WO2010150518A1 - Alkali-soluble resin, positive photosensitive resin composition, cured film, protective film, insulating film, and semiconductor device and display device both including same - Google Patents

Abstract

Disclosed is an alkali-soluble resin including a polybenzoxazole precursor structure constituted of both a bis(aminophenol) and a structure derived from a dicarboxylic acid, wherein when the two aromatic rings of the bis(aminophenol) are rotated, the rotational energy barrier for the dihedral angle, as obtained by a calculation based on computational chemistry, is 3 kcal/mol or more.

Description

Alkali-soluble resin, positive photosensitive resin composition, cured film, protective film, insulating film, and semiconductor device and display device using the same

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

Conventionally, protective films and insulating films for semiconductor elements are polyimide resins having excellent heat resistance and excellent electrical and mechanical properties, polybenzoxazole resins that are considered to have good moisture resistance reliability in addition to the above properties, etc. 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 as an alkali-soluble resin and a diazoquinone compound as a photosensitizer. The development mechanism of this positive photosensitive resin composition is as follows. When a positive photosensitive resin composition applied on a substrate is irradiated with actinic radiation through a mask on which a desired pattern is drawn, the exposed portion (exposed portion) of the diazoquinone compound undergoes a chemical change, resulting in an alkaline aqueous solution. So that the alkali-soluble resin is dissolved. On the other hand, the unexposed portion (unexposed portion) of the diazoquinone compound is insoluble in the aqueous alkali solution and becomes resistant to the interaction with the alkali-soluble resin. By utilizing the difference in solubility between the exposed portion and the unexposed portion to dissolve and remove the exposed portion, a relief pattern of only the unexposed portion can be created.

Polyimide precursor resin and polybenzoxazole precursor resin in the photosensitive resin composition having a relief pattern finally cured at a high temperature in the vicinity of 300 ° C to 350 ° C, and then dehydrated and closed, resulting in a highly heat-resistant polyimide. Resin, polybenzoxazole resin. In recent years, due to miniaturization and high integration of semiconductor elements, heat resistance has been lowered particularly in memory elements, and in order to improve productivity, polyimide precursor resins and polybenzoxazole precursor resins that can be cured at low temperatures are required. Has been.

What is important when curing at a low temperature is that, for example, in a reliability test such as a temperature cycle test of a semiconductor device, there is almost no variation in the properties of the cured product, and the heat resistance and reliability of the semiconductor device are excellent. Accordingly, it is desirable that the glass transition temperature (Tg) of the cured film has a Tg equal to or higher than the reflow temperature assuming the use of lead-free solder even when the curing temperature is low. In particular, the positive photosensitive resin composition is 250 ° C. It is desired that the Tg of the cured film after being cured at a low temperature is 260 ° C. or higher.

JP-A-56-27140

An object of the present invention is to provide an alkali-soluble resin having excellent heat resistance and reliability even when cured at a low temperature when used as a positive photosensitive resin composition.
Another object of the present invention is to provide a positive photosensitive resin composition, a cured film, a protective film, an insulating film, and a semiconductor device using the same, which are highly sensitive and have excellent heat resistance and reliability even when cured at a low temperature. It is to provide a body device.

Such an object is achieved by the present invention described in the following (1) to (14).
(1) An alkali-soluble resin containing a polybenzoxazole precursor structure composed of bis (aminophenol) and a structure derived from a dicarboxylic acid, wherein the bis (aminophenol) is obtained by calculation by computational chemistry An alkali-soluble resin, wherein an energy barrier of rotation of a dihedral angle between two aromatic rings is 3 [kcal / mol] or more.
(2) The above bis (aminophenol) has a phenolic hydroxyl group at an adjacent site of both amino groups and a substituent at an adjacent site on the opposite side of the amino group. The alkali-soluble resin described in 1.
(3) The alkali-soluble resin according to (2), wherein the bis (aminophenol) is represented by the following formula (1).

(In the formula, R ₁ is an organic group. R ₂ is an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group, which may be the same or different. R ₃ is a hydrogen atom, an alkyl group, Any one of an alkoxy group, an acyloxy group, and a cycloalkyl group, which may be the same or different.)

(4) An alkali-soluble resin comprising a polybenzoxazole precursor structure composed of bis (aminophenol) and a structure derived from dicarboxylic acid,
The dihedral angle AB—R ₄ —D of the bis (aminophenol) represented by the following formula (2) is rotated by 5 degrees in the range of −180 degrees to 180 degrees, and the heat of formation in each conformation An alkali-soluble resin, wherein the difference between the highest heat of formation and the lowest heat of formation when determined by a molecular orbital method is 3 [kcal / mol] or more.

(In the formula, R ₄ is an organic group. R ₅ is an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group, which may be the same or different. R ₆ is a hydrogen atom, an alkyl group, Any one of an alkoxy group, an acyloxy group, and a cycloalkyl group, which may be the same or different.)

(5) A positive photosensitive resin composition comprising the alkali-soluble resin according to any one of (1) to (4) above and a photosensitive agent.
(6) The positive photosensitive resin as described in (5) above, wherein a light transmittance at a wavelength of 365 nm of a 5 μm-thick film obtained after the alkali-soluble resin is applied to a substrate and dried is 30% or more. Composition.
(7) The positive photosensitive resin composition according to the above (5) or (6), wherein the glass transition temperature is 260 ° C. or higher.
(8) When the cyclization rate [A]% at 250 ° C. of the alkali-soluble resin and the cyclization rate [B]% at 320 ° C., [A] / [B] is 0.8 or more. The positive photosensitive resin composition according to the above (5) or (6).
(9) The positive photosensitive resin composition according to any one of (5) to (8), wherein the alkali-soluble resin has a cyclization rate at 250 ° C. of 80% or more.

(10) A cured film comprising a cured product of the positive photosensitive resin composition according to any one of (5) to (9) above.
(11) A protective film comprising the cured film as described in (10) above.
(12) An insulating film comprising the cured film as described in (10) above.
(13) A semiconductor device comprising the cured film according to (10).
(14) A display device having the cured film according to (10).

