JP6255740B2 - Positive photosensitive resin composition, cured film, protective film, insulating film, semiconductor device, display device, and method for producing positive photosensitive resin composition - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition, a cured film, a protective film, an insulating film, a semiconductor device, a display device, and a method for producing a positive photosensitive resin composition.

  Conventionally, polybenzoxazole resins and polyimide resins having excellent heat resistance and excellent electrical characteristics, mechanical characteristics, and the like have been used for surface protective films and interlayer insulating films of semiconductor elements. On the other hand, in order to simplify the process when a polybenzoxazole resin or a polyimide resin is used, a positive photosensitive resin composition in which a diazoquinone compound as a photosensitive agent is combined with these resins is also used. (For example, refer to Patent Document 1).

  This positive-type photosensitive resin composition is hardly soluble in an alkaline aqueous solution in an unexposed portion due to the effect of inhibiting dissolution of a diazoquinone compound in a polybenzoxazole resin, a polyimide resin, or a polyamide resin having a precursor structure thereof. . On the other hand, in the exposed area, the diazoquinone compound undergoes a chemical change, and the positive photosensitive resin composition becomes soluble in an alkaline aqueous solution. By utilizing the difference in solubility between the exposed portion and the unexposed portion and dissolving and removing the exposed portion with an alkaline aqueous solution, it becomes possible to create a coating film pattern of only the unexposed portion. Polybenzoxazole and polyimide precursors in the positive photosensitive resin composition with the coating pattern formed are finally dehydrated and closed by curing at a high temperature close to 300 ° C. It becomes a polyimide resin.

  On the other hand, when these positive photosensitive resin compositions are actually used, the sensitivity of the positive photosensitive resin composition is also important. If the sensitivity is low, the exposure time becomes long, the throughput is lowered, and the productivity is significantly adversely affected. When using the above-mentioned polybenzoxazole resin or polyimide resin, or a resin such as a polyamide resin having these precursor structures, it is difficult to adjust the dissolution rate in the developing solution, so that the intended sensitivity cannot be achieved, There have been problems such as development residue (scum) occurring in the exposed portion after development. Further, when the above resin is used, the dissolution inhibiting effect by the photosensitizer is not sufficiently exhibited, and the unexposed portion is also dissolved, so that there is a problem that the shape of the dense pattern portion is deteriorated. For this reason, recently, various proposals have been made for high-sensitivity photosensitive resin compositions that can be developed with an aqueous alkaline solution, as in the case of photoresists. (For example, see Patent Documents 2 to 6.)

Furthermore, in recent years, from the viewpoint of reducing the size, weight, functionality, and cost of electronic devices, the surface mount type has introduced an electroless plating process that forms Ni and Au layers on the pads of semiconductor wafers by electroless plating. Semiconductor wafers are increasing. In this electroless plating step, there is a zincate treatment in which a pH is 13 or more, and a positive photosensitive resin composition excellent in resistance to a strong alkaline aqueous solution is required.
However, it has been difficult for conventional positive-type photosensitive resin compositions to simultaneously satisfy the i-line high sensitivity and high resolution, and excellent resistance to strong alkaline aqueous solution. In particular, in the case of a structure in which the peripheral portion of the aluminum pad is covered with a cured film, peeling occurs between the aluminum pad and the cured film, resulting in a problem that reliability is lowered.

JP-A-56-27140 JP-A-2005-352004 JP 2005-062764 A JP-A-2005-250160 JP 2006-285037 A JP 2008-225457 A

  The present invention has been made in view of the above circumstances. The object of the present invention is to provide positive photosensitivity capable of achieving both high sensitivity and high resolution with respect to i-line, and excellent performance against strong alkaline aqueous solutions. The object is to provide a resin composition.

Such an object is achieved by the following [1] to [17].
[1] A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photoacid generator (B), and a solvent (C),
When the positive photosensitive resin composition is pre-baked at 120 ° C. for 3 minutes, and cured by heating at 150 ° C. for 60 minutes, and then at 350 ° C. for 70 minutes,
The glass transition temperature after curing is 200 ° C. or higher, the internal stress is 40 MPa or lower,
The alkali-soluble resin (A) includes a resin (A2) containing at least one structure from the group of a polybenzoxazole structure, a polybenzoxazole precursor structure, a polyimide structure, a polyimide precursor structure, and a polyamide structure. A positive photosensitive resin composition characterized by the above.
[2] A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photoacid generator (B), and a solvent (C),
When the positive photosensitive resin composition is pre-baked at 120 ° C. for 3 minutes, and cured by heating at 150 ° C. for 60 minutes, and then at 350 ° C. for 70 minutes,
The glass transition temperature after curing is 200 ° C. or higher, the internal stress is 40 MPa or lower,
The positive photosensitive resin composition further includes a phenol resin (D),
The phenol resin (D1) obtained by reacting the phenol compound (D) represented by the following general formula (1) and the aromatic aldehyde compound represented by the following general formula (2) under an acid catalyst. Including
The positive photosensitive resin composition is used for forming the positive photosensitive resin composition as a cured film constituting an apparatus.

(Wherein R1 represents an organic group selected from an alkyl group having 1 to 20 carbon atoms and an alkoxy group, and p is an integer of 1 to 3)

(Wherein R2 represents an organic group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group and a hydroxy group, and q is an integer of 0 to 3)
[3] The positive photosensitive resin according to [2], wherein the phenol resin (D1) includes one or more selected from aromatic aldehydes represented by the following formula (3) as an aromatic aldehyde compound. Composition.

[4] The positive photosensitive resin according to [2] or [3], wherein the phenol resin (D1) includes one or more selected from phenols represented by the following formula (4) as a phenol compound: Composition.

[5] The positive photosensitive resin composition according to [1] to [4], wherein the curable resin includes a hydroxystyrene resin (A1).
[6] The positive photosensitive resin composition according to [5], wherein the hydroxystyrene resin (A1) is a copolymer containing hydroxystyrene and / or a derivative of hydroxystyrene.
[7] The positive photosensitive resin composition according to [5] or [6], wherein the hydroxystyrene resin (A1) is a copolymer containing styrene and / or a derivative of styrene.
[8] The hydroxystyrene resin (A1) is a copolymer containing hydroxystyrene and a derivative thereof, and the constituent ratio of the hydroxystyrene and the derivative in the hydroxystyrene resin (A1) is 50% or more, 90 % Of the positive photosensitive resin composition according to any one of [5] to [7].
[9] The internal stress after curing when the alkali-soluble resin (A) is pre-baked at 120 ° C. for 3 minutes and then heat-cured at 150 ° C. for 60 minutes and then at 350 ° C. for 70 minutes is 30 MPa or less. The positive photosensitive resin composition as described in [1]-[8] containing curable resin.
[10] The positive photosensitive resin composition according to any one of [1] to [9], further containing a silane coupling agent (E).
[11] The positive photosensitive resin composition according to any one of [1] to [10], further containing a thermal crosslinking agent (F).
[12] A cured film composed of a cured product of the positive photosensitive resin composition according to any one of [1] to [11].
[13] A protective film composed of the cured film according to [12].
[14] An insulating film composed of the cured film according to [12].
[15] A semiconductor device having the cured film according to [12].
[16] A display device having the cured film according to [12].

  According to the present invention, the i-line has a high sensitivity and high resolution, and at the same time satisfies the performance of excellent resistance to strong alkaline aqueous solution. In the case of a structure covered with a cured film, a positive photosensitive resin composition (hereinafter simply referred to as “photosensitive resin composition”, “resin”, in which peeling does not occur between the aluminum pad and the cured film and reliability is improved. Also referred to as a “composition”.

The positive photosensitive resin composition of the present invention is a positive photosensitive resin composition comprising an alkali-soluble resin (A), a photoacid generator (B), and a solvent (C), The positive-type photosensitive resin composition has a glass transition temperature after curing of 200 ° C. or more and an internal stress of 40 MPa or less.

  The positive photosensitive resin composition of the present invention includes an alkali-soluble resin (A), a photoacid generator (B), and a solvent (C), and thus has high sensitivity and high resolution for i-line. In addition, the glass transition temperature after curing is 200 ° C. or more and the internal stress is 40 MPa or less, thereby reducing the force to peel off from the adherend, and particularly the resistance to the strong alkaline aqueous solution in the pattern opening. It is shown. Further, by combining these, higher reliability can be realized.

  Moreover, the cured film which is one Embodiment of this invention is comprised with the hardened | cured material of the said positive photosensitive resin composition. By having such a configuration, the cured film has excellent resistance to a strong alkaline aqueous solution and can achieve higher reliability.

  Moreover, the protective film which is one Embodiment of this invention is comprised by the said cured film. By having such a configuration, the protective film can achieve high reliability.

