JP5731213B2 - Tetrakisphenol compound, photosensitive agent using the same, photosensitive resin composition, cured film thereof, protective film, insulating film, semiconductor device, and display device using the same - Google Patents

Description

  The present invention relates to a tetrakisphenol compound, a photosensitive agent using the same, a photosensitive resin composition, a cured film thereof, and a protective film, an insulating film, a semiconductor device, and a display device using the tetrakisphenol compound. In particular, tetrakisphenol compounds are novel substances used in photosensitive resin compositions.

  In recent years, photosensitive resin compositions have been developed that can simplify some of the relief pattern forming process by imparting photosensitivity to the resin itself.

  Conventionally, production of a relief pattern using a positive photosensitive resin composition has been performed as follows. First, the coating film made of a positive photosensitive resin composition formed on a wafer is irradiated (exposed) with actinic radiation from above the mask with an exposure device called a stepper. Thereby, an exposed portion (hereinafter, exposed portion) and an unexposed portion (hereinafter, unexposed portion) are formed. The photosensitive diazoquinone compound present in the unexposed area is insoluble in the alkaline aqueous solution as the developer, and further has resistance to the alkaline aqueous solution by interacting with the resin in the coating film. On the other hand, the photosensitive diazoquinone compound present in the exposed area undergoes a chemical change by the action of actinic radiation due to exposure, solubilizes in an alkaline developer, and further promotes dissolution of the resin in the coating film. Therefore, by utilizing the difference in solubility between the exposed portion and the unexposed portion to dissolve and remove only the exposed portion, a relief pattern composed of the unexposed portion can be produced.

  Such a relief pattern is the second and subsequent layers in wafer level package redistribution technology for the purpose of reducing the stress of solder balls and reducing the size and weight of the package in a flip chip structure corresponding to the increase in the number of pins of semiconductor elements. The resin layer is used for patterning. In addition, the relief pattern is increasingly processed from a thick resin layer exceeding 10 μm. Therefore, a photosensitive resin composition with higher sensitivity is strongly desired. In addition, with the high integration of semiconductor elements, the relief pattern itself is miniaturized, and it is important to increase the resolution of the photosensitive resin composition.

  On the other hand, from the viewpoint of safety, a positive photosensitive resin composition that can be developed with an alkaline aqueous solution has been developed. For example, Patent Document 1 discloses a positive resist using a polybenzoxazole precursor as an alkali-soluble resin and based on photosensitive diazoquinone.

  The photosensitive diazoquinone used in such a photosensitive agent uses a phenol compound as a support. For example, in Patent Document 2, a tetrakisphenol compound having an aliphatic structure in the main chain skeleton is used as a phenol compound serving as a support for a photosensitive agent, and 1,2-naphthoquinonediazide-5- (or -4-) is used. A positive photoresist composition comprising an ester compound with a sulfonic acid is disclosed.

  In Patent Document 3, α, α, α ′, α′-tetrakis (4-hydroxyphenyl) -p-xylene is used as a tetrakisphenol compound, and 1,2-naphthoquinonediazide-5- (and / or -4-) A photosensitive material obtained by reacting with sulfonium chloride, and a positive photoresist composition containing the photosensitive material and an alkali-soluble resin are disclosed.

Japanese Examined Patent Publication No. 1-46862 JP 2001-240589 A JP-A-5-249665

  However, the photosensitizers described in the above-mentioned patent documents have poor solvent solubility, so that they may crystallize and precipitate during storage. Further, in the manufacturing process of the semiconductor device, the yield tends to decrease when the photosensitive agent stays for a long time.

  In addition, when the photosensitive agent is applied to a photosensitive resin composition together with a polyamide resin such as a polyimide precursor or a polybenzoxazole precursor, the sensitivity is insufficient when patterning the photosensitive resin composition film, There were problems such as increased exposure time.

  On the other hand, if too much photosensitizer is added in order to improve exposure sensitivity, the bottom of the pattern after development of the exposed area is dissolved by the photosensitive resin composition that has not become an alkali-soluble compound due to the action of actinic radiation. The remainder (scum) tends to occur, and as a result, the resolution tends to decrease. In particular, when photosensitive diazoquinone was used as a photosensitive agent, the exposure sensitivity could be improved by increasing the esterification rate of naphthoquinonediazidesulfonic acid, which is a photosensitive group, but the above scum generation problem could not be solved. . Thus, in the positive photosensitive resin composition, exposure sensitivity and resolution were in a trade-off relationship.

  The present invention has been made in view of the above circumstances, has a novel storage stability and a novel tetrakisphenol compound that can achieve both exposure sensitivity and resolution, a photosensitive agent using the same, and a photosensitive resin composition The present invention provides a cured film, and a protective film, an insulating film, a semiconductor device, and a display device using the cured film.

According to the present invention, the tetrakisphenol compound represented by the general formula (1) ,
A tetrakisphenol compound is provided , wherein Ar in the general formula (1) is a group represented by the following general formula (2) .

（式（１）中、Ａｒはフェノール性水酸基を有するアリール基であり、同一でも異なってもよく、２位、３位、４位、５位、６位のいずれかで置換したものである。）

（式（２）中、＊は一般式（１）の−ＣＨ基に結合することを示す。Ｒ _１ はアルキル基、アルコキシ基、アルケニル基、シクロアルキル基から選ばれる基であり、複数ある場合は同一でも異なってもよい。ａは０〜４の整数である。）

(In the formula (1), Ar is an aryl group having a phenolic hydroxyl group, which may be the same or different, and is substituted at any of the 2-position, 3-position, 4-position, 5-position, and 6-position. )

(In the formula (2), * represents bonding to the —CH group in the general formula (1). R ₁ is a group selected from an alkyl group, an alkoxy group, an alkenyl group, and a cycloalkyl group. May be the same or different, and a is an integer of 0 to 4.)

（式（３）中、Ｒ _２ ，Ｒ _３ ，Ｒ _４ ，Ｒ _５ はそれぞれアルキル基、アルコキシ基、アルケニル基、シクロアルキル基から選ばれる基であり、それぞれ複数ある場合は同一でも異なってもよい。ｂ，ｃ，ｄ，ｅはそれぞれ０〜４の整数である。Ｑは、水素原子、式（４）または式（５）のいずれかから選ばれるものである。また式（３）中の各Ｑのうち、少なくとも１つは式（４）または式（５）で表される。）

Further, according to the present invention, and tetrakis phenol compound with 1,2-naphthoquinonediazide-4-sulfonic acid and 1,2 at least one of the naphthoquinonediazide ester diazide-5-sulfonic acid and, in configured Ru sensitizer Yes,
A photosensitive agent is provided in which the photosensitive agent is represented by the following general formula (3) .

(In the formula (3), R ₂ , R ₃ , R ₄ and R ₅ are each a group selected from an alkyl group, an alkoxy group, an alkenyl group and a cycloalkyl group. B, c, d and e are each an integer of 0 to 4. Q is a hydrogen atom, selected from the formula (4) or the formula (5), and in the formula (3) (At least one of each Q is represented by Formula (4) or Formula (5).)

  Moreover, according to this invention, the photosensitive resin composition characterized by including the said photosensitive agent and alkali-soluble resin is provided.

  Furthermore, according to the present invention, a cured film comprising the cured product of the photosensitive resin composition, and a protective film and an insulating film comprising the cured film. In addition, a semiconductor device and a display pair device having the cured film are provided.

