TWI666515B - Photosensitive resin composition, cured film, protective film, insulating film and electronic device - Google Patents

Abstract

According to the present invention, there is provided a photosensitive resin composition containing an alkali-soluble resin (A), a silane compound (B) represented by the following general formula (1), and a photoacid generator (C).

A 〔Si (R1) _a (OR2) _b 〕 _m 〔Si (R3) _c (OR4) _d 〕 _n (1)

(In the formula, A represents a (m + n) -valent organic group having a cyclic structure, R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, and R2 and R4 represent A substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a and b represent 0 to 3 that satisfy a + b = 3 Integers, c and d represent integers from 0 to 3 that satisfy c + d = 3, m and n represent integers from 0 to 2, m + n ≠ 0)

Description

Photosensitive resin composition, cured film, protective film, insulating film, and electronic device

The present invention relates to a photosensitive resin composition, a cured film, a protective film, an insulating film, and an electronic device.

Conventionally, as the protective film and the insulating film in the semiconductor device, a photosensitive resin composition is used, which contains an alkali-soluble resin that is excellent in heat resistance and has excellent electrical and mechanical characteristics and can be patterned.

Here, when using a photosensitive resin composition containing an alkali-soluble resin, in order to simplify the manufacturing process, it is common to combine a diazoquinone compound of a photoacid generator with these resins to produce a photosensitive resin composition. For example, Patent Document 1 describes a photosensitive resin composition containing an alkali-soluble phenol resin and a photosensitive resin composition, an organic solvent, and an alkoxysilyl-containing adhesive agent.

Patent Document 1: Japanese Patent Application Laid-Open No. 2008-164816

Generally, the production of a protective film or an insulating film of a semiconductor element using a photosensitive resin composition is performed through the following steps: formation of a resin film by application to a support of the photosensitive resin composition; Radiation exposure, patterning using development in an alkaline developer, washing with pure water, and hardening using heating.

However, when the adhesiveness of the resin film to a support is poor, it may be difficult to perform stable patterning. Therefore, it is required to improve the adhesiveness of the resin film obtained by using the photosensitive resin composition.

In addition, when the transparency of the resin film is insufficient, the visibility of the pattern on the surface of the support is reduced, so that the productivity in the subsequent steps after patterning or curing may be reduced. Therefore, it is required to improve the transparency of a resin film obtained by using a photosensitive resin composition.

Therefore, the present invention provides a photosensitive resin composition that can obtain a resin film that can form a pattern with high adhesion and stable, and that has sufficient transparency. The present invention also provides a cured film composed of a cured product of the photosensitive resin composition, a protective film and an insulating film composed of the cured film, and an electronic device including the cured film.

The present invention is achieved by the following [1] to [14].

[1] A photosensitive resin composition containing an alkali-soluble resin (A), a silane compound (B) represented by the following general formula (1), and a photoacid generator (C).

A 〔Si (R1) _a (OR2) _b 〕 _m 〔Si (R3) _c (OR4) _d 〕 _n (1)

(In the formula, A represents a (m + n) -valent organic group having a cyclic structure, R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, and R2 and R4 represent A substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a and b represent 0 to 3 that satisfy a + b = 3 Integers, c and d represent integers from 0 to 3 that satisfy c + d = 3, m and n represent integers from 0 to 2, m + n ≠ 0)

[2] The photosensitive resin composition according to the above [1], wherein A in the general formula (1) of the silane compound (B) is an organic group having an aromatic ring.

[3] The photosensitive resin composition according to the above [1] or [2], wherein A in the general formula (1) of the silane compound (B) is selected from the organic group represented by the following formula (2) Of its organic base.

(In the formula, X1 represents a single bond, C (-Y1) (-Y2), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing amidino group, and Y1 and Y2 each independently represent a hydrogen atom, Trifluoromethyl, substituted or unsubstituted saturated alkyl having 1 to 10 carbons, substituted or unsubstituted unsaturated alkyl having 1 to 10 carbons, substituted or unsubstituted phenyl, Or substituted or unsubstituted cyclohexyl)

[4] The photosensitive resin composition according to the above [1], wherein A in the general formula (1) of the silane compound (B) is an organic group having an aliphatic ring.

[5] The photosensitive resin composition according to the above [1] or [4], wherein the silane compound A in the general formula (1) of (B) is an organic group selected from the group of organic groups represented by the following formula (3).

(In the formula, X2 represents a single bond, C (-Y3) (-Y4), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing amidino group, and Y3 and Y4 each independently represent a hydrogen atom, Trifluoromethyl, substituted or unsubstituted saturated alkyl having 1 to 10 carbons, substituted or unsubstituted unsaturated alkyl having 1 to 10 carbons, substituted or unsubstituted phenyl, Or substituted or unsubstituted cyclohexyl)

[6] The photosensitive resin composition according to any one of the above [1] to [5], wherein the alkali-soluble resin (A) contains a material selected from the group consisting of polybenzo Azole, polybenzo At least one or more of an azole precursor, a polyimide, and a polyimide precursor.

[7] The photosensitive resin composition according to any one of the above [1] to [6], further comprising a phenol resin (D) obtained by reacting a phenol compound and an aromatic aldehyde compound.

[8] The photosensitive resin composition according to the above [7], wherein the aromatic aldehyde compound includes an aromatic aldehyde compound represented by the following formula (4).

(In the formula, R ₁ represents an organic group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and a hydroxyl group, and t is an integer of 0 to 3)

[9] The photosensitive resin composition according to the above [7] or [8], wherein the phenol compound includes a phenol compound represented by the following formula (5).

(In the formula, X3 represents a single bond, C (-Y7) (-Y8), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing amidino group. Y7 and Y8 each independently represent a hydrogen atom, Trifluoromethyl, substituted or unsubstituted saturated alkyl having 1 to 10 carbons, substituted or unsubstituted unsaturated alkyl having 1 to 10 carbons, substituted or unsubstituted phenyl, Or substituted or unsubstituted cyclohexyl, Y5 and Y6 each independently represent a substituted or unsubstituted saturated alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted unsaturated alkyl group having 1 to 20 carbon atoms Group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted phenyl group, or substituted or unsubstituted cyclohexyl group; p and q each independently represent 1 to 3 Integer, r and s each independently represent an integer of 0 ~ 3)

[10] The photosensitive resin composition according to any one of the above [1] to [9], which further contains a thermal crosslinking agent (E).

[11] A cured film composed of a cured product of the photosensitive resin composition according to any one of the above [1] to [10].

[12] A protective film composed of the hardened film of the above [11].

[13] An insulating film composed of the hardened film of the above [11].

[14] An electronic device having the cured film of [11].

According to the present invention, it is possible to provide a photosensitive resin composition capable of obtaining a resin film capable of forming a pattern with high adhesion and stable, and having sufficient transparency.

10‧‧‧ substrate

12‧‧‧ Opposite substrate

14‧‧‧LCD layer

20‧‧‧ insulating film

22, 24, 26‧‧‧ opening

30‧‧‧ Transistor

31‧‧‧Gate electrode

32‧‧‧Source electrode

33‧‧‧ Drain electrode

34‧‧‧Gate insulation film

35‧‧‧Semiconductor layer

40, 42‧‧‧ Wiring

50, 52, 54‧‧‧ insulating film

70‧‧‧ rewiring

72‧‧‧ Top-level wiring

74‧‧‧ bump

80‧‧‧ redistribution layer

90, 92‧‧‧alignment film

100‧‧‧ electronic device

The above-mentioned objects, and other objects, features, and advantages will be made clearer by suitable embodiments described below and the following drawings attached thereto.

FIG. 1 is a cross-sectional view showing an example of an electronic device according to this embodiment.

FIG. 2 is a cross-sectional view showing an example of an electronic device according to this embodiment.

Hereinafter, the embodiment will be appropriately described using drawings. In all drawings, the same constituent elements are assigned the same reference numerals, and descriptions thereof are appropriately omitted. In addition, "~" means above to below unless otherwise specified.

The photosensitive resin composition of this embodiment contains an alkali-soluble resin (A), a silane compound (B) represented by the following general formula (1), and a photoacid generator (C).

A 〔Si (R1) _a (OR2) _b 〕 _m 〔Si (R3) _c (OR4) _d 〕 _n (1)

(In the formula, A represents a (m + n) -valent organic group having a cyclic structure, and R1 and R3 are independent of each other. Represents a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, and R2 and R4 represent a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon Unsaturated alkyl groups of 1 to 10, a and b represent integers from 0 to 3 satisfying a + b = 3, c and d represent integers from 0 to 3 satisfying c + d = 3, and m and n represent 0 to An integer of 2, m + n ≠ 0)

As described above, the protective film or the insulating film is formed by, for example, the following steps: formation of a resin film by application to a support of a photosensitive resin composition; exposure by actinic rays; Patterning for development, washing with pure water, and hardening with heating. However, when the adhesiveness to the support of the said resin film is bad, it may be difficult to perform stable patterning. For example, when the adhesiveness of the resin film is poor, there is a possibility that the pattern disappears or deforms during development in an alkaline developing solution. In addition, when the transparency of the resin film is insufficient, the visibility of the pattern on the surface of the support is reduced, so that the productivity in the subsequent steps after patterning or curing may be reduced. For example, when an electronic device is assembled by singulating a support in a subsequent step, since the visibility of the pattern on the surface of the support is reduced, there is a possibility that the identification of the singulated support may be incorrect and the output may be reduced. Therefore, in order to realize stable manufacturing of electronic devices, it is important to improve both the adhesion and transparency.

As a result of diligent research, the inventors have found that by including a specific silane compound, both the adhesion and transparency of the photosensitive resin composition are improved. Based on such findings, the present embodiment realizes a photosensitive resin composition containing an alkali-soluble resin (A), a silane compound (B) represented by the following general formula (1), and a photoacid generator (C). Therefore, according to this embodiment, a photosensitive resin composition excellent in adhesiveness and transparency can be realized. Accordingly, an electronic device having excellent manufacturing stability can also be realized.

A 〔Si (R1) _a (OR2) _b 〕 _m 〔Si (R3) _c (OR4) _d 〕 _n (1)

(In the formula, A represents a (m + n) -valent organic group having a cyclic structure, R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, and R2 and R4 represent A substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a and b represent 0 to 3 that satisfy a + b = 3 Integers, c and d represent integers from 0 to 3 that satisfy c + d = 3, m and n represent integers from 0 to 2, m + n ≠ 0)

Hereinafter, the configuration of the photosensitive resin composition and the electronic device including the permanent film formed using the photosensitive resin composition of the present embodiment will be described in detail.

First, the photosensitive resin composition of this embodiment is demonstrated.

The photosensitive resin composition is used for forming a permanent film, for example. By curing the photosensitive resin composition, a resin film constituting a permanent film can be obtained. In this embodiment, a permanent film is formed by, for example, patterning a coating film made of a photosensitive resin composition into a desired shape by exposure and development, and then curing the coating film by heat treatment or the like.

