KR101846114B1 - Photosensitive resin composition, cured film, protective film, insulating film, and electronic device - Google Patents

Abstract

(식 중 A는 환상 구조를 갖는 (m+n)가의 유기기를 나타내며, R1 및 R3은 각각 독립적으로 수소 원자, 치환 혹은 무치환의 탄소수 1~10의 포화 알킬기를 나타내고, R2 및 R4는 치환 혹은 무치환의 탄소수 1~10의 포화 알킬기, 치환 혹은 무치환의 탄소수 1~10의 불포화 알킬기를 나타내며, a 및 b는 a+b=3을 충족시키는 0~3의 정수를 나타내고, c 및 d는 c+d=3을 충족시키는 0~3의 정수를 나타내며, m 및 n은 0~2의 정수를 나타내고 m+n≠0이다)According to the present invention, there is provided 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).

(Wherein A represents an (m + n) -valent organic group having a cyclic structure, R 1 and R 3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a and b represent an integer of 0 to 3 satisfying a + b = c + d = 3, m and n each represent an integer of 0 to 2, and m + n? 0.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a cured film, a protective film, an insulating film and an 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 a protective film and an insulating film in a semiconductor device, a photosensitive resin composition containing an alkali-soluble resin excellent in heat resistance, excellent in electrical characteristics, mechanical characteristics, and capable of patterning has been used.

Here, when a photosensitive resin composition containing an alkali soluble resin is used, in order to simplify the process, a diazoquinone compound of a photo acid generator is generally used in combination with these resins to prepare a photosensitive resin composition . For example, Patent Document 1 describes a photosensitive resin composition comprising an alkali-soluble phenol resin, a photosensitive resin composition, an organic solvent, and an alkoxysilyl group-containing adhesion aid.

Japanese Patent Application Laid-Open No. 2008-164816

Generally, a protective film or insulating film of a semiconductor element using a photosensitive resin composition can be produced by forming a resin film by applying the photosensitive resin composition to a support, exposing it by actinic radiation, patterning by development using an alkaline developer, , Curing by heating, or the like.

However, when the adhesion of the resin film to the support is not good, it may be difficult to perform stable patterning. Therefore, it has been required to improve the adhesion 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 lowered, so that the productivity in the post-process after the patterning or curing may be lowered. Therefore, it has been required to improve the transparency of the resin film obtained using the photosensitive resin composition.

Therefore, the present invention provides a photosensitive resin composition capable of forming a pattern with high adhesion and stably, and capable of obtaining a resin film having sufficient transparency. The present invention also provides a cured film composed of a cured product of the photosensitive resin composition, a protective film composed of the cured film and an insulating film, and further, an electronic device having the cured film.

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

[1] A process for producing an alkali-soluble resin (A)

A silane compound (B) represented by the following general formula (1)

The photoacid generator (C)

.

[Chemical Formula 1]

(Wherein A represents an (m + n) -valent organic group having a cyclic structure, R 1 and R 3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a and b represent an integer of 0 to 3 satisfying a + b = c + d = 3, m and n represent integers of 0 to 2, and m + n? 0.

[2] The photosensitive resin composition according to [1]

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 [1] or [2]

Wherein A in the general formula (1) of the silane compound (B) is an organic group selected from the group of organic groups represented by the following formula (2).

(2)

(Wherein X1 represents a divalent organic group containing a single bond, C (-Y1) (-Y2), a sulfur atom, an ether group, a carbonyl group, an ester group or an amide group, Y1 and Y2 each independently represent hydrogen A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, .

[4] The photosensitive resin composition according to [1]

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 [1] or [4]

Wherein A in the general formula (1) of the silane compound (B) is an organic group selected from the group of organic groups represented by the following formula (3).

(3)

(Wherein X2 represents a divalent organic group containing a single bond, C (-Y3) (-Y4), a sulfur atom, an ether group, a carbonyl group, an ester group or an amide group, Y3 and Y4 each independently represent hydrogen A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, .

[6] The photosensitive resin composition according to any one of [1] to [5]

Wherein the alkali-soluble resin (A) comprises at least one selected from polybenzoxazole, polybenzoxazole precursor, polyimide, and polyimide precursor.

[7] The photosensitive resin composition according to any one of [1] to [6]

A photosensitive resin composition further comprising a phenol resin (D) obtained by reacting a phenol compound with an aromatic aldehyde compound.

[8] The photosensitive resin composition according to [7]

Wherein the aromatic aldehyde compound comprises an aromatic aldehyde compound represented by the following formula (4).

[Chemical Formula 4]

(Wherein R ₁ represents hydrogen, an organic group selected from 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 [7] or [8]

Wherein the phenolic compound comprises a phenol compound represented by the following formula (5).

[Chemical Formula 5]

(Wherein X3 represents a divalent organic group containing a single bond, C (-Y7) (-Y8), a sulfur atom, an ether group, a carbonyl group, an ester group, or an amide group, Y7 and Y8 each independently represent hydrogen A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, And Y5 and Y6 each independently represent 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, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, Or a substituted or unsubstituted cyclohexyl group, p and q each independently represent an integer of 1 to 3, and r and s each independently represent an integer of 0 to 3. )

[10] The photosensitive resin composition according to any one of [1] to [9]

A photosensitive resin composition further comprising a heat crosslinking agent (E).

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

[12] A protective film composed of the cured film described in [11].

[13] An insulating film comprising a cured film according to [11].

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

According to the present invention, it is possible to provide a photosensitive resin composition which can form a pattern with high adhesion and stably, and can obtain a resin film having sufficient transparency.

The foregoing and other objects, features and advantages of the present invention will become more apparent from the following detailed description of preferred embodiments thereof with reference to the accompanying drawings.
1 is a cross-sectional view showing an example of an electronic device according to the present embodiment.
2 is a cross-sectional view showing an example of an electronic device according to the present embodiment.

Best Mode for Carrying Out the Invention Hereinafter, the embodiments will be described using appropriate drawings. In all the drawings, the same components are denoted by the same reference numerals, and a description thereof will be omitted. In addition, "~ " indicates the following unless otherwise stated.

The photosensitive resin composition according to the present embodiment is 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).

[Chemical Formula 6]

(Wherein A represents an (m + n) -valent organic group having a cyclic structure, R 1 and R 3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a and b represent an integer of 0 to 3 satisfying a + b = c + d = 3, m and n each represent an integer of 0 to 2, and m + n? 0.

As described above, the protective film or insulating film can be formed, for example, by forming a resin film by coating the support of the photosensitive resin composition, exposure by actinic radiation, patterning by development using an alkaline developer, cleaning by pure water, Curing or the like. However, when the adhesion of the resin film to the support is not good, it may be difficult to perform stable patterning. For example, when the adhesion of the resin film is not good, the pattern may be lost (lost) or deformed at the time of development by the alkali developer. In addition, when the transparency of the resin film is insufficient, the visibility of the pattern on the surface of the support is lowered, so that the productivity in the post-process after the patterning or curing may be lowered. For example, when the electronic device is assembled by disassembling the supporting body in the post-process, the pattern visibility of the supporting body surface is lowered, thereby causing errors in recognition of the separated supporting body, and there is a fear that the throughput is lowered have. For this reason, in order to realize the production of a stable electronic device, it was important to improve adhesion and transparency at the same time.

As a result of intensive investigations, the inventors of the present invention have found that the inclusion of a specific silane compound enhances both the adhesiveness and transparency of the photosensitive resin composition. The present embodiment realizes 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) will be. Therefore, according to this embodiment, a photosensitive resin composition excellent in adhesion and transparency can be realized. This makes it possible to realize an electronic device having excellent manufacturing stability.

(7)

(Wherein A represents an (m + n) -valent organic group having a cyclic structure, R 1 and R 3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a and b represent an integer of 0 to 3 satisfying a + b = c + d = 3, m and n each represent an integer of 0 to 2, and m + n? 0.

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

First, the photosensitive resin composition according to the present embodiment will be described.

The photosensitive resin composition is used, for example, to form a permanent film. By curing the photosensitive resin composition, a resin film constituting the permanent film is obtained. In the present embodiment, a permanent film is formed by, for example, patterning a coating film formed by a photosensitive resin composition into a desired phenomenon by exposure and development, and then curing the coating film by heat treatment or the like.

Specific uses of the permanent film formed using the photosensitive resin composition include, for example, an interlayer film, a surface protective film, or a dam material. The use of the photosensitive resin composition is not limited thereto.

The interlayer film refers to an insulating film provided in the multilayer structure, and the kind thereof is not particularly limited. Examples of the interlayer film include those used in semiconductor device applications such as an interlayer insulating film constituting a multilayer interconnection structure of a semiconductor element, a build-up layer constituting a wiring substrate, or a core layer. As the interlayer film, a flattening film covering a thin film transistor (TFT (Thin Film Transistor)) in a display device, a liquid crystal alignment film, and a color filter substrate of a MVA (Multi Domain Vertical Alignment) Or a barrier for forming a cathode of the organic EL element, and the like.

The surface protective film refers to an insulating film formed on the surface of an electronic component or an electronic device to protect the surface, and the kind thereof is not particularly limited. Examples of such a surface protective film include a passivation film or a buffer coat layer provided on a semiconductor element, or a cover coat provided on a flexible substrate. The dam member may be, for example, a spacer used for forming a hollow portion for disposing an optical element or the like on a substrate.