  According to the present invention, a novel tetrakisphenol compound that has good storage stability and can achieve both exposure sensitivity and resolution, a photosensitive agent using the same, a photosensitive resin composition, a cured film thereof, and the use thereof A protective film, an insulating film, a semiconductor device, and a display device can be provided.

  Hereinafter, a novel tetrakisphenol compound of the present invention, a photosensitive agent using the same, a photosensitive resin composition, a cured film thereof, and a protective film, an insulating film, a semiconductor device, and a display device using the same will be described. .

(Tetrakisphenol compound)
The tetrakisphenol compound (hereinafter referred to as tetrakisphenol compound (a)) represented by the general formula (1) of the present invention is a novel substance, and α, α, α ′, α′-tetrakis (hydroxyphenyl)- 4,4′-dimethyldiphenyl ether compounds.

（式（１）中、Ａｒはフェノール性水酸基を有するアリール基であり、同一でも異なってもよく、２位、３位、４位、５位、６位のいずれかで置換したものである。）

(In the formula (1), Ar is an aryl group having a phenolic hydroxyl group, which may be the same or different, and is substituted at any of the 2-position, 3-position, 4-position, 5-position, and 6-position. )

  Examples of Ar in the general formula (1) include aryl compounds having a phenolic hydroxyl group represented by the following general formula (2).

（式（２）中、＊は一般式（１）中の−ＣＨ基に結合することを示す。Ｒ_１は、アルキル基、アルコキシ基、アルケニル基、シクロアルキル基の中から選ばれる基であり、それぞれ複数ある場合は同一でも異なってもよい。ａは、０〜４の整数である。）

(In formula (2), * represents bonding to the —CH group in general formula (1). R ₁ is a group selected from an alkyl group, an alkoxy group, an alkenyl group, and a cycloalkyl group. In the case where there are a plurality of them, they may be the same or different, and a is an integer of 0 to 4.)

In R ₁ in the general formula (2), the alkyl group includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the alkenyl group include an ethenyl group, a propenyl group, and a butenyl group. Examples of the cycloalkyl group include , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. Among these, a methyl group, an ethyl group, and a cyclohexyl group are particularly preferable from the viewpoint of excellent sensitivity and resolution of the photosensitive resin composition.

  Specific examples of the aryl compound having a phenolic hydroxyl group include phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5- Dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-methoxyphenol, 3-methoxyphenol, 4 -Methoxyphenol, 2,3-dimethoxyphenol, 2,4-dimethoxyphenol, 2,5-dimethoxyphenol, 2,6-dimethoxyphenol, 3,4-dimethoxyphenol, 3,5-dimethoxyphenol, 2-propenylphenol , 2-allylfe 4-hydroxystilbene, 3-hydroxyphenylacetylene, 2-allyl-6-methylphenol, 2-methoxy-4-vinylphenol, 2-methoxy-4-propenylphenol, 4-allyl-2-methoxyphenol, 2-allyl-6-methoxyphenol, 4-allyl-2,6-dimethoxyphenol, 2-cyclohexylphenol, 2-methyl-5-cyclohexylphenol, 2-methoxy-4-methylphenol, 2-methoxy-5-methyl Examples thereof include phenol and 3-methoxy-5-methylphenol. Among these, from the reactivity when synthesizing a tetrakisphenol compound and the sensitivity of the photosensitive resin composition, phenol, 2-methylphenol, 4-methylphenol, 2,5-dimethylphenol, 2-cyclohexylphenol, 2-methyl- 5-cyclohexylphenol is preferred.

  Although it does not specifically limit as a tetrakisphenol compound (a), For example, what is shown by following formula (8) is mentioned.

  The tetrakisphenol compound (a) can be produced as follows. For example, it can be produced by condensing 4,4′-diformyldiphenyl ether represented by the general formula (6) and phenols in the presence of hydrogen chloride and alkyl mercaptans as a catalyst.

  The production method of 4,4′-diformyl diphenyl ether represented by the general formula (6) as a raw material is not particularly limited, but as an example, 4,4′-diphenyl ether dicarboxylic acid or 4,4′-dimethyl diphenyl ether is used as a starting material. The manufacturing method etc. which used it as a raw material are mentioned.

  When 4,4′-diphenyl ether dicarboxylic acid is used as a starting material, first an acid chloride using an acid halogenating agent such as thionyl chloride is used to form lithium chloride, such as lithium aluminum hydride or sodium bis (2-methoxyethoxy) aluminum hydride. After induction into a dialcohol with a reducing agent, oxidation with manganese dioxide, oxidation with a combination of dimethyl sulfoxide (DMSO) and oxalyl chloride, dicyclohexylcarbodiimide, acetic anhydride, or the like, 2,2,6,6-tetramethylpiperidine- It can be oxidized by oxidation with a combination of 1-oxyl (TEMPO) and hypochlorous acid to obtain 4,4′-diformyldiphenyl ether.

  Moreover, after making alcohol act on acid chloride or making dicarboxylic acid into a diester body using dialkyl sulfuric acid or alcohol and an acid catalyst, reduction, such as lithium aluminum hydride and sodium bis (2-methoxyethoxy) aluminum hydride, etc. There is also a method in which a dialcohol is formed by an agent and oxidized by the method described above.

  When 4,4'-dimethyldiphenyl ether is used as a starting material, first, after halogenating the side chain using a halogenating agent such as chlorine, bromine, N-chlorosuccinimide, or N-bromosuccinimide, 4,4′-diformyl diphenyl ether is obtained directly by hydrolysis to dialcohol, oxidation by the above-mentioned method, or Sommere reaction in which side chain halide is reacted with hexamethylenetetramine to hydrolyze. There is also a method.

  In this reaction, 4,4′-diformyldiphenyl ether, phenols, and alkyl mercaptan as a catalyst are respectively charged into a pressure vessel in a predetermined amount and heated to a predetermined reaction temperature with stirring to form a reaction solution. The hydrogen chloride gas is supplied until a predetermined pressure is reached.

  The stoichiometric amount of phenols may be 4 moles of phenols per mole of 4,4'-diformyldiphenyl ether, but it is usually used as a solvent. Is also possible. The amount used is 4 to 50 moles, preferably 6 to 30 moles, with respect to 4,4′-diformyldiphenyl ether.

  As the catalyst hydrogen chloride, anhydrous hydrogen chloride gas is preferably used. The amount of hydrogen chloride gas used is preferably 0.15 mol or more based on 4,4′-diformyl diphenyl ether in order to obtain a sufficient reaction rate. There is no particular upper limit on the amount of hydrogen chloride used.

  Examples of alkyl mercaptans used as a catalyst together with hydrogen chloride include, but are not limited to, ethyl mercaptan, propyl mercaptan, butyl mercaptan, and the like. The amount of the alkyl mercaptan used is usually 0.01 to 0.5 mol times, preferably 0.05 to 0.3 mol times based on 4,4′-diformyl diphenyl ether.

  The reaction temperature is not particularly limited as long as the reaction proceeds, but it is usually performed at room temperature to 100 ° C. The reaction time is usually 1 to 24 hours, although it depends on conditions such as the amount of hydrogen chloride and alkyl mercaptans, reaction temperature and the like.

  The main product of this reaction is the one substituted at any of the 2-position, 3-position, 4-position, 5-position or 6-position of phenols, but one compound substituted at another position or two A compound substituted at a position may also be generated. When a single structure with high purity is required, it can be separated using means such as recrystallization or column chromatography.

