JP5521939B2 - Photosensitive resin composition, cured film, protective film, insulating film, and semiconductor device and display device using the same - Google Patents

Description

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

Conventionally, a protective film and an insulating film of a semiconductor element include a polyimide resin having excellent heat resistance and excellent electrical characteristics and mechanical characteristics, and a polybenzoxazole resin which is considered to have good moisture resistance reliability in addition to the above characteristics. It was used. In addition, polyimide resin, polybenzoxazole resin, and their precursor resins themselves are given photosensitivity so that part of the relief pattern creation process can be simplified, while having high sensitivity and fine processability, and high heat resistance. A photosensitive resin composition has been developed that has high performance, excellent electrical and mechanical properties, and is effective in shortening the process and improving yield (productivity). It also has potential as a composition.
More recently, positive photosensitive resin compositions that can be developed with an aqueous alkaline solution have been developed from the viewpoint of safety. For example, Patent Document 1 discloses a positive photosensitive resin composition composed of a polybenzoxazole precursor and a diazoquinone compound as a photosensitizer as an alkali-soluble resin.

  Polyimide precursor resin and polybenzoxazole precursor resin in the photosensitive resin composition in which the relief pattern is formed are dehydrated and ring-closed by finally curing at a high temperature of about 300 ° C. to 350 ° C. Resin, polybenzoxazole resin. In recent years, due to miniaturization and high integration of semiconductor elements, the heat resistance of the memory elements has been particularly low, and a polyimide precursor resin and a polybenzoxazole precursor that can be cured at a low temperature of about 200 ° C. in order to improve productivity. Resin is needed.

It is important to ensure the reliability of the semiconductor device when cured at a low temperature. The mechanical properties of the cured film, particularly the strength and elongation of the cured film, and the heat resistance, particularly the glass transition temperature (Tg). A balance is required.
The strength and elongation of the cured film cured at low temperature are required to have the same characteristics as when cured at high temperature, and Tg is a reflow that assumes the use of lead-free solder in consideration of the environment and the human body in recent years. It is desirable that the temperature is higher than the temperature, and it is particularly desirable that the Tg of the cured film after heat treatment at a low temperature of 200 ° C. is 250 ° C. or higher.
As a method for obtaining a photosensitive resin composition curable at a low temperature, there is a method of introducing an aliphatic hydrocarbon bond or the like into the main skeleton of the resin. In this case, not only the strength of the cured film becomes weak, but also Tg Decreases.
There is also a method of adding an auxiliary compound such as a crosslinking agent, but the cured film becomes stiff and brittle and the elongation cannot be obtained, or the addition of additives other than the photosensitive agent affects the preservability of the photosensitive resin composition. And the inherent characteristics of the resin cannot be fully exhibited, and the reliability of the semiconductor device is affected.
Therefore, development of a photosensitive resin composition having excellent mechanical properties and heat resistance even when cured at a low temperature of about 200 ° C. has been strongly desired recently.

Japanese Examined Patent Publication No. 1-46862

  An object of the present invention is to provide a cured film with high sensitivity, high resolution, and high reliability with respect to a semiconductor device, which is excellent in strength, elongation and heat resistance only by a resin and a photosensitive agent even when cured at a low temperature of about 200 ° C. It is an object to provide a photosensitive resin composition, a protective film, an insulating film, a semiconductor device using the same, and a display device using the same.

Such an object is achieved by the present invention described in the following (1) to (11).
(1) A photosensitive resin composition comprising an alkali-soluble resin having a conjugated double bond structure at at least one terminal, an alkali-soluble resin having a dienophile structure at at least one terminal, and a photosensitizer.
(2) The photosensitive resin composition according to (1), wherein the alkali-soluble resin has at least one of a benzoxazole precursor structure and an imide precursor structure.
(3) The photosensitive resin composition according to (1) or (2), wherein the conjugated double bond structure is a conjugated diene structure.
(4) The photosensitive resin composition according to any one of (1) to (3), wherein the dienophile structure is a maleimide structure.
(5) the conjugated diene structure, -CH = CH-CH = CH -R 1 in which the (3) or photosensitive resin composition according to (4).
(R ₁ represents a hydrogen atom, an alkyl group or an aromatic group.)
(6) The photosensitive resin composition according to (4) or (5), wherein the maleimide structure is a structure derived from N-phenylmaleimide.
(7) A cured film comprising a cured product of the photosensitive resin composition according to any one of (1) to (6).
(8) A protective film comprising the cured film according to (7).
(9) An insulating film comprising the cured film according to (7).
(10) A semiconductor device comprising the cured film according to (7).
(11) A display device comprising the cured film according to (7).

  According to the present invention, high sensitivity, high resolution, and photosensitivity capable of obtaining a cured film having excellent strength, elongation and heat resistance even when cured at a low temperature of about 200 ° C. and having high reliability for a semiconductor device. A resin composition, a protective film, an insulating film, a semiconductor device using the same, and a display device can be provided.

Hereinafter, the photosensitive resin composition, the cured film, the protective film, the insulating film, the semiconductor device using the same, and the display device of the present invention will be described.
The photosensitive resin composition of the present invention comprises an alkali-soluble resin having a conjugated double bond structure at at least one terminal, an alkali-soluble resin having a dienophile structure at at least one terminal, and a photosensitizer.
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.
In addition, a semiconductor device and a display device according to the present invention are configured by the cured film.

Below, each component of the photosensitive resin composition of this invention is demonstrated in detail. The following is an example, and the present invention is not limited to the following.
The alkali-soluble resin has a hydroxyl group, particularly a phenolic hydroxyl group and / or a carboxyl group. For example, an acrylic resin such as a cresol type novolak resin, a hydroxystyrene resin, a methacrylic acid resin, a methacrylic ester resin, or a cyclic olefin Of these, polyamide resins are preferable. Among these, polyamide resins are preferable.
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 the structure represented by the following formula (1), the imide precursor structure refers to the structure represented by the following formula (2), and the benzoxazole structure refers to the following The structure represented by Formula (3) is pointed out, the imide structure refers to the structure represented by Formula (4) below, and the amido ester structure refers to the structure represented by Formula (5) below.

  In addition, D and R in said formula (1)-(5) show an organic group. Among these polyamide resins, a polyamide resin represented by the following general formula (6) is preferable.