Hereinafter, each component of the photosensitive resin composition according to this embodiment will be described in detail. The following is an example, and the present invention is not limited to 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 in the main chain or side chain, and examples thereof include phenol resins, phenol aralkyl resins, hydroxystyrene resins, Acrylic resins such as acrylic resin, acrylic acid resin and methacrylic acid ester resin, cyclic olefin resin and polyamide resin. Of these, a phenol resin, a phenol aralkyl resin, a hydroxystyrene resin and a polyamide resin are preferable, and more preferable are polybenzoxazole, polybenzoxazole precursor having excellent heat resistance and film toughness, Polyamide resins such as polyimide, polyimide and polyimide precursors. These alkali-soluble resins may be used alone or in combination of two or more.

As the phenol resin in the alkali-soluble resin (A), a reaction product of a phenol compound and an aldehyde compound typified by a novolak type phenol resin and a reaction product of a phenol compound and a dimethanol compound represented by phenol aralkyl resin can be used have. However, as the phenol resin in the alkali-soluble resin (A), a phenol resin different from the phenol resin (D) described later is used.

Examples of the phenol compound used in the novolak type phenol resin in the alkali-soluble resin (A) include phenol; cresols such as o-cresol, m-cresol and p-cresol; Dimethylphenols such as 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol and 3,5-dimethylphenol; ethyl phenols such as o-ethyl phenol, m-ethyl phenol and p-ethyl phenol; But are not limited to, alkylphenols such as isopropylphenol, butylphenol and p-tert-butylphenol, and polyhydric phenols such as resorcin, catechol, hydroquinone, pyrogallol and fluoroglucine. These phenols may be used alone or in combination of two or more.

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

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

The phenol aralkyl resin can be obtained by reacting this phenol compound with a compound such as a dimethanol compound shown below.

Examples of the dimethanol compounds used in the phenol aralkyl resin in the alkali-soluble resin (A) include 1,4-benzene dimethanol, 1,3-benzene dimethanol, 4,4'-biphenyl dimethanol, 3 , 4'-biphenyl dimethanol, 3,3'-biphenyl dimethanol and 2,6-naphthalenedimethanol.

(Methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 4,4'-bis (methoxymethyl) biphenyl, 3,4'-bis (Alkoxymethyl) compounds such as (methoxymethyl) biphenyl, 3,3'-bis (methoxymethyl) biphenyl and 2,6-naphthalenedicarboxylate; (Chloromethyl) benzene, 1,3-bis (bromomethyl) benzene, 4,4'-bis (chloromethyl) benzene, Bis (chloromethyl) biphenyl, 3,3'-bis (chloromethyl) biphenyl, 4,4'-bis (Halogenoalkyl) compounds such as 4'-bis (bromomethyl) biphenyl and 3,3'-bis (bromomethyl) biphenyl are reacted with a phenol compound to obtain a phenol aralkyl resin have. These compounds may be used alone or in combination of two or more.

As the hydroxystyrene resin in the alkali-soluble resin (A), a polymerization reaction product or a copolymerization reaction product obtained by radical polymerization, cationic polymerization or anionic polymerization of hydroxystyrene, styrene and derivatives thereof can be used.

The polyamide resin in the alkali-soluble resin (A) refers to a resin having a benzoxazole precursor structure and / or an imide precursor structure. The polyamide resin can be produced by a benzoxazole structure, an imide precursor structure, a benzoxazole structure generated by a part of the benzoxazole precursor structure by a ring-closing reaction, and a part of the imide precursor structure by a ring-closing reaction And may have an amide acid ester structure.

The specific benzoxazole precursor structure refers to the structure represented by the following formula (6), the imide precursor structure refers to the structure represented by the following formula (7), and the benzoxazole structure refers to the structure represented by the following formula (8) , The imide structure refers to the structure represented by the following formula (9), and the amide acid ester structure refers to the structure represented by the following formula (10).

[Chemical Formula 8]

In the formulas (6) to (10), D and R '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 preferable from the viewpoint of the heat resistance of the cured product of the photosensitive resin composition of the present embodiment.

[Chemical Formula 9]

(In the formula, X, Y is an organic group. R ₂ is a hydroxyl group, -OR _4, an alkyl group, an acyloxy group or a cycloalkyl group, it may be the case with a plurality, and each may be the same different. R ₃ is a hydroxyl group , a carboxyl group, -OR ₄ or -COO-R ₄ and, if a plurality, may each be the same or different. R ₂ and R ₃ of R ₄ in is an organic group having a carbon number of 1 to 15. here, in the formula (11), when the R ₂ do not have hydroxyl groups, at least one R ₃ is a carboxyl group. in addition, when the R ₃ is not the carboxyl group, at least one hydroxyl group of R _2. k is 0-8 And l is an integer of 0 to 8. e is an integer of 2 to 100.)

In the polyamide resin having the structure represented by the general formula (11), as the R ₂ and R ₃ , a group in which the hydroxyl group and the carboxyl group are protected with the protecting group R ₄ in controlling the solubility of the polyamide resin in an aqueous alkali solution And specific examples thereof include -OR ₄ as R ₂ , -OR ₄ and -COO-R ₄ as R ₃ . Examples of the organic group having 1 to 15 carbon atoms as R ₄ include a formyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tertiary butyl group, a tertiary butoxycarbonyl group, a phenyl group, a benzyl group, a tetrahydrofuranyl group, Tetrahydropyranyl group and the like.

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

[Chemical formula 10]

(Wherein Z represents an alkylene group, a substituted alkylene group, -OC ₆ H ₄ -O-, -O-, -S (O) -, -SO ₂ -, -C (═O) -, -NHC (═O) - or a single bond R ₅ represents one selected from an alkyl group, an alkyl ester group and a halogen atom, R ₆ 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 each represent a monovalent or divalent group Device.

In the above formula (12), the substituent R ₂ of X in the formula (11) is omitted.)

Among the groups represented by the above formula (12), particularly preferred ones are those represented by the following formula (13) (those having R ₂ in the formula (11)).

(11)

. (Wherein (13), * represents that bound to NH in formula (11) wherein 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 a single bond R ₁₁ is one selected from an alkyl group, an alkoxy group, an acyloxy group and a cycloalkyl group, and when there are a plurality of R _{11 s} , they may be the same or different, and v is an integer of 0 or more and 3 or less.

Among the groups represented by the above formula (13), particularly preferred ones are those represented by the following formula (14) (some of them have R ₂ in the formula (11)).

[Chemical Formula 12]

(Wherein R ₁₂ represents an alkylene group, a substituted alkylene group, -O-, -S-, -SO ₂ -, -C ( = O) -, -NHC (= O) -, -C (CF 3) 2 -, an organic group selected from a single bond).

Specific examples of the alkylene group and the substituted alkylene group as R _{12 in} the formula (12) and the formula (13) and the 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 ) -. Among _{these, -CH 2 -, -CH (CH} 3) -, -C (CH 3) 2 - a, as well as an alkaline aqueous solution, has a sufficient solubility even in a solvent, it is possible to obtain the polyamide resin is more excellent balance desirable.

In the polyamide resin having the structure represented by the general formula (11), Y is an organic group. Examples of such organic groups are the same as X above. For example, an aromatic group having a structure such as a benzene ring, a naphthalene ring and a bisphenol structure; A heterocyclic organic group having a structure such as a pyrrole ring, a pyridine ring, and a furan ring; And a siloxane group, and more specifically, those represented by the following formula (15) are preferable. These may be used alone or in combination of two or more.

[Chemical Formula 13]

(In the formula (15), * represents a bond to the C═O group in the general formula (11), J represents -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, -S -, -SO ₂ -, -C (═O) -, -NHC (═O) -, -C (CF ₃ ) ₂ - or a single bond R ₁₃ represents an alkyl group, an alkyl ester group, R ₁₄ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom, and w represents an integer of 0 or more and 2 or more, And R ₁₅ to R ₁₈ are each a monovalent or divalent organic group.

In the formula (15), the substituent R ₃ of Y in the formula (11) is omitted.)

Particularly preferred among the groups represented by the formula (15) are those represented by the following formula (16) (some of them have R ₃ in the formula (11)).

The structure derived from the tetracarboxylic acid dianhydride in the following formula (16) is that the positions bonding to the C = O group in the general formula (11) are both meta positions and both are para positions, Or a structure including a meta position and a para position, respectively.

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

(In the formula (16), * represents a bond to the C = O group in the general formula (11). R ₁₉ represents an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group and a halogen atom R ₂₀ represents one selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms and may be partially substituted, and x is an integer of 0 or more and 2 or less .)

In the case of the polyamide resin represented by the general formula (11), the amino group at the end of the polyamide resin is substituted with an alkenyl group, an alkynyl group and a hydroxyl group Or an acid anhydride or a monocarboxylic acid having a cyclic compound group and at least one selected from the group consisting of an aliphatic group and a cyclic compound group, may be end-capped (sealed) as an amide.

Examples of the acid anhydride or monocarboxylic acid having 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, citraconic anhydride, 2,3-dimethyl maleate Cyclohexene-1,2-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, Methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, HET anhydride, 5-norbornene-2-carboxylic acid, 4-ethynyl phthalic anhydride And 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid and the like. These may be used alone, or two or more of them may be used in combination, or a part of the amide portion sealed at the end may be subjected to dehydration ring closure.

The method of the present invention is not limited to this method. The terminal carboxylic acid residue contained in the polyamide resin may be an aliphatic group having at least one organic group selected from an alkenyl group, an alkynyl group and a hydroxyl group, or an amine derivative containing a cyclic compound group May be used to end-cap as an amide.

