを特徴とする上記１または２に記載のナフトキノンジアジド化合物。
４．Ｒ_１、Ｒ_２、Ｒ_４、及びＲ_５がフェニル基でありＲ_３及びＲ_６が水素原子であり、Ｘが−ＳＯ_２−または−Ｃ（ＣＨ_３）_２−であることを特徴とする上記３に記載のナフトキノンジアジド化合物。
５．下記一般式（３）で表されるアミドフェノール化合物。

（式中、Ｒ_９およびＲ₁₂はフェニル基を有する１価の有機基であり、Ｒ₁₀、Ｒ₁₁、Ｒ₁₃およびＲ₁₄は互いに独立に水素原子または１価の有機基である。また、Ｘはハロゲン元素を含まない２価の基または単結合である。）
６．Ｒ_９、Ｒ₁₀、Ｒ₁₂、及びＲ₁₃はフェニル基を有する１価の有機基であり、Ｒ₁₁およびＲ₁₄は互いに独立に水素原子または１価の有機基であることを特徴とする上記５に記載のアミドフェノール化合物。
７．Ｘが−ＳＯ_２−または、−ＣＲ₁₅Ｒ₁₆−、（ここで、Ｒ₁₅およびＲ₁₆は互いに独立に炭素数が１〜４の１価の有機基である。）であることを特徴とする上記５または６に記載のアミドフェノール化合物。
８．Ｒ_９、Ｒ₁₀、Ｒ₁₂、及びＲ₁₃がフェニル基でありＲ₁₁及びＲ₁₄が水素原子であり、Ｘが−ＳＯ_２−または−Ｃ（ＣＨ_３）_２−であることを特徴とする上記７に記載のアミドフェノール化合物。
９．アルカリ可溶性樹脂１００質量部と上記１〜４のいずれか１項に記載のナフトキノンジアジド化合物１〜５０質量部を含有することを特徴とするポジ型感光性樹脂組成物。
１０．上記９に記載のポジ型感光性樹脂組成物から形成された耐熱性被膜を有することを特徴とする半導体装置。
１１．上記９に記載のポジ型感光性樹脂組成物を半導体素子上に塗布し、プリベーク、露光、現像、加熱することを特徴とする半導体装置の製造方法。 The present inventor has found that a naphthoquinonediazide compound obtained from an amidophenol compound having a specific structure can satisfy the above-mentioned characteristics, and has completed the present invention.
That is, the present invention is as follows.
1. A naphthoquinonediazide compound represented by the following general formula (1).

(Wherein R ₁ and R ₄ are monovalent organic groups having a phenyl group, and R ₂ , R ₃ , R ₅ and R ₆ are each independently a hydrogen atom or a monovalent organic group. Q ₁ and Q ₂ are independent from each other, and at least one of them is one of two groups represented by the following formula (2), and X is a divalent group not containing a halogen element or a single bond. .)

2. R ₁ , R ₂ , R ₄ , and R ₅ are monovalent organic groups having a phenyl group, and R ₃ and R ₆ are each independently a hydrogen atom or a monovalent organic group, The naphthoquinone diazide compound according to 1.
3. X is —SO ₂ — or —CR ₇ R ₈ —, wherein R ₇ and R ₈ are each independently a monovalent organic group having 1 to 4 carbon atoms. The naphthoquinone diazide compound according to 1 or 2 above.
4). R ₁ , R ₂ , R ₄ , and R ₅ are phenyl groups, R ₃ and R ₆ are hydrogen atoms, and X is —SO ₂ — or —C (CH ₃ ) ₂ —. 4. The naphthoquinone diazide compound as described in 3 above.
5). An amidophenol compound represented by the following general formula (3).