(Photosensitive agent)
The photosensitizer of the present invention comprises the above tetrakisphenol compound (a) and at least one of esters of 1,2-naphthoquinonediazide-4-sulfonic acid and 1,2-naphthoquinonediazide-5-sulfonic acid (hereinafter referred to as photosensitivity). Agent (A). The photosensitizer of the present invention is prepared by, for example, dissolving the tetrakisphenol compound (a) and 1,2-naphthoquinonediazide-4- (or -5) sulfonyl chloride in a solvent such as tetrahydrofuran, dioxane, acetone or the like. After that, a basic catalyst such as triethylamine or pyridine is slowly dropped while paying attention to heat generation. After reacting at room temperature for several hours, the reaction solution is poured into water, and the precipitated product is filtered, washed with water, and dried. Can be obtained.

(Photosensitive resin composition)
The photosensitive resin composition of this invention contains the said photosensitive agent (A) and alkali-soluble resin (B). Thereby, even if the film thickness of the photosensitive resin composition exceeds 10 μm, good storage stability can be obtained while achieving both exposure sensitivity and resolution. The reason is considered as follows.

  In the photosensitive agent (A), the distance between the photosensitive groups represented by the 1,2-naphthoquinonediazide-4- (or-5-) sulfonic acid ester structure is larger than that of the conventional photosensitive agent. Therefore, even a small amount can cause interaction with a wide range of alkali-soluble resin, and the resistance (dissolution inhibiting ability) to the developer in the unexposed area is increased. Thereby, the resolution can be improved. Further, in the case of a general phenol compound, a hydroxyl group is also present in the main skeleton other than the terminal, but due to steric hindrance, 1,2-naphthoquinone-2-diazido-5- (and / or -4-) sulfonic acid and These esters are difficult to be formed and often exist as they are. In this case, since the resistance (dissolution prevention ability) of the unexposed portion to the developer is reduced, the resolution is lowered due to the occurrence of scum or the dissolution contrast. Therefore, it is considered that the aromatic ring in the main skeleton of the tetrakisphenol compound (a) of the present invention does not have a hydroxyl group, and the hydrophobicity increases due to the large number of aromatic rings, thereby improving the resolution.

  On the other hand, in the exposed area, the tetrakisphenol compound (a) of the present invention has a hydroxyl group only at the terminal, so that 1,2-naphthoquinonediazide-4- (or-5-) sulfonic acid ester structure is substituted there. It is possible to react when an alkali-soluble resin existing in a wide range around can be dissolved. Thereby, melt | dissolution to the developing solution of the resin of an exposure part can be accelerated | stimulated. In general, it is considered that the developer enters further into the space formed after dissolution in the developer, thereby removing the resin and forming a pattern. Therefore, since the tetrakisphenol compound (a) of the present invention has a large molecular weight, it is considered that the alkali-soluble resin is liable to collapse when a larger amount of the developer enters, and the resin in the exposed area is easily removed. As a result, it is considered that the exposure sensitivity is improved.

  In addition, the tetrakisphenol compound (a) of the present invention is highly preserved in that it does not cause a change over time such as high solvent solubility, chemical stability, and precipitation due to a freely rotatable ether bond of the aromatic ring linking group in the main skeleton. It is thought that stability is demonstrated. As one of the factors, since it contains many aromatic rings, it can be considered that the affinity with alkali-soluble resins such as polyamide resins is high.

  Furthermore, the photosensitive resin composition of the present invention has scum-free properties. That is, according to the present invention, even when a resin having a low molecular weight of an alkali-soluble resin and a high solubility in an aqueous alkali solution is used, the relief pattern of the unexposed area collapses and scum is formed at the bottom of the exposed area. The generation of scum can be suppressed even when the esterification rate of naphthoquinonediazidesulfonic acid, which is a photosensitive group, is increased.

  Specifically, the photosensitive agent (A) is a photosensitive diazoquinone compound represented by the following general formula (3).

（式（３）中、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５はそれぞれアルキル基、アルコキシ基、アルケニル基、シクロアルキル基から選ばれる基であり、それぞれ複数ある場合は同一でも異なってもよい。ｂ、ｃ、ｄ、ｅはそれぞれ０〜４の整数である。Ｑは、水素原子、式（４）または式（５）のいずれかから選ばれるものである。式（３）中の各Ｑのうち、少なくとも１つは式（４）または式（５）で表される。）

(In the formula (3), R ₂ , R ₃ , R ₄ and R ₅ are each a group selected from an alkyl group, an alkoxy group, an alkenyl group and a cycloalkyl group, and when there are plural groups, they may be the same or different. B, c, d and e are each an integer of 0 to 4. Q is a hydrogen atom, selected from the formula (4) or the formula (5), each of the formula (3) (At least one of Q is represented by Formula (4) or Formula (5).)

R ₂ , R ₃ , R ₄ and R ₅ in the general formula (3) are groups selected from an alkyl group, an alkoxy group, an alkenyl group, and a cycloalkyl group. May be. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. A methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like are mentioned. Examples of the alkenyl group include an ethenyl group, a propenyl group, a butenyl group, and the like. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, A cyclohexyl group and the like can be mentioned. Among them, a methyl group, an ethyl group, and a cyclohexyl group are particularly preferable from the viewpoint of excellent sensitivity and resolution of the photosensitive resin composition.

  Specific examples of the photosensitive agent (A) include those represented by the following formula (9).

  Although content of a photosensitizer (A) is not specifically limited, 1-50 weight part is preferable with respect to 100 weight part of alkali-soluble resin (B), and 10-40 weight part is especially preferable. By setting the content within the above range, a positive photosensitive resin composition having good sensitivity and resolution without scum can be obtained.

  In addition, the positive photosensitive resin composition of the present invention can be used in combination with other photosensitive agents as long as the sensitivity, resolution, and storage stability are not greatly affected. As the photosensitive agent that can be used, a compound capable of generating an acid upon irradiation with actinic radiation having a wavelength of 200 to 500 nm, particularly preferably 350 to 450 nm is preferable.

  Specifically, photosensitive diazoquinone compounds using phenolic compounds other than the present invention, onium salts such as diaryliodonium salts, triarylsulfonium salts, sulfonium borate salts, 2-nitrobenzyl ester compounds, N-iminosulfonate compounds An imide sulfonate compound, a 2,6-bis (trichloromethyl) -1,3,5-triazine compound, a dihydropyridine compound, or the like can be used.

  As the phenolic compound that is a support of the photosensitive diazoquinone compound that can be used in combination, a phenolic compound having about 1 to 10 phenol nuclei, a low molecular weight novolak resin, or the like can be used. Specifically, bisphenol, trisphenol, tetrakisphenol other than the tetrakisphenol compound (a) of the present invention, a phenol compound in which about 3 to 6 phenol nuclei are linearly bonded via a methylene bond, and the like are used. Can do.

  More specifically, there can be mentioned phenol compounds represented by the formulas (10) and (11), which are excellent in sensitivity, but are not particularly limited. These esters with 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid may be used alone or in combination of two or more. Also good.

  The alkali-soluble resin (B) in the present invention has a hydroxyl group, particularly a phenolic hydroxyl group and / or a carboxyl group. For example, acrylic resin such as cresol type novolak resin, hydroxystyrene resin, methacrylic acid resin, methacrylic ester resin, etc. -Based resins, cyclic olefin-based resins, polyamide resins and the like are mentioned, and among these, polyamide resins are preferable.

  Here, in the present invention, the polyamide resin refers to a resin having a benzoxazole precursor structure and / or an imide precursor structure. In addition, the polyamide resin may have a benzoxazole structure or an imide structure generated by a ring-closing reaction of a part of the benzoxazole precursor structure or imide precursor structure, and also has an amic acid ester structure. May be.