According to the present invention, when used as a positive photosensitive resin composition, it is possible to provide an alkali-soluble resin that is highly sensitive and excellent in heat resistance and reliability even when cured at a low temperature.
Further, according to the present invention, a positive photosensitive resin composition, a cured film, a protective film, an insulating film, and a semiconductor device using the same, which are highly sensitive and have excellent heat resistance and reliability even when cured at a low temperature A body device can be provided.

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

The alkali-soluble resin used in the present invention includes a polybenzoxazole precursor structure composed of bis (aminophenol) and a structure derived from dicarboxylic acid, and the bis (aminophenol) is included therein. When the two aromatic rings are rotated, the energy barrier in dihedral angle rotation calculated by computational chemistry is 3 [kcal / mol] or more. The positive photosensitive resin composition contains the alkali-soluble resin and the photosensitive agent.

Further, the protective film and the insulating film of the present invention are characterized in that they are composed of a cured film that is a cured product of the positive photosensitive resin composition.

Further, the semiconductor device and the display device of the present invention are characterized by having the cured film.

First, the alkali-soluble resin of the present invention will be described in detail.

The alkali-soluble resin of the present invention contains a polybenzoxazole precursor structure composed of bis (aminophenol) and a structure derived from dicarboxylic acid, and includes two aromatic rings contained in the bis (aminophenol). When rotating, the energy barrier in rotation of the dihedral angle calculated by computational chemistry is 3 [kcal / mol] or more.

The energy barrier for rotation of the dihedral angle of bis (aminophenol) can be calculated by using, for example, the PM5 method of MOPAC 2006 with a Scigress Explorer manufactured by Fujitsu Limited. Specifically, the structure of bis (aminophenol) represented by the formula (2) is drawn, and the dihedral angle ABCR ₄ -D is rotated by 5 degrees in the range of −180 degrees to 180 degrees, and the heat of formation is reduced. The value of the energy barrier can be obtained by calculation.

(In the formula, R ₄ is an organic group. R ₅ is an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group, which may be the same or different. R ₆ is a hydrogen atom, an alkyl group, Any one of an alkoxy group, an acyloxy group, and a cycloalkyl group, which may be the same or different.)

In order to be excellent in heat resistance and reliability even when cured at low temperature, an alkali-soluble resin in which the cured film of the positive photosensitive resin composition exhibits a high Tg is required, but Tg decreases as the curing temperature decreases. Therefore, conventionally, there has been no alkali-soluble resin having a polybenzoxazole precursor structure having a high Tg and excellent heat resistance even when cured at a low temperature.

Generally, techniques for increasing the Tg of a polymer include improvement of rigidity of the main chain, improvement of symmetry, use of intermolecular interactions such as introduction of polar groups, and the like. On the other hand, in this invention, the method of obstructing the rotational movement of a molecule | numerator and obtaining high Tg by requiring a high thermal energy for glass transition was examined. Therefore, the difficulty of the rotational movement of the molecule is regarded as an energy barrier in the rotation of the molecule, and the difference between the maximum value and the minimum value of the generated heat in the rotation of the dihedral angle is calculated by computational chemistry. kcal / mol] or higher, a positive photosensitive resin composition having a Tg of 260 ° C. or higher and excellent heat resistance even when cured at a low temperature of 250 ° C. is obtained. I found out.

The difference between the heat of formation of the most stable structure and the heat of formation of the most unstable structure is more preferably 4 [kcal / mol] or more, and particularly preferably 5 [kcal / mol] or more. When the difference is within the above range, the heat resistance is particularly excellent.

In addition, as an upper limit, it is preferable that it is 30 [kcal / mol] or less. If it is larger than the above upper limit, it is necessary to introduce a very large substituent on the aromatic ring. Therefore, the synthesis of such aminophenol is very difficult due to steric hindrance, and Since the yield becomes very low, it is not preferable.

In order to make the difference in heat of generation 3 [kcal / mol] or more, bis (aminophenol) has a structure in which rotational motion is difficult to occur, for example, R ₁ shown in Formula (1) is bulky, or an amide bond And a method of introducing a substituent on two aromatic rings. Among them, the difference in heat of formation can be remarkably increased by introducing a substituent on two aromatic rings, particularly by introducing a substituent at an ortho position adjacent to the amino group.

Specific examples of the bis (aminophenol) satisfying that the difference in heat of generation is 3 [kcal / mol] or more include bis (aminophenol) represented by the formula (3). In the bis (aminophenol) represented by the formula (3), it is considered that the rotation of the two aromatic rings is more difficult to rotate by the substituent (R ₈ ) in the ortho position of the amino group, and is higher until the glass transition occurs. It is thought that heat energy will be required.

(In the formula, R ₇ is an organic group. R ₈ is an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group, which may be the same or different. R ₉ is a hydrogen atom or an alkyl group. , An alkoxy group, an acyloxy group, or a cycloalkyl group, which may be the same or different.

Specific examples of the organic group represented by R ₇ include alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —Si (CH ₃ ) ₂ —, —C ₆ H ₄ —, —CO—, —NHCO—, —COO—, —C (CF ₃ ) ₂ — and the like.

More preferably, it is bis (aminophenol) represented by the following formula (4).

(Wherein R ₁₀ is an organic group selected from alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —CO—, —C (CF ₃ ) ₂ —. R ₁₁ is alkyl) R ₁₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. May be different.)

Particularly preferred is bis (aminophenol) represented by the following formula (5).

_{(Wherein, R 13} is an alkylene, substituted _{alkylene, -O -, - S -,} - SO 2 -, - CO -, - C (CF 3) 2 -, an organic group selected from _{.R 14} is R ₁₅ is any one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. May be.)

Specific examples of R ₁ in formula ( ₁ ), R ₇ in formula (3), R _{10 in} formula (4), and R _{13 in} formula (5) and substituted alkylene include, for example, —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 _{H 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 others as mentioned, _-CH 2 among them _{-, - CH (CH 3)} -, - C (CH 3) 2 - are more It is preferable because an alkali-soluble resin having sufficient solubility in not only an alkaline aqueous solution but also a solvent can be obtained while maintaining a higher Tg even when cured at a low temperature.