(Wherein R ₉ and R ₁₂ are monovalent organic groups having a phenyl group, and R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each independently a hydrogen atom or a monovalent organic group. X is a divalent group not containing a halogen element or a single bond.)
6). R ₉ , R ₁₀ , R ₁₂ , and R ₁₃ are monovalent organic groups having a phenyl group, and R ₁₁ and R ₁₄ are each independently a hydrogen atom or a monovalent organic group. 5. The amidophenol compound according to 5.
7). X is —SO ₂ — or —CR ₁₅ R ₁₆ —, wherein R ₁₅ and R ₁₆ are each independently a monovalent organic group having 1 to 4 carbon atoms. The amidophenol compound according to 5 or 6 above.
8). R ₉ , R ₁₀ , R ₁₂ , and R ₁₃ are phenyl groups, R ₁₁ and R ₁₄ are hydrogen atoms, and X is —SO ₂ — or —C (CH ₃ ) ₂ —. 8. The amidophenol compound as described in 7 above.
9. A positive photosensitive resin composition comprising 100 parts by mass of an alkali-soluble resin and 1 to 50 parts by mass of the naphthoquinonediazide compound described in any one of 1 to 4 above.
10. 10. A semiconductor device comprising a heat-resistant film formed from the positive photosensitive resin composition as described in 9 above.
11. 10. A method for producing a semiconductor device, comprising applying the positive photosensitive resin composition described in 9 above onto a semiconductor element, prebaking, exposing, developing, and heating.

  The naphthoquinone diazide compound of the present invention does not contain a halogen element, exhibits high sensitivity and high resolution when used in a positive photosensitive resin composition, and has good storage stability.

Hereinafter, the present invention will be described in detail.
The naphthoquinone diazide compound of the present invention is synthesized from a specific aminophenol compound via an amidophenol compound.
<Synthesis Method of Amidophenol Compound>
The amidophenol compound of the present invention can be obtained by allowing 1.5 to 2.5 equivalents of carboxylic acid chloride to act on 1 equivalent of aminophenol compound. Further, 1.5 to 2.5 equivalents of carboxylic acid can be obtained in the presence of dicyclohexylcarbodiimide (hereinafter also referred to as “DCC”) with respect to 1 equivalent of aminophenol compound. The amount of DCC added is preferably 2 to 3 equivalents with respect to 1 equivalent of the phenyl group of aminophenol.
The reaction conditions are as follows. In the case obtained by the action of carboxylic acid chloride, a base catalyst is added, and the reaction is carried out at −10 to 10 ° C. for 1 to 3 hours. It can be carried out at 0 to 70 ° C. for 1 to 20 hours to obtain an amidophenol compound. Specific examples of the aminophenol compound include the following.

Specific examples of carboxylic acid and carboxylic acid chloride that act on aminophenol compounds include phenylacetic acid, phenoxyacetic acid, phenylacetyl chloride, phenoxyacetyl chloride, 2-phenylbutyryl chloride, diphenylacetic acid, diphenylpropionic acid, diphenylacetic acid. Compounds having a phenyl group such as chloride are preferable, and among them, compounds having two or more phenyl groups such as diphenylacetic acid, diphenylpropionic acid and diphenylacetic acid chloride are preferable.
When synthesizing the amide phenol compound, a solvent usually used is preferably a solvent that dissolves both the starting aminophenol compound and carboxylic acid or carboxylic acid chloride, and N, N-dimethylacetamide (hereinafter referred to as “DMAc”). ), Dimethylformamide, N-methyl-2-pyrrolidone (hereinafter also referred to as “NMP”), γ-butyrolactone (hereinafter also referred to as “GBL”), dimethyl sulfoxide (hereinafter also referred to as “DMSO”). ), Tetrahydrofuran (hereinafter also referred to as “THF”), and the like. The solvent may be added in any amount as long as the selected aminophenol and carboxylic acid can be dissolved, but is preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the amide phenol compound.

A base catalyst is added to accelerate the synthesis reaction of the amidophenol compound. For example, pyridine, picoline, collidine, lutidine, triethylamine, 4-dimethylaminopyridine, 1,4-diazabicyclo [2.2.2]. And octane (hereinafter also referred to as “DABCO”) and diazabicycloundecene (hereinafter also referred to as “DBU”).
The addition amount of a base catalyst is 1-2 equivalent with respect to 1 equivalent of phenol groups which aminophenol has.
The amide phenol compound synthesized in this way can be reprecipitated in a poor solvent such as water, and then redissolved in a solvent such as THF and treated with a cation exchange resin to remove the basic compound. When synthesizing an amide phenol compound, when a chloride ion or the like is generated due to the use of carboxylic acid chloride or the like, it is preferable to use an anion exchange resin in combination in order to remove this. The target product can be isolated by reprecipitation of the solution thus treated in water, followed by filtration and heat drying.