  The benzoxazole precursor structure refers to a structure represented by the following formula (12), the imide precursor structure refers to a structure represented by the following formula (13), and the benzoxazole structure refers to the following The structure represented by Formula (14) is pointed out, the imide structure refers to the structure represented by Formula (15) below, and the amido ester structure refers to the structure represented by Formula (16) below.

  In addition, D and R in said formula (12)-(16) show an organic group. Among these polyamide resins, a polyamide resin having a repeating unit represented by the following general formula (17) is preferable.

（式（１７）中、Ｘ、Ｙは有機基である。Ｒ_７は水酸基、−Ｏ−Ｒ_９、アルキル基、アシルオキシ基、シクロアルキル基であり、同一でも異なってもよい。Ｒ_８は水酸基、カルボキシル基、−Ｏ−Ｒ_９、−ＣＯＯ−Ｒ_９のいずれかであり、同一でも異なってもよい。ｇは０〜８の整数、ｈは０〜８の整数である。Ｒ_９は炭素数１〜１５の有機基である。ここで、Ｒ_７が複数ある場合は、それぞれ異なっていても同じでもよい。Ｒ_７として水酸基がない場合は、Ｒ_８は少なくとも１つはカルボキシル基でなければならない。また、Ｒ_８としてカルボキシル基がない場合、Ｒ_７は少なくとも１つは水酸基でなければならない。）

(In formula (17), X and Y are organic groups. R ₇ is a hydroxyl group, —O—R ₉ , an alkyl group, an acyloxy group, or a cycloalkyl group, which may be the same or different. R ₈ is a hydroxyl group. , A carboxyl group, —O—R ₉ or —COO—R ₉ , which may be the same or different, g is an integer of 0 to 8, h is an integer of 0 to 8. R ₉ is carbon. In the case where there are a plurality of R _{7 s} , they may be different or the same, and when R ₇ has no hydroxyl group, at least one R ₈ must be a carboxyl group. In addition, when there is no carboxyl group as R ₈ , at least one R ₇ must be a hydroxyl group.

In the polyamide resin represented by general formula _{(17), O-R 9} , COO-R 9 as substituents _O-R 9, Y as a substituent of X is soluble hydroxyl, an alkaline aqueous solution of the carboxyl group Is a group protected by R ₉ , which is an organic group having 1 to 15 carbon atoms, and a hydroxyl group or a carboxyl group may be protected if necessary. Examples of R ₉ include formyl, methyl, ethyl, propyl, isopropyl, tertiary butyl, tertiary butoxycarbonyl, phenyl, benzyl, tetrahydrofuranyl, tetrahydropyranyl and the like. It is done.

  The polyamide resin having the structure represented by the general formula (17) 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, 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.

  When the polyamide resin represented by the general formula (17) is heated at a high temperature, it is 280 ° C to 380 ° C, and when it is heated at a low temperature, it is dehydrated and ring-closed when treated at 150 ° C to 280 ° C. Alternatively, a heat resistant resin can be obtained in the form of copolymerization of both.

  X of the polyamide resin represented by the general formula (17) is not particularly limited. For example, aromatic compounds such as benzene ring and naphthalene ring, and heterocyclic compounds such as bisphenols, pyrroles and furans. And siloxane compounds, and more specifically, those represented by the following formula (18) can be mentioned as preferred examples. These may be used alone or in combination of two or more.

（式（１８）中＊は、ＮＨ基に結合することを示す。Ａは、アルキレン、置換アルキレン、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、−Ｃ（ＣＦ_３）_２−または単結合である。Ｒ_１０は、アルキル基、アルキルエステル基、ハロゲン原子から選ばれた１つを示し、それぞれ同じでも異なってもよい。Ｒ_１１は、水素原子、アルキル基、アルキルエステル基、ハロゲン原子から選ばれた１つを示す。Ｒ_１２〜Ｒ_１５は、有機基である。ｉ＝０〜２の整数である。）

(In formula (18), * represents bonding to an NH group. A represents alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —C (═O) —, —NHC ( ═O) —, —C (CF ₃ ) ₂ — or a single bond, R ₁₀ represents one selected from an alkyl group, an alkyl ester group and a halogen atom, and may be the same or different. ₁₁ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom, R _{12 to} R ₁₅ are organic groups, and i is an integer of 0 to 2.

As shown in the above formula (17), 0 to 8 R ₇ are bonded to X (in formula (17), R ₇ is omitted).

  Particularly preferred among the above formula (18) are those represented by the following formula (19) and the following formula (20).

（式（１９）、式（２０）中、＊はＮＨ基に結合することを示す。式（１９）中、Ａ_１は、アルキレン、置換アルキレン、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、−Ｃ（ＣＦ_３）_２−、又は単結合である。式中Ａ_２は、アルキレン、置換アルキレン、−Ｏ−、−ＳＯ_２−、または単結合である。Ｒ_１６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よい。ｊは０〜３の整数である。）

(In formula (19) and formula (20), * represents bonding to an NH group. In formula (19), A ₁ represents alkylene, substituted alkylene, —O—, —S—, —SO ₂ —. , —C (═O) —, —NHC (═O) —, —C (CF ₃ ) ₂ —, or a single bond, wherein A ₂ is alkylene, substituted alkylene, —O—, —SO _2. -Or a single bond, R ₁₆ is an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group, which may be the same or different, and j is an integer of 0 to 3.

  Particularly preferred among the above formulas (19) and (20) are those represented by the following formula (21).

（式（２１）中＊は、ＮＨ基に結合することを示す。式中Ａ_３は、アルキレン、置換アルキレン、−Ｏ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、又は単結合である。Ｒ_１７はアルキレン、置換アルキレン、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、−Ｃ（ＣＦ_３）_２−、単結合から選ばれる有機基である。）

(In formula (21), * represents bonding to an NH group. In the formula, A ₃ represents alkylene, substituted alkylene, —O—, —SO ₂ —, —C (CF ₃ ) ₂ —, or a single bond). R ₁₇ is alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —C (═O) —, —NHC (═O) —, —C (CF ₃ ) ₂ —, simple An organic group selected from a bond.)

Specific examples of A in the above formula (18), A ₁ and A _{2 in} the above formula (19), R ₁₇ and A _{3 in} the above formula (21), and substituted alkylene include —CH ₂ —, — _{CH (CH 3) -, -} C (CH 3) 2 -, - CH (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 3) -, - C (CH 2 CH 3) (CH _{2 CH 3) -, - CH} (CH 2 CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - CH (CH (CH 3) 2) -, - C (CH _{3) (CH (CH 3)} 2) -, - CH (CH 2 CH 2 CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 2 CH 3) -, - CH (CH 2 CH _{(CH 3) 2) -,} - C (CH 3) (CH 2 CH (CH 3) 2) -, - CH (CH 2 CH 2 _{CH 2 CH 2 CH 3) -} , - C (CH 3) (CH 2 CH 2 CH 2 CH 2 CH 3) -, - CH (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) -, - C ( CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) — and the like can be mentioned. Among them, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ — are alkaline. It is preferable because a polyamide resin having sufficient solubility in not only an aqueous solution but also a solvent and having a better balance can be obtained.

  Y in the formula (17) is an organic group, and examples thereof include those similar to X. For example, aromatic compounds such as a benzene ring and a naphthalene ring, complex compounds such as bisphenols, pyrroles, pyridines and furans. A cyclic compound, a siloxane compound, etc. are mentioned, More specifically, what is shown by following formula (22) can be mentioned preferably. These may be used alone or in combination of two or more.