（式中、Ｘ、Ｙは有機基である。Ｒ_２は水酸基、−Ｏ−Ｒ_４、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良い。Ｒ_３は水酸基、カルボキシル基、−Ｏ−Ｒ_４、−ＣＯＯ−Ｒ_４のいずれかであり、同一でも異なっても良い。ｍは０〜８の整数、ｎは０〜８の整数である。Ｒ_４は炭素数１〜１５の有機基である。ここで、Ｒ_２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_２として水酸基がない場合は、Ｒ_３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_３としてカルボキシル基がない場合、Ｒ_２は少なくとも１つは水酸基でなければならない。）

(Wherein X and Y are organic groups. R ₂ is a hydroxyl group, —O—R ₄ , an alkyl group, an acyloxy group, or a cycloalkyl group, which may be the same or different. R ₃ is a hydroxyl group or a carboxyl group. , -O-R ₄ , or -COO-R ₄ , which may be the same or different, m is an integer of 0 to 8, n is an integer of 0 to 8. R ₄ is an integer of 1 to Here, when there are a plurality of R _{2 s} , they may be different or the same, and when R ₂ has no hydroxyl group, at least one R ₃ must be a carboxyl group. In addition, when R ₃ has no carboxyl group, at least one R ₂ must be a hydroxyl group.

In the polyamide resin represented by general formula _{(6), O-R 4} , COO-R 4 as a substituent of _O-R 4, Y as a substituent of X is soluble hydroxyl, an alkaline aqueous solution of the carboxyl group Is a group protected by R ₄ , 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 ₄ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. It is done.

The polyamide resin containing the structure represented by the general formula (6) 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 (6) 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 closed when treated at 150 ° C to 280 ° C to form a polyimide resin or polybenzoxazole. A heat resistant resin can be obtained in the form of resin or copolymerization of both.
X of the polyamide resin represented by the general formula (6) is not particularly limited. For example, an aromatic compound such as a benzene ring or a naphthalene ring, a heterocyclic group such as a bisphenol, a pyrrole, or a furan. A compound, a siloxane compound, etc. are mentioned, More specifically, what is shown by a following (7) formula can be mentioned preferably. These may be used alone or in combination of two or more.

（ここで、＊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_５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良い。Ｒ_６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。ｓ＝０〜２の整数である。）

(Here, * 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 ₅ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and may be the same or different. R ₆ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom. s = 0 is an integer of 0-2. )

（ここで、＊は、ＮＨ基に結合することを示す。Ｒ_７〜Ｒ_１０は、有機基である。）

(Here, * indicates binding to an NH group. R _{7 to} R ₁₀ are organic groups.)

As shown in the above formula (6), 0 to 8 R ₂ are bonded to X (in formula (7), R ₂ is omitted).
Particularly preferable examples of the above formula (7) include those represented by the following formula (8) and the following formula (9).

（式中、＊はＮＨ基に結合することを示す。式中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−、又は単結合である。Ｒ_１１は、アルキル基、アルコキシ基、アシルオキシ基、シクロアルキル基のいずれかであり、同一でも異なっても良い。ｃ＝１〜３の整数である。）

(In the formula, * represents bonding to an NH group. In the formula, A represents alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —C (═O) —, —NHC (= O) —, —C (CF ₃ ) ₂ —, or a single bond, and R ₁₁ is any one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. It is an integer from 1 to 3.)

  Particularly preferred among the above formulas (8) and (9) are those represented by the following formula (10).

（ここで＊はＮＨ基に結合することを示す。Ｒ_１２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。）

(Here, * represents bonding to an NH group. R ₁₂ represents alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —C (═O) —, —NHC (═O) —). , —C (CF ₃ ) ₂ —, an organic group selected from a single bond.

Specific examples of A in the above formula (7), A in the above formula (8), R ₁₂ alkylene in the above formula (10) 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 are mentioned. Among them, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ — are not limited to the aqueous alkali solution but also to the solvent. It is preferable that a polyamide resin having sufficient solubility and excellent balance can be obtained.

  Y in the formula (6) is an organic group, and examples thereof include those similar to X. For example, aromatic compounds such as benzene ring and 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 (11) can be mentioned preferably. These may be used alone or in combination of two or more.

（ここで、＊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。
Ｒ_１３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良い。Ｒ_１４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。ｔ＝０〜２の整数である。）

(Here, * 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.
R ₁₃ 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. R ₁₄ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom. t is an integer of 0-2. )

（ここで、＊は、Ｃ＝Ｏ基に結合することを示す。Ｒ_１５〜Ｒ_１８は、有機基である。）

(Here, * indicates bonding to a C═O group. R _{15 to} R ₁₈ are organic groups.)

As shown in Formula (6), 0 to 8 R ₃ are bonded to Y (in Formula (11), R 3
₃ is omitted).

Among these, a compound represented by the following formula (12) is particularly preferable.
Regarding the structure derived from tetracarboxylic dianhydride in the following formula (12), the position where both C═O groups are bonded to the meta position, and both the positions in the para position are listed. A structure including each of the para positions may be used.

（式中、＊はＣ＝Ｏ基に結合することを示す。Ｒ_１９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_２０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。ｕ＝０〜２の整数である。
）

(In the formula, * indicates bonding to a C═O group. R ₁₉ represents one selected from an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and a halogen atom, R ₂₀ represents one selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms, and may be partially substituted, and is an integer of u = 0 to 2. is there.
)

（式中、＊はＣ＝Ｏ基に結合することを示す。Ｒ_２０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。）

(In the formula, * represents bonding to a C═O group. R ₂₀ represents one selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms, and may be partially substituted. .)

The alkali-soluble resin contained in the photosensitive resin composition of the present invention may have a conjugated double bond structure at at least one terminal of the alkali-soluble resin and a dienophile structure at at least one terminal of the alkali-soluble resin. is important.
Thereby, even if it hardens | cures at about 200 degreeC low temperature, chain | strand extension reaction is performed, forming the 6-membered ring by terminal Diels-Alder reaction. Therefore, the effect of improving heat resistance having a Tg equal to or higher than the curing temperature by cyclization and ensuring the same mechanical strength as a cured film cured at high temperature, and ensuring the same elongation as the cured film cured at high temperature by chain extension. Can be compatible.
In this way, since the conjugated double bond structure and the dienophile structure react 1: 1, when synthesizing the alkali-soluble resin, the charged mol% of the conjugated double bond structure with respect to all terminals is a, and the charged mole of the dienophile structure. When% is b, the maximum effect is obtained when 0.9 <a / b <1.1.