R ₂ and R ₃ in formula (1), R ₈ and R ₉ in formula (3), R ₁₁ and R ₁₂ in formula (4), and R ₁₄ and R ₁₅ in formula (5) are alkyl groups or alkoxy It is preferable to use the group bis (aminophenol), thereby maintaining a higher Tg even when cured at a low temperature, and having a sufficient solubility in an aqueous alkali solution and a better balance. An alkali-soluble resin is obtained. Specific examples of the alkyl group include, for example, —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ , —CH (CH ₃ ) ₂ , —CH ₂ CH ₂ CH ₂ CH ₃ , —CH _2. CH (CH ₃ ) ₂ , —CH (CH ₃ ) (CH ₂ CH ₃ ), —C (CH ₃ ) ₃ , —CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , —CH ₂ CH ₂ CH (CH ₃ ) ₂ , —CH ₂ CH (CH ₃ ) (CH ₂ CH ₃ ), —CH (CH ₂ CH ₃ ) (CH ₂ CH ₃ ), —CH (CH ₃ ) (CH ₂ CH ₂ CH ₃ ), —CH ( CH ₃ ) (CH (CH ₃ ) ₂ ), —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , —CH (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₃ ), —CH (CH ₃ ) ( _{CH 2 CH (CH 3) 2} ), - CH 2 CH 2 CH _{CH 2 CH 2 CH 2 CH 3} , etc. _{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 CH 3 and the like. Specific examples of the alkoxy group include, for example, —OCH ₃ , —OCH ₂ CH ₃ , —OCH ₂ CH ₂ CH ₃ , —OCH (CH ₃ ) ₂ , —OCH ₂ CH ₂ CH ₂ CH ₃ , —OCH ₂ CH (CH ₃ ) ₂ , —OCH (CH ₃ ) (CH ₂ CH ₃ ), —OC (CH ₃ ) _{3 and the} like can be mentioned.

The alkali-soluble resin used in the present invention has a polybenzoxazole precursor structure, but is not limited thereto and may have another structure.
Examples of other structures include a structure having at least one of a polybenzoxazole structure and a polyimide structure, and having a hydroxyl group, a carboxyl group, an ether group or an ester group in the main chain or side chain, a polyimide precursor structure, a polyamide It is an acid ester structure.
For example, a polyamide resin having a structure represented by formula (6-1) is preferable from the viewpoint of heat resistance and reliability after final heating. More preferred is a polybenzoxazole precursor resin represented by the formula (6-2).

(In the formula (6), X and Y are organic groups. A, b, c and d represent mole percentages, and a + b = 100 and c + d = 100, and a and c are 60 or more and 100 or less, b, each d is from 0 to 40. R ₁₉ and R ₂₄ are a hydroxyl group or —O—R ₂₅ , which may be the same or different, and R ₂₀ is a hydroxyl group, a carboxyl group, —O—R ₂₅ , —COO—. Any one of R ₂₅ , which may be the same or different, m is an integer of 0 to 2, n is an integer of 0 to 4, p is an integer of 0 to 2. R ₂₅ is an integer of 1 to 15 carbon atoms In the formula (6-1), when R ₁₉ has no hydroxyl group, at least one R ₂₀ must be a carboxyl group, and when R ₂₀ does not have a carboxyl group, R ₁₉ must be at least one must be a hydroxyl group .R ₁ , _{R 21} is alkylene, substituted _{alkylene, -O -, - S -,} - SO 2 -, - CO -, - NHCO -, - C (CF 3) 2 - from an organic group selected _.R 17, R ₂₂ is an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group, which may be the same or different, and R ₁₈ and R ₂₃ are any of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group. And may be the same or different.)

Specific examples of the alkylene and substituted alkylene of R ₁₆ and R _{21 in} the formula (6) 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 ) —, —C—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 _{H 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) - Etc.

Specific examples of the alkyl group of R ₁₇ , R ₁₈ , R ₂₂ and R _{23 in} the formula (6) include —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ , —CH (CH ₃ ) ₂ , —CH ₂ CH ₂ CH ₂ CH ₃ , —CH ₂ CH (CH ₃ ) ₂ , —CH (CH ₃ ) (CH ₂ CH ₃ ), —C (CH ₃ ) ₃ , —CH ₂ CH ₂ CH _{2 CH 2 CH 3, -CH 2} CH 2 CH (CH 3) 2, -CH 2 CH (CH 3) (CH 2 CH 3), - CH (CH 2 CH 3) (CH 2 CH 3), - CH (CH ₃ ) (CH ₂ CH ₂ CH ₃ ), —CH (CH ₃ ) (CH (CH ₃ ) ₂ ), —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , —CH (CH ₃ ) (CH _{2 CH 2 CH 2 CH 3)} , - CH (CH 3) (CH 2 _{H (CH 3) 2),} - CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3, etc. _{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 CH 3 and the like. Specific examples of the alkoxy group include —OCH ₃ , —OCH ₂ CH ₃ , —OCH ₂ CH ₂ CH ₃ , —OCH (CH ₃ ) ₂ , —OCH ₂ CH ₂ CH ₂ CH ₃ , —OCH ₂ CH _{(CH 3) 2, -OCH (} CH 3) (CH 2 CH 3), - OC (CH 3) 3 and the like.

Also, it is important that the light transmittance at a wavelength of 365 nm per film thickness of 5 μm formed after applying and drying the alkali-soluble resin is 30% or more. When the transmittance of the film is high, the sensitivity is improved because more actinic rays reach the inner part of the film. When the sensitivity is improved, the exposure time is shortened to improve productivity. More preferably, the light transmittance is 50% or more.

By using bis (aminophenol) of the formula (1), an alkali-soluble resin having a high light transmittance of a film with respect to actinic radiation having a wavelength of 365 nm, which is often used as an exposure light source for forming a relief pattern, can be obtained. . The reason for this is that the aromatic structure via R ₁ is bent due to the steric hindrance between the substituents represented by R ₂ in the formula (1), making it difficult to obtain a planar structure and charge transfer is less likely to occur. Conceivable.

The polyamide resin having the structure represented by the formula (6-1) is, for example, a bis (aminophenol) represented by the formula (4) and a diamine or bis (aminophenol) containing 2, if necessary, 2,4-diamino. A compound selected from phenol and the like, and a compound selected from tetracarboxylic dianhydride, trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative and the like containing Y It is obtained by reaction.

