WO2008038460A1

WO2008038460A1 - Photosensitive resin composition

Info

Publication number: WO2008038460A1
Application number: PCT/JP2007/065300
Authority: WO
Inventors: Takashi Chiba; Mibuko Shimada; Shigehito Asano
Original assignee: Jsr Corporation
Priority date: 2006-09-25
Filing date: 2007-08-03
Publication date: 2008-04-03
Also published as: JPWO2008038460A1; JP5024292B2

Abstract

A photosensitive resin composition comprising (A) a polyimide resin, (B) a photo-acid generator, (C) a crosslinking agent having an alkoxyalkylated amino group, and (D) a compound represented by the general formula (1) [wherein R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and R2, R3 and R4 independently represent an alkyl group having 1 to 5 carbon atoms.

Description

Specification

Photosensitive resin composition

Technical field

The present invention relates to a photosensitive resin composition used for an interlayer insulating film (passivation film), a surface protective film (overcoat film), an insulating film for a high-density mounting substrate, and the like of a semiconductor element. More specifically, a surface protective film that has excellent storage stability, high film thickness coating with high solubility in common solvents and alkali development, and can obtain a cured product with high resolution. The present invention relates to a photosensitive resin composition suitable for use in interlayer insulating films and insulating films for high-density mounting substrates.

Background art

Conventionally, polyimide-based resins having excellent heat resistance, mechanical properties, and the like have been widely used for surface protective films, interlayer insulating films, and the like used in semiconductor elements of electronic devices. In addition, various photosensitive polyimide resins that have been given photosensitivity to improve film formation accuracy due to high integration of semiconductor elements have been proposed, and side-chain polymerizable negative photosensitive polyimide is widely used. .

[0003] For example, Patent Document 1 discloses a photosensitive composition using an aromatic polyimide precursor having an acrylic side chain. However, this photosensitive composition has problems that it is difficult to cope with a high film thickness due to the problem of light transmittance and that the residual stress after curing is large. Furthermore, there have been problems with the environment and safety due to solvent development. Since it is necessary to use an organic solvent as the developer, development of an alkali development type radiation-sensitive resin composition is desired.

[0004] In order to solve these problems, many proposals have been conventionally made. For example, Patent Documents 2 and 3 propose positive photosensitive polyimide compositions that can be alkali-developed. However, the coating properties of these photosensitive polyimide compositions are not always good, and it has been difficult to cope with a high film thickness of, for example, 15 m or more. There was also a problem that it was difficult to obtain a sufficiently high resolution. For this reason, it can be used for surface protective films, interlayer insulating films and insulating films for high-density mounting substrates that require high film thickness coating and high resolution. When it was difficult, there was a problem.

[0005] Many other patents have been filed, but it is difficult to sufficiently satisfy the required characteristics due to high integration and thinning of semiconductor elements. In addition, these compositions may be difficult to use over time because their viscosity is likely to change over time. Therefore, development of a composition having good storage stability with little change in viscosity with time is desired.

[0006] Patent Document 1: Japanese Patent Laid-Open No. 63-125510

Patent Document 2: Japanese Patent Laid-Open No. 3-204649

Patent Document 3: Japanese Patent Laid-Open No. 3-209478

Disclosure of the invention

[0007] The present invention has been made in view of the above-described problems of the prior art, and the object is to provide a high film that has excellent storage stability and high solubility in common solvents. A photosensitive resin composition suitable for use in surface protective films, interlayer insulating films, and insulating films for high-density mounting substrates, capable of thick coating and alkali development, and capable of obtaining a cured product with high resolution. It is to provide.

[0008] As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the above-described problems can be achieved by adopting the following configuration, and have completed the present invention. The That is, according to the present invention, the following photosensitive resin composition is provided.

[1] (A) a polyimide resin, (B) a photoacid generator, (C) a cross-linking agent having an alkoxyalkylated amino group, and (D) a compound represented by the following general formula (1) And a photosensitive resin composition.

[0010] [Chemical 1]

(In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ^;, and R ⁴ are independently of each other, an alkyl group having! Indicate)

[0011] [2] The sensation according to [1], wherein R ¹ in the general formula (1) is a hydrogen atom or a methyl group. Photopolymer composition.