In the case of the polyamide resin represented by the general formula (11), a group end-capped with a nitrogen-containing cyclic compound is present on at least one side of the terminal so as not to affect the mechanical properties and heat resistance of the cured product cured at a low temperature . This makes it possible to improve adhesion with metal wiring (particularly, copper wiring) and the like.

Examples of the nitrogen-containing cyclic compound include 1- (5-1H-triazolyl) methylamino group, 3- (1H-pyrazolyl) amino group, 4- (1H-pyrazolyl) methylamino group, 1- (3-1H-pyrazolyl) methylamino group, 1- (1 H-tetrazol-5-yl) methyl-amino group and 3- (1H-tetrazol-5-yl) benz-amino group.

The polyamide resin having such a structure represented by the general formula (11) can be produced, for example, by reacting a diamine, bis (aminophenol) or 2,4-diaminophenol , And a compound selected from tetracarboxylic dianhydride, trimellitic anhydride, dicarboxylic acid, dicarboxylic acid dichloride or dicarboxylic acid derivative containing Y and the like, .

In the case of using a dicarboxylic acid, in order to increase the reaction yield and the like of the polyamide resin, an active ester type May be used as the dicarboxylic acid derivative.

The polyamide resin having the structure represented by the general formula (11) is subjected to dehydration ring closure by heating to obtain a heat resistant resin in the form of a polyimide resin, a polybenzoxazole resin, or copolymerization of both. The temperature for carrying out dehydration ring closure can be 280 ° C to 380 ° C for heating at a high temperature and 150 ° C to 280 ° C for heating at a low temperature.

[Silane compound (B)]

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

[Chemical Formula 17]

(Wherein A represents an (m + n) -valent organic group having a cyclic structure, R 1 and R 3 each independently represent a hydrogen atom, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, a and b represent an integer of 0 to 3 satisfying a + b = c + d = 3, m and n each represent an integer of 0 to 2, and m + n? 0.

The silane compound (B) represented by the formula (1) can improve the adhesiveness and transparency in the photosensitive resin composition in that A in the formula (1) is an organic group having a cyclic structure. That is, since A in the formula (1) is an organic group having a rigid cyclic structure, adhesion with a support can be improved, and an organic group having a bulky cyclic structure can be used to improve the transparency of the photosensitive resin composition .

The silane compound (B) is not particularly limited, but it is preferable that the cyclic structure in A in the formula (1) and the Si in the formula (1) are directly bonded. By adopting such a structure, it is possible to realize the effect of improving the adhesion by the annular structure and the transparency more effectively.

The silane compound (B) is not particularly limited, but 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. Within this range, the adhesion can be further improved.

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

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

The silane compound (B) is not particularly limited, but is preferably 1 or more and 2 or less with respect to m and n from the viewpoint of improving adhesion, and from the viewpoint of improving transparency, 1 or less is preferable.

The silane compound (B) is not particularly limited, but from the viewpoint of improving the adhesion and transparency in balance, for example, the compound represented by the following formula (17) is preferably used.

[Chemical Formula 18]

(Wherein A 'represents a divalent organic group having a cyclic structure, the cyclic structure is directly bonded to the Si atom, A' 'represents a monovalent organic group having a cyclic structure, and the cyclic structure is bonded directly 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 a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted A and b represent an integer of 0 to 3 satisfying a + b = 3, and c and d represent an integer of 0 to 3 satisfying c + d = 3. )

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

[Chemical Formula 19]

(Wherein X1 represents a divalent organic group containing a single bond, C (-Y1) (-Y2), a sulfur atom, an ether group, a carbonyl group, an ester group or an amide group, Y1 and Y2 each independently represent hydrogen A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, .

The silane compound (B) represented by the formula (1) is not particularly limited when it contains an organic group having an aromatic ring in A in the formula (1), and among them, a silane compound represented by the following formula (18) Or a divalent organic group is preferable.

[Chemical Formula 20]

(Wherein X1 represents a divalent organic group containing a single bond, C (-Y1) (-Y2), a sulfur atom, an ether group, a carbonyl group, an ester group or an amide group, Y1 and Y2 each independently represent hydrogen A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, .

The silane compound (B) is not particularly limited, but is preferably an organic group having an aliphatic ring in A in the formula (1) from the viewpoint of further improving transparency. Examples of the aliphatic ring include, but are not particularly limited to, monocyclic rings such as cyclohexane, bicyclic rings such as bicyclo pentane, and polycyclic rings such as adamantane. By having a plurality of aliphatic rings, adhesion and transparency can be improved in a well-balanced manner. Among them, an organic group selected from the group of organic groups represented by the following formula (3) is preferable, and adhesion and transparency can be further improved.

[Chemical Formula 21]

(Wherein X2 represents a divalent organic group containing a single bond, C (-Y3) (-Y4), a sulfur atom, an ether group, a carbonyl group, an ester group or an amide group, Y3 and Y4 each independently represent hydrogen A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, .

The silane compound (B) represented by the formula (1) is not particularly limited when it contains an organic group having an aliphatic ring in A in the formula (1), and among them, a silane compound represented by the following formula (19) Or a divalent organic group is preferable.

[Chemical Formula 22]

(Wherein X2 represents a divalent organic group containing a single bond, C (-Y3) (-Y4), a sulfur atom, an ether group, a carbonyl group, an ester group or an amide group, Y3 and Y4 each independently represent hydrogen A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, .

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

(23)

The content of the silane compound (B) in the photosensitive resin composition of the present embodiment is not particularly limited, but is preferably 0.1 part by mass or more and 50 parts by mass or less based on 100 parts by mass of the total amount of the alkali-soluble resin (A) And more preferably 0.5 parts by mass or more and 20 parts by mass or less. The additive amount is within the above range, so that sufficient adhesion and transparency can be exhibited.

[Photo acid generator (C)]

The photoacid generator (C) used in the present embodiment is a compound which generates an acid by light. For example, a photosensitizer capable of positive patterning can be used. A wavelength of 200 to 500 nm, particularly preferably, A compound which generates an acid by irradiation with an actinic ray having a wavelength of 350 to 450 nm is preferable.

Specific examples thereof include onium salts such as photosensitive diazoquinone compounds, diaryl iodonium salts, triarylsulfonium salts and sulfonium borate salts, 2-nitrobenzyl ester compounds, N-iminosulfonate compounds, imide sulfo compounds 2,6-bis (trichloromethyl) -1,3,5-triazine compound, dihydropyridine compound and the like can be used. Among them, a photosensitive diazoquinone compound having excellent sensitivity and solvent solubility is preferable.

The photosensitive diazoquinone compound can be produced, for example, by reacting a phenol compound with 1,2-naphthoquinone-2-diazido-5-sulfonic acid or 1,2-naphthoquinone- ≪ / RTI >

In the case of the positive type, it is considered that the photoacid generator remaining in the relief pattern of the unexposed portion is decomposed into heat at the time of curing to generate an acid, and the photoacid generator also plays an important role as a reaction promoter. In the case of such a photosensitive diazoquinone compound, an ester of 1,2-naphthoquinone-2-diazepin-4-sulfonic acid which is more likely to be thermally decomposed is preferable.

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

[Phenolic resin (D)]

The photosensitive resin composition of the present embodiment may include a phenol resin (D) obtained by reacting a phenol compound and an aromatic aldehyde compound, if necessary. By using an aromatic aldehyde compound in the phenol resin (D), rotation in the molecule can be suppressed, and the cured film in this embodiment can be given high heat resistance. In addition, even when dimers and trimers remain, the molecular weight of the dimer and the trimmer is larger than that of the phenol resin obtained by reacting formaldehyde, and the heat resistance of the cured film can be kept high. By including the phenol resin (D) in this manner, the heat resistance and mechanical characteristics of the resulting cured film are improved, and more excellent heat resistance and mechanical characteristics can be realized as a protective film and an insulating film.

As the aromatic aldehyde compound, an aromatic aldehyde compound represented by the following general formula (4) is preferable.

≪ EMI ID =

Wherein R ₁ represents hydrogen, an organic group selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and a hydroxyl group, and t is an integer of 0 or more and 3 or less.

As the aromatic aldehyde compound, an aromatic aldehyde compound which is unsubstituted or has 3 or less substituents is used. As the substituent, an organic group selected from an alkyl group, an alkoxy group and a hydroxyl group having 1 to 20 carbon atoms is exemplified. Specific examples of the alkyl and alkoxy groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, methoxy and ethoxy groups. Examples of such aromatic aldehyde compounds include benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 2,3-dimethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 2 Dimethylbenzaldehyde, 2,3-trimethylbenzaldehyde, 2,3,5-trimethylbenzaldehyde, 2,3,6-trimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde, 2,4,6- , 5-trimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde, 3,4,5-trimethylbenzaldehyde, 4-ethylbenzaldehyde, 4-tert- butylbenzaldehyde, 4-isobutylbenzaldehyde, 4-methoxybenzaldehyde, 2-hydroxybenzaldehyde, 2-hydroxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 3-methylsalicylaldehyde, 5-dihydroxybenz Dihydroxybenzaldehyde, and the like, but not limited thereto. Among them, an aromatic aldehyde compound in which R ₁ in the general formula (4) is a hydrogen, a methyl group or a hydroxy group is preferable, and it is more preferable to select an aromatic aldehyde compound represented by the following formula (21). These aldehydes may be used alone or in combination of two or more.