Specific examples of the permanent film formed using the photosensitive resin composition include an interlayer film, a surface protective film, and a barrier material. The use of the photosensitive resin composition is not limited to this.

The interlayer film refers to an insulating film provided in a multilayer structure, and its type is not particularly limited. Examples of the interlayer film include an interlayer insulating film constituting a multilayer wiring structure of a semiconductor element, an additional layer constituting a wiring substrate, or a core layer that is equivalent to a user of a semiconductor device. In addition, as the interlayer film, for example, a planarization film covering a thin film transistor (TFT (Thin Film Transistor)) in a display device, a liquid crystal alignment film, and an MVA (Multi Domain Vertical) Alignment (multi-domain vertical alignment) type liquid crystal display device, the protrusions on the color filter substrate, or the partition wall used to form the cathode of the organic EL element is equal to the user of the display device.

The surface protective film refers to an insulating film formed on the surface of an electronic component or an electronic device for protecting the surface, and the type thereof is not particularly limited. Examples of such a surface protection film include a passivation film or a buffer coating layer provided on a semiconductor element, or a cover coat provided on a flexible substrate. Examples of the barrier material include a spacer used to form a hollow portion for arranging an optical element on a substrate.

Hereinafter, each component of the photosensitive resin composition of this embodiment is demonstrated in detail. In addition, the following is an example, and this invention is not limited at all by the following.

[Alkali soluble resin (A)]

Examples of the alkali-soluble resin (A) used in the present embodiment include those having a hydroxyl group, particularly a phenolic hydroxyl group and / or a carboxyl group, on a main chain or a side chain, and examples thereof include a phenol resin, a phenol aralkyl resin, Acrylic resins such as hydroxystyrene resin, methacrylic resin, and methacrylate resin, cyclic olefin resin, polyamide resin, and the like. Among these, a phenol resin, a phenol aralkyl resin, a hydroxystyrene resin, and a polyamide resin are preferred, and a polybenzo is particularly preferably selected from the group consisting of particularly excellent heat resistance and film toughness. Azole, polybenzo One or two or more of polyimide resins such as an azole precursor, a polyimide, and a polyimide precursor. These alkali-soluble resins can be used singly or in combination of two or more kinds.

As the phenol resin in the alkali-soluble resin (A), a reactant of a phenol compound represented by a novolac phenol resin and an aldehyde compound, or a phenol compound represented by a phenol aralkyl resin and a dimethanol compound can be used. Of reactants, etc. Among them, as the phenol resin in the alkali-soluble resin (A), a phenol resin different from the phenol resin (D) described below is used.

Used as a novolac-type phenol resin in the alkali-soluble resin (A) Examples of the phenol compound to be used include phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-dimethylphenol, 2,4-dimethylphenol, and 2,5-diphenol Dimethylphenols such as methylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol; o-ethylphenol, m-ethylphenol, p-ethylphenol Ethylphenols such as phenol; Alkylphenols such as isopropylphenol, butylphenol, and p-tert-butylphenol; in addition, catechol, catechol, hydroquinone, and catechol Polyphenols such as, and resorcinol, but are not limited to these. These phenols can be used individually or in combination of 2 or more types.

Used as a novolac-type phenol resin in the alkali-soluble resin (A) Examples of the aldehyde compound used include, but are not limited to, formaldehyde, paraformaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

As the above-mentioned phenol aralkyl resin in the above-mentioned alkali-soluble resin (A) As the phenol compound to be used, the same phenol compound as the phenol compound used in the novolac phenol resin can be used.

A phenol aralkyl resin can be obtained by reacting this phenol compound with a compound such as a dimethyl alcohol compound as shown below.

Examples of the dimethanol compounds used in the phenol aralkyl resin in the alkali-soluble resin (A) include 1,4-benzenedimethanol, 1,3-benzenedimethanol, and 4,4'-diamine. Dimethanol compounds such as xylylene glycol, 3,4'-biphenyldimethanol, 3,3'-biphenyldimethanol, and 2,6-naphthalenedimethanol.

It is also possible to use this dimethanol compound and other 1,4-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 4,4'-bis (methoxymethoxy) Phenyl) biphenyl, 3,4'-bis (methoxymethyl) Biphenyls, 3,3'-bis (methoxymethyl) biphenyls, and bis (alkoxymethyl) compounds such as methyl 2,6-naphthalenedicarboxylate; 1,4-bis (chloromethyl) Benzene, 1,3-bis (chloromethyl) benzene, 1,4-bis (bromomethyl) benzene, 1,3-bis (bromomethyl) benzene, 4,4'-bis (chloromethyl) biphenyl Benzene, 3,4'-bis (chloromethyl) biphenyl, 3,3'-bis (chloromethyl) biphenyl, 4,4'-bis (bromomethyl) biphenyl, 3,4'-bis (Bromomethyl) biphenyl and bis (haloalkyl) compounds such as 3,3'-bis (bromomethyl) biphenyl and the like are reacted with a phenol compound to obtain a phenolaralkyl resin. These compounds may be used singly or in combination of two or more kinds.

The hydroxystyrene resin in the alkali-soluble resin (A) may be A polymerization reaction product or a copolymerization reaction product obtained by subjecting hydroxystyrene or styrene and derivatives thereof to radical polymerization, cationic polymerization, or anionic polymerization is used.

In the alkali-soluble resin (A), the above-mentioned so-called polyamine resin refers to a resin having benzo Resin with an azole precursor structure and / or an imine precursor structure. The polyamide resin may have a benzo Azole precursor structure, pyrimide precursor structure, benzo Benzene produced by ring-closing reaction of part of the structure of the azole precursor An azole structure, a fluorene imine structure produced by a ring-closing reaction of a part of the fluorene imine precursor structure, and may also have a fluorin acid ester structure.

Benzo The azole precursor structure refers to the structure represented by the following formula (6). The so-called fluorene imine precursor structure refers to the structure represented by the following formula (7). The azole structure refers to the structure represented by the following formula (8). The so-called imine structure refers to the structure represented by the following formula (9). structure.

In addition, D and R 'in the formulae (6) to (10) represent a monovalent or divalent organic group. Among these polyamide resins, a polyamide resin having a repeating unit represented by the following general formula (11) is preferred from the viewpoint of the heat resistance of the cured product of the photosensitive resin composition of this embodiment. .

(In the formula, X and Y are organic groups; R ₂ is a hydroxyl group, -OR ₄ , an alkyl group, a fluorenyl group, or a cycloalkyl group. When there are a plurality of groups, each may be the same or different; R ₃ is a hydroxyl group when, a carboxyl group, -OR ₄ or -COO-R _4, having a plurality of situations, each may be the same or different; R ₂ and R ₃ the carbon number of R ₄ is an organic group of 1 to 15; here, In formula (11), when there is no hydroxyl group in R ₂ , at least one of R ₃ is a carboxyl group; and when there is no carboxyl group in R ₃ , at least one of R ₂ is a hydroxyl group; k is 0 ~ 8 integer, l is an integer from 0 to 8; e is an integer from 2 to 100)

In a polyamide resin having a structure represented by the general formula (11), as R ₂ and R ₃ , in order to adjust the solubility of the polyamide resin to an alkaline aqueous solution, it can be protected with a protective group R ₄ from the carboxyl group and hydroxyl group, specifically, may be used as the -OR ₄ R _2, R ₃ is -OR _4, and the -COO-R _4. Examples of such an organic group having 1 to 15 carbon atoms of R ₄ include methylamino, methyl, ethyl, propyl, isopropyl, third butyl, third butoxycarbonyl, phenyl, and benzyl. Group, tetrahydrofuranyl, tetrahydropyranyl and the like.

The polyamine resin having the structure represented by the above general formula (11) is X The organic group is not particularly limited, and examples thereof include an aromatic group composed of a structure such as a benzene ring, a naphthalene ring and a bisphenol structure; a heterocyclic organic group composed of a structure such as a pyrrole ring and a furan ring; and a siloxane Base etc. More specifically, it is preferably represented by the following formula (12). These may be used singly or in combination of two or more kinds as necessary.

(In the formula (12), * represents an NH group bonded to the general formula (11); Z is an alkylene group, a substituted alkylene group, -OC 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, each of which may be The same or different; R ₆ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom; u is an integer of 0 to 4; R ₇ to R ₁₀ are monovalent or divalent organic groups, respectively ; Furthermore, in the above formula (12), the substituent R ₂ of X in the above general formula (11) is omitted)

Among the bases represented by the above formula (12), particularly preferred ones include those represented by the following formula (13) (there are also those having R ₂ in the general formula (11)).

(In formula (13), * represents an NH group bonded to general formula (11); where Z is 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 single bond; R ₁₁ is one selected from the group consisting of an alkyl group, an alkoxy group, a fluorenyloxy group, and a cycloalkyl group. When there are multiple R ₁₁ groups, each may be the same or different; v is an integer of 0 or more and 3 or less. )

Among the bases represented by the above formula (13), particularly preferred ones include those represented by the following formula (14) (there are also those having R ₂ in the general formula (11)).

(In formula (14), * represents an NH group bonded to general formula (11); R ₁₂ is selected from the group consisting of alkylene, substituted alkylene, -O-, -S-, -SO ₂ -,- C (= O)-, -NHC (= O)-, -C (CF ₃ ) _2- , organic group in single bond)

Specific examples of Z in the formulae (12) and (13) and the alkylene group and substituted alkylene group as R ₁₂ in the formula (14) include -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) (CH ₂ CH ₃ )-, -CH (CH ₂ CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -CH (CH (CH ₃ ) ₂ )-, -C (CH ₃ ) ( CH (CH ₃ ) ₂ )-, -CH (CH ₂ CH ₂ CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH (CH ₂ CH (CH ₃ ) ₂ )-, -C (CH ₃ ) (CH ₂ CH (CH ₃ ) ₂ )-, -CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, and -C (CH ₃ ) (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, etc. Among these, -CH _2- , -CH (CH ₃ )-, and -C (CH ₃ ) ₂ -can obtain sufficient solubility not only for alkaline aqueous solutions and solvents, but also have excellent balance. Polyamine resin is preferred.

Further, Y in the polyamide resin having a structure represented by the general formula (11) is an organic group, and examples of such an organic group include the same ones as X described above. For example: from benzene Aromatic groups consisting of structures such as rings, naphthalene rings, and bisphenol structures; heterocyclic organic groups consisting of structures such as pyrrole rings, pyridine rings, and furan rings; silyl groups, etc., more specifically, can be compared with The following formula (15) is preferably used. These may be used singly or in combination of two or more kinds.

(In formula (15), * represents a C = O group bonded to general formula (11); J is -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 a group selected from an alkyl group, an alkyl ester group, an alkyl ether group, One of a benzyl ether group and a halogen atom may be the same or different; R ₁₄ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom; w is 0 or more and 2 or less An integer; R ₁₅ to R ₁₈ are a monovalent or divalent organic group; further, in the above formula (15), the substituent R ₃ of Y in the above general formula (11) is omitted)

Among the bases represented by the formula (15), particularly preferable ones include those represented by the following formula (16) (there is also one having R ₃ in the general formula (11)).