[0012] The photosensitive resin composition according to [1] or [2], wherein the compound (D) is an orthoformate ester.

[4] The photosensitive resin composition according to any one of [1] to [3] above, further containing a resin having a phenolic hydroxyl group.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the (A) polyimide resin strength is alkali-soluble.

[6] The above (A) polyimide resin contains a repeating unit represented by the following general formula (2):

The photosensitive resin composition according to [1] to [5]!

[0016] [Chemical 2]

(In the general formula (2), X represents a tetravalent aromatic or aliphatic hydrocarbon group, and A represents a divalent group having a hydroxyl group)

[7] The photosensitive resin composition according to [6], wherein X in the general formula (2) is a tetravalent aliphatic hydrocarbon group.

[8] The above [6] or [7] wherein A in the general formula (2) is a group represented by the following general formula (3):

] The photosensitive resin composition as described in above.

[0019] [Chemical 3]

(In the general formula (3), R ⁵ represents a single bond, oxygen atom, sulfur atom, sulfone group, carbonyl group, methylene group, dimethylenolemethylene group,

At least one group selected from the group, R ⁶ independently of each other represents a hydrogen atom, an acyl group, or an alkyl group, n ¹ and n ² represent an integer of 0 to 4, n ¹ and n ^At least one of ² is 1 or more, and at least one of R ⁶ is a hydrogen atom) [0020] The photosensitive resin composition of the present invention is excellent in storage stability, can be applied to a high film thickness with high solubility in general solvents, and can be developed with an alkali, and a cured product with high resolution can be obtained. It is suitable for surface protection films, interlayer insulation films, and insulation films for high-density mounting substrates.

Brief Description of Drawings

FIG. 1 is a schematic cross-sectional view of a semiconductor element having an insulating resin layer formed using the photosensitive resin composition of the present invention.

FIG. 2 is a schematic cross-sectional view of a semiconductor element having an insulating resin layer formed using the photosensitive resin composition of the present invention.

Explanation of symbols

[0022] 1: substrate, 2: metal pad, 3: insulating film, 4: metal wiring, 5: insulating film

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the best mode for carrying out the present invention will be described. However, the present invention is not limited to the following embodiment, and is within the scope of the gist of the present invention. Based on the above, it should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.

[0025] One embodiment of the photosensitive resin composition of the present invention includes (A) a polyimide resin, (B) a photoacid generator, (C) a crosslinking agent having an alkoxyalkylated amino group, and (D) It contains a compound represented by the following general formula (1). The details will be described below.

[0026] ((A) Polyimide resin)

(A) The polyimide resin is not particularly limited as long as it is a polymer (resin) containing a polyimide skeleton in its molecular structure, but is preferably an alkali-soluble resin. Specific examples of the (A) polyimide resin include those containing a repeating unit represented by the general formula (2). Here, X in the general formula (2) is a tetravalent aromatic hydrocarbon group or a tetravalent aromatic group. An aliphatic hydrocarbon group, preferably a tetravalent aliphatic hydrocarbon group. Specific examples of the tetravalent aromatic hydrocarbon group include a tetravalent group in which four hydrogen atoms in the aromatic hydrocarbon mother skeleton are replaced.

[0027] Examples of the aromatic hydrocarbon group include the following groups.

[0028] [Chemical 4]

(a— 7) (a— 8)

[0029] Examples of the tetravalent aliphatic hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an alkyl alicyclic hydrocarbon group. More specifically, it is possible to cite a tetravalent group in which four hydrogens in the base skeleton of a chain hydrocarbon group, an alicyclic hydrocarbon, or an alkyl alicyclic hydrocarbon are substituted. These tetravalent aliphatic hydrocarbon groups may include an aromatic ring in at least a part of the structure. Examples of chain hydrocarbons include ethane, n-pronone, n-pentane, n-pentane, n-hexane, n-year-old kutan, n-decane, and n-dodecane. In addition, specific examples of alicyclic hydrocarbons include the ability S to include monocyclic hydrocarbon groups, bicyclic hydrocarbon groups, tricyclic or higher hydrocarbons, and the like.