（式（２２）中＊は、Ｃ＝Ｏ基に結合することを示す。Ｊは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、−Ｃ（ＣＦ_３）_２−または単結合である。Ａは、アルキレン、置換アルキレン、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、−Ｃ（ＣＦ_３）_２−または単結合である。Ｒ_１８は、アルキル基、アルキルエステル基、アルキルエーテル基、ベンジルエーテル基、ハロゲン原子から選ばれた１つを示し、それぞれ同じでも異なってもよい。Ｒ_１９は、水素原子、アルキル基、アルキルエステル基、ハロゲン原子から選ばれた１つを示す。Ｒ_２０〜Ｒ_２３は、有機基である。ｋ＝０〜２の整数である。）

(In formula (22), * indicates bonding to a C═O group. J represents —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —C (═O) —, —NHC (═O) —, —C (CF ₃ ) ₂ — or a single bond, A is alkylene, substituted alkylene, —O—, —S—, —SO ₂ —. , —C (═O) —, —NHC (═O) —, —C (CF ₃ ) ₂ — or a single bond, R ₁₈ represents an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, R ₁₉ represents one selected from a halogen atom, which may be the same or different, and R ₁₉ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom, and R _{20 to} R ₂₃ represent An organic group, k is an integer of 0 to 2.)

As shown in equation (17), the Y _{R 8} is 0 to 8 binding (in the formula (17), _{R 8} is omitted).

  Among these, a compound represented by the following formula (23) is particularly preferable. As for the structure derived from tetracarboxylic dianhydride in the following formula (23), 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.

（式（２３）中、＊はＣ＝Ｏ基に結合することを示す。式中、Ａ_４は、−Ｏ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−から選ばれる有機基である。式中Ａ_５、Ａ_６は、−Ｃ（ＣＨ_３）_２−、−Ｃ（＝Ｏ）−、−Ｏ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、又は単結合である。Ｒ_２４は、アルキル基、アルキルエステル基、アルキルエーテル基、ベンジルエーテル基、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。Ｒ_２５は、水素原子又は炭素数１〜１５の有機基から選ばれた１つを示し、一部が置換されていてもよい。ｌ＝０〜２の整数である。）

(In the formula (23), * represents bonding to a C═O group. In the formula, A ₄ is an organic group selected from —O—, —SO ₂ —, and —C (═O) —). In the formula, A ₅ and A ₆ are —C (CH ₃ ) ₂ —, —C (═O) —, —O—, —SO ₂ —, —C (CF ₃ ) ₂ —, or a single bond. R ₂₄ represents one selected from an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and a halogen atom, and may be the same or different, and R ₂₅ represents a hydrogen atom or a carbon atom. 1 represents one selected from organic groups of 1 to 15, and a part thereof may be substituted. L is an integer of 0 to 2.)

The polyamide resin having the repeating unit represented by the general formula (17) is an aliphatic group having a terminal amino group and at least one alkenyl group or alkynyl group, or a cyclic group. It is preferred to cap as an amide using an acid anhydride containing a formula compound group. Thereby, preservability can be improved.
Examples of such a group derived from an acid anhydride containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group include formula (24) and formula (25 ) And the like. These may be used alone or in combination of two or more.

  The method is not limited to this method, and the terminal carboxylic acid contained in the polyamide 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.

  Furthermore, in the case of the polyamide resin represented by the above formula (17), at least one of the terminals may have a nitrogen-containing cyclic compound to the extent that it does not affect the mechanical properties and heat resistance when cured at a low temperature. . Thereby, adhesiveness with a metal wiring (especially copper wiring) etc. can be improved.

  Examples of the nitrogen-containing cyclic compound include 1- (5-1H-triazoyl) methylamino group, 3- (1H-pyrazoyl) amino group, 4- (1H-pyrazoyl) amino group, and 5- (1H-pyrazoyl) amino. Group, 1- (3-1H-pyrazolyl) methylamino group, 1- (4-1H-pyrazoyl) methylamino group, 1- (5-1H-pyrazolyl) methylamino group, (1H-tetrazol-5-yl) An amino group, 1- (1H-tetrazol-5-yl) methyl-amino group, 3- (1H-tetrazol-5-yl) benz-amino group and the like can be mentioned.

  Furthermore, in the present invention, a phenolic compound can be added so that patterning can be performed with high sensitivity and without resin residue (scum) after development.

  The resin composition and the photosensitive resin composition in the present invention include an oxirane compound, an oxirane resin, a methylol group-containing compound, an alkoxyalkyl group-containing compound, an N-alkoxyalkyl group-containing compound, and a bifunctional or more unsaturated double as necessary. Bonding agents such as bonds or triple bond-containing compounds, leveling agents such as acrylics, silicones, fluorines and vinyls, silane coupling agents, antioxidants, compounds that generate acids by heat, and dissolution in alkaline aqueous solutions An additive such as an inhibitor and a plasticizer may be included.

  In the present invention, these components are dissolved in a solvent and used in the form of a varnish. Solvents 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, 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 and the like may be mentioned, and these may be used alone or in combination.

  In the method of using the photosensitive resin composition of the present invention, first, the composition is applied to a suitable support such as a silicon wafer, a ceramic substrate, an aluminum substrate and 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 film and insulating film for semiconductor elements, and if the film thickness exceeds the upper limit value, it will be difficult to obtain a fine relief pattern. , Processing takes time and throughput decreases. 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 (curing) is performed to form an oxazole ring, or an oxazole ring and an imide ring, and a cured product having high heat resistance is obtained.

  The heat treatment can be performed at a high temperature or a low temperature, and the heat treatment temperature at a high temperature is preferably 280 ° C to 380 ° C, more preferably 290 ° C to 350 ° C. The heat treatment temperature at low temperature is preferably 150 ° C. to 280 ° C., more preferably 180 ° C. to 260 ° C. An oven, a hot plate, an electric furnace (furnace), infrared rays, microwaves, etc. are used for the heat treatment.

(Protective film, insulating film)
In addition, the protective film and the insulating film of the present invention are characterized by being composed of a cured film that is a cured product of the photosensitive resin composition. 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.

(Semiconductor device, display device)
In addition, a semiconductor device and a display device according to the present invention are configured by the cured 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. A 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-described photosensitive resin composition on a circuit formed on a semiconductor element, an α-ray blocking film, a flat surface Examples thereof include a chemical 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 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.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to this. The analysis was performed using high performance liquid chromatography.

(Synthesis Example 1) Synthesis of 4,4′-diphenyl ether dicarboxylic acid chloride In a 300 mL four-necked flask, 22.0 g (0.085 mol) of 4,4′-diphenyl ether dicarboxylic acid, 99.0 g of toluene, N, N-dimethyl 0.20 g (0.003 mol) of formamide was charged, the temperature was raised to 75 ° C., and 30.4 g (0.256 mol) of thionyl chloride was added dropwise at 75 to 80 ° C. After maintaining at the same temperature for 7 hours, the mixture was cooled to 30 ° C. and 2.19 g of activated carbon was added and maintained for 1 hour. After the activated carbon was filtered and the activated carbon was washed with toluene, the solvent was distilled off until the total amount of substances in the flask reached 50 g. 21.6 g of heptane was added dropwise at room temperature, and the temperature was raised to 70 ° C. to dissolve. Insoluble matter was filtered while maintaining the temperature at 60 ° C. or higher, and the obtained filtrate was cooled to 50 ° C., 1 g of seed crystals was added, cooled to 0 ° C., and then kept for 2 hours. The precipitated crystals were filtered, washed with a mixed solvent of 10.0 g of heptane and 6.60 g of toluene, and dried under reduced pressure at 20 ° C. to obtain 21.0 g of 4,4′-diphenyl ether dicarboxylic acid chloride. The yield was 83.4% and the HPLC purity was 99.4%.