(25)

The phenol compound used in the phenolic resin (D) can be the same as the phenolic compound used in the novolac phenolic resin in the alkali-soluble resin (A). For example, phenol; cresols such as o-cresol, m-cresol and p-cresol; Dimethylphenols such as 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol and 3,5-dimethylphenol; ethyl phenols such as o-ethyl phenol, m-ethyl phenol and p-ethyl phenol; But are not limited to, alkylphenols such as isopropylphenol, butylphenol and p-tert-butylphenol, and polyhydric phenols such as resorcin, catechol, hydroquinone, pyrogallol and phloroglucine. These phenols may be used alone or in combination of two or more.

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

(26)

(Wherein X3 represents a divalent organic group containing a single bond, C (-Y7) (-Y8), a sulfur atom, an ether group, a carbonyl group, an ester group, or an amide group, Y7 and Y8 each independently represent hydrogen A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, And Y5 and Y6 each independently represent 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, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, Or a substituted or unsubstituted cyclohexyl group, p and q each independently represent an integer of 1 to 3, and r and s each independently represent an integer of 0 to 3. )

The substituents Y5 and Y6 of the bisphenol compound represented by the general formula (5) are each independently 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, a substituted or unsubstituted An alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted cyclohexyl group. Such a bisphenol compound is not particularly limited, but is preferably selected from bisphenols represented by the following formula (22). These bisphenols may be used alone or in combination of two or more. By using the bisphenol compound, it is possible to obtain a phenol resin which suppresses the intramolecular rotation, has sufficient heat resistance required for the photosensitive resin composition, and has flexibility in the molecular structure, thereby resulting in sufficient elongation properties.

(27)

In the synthesis reaction of the phenolic resin (D), the aldehyde compound is preferably reacted in an amount of 0.5 mol or more to 2 mol or less, more preferably 0.6 mol or more and 1.2 mol or less, and more preferably 0.7 mol Or more and 1.0 mole or less. By setting the molar ratio, a molecular weight capable of exhibiting sufficient properties as the photosensitive resin composition can be obtained.

For the synthesis reaction of the phenol resin (D), it is preferable to use an acid catalyst. By using an acid catalyst, a novolak type phenolic resin can be synthesized in general, and a novolak type phenol resin can easily adjust molecular weight and hydroxyl group 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, But are not limited to these. Among them, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, phenol sulfonic acid and sulfuric acid are preferable in terms of reactivity. The addition amount is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 8 parts by mass or less, based on 100 parts by mass of the phenol charge.

The polycondensation reaction in the synthesis of the phenol resin (D) proceeds by stirring for several hours under heating. The reaction temperature is preferably 50 占 폚 to 160 占 폚. It is also possible to carry out the reaction in a solvent by adding a solvent at the time of the reaction. Examples of the reaction solvent include alcohols such as methanol, ethanol, isopropanol, diethylene glycol monomethyl ether and diethylene glycol; Ketone solvents such as acetone, methyl ethyl ketone and methyl amyl ketone; Ethers such as diethylene glycol monomethyl ether acetate; Cyclic ethers such as tetrahydrofuran and dioxane; lactones such as? -butyrolactone; Pure water, and the like. The amount of the solvent to be added is preferably 10 parts by mass or more and 200 parts by mass or less based on 100 parts by mass of the phenol charge.

After completion of the reaction, the acid catalyst is neutralized with a base such as pyridine, triethylamine or sodium hydroxide, and if necessary, the neutralized salt is removed by extraction with an aqueous layer (water layer), followed by dehydration and monomer removal, do.

After the synthesis of the phenol resin (D), a monomer removal step is usually carried out. As a method for removing the monomer, a solvent fractionation method for removing the aqueous layer by adding a solvent and water or a method for volatilizing the monomer by heating under reduced pressure can be selected. In the solvent fractionation method, a solvent such as acetone, methanol, isopropanol or butanol which is a good soluble solvent and a solvent such as pure water which is a poorly soluble solvent with respect to the phenol resin are added to the phenol resin at a predetermined ratio , And the separated water layer is removed after standing, whereby the monomer moved to the water layer side can be removed. In the method of volatilizing the monomer, the monomer may be removed by volatilization by heating and stirring at 150 캜 to 250 캜 while reducing the pressure to 50 mmHg or lower. In the case of removing the monomer by volatilization, a solvent, pure water, steam, N ₂ gas and the like may be added in order to increase the monomer removal efficiency. The solvent is not particularly limited as long as it does not affect the phenol resin. Examples of the solvent include ethylene glycol, ethylene glycol alkyl ether, propylene glycol alkyl ether, propylene glycol alkyl ether acetate, di Glycols such as ethylene glycol, diethylene glycol alkyl ether, triethylene glycol and triethylene glycol alkyl ether,? -Butyrolactone,? -Valerolactone,? -Valerolactone and the like Polar (polarity) polarities such as N, N-dimethylformamide, N, N-diethylformamide, dimethylsulfoxide and dimethylimidazolidinone, such as N-methylpyrrolidone, N, N-dimethylacetamide, ) Aprotic solvent. In both the fractionation method and the monomer volatilization method, the removal efficiency of the monomer can be increased by repeating the operation depending on the residual amount of the monomer.

The weight average molecular weight of the phenol resin (D) thus obtained, as determined by gel permeation chromatography, in terms of polystyrene is preferably 500 or more and 10000 or less, and more preferably 700 or more and 7000 or less. When the weight average molecular weight is not lower than the lower limit value, heat resistance and film toughness as a photosensitive resin composition can be further improved. When the weight average molecular weight is not more than the upper limit value, residues generated in the openings can be further suppressed by patterning.

The phenol resin (D) thus obtained can be finally recovered as a flaky product or a solvent-dissolved product. Examples of the solvent that can be recovered as the solvent-soluble product include N-methyl-2-pyrrolidone,? -Butyrolactone, N, N- dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether , Diethylene glycol diethyl ether, diethylene glycol di butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, lactic acid Butyl, methyl-1,3-butylene glycol acetate, 1,3-butyleneglycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate and methyl-3-methoxy propionate. They may be used singly or in combination.

When the phenolic resin (D) is contained in the photosensitive resin composition of the present embodiment, the content of the phenolic resin (D) is not particularly limited, but it is preferably 5 parts by mass per 100 parts by mass of the total amount of the alkali- Or more, more preferably 10 parts by mass or more, and still more preferably 25 parts by mass or more. It is preferably not more than 1900 parts by mass, more preferably not more than 400 parts by mass, and most preferably not more than 150 parts by mass. The amount 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. The addition amount is within the above-mentioned range, and good patterning performance and curability can be exhibited in a balanced manner.

The alkali-soluble resin (A) is preferably at least 5/95, more preferably at least 20/80, and even more preferably at least 40/60 by weight (A / D) with respect to the phenol resin (D). It is preferably 95/5 or less, more preferably 90/10 or less, and further preferably 80/20 or less. Further, it is preferably 20/80 or more and 95/5 or less, more preferably 20/80 or more and 80/20 or less, still more preferably 40/60 or more and 80/20 or less. When used in this range, good properties can be realized as a photosensitive resin composition. When the weight ratio (A / D) is not less than the lower limit value, the heat resistance and film properties required for the photosensitive resin composition can be further improved. When the weight ratio (A / D) is not more than the upper limit value, the sensitivity at the time of patterning can be improved, and the throughput can be further improved.

[solvent]

The photosensitive resin composition of the present embodiment can be used in the form of a varnish by dissolving each of the above components in a solvent. Examples of the solvent include N-methyl-2-pyrrolidone,? -Butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, di Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butyllene, ethyl lactate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate and methyl-3-methoxy propionate. These may be used singly or in combination.

The content of the solvent in the photosensitive resin composition of the present embodiment is not particularly limited, but is preferably 50 parts by mass or more and 300 parts by mass or less, more preferably 100 parts by mass or more per 100 parts by mass of the alkali-soluble resin (A) More preferably 200 parts by mass or less. When the amount added is within the above range, the resin can be sufficiently dissolved to produce a varnish having high handling properties.

[Heat crosslinking agent (E)]

The photosensitive resin composition of the present embodiment may further contain a heat 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 the phenol resin (D) by heat. Examples thereof include 1,2- Benzene dimethanol, 1,4-benzene dimethanol, 1,3,5-benzene trimethanol, 4,4-biphenyl dimethanol, 2,6-pyridine dimethanol, 2,6- A compound having a methylol group typified by 4-methylenebis (2,6-dialkoxymethylphenol), and the like; Bis (methoxymethyl) benzene, 4,4'-bis (methoxymethyl) biphenyl, 3,4'-bis (methoxymethyl) Alkoxymethyl groups represented by phenyl, 3,3'-bis (methoxymethyl) biphenyl, 2,6-naphthalenedicarboxylic acid methyl, and 4,4'-methylenebis (2,6-dimethoxymethylphenol) ≪ / RTI > Methylolmelamine compounds such as hexamethylol melamine, hexabutanol melamine and the like; Alkoxymelamine compounds represented by hexamethoxy melamine and the like; Alkoxymethyl glycoluril compounds represented by tetramethoxymethyl glycoluril and the like; Methylol urea compounds represented by methylol benzoguanamine compounds, dimethylol ethylene urea, and the like; Cyano compounds represented by dicyanoaniline, dicyanophenol, cyanophenylsulfonic acid and the like; Isocyanate compounds represented by 1,4-phenylene diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate and the like; Ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, isocyanuric acid triglycidyl, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, Epoxy group-containing compounds typified by boric resin epoxy resins and the like; Maleimide compounds represented by N, N'-1,3-phenylene dimaleimide, N, N'-methylene dimaleimide and the like, but are not limited thereto. These thermal crosslinking agents may be used alone or in combination of two or more.