Regarding the structure of the tetracarboxylic dianhydride derived from the following formula (16), although the positions bonded to the C = O group in the general formula (11) are all meta-positions and para-positions , But can also be included separately The structure of meta and para.

(In the formula (16), * represents a C = O group bonded to the general formula (11); R ₁₉ represents a group selected from an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and a halogen atom. One of them may be the same or different; R ₂₀ represents one selected from a hydrogen atom or an organic group having a carbon number of 1 to 15 and a part may be substituted; x is an integer of 0 to 2)

Also, in the case of the polyamide resin represented by the general formula (11), it is possible to use a resin containing at least one resin to such an extent that it does not affect the mechanical properties and heat resistance of the cured product cured at a low temperature. An acidic anhydride or monocarboxylic acid of an aliphatic group or a cyclic compound group of an organic group selected from an alkenyl group, an alkynyl group, and a hydroxyl group, the amine group at the terminal of the polyamidoresin resin is capped in the form of amido.

Examples of the acid anhydride or monocarboxylic acid containing an aliphatic group or a cyclic compound group having at least one organic group selected from an alkenyl group, an alkynyl group, and a hydroxyl group include maleic anhydride and methyl maleic acid. Glycolic anhydride, 2,3-dimethyl maleic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydro Phthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, chloro bridge acid (HET acid) anhydride, 5-norbornene-2-carboxylic acid, 4-ethynyl phthalic anhydride and 4-phenylethynyl phthalic anhydride, 4-hydroxyphthalic anhydride, 4-hydroxybenzoic acid, 3- Hydroxybenzoic acid and so on. These can be used alone It can also be used in combination of two or more kinds, and a part of the capped amidine part can also be dehydrated and closed.

The method is not limited, and the polyamidoresin-based resin may be used by using an amine derivative containing an aliphatic group or a cyclic compound group having at least one organic group selected from alkenyl, alkynyl, and hydroxyl groups. The terminal carboxylic acid residue contained in the terminal is capped with amidine.

Furthermore, in the case of the polyamide resin represented by the above-mentioned general formula (11), it is possible to have at least one end of the terminal to such an extent that it does not affect the mechanical properties and heat resistance of the cured product cured at a low temperature. A group obtained by capping with a nitrogen-containing cyclic compound. Thereby, the adhesiveness with metal wiring (especially copper wiring) etc. can be improved.

Examples of the nitrogen-containing cyclic compound include 1- (5-1H-triazolyl) methylamino, 3- (1H-pyrazolyl) amino, and 4- (1H-pyrazolyl) amine. Base, 5- (1H-pyrazolyl) amino, 1- (3-1H-pyrazolyl) methylamino, 1- (4-1H-pyrazolyl) methylamino, 1- (5 -1H-pyrazolyl) methylamino, (1H-tetrazol-5-yl) amino, 1- (1H-tetrazol-5-yl) methylamino, 3- (1H-tetrazole- 5-yl) benzoamino and the like.

Such a polyamide resin having a structure represented by the general formula (11) can be selected from the group consisting of diamine, bis (aminophenol), 2,4-diaminophenol, and the like containing X in the general formula (11). A compound in Y is synthesized by reacting a compound selected from tetracarboxylic dianhydride, 1,2,4-tricarboxylic anhydride, dicarboxylic acid, dicarboxylic acid dichloride, or dicarboxylic acid derivative containing Y.

In addition, in the case of using a dicarboxylic acid, in order to improve the reaction yield of the polyamide resin, etc., the dicarboxylic acid may be reacted with 1-hydroxy-1,2,3-benzotriazole or the like in advance. A dicarboxylic acid derivative of the active ester type.

The polyfluorine resin having the structure represented by the general formula (11) can be heated to perform dehydration and ring closure, and the polyfluorine resin or polybenzo A heat-resistant resin is obtained in the form of an azole resin or a copolymer thereof. In addition, as the temperature for carrying out the dehydration closed loop, when heating is performed at a high temperature, processing can be performed at 280 ° C to 380 ° C, and when heating is performed at a low temperature, processing can be performed at 150 ° C to 280 ° C.

[Silane compound (B)]

The silane compound (B) used in this embodiment is represented by the following general formula (1).

A 〔Si (R1) _a (OR2) _b 〕 _m 〔Si (R3) _c (OR4) _d 〕 _n (1)

(In the formula, A represents a (m + n) -valent organic group having a cyclic structure, R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, and R2 and R4 represent A substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a and b represent 0 to 3 that satisfy a + b = 3 Integers, c and d represent integers from 0 to 3 that satisfy c + d = 3, m and n represent integers from 0 to 2, m + n ≠ 0)

Regarding the silane compound (B) represented by the formula (1), since A in the formula (1) is an organic group having a cyclic structure, the adhesion and transparency of the photosensitive resin composition can be improved. That is, since A in the formula (1) is an organic group having a rigid cyclic structure, the adhesion with the support can be improved, and further, since it is an organic group having a cyclic structure with a large volume, the sensitivity can be improved. Transparency of the resin composition.

The silane compound (B) is not particularly limited, and preferably, the cyclic structure of A in Formula (1) and Si in Formula (1) are directly bonded. By having such a structure, the effect of improving the adhesion and transparency benefiting from the ring structure can be achieved more effectively.

The silane compound (B) is not particularly limited, and a and c are preferably 0 or more and 1 or less, and b and d are preferably 2 or more and 3 or less. By being in the said range, adhesiveness can be improved further.

The silane compound (B) is not particularly limited, and R1 and R3 are preferably an organic group selected from a hydrogen atom, a methyl group, and an ethyl group. By having such an organic group, the effect of improving adhesiveness and transparency can be further enhanced.

The silane compound (B) is not particularly limited, and R2 and R4 are preferably an organic group selected from a hydrogen atom, a methyl group, and an ethyl group. By having such an organic group, the effect of improving adhesiveness and transparency can be further enhanced.

The silane compound (B) is not particularly limited. From the viewpoint of further improving the adhesiveness, m and n are preferably 1 or more and 2 or less. From the viewpoint of further improving the transparency, m and n are more preferable. It is preferably 0 or more and 1 or less.

The silane compound (B) is not particularly limited, and a compound represented by the following formula (17) can be preferably used, for example, from the viewpoint of improving the adhesiveness and transparency with good balance.

(In the formula, A 'represents a divalent organic group having a cyclic structure, and the cyclic structure is directly connected to the Si atom. Bonding. A "represents a monovalent organic group having a cyclic structure, which is directly bonded to the Si atom; R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, R2 and R4 represent substituted or unsubstituted saturated alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted unsaturated alkyl groups having 1 to 10 carbon atoms, and a and b represent those satisfying a + b = 3. Integers from 0 to 3, c and d represent integers from 0 to 3 that satisfy c + d = 3)

The silane compound (B) is not particularly limited, and from the viewpoint of further improving the adhesiveness, it is preferred that A in the formula (1) is an organic group having an aromatic ring. The aromatic ring is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a fluorene ring, and an anthracene ring. From the viewpoint of further improving the adhesiveness, it is considered that a structure including a plurality of aromatic rings becomes a more rigid structure and the adhesiveness is further improved. Among them, an organic group selected from the organic group group represented by the following formula (2) is preferred, and the adhesiveness and transparency can be improved in a good balance.

(In the formula, X1 represents a single bond, C (-Y1) (-Y2), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing amidino group, and Y1 and Y2 each independently represent a hydrogen atom, Trifluoromethyl, substituted or unsubstituted saturated alkyl having 1 to 10 carbons, substituted or unsubstituted unsaturated alkyl having 1 to 10 carbons, substituted or unsubstituted phenyl, Or substituted or unsubstituted cyclohexyl)

The silane compound (B) represented by the formula (1) is not particularly limited when the organic group having an aromatic ring is contained in A in the formula (1), and the following formula is preferred. (18) A monovalent or divalent organic group.

(In the formula, X1 represents a single bond, C (-Y1) (-Y2), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing amidino group, and Y1 and Y2 each independently represent a hydrogen atom, Trifluoromethyl, substituted or unsubstituted saturated alkyl having 1 to 10 carbons, substituted or unsubstituted unsaturated alkyl having 1 to 10 carbons, substituted or unsubstituted phenyl, Or substituted or unsubstituted cyclohexyl)

In addition, the silane compound (B) is not particularly limited. From the viewpoint of further improving transparency, it is preferable that A in the formula (1) is an organic group having an aliphatic ring. The aliphatic ring is not particularly limited, and examples thereof include monocyclic rings such as cyclohexane, bicyclic rings such as dicyclopentane, and polycyclic rings such as adamantane. By having a plurality of aliphatic rings, adhesion and transparency can be improved in a good balance. Among them, an organic group selected from the organic group group represented by the following formula (3) is preferable, and adhesion and transparency can be further improved.

(In the formula, X2 represents a single bond, C (-Y3) (-Y4), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing amidino group, and Y3 and Y4 each independently represent a hydrogen atom, Trifluoromethyl, Substituted or unsubstituted saturated alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted unsaturated alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted phenyl group, or substituted or unsubstituted (Substituted cyclohexyl)

The silane compound (B) represented by the formula (1) is not particularly limited when the organic group having an aliphatic ring is contained in A in the formula (1). Among them, the following formula (19) is preferred It is a monovalent or divalent organic group.

(In the formula, X2 represents a single bond, C (-Y3) (-Y4), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing amidino group, and Y3 and Y4 each independently represent a hydrogen atom, Trifluoromethyl, substituted or unsubstituted saturated alkyl having 1 to 10 carbons, substituted or unsubstituted unsaturated alkyl having 1 to 10 carbons, substituted or unsubstituted phenyl, Or substituted or unsubstituted cyclohexyl)

Such a silane compound (B) is not particularly limited, and for example, a silane compound represented by the following formula (20) can be used.

The content of the silane compound (B) in the photosensitive resin composition of this embodiment The amount is not particularly limited, but is preferably 0.1 parts by mass or more and 50 parts by mass or less, and more preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total weight of the alkali-soluble resin (A). When the addition amount is within the above range, sufficient adhesion and transparency can be exhibited.

[Photo acid generator (C)]

The photoacid generator (C) used in this embodiment is a compound that generates an acid by light. For example, a positive-type patterning photosensitizer can be used, and it is preferably 200 to 500 nm by irradiation. The wavelength is particularly preferably a compound that generates an acid by actinic rays having a wavelength of 350 to 450 nm.

Specifically, an onium salt such as a photosensitive diazoquinone compound, a diarylsulfonium salt, a triarylsulfonium salt, a sulfonium borate, a 2-nitrobenzyl ester compound, an N-iminosulfonate compound, or the like can be used.醯 Imine sulfonate compound, 2,6-bis (trichloromethyl) -1,3,5-tri Compounds, dihydropyridine compounds, and the like. Among these, a photosensitive diazoquinone compound excellent in sensitivity and solvent solubility is preferable.