Synthesis Example 2 Synthesis of 4,4′-bis (hydroxymethyl) diphenyl ether A 300 mL four-necked flask was charged with 3.86 g (0.102 mol) of lithium aluminum hydride and 150 g of tetrahydrofuran, and 4,4′-diphenyl ether dicarboxylic acid. 10 g (0.034 mol) of acid chloride was added in portions of 1 g. The temperature was raised to reflux, the temperature was maintained for 6 hours, and then cooled to 10 ° C. Thereto, 60 g of water was added dropwise over 1 hour, then 4.30 g of 35% hydrochloric acid was added dropwise, and 50 g of ethyl acetate was added. Insoluble matter was filtered off, and the solvent was distilled off from the resulting filtrate, followed by drying at 50 ° C. to obtain 7.45 g of white 4,4′-bis (hydroxymethyl) diphenyl ether. The yield was 95.5% and the HPLC purity was 97.5%.

(Synthesis Example 3) Synthesis of 4,4'-diformyldiphenyl ether (II) In a 1 L four-necked flask, 10 g (0.043 mol) of 4,4'-bis (hydroxymethyl) diphenyl ether, 200 g of methylene chloride, and TEMPO were 0. .14 g (0.001 mol) and 4.52 g (0.004 mol) of an aqueous potassium bromide solution were charged and cooled to −10 ° C. A mixture of 142.2 g (0.096 mol) of 5% sodium hypochlorite and 2.42 g (0.029 mol) of sodium hydrogen carbonate was added dropwise thereto over 20 minutes, and the mixture was kept at 0 to 10 ° C. for 1 hour. Later it was separated. The aqueous layer was extracted with 80 g of methylene chloride, mixed with the organic layer, and washed with 50 g of 10% hydrochloric acid, 50 g of 10% aqueous sodium thiosulfate, and finally with 50 g of water. By distilling off the solvent, 9.9 g of brown liquid 4,4′-diformyldiphenyl ether (II) was quantitatively obtained. The HPLC purity was 99.3%.

(Example 1) Synthesis of α, α, α ′, α′-tetrakis (3-methyl-4-hydroxyphenyl) -4,4′-dimethyldiphenyl ether In a 300 mL glass autoclave equipped with a thermometer and a stirrer, After adding 12.9 g (0.057 mol) of 4,4′-diformyl diphenyl ether, 148 g (1.369 mol) of 2-methylphenol and 0.82 g (0.009 mol) of 1-butanethiol, 60 ° C. The temperature was raised to. The inside of the system was replaced with 0.1 MPa of nitrogen three times, 1 g (0.027 mol) of hydrogen chloride gas was added to make the internal pressure about 0.02 MPa, and the reaction was carried out at 60 ° C. for 8 hours. After completion of the reaction, the inside of the system was replaced with nitrogen, and then the reaction mixture was transferred to a 500 mL four-necked flask, and 2-methylphenol was distilled off at 80 to 110 ° C. A mixture of 194 g of toluene and 2.6 g of activated carbon was added to the residue and kept at room temperature for 2 hours. Activated carbon was filtered and toluene was distilled off to obtain 57.9 g of a crude product. From the HPLC analysis, the reaction yield was 74.3%. The composition of the crude product was 55.9% pure, 23.4% isomers differing in one 2-methylphenol substitution position, and 2.1 isomers differing in two 2-methylphenol isomer substitution positions. %Met.

(Example 2) Purification of α, α, α ', α'-tetrakis (3-methyl-4-hydroxyphenyl) -4,4'-dimethyldiphenyl ether (I) The crude product obtained in Example 1 was treated with acetic acid. It was dissolved in ethyl and purified by silica gel column chromatography. Chloroform / ethyl acetate (ratio 8/1 to 6/1) was used as a developing solvent, and the solvent was distilled off from the fractions, followed by drying at 70 ° C. under reduced pressure to obtain the title compound (I). The HPLC purity was 99.8%.

1H-NMR (CDCl3, [delta]): 2.18 (s, 12H), 4.65 (br, s, 4H), 5.31 (s, 2H), 6.66 (d, 4H, J = 8. 3 Hz), 6.76 (dd, 4H, J = 2.3, 8.3 Hz), 6.85 (d, 4H, J = 2.3 Hz), 6.89 (m, 4H), 7.01 ( m, 4H)
MS (EI) m / z: 622 [M +]

(Example 3)
First, a photosensitive agent (Q-1) was synthesized as follows.
12.46 g (0.020 mol) of the crude product α, α, α ′, α′-tetrakis (3-methyl-4-hydroxyphenyl) -4,4′-dimethyldiphenyl ether obtained in Example 1 Separation of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride (17.20 g, 0.064 mol) and acetone (170 g) with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet pipe It was put into a bull flask and stirred and dissolved. Next, a mixed solution of 7.12 g (0.070 mol) of triethylamine and 6.0 g of acetone was slowly added dropwise while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C. After reacting for 3 hours at room temperature, 1.00 g (0.016 mol) of acetic acid was added, and the reaction was further continued for 30 minutes. After filtering the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (990 ml / 10 ml), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and α, α, α ′, α Photosensitizer in which 80% of hydroxyl groups of '-tetrakis (3-methyl-4-hydroxyphenyl) -4,4'-dimethyldiphenyl ether are substituted with an ester of 1,2-naphthoquinone-2-diazido-4-sulfonic acid ( Q-1) 20.7g (yield 78.8%) was obtained.

  The obtained photosensitizer (Q-1) was analyzed by HPLC (LC-2000 manufactured by JASCO Corporation). From the peak area ratio, the tetraester form was 60.3%, the triester form was 21.1%, and the diester. The body was found to be a 3.1% mixture.

1H-NMR (DMSO-d6, δ): 2.01 (s, 2H), 2.10 (s, 10H), 5.47 (s, 2H), 6.67 (d, 2H), 6.78 -6.90 (m, 10H), 7.01-7.05 (m, 8H), 7.64-7.70 (m, 4H), 7.87-7.91 (m, 4H), 8 .25-8.30 (m, 7H), 8.46 (s, 3H)

Next, the alkali-soluble resin (A-1) was synthesized as follows.
418.59 g (0) of a dicarboxylic acid derivative (active ester) obtained by reacting 0.85 mol of diphenyl ether-4,4′-dicarboxylic acid with 1.70 mol of 1-hydroxy-1,2,3-benzotriazole .85 mol) and 366.26 g (1.00 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane are provided with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. The flask was placed in a four-necked separable flask, and 3200 g of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 16 hours using an oil bath. Next, 51.64 g (0.30 mol) of 4-ethynylphthalic anhydride dissolved in 150 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 3 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the number average molecular weight was 10700. Thus, a polybenzoxazole precursor resin was obtained as the alkali-soluble resin (A-1) having a blending amount shown in Table 1.