The content of the thermosetting agent (E) in the photosensitive resin composition of the present embodiment is not particularly limited, but is preferably 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A) And more preferably not less than 20 parts by mass. When the addition amount is within the above range, a cured film excellent in residual film ratio and heat resistance at the time of curing can be formed.

[Silane coupling agent (F)]

In the photosensitive resin composition of the present embodiment, a silane coupling agent different from the silane compound (B) may be used (hereinafter also referred to as a silane coupling agent (F)) within a range that does not impair transparency from the viewpoint of further improving adhesion. ). Examples of the silane coupling agent (F) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryl Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane , Bis (triethoxypropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and While the silicon compound and the acid having a diamino be mentioned silicon compounds obtained by reacting the anhydride or the acid anhydride, but is not limited thereto.

Examples of the silicon compound having an amino group include, but are not limited to, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- Dimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, and the like.

Examples of the acid dianhydride or acid anhydride include, but are not limited to, maleic anhydride, chloromeric maleic acid, cyano maleic anhydride, citraconic acid, phthalic anhydride, pyromellitic acid anhydride, Biphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-carbonyldiphthalic anhydride, and the like. In use, they may 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, but is preferably 0.05 to 50 parts by mass per 100 parts by mass of the alkali- , And more preferably 0.1 to 20 parts by mass. When the amount of addition is within the above range, the adhesiveness to the substrate and the preservability of the photosensitive resin composition can be suitably matched.

[Dissolution accelerator]

The photosensitive resin composition of the present embodiment may contain a dissolution promoting agent.

The dissolution enhancer is a component capable of improving the solubility of the exposed portion of a coating film formed using a photosensitive resin composition in a developing solution and improving the scum at the time of patterning.

As the dissolution promoting agent, a compound having a phenolic hydroxyl group is particularly preferable.

[Other components]

 If necessary, an additive such as an antioxidant, a filler, a surfactant, a photopolymerization initiator, a terminal blocking agent and a sensitizer may be added to the photosensitive resin composition of the present embodiment.

In the above photosensitive resin composition, the ratio of each component is, for example, as follows.

The proportion of the alkali-soluble resin (A) is preferably 20 mass% or more and 95 mass% or less, and the total amount of the silane compound (B) and the silane compound (B) is preferably 100 mass% Is not less than 0.1 mass% and not more than 30 mass%, and the ratio of the photoacid generator (C) is not less than 1 mass% and not more than 30 mass%.

More preferably, the proportion of the alkali-soluble resin (A) is 30% by mass or more and 90% by mass or less, the proportion of the silane compound (B) is 0.5% by mass or more and 20% by mass or less, Is not less than 5 mass% and not more than 20 mass%.

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 when the phenol resin (D) (C) is 1% by mass or more and 30% by mass or less, and the proportion of the phenol resin (D) is 1% by mass or more and 30% by mass or less.

The photosensitive resin composition is prepared by mixing and dissolving an alkali-soluble resin (A), a silane compound (B), a photo acid generator (C), and other components as necessary in an organic solvent. In the present embodiment, it is possible to prepare a photosensitive resin composition by mixing and dissolving each component in an organic solvent under a nitrogen flow, for example. The alkali-soluble resin (A) may also be synthesized under a nitrogen flow, for example. By thus suppressing the amount of oxygen or moisture contained in the photosensitive resin composition, the characteristics of the photosensitive resin composition can be improved.

[Coating film]

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

The photosensitive resin composition of this embodiment can be made into a cured film by curing. Specifically, the composition is first applied to a suitable support, for example, a silicon wafer, a ceramic substrate, an aluminum substrate, or the like. When applied on a semiconductor element, the coating amount is generally applied so that the final film thickness after curing becomes 0.1 to 30 μm. By setting such a numerical range, a function as a protective film and an insulating film of a semiconductor element can be sufficiently exhibited to obtain a fine relief pattern.

Examples of application methods include spin coating using a spin coater, spray coating using a spray coater, dipping, printing, and roll coating.

Next, in the case of forming a relief pattern after drying the coating film by pre-baking at 60 to 130 DEG C, the chemical ray is irradiated in a desired pattern shape. As the actinic rays, X-rays, electron rays, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable.

Next, the irradiated portion is dissolved and removed with a developer to obtain a relief pattern. Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Alcohol amines such as dimethylethanolamine and triethanolamine; Quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; An aqueous solution containing an appropriate amount of a water-soluble organic solvent such as alcohols such as methanol and ethanol, or a surfactant may be suitably used. As the developing method, a method such as spraying, puddling, immersion, and ultrasonic waves is possible.

Next, the relief pattern formed by the development is rinsed. As the rinsing liquid, distilled water is used. Next, a heat treatment (curing) is carried out to obtain a cured film as a cured product having excellent heat resistance.

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

The light transmittance T (%) of the cured product obtained by heating and curing the photosensitive resin composition in terms of a film thickness of 10 m for a light beam having a wavelength of 630 nm is preferably 75% or more, more preferably 78% or more, Is at least 80%, particularly preferably at least 82%, particularly preferably at least 85%. The upper limit value of the light transmittance T (%) in terms of a film thickness of 10 μm with respect to a light beam having a wavelength of 630 nm is not particularly limited, but is, for example, 99% or less. When the light transmittance T (%) of the cured product in terms of a film thickness of 10 μm with respect to a light beam having a wavelength of 630 nm is within the above range, the visibility of an adherend such as a semiconductor element or a display element, The productivity of the semiconductor device or the display device can be improved. The measurement of the light transmittance is carried out by using a general UV spectrophotometer, for example, UV-160A manufactured by Shimadzu Corporation. The measured light transmittance can be converted into a value of 10 mu m in film thickness by the Lambert-Beer's law, for example.

The glass transition temperature of the cured product obtained by thermally curing the photosensitive resin composition by differential scanning calorimetry (temperature raising rate 5 占 폚 / min) is preferably 200 占 폚 or higher, more preferably 220 占 폚 or higher, Gt; 250 < / RTI > The upper limit value of the glass transition temperature is not particularly limited, but is, for example, 400 DEG C or less. When the glass transition temperature of the cured product is within the above range, the heat resistance and mechanical properties of the resulting cured film can be further improved.

The elongation percentage by a tensile test (stretching speed: 5 mm / minute) of a cured product (dimension: 10 mm x 60 mm x 10 m thickness) obtained by thermally curing the photosensitive resin composition is preferably 20% or more, more preferably 30 %. The upper limit value of the tensile elongation is not particularly limited, but is, for example, 300% or less. When the elongation percentage of the cured product is within the above range, the risk of cracking due to the stress at the time of film deformation is reduced, and the reliability as a protective film can be further improved.

The tensile modulus of the cured product (dimension: 10 mm x 60 mm x 10 m thickness) obtained by thermally curing the photosensitive resin composition is preferably 0.5 GPa or more and 10 GPa or less, more preferably 0.5 GPa or more and 10 GPa or less Is not less than 1.0 GPa and not more than 8.0 GPa. When the tensile modulus of elasticity of the cured product is within the above range, the cured film obtained can have sufficient strength, and reliability as a protective film can be further improved.

<Applications>

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

The cured film formed using the photosensitive resin composition of the present embodiment can be used not only for semiconductor devices such as semiconductor devices but also for display device applications such as TFT type liquid crystals and organic EL devices and for interlayer insulating films and flexible copper plates Plate), a solder resist film, and a liquid crystal alignment film.

Examples of the application of the semiconductor device include a passivation film formed by forming a cured film of the photosensitive resin composition on a semiconductor element and a protective film such as a buffer coat film formed by forming a cured film of the photosensitive resin composition on the passivation film, An insulating film such as an interlayer insulating film formed by forming a cured film of the above-mentioned photosensitive resin composition on the formed circuit, an? Ray shielding film, a planarizing film, a projection (resin post), and a barrier rib.

Examples of applications of the display device include a protective film formed by forming a cured film of the photosensitive resin composition of the present embodiment on a display element, an insulating film or a planarizing film for a TFT element or a color filter, a projection for an MVA type liquid crystal display device, A barrier rib for an organic EL element cathode, and the like.

The method of use is to form a patterned photosensitive resin composition layer on a substrate on which a display element or a color filter is formed in accordance with the use of a semiconductor device by the above-described method. High transparency is required for the use of a display device, particularly an insulating film or a planarizing film. However, a resin layer having excellent transparency can be obtained by introducing a post-exposure process before curing the coating film of the photosensitive resin composition of the present embodiment, It is more preferable in practical use.

As semiconductor devices, semiconductor chips (elements) are formed on a semiconductor substrate and sealed by hermetic sealing or using a mold material. Specifically, various semiconductor packages and wafer level chip size packages (WLP) in which transistors, solar cells, diodes, solid state image pickup devices, and semiconductor chips are stacked and sealed can be given.

Examples of the display device include a TFT type liquid crystal, an organic EL, and a color filter.

Hereinafter, an example of an electronic device having a film formed using the photosensitive resin composition of the present embodiment will be described.

<Electronic Apparatus>

1 and 2 are sectional views showing an example of an electronic device 100 according to the present embodiment, respectively. In any of them, a part including the insulating film in the electronic device 100 is shown.