  Moreover, the insulating film which is one Embodiment of this invention is comprised by the said cured film. By having such a configuration, the protective film can achieve high insulation and reliability.

  Moreover, the semiconductor device which is one Embodiment of this invention has the said cured film. The semiconductor device can achieve high reliability by having such a configuration.

  Moreover, the display body apparatus which is one Embodiment of this invention has the said cured film. The display device can achieve high reliability by having such a configuration.

  Moreover, the manufacturing method of the positive photosensitive resin composition which is one Embodiment of this invention is a melt | dissolution process which dissolves alkali-soluble resin (A) and a photo-acid generator (B) in a solvent (C). The alkali-soluble resin (A) includes a curable resin having an internal stress after curing of 30 MPa or less.

  The manufacturing method of the positive photosensitive resin composition has a configuration as described above, so that it can provide a cured film that is highly sensitive to i-line and has high resolution and that exhibits resistance to a strong alkaline aqueous solution. The photosensitive resin composition can be provided more simply.

  Hereinafter, the positive photosensitive resin composition, the cured film, the protective film, the insulating film, the semiconductor device, the display device, and the method for producing the positive photosensitive resin composition of the present invention will be described.

<Positive photosensitive resin composition>
First, the positive photosensitive resin composition of the present invention will be described. The positive photosensitive resin composition of the present invention is a positive photosensitive resin composition comprising an alkali-soluble resin (A), a photoacid generator (B), and a solvent (C), The positive-type photosensitive resin composition has a glass transition temperature after curing of 200 ° C. or more and an internal stress of 40 MPa or less.

[Alkali-soluble resin (A)]
The alkali-soluble resin (A) is not particularly limited, but a resin generally used as an alkali-soluble resin can be used. For example, a hydroxystyrene resin (A1), a polybenzoxazole structure, a polybenzoxazole precursor structure, a polyimide structure, a resin (A2) that includes at least one structure from the group of a polyimide precursor structure and a polyamide structure (hereinafter, Also referred to as “resin (A2)”, acrylic resin, polyvinyl ether resin, and the like. The alkali-soluble resin (A) can be used in combination of a plurality of resins generally used as alkali-soluble resins. The positive photosensitive resin composition contains an alkali-soluble resin (A), so that a cured film can be formed by coating on a support, and the action with the photoacid generator (B). Thus, positive patterning is possible. The content of the alkali-soluble resin is not particularly limited, but is preferably 30% by weight or more, and more preferably 40% by weight or more based on the total solid content not including the solvent (C) in the positive photosensitive resin composition. . Moreover, 99 weight% or less is preferable and 95 weight% or less is more preferable. By being within the preferable range, reliability can be improved.

Moreover, from the viewpoint of further improving the resistance to strong alkaline aqueous solution of the positive photosensitive resin composition, the alkali-soluble resin (A) can include a curable resin having an internal stress after curing of 30 MPa or less. . Such a curable resin preferably contains 30% by weight or more, more preferably 40% by weight or more of the entire alkali-soluble resin (A). By including a curable resin having an internal stress of 30 MPa or less after curing within the preferred range, the design of the internal stress after curing of the positive photosensitive resin composition is facilitated. Furthermore, the alkali-soluble resin (A) preferably contains a hydroxystyrene resin (A1) as a curable resin having an internal stress after curing of 30 MPa or less. A general hydroxystyrene resin (A1) having an internal stress after curing of 15 MPa or more and 30 MPa or less and an internal stress after curing of 30 MPa or less can be prepared at low cost. Here, the internal stress of the curable resin is measured by, for example, applying the curable resin onto a circular substrate such as a silicon wafer, and then volatilizing the solvent with a hot plate or the like to form a coating film. The film is heated and cured to produce a circular substrate having a cured film, the warpage of the circular substrate having the cured film is measured, and measurement can be performed using the following Stoney equation. Here, when the resin is difficult to apply, the resin is mixed with a film-forming resin and applied, and after measuring the internal stress as the mixture, the internal stress due to the film-forming resin is removed. Can be measured.
(Σ: internal stress of thin film, L: radius of circular substrate, E _S : Young's modulus of circular substrate, V _S : Poisson's ratio of circular substrate, t _S : thickness of circular substrate, t _f : thickness of thin film, R: Curvature radius of circular substrate with cured film)

[Hydroxystyrene resin (A1)]
The hydroxystyrene resin (A1) is a polymer containing hydroxystyrene and / or a derivative thereof, and is not particularly limited, but may be a copolymer containing hydroxystyrene and / or a derivative thereof and a monomer other than these. Examples of the monomer used here include ethylene, propylene, 1-butene, 2-methylpropene, styrene and derivatives thereof. Among these, from the viewpoint of easily adjusting the solubility in an alkaline solution, a copolymer composed of hydroxystyrene and / or a derivative thereof and styrene and / or a derivative thereof is preferable. The above derivatives are those in which an alkyl group, an alkoxyl group, a hydroxyl group or the like is substituted at the ortho, meta, and para positions of the aromatic ring of hydroxystyrene and styrene. The hydroxystyrene of the hydroxystyrene resin (A1) may be any of orthohydroxystyrene, metahydroxystyrene, and parahydroxystyrene. A plurality of the above hydroxystyrenes may be mixed.

The constituent ratio of the hydroxystyrene and its derivative in the hydroxystyrene resin (A1) is preferably 50% or more, more preferably 60% or more, preferably 90% or less, more preferably 80% or less. By setting it as the above range, it becomes easy to design the internal stress after curing within the preferable range, and improves the resistance to strong alkaline aqueous solution of the cured product of the positive photosensitive resin composition. The effect is excellent in reducing both residue and increasing sensitivity.
The weight average molecular weight (Mw) of the hydroxystyrene resin (A1) is preferably 1,000 or more, more preferably 2,000 or more, particularly preferably 2,500 or more, and preferably 10,000 or less, Preferably it is 8,000 or less, Most preferably, it is 7,000 or less. By setting it as the said range, it is excellent in high-sensitivity, and also has the effect excellent also about the normal temperature storage stability of the varnish.

  Although content of the said hydroxy styrene resin (A1) is not specifically limited, 20 weight% or more is preferable in the said alkali-soluble resin (A) whole, and 30% or more is more preferable. Moreover, 90% or less is preferable and 80% or less is more preferable. By being included in the preferable range, it becomes easy to design the internal stress after curing of the positive photosensitive resin composition within a preferable range, and higher reliability can be realized in the cured film.

[Resin (A2)]
The resin (A2) includes a polybenzoxazole structure, a polybenzoxazole precursor structure, a polyimide structure, a polyimide precursor structure, and a polyamide structure. By including these, the glass transition temperature after curing in the positive photosensitive resin composition can be further increased, thereby improving the heat resistance as a cured film and obtaining the effect of further improving the reliability. be able to. Furthermore, by combining with the hydroxystyrene resin (A1), it is highly sensitive and has high resolution, and as a cured film, an effect of having a strong alkaline aqueous solution resistance, heat resistance, and mechanical properties in a balanced manner can be obtained. In addition, the resin (A2) has a polybenzoxazole precursor structure, a polyimide precursor structure, a polybenzoxazole structure produced by a ring-closing reaction of a part of the polybenzoxazole precursor structure, and a part of the polyimide precursor structure. It may have a polyimide structure generated by a ring-closing reaction or may have an amic acid ester structure. Such resin (A2) is preferably contained in an amount of 50% by weight or more, and more preferably 60% by weight or more in the entire alkali-soluble resin (A). Moreover, 80 weight% or less is preferable and 70 weight% or less is more preferable. By including the resin (A2) within the preferred range, the glass transition temperature after curing of the positive photosensitive resin composition can be designed more easily.

  A specific polybenzoxazole precursor structure refers to a structure represented by the following formula (5), a polyimide precursor structure refers to a structure represented by the following formula (6), and a polybenzoxazole structure: , Refers to the structure represented by the following formula (7), the polyimide structure refers to the structure represented by the following formula (8), and the amic acid ester structure refers to the structure represented by the following formula (9). Point to.

  In addition, D and R in said formula (5)-(9) show an organic group. Among these polyamide resins, from the viewpoint of heat resistance of the cured product of the positive photosensitive resin composition of the present invention, a polyamide resin having a repeating unit represented by the following general formula (10) is preferable.

(In the formula, 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. good .R ³ also represents a hydroxyl group, a carboxyl group, an ^{-O-R 4} or ^{-COO-R 4,} when a plurality having, ^{R 4} in good .R ² and ^{R 3} be the same or different each In the formula (10), when R ² has no hydroxyl group, at least one of R ³ is a carboxyl group, and R ³ is a carboxyl group. In the absence of a group, at least one of R ² is a hydroxyl group, m is an integer from 0 to 8, and n is an integer from 0 to 8.)