[0030] Examples of the monocyclic hydrocarbon include cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, and cyclooctane. Bicyclic hydrocarbons include bicyclo [2.2.1] heptane, bicyclo [3.1.1] heptane, Examples include [3.1.1] hepto-2en, bicyclo [2 · 2.2] octane, bicyclo [2 · 2.2] oct 7-en. Tricyclic or higher hydrocarbons include tricyclo

Include [5.2.1.0 ² ^'6] decane, tricyclo ^[5 · 2.1.0 ^{^2'6]} dec one 4 E down, Adamantan, Tet Rashikuro ^{[6 · 2.1. I 3'} 6 .0 2 '7] dodecane or the like be able to.

[0031] Examples of the alkyl alicyclic hydrocarbon include those obtained by substituting the alicyclic hydrocarbon with an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group. More specifically, methylcyclopentane, 3-ethyl-1-methyl-1-cyclohexene, 3-ethyl-1-cyclohexene and the like can be mentioned. In addition, as a tetravalent aliphatic hydrocarbon group containing an aromatic ring in at least a part of its structure, the number of aromatic rings contained in one molecule is 3 or less. Particularly preferred is one. More specifically, 1-ethyl-6-methyl-1,2,3,4-tetrahydronaphthalene, 1-ethyl-1,2,3,4 tetrahydronaphthalene and the like can be mentioned.

As the mother nucleus of a tetravalent group preferable as X, η-butane, cyclobutane, cyclopentane, cyclohexane, bicyclo [2 · 2.1] heptane, bicyclo [2 · 2.2] octane, bicyclo [2.2.2 ] Okuto 7 E down, tetracyclo ^{^{[6.2.1. I 3 '6 .0}} 2' 7] dodecane, can be exemplified Mechirushikurope lanthanum like.

[0033] More preferable as X is

[0034] [Chemical 5]

(b— 4) (b— 5) (b— 6)

(b- 7) (b— 8) It is.

[0035] Particularly preferred as X is

[0036] [Chemical 6]

(b— 1) (b— 6). These X can be used alone or in combination of two or more.

Yes

[0037] A in the general formula (2) is a divalent group having a hydroxyl group. Preferred examples of the divalent group having a hydroxyl group include the group represented by the general formula (3). Here, R ⁵ in the general formula (3) is a single bond, oxygen atom, sulfur atom, sulfone group, carboninole group, methylene group, dimethylmethylene group, bis (trifluoromethyl) methylene group, and 9, 9 At least one group selected from the group consisting of fluorenylene groups. In the general formula (3), R ^{6 s} independently represent a hydrogen atom, an acyl group or an alkyl group. Preferred examples of the acyl group include a formyl group, a acetyl group, a propionyl group, a butyroyl group, and an isobutyroyl group. Preferred alkyl groups include, for example, a methyl group, an ethyl group, an npropyl group, an isopropyl group, an n A butyl group, n pentyl group, n hexyl group, n octyl group, n decyl group, n dodecyl group and the like can be mentioned. Note that at least one of R ⁶ is a hydrogen atom. In the general formula (3), n ¹ and n 2 are integers of 0 to 4, and at least one of n ¹ and n ² is 1 or more.

[0038] Further, as A (divalent group having a hydroxyl group) in the general formula (2), specifically,

[0039] [Chemical 7]

a divalent group having one hydroxyl group such as (c 1),

[0040] [Chemical 8]

(c-5)

(c 1 6) (c 1 7) (c-8)

a divalent group having two hydroxyl groups such as (c— 1 1) (c _ 1 2)

[0041] [Chemical 9]

A divalent group having three hydroxyl groups such as

[0042] [Chemical 10]

_C hydroxyl groups can be the mentioned divalent group of four chromatic etc.

[0043] Of these, divalent groups having two hydroxyl groups are preferred.

[0044] [Chemical 11]

Is more preferable.

[0045] As the structure represented by the general formula (2), a combination in which X is a tetravalent aliphatic hydrocarbon group and A is (c 3) or (c 4) is used in a solvent or a developer. This is preferable because the affinity tends to increase and the resolution becomes high.