Examples of the photosensitive diazoquinone compound include a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. ester.

In the case of a positive type, it is considered that the photoacid generator remaining in the relief pattern of the unexposed portion is decomposed by heat during hardening to generate an acid, and the photoacid generator also plays an important role as a reaction accelerator. In the case of such a photosensitive diazoquinone compound, an ester of 1,2-naphthoquinone-2-diazide-4-sulfonic acid which is more easily decomposed by heat is preferable.

The content of the photoacid generator (C) in the photosensitive resin composition of this embodiment is not particularly limited, and is preferably 1 part by mass or more and 50 parts by mass relative to 100 parts by mass of the total weight of the alkali-soluble resin (A). It is preferably 5 parts by mass or more and 20 parts by mass or less. When the addition amount is within the above range, good patterning performance can be exhibited.

[Phenol resin (D)]

The photosensitive resin composition of this embodiment may contain the phenol resin (D) obtained by making a phenol compound and an aromatic aldehyde compound react as needed. In the phenol resin (D), by using an aromatic aldehyde compound, it is possible to suppress intramolecular rotation, and to impart high heat resistance to the cured film in this embodiment. In addition, even if the dimer and trimer remain, the molecular weight of the dimer and trimer is higher than that of the phenol resin obtained by reacting formaldehyde, and the heat resistance of the cured film can be kept high. In this way, by including the phenol resin (D), the heat resistance and mechanical characteristics of the obtained cured film can be improved, and more excellent heat resistance and mechanical characteristics can be achieved as a protective film and an insulating film.

The aromatic aldehyde compound is preferably an aromatic aldehyde compound represented by the following general formula (4).

(In the formula, R ₁ represents an organic group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and a hydroxyl group, and t is an integer of 0 to 3)

As said aromatic aldehyde compound, the aromatic aldehyde compound which is unsubstituted or has 3 or less substituents is used. Examples of the substituent include organic groups selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and a hydroxyl group. Examples of the alkyl group and alkoxy group having 1 to 20 carbon atoms include methyl, ethyl, propyl, methoxy, and ethoxy groups. As such an aromatic aldehyde compound, for example, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 2,3-dimethylbenzaldehyde, 2,4-bis Methylbenzaldehyde, 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-tri Methylbenzaldehyde, 3,4,5-trimethylbenzaldehyde, 4-ethylbenzaldehyde, 4-tert-butylbenzaldehyde, 4-isobutylbenzaldehyde, 4-methoxybenzaldehyde, water salicylaldehyde oxime, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 3-methyl-salicylaldehyde oxime, 4 ^- methyl salicyl aldoxime, 2-hydroxy-5-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2 2,5-Dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, etc. are not limited to these. Among these, an aromatic aldehyde compound in which R ₁ in the general formula (4) is hydrogen, methyl, or hydroxyl is preferable, and one selected from the aromatic aldehyde compounds represented by the following formula (21) is more preferable. . Furthermore, these aldehydes can be used alone or in combination of two or more.

As the phenol compound used in the phenol resin (D), the same phenol compound used in the novolac-type phenol resin in the alkali-soluble resin (A) can be used. Examples include: phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2 Dimethylphenols such as 1,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol Class; alkylphenols such as isopropylphenol, butylphenol, p-tert-butylphenol; etc. In addition, resorcinol, catechol, hydroquinone, catechol, resorcinol, etc. Polyphenols are not particularly limited. These phenols can be used individually or in combination of 2 or more types.

The phenol compound used in the phenol resin (D) is not particularly limited, and is preferably A phenol resin obtained by reacting a phenol compound represented by the following general formula (5) with an aromatic aldehyde compound. With such a configuration, it is possible to provide a photosensitive resin composition having more excellent heat resistance and mechanical properties as a protective film or an insulating film.

(In the formula, X3 represents a single bond, C (-Y7) (-Y8), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing amidino group. Y7 and Y8 each independently represent a hydrogen atom, Trifluoromethyl, substituted or unsubstituted saturated alkyl having 1 to 10 carbons, substituted or unsubstituted unsaturated alkyl having 1 to 10 carbons, substituted or unsubstituted phenyl, Or substituted or unsubstituted cyclohexyl, Y5 and Y6 each independently represent a substituted or unsubstituted saturated alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted unsaturated alkyl group having 1 to 20 carbon atoms Group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted phenyl group, or substituted or unsubstituted cyclohexyl group; p and q each independently represent 1 to 3 Integer, r and s each independently represent an integer of 0 ~ 3)

The substituents Y5 and Y6 of the bisphenol compound represented by the above general formula (5) are independently It is selected from a substituted or unsubstituted saturated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted unsaturated alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted carbon number 1 to 20 alkoxy, substituted or unsubstituted phenyl, or organic groups in substituted or unsubstituted cyclohexyl. The bisphenol compound is not particularly limited, and it is preferably selected from bisphenols represented by the following formula (22). Furthermore, these bisphenols can be used individually or in mixture of 2 or more types. By using the above-mentioned bisphenol compound, the intramolecular rotation is suppressed, and sufficient heat resistance required for the photosensitive resin composition is provided, and at the same time, the molecular structure is flexible, thereby obtaining a phenol resin having sufficient elongation characteristics.

In the synthesis reaction of the phenol resin (D), it is preferred that the aldehyde compound is reacted at 0.5 mol or more and 2 mol or less with respect to the phenol compound 1 mol, and more preferably 0.6 mol or more and 1.2 mol. The reaction is performed below the ear, and particularly preferably, the reaction is performed at 0.7 mol or more and 1.0 mol or less. By setting the molar ratio as described above, a molecular weight capable of exhibiting sufficient characteristics as a photosensitive resin composition can be obtained.

In the synthesis reaction of the phenol resin (D), an acid catalyst is preferably used. By using an acid catalyst, novolac-type phenol resins can usually be synthesized, and novolac-type phenol resins are easily synthesized. Adjust molecular weight or hydroxyl concentration. Examples of the acid catalyst used in the synthesis reaction of the phenol resin (D) include oxalic acid, nitric acid, sulfuric acid, diethyl sulfate, acetic acid, p-toluenesulfonic acid, phenolsulfonic acid, benzenesulfonic acid, and xylenesulfonic acid. Acids and the like are not limited thereto. Among these, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, and sulfuric acid are preferred in terms of reactivity. The addition amount is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the phenol addition amount, and more preferably 0.5 parts by mass or more and 8 parts by mass or less.

The polycondensation reaction in the synthesis of the phenol resin (D) is performed by stirring under heating for several hours. The reaction temperature is preferably 50 ° C to 160 ° C. Moreover, you may add a solvent at the time of reaction, and may perform a reaction in a 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 pentanone; diethyl Ethers such as glycol monomethyl ether acetate; tetrahydrofuran, di Cyclic ethers such as alkane; lactones such as γ-butyrolactone; pure water and the like, but are not limited to these. 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 addition amount.

After the reaction is completed, by using a base such as pyridine, triethylamine, sodium hydroxide, etc., The acid catalyst is neutralized. If necessary, the neutralized salt is extracted into the water layer and removed, and then dehydration and monomer removal steps are performed to recover it.

After the synthesis of the phenol resin (D), a monomer removal step is usually performed. single The method for removing the solid can be selected from a solvent fractionation method in which a solvent and water are added and the water layer is removed, or a method in which the monomer is volatilized by heating while reducing the pressure. In the above-mentioned solvent fractionation method, a solvent such as acetone, methanol, isopropanol, and butanol, which is a good solvent for phenol resin, and a solvent, such as pure water, which is a poorly soluble solvent for phenol resin, are added and stirred at a certain ratio. Will be left behind The separated water layer is removed, whereby the monomers moving to the water layer side can be removed. In the method for volatilizing the above monomer, the pressure may be reduced to 50 mmHg or less while heating and stirring at 150 ° C to 250 ° C to volatilize and remove the monomer. When the monomer is volatilized and removed, a solvent, pure water, water vapor, nitrogen, etc. may be added in order to improve the monomer removal efficiency. The solvent at this time 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, and propylene glycol alkyl ether acetate. , Diethylene glycol, diethylene glycol alkyl ether, triethylene glycol, triethylene glycol alkyl ether and other diols, γ-butyrolactone, γ-valerolactone, δ-valerolactone, etc. Esters, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, dimethylmethane, Polar aprotic solvents such as dimethylimidazolidone. Based on the fractionation method and the monomer volatilization method, the operation can be repeated based on the residual amount of the monomer to improve the removal efficiency of the monomer.

The phenol resin (D) obtained in the above manner was subjected to gel permeation chromatography. The measured polystyrene-equivalent weight average molecular weight is preferably 500 or more and 10,000 or less, and more preferably 700 or more and 7,000 or less. When the weight average molecular weight is more than the above-mentioned lower limit value, the heat resistance and film toughness of the photosensitive resin composition can be further improved. In addition, if the weight average molecular weight is equal to or less than the above-mentioned upper limit value, residues generated in the openings due to patterning can be further suppressed.

In addition, the phenol resin (D) obtained in the above manner can be finally made into chips or The solvent was recovered and recovered. Examples of the solvent that can be recovered as a solvent solubilized substance include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamidamine, and dimethylsulfine. , 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 ,milk Butyl ester, methyl-1,3-butanediol acetate, 1,3-butanediol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, and methyl 3-methoxypropionate Ester and the like can be used alone or in combination.

A phenol resin (D) is contained in the photosensitive resin composition of this embodiment. In this case, the content of the phenol resin (D) is not particularly limited, and is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 100 parts by mass of the total weight of the alkali-soluble resin (A). 25 parts by mass or more. The amount is preferably 1900 parts by mass or less, more preferably 400 parts by mass or less, and still more preferably 150 parts by mass or less. Moreover, it is preferably 5 parts by mass or more and 400 parts by mass or less, more preferably 25 parts by mass or more and 400 parts by mass or less, and still more preferably 25 parts by mass or more and 150 parts by mass or less. When the addition amount is within the above range, good patterning performance and hardenability can be exhibited with good balance.

The weight ratio (A / D) of the alkali-soluble resin (A) to the phenol resin (D) is preferably 5/95 or more, more preferably 20/80 or more, and even more preferably 40/60 or more. In addition, it is preferably 95/5 or less, more preferably 90/10 or less, and even more preferably 80/20 or less. Furthermore, it is preferably 20/80 or more and 95/5 or less, more preferably 20/80 or more and 80/20 or less, and still more preferably 40/60 or more and 80/20 or less. By using together in this range, favorable characteristics as a photosensitive resin composition can be achieved. When the weight ratio (A / D) is at least the above-mentioned lower limit value, the heat resistance and film characteristics required as a photosensitive resin composition can be further improved. If the weight ratio (A / D) is equal to or less than the above-mentioned upper limit value, the sensitivity during patterning can be increased, and the yield can be further increased.