In the polyamide resin having the structure represented by the general formula (10), as R ₂ and R ₃ , a hydroxyl group and a carboxyl group are protected with a protecting group R ⁴ in order to adjust the solubility of the polyamide resin in an alkaline aqueous solution. a radicals can be used ^{-O-R 4} and ^{-COO-R 4} as ^-O-R 4, R ³ as ^{R 2.} Examples of the organic group having 1 to 15 carbon atoms as R ⁴ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, Examples include a tetrahydrofuranyl group and a tetrahydropyranyl group.

  The organic group as X of the polyamide resin having the structure represented by the general formula (10) is not particularly limited. For example, the aromatic group has a structure such as a benzene ring, a naphthalene ring, and a bisphenol structure. , Heterocyclic organic groups having a structure such as a pyrrole ring and a furan ring, and siloxane groups. More specifically, what is represented by following formula (11) is preferable. These may be used alone or in combination of two or more.

(In formula (11), * represents bonding to the NH group in general formula (11). A represents an alkylene group, a substituted alkylene group, —O—C ₆ H ₄ —O—, —O—, —S—, —SO ₂ —, —C (═O) —, —NHC (═O) — or a single bond, R ⁵ represents one selected from an alkyl group, an alkyl ester group and a halogen atom; R ⁶ is one selected from a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom, and s is an integer of 0 to 4. ^{7 to} R ¹⁰ are each an organic group.
In the above formula (11), the substituent R ₂ of X in the above general formula (10) is omitted. )

Particularly preferred among the groups represented by the above formula (11) are those represented by the following formula (12) (some of them have R ₂ in the general formula (10)).

(In formula (12), * represents bonding to the NH group in formula (10). In the formula, A represents an alkylene group, a substituted alkylene group, —O—, —S—, —SO ₂ —, — _{C (= O) -, -} NHC (= O) -, - CH 3 -, - C (CH 3) H -, - C (CH 3) 2 -, - C (CF 3) 2 -, or a single bond R ₁₁ is one selected from an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group, and when there are a plurality of R _{11 s} , they may be the same or different, and c is 0 or more and 3 or less. (It is an integer.)

Among the groups represented by the above formula (12), those particularly preferred from the viewpoint of workability during development are those represented by the following formula (13) (having R ₂ in the general formula (10)) There is also).

(In formula (13), * represents bonding to the NH group in general formula (10). R ₁₂ represents an alkylene group, a substituted alkylene group, —O—, —S—, —SO ₂ —, —C ( ═O) —, —NHC (═O) —, —C (CF ₃ ) ₂ —, an organic group selected from a single bond.

Specific examples of the alkylene group and substituted alkylene group as A in Formula (12) and Formula (13) and R ₁₂ in Formula (13) 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 C _{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) - and -C (CH _{3) (CH 2 CH 2 CH} 2 CH 2 CH 2 CH 3) - , and the like. Among these, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ — has sufficient solubility in not only an alkaline aqueous solution but also a solvent, and a polyamide having a better balance. A resin can be obtained, which is preferable.

  Y in the polyamide resin having the structure represented by the general formula (10) is an organic group, and examples of such an organic group include the same as those described above for X. Examples include aromatic groups composed of structures such as benzene rings, naphthalene rings and bisphenol structures, heterocyclic organic groups composed of structures such as pyrrole rings, pyridine rings and furan rings, and siloxane groups. What is shown by following formula (14) can be mentioned preferably. These may be used alone or in combination of two or more.

(In formula (14), * indicates bonding to the C═O group in general formula (10). 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 an alkyl group, an alkyl ester group, an alkyl ether. R ₁₄ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom, each of which may be the same or different. t is an integer from 0 to 2. R _{15 to} R ₁₈ are organic groups.
In the above formula (14), the substituent R ₃ for Y in the above general formula (10) is omitted. )

Of these groups represented by the formula (14), those particularly preferred from the viewpoint of workability during development include those represented by the following formula (15) (some having R ₃ in the general formula (10)). Yes).
Regarding the structure derived from tetracarboxylic dianhydride in the following formula (15), mention is made of those in which both positions bonded to the C═O group in the general formula (10) are in the meta position and both are in the para position. However, it may have a structure including a meta position and a para position.

(In the formula (15), * indicates bonding to the C═O group in the general formula (10). R ₁₉ represents an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and a halogen atom. Each of which may be the same or different, and R ₂₀ represents one selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms, and may be partially substituted. U is an integer from 0 to 2.

In the case of the polyamide resin represented by the general formula (10), the terminal amino group of the polyamide resin is alkenyl group or It is also possible to use an acid anhydride or monocarboxylic acid containing an aliphatic group having at least one alkynyl group or a cyclic compound group, or end-capping as an amide. By end-capping, the preservability of the positive-type photosensitive resin composition can be improved, and by having an alkenyl group or alkynyl group at the end, the positive-type photosensitive resin composition after curing is cured. The glass transition temperature can be further increased, whereby the heat resistance of the cured film is improved, and the effect of further improving the reliability is obtained.
Examples of the acid anhydride or monocarboxylic acid containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group include maleic anhydride, citraconic anhydride, and 2,3-dimethylmaleic anhydride. 4-cyclohexene-1,2-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, Methyl-5-norbornene-2,3-dicarboxylic acid anhydride, itaconic acid anhydride, het acid anhydride, 5-norbornene-2-carboxylic acid, 4-ethynylphthalic acid anhydride and 4-phenylethynylphthalic acid anhydride Etc. These may be used alone or in combination of two or more, and a part of the end-capped amide moiety may be dehydrated and closed.

  Further, the present invention is not limited to this method, and an amine derivative containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group as a terminal carboxylic acid residue contained in the polyamide-based resin. Can also be used to end-cleave as amides.

Furthermore, in the case of the polyamide resin represented by the general formula (10), at least one of the terminals is end-capped with a nitrogen-containing cyclic compound to the extent that it does not affect the mechanical properties and heat resistance of the cured product cured at low temperature. It may have a stopped group. 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.

The polyamide resin having the structure represented by the general formula (10) is, for example, a compound selected from diamine, bis (aminophenol), 2,4-diaminophenol and the like containing X in the general formula (10) Can be synthesized by reacting Y and a compound selected from tetracarboxylic dianhydride, trimellitic anhydride, dicarboxylic acid, dicarboxylic acid dichloride, dicarboxylic acid derivative, and the like.
In the case of using dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like with dicarboxylic acid in advance in order to increase the reaction yield of the polyamide resin. May be used.

  The polyamide resin having the structure represented by the general formula (10) is heated and dehydrated and closed to obtain a heat resistant resin in the form of polyimide resin, polybenzoxazole resin, or copolymerization of both. In addition, although it does not specifically limit as temperature which performs dehydration ring closure, It can process at 280 degreeC-380 degreeC.

[Photoacid generator (B)]
The photoacid generator (B) is a compound that generates an acid by light, and the positive photosensitive resin composition of the present invention contains the photoacid generator (B) and is irradiated with light to emit the light. The acid generator (B) generates an acid, and the acid is dissolved in an alkaline aqueous solution, whereby positive patterning is possible. Further, the photoacid generator includes a photosensitizer capable of positive patterning. By using such a photosensitizer, the photoacid generator and the alkali-soluble resin (A) are irradiated with light. The function of inhibiting dissolution in an aqueous alkaline solution that has been acting on the surface disappears, and the solubility in these aqueous alkaline solutions is manifested, whereby the sensitivity of the positive photosensitive resin composition of the present invention can be further improved. . Such a photoacid generator (B) is preferably 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.
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 compounds, dihydropyridine compounds, and the like can be used. Among these, a photosensitive diazoquinone compound excellent in sensitivity and dissolution inhibiting function is preferable.

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.
In the case of the positive type, the photosensitizer remaining in the relief pattern in the unexposed area is considered to be decomposed by heat at the time of curing to generate an acid. As a reaction accelerator, a photoacid generator (B), and a photoacid Photosensitizers that can be used as generators play an important role. However, when used in contact with the aluminum pad portion of the semiconductor wafer, the acid generated during curing may hinder the interaction between the aluminum pad and the positive photosensitive resin composition of the present invention, and thus the photosensitivity. In the case of a diazoquinone compound, by using an ester of 1,2-naphthoquinone-2-diazido-5-sulfonic acid, which is more difficult to decompose by heat, the positive photosensitive resin composition and its cured film, an aluminum pad part, Can be improved.

  The content of the photoacid generator (B) in the photosensitive resin composition of the present invention is not particularly limited, but is 1 part by mass or more and 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). The amount is preferably equal to or less than mass parts, and more preferably 5 mass parts to 30 mass parts. When the addition amount is within the above range, good patterning performance can be exhibited.