The polybenzoxazole precursor resin represented by the formula (6-2) includes, for example, a bis (aminophenol) represented by the formula (4) and, if necessary, bis (aminophenol), 2,4-diaminophenol And a compound selected from a dicarboxylic acid containing Y, a dicarboxylic acid dichloride, a dicarboxylic acid derivative, or the like. In the case of dicarboxylic acid, an active ester 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 and the like.

When a and c in the formula (6) are 60 mole percent or more, an alkali-soluble resin having a cured film Tg of 260 ° C. or higher can be obtained even when cured at a low temperature of 250 ° C.

In the alkali-soluble resin represented by the formula (6), —O—R ₂₅ as a substituent of X, —O—R ₂₅ and —COO—R ₂₅ as a substituent of Y are an aqueous alkali solution of a hydroxyl group and a carboxyl group Is a group protected with R ₂₅ , 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 ₂₅ 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.

When this alkali-soluble resin is heated at a low temperature of 150 ° C. or higher and lower than 280 ° C., when heated at a high temperature of 280 ° C. or higher and 380 ° C. or lower, it undergoes dehydration and ring closure, resulting in polybenzoxazole resin or polybenzoxazole resin and polyimide resin A heat-resistant resin is obtained in the form of copolymerization with. Heat treatment at a low temperature is effective in improving yield even in a semiconductor element having low heat resistance.

X in the formula (6) is an organic group, and examples thereof include aromatic compounds such as benzene ring and naphthalene ring, heterocyclic compounds such as bisphenols, pyrroles and furans, and siloxane compounds. Preferred examples include those represented by the following formula (7). These may be used singly or in combination of two or more if necessary so as not to affect Tg when cured at low temperature.

(In the formula, * represents bonding to an NH group. A represents —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, — NHCO—, —C (CF ₃ ) ₂ —, or a single bond R ₂₆ represents one selected from an alkyl group, an alkyl ester group, an alkyl ether group, and a halogen atom, and each is the same or different. R ₂₇ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom, R is an integer of 0 to 2, and R ₂₈ to R ₃₁ are organic groups.)

Specific examples of the alkyl group represented by R ₂₆ and R _{27 in} the formula (7) include —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ , —CH (CH ₃ ) ₂ , —CH _2. CH ₂ CH ₂ CH ₃ , —CH ₂ CH (CH ₃ ) ₂ , —CH (CH ₃ ) (CH ₂ CH ₃ ), —C (CH ₃ ) ₃ , —CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , —CH ₂ CH ₂ CH (CH ₃ ) ₂ , —CH ₂ CH (CH ₃ ) (CH ₂ CH ₃ ), —CH (CH ₂ CH ₃ ) (CH ₂ CH ₃ ), —CH (CH ₃ ) (CH ₂ CH ₂ CH ₃ ), —CH (CH ₃ ) (CH (CH ₃ ) ₂ ), —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , —CH (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH _{3), - CH (CH 3} ) (CH 2 CH (CH 3) 2 _{, -CH 2 CH 2 CH 2 CH} 2 CH 2 CH 2 CH 3, etc. _{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 CH 3 and the like.

As shown in Formula (6), 0 to 2 R ₁₉ or R ₂₄ are bonded to X. (In the formula (7), R ₁₉ and R ₂₄ are omitted).

In the formula (6), b and d, which are mole percentages of repeating units including X, may be zero.

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 (8) can be mentioned preferably. These may be used alone or in combination of two or more.

(In the formula, * represents bonding to a C═O group. A represents —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—). , —NHCO—, —C (CF ₃ ) ₂ —, or a single bond, R ₃₂ represents one selected from an alkyl group, an alkyl ester group, an alkyl ether group, and a halogen atom, and may be the same or different. R ₃₃ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom, and is an integer of t = 0 to 2. R ₃₄ to R ₃₇ are organic groups. .)

Specific examples of the alkyl group represented by R ₃₂ and R ₃₃ in Formula (8) include —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ , —CH (CH ₃ ) ₂ , —CH _2. CH ₂ CH ₂ CH ₃ , —CH ₂ CH (CH ₃ ) ₂ , —CH (CH ₃ ) (CH ₂ CH ₃ ), —C (CH ₃ ) ₃ , —CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , —CH ₂ CH ₂ CH (CH ₃ ) ₂ , —CH ₂ CH (CH ₃ ) (CH ₂ CH ₃ ), —CH (CH ₂ CH ₃ ) (CH ₂ CH ₃ ), —CH (CH ₃ ) (CH _{2 CH 2 CH 3), -} CH (CH 3) (CH (CH 3) 2), - CH 2 CH 2 CH 2 CH 2 CH 2 CH 3, -CH (CH 3) (CH 2 CH 2 CH 2 CH _{3), - CH (CH 3} ) (CH 2 CH (CH 3) 2 _{, -CH 2 CH 2 CH 2 CH} 2 CH 2 CH 2 CH 3, etc. _{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 CH 3 and the like.

As shown in Formula (6), 0 to 4 R ₂₀ are bonded to Y (in Formula (8), R ₂₀ is omitted).

Among these, a compound represented by the following formula (9) is particularly preferable.
Regarding the structure derived from tetracarboxylic dianhydride in the following formula (9), the position where both C═O groups are bonded is in the meta position, and both are in the para position. A structure including each of the para positions may be used.

(In the formula, * represents bonding to a C═O group. R ₃₈ represents one selected from an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and a halogen atom, R ₃₉ 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.)

Specific examples of the alkyl group for _{R 38} of formula _{(9), -CH 3, -CH} 2 CH 3, -CH 2 CH 2 CH 3, -CH (CH 3) 2, -CH 2 CH 2 CH ₂ CH ₃ , —CH ₂ CH (CH ₃ ) ₂ , —CH (CH ₃ ) (CH ₂ CH ₃ ), —C (CH ₃ ) ₃ , —CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , —CH ₂ CH ₂ CH (CH ₃ ) ₂ , —CH ₂ CH (CH ₃ ) (CH ₂ CH ₃ ), —CH (CH ₂ CH ₃ ) (CH ₂ CH ₃ ), —CH (CH ₃ ) (CH ₂ CH ₂ CH ₃ ), —CH (CH ₃ ) (CH (CH ₃ ) ₂ ), —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , —CH (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₃ ), —CH (CH ₃ ) (CH ₂ CH (CH ₃ ) ₂ ), —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _{3 and the} like can be mentioned.