[0046] (A) The polyimide resin is usually a monomer represented by the following general formula (4) (hereinafter also referred to as "monomer (4)"! /), And a monomer represented by the following general formula (5) ( Hereinafter, “monomer (5)” can be obtained by reacting! /,) In a polymerization solvent to synthesize a polyamic acid, and further carrying out an imidization reaction. The procedure for synthesizing the polyamic acid is a general method of dissolving the monomer (5) in a polymerization solvent and then reacting the monomer (4).

[0047] [Chemical 12]

(X in the general formula (4) has the same meaning as X in the general formula (2), and R ′ in the general formula (5),

And n ² have the same meanings as R ⁵ , R ⁶ , and n ^{2 in the} general formula (2). )

[0048] As the monomer represented by the general formula (4), when X is an aromatic hydrocarbon group,

[0049] [Chemical 13]

(a-4-1) 1) (a— 6— 1)

(a—7 1) and (a—8 — 1) are preferred. As the monomer represented by the general formula (4), when X is an aliphatic hydrocarbon group,

[Chemical 14]

(b-5-1) (b- 6-1) (b— 7— 1) (b- 8-1)

(b-9-1) (b_ 1 0— 1)

(b— 1 1-1) (b-1 2-1) is preferred. Among the above, 1, 2, 3, 4 butanetetracarboxylic dianhydride (b— 1— 1) , Bicyclo [2.2.2] Otada-7-ene— 2, 3, 5, 6- -tetracarboxylic dianhydride (b— 6

—1) is particularly preferred.

[0051] As the monomer represented by the general formula (5),

[0052] [Chemical 15]

(c— 10— 1)

(c-1 1-1) (c-12-1)

(c 1 3-1) (c 4 1: (c-5 -1)) is particularly preferred.

[0054] When (A) the polyimide resin is obtained, a diamine compound other than the monomer (5) can be reacted as necessary. Examples of diamine compounds that can be reacted include p-phenylenediamine, m-phenylenediamine, 4, 4, -diaminodiphenyl.

4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, 4 , 4'-diaminodiphenylsulfone, 3, 3, monodimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, bis (4-aminophenyl) ether, 1,5-diaminonaphth Thalene, 2, 2 'dimethyl-4,4'-diaminobiphenyl, 5 amino-11 (4'-aminophenyl) 1,3,3-trimethylindane, 6-amino 1- (4, aminophenol ) 1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2, 2 screw

[4— (4 aminophenoxy) phenole] propane, 2, 2 bis [4 (4-aminophenol) phenenole] hexafluoropropane, 2,2 bis (4-aminophenol) Xafluoropropane, 2,2bis [4- (4aminophenoxy) phenole] sulfone, 1,4bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3 —Aminophenoxy) benzene, 9, 9 bis (4 aminophenyl) 1 10 hydroanthracene, 2, 7 diaminofluorene, 9, 9 bis (4 aminophenol) fluorene, 4, 4'-methylen bis (2 chloroaniline), 2,2 ', 5,5, -tetrachloro-4,4'-diaminobiphenyl, 2,2,1 dichroic 4,4'-diamino-1,5,5,1 dimethoxybiphenyl, 3, 3, -dimethoxy-1,4'-diaminobihue 1, 4, 4'— (ρ phenylene isopropylidene) bisaniline, 4, 4 'one (m phenylene isopropylidene) bisaniline, 2, 2, 1 bis [4 1 (4 amino-2 trifluoro) Methylphenoxy) phenyl] hexafluoropropane, 4, 4, 1-diamino-1, 2, 2, 1-bis (trifluoromethinole) biphenyl, 4, 4, 1-bis [(4 amino-1-2 trifur) Olomechinole) phenoxy] —aromatic diamines such as otatafluorobiphenyl, bis (4-aminophenyl) -4-hydroxyphenylmethane, metaxylylenediamine, paraxylylenediamine, etc .;

1, 3 Propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, otamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, 1,3-bis (aminomethinole) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, isophorone Diamine, Tetrahydrodicyclopentadiene Direndiamine, Hexahydro-4,7-Methanoindanylenediethylene methylenediamine, Tricyclo

[6. 2. 1. 0 ² ' ⁷ ] —Undecylenedimethyldiamine, 4, 4'-methylenebis (cyclohexyl Mention may be made of aliphatic and cycloaliphatic diamines such as (Luamine).