[Solvent (C)]
The photosensitive resin composition of the present invention can be used in the form of a varnish by dissolving the above components and the components described below in a solvent (C). Examples of such a solvent (C) 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 and methyl -3-Methoxypropionate and the like may be mentioned, and these may be used alone or in combination.

  Although content of the solvent in the said photosensitive resin composition is not specifically limited, 50 mass parts or more and 300 mass parts or less with respect to 100 mass parts of total weight of solid content including alkali-soluble resin etc. It is preferable that it is 100 mass parts or more and 200 mass parts or less. When the addition amount is within the above range, the solid content can be sufficiently dissolved and a varnish with high handling properties can be produced.

[Phenolic resin (D)]
The photosensitive resin composition may further contain a phenol resin (D). By including the phenol resin (D), the i-line has high sensitivity and high resolution. For example, when used in contact with the aluminum pad portion of a semiconductor wafer, the aluminum pad portion and the positive photosensitive resin composition The hardened film composed of the positive photosensitive resin composition is prevented from being damaged particularly by the strong alkaline aqueous solution. Resistance to strong alkaline aqueous solution can be further improved. Further, by using the hydroxystyrene resin (A1) and the phenol resin (D) in combination, for example, when used in contact with the aluminum pad portion of the semiconductor wafer, low stress and strongly interact with the aluminum pad portion. The cured film composed of the positive photosensitive resin composition of the present invention sufficiently prevents the aluminum pad portion from being damaged by the strong alkaline aqueous solution, and exhibits extremely excellent strong alkaline aqueous solution resistance. Furthermore, a cured film using such a positive photosensitive resin composition, a protective film and an insulating film made of the cured product, and a semiconductor device and a display device having the cured film are excellent in reliability. It becomes.

  The phenol resin (D) is not particularly limited, but a phenol aralkyl obtained by synthesizing a novolac type phenol resin obtained by condensing a phenol compound and an aldehyde compound, a resol type phenol resin, and a phenol compound and a dimethanol compound. Resin or the like can be used.

  Although content of the said phenol resin (D) in the said positive photosensitive resin composition is not specifically limited, 5 mass parts or more are preferable with respect to 100 mass parts of said alkali-soluble resins (A), 15 mass parts The above is more preferable. Moreover, it is preferable that it is 100 mass parts or less, and it is more preferable that it is 80 mass parts or less. By being in the preferable range, the resistance to a strong alkaline aqueous solution can be further improved.

Further, from the viewpoint of imparting more heat resistance to the phenol resin (D), a phenol compound represented by the following general formula (1) and an aromatic aldehyde compound represented by the following general formula (2) are acidified. A phenol resin (D1) synthesized by reacting under a catalyst can be used.

(Wherein R ₁ represents an organic group selected from an alkyl group having 1 to 20 carbon atoms and an alkoxy group, and p is an integer of 1 to 3)

(Wherein R ₂ represents an organic group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and a hydroxy group, and q is an integer of 0 to 3)

  In the phenol resin (D1), by using an aromatic aldehyde as the aldehyde, it is possible to suppress intramolecular rotation and thereby impart high heat resistance. Even if dimers and trimers remain, the molecular weight of the dimers and trimers is higher than when formalin is used, and heat resistance can be kept high.

Although it does not specifically limit as a phenolic compound represented by the said General formula (1), A substituent can use a phenol compound 1 or more and 3 or less. As the substituent, an organic group selected from an alkyl group having 1 to 20 carbon atoms and an alkoxy group can be used. Specific examples of the alkyl group and alkoxy group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a methoxy group, and an ethoxy group. As such a phenol compound, for example, orthocresol, metacresol, paracresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5 are preferable. -Dimethylphenol, 2-methyl-3-ethyl-phenol, 2-methyl-3-methoxyphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, etc. Among them, the phenol represented by the following formula (4), that is, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,6-di More preferably contains butylphenol. Furthermore, these phenols can be used alone or in combination of two or more.
In the above-mentioned phenol compound, in particular, by using a phenol compound having two or more substituents, it is possible to obtain a phenol resin having sufficient heat resistance necessary for the photosensitive resin composition by suppressing intramolecular rotation.

Although it does not specifically limit as an aromatic aldehyde compound represented by the said General formula (2), Unsubstituted or the aromatic aldehyde compound whose substituent is 3 or less can be used. As the substituent, an organic group selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and a hydroxy group can be used. Specific examples of the alkyl group and alkoxy group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a methoxy group, and an ethoxy group. Examples of such an aromatic aldehyde compound include benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 2,3-dimethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 2,6-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde, 2,3,4-trimethylbenzaldehyde, 2,3,5-trimethylbenzaldehyde, 2,3,6-trimethylbenzaldehyde, 2, 4,5-trimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde, 3,4,5-trimethylbenzaldehyde, 4-ethylbenzaldehyde, 4-tert-butylbenzaldehyde, 4-i Butylbenzaldehyde, 4-methoxybenzaldehyde, salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 3-methylsalicylaldehyde, 4-methylsalicylaldehyde, 2-hydroxy-5-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2 , 5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, and the like can be used, but not limited thereto, among them, R ₂ in the general formula (2) is hydrogen, methyl group, hydroxy, The aromatic aldehyde compound which is a group is preferable, and further, from the viewpoint of heat resistance, those selected from aromatic aldehydes represented by the following formula (3) are more preferable. Furthermore, these aldehydes can be used alone or in combination. In addition, an aldehyde compound such as formaldehyde may be included as long as characteristics such as heat resistance are not impaired.

  In the synthesis reaction of the phenol resin (D1), the aromatic aldehyde compound is preferably reacted at 0.5 mol or more and 2 mol or less with respect to 1 mol of the phenol compound. By setting it as the said molar ratio, the photosensitive resin composition excellent in the thermomechanical characteristic of a cured film can be obtained.

  The acid catalyst used in the synthesis reaction of the phenol resin (D1) is not particularly limited. For example, oxalic acid, nitric acid, sulfuric acid, diethyl sulfate, acetic acid, p-toluenesulfonic acid, phenolsulfonic acid, benzenesulfonic acid, methane Although sulfonic acid, xylene sulfonic acid, etc. can be used, it is not limited to these. Among these, p-toluenesulfonic acid, phenolsulfonic acid, benzenesulfonic acid, and xylenesulfonic acid are preferable in terms of reactivity. The addition amount is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.5 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the phenol charge. If it is less than 0.1 parts by mass, the reactivity is poor, and if it exceeds 10 parts by mass, it becomes difficult to control the reaction.

  The polycondensation reaction in the synthesis of the phenol resin (D1) proceeds by stirring for several hours under heating. The reaction temperature is preferably 30 ° C to 140 ° C. In addition, a solvent can be added during the reaction to carry out the reaction in the solvent. Examples of the reaction solvent include alcohols such as methanol, ethanol, isopropanol, diethylene glycol monomethyl ether and diethylene glycol, ketone solvents such as acetone, methyl ethyl ketone and methyl amyl ketone, ethers such as diethylene glycol monomethyl ether acetate, and cyclic ethers such as tetrahydrofuran and dioxane. , Lactones such as γ-butyrolactone, pure water and the like, but are not limited thereto. The addition amount of the solvent is preferably 10 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the phenol charge.

  After completion of the reaction, neutralize the acid catalyst with a base such as pyridine, triethylamine, sodium hydroxide, etc., and remove the neutralized salt by extraction into the aqueous layer as necessary, followed by dehydration and monomer removal step To be collected.

Monomer removal is performed after the synthesis reaction of the phenol resin (D1). As a method for removing the monomer, a solvent fractionation method in which a solvent and water are added to remove the aqueous layer, a method in which the monomer is volatilized by heating while reducing pressure, or the like can be selected. In the solvent fractionation method, a solvent such as acetone, methanol, isopropanol, and butanol that is a good solubility solvent for a phenol resin, and a solvent such as pure water that is a poor solubility solvent for a phenol resin. Is added and stirred at a constant ratio, and the monomer that has moved to the aqueous layer side can be removed by removing the aqueous layer separated after standing. In the method of volatilizing the monomer, the monomer can be volatilized and removed by heating and stirring from 150 ° C. to 250 ° C. while reducing the pressure to 50 mmHg or less. When the monomer is removed by volatilization, a solvent, pure water, water vapor, N ₂ gas or the like may be added in order to increase the monomer removal efficiency. The solvent in this case is not particularly limited as long as it does not affect the phenol resin, and examples thereof include ethylene glycol, ethylene glycol alkyl ether, propylene glycol alkyl ether, propylene glycol alkyl ether acetate, diethylene glycol, diethylene glycol alkyl ether, Glycols such as triethylene glycol and triethylene glycol alkyl ether, lactones such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone, N-methylpyrrolidone, N, N-dimethylacetamide, N, N- Polar aprotic solvents such as dimethylformamide, N, N-diethylformamide, dimethyl sulfoxide, dimethylimidazolidinone and the like can be mentioned.
In both the fractionation method and the monomer volatilization method, the efficiency of monomer removal can be increased by repeating the operation according to the residual amount of monomer.