[Solvent]

The photosensitive resin composition of the present embodiment can be used by dissolving each of the above-mentioned components in a solvent to make it a varnish. Examples of such a solvent include N-methyl-2-pyrrolidone and γ-butane. Lactone, N, N-dimethylacetamidamine, dimethyl sulfene, 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-butanediol acetate, 1,3-butanediol-3-monomethyl ether Ether, methyl pyruvate, ethyl pyruvate, and methyl 3-methoxypropionate can be used alone or in combination.

The content of the solvent in the photosensitive resin composition of this embodiment is not particularly limited. Limitation is preferably 50 parts by mass or more and 300 parts by mass or less, more preferably 100 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A). When the addition amount is within the above range, a varnish with sufficient resin dissolution and high handleability can be produced.

[Heat crosslinker (E)]

The photosensitive resin composition of this embodiment may further contain a thermal crosslinking agent (E). The thermal crosslinking agent (E) is not particularly limited as long as it is a compound having a group capable of reacting with the alkali-soluble resin (A) and / or phenol resin (D) by heat, and may be, for example, Examples: from 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,3,5-benzenetrimethanol, 4,4-biphenyldimethanol, 2,6- Pyridyldimethanol, 2,6-bis (hydroxymethyl) -p-cresol, 4,4'-methylenebis (2,6-dialkoxymethylphenol), etc. Compounds; from 1,4-bis (methoxymethyl) 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) and other compounds having alkoxymethyl; hydroxymethylmelamine compounds represented by hexamethylolmelamine, hexabutanolmelamine, etc .; and hexamethoxy Alkoxymelamine compounds represented by melamine, etc .; Alkoxymethyl glycoluril compounds represented by tetramethoxymethyl glycoluril, etc .; Hydroxymethyl urea compounds represented by guanguanamine compounds, dimethylol vinyl urea, etc .; cyano compounds represented by dicyanoaniline, dicyanophenol, cyanophenylsulfonic acid, etc .; by 1,4 -Isocyanate compounds represented by phenylene diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, etc .; ethylene glycol diglycidyl ether, bisphenol A bicyclic Oxypropyl ether, triglycidyl isocyanurate, bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, phenol novolac Epoxy-containing compounds represented by resin-type epoxy resins, etc .; composed of N, N'-1,3-phenylene dicis butylene diimide, N, N'-methylene dicis butene The cis-butene diimide compounds represented by diammonimine and the like are not limited thereto. These thermal crosslinking agents can be used singly or in combination of two or more kinds.

Content of the thermal crosslinking agent (E) in the photosensitive resin composition of this embodiment Although it does not specifically limit, 1 mass part or more and 50 mass parts or less is preferable with respect to 100 mass parts of alkali-soluble resin (A), More preferably, it is 2 mass parts or more and 20 mass parts or less. When the addition amount is within the above range, a cured film having excellent residual film rate and heat resistance during curing can be formed.

[Silane coupling agent (F)]

From the viewpoint of further improving the adhesion, in the photosensitive resin composition of this embodiment, a silane coupling agent different from the silane compound (B) (hereinafter also referred to as " Is a silane coupling agent (F)). Examples of such a silane coupling agent (F) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidyl Oxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N -2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3- Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Trimethoxysilane, bis (triethoxypropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, and by reacting a silicon compound having an amine group with an acid dianhydride or anhydride The obtained silicon compounds and the like are not limited thereto.

The silicon compound having an amine group is not particularly limited, and examples thereof include Examples: 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, and the like.

The acid dianhydride or acid anhydride is not particularly limited, and examples thereof include anhydrous maleic acid, chlorine anhydrous maleic acid, cyano anhydrous maleic acid, and methyl maleic acid (Citraconic acid), phthalic anhydride, pyrolite anhydride, 4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-carbonyldiphthalate Phthalic anhydride and so on. When used, they can be used alone or in combination of two or more.

When the silane coupling agent (F) is contained in the photosensitive resin composition, the amount of the silane coupling agent (F) to be added is not particularly limited, and it is preferably 100 parts by mass based on the weight of the alkali-soluble resin (A). 0.05 to 50 parts by mass, more preferably 0.1 to 20 parts by mass. When the addition amount is within the above range, it is possible to suitably have both the adhesiveness with the substrate and the preservation property of the photosensitive resin composition.

[Solution accelerator]

Moreover, the photosensitive resin composition of this embodiment may contain a dissolution accelerator.

The dissolution accelerator can improve the exposure of the coating film formed using the photosensitive resin composition. The solubility of the developing solution improves the foaming component during patterning.

As the dissolution promoter, a compound having a phenolic hydroxyl group is particularly preferred.

[Other ingredients]

In addition, to the photosensitive resin composition of this embodiment, additives such as an antioxidant, a filler, a surfactant, a photopolymerization initiator, a blocking agent, and a sensitizer may be added as necessary.

The ratio of each component in the said photosensitive resin composition is as follows, for example.

When the total solid content of the photosensitive resin composition (ie, components other than the solvent) is 100% by mass, the ratio of the alkali-soluble resin (A) is preferably 20% by mass to 95% by mass. The ratio of the silane compound (B) is from 0.1% by mass to 30% by mass, and the ratio of the photoacid generator (C) is from 1% by mass to 30% by mass.

More preferably, the ratio of the alkali-soluble resin (A) is 30% by mass or more and 90% by mass or less, the ratio of the silane compound (B) is 0.5% by mass or more and 20% by mass or less, and the ratio of the photoacid generator (C) is 5 mass% or more and 20 mass% or less.

When the phenol resin (D) is further contained, the ratio of the alkali-soluble resin (A) is 30% by mass or more and 90% by mass or less, and the ratio of the silane compound (B) is 0.1% by mass or more and 30% by mass or less. The ratio of the acid generator (C) is 1% by mass to 30% by mass, and the ratio of the phenol resin (D) is 1% by mass to 30% by mass.

The photosensitive resin composition is prepared by mixing and dissolving an alkali-soluble resin (A), a silane compound (B), a photoacid generator (C), and other components as necessary in an organic solvent. In this embodiment, for example, the photosensitive resin composition can be prepared by mixing and dissolving each component in an organic solvent under a nitrogen gas flow. In addition, it can also be fed under a nitrogen gas flow, for example. Synthesis of alkali soluble resin (A). By suppressing the amount of oxygen or moisture mixed into the photosensitive resin composition as described above, the characteristics of the photosensitive resin composition can be improved.

[Hardened film]

An example of the method of using the photosensitive resin composition of this embodiment is shown below.

The photosensitive resin composition of this embodiment can be cured to form a cured film. Specifically, the composition is first applied to an appropriate support, such as a silicon wafer, a ceramic substrate, or an aluminum substrate. Regarding the coating amount, when coating on a semiconductor element, the coating is usually performed so that the final film thickness after curing becomes 0.1 to 30 μm. By setting it as such a numerical range, it can fully function as a protective film and an insulating film of a semiconductor element, and obtain a fine convex pattern.

Examples of the coating method include spin coating using a spin coater, spray coating using a spray coater, dipping, printing, and roll coating.

Next, after pre-baking at 60 to 130 ° C. to dry the coating film, when a relief pattern is formed, actinic rays are irradiated in a desired pattern shape. As actinic rays, X-rays, electron beams, ultraviolet rays, visible light, and the like can be used, and those having a wavelength of 200 to 500 nm are preferred.

Secondly, the irradiated portion is dissolved and removed with a developing solution to obtain a relief pattern. case. As the developer, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia can be suitably used; primary amines such as ethylamine and n-propylamine; diethyl Secondary amines such as amines and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide and Aqueous solutions of alkalis such as quaternary ammonium salts such as tetraethylammonium hydroxide; and aqueous solutions prepared by appropriately adding water-soluble organic solvents such as methanol and ethanol or surfactants to these. As a developing method, spray, paddle, or dip Stains, ultrasound, etc.

Next, the relief pattern formed by development is washed. Use distilled water as the rinse solution. Next, heat treatment (curing) is performed to obtain a cured film that is a cured product excellent in heat resistance.

The heat treatment may be either high temperature or low temperature. The heat treatment temperature at high temperature is preferably 280 ° C to 380 ° C, and more preferably 290 ° C to 350 ° C. The heat treatment temperature at a low temperature is preferably 150 ° C to 280 ° C, and more preferably 180 ° C to 260 ° C. The heat treatment uses an oven, a hot plate, a furnace, infrared rays, microwaves, and the like.

The light transmittance T (%) of a cured product obtained by heating and curing the photosensitive resin composition with respect to light having a wavelength of 630 nm in terms of a film thickness of 10 μm is preferably 75% or more, and more preferably 78% or more. It is preferably 80% or more, particularly preferably 82% or more, and still more preferably 85% or more. The upper limit of the light transmittance T (%) in terms of a film thickness of 10 μm in terms of a film thickness of 630 nm is not particularly limited, and is, for example, 99% or less. If the light transmittance T (%) of the hardened material with respect to the light having a wavelength of 630 nm in terms of a film thickness of 10 μm is within the above range, the visibility of the adherend such as a semiconductor element or a display element as a support can be improved. , And can improve the productivity of semiconductor devices or display devices. The measurement of the light transmittance is performed using, for example, a general UV spectrophotometer, for example, UV-160A manufactured by Shimadzu Corporation. The measured light transmittance can be converted to a film thickness of 10 μm by, for example, the Lambert-Beer rule.

The glass transition temperature of the differential scanning calorimetry (heating rate 5 ° C / min) of the cured product obtained by heating and curing the photosensitive resin composition is preferably 200 ° C or higher, more preferably 220 ° C or higher, and even more preferably 250 Above ℃. The upper limit of the glass transition temperature is not particularly limited The temperature is, for example, 400 ° C or lower. When the glass transition temperature of the hardened material is within the above range, the heat resistance and mechanical properties of the obtained hardened film can be further improved.

A cured product obtained by heating and curing the photosensitive resin composition Inch: 10mm × 60mm × 10μm thick) The elongation of the tensile test (elongation speed: 5mm / min) is preferably 20% or more, more preferably 30% or more. The upper limit of the tensile elongation is not particularly limited, and is, for example, 300% or less. If the elongation of the hardened material is within the above range, the risk of cracking due to stress during film deformation can be reduced, and the reliability as a protective film can be further improved.

The tensile elastic modulus of a tensile test (elongation speed: 5 mm / min) of a cured product (size: 10 mm × 60 mm × 10 μm thick) obtained by heating and curing the photosensitive resin composition is preferably 0.5 GPa or more and 10 GPa or less. Hereinafter, it is more preferably 1.0 GPa or more and 8.0 GPa or less. If the tensile elastic modulus of the hardened material is within the above range, the obtained hardened film can have sufficient strength, and the reliability as a protective film can be further improved.

<Use>

Next, applications of the photosensitive resin composition will be described.