In order to have excellent heat resistance even when the positive photosensitive resin composition comprising the alkali-soluble resin is cured at a low temperature of 250 ° C., X and Y in the formula (6) are preferably cyclic compounds, particularly aromatic. Group compounds are preferred.

The alkali-soluble resin represented by the above formula (6) is an acid anhydride containing an amino group at the terminal of the alkali-soluble resin, an aliphatic group having at least one alkenyl group or alkynyl group, or a cyclic compound group. Preferably, the product is capped as an amide. Thereby, preservability can be improved. Examples of such a group derived from an acid anhydride containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group include formula (10) and formula (11). ) And the like. These may be used alone or in combination of two or more.

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

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

(Positive photosensitive resin composition)
Next, the positive photosensitive resin composition will be described in detail. The positive photosensitive resin composition contains the alkali-soluble resin and the photosensitive agent.

As the photosensitizer used in the present invention, a photosensitizer capable of positive patterning can be used. Specifically, a compound that generates an acid by light, such as a photosensitive diazoquinone compound or an onium salt, or a dihydropyridine compound is used. be able to. Examples of the photosensitive diazoquinone compound include esters of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. Specific examples include ester compounds represented by formula (13) to formula (16). These may be used alone or in combination of two or more.

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

The positive-type photosensitive resin composition of the present invention uses an alkali-soluble resin having a polybenzoxazole precursor structure composed of bis (aminophenol) of the present invention represented by formulas (3), (4), and (5). In this case, not only the Tg but also the cyclization rate is improved when cured at a low temperature. This is considered to be due to the amide bond in the polybenzoxazole precursor structure being pushed out to the hydroxyl group side by steric hindrance with the substituent at the ortho position of the amino group.

Conventionally, there has been no alkali-soluble resin having a polybenzoxazole precursor structure that is excellent in heat resistance and reliability even when cured at a low temperature. The cause is that the Tg of the polymer is low at the time of low-temperature curing as described above, and the cyclization reaction has not sufficiently progressed at the time of curing at low temperature. This is thought to be due to the increase.

On the other hand, as a result of intensive studies in the present invention, when the cyclization rate [A]% of the alkali-soluble resin at 250 ° C. and the cyclization rate [B]% at 320 ° C., [A] / [ It was found that the positive photosensitive resin composition using the alkali-soluble resin having B] of 0.8 or more has a low water absorption even when cured in a wide temperature range and is excellent in reliability.

Examples of a method for obtaining an alkali-soluble resin that achieves a value equal to or higher than the ratio described above include, for example, reducing the weight-average molecular weight of the alkali-soluble resin to 10,000 or less, or forming a siloxane bond, an aliphatic hydrocarbon bond, etc. Among them, a method using bis (aminophenol) represented by the following formulas (3), (4) and (5) is preferable.

Specifically, bis (aminophenol) has a phenolic hydroxyl group at the site adjacent to both amino groups, and further has a substituent at the site adjacent to the opposite side of the amino group.

More specifically, examples of the bis (aminophenol) include a compound represented by the formula (3). As a result, the amide bond in the alkali-soluble resin is pushed out to the hydroxyl group side by steric hindrance with the substituent (R ₈ ) at the ortho position of the amino group of formula (3), and the carbonyl carbon of the amide bond and the oxygen atom of the hydroxyl group When the oxygen atom of the hydroxyl group derived from bis (aminophenol) in the cyclization reaction is easily nucleophilic attacked to the carbon atom of the carbonyl group in the amide bond and cured at a low temperature of 250 ° C. Since the cyclization rate is 80% or more, since the high cyclization rate is exhibited by curing in a wide temperature range, the above-described effect of increasing the Tg is also synergistic, and more excellent reliability can be given.

(In the formula, R ₇ is an organic group. R ₈ is an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group, which may be the same or different. R ₉ is a hydrogen atom or an alkyl group. , An alkoxy group, an acyloxy group, or a cycloalkyl group, which may be the same or different.

Specific examples of the organic group for R ₇ include alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —Si (CH ₃ ) ₂ —, —C ₆ H ₄ —, —CO—. , —NHCO—, —COO—, —C (CF ₃ ) ₂ — and the like.

The bis (aminophenol) is more preferably a bis (aminophenol) represented by the formula (4).

(Wherein R ₁₀ is an organic group selected from alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —CO—, —C (CF ₃ ) ₂ —. R ₁₁ is alkyl) R ₁₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and may be the same or different. May be different.)

Particularly preferred is bis (aminophenol) represented by the formula (5). This is because when a bis (aminophenol) having a substituent at the ortho position (R ₁₅ ) of the phenolic hydroxyl group is used, the phenolic hydroxyl group is pushed out to the amide bond side due to steric hindrance with the substituent as described above. It is because it is thought that it approaches.

(Wherein R ₁₃ is an organic group selected from alkylene, substituted alkylene, —O—, —S—, —SO ₂ —, —CO—, —C (CF ₃ ) ₂ —. R ₁₄ is alkyl) A group, an alkoxy group, an acyloxy group or a cycloalkyl group, which may be the same or different, and R ₁₅ is an alkyl group, an alkoxy group, an acyloxy group or a cycloalkyl group, which may be the same or different. Good.)

Specific examples of R ₇ in formula (3), R ₁₀ in formula (4), and R ₁₃ alkylene in formula (5) and substituted alkylene include, for example, —CH ₂ — and —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 C _{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 ) —, etc., among which —CH ₂ —, —CH (CH ₃ ) —, and —C (CH ₃ ) ₂ — are cured at a lower temperature. In addition, while maintaining a higher cyclization rate, an alkali-soluble resin having sufficient solubility in not only an aqueous alkali solution but also a solvent and having a better balance can be obtained, which is preferable.