  The weight average molecular weight measured by gel permeation chromatography of the phenol resin (D1) thus obtained is preferably 1,000 or more, more preferably 1,500 or more, preferably 10,000 or less, 8,000 or less is more preferable. Although it can be used outside the range of such a weight molecular weight, by being more than the lower limit, sufficient heat resistance as a photosensitive resin composition, film toughness can be sufficiently exhibited, the upper limit By being below, it can suppress that a residue generate | occur | produces in an opening part by patterning.

  Moreover, the phenol resin (D1) obtained in this way can be finally recovered as flakes or a solvent-dissolved product. Examples of the solvent that can be recovered as a solvent-soluble product 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 And methyl-3-methoxypropionate and the like may be used alone or in combination.

[Silane coupling agent (E)]
A silane coupling agent (E) can be used for the said photosensitive resin composition, when improving adhesiveness. Examples of the silane coupling agent (E) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and p-styryltrimethoxy. Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N- 2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3 -Aminopro Rutrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, 3 -Isocyanatepropyltriethoxysilane, and silicon compounds obtained by reacting a silicon compound having an amino group with an acid dianhydride or an acid anhydride, but are not limited thereto. These silane coupling agents can be used alone or in combination of two or more.

The silicon compound having an amino group is not particularly limited, and examples thereof include 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyl. Examples include methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, and 3-aminopropyltriethoxysilane.
The acid dianhydride or acid anhydride is not particularly limited. For example, maleic anhydride, chloromaleic anhydride, cyanomaleic anhydride, cytoconic acid, phthalic anhydride, pyromellitic anhydride, Examples include 4,4′-biphthalic dianhydride, 4,4′-oxydiphthalic dianhydride, 4,4′-carbonyldiphthalic anhydride, and the like. Moreover, in using, it can be used individually or in combination of 2 or more types.
The addition amount of the silane coupling agent (E) is not particularly limited, but is preferably 0.05 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the total weight of the resin. The amount is more preferably 1 part by weight or more and 20 parts by weight or less. When the addition amount is within the above range, both the adhesion to the substrate and the storage stability of the photosensitive resin composition can be suitably achieved.

[Thermal crosslinking agent (F)]
In the photosensitive resin composition of the present invention, a thermal crosslinking agent (F) can be further used. As such a thermal crosslinking agent, a functional group capable of reacting with the alkali-soluble resin (A) by heat. If it is a compound which has this, it will not specifically limit, Furthermore, the compound which has the functional group which can react with the said phenol resin (D) with a heat | fever is preferable. For example, 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,3,5-benzenetrimethanol, 4,4-biphenyldimethanol, 2,6-pyridinedimethanol Compounds having a methylol group typified by methanol, 2,6-bis (hydroxymethyl) -p-cresol, 4,4′-methylenebis (2,6-dialkoxymethylphenol), etc .; 1,4-bis (methoxy Methyl) benzene, 1,3-bis (methoxymethyl) benzene, 4,4′-bis (methoxymethyl) biphenyl, 3,4′-bis (methoxymethyl) biphenyl, 3,3′-bis (methoxymethyl) biphenyl , Methyl 2,6-naphthalenedicarboxylate, 4,4′-methylenebis (2,6-dimethoxymethylphenol), etc. A compound having an alkoxymethyl group; a methylol melamine compound typified by hexamethylol melamine, hexabutanol melamine or the like; an alkoxy melamine compound typified by hexamethoxy melamine or the like; an alkoxymethyl glycol typified by tetramethoxymethyl glycoluril or the like Methylolurea compounds represented by uryl compounds, methylolbenzoguanamine compounds, dimethylolethyleneurea, etc .; cyano compounds represented by dicyanoaniline, dicyanophenol, cyanophenylsulfonic acid, etc .; 1,4-phenylene diisocyanate, 3,3 Isocyanate compounds typified by '-dimethyldiphenylmethane-4,4'-diisocyanate; ethylene glycol diglycidyl ether, bisphenol Epoxy group-containing compounds typified by A diglycidyl ether, triglycidyl isocyanurate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, phenol novolac resin type epoxy resin, etc .; N, Examples thereof include, but are not limited to, maleimide compounds represented by N′-1,3-phenylene dimaleimide, N, N′-methylene dimaleimide, and the like. These thermal crosslinking agents can be used alone or in combination of two or more.

  Although content of the thermal crosslinking agent (F) in the said photosensitive resin composition is not specifically limited, 1 mass part or more and 50 with respect to 100 mass parts of total weight of solid content in the photosensitive resin composition. It is preferably no greater than 2 parts by weight, and more preferably no less than 2 parts by weight and no greater than 20 parts by weight. When the addition amount is within the above range, a cured film having excellent residual film ratio and heat resistance upon curing can be formed.

[Solution Accelerator]
In addition, a dissolution accelerator may be included in the photosensitive resin composition of the present invention.
The dissolution accelerator is a component capable of improving the solubility of the exposed portion of the coating film formed using the photosensitive resin composition in the developer and improving scum during patterning.
As the dissolution accelerator, a compound having a phenolic hydroxyl group is particularly preferable.

  Further, in the photosensitive resin composition of the present invention, additives such as an antioxidant, a filler, a surfactant, a photopolymerization initiator, a terminal blocking agent, and a sensitizer may be added as necessary. Good.

[Method for producing positive photosensitive resin composition]
The alkali-soluble resin (A), the photoacid generator (B), and the solvent (C) are mixed in a container, uniformly dissolved, and filtered to obtain a varnish-like positive photosensitive resin composition. Get. Other examples of the compound that can be used include a phenol resin (D), a silane coupling agent (E), and a thermal crosslinking agent (F). Further, a dissolution accelerator, an antioxidant, a filler, a surfactant, end-capping and the like can be added as necessary. Moreover, after preparing in the varnish state which dissolved alkali-soluble resin (A), phenol resin (D), etc. in the solvent previously, it can also manufacture by adding another component. Such a production method can be preferably used particularly when produced by polymerizing hydroxystyrene resin (A1), resin (A2), phenol resin (D1) and the like in a solution. Furthermore, as the alkali-soluble resin (A), by including a curable resin having an internal stress after curing of 30 MPa or less, a positive photosensitive resin composition showing resistance to a strong alkaline aqueous solution in the pattern opening, Can be obtained efficiently. Moreover, you may include filtration and a defoaming process as needed. By including filtration and defoaming treatment, it is possible to obtain an effect of improving the appearance when the positive photosensitive resin composition is applied. Here, the viscosity of the obtained positive photosensitive resin composition depends on the coating method described later, and is not particularly limited, but is preferably 1 mPa · s or more, and more preferably 2 mPa · s or more. It is preferably 10,000 mPa · s or less, and more preferably 8,000 mPa · s or less. When the viscosity of the positive photosensitive resin composition is within the above range, the final film thickness after curing can be easily controlled, and a cured film excellent in insulation and heat resistance can be formed.

[Positive photosensitive resin composition]
The positive photosensitive resin composition has a glass transition temperature (Tg) of the cured product of 200 ° C. or higher, and more preferably 240 ° C. or higher. Sufficient heat resistance can be shown by being more than the said lower limit. The method for measuring Tg is not particularly limited, but after coating the positive photosensitive resin composition, a coating film is formed by volatilizing the solvent with a hot plate or the like, and the coating film is further heated and cured. The cured product thus obtained can be measured by using a thermal analyzer such as TMA.

  The positive photosensitive resin composition has a cured product having an internal stress of 40 MPa or less, preferably 38 MPa or less, and more preferably 35 MPa or less. By being below the upper limit, the force with which the cured film tends to peel from the adherend is reduced, and in particular, the resistance to the strong alkaline aqueous solution at the pattern opening can be sufficiently secured. Such a method for measuring internal stress can be measured in the same manner as the above-described measurement of internal stress of the curable resin.

  The positive photosensitive resin composition can have a suitable balance of heat resistance and resistance to a strong alkaline aqueous solution by having the glass transition temperature and the internal stress as described above.

  In the positive photosensitive resin composition, the 5% thermal weight loss temperature (Td5) of the cured product is preferably 300 ° C or higher, more preferably 350 ° C or higher, and further preferably 390 ° C or higher. By being more than the said lower limit, higher heat resistance can be shown. The method for measuring Td5 is not particularly limited, but the cured product obtained as described above can be measured by using a thermal analyzer such as TG-DTA.