The cured film formed using the photosensitive resin composition of this embodiment is not only It is useful as a semiconductor device such as a semiconductor element, as a display device such as a TFT liquid crystal or an organic EL, as an interlayer insulating film for a multilayer circuit or as a cover coat for a flexible copper foil, a solder resist film, or a liquid crystal alignment film.

As an example of the use of a semiconductor device, formation on a semiconductor element may be mentioned. The passivation film formed of the cured film of the photosensitive resin composition, the protective film such as a buffer coating film formed by forming the cured film of the photosensitive resin composition on the passivation film, and the above is formed on a circuit formed on a semiconductor element. Insulating films such as interlayer insulating films made of cured films of photosensitive resin compositions, Alpha ray blocking film, flattening film, protrusion (resin column), partition wall, and the like.

As an example of the use of the display device, there is a method of forming the display device on the display device. A protective film made of a cured film of the photosensitive resin composition of the embodiment, an insulating film or a flattening film for a TFT element or a color filter, a protrusion for a MVA type liquid crystal display device, a cathode for an organic EL element, etc. The partition wall and so on.

The method of use depends on the method for forming a patterned photosensitive resin composition layer on a substrate on which a display element or a color filter is formed according to the use of a semiconductor device. High display transparency is required for display device applications, especially for insulating films or flattening films. It can also be obtained by introducing a post-exposure step before curing the coating film of the photosensitive resin composition of this embodiment. A resin layer having excellent transparency is more practically preferred.

As a semiconductor device, a semiconductor wafer (element Pieces), and use air-tight seals or mold materials for sealing. Specific examples include transistors, solar cells, diodes, solid-state imaging devices, various semiconductor packages in which semiconductor wafers are laminated and sealed, and wafer-level wafer-scale packages (WLP).

Examples of the display device include a TFT-type liquid crystal, an organic EL, and a color filter. An example of an electronic device having a film formed using the photosensitive resin composition of this embodiment will be described below.

<Electronic device>

1 and 2 are cross-sectional views each showing an example of an electronic device 100 according to this embodiment. In each of them, a part including the insulating film in the electronic device 100 is exemplified.

The electronic device 100 according to this embodiment is formed by, for example, a cured film formed using the photosensitive resin composition of this embodiment to form the insulating film.

As an example of the electronic device 100 according to this embodiment, a liquid crystal is illustrated in FIG. 1. Display device. However, the electronic device 100 according to this embodiment is not limited to a liquid crystal display device, and includes other electronic devices including a permanent film made of the photosensitive resin composition of this embodiment.

As shown in FIG. 1, an electronic device 100 as a liquid crystal display device includes, for example, a substrate 10, a transistor 30 provided on the substrate 10, an insulating film 20 provided on the substrate 10 so as to cover the transistor 30, and The wiring 40 on the insulating film 20.

The substrate 10 is, for example, a glass substrate.

The transistor 30 is, for example, a thin film transistor constituting a switching element of a liquid crystal display device. On the substrate 10, a plurality of transistors 30 are arranged in an array, for example. The transistor 30 in this embodiment includes, for example, a gate electrode 31, a source electrode 32, a drain electrode 33, a gate insulating film 34, and a semiconductor layer 35. The gate electrode 31 is provided on the substrate 10, for example. The gate insulating film 34 is provided on the substrate 10 so as to cover the gate electrode 31. The semiconductor layer 35 is provided on the gate insulating film 34. The semiconductor layer 35 is, for example, a silicon layer. The source electrode 32 is provided on the substrate 10 so that a part of the source electrode 32 is in contact with the semiconductor layer 35. The drain electrode 33 is provided on the substrate 10 so as to be separated from the source electrode 32 and part of the drain electrode 33 is in contact with the semiconductor layer 35.

The insulating film 20 functions as a flattening film for eliminating a step difference caused by the transistor 30 and the like to form a flat surface on the substrate 10. The insulating film 20 is made of a cured product of the photosensitive resin composition of this embodiment. The insulating film 20 is provided with an opening 22 penetrating the insulating film 20 so as to be connected to the drain electrode 33.

A wiring 40 connected to the drain electrode 33 is formed on the insulating film 20 and in the opening 22. The wiring 40 functions as a pixel electrode constituting a liquid crystal and a pixel.

An alignment film 90 is provided on the insulating film 20 so as to cover the wiring 40.

An opposing substrate 12 is disposed above the one surface of the substrate 10 on which the transistor 30 is provided, so as to oppose the substrate 10. A wiring 42 is provided on a surface of the counter substrate 12 that faces the substrate 10. The wiring 42 is provided at a position facing the wiring 40. An alignment film 92 is provided on the above-mentioned surface of the counter substrate 12 so as to cover the wiring 42.

Liquid crystal constituting the liquid crystal layer 14 is filled between the substrate 10 and the opposite substrate 12.

The electronic device 100 shown in FIG. 1 is formed in the following manner, for example.

First, a transistor 30 is formed on a substrate 10. Then, on one surface of the substrate 10 on which the transistor 30 is provided, a photosensitive resin composition is applied by a printing method or a spin coating method to form an insulating film 20 covering the transistor 30. Thereby, a planarization film covering the transistor 30 provided on the substrate 10 is formed.

Then, the insulating film 20 is exposed and developed, and an opening 22 is formed in a part of the insulating film 20. At this time, the unexposed portion was dissolved in the developing solution, and the exposed portion remained. This aspect is the same in each example of the electronic device 100 described below.

Then, the insulating film 20 is heat-hardened. Then, a wiring 40 connected to the drain electrode 33 is formed in the opening 22 of the insulating film 20. Thereafter, a counter substrate 12 is disposed on the insulating film 20, and liquid crystal is filled between the counter substrate 12 and the insulating film 20 to form a liquid crystal layer 14.

Thereby, the electronic device 100 shown in FIG. 1 is formed.

In addition, as an example of the electronic device 100 according to this embodiment, FIG. 2 illustrates a semiconductor device in which a redistribution layer 80 is formed by a permanent film made of a photosensitive resin composition.

The electronic device 100 shown in FIG. 2 includes a semiconductor substrate provided with a semiconductor element such as a transistor. And a multilayer wiring layer (not shown) provided on the semiconductor substrate. In the uppermost layer among the multilayer wiring layers, an insulating film 50 as an interlayer insulating film and an uppermost wiring 72 provided on the insulating film 50 are provided. The uppermost wiring 72 is made of, for example, aluminum (Al).

A redistribution layer 80 is provided on the insulating film 50. The redistribution layer 80 has: The insulating film 52 is provided on the insulating film 50 so as to cover the uppermost wiring 72; the rewiring 70 is provided on the insulating film 52; the insulating film 54 is provided on the insulating film 52 and the rewiring 70.

An opening 24 is formed in the insulating film 52 to be connected to the uppermost layer wiring 72. The rewiring 70 is formed on the insulating film 52 and inside the opening 24, and is connected to the uppermost wiring 72. The insulating film 54 is provided with an opening 26 connected to the rewiring 70.

The insulating film 52 and the insulating film 54 are composed of a permanent film composed of a photosensitive resin composition. The insulating film 52 can be obtained, for example, by exposing and developing the photosensitive resin composition coated on the insulating film 50 to form the opening 24 and then heat-hardening the opening 24. In addition, the insulating film 54 can be obtained, for example, by exposing and developing the photosensitive resin composition applied on the insulating film 52 to form the openings 26 and then heating and curing them.

A bump 74 is formed in the opening 26, for example. The electronic device 100 is connected to a wiring substrate or the like via a bump 74, for example.

Furthermore, the electronic device 100 according to this embodiment may be an optical device in which a microlens is formed by using a permanent film made of a photosensitive resin composition. Examples of the optical device include a liquid crystal display device, a plasma display, a field emission display, and an electroluminescence display.

The embodiments of the present invention have been described above, but these are the For example, various configurations other than the above may be adopted.

In addition, the present invention is not limited to the above-mentioned embodiments, and modifications, improvements, and the like within a range that can achieve the object of the present invention are included in the present invention.

[Example]

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited thereto.

<Synthesis of alkali-soluble resin (A-1)>

To a four-neck separable flask equipped with a thermometer, a stirrer, a raw material input port, and a dry nitrogen introduction tube, 21.43 g (0.083 mole) of diphenyl ether-4,4'-dicarboxylic acid and 1-hydroxyl- 40.87 g (0.083 mole) of a mixture of dicarboxylic acid derivatives obtained by reacting 22.43 g (0.166 mole) of 1,2,3-benzotriazole monohydrate and hexafluoro-2,2-bis ( 36.62 g (0.100 mole) of 3-amino-4-hydroxyphenyl) propane was added, and 296.96 g of N-methyl-2-pyrrolidone was added to dissolve it. Then, it reacted at 75 degreeC using the oil bath for 15 hours.

Next, 6.98 g (0.0425 mol) of 3,6-endemethylene-1,2,3,6-tetrahydrophthalic anhydride dissolved in 34.88 g of N-methyl-2-pyrrolidone was added. , And further stirred for 3 hours to complete the reaction.

After filtering the reaction mixture, put the reaction mixture into a solution of water / isopropanol = 3/1 (volume ratio), collect the precipitate by filtration, wash it thoroughly with water, and then dry it under vacuum to obtain the target Polyamine resin (alkali soluble resin (A-1)). The weight-average molecular weight of the obtained compound was 13,040.

<Synthesis of Alkali Soluble Resin (A-2)>

Divided into four ports with thermometer, mixer, raw material input port and dry nitrogen inlet pipe In a separable flask, 30.0 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added, and 400 ml of acetone was added to dissolve it.

Next, 12.4 g (0.18 mol) of p-nitrobenzidine chloride dissolved in 100 mL of acetone was cooled while the temperature became less than 20 ° C, and the mixture was added dropwise over 30 minutes to obtain a mixture. After the dropwise addition, the temperature of the mixture was heated to 40 ° C. and stirred for 2 hours. Next, 30.0 g (0.218 mol) of potassium carbonate was slowly added, followed by stirring for 2 hours. The heating was stopped, and the mixture was further stirred at room temperature for 18 hours. Thereafter, while vigorously stirring the mixture, a sodium hydroxide aqueous solution was slowly added, and after the addition, the mixture was heated to 55 ° C and stirred for 30 minutes. After the stirring was completed, the mixture was cooled to room temperature, and a 37% by weight aqueous solution of hydrochloric acid and 500 ml of water were added, and the pH of the solution was adjusted to be within a range of 6.0 to 7.0. Next, the obtained precipitate was separated by filtration, and the filtrate was washed with water, and then dried at 60 to 70 ° C. to obtain bis-N, N '-(p-nitrobenzyl) hexafluoro-2. , 2-bis (4-hydroxyphenyl) propane as a solid.