The alkali-soluble resin of the present invention contains a resin having a conjugated double bond structure at at least one terminal and a resin having a dienophile structure at at least one terminal. However, a resin having a conjugated double bond structure at at least one end may be a resin having a conjugated double bond structure at at least one end and a molecular chain having a dienophile structure at the other end. In that case, a resin having a conjugated double bond structure at at least one end and a resin having a dienophile structure at at least one end are the same resin. Further, it may be a resin including a molecular chain having both a conjugated double bond structure and a dienophile structure at at least one terminal. Also in that case, the resin having a conjugated double bond structure at at least one terminal and the resin having a dienophile structure at at least one terminal are the same resin.
Further, the alkali-soluble resin of the present invention has a resin having a conjugated double bond at both ends of a molecular chain contained in a resin having a conjugated double bond structure at at least one terminal, and a dienophile structure at at least one terminal. It may be in a state where a resin having a dienophile structure is mixed at both ends of the molecular chain contained in the resin. Further, a resin having a conjugated double bond at both ends and a resin having a dienophile structure at both ends may be synthesized and blended when preparing a photosensitive resin composition.

In the polyamide resin represented by the above formula (6), when the terminal is an amino group, a carboxyl group containing a functional group selected from a group having a conjugated double bond structure, a group having a dienophile structure, and a group having both structures is used. It is preferable to cap the amide with an acid compound or an acid anhydride.
Thereby, preservability can be improved. In the case of a carboxylic acid compound, an active ester type carboxylic 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.
The group having a conjugated double bond structure is preferably a group having a conjugated diene structure. More preferably, it is a group having a structure of —CH═CH—CH═CH—R ₁ . (R ₁ represents a hydrogen atom, an alkyl group or an aromatic group.)
Thereby, coloring of the cured film can be suppressed, and absorption at the time of exposure can be suppressed, so that a highly sensitive alkali-soluble resin can be obtained.

As such a carboxylic acid compound containing a group having a conjugated diene structure and an acid anhydride, 2,4-pentadienoic acid, sorbic acid, 5-phenylpenta-2,4-dienoic acid, 2-anthracenecarboxylic acid, 2-furancarboxylic acid, 3-furancarboxylic acid, 2-methylfuran-3-carboxylic acid, 3-methyl-2-furancarboxylic acid, 5-phenylfurancarboxylic acid, 5- (4-methylphenyl) -2- Furanic acid, 5- (4-methoxyphenyl) -2-furanic acid, 3- (2-furyl) propionic acid, 2,5-dimethyl-3-furanic acid, 4- (1H-pyrrol-1-yl) benzoic acid Acid, 2-hydroxy-5- (1H-pyrrol-1-yl) benzoic acid, trans-N- (2-furfurideneacetyl) glycine, 3- (2-furyl) acrylic acid, trans 3-furan acrylic acid, N-(2-furoyl) glycine, coumaric acid, and the like 2,3-anthracene dicarboxylic acid anhydride. These may be used alone or in combination of two or more.
Among these, 2,4-pentadienoic acid, sorbic acid, and 5-phenylpenta-2,4-dienoic acid are preferable from the viewpoint of reactivity, and sorbic acid is particularly preferable.

Carboxylic acid compounds containing a group having a dienophile structure, and acid anhydrides include 3-maleimidobenzoic acid, 4-maleimidobenzoic acid, 3-maleimidopropionic acid, 2- (2,5-dioxo-2,5-dihydroxypyrrole -1-yl) propionic acid, 4-maleimidyl salicylic acid, citraconic anhydride and the like. These may be used alone or in combination of two or more.
The group having a dienophile structure is preferably a group having a maleimide group from the viewpoint of reactivity. More preferably, it has an N-phenylmaleimide group excellent in strength and heat resistance.
Particularly preferred are 3-maleimidobenzoic acid, 4-maleimidobenzoic acid and 4-maleimidylsalicylic acid.

In addition, a carboxylic acid compound having a plurality of amino groups is used as a support, and the carboxylic acid compound or acid anhydride containing a group having the conjugated diene structure described above is reacted with a carboxylic acid compound or acid anhydride containing a group having a dienophile structure. You may use a thing as an end cap material.
Examples of such a support include 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,5-bis (4-aminophenoxy) benzoic acid, L (+) lysine, and the like.

In addition, in the polyamide resin represented by the above formula (6), when the terminal is a carboxylic acid, a functional group selected from a group having a conjugated double bond structure, a group having a dienophile structure, and a group having both structures is included. An amine derivative can be similarly capped as an amide.
As described above, the conjugated double bond structure is preferably a conjugated diene structure. Examples of the amine derivative containing a group having such a conjugated diene structure include furfurylamine, 5-methylfurfurylamine, 2- (furan- 2-ylmethoxy) phenylamine, 4- (furan-2-ylmethoxy) phenylamine, 2- (furfurylthio) ethylamine and the like. These may be used alone or in combination of two or more.
Examples of amine derivatives containing a group having a dienophile structure include 3-aminophenylmaleimide and 4-aminophenylmaleimide. These may be used alone or in combination of two kinds.

Further, an amine derivative having a plurality of carboxyl groups may be used as a support, and an amine derivative containing a group having a conjugated diene structure as described above, or an amine derivative containing a group having a dienophile structure may be used as a terminal cap material. .
Examples of such a support include 5-aminoisophthalic acid and 2-aminoterephthalic acid.

Further, in the case of the polyamide resin represented by the above formula (6), the terminal amino group of the polyamide resin is replaced with another alkenyl group or an amount not affecting the mechanical properties and heat resistance when cured at a low temperature. An amide can be capped using an acid anhydride containing an aliphatic group or a cyclic compound group having at least one alkynyl group.
Examples of the aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group include groups represented by formula (13) and formula (14). 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 an amide using an amine derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group. Can also be capped.

Furthermore, in the case of the polyamide resin represented by the above formula (6), 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.