In the electronic device 100 according to the present embodiment, the insulating film is formed by, for example, a cured film formed by the photosensitive resin composition of the present embodiment.

As an example of the electronic device 100 according to the present embodiment, a liquid crystal display device is shown in Fig. However, the electronic device 100 according to the present embodiment is not limited to the liquid crystal display device, but includes another electronic device having a permanent film made of the photosensitive resin composition of the present embodiment.

1, an electronic device 100 as a liquid crystal display device includes a substrate 10, a transistor 30 provided on the substrate 10, a substrate 10 An insulating film 20 provided on the insulating film 20 and wirings 40 provided 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, for example, a plurality of transistors 30 are arrayed. The transistor 30 according to the present embodiment is constituted by the gate electrode 31, the source electrode 32, the drain electrode 33, the gate insulating film 34, and the semiconductor layer 35 do. The gate electrode 31 is provided on the substrate 10, for example. A 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 such that a part of the source electrode 32 comes into contact with the semiconductor layer 35. The drain electrode 33 is provided on the substrate 10 such that the drain electrode 33 is separated from the source electrode 32 and a part of the drain electrode 33 is in contact with the semiconductor layer 35. [

The insulating film 20 functions as a planarizing film for forming a flat surface on the substrate 10 by eliminating steps caused by the transistor 30 and the like. The insulating film 20 is constituted by a cured product of the photosensitive resin composition of the present embodiment. The insulating film 20 is provided with an opening 22 through which the insulating film 20 is connected so as to be connected to the drain electrode 33.

Wirings 40 connected to the drain electrodes 33 are formed on the insulating film 20 and in the openings 22. The wiring 40 functions as a pixel electrode constituting a pixel together with the liquid crystal.

On the insulating film 20, an alignment film 90 is provided 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 face the substrate 10. [ On one surface of the counter substrate 12 facing the substrate 10, a wiring 42 is provided. The wiring 42 is provided at a position facing the wiring 40. [ An alignment film 92 is provided on the one surface of the counter substrate 12 so as to cover the wirings 42.

Between the substrate 10 and the counter substrate 12, the liquid crystal constituting the liquid crystal layer 14 is filled.

The electronic device 100 shown in Fig. 1 is formed, for example, as follows.

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

Then, the insulating film 20 is exposed and developed to form an opening 22 in a part of the insulating film 20. Then, as shown in Fig. At this time, the unexposed portion is dissolved in the developer, and the exposed portion remains. This is the same in each example of the electronic device 100 described later.

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

Thus, the electronic device 100 shown in Fig. 1 is formed.

As an example of the electronic device 100 according to the present embodiment, FIG. 2 shows a semiconductor device in which a re-wiring layer 80 is constituted by a permanent film made of a photosensitive resin composition.

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

On the insulating film 50, a redistribution layer 80 is provided. The redistribution layer 80 includes an insulating film 52 provided on the insulating film 50 to cover the uppermost wiring 72, a redistribution line 70 provided on the insulating film 52, And an insulating film 54 provided on the insulating film 70.

In the insulating film 52, an opening 24 to be connected to the uppermost-level wiring 72 is formed. The rewiring lines 70 are formed on the insulating film 52 and in the openings 24 and connected to the uppermost layer wiring 72. The insulating film 54 is provided with an opening 26 connected to the redistribution line 70.

The insulating film 52 and the insulating film 54 are formed of a permanent film made of a photosensitive resin composition. The insulating film 52 is obtained, for example, by forming the opening 24 by performing exposure and development on the photosensitive resin composition applied on the insulating film 50, followed by heating and curing it. The insulating film 54 is obtained, for example, by forming the opening 26 by performing exposure and development on the photosensitive resin composition applied on the insulating film 52, followed by heating and curing the same.

In the opening 26, for example, a bump 74 is formed. The electronic device 100 is connected to a wiring board or the like through a bump 74, for example.

The electronic device 100 according to the present embodiment may be an optical device constituting a microlens by a permanent film made of a photosensitive resin composition. The optical device includes, for example, a liquid crystal display device, a plasma display, a field emission display, or an electroluminescence display.

Although the embodiments of the present invention have been described above, they are examples of the present invention, and various configurations other than the above may be employed.

It should be noted that the present invention is not limited to the above-described embodiments, and variations, modifications, and the like within the scope of achieving the object of the present invention are included in the present invention.

Example

Hereinafter, the present invention will be described in detail by way of examples and comparative examples, but the present invention is not limited thereto.

&Lt; Synthesis of alkali-soluble resin (A-1) >

(0.083 mol) of diphenyl ether-4,4'-dicarboxylic acid and 1-hydroxy-1,2-dicarboxylic acid were added to four separable flasks equipped with a stirrer, a thermometer, a stirrer, (0.083 mol) of a mixture of dicarboxylic acid derivatives obtained by reacting 3-benzotriazole monohydrate (22.43 g, 0.166 mol) with hexafluoro-2,2-bis 36.62 g (0.100 mol) of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the reaction was carried out at 75 DEG C for 15 hours using an oil bath.

Then, 6.98 g (0.0425 mol) of 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride dissolved in 34.88 g of N-methyl-2-pyrrolidone was added and stirred for 3 hours To complete the reaction.

After the reaction mixture was filtered, the reaction mixture was poured into a solution of water / isopropanol = 3/1 (volume ratio), the precipitate was collected by filtration, sufficiently washed with water and then dried under vacuum to obtain the desired polyamide resin Resin (A-1)) was obtained. The weight average molecular weight of the obtained compound was 13,040.

&Lt; Synthesis of alkali-soluble resin (A-2) >

30.0 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was placed in a four-neck separable flask equipped with a thermometer, stirrer, feed inlet and dry nitrogen gas inlet tube , And 400 ml of acetone were added and dissolved.

Next, 12.4 g (0.18 mol) of para-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise over 30 minutes while cooling to a temperature of less than 20 DEG C to obtain a mixture. After the dropwise addition, the temperature of the mixture was heated to 40 占 폚 and stirred for 2 hours. Then, 30.0 g (0.218 mol) of potassium carbonate was slowly added thereto and further stirred for 2 hours. Heating was stopped, and the mixture was further stirred at room temperature for 18 hours. Then, while stirring the mixture vigorously, an aqueous solution of sodium hydroxide was gradually added, and the mixture was heated to 55 캜 and further stirred for 30 minutes. After the completion of the stirring, the mixture was cooled to room temperature, and 37% by weight hydrochloric acid aqueous solution and 500 ml water were added to adjust the solution pH to 6.0-7.0. Subsequently, 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 '- (para-nitrobenzoyl) hexafluoro-2,2-bis Hydroxyphenyl) propane. &Lt; / RTI &gt;

To 51.0 g of the obtained solid was added 316 g of acetone and 158 g of methanol, and the mixture was heated to 50 캜 to completely dissolve it. There, 300 mL of pure water at 50 DEG C was added for 30 minutes and heated to 65 DEG C. [ Thereafter, the crystals were slowly cooled to room temperature, and the precipitated crystals were filtered, and the crystals were purified by drying at 70 ° C to give bis-N, N '- (para-nitrobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane.

20 g of bis-N, N '- (para-nitrobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane obtained above was placed in a flask of 1 L and a 5% palladium- g and 180.4 g of ethyl acetate were added to make a suspension. Thereafter, the hydrogen gas was purged, and the reaction was conducted by shaking for 35 minutes while heating at 50 to 55 캜. After completion of the reaction, the reaction mixture was cooled to 35 DEG C and nitrogen was purged from the suspension. After the catalyst was removed by filtration separation, the filtrate was put into an evaporator and the solvent was evaporated. The obtained product was dried at 90 占 폚 to obtain bis-N, N '- (para-aminobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane.

N, N '- (para-aminobenzoyl) hexafluoro-2,2-bis (4-methylpentanoate) Hydroxyphenyl) propane (14.0 g, 0.024 mol) were added, and 40 g of? -Butyrolactone was added and dissolved. Then, 6.8 g (0.022 mol) of 4,4'-oxydiphthalic anhydride and 12.0 g of? -Butyrolactone were added thereto, and the mixture was stirred at 20 ° C for 1.5 hours. Thereafter, the mixture was heated to 50 DEG C and stirred for 3 hours. Then, 5.2 g (0.044 mol) of N, N-dimethylformamide dimethylacetal and 10.0 g of gamma -butyrolactone were added and the mixture was further stirred at 50 DEG C for 1 hour . After completion of the reaction, the reaction mixture was cooled to room temperature to obtain a target polyamide resin (alkali-soluble resin (A-2)). The weight average molecular weight of the obtained compound was 13,200.

&Lt; Synthesis of alkali-soluble resin (A-3) >

(0.60 mol) of m-cresol, 43.3 g (0.40 mol) of p-cresol and 30 wt% of p-cresol were placed in a four-necked round bottom flask equipped with a stirrer, a thermometer, a stirrer, 65.1 g of formaldehyde aqueous solution (0.65 mol of formaldehyde) and 0.63 g (0.005 mol) of oxalic acid dihydrate were introduced, and the mixture was immersed in an oil bath and subjected to a polycondensation reaction at 100 DEG C for 4 hours while refluxing the reaction solution. Thereafter, the temperature of the oil bath was raised to 200 占 폚 for 3 hours. Thereafter, the pressure in the flask was reduced to 50 mmHg or lower to remove water and volatile components, and the resin was cooled to room temperature to obtain a novolak type phenol resin (alkali-soluble resin (A-3)) having a weight average molecular weight of 3200.