To 51.0 g of the obtained solid, 316 g of acetone and 158 g of methanol were added, and Heat to 50 ° C to completely dissolve. 300 mL of pure water at 50 ° C was added thereto over 30 minutes, and heated to 65 ° C. Thereafter, it was slowly cooled to room temperature, and the precipitated crystals were filtered, and the crystals were purified by drying at 70 ° C to obtain bis-N, N '-(p-nitrobenzyl) hexafluoro. -2,2-bis (4-hydroxyphenyl) propane.

In a 1 L flask, add the bis-N, N '-(p-nitrobenzene) obtained above. 20 g of formamyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane was added, and 1.0 g of 5% palladium-carbon catalyst and 180.4 g of ethyl acetate were added to the suspension state. In this, the hydrogen was flushed, and while being heated to 50 to 55 ° C., it was shaken for 35 minutes to perform a reduction reaction. After the reaction was completed, the temperature was cooled to 35 ° C, and the suspension was flushed with nitrogen. After removing the catalyst by filtration, the filtrate was removed. Place on an evaporator and allow the solvent to evaporate. The obtained product was dried at 90 ° C to obtain bis-N, N '-(p-aminobenzyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane.

In the fourth with thermometer, mixer, raw material input port and dry nitrogen introduction tube In a separable flask, add 14.5 g (0.024 mol) of the bis-N, N '-(p-aminobenzo) hexafluoro-2,2-bis (4-hydroxyphenyl) propane obtained above. Then, 40 g of γ-butyrolactone was added to dissolve it, and while stirring, cooled to 15 ° C. To this, 6.8 g (0.022 mol) of 4,4'-oxydiphthalic anhydride and 12.0 g of γ-butyrolactone were added, and stirred at 20 ° C for 1.5 hours. Thereafter, after heating to 50 ° C and stirring for 3 hours, 5.2 g (0.044 mol) of N, N-dimethylformamide dimethyl acetal and 10.0 g of γ-butyrolactone were added, and the mixture was further stirred at 50 ° C for 1 hour. hour. After the reaction was completed, it was cooled to room temperature to obtain the desired polyamide resin (alkali soluble resin (A-2)). The weight-average molecular weight of the obtained compound was 13,200.

<Synthesis of Alkali Soluble Resin (A-3)>

In a four-necked round-bottomed flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen introduction tube, under a stream of dry nitrogen, 64.9 g (0.60 mole) of m-cresol and 43.3 g (0.40 mole) of p-cresol were added. , 65.1 g of a 30% by weight aqueous formaldehyde solution (formaldehyde 0.65 mol), and 0.63 g (0.005 mol) of oxalic acid dihydrate, and then immersed in an oil bath, while refluxing the reaction solution, while performing polycondensation at 100 ° C for 4 hours reaction. Thereafter, the temperature of the oil bath was raised to 200 ° C over 3 hours. Thereafter, the pressure in the flask was reduced to 50 mmHg or less, and after removing moisture and volatile components, the resin was cooled to room temperature to obtain a novolac-type phenol resin (alkali soluble resin (A-3) having a weight average molecular weight of 3200. )).

<Silane Compound (B)>

Prepare the silane compounds (B-1), (B-2), (B-3), and (B) represented by the following formula (23) -4).

<Synthesis of Photoacid Generator (C-1)>

In a four-neck separable flask equipped with a thermometer, a stirrer, a raw material input port, and a dry nitrogen introduction tube, 11.04 g (0.026 mole) of a phenol compound represented by the formula (P-1) and 1,2-naphthoquinone- 18.81 g (0.070 mol) of 2-diazide-4-sulfohydrazone chloride and 170 g of acetone were stirred and dissolved.

Next, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise while the flask was cooled with a water bath so that the temperature of the reaction solution did not become higher than 35 ° C. After reacting for 3 hours at room temperature in this state, 1.05 g (0.017 mol) of acetic acid was added, and the reaction was further performed for 30 minutes. Next, the reaction mixture was filtered, and the filtrate was put into a mixed solution of water / acetic acid (990ml / 10ml). Thereafter, the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum. This gives a photoacid generator (C-1) represented by the structure of the formula (Q-1).

<Synthesis of phenol resin (D-1)>

In a four-necked round-bottomed flask equipped with a thermometer, a stirrer, a raw material input port, and a dry nitrogen introduction tube, under a stream of dry nitrogen, 150.0 g (0.75 mol) of bisphenol F (trade name, manufactured by Honshu Chemical Industry), After 63.7 g (0.60 mol) of formaldehyde and 3.0 g (0.02 mol) of benzenesulfonic acid, they were immersed in an oil bath, and while the reaction solution was refluxed, a polycondensation reaction was performed at 100 ° C for 2 hours. Thereafter, while the flask was cooled, 75 g of acetone and 3.0 g (0.03 mol) of triethylamine were added and stirred for 30 minutes, and then 150 g of pure water was added and stirred for 30 minutes. After cooling to room temperature, the stirring was stopped, the separated water layer was removed, and 37.5 g of γ-butyrolactone was added. The temperature of the oil bath was raised to 170 ° C. over 3 hours, and then the pressure in the flask was reduced. After removing the volatile components to 50 mmHg or less, the resin was cooled to room temperature to obtain a phenol resin (D-1) having a weight average molecular weight of 2900.

<Synthesis of phenol resin (D-2)>

In a four-necked round-bottomed flask equipped with a thermometer, a stirrer, a raw material input port, and a dry nitrogen introduction tube, 171.0 g (0.75 mol) of 2,2'-bis (4-hydroxyphenyl) propane was added under a stream of dry nitrogen. , 63.7 g of benzaldehyde (0.60 mol), and 3.0 g of benzenesulfonic acid (0.02 mol), and then immersed in an oil bath to perform a polycondensation reaction at 100 ° C for 2 hours while refluxing the reaction solution. Thereafter, while the flask was cooled, 75 g of acetone and 3.0 g (0.03 mol) of triethylamine were added and stirred. After 30 minutes, 150 g of pure water was added and stirred for 30 minutes. After cooling to room temperature, the stirring was stopped, the separated water layer was removed, and 37.5 g of γ-butyrolactone was added. The temperature of the oil bath was raised to 170 ° C. over 3 hours, and then the pressure in the flask was reduced. After removing the volatile components to 50 mmHg or less, the resin was cooled to room temperature to obtain a phenol resin (D-2) having a weight average molecular weight of 2540.

<Thermal Crosslinking Agent (E)>

As the thermal cross-linking agent (E-1), 1,4-benzenedimethanol was prepared.

<Silane coupling agent (F)>

3-Glycidoxypropyltrimethoxysilane was prepared as a silane coupling agent (F-1) and a silane coupling agent (F-2) represented by the following formula (24).

<< Example 1 >>

20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone. Thereafter, 0.5 g of the silane compound (B-1) was added and mixed over 30 minutes, and finally, it was filtered through a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 1.

<< Example 2 >>

20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone. Thereafter, it took 30 minutes to add 0.5 g of the silane compound (B-2) was added and mixed, and finally filtered through a fluororesin filter having a pore size of 0.2 μm to obtain a photosensitive resin composition of Example 2.

"Example 3"

20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone. Then, 0.5 g of the silane compound (B-3) was added and mixed over 30 minutes, and finally, it was filtered with a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 3.

"Example 4"

20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone. Then, 0.5 g of the silane compound (B-4) was added and mixed over 30 minutes, and finally, it was filtered with a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 4.

"Example 5"

20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone. Thereafter, 0.8 g of the silane compound (B-3) was added and mixed over 30 minutes, and finally, it was filtered through a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 5.

<< Example 6 >>

20 g of the alkali-soluble resin (A-2) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone. Thereafter, 0.5 g of the silane compound (B-3) was added and mixed over 30 minutes, and finally, it was filtered through a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 6.

"Example 7"

14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of the alkali-soluble resin (A-3), and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in γ-butane. 25g of ester. Thereafter, 0.5 g of the silane compound (B-3) was added and mixed over 30 minutes, and finally, it was filtered through a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 7.

"Example 8"

14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of the phenol resin (D-1), and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in γ-butyrolactone. 25g. Then, 0.5 g of the silane compound (B-3) was added and mixed over 30 minutes, and finally, it was filtered with a fluororesin filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition of Example 8.

<< Example 9 >>

14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of the phenol resin (D-2), and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in γ-butyrolactone. 25g. Thereafter, 0.5 g of the silane compound (B-3) was added and mixed over 30 minutes, and finally, it 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 >>

14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of the phenol resin (D-1), and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in γ-butyrolactone. 25g. Thereafter, 0.5 g of the silane compound (B-3) was added and mixed over 30 minutes, and further After adding 0.1 g of the silane coupling agent (F-1) for 30 minutes, it was filtered through a fluororesin filter having a pore size of 0.2 μm to obtain a photosensitive resin composition of Example 10.

<< Example 11 >>

14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of the phenol resin (D-1), and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in γ-butyrolactone. 25g. Thereafter, 0.5 g of the silane compound (B-3) was added and mixed over 30 minutes, and 0.4 g of the silane coupling agent (F-2) was added over 30 minutes, followed by filtration through a fluororesin filter having a pore size of 0.2 μm. A photosensitive resin composition of Example 11 was obtained.

<< Example 12 >>

14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of the phenol resin (D-1), and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in γ-butyrolactone. 25g. Thereafter, 0.5 g of the silane compound (B-3) was added and mixed over 30 minutes, and then 0.1 g of the silane coupling agent (F-1) was added over 30 minutes, and then a fluorine-based surfactant (MEGAFACF557, DIC Corporation) was added. (Manufactured) 0.05 g, and finally filtered through a fluororesin filter having a pore size of 0.2 μm to obtain a photosensitive resin composition of Example 12.

<< Example 13 >>

14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of the phenol resin (D-1), 1.1 g of the thermal crosslinking agent (E-1), and the photoacid generator (C-1) synthesized above ) 2.8 g were mixed and dissolved in 25 g of γ-butyrolactone. Thereafter, 0.5 g of the silane compound (B-3) was added and mixed over 30 minutes, and then 0.1 g of the silane coupling agent (F-1) was added over 30 minutes, and then a fluorine-based surfactant (MEGAFAC F557, DIC Corporation Limited) was added. 0.05g), and finally filtered with a fluororesin filter with a pore size of 0.2 μm to obtain the photosensitive tree of Example 13. Fat composition.

Comparative Example 1

20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone, and then a pore size of 0.2 μm was used. The fluororesin filter was filtered to obtain the photosensitive resin composition of Comparative Example 1.

Comparative Example 2

20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photoacid generator (C-1) synthesized above were mixed and dissolved in 25 g of γ-butyrolactone. Thereafter, 0.4 g of a silane coupling agent (F-2) was added over 30 minutes, and finally, filtration was performed using a fluororesin filter having a pore size of 0.2 μm to obtain a photosensitive resin composition of Comparative Example 2.

The photosensitive resin composition obtained in each Example and each comparative example was evaluated by the following items.