[Curing film]
In the method of using the photosensitive resin composition of the present invention, first, the composition is applied to a suitable support such as a silicon wafer, a ceramic substrate, an aluminum substrate and the like. When applying on a semiconductor element, the application amount is generally applied so that the final film thickness after curing is 0.1 to 30 μm. By setting it as such a numerical value range, the function as a protective film of a semiconductor element and an insulating film is fully exhibited, and a fine relief pattern can be obtained.
Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and ink jet coating.
Next, when a relief pattern is formed after pre-baking at 60 to 130 ° C. and drying the coating film, the desired pattern shape is irradiated with actinic radiation. 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 obtained by adding an appropriate amount of a water-soluble organic solvent or a surfactant such as an alcohol such as methanol and ethanol to the aqueous solution 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. The rinsing liquid is not particularly limited as long as it is generally used as a rinsing liquid, but it is preferable to use distilled water in view of cost reduction and environmental influences. Next, heat treatment (curing) is performed to obtain a cured film as a cured product having excellent heat resistance.
Depending on the physical properties of the support and the design of the semiconductor device or display device, the heat treatment can be performed at a high temperature or the heat treatment may be inappropriate. Can be heat treatment at high temperature or heat treatment at low temperature. When heat treatment at high temperature is possible, the heating temperature is preferably 280 ° C. or higher and 380 ° C. or lower, more preferably 290 ° C. or higher and 360 ° C. or lower. It is. When heat treatment at a low temperature is required, the heating temperature is preferably 150 ° C. or higher and 280 ° C. or lower, more preferably 180 ° C. or higher and 260 ° C. or lower. An oven, a hot plate, an electric furnace (furnace), infrared rays, microwaves, etc. are used for the heat treatment.

  In the heat treatment, the thickness of the cured film changes before and after the heating due to the curing reaction of the curable resin contained in the positive photosensitive resin composition. When the film thickness change before and after curing is defined as the remaining film ratio, the remaining film ratio is preferably 50% or more, more preferably 60% or more, and further preferably 70% or more. By being in the preferable range, film thickness uniformity, flatness, and productivity can be further improved.

  The cured film formed using the positive photosensitive resin composition is not only used for semiconductor devices such as semiconductor elements, but also used for display devices such as TFT liquid crystal and organic EL, interlayer insulating films for flexible circuits, and flexible films. It is also useful as a copper clad 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 photosensitive resin composition of the present invention on a display element, an insulating film or a flattening film for TFT elements, color filters, etc., MVA type Examples thereof include protrusions for liquid crystal 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, but by introducing a post-exposure step before curing the coating film of the photosensitive resin composition of the present invention, it is transparent. A resin layer having excellent properties can be obtained, which is more preferable in practical use.

As a semiconductor device, a semiconductor chip (element) is formed on a semiconductor substrate and sealed with an airtight seal or a molding material. Specific examples include transistors, solar cells, diodes, solid-state imaging devices, various semiconductor packages in which semiconductor chips are stacked and sealed, and wafer level chip size packages (WLP).
Examples of the display device include a TFT liquid crystal, an organic EL, and a color filter.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to this.

[Synthesis of alkali-soluble resin (A2-1)]
Dicarboxylic acid obtained by reacting 21.43 g (0.083 mol) of diphenyl ether-4,4′-dicarboxylic acid with 22.43 g (0.166 mol) of 1-hydroxy-1,2,3-benzotriazole 40.87 g (0.083 mol) of the derivative mixture and 36.62 g (0.100 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane were added to a thermometer, a stirrer, Into a four-necked separable flask equipped with a raw material inlet and a dry nitrogen gas inlet tube, 296.96 g of N-methyl-2-pyrrolidone was added and dissolved. Then, it was made to react at 75 degreeC for 15 hours using the oil bath. Next, 6.98 g (0.0425 mol) of 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride dissolved in 34.88 g of N-methyl-2-pyrrolidone was added. The reaction was terminated by stirring for 3 hours. After the reaction mixture is filtered, the reaction mixture is poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate is collected by filtration, washed thoroughly with water, and dried under vacuum to obtain the desired alkali-soluble resin. (A2-1) was obtained. The weight average molecular weight was 13,040. Moreover, after apply | coating alkali-soluble resin (A2-1) on an 8-inch silicon wafer using a spin coater, it prebaked for 3 minutes at 120 degreeC with the hotplate, and obtained the coating film with a film thickness of about 10 micrometers. The coating film was heated in an oven at 150 ° C. for 60 minutes and then at 350 ° C. for 70 minutes while maintaining the oxygen concentration at 1000 ppm or less, and the warpage of the silicon wafer after returning to room temperature was measured with a laser microscope. The internal stress was measured from the formula of 39 MPa.

[Synthesis of alkali-soluble resin (A2-2)]
Dicarboxylic acid obtained by reacting 21.43 g (0.083 mol) of diphenyl ether-4,4′-dicarboxylic acid with 22.43 g (0.166 mol) of 1-hydroxy-1,2,3-benzotriazole 40.87 g (0.083 mol) of a mixture of derivatives, 21.98 g (0.060 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane and 4,4′-methylenebis ( 2-aminophenol) 9.21 g (0.040 mol) was placed in a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet tube, and N-methyl-2- Pyrrolidone 296.96 g was added and dissolved. Then, it was made to react at 75 degreeC for 15 hours using the oil bath. Next, 6.98 g (0.0425 mol) of 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride dissolved in 34.88 g of N-methyl-2-pyrrolidone was added. The reaction was terminated by stirring for 3 hours. After the reaction mixture is filtered, the reaction mixture is poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate is collected by filtration, washed thoroughly with water, and dried under vacuum to obtain the desired alkali-soluble resin. (A2-2) was obtained. The weight average molecular weight was 21,170. Moreover, it was 37 Mpa when the internal stress was measured similarly to alkali-soluble resin (A2-1).

[Synthesis of alkali-soluble resin (A2-3)]
4-nose Separa equipped with 30.0 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane equipped with a thermometer, stirrer, raw material inlet and dry nitrogen gas inlet tube The solution was placed in a bull flask and dissolved by adding 400 ml of acetone. Next, 12.4 g (0.18 mol) of para-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise over 30 minutes while cooling so that the temperature was less than 20 ° C. to obtain a mixture. After the dropwise addition, the temperature of the mixture was heated to 40 ° C. and stirred for 2 hours, and then 30.0 g (0.218 mol) of potassium carbonate was gradually added and further stirred for 2 hours. Heating was stopped and the mixture was further stirred at room temperature for 18 hours. Thereafter, while vigorously stirring the mixture, an aqueous sodium hydroxide solution was gradually added. After the addition, the mixture was heated to 55 ° C. and further stirred for 30 minutes. After completion of the stirring, the mixture was cooled to room temperature, 37% by weight hydrochloric acid aqueous solution and 500 ml of water were added, and the pH of the solution was adjusted to be in the range of 6.0 to 7.0. The resulting precipitate was filtered off, the filtrate was washed with water, dried at 60 to 70 ° C., and bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis. A solid of (4-hydroxyphenyl) propane was obtained. To 51.0 g of the obtained solid, 316 g of acetone and 158 g of methanol were added and heated to 50 ° C. to be completely dissolved. Thereto, 300 mL of pure water at 50 ° C. was added over 30 minutes and heated to 65 ° C. Thereafter, the crystals which have been slowly cooled to room temperature are filtered, and the crystals are purified by drying at 70 ° C. to obtain bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis. (4-Hydroxyphenyl) propane was obtained.

  20 g of the bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane obtained above was placed in a 1 L flask and 1.0 g of 5% palladium-carbon and acetic acid. 180.4 g of ethyl was added to make a suspension. Hydrogen gas was purged there, and the mixture was shaken for 35 minutes while being heated to 50 to 55 ° C. to carry out a reduction reaction. After completion of the reaction, it was cooled to 35 ° C. and the suspension was purged with nitrogen. After removing the catalyst by filtration, the filtrate was subjected to an evaporator to evaporate the solvent. The obtained product was dried at 90 ° C. to obtain bis-N, N ′-(para-aminobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane.

  14.27 g (0.024 mol) of bis-N, N ′-(para-aminobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane obtained above was added to a thermometer, a stirrer, and a raw material inlet. And put into a four-necked separable flask equipped with a dry nitrogen gas inlet tube, 40 g of γ-butyrolactone was added and dissolved, and the mixture was cooled to 15 ° C. with stirring. Thereto, 6.86 parts by weight (0.022 mol) of 4,4′-oxydiphthalic anhydride and 12.0 parts by weight of γ-butyrolactone were added and stirred at 20 ° C. for 1.5 hours. Thereafter, the mixture was heated to 50 ° C. and stirred for 3 hours, and then 5.27 g (0.044 mol) of N, N-dimethylformamide dimethylacetal and 10.0 g of γ-butyrolactone were added, and the mixture was further stirred at 50 ° C. for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature to obtain an alkali-soluble resin represented by the structure of formula (A2-3). The weight average molecular weight was 13,200. Moreover, it was 41 Mpa when the internal stress was measured similarly to alkali-soluble resin (A2-1).