_{R 8} and _{R 9} of formula (3), _{R 14} and _{R 15} is an alkyl group of the formula _{R 11} and _{R 12} and wherein the (4) (5) or the use of bis (aminophenol) is an alkoxy group, Thus, it is possible to obtain an alkali-soluble resin having sufficient solubility in an aqueous alkali solution and having a better balance while maintaining a higher cyclization rate even when cured at a low temperature. Specific examples of the alkyl group include, for example, —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ , —CH (CH ₃ ) ₂ , —CH ₂ CH ₂ CH ₂ CH ₃ , —CH _2. CH (CH ₃ ) ₂ , —CH (CH ₃ ) (CH ₂ CH ₃ ), —C (CH ₃ ) ₃ , —CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , —CH ₂ CH ₂ CH (CH ₃ ) ₂ , —CH ₂ CH (CH ₃ ) (CH ₂ CH ₃ ), —CH (CH ₂ CH ₃ ) (CH ₂ CH ₃ ), —CH (CH ₃ ) (CH ₂ CH ₂ CH ₃ ), —CH ( CH ₃ ) (CH (CH ₃ ) ₂ ), —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , —CH (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₃ ), —CH (CH ₃ ) ( _{CH 2 CH (CH 3) 2} ), - CH 2 CH 2 CH _{CH 2 CH 2 CH 2 CH 3} , etc. _{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 CH 3 and the like. Specific examples of the alkoxy group include, for example, —OCH ₃ , —OCH ₂ CH ₃ , —OCH ₂ CH ₂ CH ₃ , —OCH (CH ₃ ) ₂ , —OCH ₂ CH ₂ CH ₂ CH ₃ , —OCH ₂ CH (CH ₃ ) ₂ , —OCH (CH ₃ ) (CH ₂ CH ₃ ), —OC (CH ₃ ) _{3 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 may contain additives such as a leveling agent and a silane coupling agent as necessary.

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 application amount is such that the final film thickness after curing is 0.1 to 30 μm. If the film thickness is lower than the lower limit, it may be difficult to fully function as a protective film or insulating film for the semiconductor element, and if the upper limit is exceeded, it is difficult to obtain a fine relief pattern. In addition, processing may take time and throughput may decrease. 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 pre-baking 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. Examples of the developer 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, 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 high temperature or low temperature, and the heat treatment temperature at high temperature is preferably 280 ° C. to 380 ° C., more preferably 290 ° C. to 350 ° C. The heat treatment temperature at a low temperature is preferably 150 ° C. to 280 ° C., more preferably 180 ° C. to 260 ° C.

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.

Hereinafter, the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited thereto.

<Example 1>
(Synthesis of alkali-soluble resin)
Dicarboxylic acid derivative (active) obtained by reacting 0.36 mol of isophthalic acid, 0.54 mol of diphenyl ether-4,4′-dicarboxylic acid and 1.8 mol of 1-hydroxy-1,2,3-benzotriazole Ester) 410.04 g (0.9 mol), 4,4′-methylenebis (2-amino-3,6-dimethylphenol) 171.82 g (0.6 mol), 4,4′-methylenebis (2- Aminophenol) (92.10 g, 0.4 mol) was placed in a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube, and 3370 g of N-methyl-2-pyrrolidone was added. In addition, it was dissolved. Thereafter, the mixture was reacted at 75 ° C. for 16 hours using an oil bath. Next, 43.04 g (0.25 mol) of 4-ethynylphthalic anhydride dissolved in 215 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 3 hours to complete the reaction. After the reaction mixture was filtered, the reaction mixture was put into a solution of water / isopropanol = 7/4 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum to obtain the formula (6-2 The target alkali-soluble resin (A-1) comprising the compounds shown in Table 1 was obtained with c = 60, d = 40 and p = 2.

Energy barrier evaluation of dihedral rotation:
For the calculation, a personal computer MY18A / E-1 manufactured by NEC Corporation equipped with a memory of 504 MB was used.
4,4′-methylenebis (2-amino-3,6-dimethylphenol) was drawn on a Scigress Explorer Workspace manufactured by Fujitsu Limited. The dihedral angle AB—R ₄ —D shown in Formula (2) is rotated by 5 degrees in the range of −180 degrees to 180 degrees, and the heat of formation at each conformation is obtained by the molecular orbital method (PM5 method). , Created its energy map.
The highest generated heat and the lowest generated heat were read from the energy map, and the difference between them was 4.7 [kcal / mol]. Similarly, when calculation was performed for 4,4′-methylenebis (2-aminophenol), the difference in heat of formation was 1.0 [kcal / mol]. Alkali-soluble resin (A-1) is a mixture of 60% aminophenol and 40% 4,4'-methylenebis (2-amino-3,6-dimethylphenol) and 40% 4,4'-methylenebis (2-aminophenol). The difference in heat of formation is 4,4′-methylenebis (2-amino-3,6-dimethylphenol) 4.7 times [kcal / mol] multiplied by 0.6 and 4,4 The value obtained by adding 1.0 [kcal / mol] of '-methylenebis (2-aminophenol) to 0.4 times was 3.2 [kcal / mol]. The difference between the heat generated during the re-stable structure of the amine and the heat generated during the re-stable structure was defined as the energy barrier [kcal / mol] for dihedral angle rotation.

Transmittance evaluation:
A resin in which 4.0 g of alkali-soluble resin (A-1) is dissolved in 8.0 g of γ-butyrolactone is applied to a quartz plate using a spin coater, and then dried on a hot plate at 120 ° C. for 4 minutes to obtain a film thickness of 5 μm. Coating film was obtained. The transmittance of this coating film was measured with an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation). The transmittance at a wavelength of 365 nm was 31%.

Cyclization rate evaluation (alkali-soluble resin):
The alkali-soluble resin was applied onto three silicon wafers 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 5 μm. Next, one film-coated silicon wafer was immersed in 2% hydrofluoric acid to obtain a film. The film was measured using a Fourier transform infrared spectrophotometer PARAGON1000 (Perkin Elmer) was calculated ratio of the peak (a) with the wholly aromatic amide group and 1490cm ^-1 of 1650 cm ^-1. Next, after another silicon wafer with a coating film was heated at 250 ° C./90 minutes using an oven, a cured film was obtained in the same manner, and measured by a Fourier transform infrared spectrophotometer at 1650 cm ^−1. The peak ratio (b) associated with the amide group of 1490 cm ^{−1 and} the total aromatic was calculated. The remaining one coated silicon wafer was similarly heated at 320 ° C./30 minutes, and then a cured film was obtained in the same manner. From the measurement with a Fourier transform infrared spectrophotometer, the 1650 cm ⁻¹ amide group and The peak ratio (c) associated with the total aromatic at 1490 cm ⁻¹ was calculated.