  After dissolving 10 g of the alkali-soluble resin (A-1) synthesized above and 1.5 g of the photosensitizer (Q-1) in a mixed solvent of 1.5 g of N-methyl-2-pyrrolidone and 13.5 g of γ-butyrolactone, The mixture was filtered through a 0.2 μm Teflon (registered trademark) filter and received in a polypropylene container to obtain a photosensitive resin composition. The obtained photosensitive resin composition was evaluated, and the results are shown in Table 1.

(Processability evaluation)
The obtained 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 13 μm. Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern of 0.88 to 50 μm in width and a removal pattern is drawn) is passed through an i-line stepper (Nikon Corporation NSR- 4425i) was used for irradiation with varying exposure.
Next, using a 2.38% tetramethylammonium hydroxide aqueous solution as the developer, the development time is adjusted so that the difference between the film thickness after pre-baking and the film thickness after development is 2.0 μm, and paddle development is performed twice. Then, the exposed portion was dissolved and removed, and then rinsed with pure water for 10 seconds. Thereafter, the exposed portion was observed to check sensitivity and resolution, and to check for the occurrence of scum.

(Evaluation of storage stability)
(I) When left at room temperature for 2 months The polypropylene container containing the obtained photosensitive resin composition was left in a yellow room at room temperature for 2 months. Thereafter, two sheets of this photosensitive resin composition were applied on a 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 10 μm. The appearance of the coating film obtained after prebaking was observed with a metallographic microscope, and the presence or absence of a crystalline substance was examined.
Next, another silicon wafer with a coating film was developed using a 2.38% tetramethylammonium hydroxide aqueous solution so that the difference between the film thickness after pre-baking and the film thickness after development was about 2 μm. And paddle development was performed twice. The appearance of the coated film after development was observed with a metal microscope, and the presence or absence of a crystal was examined.
(Ii) When stored for one week in a frozen state Further, a polypropylene container containing the photosensitive resin composition is placed in a polystyrene container so that the dry ice and the dry ice are in direct contact with each other. Left in a freezer for 1 week. Then, thaw to room temperature, apply the photosensitive resin composition on a silicon wafer using a spin coater in the same way as above, observe the appearance of the coating film after pre-baking and development, and check for the presence of crystals. It was.

Example 4
Photosensitive agent (Q-2) was synthesized as follows.
12.46 g (0.020 mol) of the title compound (I) obtained in Example 2, 17.20 g (0.064 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and acetone 170 g was put into a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, and stirred and dissolved. Next, a mixed solution of 7.12 g (0.070 mol) of triethylamine and 6.0 g of acetone was slowly added dropwise while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C. After reacting for 3 hours at room temperature, 1.00 g (0.016 mol) of acetic acid was added, and the reaction was further continued for 30 minutes. After filtering the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (990 ml / 10 ml), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and α, α, α ′, α Photosensitizer in which 80% of hydroxyl groups of '-tetrakis (3-methyl-4-hydroxyphenyl) -4,4'-dimethyldiphenyl ether are substituted with an ester of 1,2-naphthoquinone-2-diazido-4-sulfonic acid ( Q-2) 23.4 g (yield 89.1%) was obtained.

  When the obtained photosensitizer (Q-2) was analyzed by HPLC, it was a mixture of a tetraester form of 52.8%, a triester form of 24.5%, and a diester form of 15.6% from the peak area ratio. I understood that.

1H-NMR (DMSO-d6, δ): 2.02 (s, 5H), 2.10 (s, 15H), 5.47 (s, 2H), 6.65 (s, 2H), 6.78 -6.90 (m, 18H), 7.01-7.05 (m, 12H), 7.64-7.69 (m, 6H), 7.87-7.91 (m, 6H), 8 .25 to 8.30 (m, 10H), 8.47 (s, 4H)

  In the photosensitive resin composition of Example 3, a photosensitive resin composition was prepared in the same manner as in Example 3 except that the photosensitive agent (Q-2) was used instead of the photosensitive agent (Q-1). Evaluation was performed in the same manner as in Example 3. The results are shown in Table 1.

(Example 5)
Alkali-soluble resin (A-2) was synthesized as follows.
A 4-neck separable flask equipped with 29.74 g (0.15 mol) of 3,3′-diaminodiphenylmethane and 300 g of N-methyl-2-pyrrolidone equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube And dissolved. After adding 40.02 g (0.13 mol) of 4,4′-oxydiphthalic anhydride and reacting at room temperature for 1 hour, it was reacted at 65 ° C. for 2 hours using an oil bath. Next, 311.32 g (0.85 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane, 0.73 mol of diphenyl ether-4,4′-dicarboxylic acid and 1-hydroxy-1 , 2,3-benzotriazole 1.46 mol of a dicarboxylic acid derivative (active ester) obtained by reaction with 35.99 g (0.73 mol) was added together with 2600 g of N-methyl-2-pyrrolidone at 75 ° C. For 16 hours. Next, 48.20 g (0.28 mol) of 4-ethynylphthalic anhydride dissolved in 150 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 3 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum. The number average molecular weight was 8600. Thus, a polybenzoxazole precursor resin was obtained as the alkali-soluble resin (A-2) having the blending amount shown in Table 1.

  In the photosensitive resin composition of Example 3, an alkali-soluble resin (A-2) was used instead of the alkali-soluble resin (A-1), and a photosensitive agent (Q-1) was used instead of 1.5 g of the photosensitive agent (Q-1). -2) A photosensitive resin composition was prepared in the same manner as in Example 3 except that 1.8 g was used and 15 g of γ-butyrolactone was used instead of the mixed solvent of N-methyl-2-pyrrolidone and γ-butyrolactone. Evaluation was performed in the same manner as in Example 3. The results are shown in Table 1.

(Example 6)
An alkali-soluble resin (A-3) was synthesized as follows.
A dicarboxylic acid derivative (activity) obtained by reacting 0.34 mol of isophthalic acid, 0.50 mol of diphenyl ether-4,4′-dicarboxylic acid and 1.68 mol of 1-hydroxy-1,2,3-benzotriazole Ester) 382.61 g (0.84 mol), bis (3-amino-4-hydroxy-2,5-dimethylphenyl) methane 85.91 g (0.30 mol), bis (3-amino-4- Hydroxyphenyl) methane 69.08 g (0.30 mol) and hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane 146.50 g (0.40 mol) were thermometer, stirrer and raw material. Into a four-necked separable flask equipped with an inlet and a dry nitrogen gas inlet tube, 2000 g of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 16 hours using an oil bath. Next, 55.08 g (0.32 mol) of 4-ethynylphthalic anhydride dissolved in 200 g of N-methyl-2-pyrrolidone was added and further stirred for 3 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the number average molecular weight was 9800. Thus, a polybenzoxazole precursor resin was obtained as the alkali-soluble resin (A-3) having the blending amount shown in Table 1.

  In the photosensitive resin composition of Example 3, an alkali-soluble resin (A-3) was used instead of the alkali-soluble resin (A-1), and a photosensitive agent (Q-2) was used instead of the photosensitive agent (Q-1). A photosensitive resin composition was prepared in the same manner as in Example 3 except that the addition amount was further changed to 1.6 g using, and evaluated in the same manner as in Example 3. The results are shown in Table 1.

(Comparative Example 1)
Photosensitive agent (Q-3) was synthesized as follows.
4,4 ′, 4 ″ -trihydroxyphenylmethane 5.85 g (0.020 mol), 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride 12.90 g (0.024 mol) and acetone 106 g Was stirred and dissolved in a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. Next, a mixed solution of 5.34 g (0.053 mol) of triethylamine and 3.0 g of acetone was slowly added dropwise while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C. After reacting for 3 hours at room temperature, 0.72 g (0.012 mol) of acetic acid was added, and the reaction was further continued for 30 minutes. After filtering the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (600 ml / 6 ml), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and 4,4 ′, 4 ″. -14.5 g (yield: 89.5%) of a photosensitizer (Q-3) in which 80% of the hydroxyl groups of trihydroxyphenylmethane were substituted with 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester Obtained.