[Synthesis of phenol resin (D1-1)]
In a four-necked round bottom flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 122.2 g (1.00 mol) of 2,3-xylenol and 116.0 g of salicylaldehyde in a dry nitrogen stream. (0.95 mol) and 3.4 g (0.02 mol) of p-toluenesulfonic acid were charged, followed by immersion in an oil bath, and a polycondensation reaction was performed at 100 ° C. for 4 hours while refluxing the reaction solution. Thereafter, 100 g of acetone and 2.0 g (0.02 mol) of triethylamine were added and stirred for 30 minutes while cooling the flask, and then 300 g of pure water was further added and stirred for 30 minutes. After cooling to room temperature, stirring is stopped, the separated aqueous layer is removed, 20 g of γ-butyrolactone is added, the temperature of the oil bath is raised to 200 ° C. over 3 hours, and then the pressure in the flask is increased. After reducing the pressure to 50 mmHg or less and removing volatile components, the resin was cooled to room temperature to obtain a phenol resin (D1-1).

[Synthesis of phenol resin (D1-2)]
In a four-necked round bottom flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube, 61.11 g (0.50 mol) of 2,3-xylenol and 3,5-xylenol under a dry nitrogen stream After charging 61.11 g (0.50 mol), salicylaldehyde 61.1 g (0.5 mol), benzaldehyde 47.8 g (0.45 mol) and paratoluenesulfonic acid 3.4 g (0.02 mol) Then, it was immersed in an oil bath, and a polycondensation reaction was carried out at 100 ° C. for 4 hours while refluxing the reaction solution. Thereafter, 100 g of acetone and 2.0 g (0.02 mol) of triethylamine were added and stirred for 30 minutes while cooling the flask, and then 300 g of pure water was further added and stirred for 30 minutes. After cooling to room temperature, stirring is stopped, the separated aqueous layer is removed, 20 g of diethylene glycol monomethyl ether is added, the temperature of the oil bath is raised to 200 ° C. over 3 hours, and then the pressure in the flask is increased. After reducing the pressure to 50 mmHg or less to remove volatile components, the resin was cooled to room temperature to obtain a phenol resin (D1-2).

[Synthesis of Photoacid Generator (Q-1)]
11.22 g (0.026 mol) of phenol represented by the formula (C-1), 18.78 g (0.070 mol) of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, and 170 g of acetone, 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 7.78 g (0.077 mol) of triethylamine and 5.5 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. The reaction was allowed to proceed at room temperature for 3 hours, and then 1.05 g (0.017 mol) of acetic acid was added and the reaction was continued for another 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.

Example 1
50 g of hydroxystyrene resin (A1-1) (Marcalinker CST-60, Maruzen Petrochemical Co., Ltd., hydroxystyrene: styrene = 60: 40, Mw = 3,360), phenol resin synthesized above (D1-1) 50 g and 18.5 g of the photoacid generator (Q-1) synthesized above were mixed and dissolved in 160 g of γ-butyrolactone, and then filtered through a fluororesin filter having a pore size of 0.2 μm. A photosensitive resin composition was obtained. In addition, about the said hydroxystyrene resin (A1-1), it measured like the alkali-soluble resin (A2-1) using what mixed the internal stress after hardening with the said alkali-soluble resin (A2-1). As a result, it was confirmed that the pressure was 30 MPa or less.

<< Example 2 >>
40 g of the hydroxystyrene resin (A1-1) described above, 60 g of the phenol resin (D1-1) synthesized above, and 18.5 g of the photoacid generator (Q-1) synthesized above were added to 160 g of γ-butyrolactone. After mixing and dissolving, the mixture was filtered through a fluororesin filter having a pore size of 0.2 μm to obtain a photosensitive resin composition of Example 2.

Example 3
50 g of hydroxystyrene resin (A1-2) (Maruka Linker CST-70, Maruzen Petrochemical Co., Ltd., hydroxystyrene: styrene = 70: 30, Mw = 3,200), phenol resin synthesized above (D1-1) 50 g and 18.5 g of the photoacid generator (Q-1) synthesized above were mixed and dissolved in 160 g of γ-butyrolactone, and then filtered through a fluororesin filter having a pore size of 0.2 μm. A photosensitive resin composition was obtained. In addition, about the said hydroxystyrene resin (A1-2), when the internal stress after hardening was measured similarly to the said hydroxystyrene resin (A1-1), it confirmed that it was 30 Mpa or less.

Example 4
50 g of hydroxystyrene resin (A1-2), 50 g of phenol resin (D1-2) synthesized above and 18.5 g of photoacid generator (Q-1) synthesized above are mixed with 160 g of γ-butyrolactone and dissolved. Then, the mixture was filtered through a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 4.

Example 5
50 g of the hydroxystyrene resin (A1-2) described above, 50 g of the phenol resin (D1-1) synthesized above, 18.5 g of the photoacid generator (Q-1) synthesized above, and 3 as the silane coupling agent -2 g of glycidoxypropyltrimethoxysilane (E-1) was mixed with 160 g of γ-butyrolactone and dissolved, and then filtered through a fluororesin filter having a pore size of 0.2 µm. The photosensitive resin composition of Example 5 Got.

Example 6
30 g of the hydroxystyrene resin (A1-2) described above, 30 g of the phenol resin (D1-1) synthesized above, 18.5 g of the photoacid generator (Q-1) synthesized above, and alkali-soluble synthesized above. After 40 g of resin (A2-1) was mixed and dissolved in 160 g of γ-butyrolactone, it was filtered through a fluororesin filter having a pore size of 0.2 μm to obtain a photosensitive resin composition of Example 6.

Example 7
30 g of the hydroxystyrene resin (A1-2) described above, 15 g of the phenol resin (D1-1) synthesized above, 18.5 g of the photoacid generator (Q-1) synthesized above, and alkali-soluble synthesized above. 55 g of the resin (A2-1) and 2 g of the silane coupling agent (E-1) described above were mixed and dissolved in 160 g of γ-butyrolactone, and then filtered through a fluororesin filter having a pore size of 0.2 μm. The photosensitive resin composition of Example 7 was obtained.

Example 8
30 g of the hydroxystyrene resin (A1-2) described above, 15 g of the phenol resin (D1-1) synthesized above, 18.5 g of the photoacid generator (Q-1) synthesized above, and alkali-soluble synthesized above. 55 g of resin (A2-1) and 8 g of 1,4-benzenedimethanol as thermal crosslinking agent (F-1) were mixed and dissolved in 160 g of γ-butyrolactone, and then filtered through a fluororesin filter having a pore size of 0.2 μm. Thus, a photosensitive resin composition of Example 8 was obtained.

Example 9
30 g of the hydroxystyrene resin (A1-2) described above, 30 g of the phenol resin (D1-1) synthesized above, 18.5 g of the photoacid generator (Q-1) synthesized above, and alkali-soluble synthesized above. After mixing 40 g of the resin (A2-2), 2 g of the silane coupling agent (E-1) described above and 8 g of the thermal crosslinking agent (F-1) described above in 160 g of γ-butyrolactone, The mixture was filtered through a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 9.

Example 10
30 g of the hydroxystyrene resin (A1-2) described above, 15 g of the phenol resin (D1-1) synthesized above, 18.5 g of the photoacid generator (Q-1) synthesized above, and alkali-soluble synthesized above. After 55 g of the resin (A2-2), 2 g of the silane coupling agent (E-1) described above and 8 g of the thermal crosslinking agent (F-1) were mixed and dissolved in 160 g of γ-butyrolactone, the pore diameter was 0.2 μm. And a photosensitive resin composition of Example 10 was obtained.

Example 11
30 g of the hydroxystyrene resin (A1-2) described above, 15 g of the phenol resin (D1-1) synthesized above, 18.5 g of the photoacid generator (Q-1) synthesized above, and alkali-soluble synthesized above. 55 g of the resin (A2-3) and 2 g of the silane coupling agent (E-1) described above were mixed and dissolved in 160 g of γ-butyrolactone, and then filtered through a fluororesin filter having a pore size of 0.2 μm. The photosensitive resin composition of Example 11 was obtained.

≪Comparative example 1≫
45 g of the phenol resin (D1-1) synthesized above, 18.5 g of the photoacid generator (Q-1) synthesized above, 55 g of the alkali-soluble resin (A2-1) synthesized above, and the silane cup described above 2 g of the ring agent (F-1) was mixed and dissolved in 160 g of γ-butyrolactone, and then filtered through a fluororesin filter having a pore size of 0.2 μm to obtain a photosensitive resin composition of Comparative Example 1.