[0056] The (A) polyimide resin contained in the photosensitive resin composition of the present invention has the following general formula:

It may contain a repeating unit represented by (6). By containing a repeating unit having a structure represented by the following general formula (1), a stress-reducing function can be imparted to a cured product obtained using this photosensitive resin composition.

[0057] [Chemical 17]

(In the general formula (6), X represents a tetravalent aromatic or aliphatic hydrocarbon group, B represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, and is represented by the following general formula (7) A divalent group or a divalent group represented by the following general formula (8))

[0058] [Chemical 18]

(In the general formula (7), n ^d represents an integer of 0 to 30)

[0059] [Chemical 19]

(In the general formula (8), Z represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms)

[0060] X in the general formula (6) is a tetravalent aromatic or aliphatic hydrocarbon group, and the above-described tetravalent aromatic or aliphatic hydrocarbon group can be used. B in the general formula (6) is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, a divalent group represented by the general formula (7), or 2 represented by the general formula (8). Is a valent group. Specifically, the substituted or unsubstituted alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 4 or more carbon atoms. Examples of the alkylene group having 4 or more carbon atoms include alkylene groups having 4 carbon atoms such as 1,4-butylene group; alkylene groups having 5 carbon atoms such as 1,5-pentylene group; 2-methyl- Examples thereof include alkylene groups having 6 carbon atoms such as 1,5 pentylene group and 1,6 hexylene group; alkylene groups having 7 to 20 carbon atoms such as 1,10 decylene group and 1,12 dodecylene group. Among these, an alkylene group having 7 to 20 carbon atoms, which is preferable to an alkylene group having 6 or more carbon atoms, is more preferable because of its improved solubility in a solvent.

[0061] Alternatively, when B in the general formula (6) is a divalent group represented by the general formula (7), n ³ in the general formula (7) is an integer of 0 to 30. . n ³ is preferably an integer from 1 to 20; an integer from! to 15 is particularly preferred.

[0062] When B in the general formula (6) is a divalent group represented by the general formula (8), Z in the general formula (8) is substituted or non-substituted having 2 to 20 carbon atoms. A substituted alkylene group. Specifically, the substituted or unsubstituted alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 3 or more carbon atoms. Examples of the alkylene group having 3 or more carbon atoms include alkylene groups having 3 to 5 carbon atoms such as 1,3-propylene group, 2,2 dimethylpropylene group, 1,4-butylene group, 1,5 pentylene group; 2 Examples thereof include alkylene groups having 6 carbon atoms such as methyl 1,5 pentylene group and 1,6 hexylene group; alkylene groups having 7 to 20 carbon atoms such as 1,10 decylene group and 1,12 dodecylene group.

[0063] The divalent group represented by the general formula (8) is preferably

[0064] [Chemical 20]

So o. [0065] As the compound giving a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms as B in the general formula (6), 1, 4-butylene diamine, 1, 5 pentylene diamine, Examples include 2 methylol 1,5-pentylene diamine, 1,6 hexylene diamine, 1,10 decylene diamine, 1,12 dodecylene diamine, and the like. Among these, an alkylene group having 7 to 20 carbon atoms is more preferable, and an alkylene group having 6 or more carbon atoms is more preferable because of its improved solubility in a solvent.

[0066] Examples of the compound giving a divalent group represented by the general formula (7) include a monomer represented by the following general formula (9) (hereinafter, also referred to as "monomer (9)"! /) That power S.