As the photosensitizer used in the present invention, a photosensitizer capable of positive patterning can be used, and 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, onium salts such as diaryl iodonium salts, triaryl sulfonium salts, sulfonium borate salts, 2-nitrobenzyl ester compounds, N-imino sulfonate compounds, imide sulfonate compounds, 2,6-bis (Trichloromethyl) -1,3,5-triazine compound, dihydropyridine compound and the like can be used. Among these, a photosensitive diazoquinone compound excellent in sensitivity and solvent solubility is preferable.
Examples of the photosensitive diazoquinone compound include esters of a phenol compound as a support and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid.
Since the photosensitive resin composition of the present invention utilizes the Diels-Alder reaction, the reaction is accelerated when an acid is present in the system. In the case of the positive type, it is considered that the photosensitizer remaining in the relief pattern in the unexposed area is decomposed by heat at the time of curing to generate an acid, and the photosensitizer plays an important role as a reaction accelerator. In the case of a photosensitive diazoquinone compound, an ester of 1,2-naphthoquinone-2-diazide-4-sulfonic acid that is more easily decomposed by heat is preferable.

As the phenol compound which is a support for the photosensitive diazoquinone compound, a phenol compound having a phenol nucleus number of about 1 to 10 or a low molecular weight novolak resin can be used. Specifically, bisphenol, trisphenol, tetrakisphenol, a phenol compound in which about 3 to 6 phenol nuclei are linearly bonded via a methylene bond, and the like can be used.
More specifically, there can be mentioned phenol compounds represented by the formulas (15) and (16) having excellent sensitivity. 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.

（式中、Ｂは有機基である。Ｒ_２１〜Ｒ_２４は水素原子、水酸基、ハロゲン原子、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１つであり、同一でも異なっていても良い。o〜ｒは、それぞれ０〜４の整数である。）

(In the formula, B is an organic group. R _{21 to} R ₂₄ are one selected from a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, and a cycloalkyl group, and may be the same or different. O to r are each an integer of 0 to 4.)

（式中、Ｒ_２５〜Ｒ_２７は水素原子、アルキル基であり、Ｒ_２８〜Ｒ_３０は水素原子、水酸基、ハロゲン原子、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１つであり、同一でも異なっていても良い。ｖ〜ｘは、それぞれ０〜２の整数である。ｙは０または１の整数である。）

(Wherein R _{25 to} R ₂₇ are a hydrogen atom and an alkyl group, and R _{28 to} R ₃₀ are 1 selected from a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, and a cycloalkyl group. And may be the same or different. V to x are each an integer of 0 to 2. y is an integer of 0 or 1.)

B in the above formula (15) is an organic group.
Specific examples of the organic group include alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —C (═O) —, —NHC (═O) —, aryl, cycloalkyl, or It may be a single bond and may be a form in which two or more of the above organic groups are combined.
Specific examples of the alkylene and substituted alkylene of B in the formula (15) include —CH ₂ —, — (CH ₂ ) ₂ —, —CH (CH ₃ ) —, — (CH ₂ ) ₃ —, — _{C (CH 3) 2 -,} - CH (CH 2 CH 3) -, - (CH 2) 4 -, - 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) -, include equal However, among them, —CH ₂ —, —CH (CH ₃ ) —, and —C (CH ₃ ) ₂ — suitable for solubility in an alkaline aqueous solution and solubility in a solvent are preferable.
A specific example of the form in which two or more organic groups of B in the above formula (15) are combined includes the structure shown in the formula (17).

（式中、Ｒ_３１〜Ｒ_３８は水素原子、アルキル基である。
Ｋは、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、または単結合である。ｄは０または１の整数である。）

_(Wherein, R 31 _{to R 38} is a hydrogen atom, an alkyl group.
K is —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —C (═O) —, —NHC (= O)-or a single bond. d is an integer of 0 or 1. )

In addition, R _{21 to} R _{24 in} the general formula (15) and R _{28 to} R ₃₀ in the general formula (16) are each a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, or a cycloalkyl group. It is one selected from among them, and when there are a plurality of them, they may be the same or different. Examples of the halogen atom include chlorine and bromine. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and an undecyl group. , Dodecyl groups, etc., alkoxy groups include methoxy group, ethoxy group, propoxy group, butoxy group, etc., alkenyl groups include ethenyl group, propenyl group, butenyl group, etc., cycloalkyl group Examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like, and a hydrogen atom, a methyl group, and an ethyl group, which are excellent in sensitivity and resolution of the positive photosensitive resin composition, are particularly preferable.

In addition, R _{25 to} R _{27 in} the general formula (16) and R _{31 to} R ₃₈ in the general formula (17) are hydrogen atoms or alkyl groups, and are not particularly limited. A methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dosyl group, which may be the same or different. Among these, a hydrogen atom, a methyl group, and an ethyl group, which are excellent in sensitivity and resolution of the photosensitive resin composition, are particularly preferable.
Although it does not specifically limit as a phenolic compound shown by the said General formula (15), What is shown by following formula (18) is illustrated.

  Although it does not specifically limit as a phenolic compound shown by the said General formula (16), What is shown by following formula (19) is illustrated.

  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 agent such as a bond or triple bond-containing compound, leveling agent such as acrylic, silicone, fluorine and vinyl, silane coupling agent, antioxidant, compound that generates acid by heat, dissolution inhibitor for aqueous alkali solution An additive such as 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-methoxypropio And the like, and 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, for example, a silicon wafer, a ceramic substrate, an aluminum substrate or the like. When applied on a semiconductor element, the applied amount is applied so that the final film thickness after curing is 0.1 to 30 μm. If the film thickness is below the lower limit value, it will be difficult to fully function as a protective 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.

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

  Examples of semiconductor device applications include a passivation film formed by forming a cured film of the above-described photosensitive resin composition on a semiconductor element, and a buffer formed by forming a cured film of the above-described photosensitive resin composition on the passivation film. 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.

<Example 1>
Synthesis of a terminal compound having a dienophile structure 29.15 g (0.213 mol) of 4-aminobenzoic acid and 20.85 g (0.213 mol) of maleic anhydride were added to a thermometer, stirrer, raw material inlet, and dry nitrogen gas. Into a four-necked separable flask equipped with an introduction tube, 402 g of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 50 ° C. for 3 hours using an oil bath. After cooling to room temperature, 23.87 g (0.234 mol) of acetic anhydride and 23.66 g (0.234 mol) of triethylamine were added and allowed to react overnight. The reaction product was poured into 1900 ml of water, and the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum to obtain 29.3 g of 4-maleimidobenzoic acid.