The cyclization rate [A] at 250 ° C. was obtained by multiplying (1− (b) / (a)) by 100. The cyclization rate thus determined was 89%. The cyclization rate [B] at 320 ° C. was obtained by multiplying (1− (c) / (a)) by 100. The cyclization rate thus determined was 100%. Thus, [A] / [B] was 0.89, and an alkali-soluble resin with little variation in cyclization rate was obtained even in a wide temperature range.

(Synthesis of photosensitizer)
Phenol formula (B-1) 13.53 g (0.0214 mol) and triethylamine 7.62 g (0.0737 mol), 4 ports equipped with thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet pipe Were added and dissolved in 108.65 g of tetrahydrofuran. After cooling the reaction solution to 10 ° C. or lower, 19.80 g (0.0737 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride was gradually added dropwise with 100 g of tetrahydrofuran so as not to exceed 10 ° C. . Thereafter, the mixture was stirred at 10 ° C. or lower for 5 minutes and then stirred at room temperature for 5 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was put into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum to obtain the formula (Q-1 ) Was obtained.

(Preparation of photosensitive resin composition)
100 g of the synthesized alkali-soluble resin (A-1) and 13.5 g of the photosensitizer having the structure of the formula (Q-1) are dissolved in a mixed solvent of 140 g of N-methyl-2-pyrrolidone and 60 g of γ-butyrolactone, and then 0 The mixture was filtered through a 2 μm Teflon (registered trademark) filter to obtain a photosensitive resin composition.

Sensitivity evaluation:
This photosensitive resin composition was applied onto 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 8.0 μm. An i-line stepper (Nikon Co., Ltd., 4425i) is passed through this coating film through a mask made by Toppan Printing Co., Ltd. (test chart No. 1: remaining pattern and blank pattern with a width of 0.88-50 μm are drawn). Used to irradiate with varying exposure.
Next, using a 2.38% tetramethylammonium hydroxide aqueous solution, paddle development was performed by adjusting the development time so that the film thickness difference between the pre-baked and the unexposed areas after development was 1 μm. Then, it rinsed with the pure water for 10 seconds. As a result, it was confirmed that a pattern was formed from the portion irradiated with an exposure amount of 210 mJ / cm ² . (Sensitivity is 210 mJ / cm ² ). The resolution was as high as 5 μm.

Glass transition temperature (Tg) evaluation:
The photosensitive resin composition was applied onto a 6-inch silicon wafer using a spin coater and then prebaked at 120 ° C. for 4 minutes on a hot plate to obtain a coating film having a thickness of about 10 μm. Next, the silicon wafer with a coating film was heated at 250 ° C./90 minutes using an oven. Next, the obtained cured film was immersed in 2% hydrogen fluoride water, and the film was peeled off from the silicon wafer. The obtained film was sufficiently washed with pure water and dried in an oven. The dried film was cut to a width of 5 mm to produce a sample piece, and the glass transition temperature was measured using a thermomechanical analyzer (TMA) SS6000 manufactured by Seiko Instruments Inc. As a result, it was 270 ° C.

<Example 2>
In the synthesis of the alkali-soluble resin in Example 1, 4,4′-methylenebis (2-amino-3,6-dimethylphenol) was increased to 200.46 g (0.7 mol), and 4,4′-methylenebis (2 -Aminophenol) reduced to 69.08 g (0.3 mol) and reacted in the same manner, represented by formula (6-2), c = 70, d = 30, p = 2, as shown in Table 1. An alkali-soluble resin (A-2) comprising the above compound was synthesized. Others produced the photosensitive resin composition like Example 1, and performed evaluation similar to Example 1. FIG.
The energy barrier for rotation of the dihedral angle was 3.6 [kcal / mol].

<Example 3>
Dicarboxylic acid derivative (activity) obtained by reacting 0.45 mol of isophthalic acid, 0.45 mol of diphenyl ether-4,4′-dicarboxylic acid and 1.8 mol of 1-hydroxy-1,2,3-benzotriazole Esters) 401.76 g (0.9 mol) and 4,4′-methylenebis (2-amino-3,6-dimethylphenol) 286.37 g (1 mol) were thermometer, stirrer, raw material inlet, Into a four-necked separable flask equipped with a dry nitrogen gas inlet tube, 3441 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, 43.04 g (0.25 mol) of 4-ethynylphthalic anhydride dissolved in 215 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 3 hours to complete the reaction. After the reaction mixture was filtered, the reaction mixture was put into a solution of water / isopropanol = 7/4 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum to obtain the formula (6-2 The target alkali-soluble resin (A-3) comprising the compounds shown in Table 1 was obtained with c = 100, d = 0, and p = 2. Others produced the photosensitive resin composition like Example 1, and performed evaluation similar to Example 1. FIG.
The energy barrier for rotation of the dihedral angle was 4.7 [kcal / mol].

<Example 4>
In the synthesis of the alkali-soluble resin in Example 3, 4,4′-ethylidenebis (2-amino-3,6-dimethyl) was used instead of 4,4′-methylenebis (2-amino-3,6-dimethylphenol). Phenol) 300.40 g (1 mol) was reacted in the same manner, and an alkali represented by the formula (6-2), c = 100, d = 0, p = 2 and comprising the compound shown in Table 1 A soluble resin (A-4) was synthesized. Others produced the photosensitive resin composition like Example 1, and performed evaluation similar to Example 1. FIG.
The energy barrier for rotation of the dihedral angle was 6.1 [kcal / mol].

<Comparative Example 1>
Dicarboxylic acid derivative (activity) obtained by reacting 0.27 mol of isophthalic acid, 0.63 mol of diphenyl ether-4,4′-dicarboxylic acid and 1.8 mol of 1-hydroxy-1,2,3-benzotriazole Esters) 418.33 g (0.9 mol) and 230.26 g (1 mol) of 4,4′-methylenebis (2-aminophenol) were provided with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube. The flask was placed in a four-necked separable flask, and 3243 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, 43.04 g (0.25 mol) of 4-ethynylphthalic anhydride dissolved in 215 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 3 hours to complete the reaction. After the reaction mixture was filtered, the reaction mixture was put into a solution of water / isopropanol = 7/4 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum to obtain the formula (6-2 ), And c = 0, d = 100, p = 2, and the target alkali-soluble resin (A-5) comprising the compound shown in Table 1 was obtained. Others produced the photosensitive resin composition like Example 1, and performed evaluation similar to Example 1. FIG.
The energy barrier for dihedral angle rotation was 1.0 [kcal / mol].