<Processability Evaluation>

The photosensitive resin composition obtained above was coated on a 8-inch silicon wafer using a spin coater, and then pre-baked at 120 ° C for 3 minutes using a hot plate to obtain a coating film having a thickness of about 7.5 μm. This coating film was passed through a photomask made by letterpress printing company (Test chart No. 1: Residual pattern and punching pattern with a width of 0.88 to 50 μm were drawn), and an i-ray stepper (NSR-4425i) was used. Irradiation is changed by changing the exposure amount.

Next, using a 2.38% tetramethylammonium hydroxide aqueous solution as a developer, the development time is adjusted so that the difference between the film thickness after pre-baking and the film thickness after development becomes 1.0 μm, and the paddle development is performed twice. Thereby, the exposed part was dissolved and removed, and then rinsed with pure water for 10 seconds. The value of the minimum exposure amount of a pattern forming a 100 μm square guide hole was evaluated as the sensitivity.

<Evaluation of sclerosis residual film rate>

The photosensitive resin composition obtained above was coated on a 8-inch silicon wafer using a spin coater, and then pre-baked at 120 ° C for 3 minutes using a hot plate to obtain a coating film having a thickness of about 7.5 μm. While maintaining the oxygen concentration below 1000 ppm, the coating film was heated at 150 ° C. for 30 minutes in an oven, and then heated at 300 ° C. for 30 minutes, 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 calculated according to the following formula, and it evaluated as hardening residual film rate.

Curing residual film rate = Film thickness after curing / Film thickness before curing * 100

Furthermore, in order to maintain a sufficient film thickness for protecting the semiconductor element, it is preferable that the cured residual film rate is high.

<Adhesion evaluation>

The photosensitive resin composition obtained above was coated on a 8-inch silicon wafer using a spin coater, and then pre-baked at 120 ° C for 3 minutes using a hot plate to obtain a coating film having a thickness of about 7.5 μm. Pass the coating film through a mask with a line and gap pattern and a through-hole pattern with a width of 1 to 20 μm, and use an i-ray stepper (Nikon Co., Ltd., NSR-4425i) to change the exposure and irradiate the i-rays. Next, a 2.38% tetramethylammonium hydroxide aqueous solution was used as a developing solution, and the paddle development was performed twice, thereby dissolving and removing the exposed portion. The pattern thus obtained was confirmed, and the exposure amount of the pattern forming the guide hole of 10 μm was set as the reference exposure amount. In a wafer in which the exposure portion was dissolved and removed by irradiating the reference exposure amount determined in this way, a development pattern formed by a 1 μm line and a gap pattern on the wafer was evaluated as ○, and the development pattern disappeared as ×, and the adhesion was evaluated after development.

<Evaluation of heat resistance>

The cured film obtained in the evaluation of the cured residual film rate was heated at a temperature of 5 ° C./min by differential scanning calorimetry (manufactured by DSC6000 Seiko Instruments), and the glass transition temperature (Tg) was calculated from the extrapolated point. The temperature was increased by a Tg-DTA device (TG / DTA6200 Seiko Instruments) under a condition of temperature rise of 10 ° C / min, and a 5% weight reduction temperature (Td5) was measured.

<Evaluation of elongation and elastic modulus>

The photosensitive resin material obtained above was hardened under a nitrogen environment at 300 ° C for 30 minutes, and the obtained test piece (10 mm × 60 mm × 10 μm thick) was subjected to a tensile test (extension) at 23 ° C. Speed: 5mm / min). The tensile test was performed using a tensile tester (Tensilon RTC-1210A) manufactured by Orientec. The measurement was performed on five test pieces, and the tensile elongation was calculated from the distance at which the fracture occurred and the initial distance, and the average value was used as the elongation. The tensile elastic modulus was calculated based on the initial slope of the obtained stress-strain curve, and the average value was set as the elastic modulus.

<Measurement of light transmittance>

For the cured film obtained in the evaluation of the elongation and the elastic modulus, the light transmittance T (%) in terms of a film thickness of 10 μm for a light having a wavelength of 630 nm was measured. The light transmittance T is obtained by converting the light transmittance measured using UV-160A manufactured by Shimadzu Corporation into a film thickness of 10 μm according to the Lambert-Beer rule.

Hereinafter, the blending of the examples and comparative examples and the evaluation results of the obtained photosensitive resin compositions are summarized and shown in the form of Table 1.

<Production of Semiconductor Device>

After using the analog element wafer with a pattern of aluminum circuits formed on the surface, the photosensitive resin composition obtained in the above-mentioned Examples 1 to 13 was separately coated so as to be 5 μm, and then the pattern was implemented according to the pattern formed on the wafer. Processing and hardening. Thereafter, it is divided into each wafer size and mounted on an organic substrate with a conductive paste using a die bonder (BESTEM-D02). At this time, the installation was successfully performed without a decrease in visibility caused by the photosensitive resin composition.

<Adhesiveness due to high temperature and high pressure treatment>

Furthermore, a semiconductor device was manufactured by performing sealing molding using an epoxy resin for semiconductor sealing (manufactured by SUMITOMO BAKELITE, EME-6300H). These semiconductor devices (semiconductor packages) were treated under the conditions of 85 ° C / 85% humidity for 168 hours, then immersed in a solder bath at 260 ° C for 10 seconds, and then subjected to high-temperature and high-pressure high-pressure cooking treatment (125 ° C, 2.3 atm, 100% relative humidity), and check the aluminum circuit for poor open circuit. As a result, the cured film formed using the photosensitive resin composition obtained in Examples was not confirmed to be defective or the like, and it was suggested that the cured film was used as a semiconductor device without any problems.

This application claims priority based on Japanese Patent Application No. 2014-098147, filed on May 9, 2014, and incorporates the entire disclosure thereof into this document.

Claims (13)

A photosensitive resin composition comprising an alkali-soluble resin (A), a silane compound (B) represented by the following general formula (1), and a photoacid generator (C). A in formula (1) is an organic group selected from the group of organic groups represented by the following formula (2), A [Si (R1) _a ) (OR2) _b ] _m [Si (R3) _c (OR4) _d ] _N (1) (where A represents a (m + n) -valent organic group having a cyclic structure, and R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms. , R2 and R4 represent substituted or unsubstituted saturated alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted unsaturated alkyl groups having 1 to 10 carbon atoms, and a and b represent satisfying a + b = 3 Integers from 0 to 3, c and d represent integers from 0 to 3 that satisfy c + d = 3, m and n represent integers from 0 to 2, m + n ≠ 0) (In the formula, X1 represents a single bond, C (-Y1) (-Y2), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing amidino group, and Y1 and Y2 each independently represent a hydrogen atom, Trifluoromethyl, substituted or unsubstituted saturated alkyl having 1 to 10 carbons, substituted or unsubstituted unsaturated alkyl having 1 to 10 carbons, substituted or unsubstituted phenyl, Or substituted or unsubstituted cyclohexyl). A photosensitive resin composition comprising an alkali-soluble resin (A), a silane compound (B) represented by the following general formula (1), and a photoacid generator (C). A in the formula (1) is an organic group having an aliphatic ring, A [Si (R1) _a ) (OR2) _b ] _m [Si (R3) _c (OR4) _d ] _n (1) (wherein A Represents a (m + n) -valent organic group having a cyclic structure, R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, and R2 and R4 represent substituted or unsubstituted Substituted saturated alkyl groups having 1 to 10 carbon atoms, and substituted or unsubstituted unsaturated alkyl groups having 1 to 10 carbon atoms, a and b represent integers from 0 to 3 satisfying a + b = 3, and c and d Represents an integer from 0 to 3 that satisfies c + d = 3, m and n represent integers from 0 to 2, m + n ≠ 0). For example, the photosensitive resin composition of the second patent application range, wherein A in the general formula (1) of the silane compound (B) is an organic group selected from the organic group represented by the following formula (3), (In the formula, X2 represents a single bond, C (-Y3) (-Y4), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing amidino group, and Y3 and Y4 each independently represent a hydrogen atom, Trifluoromethyl, substituted or unsubstituted saturated alkyl having 1 to 10 carbons, substituted or unsubstituted unsaturated alkyl having 1 to 10 carbons, substituted or unsubstituted phenyl, Or substituted or unsubstituted cyclohexyl). A photosensitive resin composition comprising an alkali-soluble resin (A), a silane compound (B) represented by the following general formula (1), and a photoacid generator (C), which further contains a phenol compound and an aromatic compound. Phenol resin (D) obtained by reacting an aldehyde compound, A [Si (R1) _a ) (OR2) _b ] _m [Si (R3) _c (OR4) _d ] _n (1) (wherein A represents a ring (M + n) valence organic group of the same structure, R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, and R2 and R4 represent substituted or unsubstituted carbons A saturated alkyl group having a number of 1 to 10, an unsaturated alkyl group having a substituted or unsubstituted carbon number of 1 to 10, a and b represent integers from 0 to 3 satisfying a + b = 3, and c and d represent satisfying c + d = integer of 0 ~ 3, m and n represent integers of 0 ~ 2, m + n ≠ 0). For example, the photosensitive resin composition of the fourth scope of the patent application, wherein the A in the general formula (1) of the silane compound (B) is an organic group having an aromatic ring. For example, the photosensitive resin composition according to any one of claims 1, 2, and 4, wherein the alkali-soluble resin (A) contains a material selected from the group consisting of polybenzo Azole, polybenzo At least one or more of an azole precursor, a polyimide, and a polyimide precursor. For example, the photosensitive resin composition according to claim 4 of the application, wherein the aromatic aldehyde compound includes an aromatic aldehyde compound represented by the following formula (4), (In the formula, R ₁ represents an organic group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and a hydroxyl group, and t is an integer of 0 to 3). For example, the photosensitive resin composition according to item 4 of the application, wherein the phenol compound includes a phenol compound represented by the following formula (5), (In the formula, X3 represents a single bond, C (-Y7) (-Y8), a sulfur atom, an ether group, a carbonyl group, an ester group, or a divalent organic group containing amidino group. Y7 and Y8 each independently represent a hydrogen atom, Trifluoromethyl, substituted or unsubstituted saturated alkyl having 1 to 10 carbons, substituted or unsubstituted unsaturated alkyl having 1 to 10 carbons, substituted or unsubstituted phenyl, Or substituted or unsubstituted cyclohexyl, Y5 and Y6 each independently represent a substituted or unsubstituted saturated alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted unsaturated alkyl group having 1 to 20 carbon atoms Group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted phenyl group, or substituted or unsubstituted cyclohexyl group; p and q each independently represent 1 to 3 Integer, r and s each independently represent an integer of 0 ~ 3). For example, the photosensitive resin composition according to the first patent application scope further contains a thermal crosslinking agent (E). A cured film composed of a cured product of a photosensitive resin composition according to any one of claims 1 to 9. A protective film is composed of a hardened film with the scope of patent application No. 10. An insulating film is composed of a hardened film with the scope of application for item 10. An electronic device has a hardened film in the scope of patent application No. 10.