Synthesis of alkali-soluble resin Obtained by reacting 0.010 mol of isophthalic acid, 0.057 mol of diphenyl ether-4,4′-dicarboxylic acid and 0.134 mol of 1-hydroxy-1,2,3-benzotriazole Dicarboxylic acid derivative (active ester) 32.00 g (0.067 mol), bis (3-amino-4-hydroxy-2,5-dimethylphenyl) methane 20.05 g (0.070 mol), 1,1 Put 1.90 g (0.008 mol) of '-bis (3-amino-4-hydroxyphenyl) ethane into a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube. N-methyl-2-pyrrolidone (100 g) was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 16 hours using an oil bath.
Next, after changing the reaction temperature to 60 ° C., a carboxylic acid derivative obtained by reacting 0.022 mol of 4-maleimidobenzoic acid with 0.022 mol of 1-hydroxy-1,2,3-benzotriazole ( (Active ester) 7.28 g (0.022 mol) and N-methyl-2-pyrrolidone 14 g were added, and the reaction was terminated by further stirring for 3 hours. After filtering the reaction mixture, the reaction solution 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 11000. The objective alkali-soluble resin (A-1) which consists of a compound shown by Table 1 was obtained.

Synthesis of alkali-soluble resin In the synthesis of the alkali-soluble resin (A-1), 4-maleimidobenzoic acid was replaced with sorbic acid, and 0.022 mol of sorbic acid and 1-hydroxy-1,2,3-benzotriazole 0.022 were added. It reacts in the same manner as the alkali-soluble resin (A-1) except that 4.99 g (0.022 mol) of a carboxylic acid derivative (active ester) obtained by reacting with mol is used, and the number average molecular weight is 12,000. The objective alkali-soluble resin (A-2) which consists of a compound shown by Table 1 was obtained.

Synthesis of Photosensitizer The phenol formula (B-1) 11.22 g (0.026 mol), 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride 18.78 g (0.070 mol) and acetone 170 g were heated to a temperature. The mixture was stirred and dissolved in a four-necked separable flask equipped with a total, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. Next, while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C., a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise. After reacting for 3 hours at room temperature, 1.05 g (0.017 mol) of acetic acid was added, and the mixture was further reacted for 30 minutes. After filtration of 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 of formula (Q-1). A photosensitizer represented by the structure was obtained.

Preparation of photosensitive resin composition 5 g of synthesized alkali-soluble resin (A-1), 5 g of alkali-soluble resin (A-2), and 1.6 g of photosensitive agent having the structure of formula (Q-1) were added to N-methyl-2. -After dissolving in a mixed solvent of 12 g of pyrrolidone and 8 g of γ-butyrolactone, it was filtered through a 0.2 µm Teflon (registered trademark) filter to obtain a photosensitive resin composition.

Evaluation of mechanical properties The photosensitive resin composition was applied onto a 6-inch silicon wafer using a spin coater, then pre-baked on a hot plate at 120 ° C. for 3 minutes, and coated so that the film thickness after curing was 10 μm. A membrane was obtained. Next, the silicon wafer with a coating film was heated at 200 ° C./90 minutes using an oven. The obtained silicon wafer with a cured film was cut to a width of 10 mm with a dicing saw (DFD6340, manufactured by Disco Corporation), then immersed in 2% hydrogen fluoride water, and the strip-like cured film was peeled off from the silicon wafer. . The obtained cured film was sufficiently washed with pure water and dried in an oven. Thereafter, tensile strength and elongation at break were measured using Tensilon (RTA-1210, manufactured by Orientec Co., Ltd.), and showed high values of 139 MPa and 72%, respectively.

Glass transition temperature (Tg) evaluation After the photosensitive resin composition was applied on a 6-inch silicon wafer using a spin coater, it was pre-baked on a hot plate at 120 ° C. for 3 minutes, and the film thickness after curing was 10 μm. A coating film was obtained. Next, the silicon wafer with a coating film was heated at 200 ° C./90 minutes using an oven. Next, the obtained silicon wafer with a cured film was immersed in 2% hydrogen fluoride water, and the cured film was peeled off from the silicon wafer. The obtained cured film was thoroughly washed with pure water and dried in an oven. The cured film after drying was cut into a width of 5 mm to create a sample piece, and the glass transition temperature was measured using a thermomechanical analyzer (TMA) SS6000 manufactured by Seiko Instruments Inc. As a result, a high value of 280 ° C. was shown. .

Processability Evaluation The photosensitive resin composition was applied on a silicon wafer using a spin coater, and then prebaked on a hot plate at 120 ° C. for 3 minutes to obtain a coating film having a thickness of about 9.0 μm. An i-line stepper (manufactured by Nikon Corporation, NSR-) was passed through this mask through a mask made by Toppan Printing Co., Ltd. (test chart No. 1: remaining pattern and blank pattern with a width of 0.88 to 50 μm are drawn). 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 0.5 μm, and paddle development is performed twice. Then, the exposed portion was dissolved and removed, and then rinsed with pure water for 10 seconds.
As a result, it was confirmed that a pattern was formed from a portion irradiated with an exposure amount of 340 mJ / cm ² and showed high sensitivity that could be put to practical use (sensitivity was 340 mJ / cm ² ). The resolution at the exposure amount was as high as 5 μm.

<Example 2>
Synthesis of alkali-soluble resin Dicarboxylic acid derivative (active ester) obtained by reacting 0.060 mol of diphenyl ether-4,4′-dicarboxylic acid with 0.120 mol of 1-hydroxy-1,2,3-benzotriazole 29.30 g (0.060 mol) and 25.64 g (0.070 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane were thermometer, stirrer, raw material inlet, and dried. Into a four-necked separable flask equipped with a nitrogen gas inlet tube, 102 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, after changing the reaction temperature to 60 ° C., a carboxylic acid derivative obtained by reacting 0.011 mol of 4-maleimidobenzoic acid and 0.011 mol of 1-hydroxy-1,2,3-benzotriazole ( Active ester) 3.51 g (0.011 mol), 0.011 mol of sorbic acid and 0.011 mol of 1-hydroxy-1,2,3-benzotriazole were reacted with a carboxylic acid derivative (activity) Ester) (2.41 g, 0.011 mol) and N-methyl-2-pyrrolidone (11 g) were added, and the mixture was further stirred for 3 hours to complete the reaction. After filtering the reaction mixture, the reaction solution 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 11000. The target alkali-soluble resin (A-3) comprising the compounds shown in Table 1 was obtained.