<Comparative Example 2>
Synthesis of alkali-soluble resin 198.26 g (1 mol) of 4,4′-diaminodiphenylmethane was placed in a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube. -2-pyrrolidone (3370 g) was added and dissolved. While bathing in water, 279.19 g (0.9 mol) of 4,4′-oxybisphthalic acid 1,2: 1 ′, 2′-dianhydride dissolved in 215 g of N-methyl-2-pyrrolidone was added, It returned to room temperature and stirred for 1 hour. Thereafter, the mixture was reacted at 75 ° C. for 16 hours using an oil bath. Next, 43.04 g (0.25 mol) of 4-ethynylphthalic anhydride dissolved in 215 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 3 hours to complete the reaction. After the reaction mixture was filtered, the reaction mixture was put into a solution of water / isopropanol = 7/4 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum to obtain the formula (6-1 The desired alkali-soluble resin (A-6) comprising the compounds shown in Table 1 was obtained with a = 0, b = 100, m = 0, and n = 2.

In the calculation of the energy barrier in Example 1, 4,4′-diaminodiphenylmethane was drawn instead of 4,4′-methylenebis (2-amino-3,6-dimethylphenol), and the dihedral angle shown in Formula (20) JKLM was changed by 5 ° in the range of −180 degrees to 180 degrees. Others were calculated in the same manner as in Example 1, a photosensitive resin composition was prepared, and the same evaluation as in Example 1 was performed.
The energy barrier for rotation of the dihedral angle was 1.1 [kcal / mol].

Table 1 shows the results obtained for the above Examples and Comparative Examples.

As shown in Table 1, Examples 1 to 4 had high sensitivity and high Tg even when cured at a low temperature of 250 ° C., and were excellent in heat resistance and reliability. It was also found that there was little variation in the cyclization rate even when cured in a wide temperature range, and that the cyclization rate was high even when cured at a low temperature.

<Reference example>
It was 29.2 [kcal / mol] when the energy barrier of rotation of the aminophenol which introduce | transduced five tertiary butyl groups shown in Formula (21) was calculated by computational chemistry. Although the synthesis yield is very low and has not been evaluated yet, it is presumed that the same performance as in the examples can be obtained.

According to the present invention, when used as a positive photosensitive resin composition, it is possible to provide an alkali-soluble resin that is highly sensitive and excellent in heat resistance and reliability even when cured at a low temperature.
According to the present invention, a positive photosensitive resin composition, a cured film, a protective film, an insulating film, and a semiconductor device and a display device using the same, which are highly sensitive and have excellent heat resistance and reliability even when cured at a low temperature. Can be provided.

This application claims priority based on Japanese Patent Application No. 2009-152171 filed on June 26, 2009, the entire disclosure of which is incorporated herein.

Claims (14)

1. An alkali-soluble resin containing a polybenzoxazole precursor structure composed of bis (aminophenol) and a structure derived from a dicarboxylic acid, the two fragrances of the bis (aminophenol) obtained by calculation by computational chemistry An alkali-soluble resin, wherein an energy barrier of rotation of dihedral angles between rings is 3 [kcal / mol] or more.
2. 2. The alkali-soluble compound according to claim 1, wherein the bis (aminophenol) has a phenolic hydroxyl group at a site adjacent to both amino groups and a substituent at a site adjacent to the opposite side of the amino group. resin.
3. The alkali-soluble resin according to claim 2, wherein the bis (aminophenol) is represented by the following formula (1).
   

   

   (In the formula, R ₁ is an organic group. R ₂ is an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group, which may be the same or different. R ₃ is a hydrogen atom, an alkyl group, Any one of an alkoxy group, an acyloxy group, and a cycloalkyl group, which may be the same or different.)
4. An alkali-soluble resin comprising a polybenzoxazole precursor structure composed of bis (aminophenol) and a structure derived from dicarboxylic acid,
   The dihedral angle AB—R ₄ —D of the bis (aminophenol) represented by the following formula (2) is rotated by 5 degrees in the range of −180 degrees to 180 degrees, and the heat of formation in each conformation An alkali-soluble resin, wherein the difference between the highest heat of formation and the lowest heat of formation when determined by a molecular orbital method is 3 [kcal / mol] or more.
   

   

   (In the formula, R ₄ is an organic group. R ₅ is an alkyl group, an alkoxy group, an acyloxy group, or a cycloalkyl group, which may be the same or different. R ₆ is a hydrogen atom, an alkyl group, Any one of an alkoxy group, an acyloxy group, and a cycloalkyl group, which may be the same or different.)
5. A positive photosensitive resin composition comprising the alkali-soluble resin according to any one of claims 1 to 4 and a photosensitive agent.
6. 6. The positive photosensitive resin composition according to claim 5, wherein a light transmittance at a wavelength of 365 nm of a film having a thickness of 5 μm obtained after the alkali-soluble resin is applied to a substrate and dried is 30% or more.
7. The positive photosensitive resin composition according to claim 5 or 6, wherein the glass transition temperature is 260 ° C or higher.
8. 6. The cyclization rate [A]% at 250 ° C. of the alkali-soluble resin and the cyclization rate [B]% at 320 ° C. of [A] / [B] is 0.8 or more. The positive photosensitive resin composition in any one of thru | or 7.
9. The positive photosensitive resin composition according to claim 5, wherein the alkali-soluble resin has a cyclization rate at 250 ° C. of 80% or more.
10. A cured film comprising a cured product of the positive photosensitive resin composition according to any one of claims 5 to 9.
11. A protective film comprising the cured film according to claim 10.
12. An insulating film comprising the cured film according to claim 10.
13. A semiconductor device comprising the cured film according to claim 10.
14. A display device comprising the cured film according to claim 10.