<Method of synthesizing naphthoquinone diazide compound>
A naphthoquinone diazide compound (hereinafter also referred to as “NQD”) can be obtained by converting a part or all of the phenolic hydroxyl group of the amide phenol compound into a quinone diazide sulfonate ester.
In the quinonediazide sulfonic acid esterification, various sulfonic acid derivatives having a 1,2-naphthoquinonediazide structure can be used. Preferably, 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide is used. -5-sulfonyl chloride is preferred. These esterifying agents may be used alone or in combination.
NQD is obtained by reacting 0.8 to 1 equivalent of a sulfonic acid derivative at 25 to 40 ° C. for 1 to 3 hours with respect to 1 equivalent of hydroxy group of amidophenol.

This reaction is usually performed in the presence of a dehydrohalogenating agent. Dehydrohalogenating agents generally include basic compounds capable of forming salts with hydrogen halides, for example, inorganic bases such as sodium carbonate and sodium hydrogen carbonate, ethylamine, ethanolamine, diethylamine, diethanolamine, triethylamine, triethanol. Examples include amines, amines such as N, N-dimethylaniline, N, N-diethylaniline, and pyridine.
The dehydrohalogenating agent can be used singly or in combination of several kinds, and several kinds may be added stepwise. The amount added is 1 to 1.3 equivalents relative to 1 equivalent of the hydroxy group of amidophenol.
The esterification reaction is usually performed in a solvent. Reaction solvents include ethers such as dioxolane, 1,4-dioxane, tetrahydrofuran and diethyl ether, glymes such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, lactones such as gamma butyrolactone, and amides such as N-methyl-2-pyrrolidone. , Aliphatic ketones such as acetone and methyl ethyl ketone can be used, but are not limited thereto. The solvent may be added in any amount as long as the esterification reaction proceeds, but is preferably 200 to 2000 parts by mass with respect to 100 parts by mass of amide phenol.

<Positive photosensitive resin composition>
The naphthoquinonediazide compound of the present invention is suitably used as a component of a positive photosensitive resin composition comprising an alkali-soluble polymer. In particular, the alkali-soluble polymer is a polymer having a phenolic hydroxyl group, specifically, Mw is This is useful in the case of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, novolak resin, and polyhydroxystyrene.
The addition amount of a naphthoquinone diazide compound is used in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble polymer.
Moreover, the positive photosensitive resin composition containing the naphthoquinone diazide compound of the present invention takes a varnish form in which these components are dissolved in a solvent. Examples of the solvent used here include DMAc, dimethylformamide, NMP, GBL, DMSO, THF and the like, and they may be used alone or in combination. The usage-amount of a solvent changes with film thicknesses obtained, and is used in the range of 70-1900 mass parts with respect to 100 mass parts of alkali-soluble polymers.

The positive photosensitive resin composition containing the naphthoquinone diazide compound of the present invention can be used as follows. First, the composition is applied to an appropriate substrate, for example, a silicon wafer, a ceramic substrate, an aluminum substrate, or the like by spin coating using a spinner or a roll coater. This is dried at 50 to 140 ° C. for 10 seconds to 1 hour using an oven or a hot plate, and irradiated with actinic radiation through a mask using a contact aligner or a stepper. Next, the irradiated portion is dissolved and removed with a developing solution, and then rinsing with a rinsing solution is performed to obtain a desired relief pattern. As a developing method, methods such as spray, paddle, dip, and ultrasonic can be used. As the rinsing liquid, distilled water, deionized water or the like can be used. The obtained relief pattern can be heat-treated at 200 to 380 ° C. for 10 seconds to 2 hours to form a heat resistant coating.
The positive photosensitive resin composition is useful not only for semiconductor applications but also as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, and liquid crystal alignment films. Specific preferred examples of semiconductor applications include semiconductor surface protective films, interlayer insulating films, rewiring insulating films, protective films for flip chip devices, protective films for devices having a bump structure, and the like.

Hereinafter, based on an Example, the specific example of embodiment of this invention is demonstrated.
[Reference Example 1]
<Examples of polymer production>
In a 2 liter separable flask, 197.8 g (0.54 mol) 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 71.2 g (0.9 mol) pyridine, and 692 g DMAc The mixture was stirred at room temperature (25 ° C.) to dissolve the diamine. A solution obtained by dissolving 29.6 g (0.18 mol) of 5-norbornene-2,3-dicarboxylic anhydride in 88 g of DMDG (... Name...) Separately was dropped from this dropping funnel. The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 28 ° C.
After completion of the dropwise addition, the mixture was heated to 50 ° C. in a hot water bath and stirred for 18 hours, and then the IR spectrum of the reaction solution was measured to confirm that characteristic absorption of imide groups at 1385 ⁻¹ and 1772 cm ⁻¹ appeared.