In preparation of the photosensitive resin composition of Example 1, an alkali-soluble resin (A-3) was used instead of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2), and N-methyl-2- A photosensitive resin composition was prepared in the same manner except that the amount of γ-butyrolactone was changed to 20 g instead of pyrrolidone, and the mechanical properties and Tg were evaluated in the same manner as in Example 1.
In the processability evaluation of Example 1, the pre-baking time was changed to 4 minutes, the film thickness was changed to about 10.0 μm, and the difference between the film thickness after pre-baking and the film thickness after development was 2.0 μm. The same evaluation as in Example 1 was performed.

<Example 3>
In the synthesis of the alkali-soluble resin (A-1) in Example 1, a carboxylic acid derivative (active ester) obtained by reacting 4-maleimidobenzoic acid with 1-hydroxy-1,2,3-benzotriazole Carboxylic acid obtained by changing the amount to 3.64 g (0.011 mol) and reacting 0.011 mol of sorbic acid with 0.011 mol of 1-hydroxy-1,2,3-benzotriazole instead. Other than using 2.50 g (0.011 mol) of the derivative (active ester), it reacted in the same manner as the alkali-soluble resin (A-1), had a number average molecular weight of 12,000, and was composed of the compounds shown in Table 1. An alkali-soluble resin (A-4) was obtained.

Synthesis of Photosensitizer Phenol Formula (B-2) 12.51 g (0.022 mol), 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride 17.49 g (0.065 mol) and acetone 170 g were heated to temperature. The mixture was stirred and dissolved in a four-necked separable flask equipped with a total, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. Next, a mixed solution of 7.24 g (0.072 mol) of triethylamine and 6.1 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, 0.98 g (0.016 mol) of acetic acid was added, and the reaction was further continued for 30 minutes. After filtration of 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 dried according to formula (Q-2). A photosensitizer represented by the structure was obtained.

  In preparation of the photosensitive resin composition of Example 1, an alkali-soluble resin (A-4) was used instead of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2), and a photosensitizer (Q-1) was used. ) Was changed to 0.8 g, and a photosensitive resin composition was prepared in the same manner except that 0.8 g of the photosensitive agent having the structure of the formula (Q-2) was used instead. Mechanical property evaluation, Tg evaluation, and workability evaluation were performed.

<Example 4>
Synthesis of terminal compound having conjugated double bond structure and dienophile structure 8.67 g (0.057 mol) of 3,4-diaminobenzoic acid, 0.057 mol of 4-maleimidobenzoic acid and 1-hydroxy-1,2, 19.04 g (0.057 mol) of a carboxylic acid derivative (active ester) obtained by reacting 0.057 mol of 3-benzotriazole, 0.057 mol of sorbic acid and 1-hydroxy-1,2,3 -A carboxylic acid derivative (active ester) obtained by reacting with 0.057 mol of benzotriazole (13.06 g (0.057 mol)) was equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. It put into the separable flask of 4 necks, 160 g of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 60 ° C. for 6 hours using an oil bath. After cooling to room temperature, 9.24 g (0.068 mol) of 1-hydroxy-1,2,3-benzotriazole was added, and N, N′-disichlorocyclohexyl dissolved in 25 g of N-methyl-2-pyrrolidone 14.10 g (0.068 mol) of carbodiimide was slowly added dropwise with stirring. After the reaction mixture is filtered, the reaction solution is poured into 5 L of water, the precipitate is collected by filtration, washed thoroughly with water, and then dried under vacuum to obtain a carboxylic acid derivative having a conjugated double bond structure and a dienophile structure (active Ester) 14.5 g was obtained.

In the synthesis of the alkali-soluble resin (A-1) in Example 1, a carboxylic acid derivative (active ester) obtained by reacting 4-maleimidobenzoic acid with 1-hydroxy-1,2,3-benzotriazole Instead, the same as the alkali-soluble resin (A-1) except that 9.70 g (0.022 mol) of the carboxylic acid derivative (active ester) having the conjugated double bond structure and the dienophile structure obtained above was used. The target alkali-soluble resin (A-5) consisting of the compound shown in Table 1 having a number average molecular weight of 13,000 was obtained by reaction.
In the production of the photosensitive resin composition of Example 3, a photosensitive resin composition was similarly prepared except that the alkali-soluble resin (A-5) was used instead of the alkali-soluble resin (A-4). Mechanical property evaluation, Tg evaluation, and workability evaluation similar to Example 1 were performed.

<Example 5>
In the synthesis of the alkali-soluble resin (A-3) in Example 2, hexafluoro-2
, 2-bis (3-amino-4-hydroxyphenyl) propane was changed to 0.056 mol, and 3.22 g (0.014 mol) of bis (3-amino-4-hydroxyphenyl) methane was used instead. Instead of a carboxylic acid derivative (active ester) obtained by reacting sorbic acid with 1-hydroxy-1,2,3-benzotriazole, 0.011 mol of 5-phenylpenta-2,4-dienoic acid Except that 3.21 g (0.011 mol) of a carboxylic acid derivative (active ester) obtained by reacting 0.011 mol of 1-hydroxy-1,2,3-benzotriazole with 0.011 mol of an alkali-soluble resin ( The reaction was carried out in the same manner as in A-3), and the target alkali-soluble resin (A-6) having a number average molecular weight of 10,000 and comprising the compounds shown in Table 1 was obtained.

In preparation of the photosensitive resin composition of Example 2, an alkali-soluble resin (A-6) was used instead of the alkali-soluble resin (A-3), and the formula (Q-2) was used instead of the photosensitizer (Q-1). The photosensitive resin composition was prepared in the same manner except that 1.6 g of the photosensitizer having the structure) was used, and the mechanical properties and Tg were evaluated in the same manner as in Example 1.
In the processability evaluation of Example 1, the pre-baking time was changed to 4 minutes, the film thickness was changed to about 10.0 μm, and the difference between the film thickness after pre-baking and the film thickness after development was 2.0 μm. The same evaluation as in Example 1 was performed.