&Lt; Silane compound (B) >

Silane compounds (B-1), (B-2), (B-3) and (B-4) shown in the following formula (23) were prepared.

(28)

&Lt; Synthesis of Photoacid generator (C-1) >

11.04 g (0.026 mol) of a phenol compound represented by the formula (P-1) and 0.10 g (0.026 mol) of a 1,2-naphthoquinone-2-one were added to four separable flasks equipped with a thermometer, a stirrer, (0.070 mol) of diazepin-4-sulfonyl chloride and 170 g of acetone were added thereto, followed by stirring and dissolution.

Next, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C. After the reaction was allowed to proceed at room temperature for 3 hours, 1.05 g (0.017 mol) of acetic acid was added, followed by further reaction for 30 minutes. Subsequently, the reaction mixture was filtered, and the filtrate was poured into a mixed solution of water / acetic acid (990 ml / 10 ml). Then, the precipitate was collected by filtration, sufficiently washed with water, (C-1) represented by the structure of the formula (1).

[Chemical Formula 29]

&Lt; Synthesis of phenol resin (D-1) >

(0.75 mol) of bisphenol F (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 63.7 g (0.60 mol) of benzaldehyde were placed in a four-necked round bottom flask equipped with a thermometer, a stirrer, Mol), and benzene sulfonic acid (3.0 g, 0.02 mol) were introduced, and the mixture was immersed in an oil bath and subjected to a polycondensation reaction at 100 ° C for 2 hours while refluxing the reaction solution. Then, while cooling the flask, 75 g of acetone and 3.0 g (0.03 mol) of triethylamine were added, and the mixture was stirred for 30 minutes. Further, 150 g of pure water was further added and stirred for 30 minutes. After cooling to room temperature, stirring was stopped, and 37.5 g of? -Butyrolactone was added to remove the separated aqueous layer, and the temperature of the oil bath was raised to 170 ° C for 3 hours. Thereafter, the pressure in the flask was adjusted to 50 mmHg The volatile components were removed, and the resin was cooled to room temperature to obtain a phenol resin (D-1) having a weight average molecular weight of 2900.

&Lt; Synthesis of phenol resin (D-2) >

(0.75 mol) of 2,2'-bis (4-hydroxyphenyl) propane, 63.0 g of benzaldehyde (63.7 g) was added to a four-necked round bottom flask equipped with a stirrer, a thermometer, a stirrer, g (0.60 mol) of benzene sulfonic acid and 3.0 g (0.02 mol) of benzene sulfonic acid were introduced, and the mixture was immersed in an oil bath and subjected to a polycondensation reaction at 100 DEG C for 2 hours while refluxing the reaction solution. Then, while cooling the flask, 75 g of acetone and 3.0 g (0.03 mol) of triethylamine were added, and the mixture was stirred for 30 minutes. Further, 150 g of pure water was further added and stirred for 30 minutes. After cooling to room temperature, stirring was stopped, and 37.5 g of? -Butyrolactone was added to remove the separated aqueous layer, and the temperature of the oil bath was raised to 170 ° C for 3 hours. Thereafter, the pressure in the flask was reduced to 50 mmHg To remove volatile components, and then the resin was cooled to room temperature to obtain a phenol resin (D-2) having a weight average molecular weight of 2540.

&Lt; Heat crosslinking agent (E) >

1,4-benzene dimethanol was prepared as the thermal crosslinking agent (E-1).

&Lt; 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).

(30)

&Lt; Example 1 &gt;

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

&Lt; Example 2 &gt;

20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photo acid generator (C-1) synthesized above were mixed and dissolved in 25 g of? -Butyrolactone. Thereafter, 0.5 g of the silane compound (B-2) was added for 30 minutes and mixed. Finally, the mixture was filtered with a filter made of a fluorine resin having a pore diameter of 0.2 m to obtain a photosensitive resin composition of Example 2.

&Lt; Example 3 &gt;

20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photo acid generator (C-1) synthesized above were mixed and dissolved in 25 g of? -Butyrolactone. Thereafter, 0.5 g of the silane compound (B-3) was added and mixed for 30 minutes and finally filtered through a fluororesin filter having a pore diameter of 0.2 m to obtain a photosensitive resin composition of Example 3.

&Lt; Example 4 &gt;

20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photo acid generator (C-1) synthesized above were mixed and dissolved in 25 g of? -Butyrolactone. Thereafter, 0.5 g of the silane compound (B-4) was added for 30 minutes and mixed. Finally, the mixture was filtered through a fluororesin filter having a pore diameter of 0.2 m to obtain a photosensitive resin composition of Example 4.

&Lt; Example 5 &gt;

20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photo acid generator (C-1) synthesized above were mixed and dissolved in 25 g of? -Butyrolactone. Thereafter, 0.8 g of the silane compound (B-3) was added for 30 minutes and mixed. Finally, the resultant was filtered through a fluororesin filter having a pore diameter of 0.2 m to obtain a photosensitive resin composition of Example 5.

&Lt; Example 6 &gt;

20 g of the alkali-soluble resin (A-2) synthesized above and 2.8 g of the photo acid generator (C-1) synthesized above were mixed and dissolved in 25 g of? -Butyrolactone. Thereafter, 0.5 g of the silane compound (B-3) was added for 30 minutes and mixed. Finally, the mixture was filtered through a fluororesin filter having a pore diameter of 0.2 m to obtain a photosensitive resin composition of Example 6.

&Lt; Example 7 &gt;

14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of alkali solubility (A-3) and 2.8 g of the photo acid generator (C-1) synthesized above were mixed in 25 g of? -Butyrolactone Dissolved. Thereafter, 0.5 g of the silane compound (B-3) was added for 30 minutes and mixed. Finally, the mixture was filtered through a fluororesin filter having a pore diameter of 0.2 m to obtain a photosensitive resin composition of Example 7.

&Lt; Embodiment 8 &gt;

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 photo acid generator (C-1) synthesized above were mixed in 25 g of? -Butyrolactone Dissolved. Thereafter, 0.5 g of the silane compound (B-3) was added for 30 minutes and mixed. Finally, the mixture was filtered with a filter made of a fluorine resin having a pore diameter of 0.2 m to obtain a photosensitive resin composition of Example 8.

&Lt; Example 9 &gt;

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 photo acid generator (C-1) synthesized above were mixed in 25 g of? -Butyrolactone Dissolved. Thereafter, 0.5 g of the silane compound (B-3) was added for 30 minutes and mixed. Finally, the resultant was filtered through a fluororesin filter having a pore diameter of 0.2 m to obtain a photosensitive resin composition of Example 9.

&Lt; Example 10 &gt;

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 photo acid generator (C-1) synthesized above were mixed in 25 g of? -Butyrolactone Dissolved. Thereafter, 0.5 g of the silane compound (B-3) was added and mixed for 30 minutes. Further, 0.1 g of the silane coupling agent (F-1) was added for 30 minutes, To obtain a photosensitive resin composition of Example 10.

&Lt; Example 11 &gt;

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 photo acid generator (C-1) synthesized above were mixed in 25 g of? -Butyrolactone Dissolved. Thereafter, 0.5 g of the silane compound (B-3) was added and mixed for 30 minutes. Further, 0.4 g of the silane coupling agent (F-2) was added for 30 minutes, To obtain a photosensitive resin composition of Example 11.

&Lt; Example 12 &gt;

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 photo acid generator (C-1) synthesized above were mixed in 25 g of? -Butyrolactone Dissolved. Thereafter, 0.5 g of the silane compound (B-3) was added and mixed for 30 minutes, 0.1 g of a silane coupling agent (F-1) was further added for 30 minutes, and a fluoric surfactant (Megapack F557, DIC (Manufactured by Nippon Shokubai Co., Ltd.), and finally filtered through a fluororesin filter having a pore diameter of 0.2 m to obtain a photosensitive resin composition of Example 12.

&Lt; Example 13 &gt;

14 g of the alkali-soluble resin (A-1) synthesized above, 6 g of the phenol resin (D-1), 1.1 g of the heat crosslinking agent (E-1) and 2.8 g of the photoacid generator (C- Were mixed and dissolved in 25 g of? -Butyrolactone. Thereafter, 0.5 g of the silane compound (B-3) was added and mixed for 30 minutes, 0.1 g of a silane coupling agent (F-1) was further added for 30 minutes, and a fluoric surfactant (Megapack F557, DIC (Manufactured by Mitsubishi Chemical Corporation), and finally filtered through a fluororesin filter having a pore diameter of 0.2 m to obtain a photosensitive resin composition of Example 13.

&Lt; Comparative Example 1 &gt;

20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photo acid generator (C-1) synthesized above were mixed and dissolved in 25 g of? -Butyrolactone. And filtered through a filter to obtain a photosensitive resin composition of Comparative Example 1. [

&Lt; Comparative Example 2 &gt;

20 g of the alkali-soluble resin (A-1) synthesized above and 2.8 g of the photo acid generator (C-1) synthesized above were mixed and dissolved in 25 g of? -Butyrolactone. Thereafter, 0.4 g of a silane coupling agent (F-2) was added for 30 minutes and finally filtered through a fluororesin filter having a pore diameter of 0.2 m to obtain a photosensitive resin composition of Comparative Example 2.

The photosensitive resin compositions obtained in the respective Examples and Comparative Examples were evaluated according to the following items.