  When the obtained photosensitizer (Q-3) was analyzed by HPLC, it was found from the peak area ratio that the triester form was a mixture of 59.2% and the diester form was 22.5%.

  In the photosensitive resin composition of Example 3, a photosensitive resin composition was prepared in the same manner as in Example 3 except that the photosensitive agent (Q-3) was used instead of the photosensitive agent (Q-1). Evaluation was performed in the same manner as in Example 3. The results are shown in Table 1.

(Comparative Example 2)
In the photosensitive resin composition of Example 5, a photosensitive resin composition was prepared in the same manner as in Example 5 except that the photosensitive agent (Q-3) was used instead of the photosensitive agent (Q-2). Evaluation was performed in the same manner as in Example 5. The results are shown in Table 1.

(Comparative Example 3)
In the production of the photosensitive resin composition in Example 6, a photosensitive resin composition was prepared in the same manner as in Example 6 except that the photosensitive agent (Q-3) was used instead of the photosensitive agent (Q-2). Evaluation was performed in the same manner as in Example 6. The results are shown in Table 1.

  In the table, “no problem” means that no crystal was generated.

（式（１）中、Ａｒはフェノール性水酸基を有するアリール基であり、同一でも異なってもよく、２位、３位、４位、５位、６位のいずれかで置換したものである。）
２．一般式（１）中のＡｒが、下記一般式（２）で示される基であることを特徴とする１．記載のテトラキスフェノール化合物。

（式（２）中、＊は一般式（１）の−ＣＨ基に結合することを示す。Ｒ _１ はアルキル基、アルコキシ基、アルケニル基、シクロアルキル基から選ばれる基であり、複数ある場合は同一でも異なってもよい。ａは０〜４の整数である。）
３．１．または２．に記載のテトラキスフェノール化合物と、１，２−ナフトキノンジアジド−４−スルホン酸および１，２−ナフトキノンジアジド−５−スルホン酸のエステルの少なくとも一方と、で構成されることを特徴とする感光剤。
４．前記感光剤が、下記一般式（３）で表されることを特徴とする３．に記載の感光剤。

（式（３）中、Ｒ _２ ，Ｒ _３ ，Ｒ _４ ，Ｒ _５ はそれぞれアルキル基、アルコキシ基、アルケニル基、シクロアルキル基から選ばれる基であり、それぞれ複数ある場合は同一でも異なってもよい。ｂ，ｃ，ｄ，ｅはそれぞれ０〜４の整数である。Ｑは、水素原子、式（４）または式（５）のいずれかから選ばれるものである。また式（３）中の各Ｑのうち、少なくとも１つは式（４）または式（５）で表される。）

５．３．または４．記載の感光剤と、アルカリ可溶性樹脂と、を含むことを特徴とする感光性樹脂組成物。
６．前記アルカリ可溶性樹脂が、ベンゾオキサゾール前駆体構造およびイミド前駆体構造の少なくとも一方を有することを特徴とする５．に記載の感光性樹脂組成物。
７．５．または６．に記載の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。
８．７．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。
９．７．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。
１０．７．に記載の硬化膜を有していることを特徴とする半導体装置。
１１．７．に記載の硬化膜を有していることを特徴とする表示体装置。

As shown in Table 1, it can be seen that Examples 3 to 6 are extremely excellent in sensitivity even under thick film conditions exceeding 10 μm, and have sufficient sensitivity and resolution that may interfere with semiconductor production. I understood.
Hereinafter, examples of the reference form will be added.
1. A tetrakisphenol compound represented by the general formula (1).

(In the formula (1), Ar is an aryl group having a phenolic hydroxyl group, which may be the same or different, and is substituted at any of the 2-position, 3-position, 4-position, 5-position, and 6-position. )
2. 1. Ar in the general formula (1) is a group represented by the following general formula (2) The tetrakisphenol compound described.

(In the formula (2), * represents bonding to the —CH group in the general formula (1). R ₁ is a group selected from an alkyl group, an alkoxy group, an alkenyl group, and a cycloalkyl group. May be the same or different, and a is an integer of 0 to 4.)
3.1. Or 2. And a tetrakisphenol compound described in 1) and at least one of esters of 1,2-naphthoquinonediazide-4-sulfonic acid and 1,2-naphthoquinonediazide-5-sulfonic acid.
4). 2. The photosensitive agent is represented by the following general formula (3). The photosensitive agent according to 1.

(In the formula (3), R ₂ , R ₃ , R ₄ and R ₅ are each a group selected from an alkyl group, an alkoxy group, an alkenyl group and a cycloalkyl group. B, c, d and e are each an integer of 0 to 4. Q is a hydrogen atom, selected from the formula (4) or the formula (5), and in the formula (3) (At least one of each Q is represented by Formula (4) or Formula (5).)

5.3. Or 4. A photosensitive resin composition comprising the photosensitive agent described above and an alkali-soluble resin.
6). 4. The alkali-soluble resin has at least one of a benzoxazole precursor structure and an imide precursor structure. The photosensitive resin composition as described in 2.
7.5. Or 6. A cured film comprising the cured product of the photosensitive resin composition described in 1.
8.7. A protective film comprising the cured film described in 1.
9.7. An insulating film comprising the cured film described in 1.
10.7. A semiconductor device comprising the cured film described in 1.
11.7. A display device comprising the cured film described in 1.

Claims (9)

A tetrakisphenol compound represented by the general formula (1) ,
A tetrakisphenol compound, wherein Ar in the general formula (1) is a group represented by the following general formula (2) .

(In the formula (1), Ar is an aryl group having a phenolic hydroxyl group, which may be the same or different, and is substituted at any of the 2-position, 3-position, 4-position, 5-position, and 6-position. )

(In the formula (2), * represents bonding to the —CH group in the general formula (1). R ₁ is a group selected from an alkyl group, an alkoxy group, an alkenyl group, and a cycloalkyl group. May be the same or different, and a is an integer of 0 to 4.) And tetrakis phenol compound according to claim 1, at least one and, in Ru consists photosensitive agent of the ester of 1,2-naphthoquinonediazide-4-sulfonic acid and 1,2-naphthoquinonediazide-5-sulfonic acid,
The said photosensitive agent is represented by following General formula (3), The photosensitive agent characterized by the above-mentioned.

(In the formula (3), R ₂ , R ₃ , R ₄ and R ₅ are each a group selected from an alkyl group, an alkoxy group, an alkenyl group and a cycloalkyl group. B, c, d and e are each an integer of 0 to 4. Q is a hydrogen atom, selected from the formula (4) or the formula (5), and in the formula (3) (At least one of each Q is represented by Formula (4) or Formula (5).)

A photosensitive resin composition comprising the photosensitive agent according to claim 2 and an alkali-soluble resin. The photosensitive resin composition according to claim 3 , wherein the alkali-soluble resin has at least one of a benzoxazole precursor structure and an imide precursor structure. A cured film comprising a cured product of the photosensitive resin composition according to claim 3 or 4 . A protective film comprising the cured film according to claim 5 . An insulating film comprising the cured film according to claim 5 . A semiconductor device comprising the cured film according to claim 5 . A display device comprising the cured film according to claim 5 .