<Example 6>
In the synthesis of the alkali-soluble resin (A-3) in Example 2, hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane was changed to 0.056 mol, and bis (3- Obtained by reacting sorbic acid with 1-hydroxy-1,2,3-benzotriazole using 4.01 g (0.014 mol) of amino-4-hydroxy-2,5-dimethylphenyl) methane Instead of the carboxylic acid derivative (active ester), a carboxylic acid derivative obtained by reacting 0.011 mol of 2,4-pentadienoic acid with 0.011 mol of 1-hydroxy-1,2,3-benzotriazole ( The active ester was reacted in the same manner as the alkali-soluble resin (A-3) except that 2.26 g (0.011 mol) was used, and the number average molecular weight was 12,000. To yield the desired alkali-soluble resin (A-7) comprising Compound.

In preparation of the photosensitive resin composition of Example 2, the alkali-soluble resin (A-7) was used instead of the alkali-soluble resin (A-3), and the amount of the photosensitive agent (Q-1) was changed to 1.7 g. Further, a photosensitive resin composition was prepared in the same manner except that 0.1 g of N-hydroxynaphthalimide trifluoromethanesulfonate was used as the photosensitive agent (Q-3). Tg evaluation was performed.
In the evaluation of workability in Example 1, the evaluation was the same as in Example 1 except that the film thickness was changed to about 10.0 μm and the difference between the film thickness after pre-baking and the film thickness after development was 1.0 μm. Went.

<Example 7>
In the synthesis of the alkali-soluble resin (A-1) in Example 1, isophthalic acid was changed to 0.026 mol, diphenyl ether-4,4′-dicarboxylic acid was changed to 0.039 mol, and 1-hydroxy-1,2 , 3-benzotriazole 0.130 mol, dicarboxylic acid derivative (active ester) 29.75 g (0.065 mol) obtained, and bis (3-amino-4-hydroxy-2,5- Dimethylphenyl) methane was changed to 0.054 mol, and instead of 1,1′-bis (3-amino-4-hydroxyphenyl) ethane, 5.37 g of bis (3-amino-4-hydroxyphenyl) methane (0 Carboxylic acid derivative obtained by reacting 4-maleimidobenzoic acid with 1-hydroxy-1,2,3-benzotriazole (Active ester) was changed to 0.012 mol, and instead carboxylic acid derivative obtained by reacting 0.012 mol of sorbic acid and 0.012 mol of 1-hydroxy-1,2,3-benzotriazole ( Active ester) 4.16 g (0.0
12 mol) was reacted in the same manner as the alkali-soluble resin (A-1) to obtain the target alkali-soluble resin (A-8) having a number average molecular weight of 11,000 and comprising the compounds shown in Table 1. .

Photosensitive resin composition of Example 1 was prepared in the same manner except that the alkali-soluble resin (A-8) was used instead of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2). The same mechanical property evaluation and Tg evaluation as in Example 1 were performed.
In the workability evaluation of Example 1, the same evaluation as in Example 1 was performed except that the film thickness was changed to about 10.0 μm.

<Example 8>
In the synthesis of the terminal compound having a dienophile structure of Example 1, reaction was carried out in the same manner as in Example 1 except that 3-aminobenzoic acid was used instead of 4-aminobenzoic acid, and 25.1 g of 3-maleimidobenzoic acid was obtained. Obtained.

Synthesis of alkali-soluble resin 1.44 g (0.006 mol) of 3,3′-diaminodiphenylsulfone and 100 g of N-methyl-2-pyrrolidone were equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. It was dissolved in a two-necked separable flask. 1.96 g (0.006 mol) of 4,4′-oxydiphthalic anhydride was added and reacted at room temperature for 1 hour, and then reacted at 65 ° C. for 2 hours using an oil bath. Next, 21.24 g (0.058 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane, 2.16 g (0.009 mol) of 3,3′-diaminodiphenylsulfone, diphenyl ether 27.96 g of dicarboxylic acid derivative (active ester) obtained by reacting 0.057 mol of -4,4'-dicarboxylic acid with 0.114 mol of 1-hydroxy-1,2,3-benzotriazole 057 mol) was added together with 119 g of N-methyl-2-pyrrolidone and allowed to react for 16 hours.
Next, after changing the reaction temperature to 60 ° C., a carboxylic acid derivative obtained by reacting 0.009 mol of 3-maleimidobenzoic acid with 0.009 mol of 1-hydroxy-1,2,3-benzotriazole ( Active ester) 3.15 g (0.009 mol), carboxylic acid derivative (activity) obtained by reacting 0.009 mol of sorbic acid and 0.009 mol of 1-hydroxy-1,2,3-benzotriazole Ester) 2.16 g (0.009 mol) and N-methyl-2-pyrrolidone 21 g were added, and the mixture was further stirred for 3 hours to complete the reaction. After filtering the reaction mixture, the reaction solution 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 10,000. The target alkali-soluble resin (A-9) comprising the compounds shown in Table 1 was obtained.

In preparation of the photosensitive resin composition of Example 2, the alkali-soluble resin (A-9) was used instead of the alkali-soluble resin (A-3), and the amount of the photosensitive agent (Q-1) was changed to 1.9 g. In the same manner, except that 0.1 g of (Z, E) -2- (4-methoxyphenyl) -2-[(4-methylphenylsulfonyl) oxyimino] acetonitrile was used as the photosensitive agent (Q-4). A photosensitive resin composition was prepared, and mechanical property evaluation and Tg evaluation similar to Example 1 were performed.
In the evaluation of workability in Example 2, the same evaluation as in Example 2 was performed, except that the difference between the film thickness after pre-baking and the film thickness after development was 1.0 μm.