Next, this was cooled to 8 ° C. with a water bath, and separately, 42.8′-diphenyl ether dicarboxylic acid dichloride (132.8 g, 0.45 mol) dissolved in DMDG (398 g) was added dropwise from the dropping funnel. The time required for the dropping was 80 minutes, and the maximum reaction solution temperature was 12 ° C.
Three hours after the completion of the dropping, the above reaction solution was dropped into 12 L of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, appropriately washed with water, dehydrated and then vacuum dried to obtain a polybenzoxazole precursor ( P-1) was obtained.
Thus, the weight average molecular weight by GPC of the polybenzoxazole precursor (P-1) synthesize | combined was 8900 in polystyrene conversion. The analysis conditions for GPC are described below.
Column: Trade name Shodex KF807 / 806M / 806M / 802.5 manufactured by Showa Denko KK
Separation liquid: Tetrahydrofuran 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko brand name Shodex RI RI-101

[Example 1]
<Synthesis of Amidophenol Compound>
(3,3′-diamino-4,4′-dihydroxyphenyl) sulfone 28.0 g (0.1 mol), DMAc 142 g, pyridine 15.8 g (0.2 mol) were placed in a separable flask having a capacity of 500 ml. A solution prepared by dissolving 46.1 g (0.2 mol) of diphenylacetic chloride in 230 g of GBL was added dropwise at −15 ° C. After stirring for 3 days at room temperature, the reaction was confirmed by high performance liquid chromatography (HPLC). As a result, no starting material was detected and the product was detected as a single peak with a purity of 99%. This reaction solution was added dropwise to 2 liters of ion-exchanged water with stirring to precipitate the product.

Next, the precipitate was separated by filtration, and 200 ml of THF was added thereto and dissolved by stirring. This homogeneous solution was passed through a glass column filled with 20 g of cation exchange resin: Amberlyst 15 (manufactured by Organo Corporation), and the remaining pyridine was removed. Removed. Next, this solution is dropped into 1 liter of ion-exchanged water under high-speed stirring to precipitate a product, which is filtered off and then vacuum-dried to obtain an amide phenol compound (A-1) having the following structure. Obtained in 80% yield. The measurement result of ¹ H-NMR of (A-1) is shown below. ( ¹ H-NMR signal peak: 5.6 ppm (s), 7.0 ppm (d), 7.2 to 7.4 (m), 7.5 ppm (d), 8.6 ppm (s), 9.7 ppm (S)) The spectrum data is shown in FIG.
The measurement conditions for ¹ H-NMR are described below.
Apparatus: BullkerGPX spectrometer manufactured by Bruker BioSpin Corporation Solvent: deuterated chloroform (Chloroform-D1 MERCK manufactured by Uvasol)
Measurement temperature: 25 ° C

[Example 2]
Instead of 3,3′-diamino-4,4′-dihydroxyphenyl) sulfone of Example 1, 25.8 g (0.1 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) propane was used. Then, synthesis was carried out in the same manner as in Example 1, and an amide phenol compound (A-2) having the following structure was obtained in a yield of 75%. The result of measuring ¹ H-NMR of A-2 under the same conditions as in Example 1 is shown below. ( ¹ H-NMR signal peak: 1.5 ppm (s), 5.4 ppm (s), 6.7 ppm (s), 7.2 to 7.4 (m), 7.8 ppm (s), 9.5 ppm , (S), 9.6 ppm (s)) The spectral data are shown in FIG.

[Reference Example 2]
Synthesis was performed in the same manner as in Example 1 except that 26.9 g (0.2 mol) of t-butylacetyl chloride was used instead of diphenylacetic acid chloride of Example 1, and the obtained amidophenol compound (B-1 ) Did not dissolve in acetone, and it was difficult to naphthoquinonediazide.

[Reference Example 3]
Synthesis was performed in the same manner as in Example 1 except that 39.7 g (0.2 mol) of 1-adamantanecarbonyl chloride was used instead of diphenylacetic acid chloride of Example 1, and the obtained amidophenol compound (B-2 ) Did not dissolve in acetone, and it was difficult to naphthoquinonediazide.