&Lt; Processability evaluation &

Each of the photosensitive resin compositions obtained above was applied to an 8-inch silicon wafer using a spin coater and then pre-baked at 120 DEG C for 3 minutes on a hot plate to obtain a coating film having a thickness of about 7.5 mu m. The exposure amount was changed using an i-line stepper (NSR-4425i, manufactured by Nikon Corporation) through a mask made of a grease gun (test chart No. 1: a residual pattern having a width of 0.88 to 50 袖 m and a punching pattern drawn) .

Next, using a 2.38% aqueous solution of tetramethylammonium hydroxide as a developing solution, the development time was adjusted so that the difference between the film thickness after pre-baking and the film thickness after development was 1.0 占 퐉, And then rinsed with pure water for 10 seconds. The value of the minimum exposure amount at which a via hole pattern of a square having one side of 100 mu m was formed was evaluated as the sensitivity.

&Lt; Evaluation of cured residual film ratio &

Each of the photosensitive resin compositions obtained above was applied to an 8-inch silicon wafer using a spin coater and then pre-baked at 120 DEG C for 3 minutes on a hot plate to obtain a coating film having a thickness of about 7.5 mu m. The coated film was heated in an oven at 150 占 폚 for 30 minutes and then at 300 占 폚 for 30 minutes while maintaining the oxygen concentration at 1000 ppm or less, and the film thickness after returning to room temperature was measured. The film thickness change rate after curing and the film thickness before curing was calculated from the following equation and evaluated as the cured residual film ratio.

Cured residual film ratio = film thickness after curing / film thickness before curing * 100

The cured residual film ratio is preferably high in order to maintain a sufficient film thickness for protecting semiconductor devices.

&Lt; Evaluation of adhesion &

Each of the photosensitive resin compositions obtained above was applied to an 8-inch silicon wafer using a spin coater and then pre-baked at 120 DEG C for 3 minutes on a hot plate to obtain a coating film having a thickness of about 7.5 mu m. Using this i-line stepper (NSR-4425i, manufactured by Nikon Corporation), i-line irradiation was carried out with varying the exposure dose through a mask having a line and space pattern with a width of 1 to 20 μm and a via pattern drawn on the coating film, By using a 2.38% aqueous solution of tetramethylammonium hydroxide as a developing solution, the exposed portion was dissolved and removed. The thus obtained pattern was confirmed, and the amount of exposure at which a pattern of via holes of 10 mu m was formed was defined as the reference exposure amount. A wafer having a predetermined reference exposure amount irradiated at a predetermined reference exposure dose and having the exposed portion dissolved therein was evaluated as?, And when the development pattern formed by the line and space pattern of 1 占 퐉 was formed on the wafer, , And the adhesion after development was evaluated.

&Lt; Evaluation of heat resistance &

The cured film obtained in the evaluation of the cured residual film ratio was heated with a differential scanning calorimetry (DSC6000 manufactured by Seiko Instruments Inc.) under the condition of a temperature increase of 5 deg. C / min to calculate a glass transition temperature (Tg) from an extrapolated point . Further, the temperature was raised at a temperature elevation rate of 10 deg. C / min with a Tg-DTA apparatus (TG / DTA6200 manufactured by Seiko Instruments Inc.), and a 5% weight reduction temperature (Td5) was measured.

&Lt; Evaluation of elongation and elastic modulus &

A tensile test (stretching speed: 5 mm / minute) was performed on a test piece (10 mm x 60 mm x 10 m thick) obtained by curing the photosensitive resin material obtained above under the conditions of 300 DEG C and 30 minutes under a nitrogen atmosphere in an atmosphere of 23 DEG C . The tensile test was conducted using a tensile tester (Tensilon RTC-1210A) manufactured by Orientec. Five test specimens were measured, and the tensile elongation was calculated from the fractured distance and the initial distance, and the average elongation was taken as the elongation. The tensile modulus was calculated from the initial gradient of the obtained stress-strain curve, and the tensile modulus was taken as an average.

&Lt; Measurement of light transmittance &

The light transmittance T (%) of the cured film obtained in the evaluation of the elongation and the modulus of elasticity in terms of a film thickness of 10 μm with respect to a light beam with a wavelength of 630 nm was measured. The light transmittance T was obtained by converting the light transmittance measured by using UV-160A manufactured by Shimadzu Seisakusho Co., Ltd. to a value of a film thickness of 10 mu m according to the Lambert-Beer's law.

The results of the blending of the examples and the comparative examples and the evaluation results of the obtained photosensitive resin compositions are collectively shown in Table 1 below.

[Table 1]

<Fabrication of Semiconductor Device>

After applying the photosensitive resin compositions obtained in Examples 1 to 13 to a final thickness of 5 占 퐉 using a simulated device wafer having a pattern formed by an aluminum circuit on the surface thereof, patterning was performed in accordance with the pattern formed on the wafer And cured. Thereafter, each die size (BESTEM-D02) was divided for each chip size and mounted on the organic substrate using conductive paste. At this time, the mounting could be performed without lowering the visibility by the photosensitive resin composition.

&Lt; Adhesion by high temperature and high pressure treatment >

Further, a semiconductor device was fabricated by encapsulation with an epoxy resin for semiconductor encapsulation (EME-6300H made by Sumitomo Bakelite Co., Ltd.). These semiconductor devices (semiconductor packages) were treated for 168 hours under the condition of 85 占 폚 / 85% humidity and immersed in a 260 占 폚 solder bath for 10 seconds and then subjected to high temperature and high pressure cooker treatment (125 占 폚, 2.3 atm, % Relative humidity) was performed to check the open failure of the aluminum circuit. As a result, it was suggested that the cured film of the photosensitive resin composition obtained in the examples had no defect or the like, and that it had adhesiveness that could be used without problems as a semiconductor device.

This application is based upon and claims the benefit of priority from Japanese Patent Application No. 2014-098147, filed on May 9, 2014, the entire disclosure of which is hereby incorporated by reference.

Claims (19)

The alkali-soluble resin (A)
A silane compound (B) represented by the following general formula (1)
The photoacid generator (C)
.
[Chemical Formula 1]

(1) wherein R1 and R3 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, A substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms, a and b each represent a substituted or unsubstituted saturated alkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted unsaturated alkyl group having 1 to 10 carbon atoms, c and d represent an integer of 0 to 3 satisfying c + d = 3, m and n represent an integer of 0 to 2, and m + n? 0 to be.) The method according to claim 1,
A in the general formula (1) of the silane compound (B) is an organic group having an aromatic ring. The method according to claim 1 or 2,
Wherein A in the general formula (1) of the silane compound (B) is an organic group selected from the group of organic groups represented by the following formula (2).
(2)

(Wherein X1 represents a divalent organic group containing a single bond, C (-Y1) (-Y2), a sulfur atom, an ether group, a carbonyl group, an ester group or an amide group, Y1 and Y2 each independently represent hydrogen A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, . The method according to claim 1,
A in the general formula (1) of the silane compound (B) is an organic group having an aliphatic ring. The method according to claim 1 or 4,
Wherein A in the general formula (1) of the silane compound (B) is an organic group selected from the group of organic groups represented by the following formula (3).
(3)

(Wherein X2 represents a divalent organic group containing a single bond, C (-Y3) (-Y4), a sulfur atom, an ether group, a carbonyl group, an ester group or an amide group, Y3 and Y4 each independently represent hydrogen A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, . The method according to claim 1,
Wherein the alkali-soluble resin (A) comprises at least one selected from polybenzoxazole, polybenzoxazole precursor, polyimide, and polyimide precursor. The method according to claim 1,
A photosensitive resin composition further comprising a phenol resin (D) obtained by reacting a phenol compound with an aromatic aldehyde compound. The method of claim 7,
Wherein the aromatic aldehyde compound comprises an aromatic aldehyde compound represented by the following formula (4).
[Chemical Formula 4]

(Wherein R ₁ represents hydrogen, an organic group selected from 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) The method according to claim 7 or 8,
Wherein the phenolic compound comprises a phenol compound represented by the following formula (5).
[Chemical Formula 5]

(Wherein X3 represents a divalent organic group containing a single bond, C (-Y7) (-Y8), a sulfur atom, an ether group, a carbonyl group, an ester group, or an amide group, Y7 and Y8 each independently represent hydrogen A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, And Y5 and Y6 each independently represent 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, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, Or a substituted or unsubstituted cyclohexyl group, p and q each independently represent an integer of 1 to 3, and r and s each independently represent an integer of 0 to 3. ) The method according to claim 1,
A photosensitive resin composition further comprising a heat crosslinking agent (E). A cured film composed of a cured product of the photosensitive resin composition according to claim 1. A protective film comprising the cured film according to claim 11. An insulating film composed of the cured film according to claim 11. An electronic device having the cured film according to claim 11. The method of claim 2,
Wherein the aromatic ring includes one selected from the group consisting of a benzene ring, a naphthalene ring, a biphenylene ring, a fluorene ring, a phenylene ring, and an anthracene ring. The method of claim 4,
Wherein the aliphatic ring includes one selected from the group consisting of cyclohexane, bicyclo pentane, and adamantane. The method according to claim 1,
Wherein the content of the silane compound (B) is 0.1 part by weight or more and 50 parts by weight or less based on 100 parts by weight of the total amount of the alkali-soluble resin (A). The method according to claim 1,
And a silane coupling agent (F) different from the silane compound (B). The method according to claim 1,
Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.

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