<Comparative Example 1>
In the synthesis of the alkali-soluble resin (A-3) in Example 2, a carboxylic acid derivative (active ester) obtained by reacting 4-maleimidobenzoic acid and 1-hydroxy-1,2,3-benzotriazole; Instead of a carboxylic acid derivative (active ester) obtained by reacting sorbic acid with 1-hydroxy-1,2,3-benzotriazole, 3.79 g (0.022 mol) of 4-ethynylphthalic anhydride ) Was used in the same manner as the alkali-soluble resin (A-3) to obtain the target alkali-soluble resin (A-10) having a number average molecular weight of 9000 and comprising the compounds shown in Table 2.
In the production of the photosensitive resin composition of Example 2, a photosensitive resin composition was prepared in the same manner except that the alkali-soluble resin (A-10) was used instead of the alkali-soluble resin (A-3). In the mechanical property evaluation and Tg evaluation of No. 1, a photosensitive resin composition was applied to each of two silicon wafers, one of the silicon wafers with a coating was heated at 200 ° C./90 minutes, and the other was 300 Evaluation was performed in the same manner except that the heating was performed at 60 ° C./60 minutes.
The same workability evaluation as in Example 2 was performed.

<Comparative example 2>
In preparation of the photosensitive resin composition of Example 1, the amount of the alkali-soluble resin (A-1) was changed to 10 g instead of the alkali-soluble resin (A-2), and the amount of the photosensitive agent (Q-1) was changed. A photosensitive resin composition was prepared in the same manner except that 0.8 g of the photosensitizer having the structure of the formula (Q-2) was used instead, and the same mechanical properties as in Example 1 were obtained. Evaluation and Tg evaluation were performed.
The same workability evaluation as in Example 3 was performed.

<Comparative Example 3>
In preparation of the photosensitive resin composition of Example 1, the amount of the alkali-soluble resin (A-2) was changed to 10 g instead of the alkali-soluble resin (A-1), and the amount of the photosensitive agent (Q-1) was changed. A photosensitive resin composition was prepared in the same manner except that 0.8 g of the photosensitizer having the structure of the formula (Q-2) was used instead, and the same mechanical properties as in Example 1 were obtained. Evaluation and Tg evaluation were performed.
The same workability evaluation as in Example 3 was performed.

<Comparative Example 4>
In the synthesis of the alkali-soluble resin (A-8) in Example 7, a carboxylic acid derivative (active ester) obtained by reacting 4-maleimidobenzoic acid and 1-hydroxy-1,2,3-benzotriazole; Instead of a carboxylic acid derivative (active ester) obtained by reacting sorbic acid with 1-hydroxy-1,2,3-benzotriazole, 4.13 g (0.024 mol) of 4-ethynylphthalic anhydride ) Was used in the same manner as the alkali-soluble resin (A-8) to obtain the target alkali-soluble resin (A-11) having a number average molecular weight of 10,000 and comprising the compounds shown in Table 2.
Photosensitive resin composition of Example 1 was prepared in the same manner except that the alkali-soluble resin (A-11) was used instead of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2). The same mechanical property evaluation and Tg evaluation as in Example 1 were performed.
In the workability evaluation of Example 1, the same evaluation as in Example 1 was performed except that the film thickness was changed to about 10.0 μm.

<Comparative Example 5>
In the synthesis of the alkali-soluble resin (A-9) in Example 8, a carboxylic acid derivative (active ester) obtained by reacting 3-maleimidobenzoic acid and 1-hydroxy-1,2,3-benzotriazole; In place of carboxylic acid derivative (active ester) obtained by reacting sorbic acid with 1-hydroxy-1,2,3-benzotriazole, 1.77 g (0.018 mol) of maleic anhydride is used. The objective alkali-soluble resin (A-12) comprising the compounds shown in Table 2 having a number average molecular weight of 9000 was reacted in the same manner as the alkali-soluble resin (A-9).
In preparation of the photosensitive resin composition of Example 2, the alkali-soluble resin (A-12) was used instead of the alkali-soluble resin (A-3), and the amount of the photosensitive agent (Q-1) was changed to 1.9 g. In the same manner, except that 0.1 g of (Z, E) -2- (4-methoxyphenyl) -2-[(4-methylphenylsulfonyl) oxyimino] acetonitrile was used as the photosensitive agent (Q-4). A photosensitive resin composition was prepared, and mechanical property evaluation and Tg evaluation similar to Example 1 were performed.
In the evaluation of workability in Example 2, the same evaluation as in Example 2 was performed, except that the difference between the film thickness after pre-baking and the film thickness after development was 1.0 μm.

  Tables 1 and 2 showing examples and comparative examples are shown below.

  As shown in Table 1, it can be seen that Examples 1 to 8 are excellent in strength, elongation, and heat resistance even when cured at a low temperature of 200 ° C. even if only a resin and a photosensitive agent are used. It was suggested that this is effective. In addition, it can be seen that it has sufficient sensitivity and resolution that does not interfere with semiconductor production.

  The photosensitive resin composition obtained in each example and each comparative example was coated on a semiconductor element to form a pattern in the same manner as in Example 1, and cured using an oven to form a protective film. A semiconductor device can be obtained.

  Although the semiconductor device obtained in this way is expected to operate normally, when the photosensitive resin compositions of Examples 1 to 8 are used, they have higher strength, higher elongation, and higher heat resistance than the comparative examples. Therefore, the operation is expected to be more reliable.

  According to the present invention, there is provided a cured film having high sensitivity, high resolution, high strength, elongation and heat resistance only with a resin and a photosensitive agent even when cured at a low temperature of about 200 ° C. and having high reliability for a semiconductor device. A photosensitive resin composition, a protective film, an insulating film, and a semiconductor device and a display device using the same can be provided.

Claims (11)

A photosensitive resin composition comprising: an alkali-soluble resin having a conjugated double bond structure at at least one terminal; an alkali-soluble resin having a dienophile structure at at least one terminal; and a photosensitizer.   The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin has at least one of a benzoxazole precursor structure and an imide precursor structure.   The photosensitive resin composition according to claim 1, wherein the conjugated double bond structure is a conjugated diene structure. The photosensitive resin composition according to claim 1, wherein the dienophile structure is a maleimide structure. The photosensitive resin composition according to claim 3, wherein the conjugated diene structure is —CH═CH—CH═CH—R ₁ .
(R ₁ represents a hydrogen atom, an alkyl group or an aromatic group.)   The photosensitive resin composition according to claim 4, wherein the maleimide structure is a structure derived from N-phenylmaleimide. A cured film comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 6.   A protective film comprising the cured film according to claim 7.   An insulating film comprising the cured film according to claim 7.   A semiconductor device comprising the cured film according to claim 7.   A display device comprising the cured film according to claim 7.