<Internal stress>
Each of the photosensitive resin compositions obtained above was applied on an 8-inch silicon wafer using a spin coater and then pre-baked at 120 ° C. for 3 minutes on a hot plate to obtain a coating film having a thickness of about 10 μm. . The coating film was heated in an oven at 150 ° C. for 60 minutes and then at 350 ° C. for 70 minutes while maintaining the oxygen concentration at 1000 ppm or less, returned to room temperature, and then warpage of the silicon wafer was measured with a laser microscope. The internal stress was measured from the following equation.

<Glass transition temperature>
The glass transition temperature (Tg) was measured with the thermomechanical analyzer (TMASS6100 type | mold Seiko Instruments make) using the cured film which measured the internal stress.

<Processability evaluation>
Each of the photosensitive resin compositions obtained above was applied on an 8-inch silicon wafer using a spin coater and then pre-baked at 120 ° C. for 3 minutes on a hot plate to obtain a coating film having a thickness of about 10 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, a 2.38% tetramethylammonium hydroxide aqueous solution is used as a developing solution, and the developing time is adjusted so that the difference between the film thickness after pre-baking and the film thickness after developing is 1.0 μm, and paddle twice. The exposed portion was dissolved and removed by developing, and then rinsed with pure water for 10 seconds. The value of the minimum exposure amount at which a 100 μm square via hole pattern was formed was evaluated as sensitivity. Moreover, the minimum pattern width (resolution) of the line & space which opened favorably with the exposure amount by which the pattern is formed in the unexposed part was calculated.

<Resistance to zincate solution (strong alkaline aqueous solution resistance)>
On the silicon wafer, a sputtered film having a thickness of 500 mm was formed on Ti, and subsequently, a sputtered film having a thickness of 3,000 mm was formed on Al. The positive photosensitive resin composition obtained in each example and each comparative example was coated on the silicon wafer using a spin coater, and then dried on a hot plate at 120 ° C. for 3 minutes to obtain a film thickness of about A 10 μm coating film was obtained. Through this mask, a mask made by Toppan Printing Co., Ltd. (a 1 mm square pattern) was used, and exposure was carried out with a fixed exposure time of 40 seconds using a mask aligner MA8 manufactured by SSUS. Next, the exposed portion was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution, and then rinsed with pure water for 30 seconds. At this time, the amount of film reduction in the unexposed area was about 2 μm. The patterned silicon wafer was cured in a clean oven at an oxygen concentration of 1,000 ppm or less at 150 ° C./60 minutes and 350 ° C./70 minutes. Next, this silicon wafer was added to a zincate treatment solution (Meltex Co., Ltd., Melplate FZ-7350, Melplate Zincate F-Plus and pure water mixed at a ratio of 20: 1: 79) at 25 ° C./10. It was immersed in the conditions of minutes. Next, after washing with pure water for 5 minutes, the film was dried and the surface of the film was observed with a metal microscope, and the penetration depth into the remaining pattern was measured. Evaluation was performed at n = 10. Judgment was made as follows: （(penetration width of less than 1 μm), ◯ (penetration width of 1 μm or more and less than 2 μm), Δ (penetration width of 2 μm or more and less than 5 μm), × (penetration width of 5 μm or more)

<Evaluation of cured film ratio>
Each of the photosensitive resin compositions obtained above was applied on an 8-inch silicon wafer using a spin coater and then pre-baked at 120 ° C. for 3 minutes on a hot plate to obtain a coating film having a thickness of about 10 μm. . The coating film was heated in an oven at 150 ° C. for 60 minutes and then at 350 ° C. for 70 minutes while maintaining the oxygen concentration at 1000 ppm or less, and the film thickness after returning to room temperature was measured. The film thickness change rate of the film thickness after hardening and the film thickness before hardening was computed from the following formula, and it evaluated as a hardening residual film rate.
Cured residual film ratio = film thickness after curing / film thickness before curing * 100
It should be noted that the cured residual film ratio is preferably high in order to maintain a sufficient film thickness for protecting the semiconductor element.

<Heat resistance evaluation>
About the cured film obtained by the cured residual film rate evaluation, 5% thermogravimetric reduction temperature (Td5) was measured with the Tg-DTA apparatus (TG / DTA6200 Seiko Instruments make).

<Fabrication of semiconductor device>
Each of the photosensitive resin compositions of Examples 1 to 11 was applied to a final thickness of 5 μm using a simulated element wafer having an aluminum circuit on the surface, and then cured by patterning. After that, each chip size is divided and mounted on a lead frame for 16 Pin DIP (Dual Inline Package) using a conductive paste, and then an epoxy resin for semiconductor encapsulation (EME-6300H manufactured by Sumitomo Bakelite Co., Ltd.) is used. The semiconductor device was manufactured by sealing. These semiconductor devices (semiconductor packages) are treated at 85 ° C./85% humidity for 168 hours, then immersed in a 260 ° C. solder bath for 10 seconds, and then subjected to a high temperature and high humidity pressure cooker treatment (125 ° C., 2.3 atm). , 100% relative humidity) was checked for open defects in the aluminum circuit, and no corrosion or the like was observed, and it is expected that the semiconductor device can be used without problems.

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

As is clear from the examples and comparative examples, according to the present invention, there is provided a positive photosensitive resin composition that is compatible with i-line with high sensitivity and high resolution, and also has excellent resistance to strong alkaline aqueous solutions. Can be provided.

Claims (16)

A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photoacid generator (B), and a solvent (C),
When the positive photosensitive resin composition is pre-baked at 120 ° C. for 3 minutes, and cured by heating at 150 ° C. for 60 minutes, and then at 350 ° C. for 70 minutes,
The glass transition temperature after curing is 200 ° C. or higher, the internal stress is 40 MPa or lower,
The alkali-soluble resin (A) includes a resin (A2) containing at least one structure from the group of a polybenzoxazole structure, a polybenzoxazole precursor structure, a polyimide structure, a polyimide precursor structure, and a polyamide structure. A positive photosensitive resin composition characterized by the above. A positive photosensitive resin composition comprising an alkali-soluble resin (A), a photoacid generator (B), and a solvent (C),
When the positive photosensitive resin composition is pre-baked at 120 ° C. for 3 minutes, and cured by heating at 150 ° C. for 60 minutes, and then at 350 ° C. for 70 minutes,
The glass transition temperature after curing is 200 ° C. or higher, the internal stress is 40 MPa or lower,
The positive photosensitive resin composition further includes a phenol resin (D),
The phenol resin (D1) obtained by reacting the phenol compound (D) represented by the following general formula (1) and the aromatic aldehyde compound represented by the following general formula (2) under an acid catalyst. Including
The positive photosensitive resin composition is used for forming the positive photosensitive resin composition as a cured film constituting an apparatus.

(Wherein R1 represents an organic group selected from an alkyl group having 1 to 20 carbon atoms and an alkoxy group, and p is an integer of 1 to 3)

(Wherein R2 represents an organic group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group and a hydroxy group, and q is an integer of 0 to 3) The positive photosensitive resin composition according to claim 2, wherein the phenol resin (D1) includes one or more selected from aromatic aldehydes represented by the following formula (3) as an aromatic aldehyde compound.
The positive photosensitive resin composition according to claim 2 or 3, wherein the phenol resin (D1) contains at least one selected from phenols represented by the following formula (4) as a phenol compound.
  The positive photosensitive resin composition according to claim 1, wherein the curable resin contains a hydroxystyrene resin (A1). The positive photosensitive resin composition according to claim 5, wherein the hydroxystyrene resin (A1) is a copolymer containing hydroxystyrene and / or a derivative of hydroxystyrene.   The positive photosensitive resin composition according to claim 5, wherein the hydroxystyrene resin (A1) is a copolymer containing styrene and / or a derivative of styrene. The hydroxystyrene resin (A1) is a copolymer containing hydroxystyrene and a derivative thereof, and the constituent ratio of the hydroxystyrene and the derivative in the hydroxystyrene resin (A1) is 50% or more and 90% or less. The positive photosensitive resin composition according to any one of claims 5 to 7. Curable resin whose internal stress after curing is 30 MPa or less when the alkali-soluble resin (A) is pre-baked at 120 ° C. for 3 minutes, and heat-cured at 150 ° C. for 60 minutes and then at 350 ° C. for 70 minutes. The positive photosensitive resin composition of Claims 1-8 containing these. Furthermore, the positive photosensitive resin composition of any one of Claims 1-9 containing a silane coupling agent (E). Furthermore, the positive photosensitive resin composition of any one of Claims 1-10 containing a thermal crosslinking agent (F). The cured film comprised by the hardened | cured material of the positive photosensitive resin composition of any one of Claims 1-11. The protective film comprised with the cured film of Claim 12. The insulating film comprised with the cured film of Claim 12. A semiconductor device comprising the cured film according to claim 12. The display body apparatus which has the cured film of Claim 12.