表１の結果から、本発明に用いられるアミドフェノールは、溶剤に対して優れた溶解性を示すことが分かる。 <Evaluation of solubility of amidophenol compound>
Table 1 shows the results of solubility of the amidophenol compound obtained in Reference Examples 2 and 3 and Examples 1 and 2 in GBL or acetone.

From the results in Table 1, it can be seen that the amide phenol used in the present invention exhibits excellent solubility in solvents.

<Synthesis of naphthoquinonediazide compound>
[Example 3]
Add 20.1 g (0.03 mol) of the amidophenol compound obtained in Example 1, 14.9 g (0.059 mol) of 1,2-naphthoquinonediazide-4-sulfonyl chloride, and 240 g of acetone, and stir at 20 ° C. Dissolved. A solution prepared by diluting 7.3 g (0.072 mol) of triethylamine with 35 g of acetone was added dropwise thereto at a constant rate over 30 minutes. At this time, the temperature of the reaction solution was controlled in the range of 20 to 30 ° C. using an ice water bath or the like.
After completion of the dropwise addition, the mixture was allowed to stir at 20 ° C. for another 30 minutes, and then 0.6 g of a 36% by weight aqueous hydrochloric acid solution was added. The filtrate obtained at this time was added dropwise to 1 liter of a 0.5 wt% aqueous hydrochloric acid solution over 1 hour with stirring to precipitate the desired product, which was collected by suction filtration. The obtained cake-like recovered material was again dispersed in 5 liters of ion-exchanged water, stirred, washed, collected by filtration, and this water washing operation was repeated three times. Finally, the obtained cake-like material was vacuum-dried at 40 ° C. for 24 hours to obtain a naphthoquinonediazide compound Q-1 having the following structure. The result of ¹ H-NMR measurement of Q-1 under the same conditions as in Example 1 is shown below. ( ¹ H-NMR signal peak: 5.4 ppm (s), 7.2 ppm (d), 7.2 to 7.4 (m), 7.5 to 7.7 ppm (m), 8.2 ppm (d) , 8.3 ppm (d), 8.5 ppm (s), 10.4 ppm (s)) The spectral data are shown in FIG.

[Example 4]
Synthesis was performed in the same manner as in Example 3 except that 19.4 g (0.03 mol) of the amidophenol compound obtained in Example 2 was used instead of the amidophenol compound obtained in Example 1. A naphthoquinonediazide compound Q-2 having a structure was obtained. The results of measuring ¹ H-NMR of Q-2 under the same conditions as in Example 1 are shown below. ( ¹ H-NMR signal peak: 1.5 ppm (s), 5.3 ppm (s), 6.8 ppm (m), 7.2 to 7.4 ppm (m), 7.6 to 7.8 ppm (m) , 8.2 to 8.3 ppm (m), 8.4 ppm (m)) The spectral data are shown in FIG.

<Preparation and Evaluation of Positive Photosensitive Resin Composition>
(Examples 5-6, Comparative Example 1)
100 parts by mass of the polybenzoxazole precursor (P-1) obtained in Reference Example 1, the naphthoquinonediazide compounds (Q-1 and Q-2) obtained in Examples 3 and 4, and the following compounds ( Q-3) 15 parts by mass were each dissolved in 185 parts by mass of GBL and adjusted with the combinations shown in Table 2. Then, it filtered with a 0.2 micrometer filter, the positive photosensitive resin composition was prepared, and the patterning characteristic and varnish precipitation stability were evaluated.

(1) Evaluation of patterning characteristics (sensitivity and resolution) The positive photosensitive resin composition was spin-coated on a 6-inch silicon wafer with a spin coater (CLEANTRACK MK-8) manufactured by Tokyo Electron Co., Ltd. and heated at 130 ° C. for 180 seconds. The plate was pre-baked to form an 11 μm coating film. The film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen Mfg.
This coating film was exposed through a reticle with a test pattern using a Nikon stepper (NSR2005i8A) having an exposure wavelength of i-line (365 nm) while changing the exposure stepwise.
Using an alkali developer (AZ300MIF developer, 2.38 wt% tetramethylammonium hydroxide aqueous solution) manufactured by AZ Electronic Materials, the development time was such that the film thickness after development was 9.3 μm at 23 ° C. Then, development was performed to form a positive relief pattern. Table 2 shows the development time, the sensitivity of the photosensitive resin composition, and the resolution.

The sensitivity and resolution of the photosensitive resin composition were evaluated as follows.
[Sensitivity (mJ / cm ² )]
The minimum exposure amount that can completely dissolve and remove the exposed portion of the coating film during the development time.
[Resolution (μm)]
Minimum resolution pattern size at the above exposure.
From the results shown in Table 2, it can be seen that by using the positive photosensitive resin composition of the present invention, a pattern with high sensitivity and high resolution can be formed in an appropriate development time.

(2) Evaluation of Storage Stability Table 2 shows the results of visual observation of whether or not the above-described positive photosensitive resin composition was allowed to deposit a solid content when left at room temperature for 1 week or 2 weeks. .
From the results shown in Table 2, it can be seen that the naphthoquinone diazide compound of the present invention is excellent in storage stability in the photosensitive resin composition.

  The naphthoquinone diazide compound of the present invention and the amidophenol compound, which is an intermediate useful in the production thereof, are used as components of a positive photosensitive resin composition, so that a surface protective film, an interlayer insulating film, and a rewiring of a semiconductor device are used. Insulating films for flip-chips, protective films for flip-chip devices, protective films for devices having bump structures, interlayer insulating films for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, electronic components, display elements, and liquid crystal alignment films It can be suitably used.

2 is a ¹ H-NMR measurement result of the amidophenol compound (A-1) synthesized in Example 1. FIG. It is a measurement result of ¹ H-NMR of the amidophenol compound (A-2) synthesized in Example 2. It is a measurement result of ¹ H-NMR of the naphthoquinone diazide compound (Q-1) synthesized in Example 3. 2 shows ¹ H-NMR measurement results of a naphthoquinonediazide compound (Q-2) synthesized in Example 4. FIG.

Claims (11)

A naphthoquinonediazide compound represented by the following general formula (1).

(Wherein R ₁ and R ₄ are monovalent organic groups having a phenyl group, and R ₂ , R ₃ , R ₅ and R ₆ are each independently a hydrogen atom or a monovalent organic group. Q ₁ and Q ₂ are independent from each other, and at least one of them is one of two groups represented by the following formula (2), and X is a divalent group not containing a halogen element or a single bond. .)

R ₁ , R ₂ , R ₄ , and R ₅ are monovalent organic groups having a phenyl group, and R ₃ and R ₆ are each independently a hydrogen atom or a monovalent organic group. Item 4. A naphthoquinone diazide compound according to Item 1. X is —SO ₂ — or —CR ₇ R ₈ —, wherein R ₇ and R ₈ are each independently a monovalent organic group having 1 to 4 carbon atoms. The naphthoquinone diazide compound according to claim 1 or 2. R ₁ , R ₂ , R ₄ , and R ₅ are phenyl groups, R ₃ and R ₆ are hydrogen atoms, and X is —SO ₂ — or —C (CH ₃ ) ₂ —. The naphthoquinone diazide compound according to claim 3. An amidophenol compound represented by the following general formula (3).

(Wherein R ₉ and R ₁₂ are monovalent organic groups having a phenyl group, and R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each independently a hydrogen atom or a monovalent organic group. X is a divalent group not containing a halogen element or a single bond.) R ₉ , R ₁₀ , R ₁₂ , and R ₁₃ are monovalent organic groups having a phenyl group, and R ₁₁ and R ₁₄ are each independently a hydrogen atom or a monovalent organic group. Item 6. The amidophenol compound according to Item 5. X is —SO ₂ — or —CR ₁₅ R ₁₆ —, wherein R ₁₅ and R ₁₆ are each independently a monovalent organic group having 1 to 4 carbon atoms. The amidophenol compound according to claim 5 or 6. R ₉ , R ₁₀ , R ₁₂ , and R ₁₃ are phenyl groups, R ₁₁ and R ₁₄ are hydrogen atoms, and X is —SO ₂ — or —C (CH ₃ ) ₂ —. The amidophenol compound according to claim 7.   A positive photosensitive resin composition comprising 100 parts by mass of an alkali-soluble resin and 1 to 50 parts by mass of the naphthoquinone diazide compound according to any one of claims 1 to 4.   A semiconductor device comprising a heat-resistant film formed from the positive photosensitive resin composition according to claim 9.   A method of manufacturing a semiconductor device, comprising applying the positive photosensitive resin composition according to claim 9 onto a semiconductor element, and prebaking, exposing, developing, and heating.

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