[0067] [Chemical 21]

(In the general formula (9), n ³ represents an integer of 0 to 30)

[0068] Commercially available products of monomer (9) include, for example, product names manufactured by Toshiba Silicone Co., Ltd .: TSL9386, TSL9346, TSL9306, product names manufactured by Toray * Dow Co., Ltd .: BY16-853C, BY1 6-871EG, Shin-Etsu Chemical Co., Ltd. Product name: X-22-161AS manufactured by Nihonika Co., Ltd. Product name: F2-053-01, product name manufactured by Chisso: Silaplane FM3325, FM3321, FM3311, etc. can be used.

[0069] Examples of the compound giving a divalent group represented by the general formula (8) include a monomer represented by the following general formula (10).

[0070] [Chemical 22]

(In the general formula (10), Z represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms.

)

[0071] Examples of the monomer represented by the general formula (10) include

[0072] [Chemical 23]

Raise your power with S.

[0073] When the (A) polyimide resin contained in the photosensitive resin composition of the present invention contains a repeating unit represented by the general formula (6), the general formula (4) ) And a monomer represented by the following general formula (11) (hereinafter also referred to as “monomer (11)”) in a polymerization solvent to synthesize a polyamic acid, and further carry out an imidization reaction. Power S can be obtained by The procedure for synthesizing the polyamic acid includes a general method in which the monomer (11) is dissolved in the polymerization solvent and then the monomer (4) is reacted, or the monomer (4) is dissolved in the polymerization solvent and then the monomer (1 The method of reacting 1) can be mentioned.

H N-B -NH (11)

twenty two

(In the general formula (11), B has the same meaning as B in the general formula (6).)

[0074] (A) The polyimide resin includes a repeating unit represented by the general formula (2) and the general formula (

It may contain the repeating unit shown in 6)! /.

[0075] The (A) polyimide resin contained in the photosensitive resin composition of the present invention contains a repeating unit represented by the general formula (2) and a repeating unit represented by the general formula (6). In some cases, this (A) polyimide resin is usually prepared by reacting monomer (4), monomer (5), and monomer (11) in a polymerization solvent to synthesize polyamic acid, followed by imidization reaction. You can gain the power by doing it. The procedure for synthesizing the polyamic acid consists of monomer (5) and monomer (1 I) is dissolved in the polymerization solvent and then the monomer (4) is reacted, or the monomer (4) is dissolved in the polymerization solvent and then the monomer (5) is reacted, and then the monomer is further reacted. (

A method of reacting I) can be mentioned.

[0076] (A) Polystyrene resin weight average molecular weight (hereinafter also referred to as "Mw") measured by gel permeation chromatography (GPC) of the polyimide resin is usually about 2,000-500,000. Yes, preferably about 3,000-250,000. When Mw is in the above range, sufficient mechanical properties as an insulating film and sufficient solubility in a solvent or developer can be obtained.

[0077] (A) In the synthesis of polyimide resin, all monomers (monomer (4) + monomer (5) (however, when monomer (11) is contained, monomer ( ⁴ ) + monomer (5) + monomer ( the proportion of the monomers which accounts to 11)) (4) is usually 40 to 60 mol%, preferably Ru 45 to 55 mol% der. ratio 40 to 60 mole ⁰ of monomer (4) in the total monomer If it is within the range of ₀ , it is possible to obtain a (A) polyimide resin having a sufficient molecular property as an insulating film and a sufficient solubility in a solvent or a developer, and using a diamine compound. If Te odor, the ratio of the monomer (5) to the sum of the monomers (5) and the monomer (5) other than Jiamin compound is usually 1 to 99 mol ^_0/0, preferably at from 20 to 95 mole ^_0/0 There, more preferably from 30 to 90 mole ^_0/0.

[0078] As the polymerization solvent, usually, N, N-dimethylformamide, N, N-dimethyl § Seto Ami de, N-methyl-2-pyrrolidone, _I Buchirorataton, non pro tons of solvents such as dimethyl sulfoxide; Metatarezoru such protic solvents Is used. If necessary, methanol, ethanol, propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, etc. Alcohol solvents; ether solvents such as diglyme and triglyme; aromatic hydrocarbon solvents such as toluene and xylene may be added!

[0079] Heat imidization reaction and chemical imidation reaction are generally known as imidization reaction. (I) It is preferable to synthesize a polyimide resin by heat imidization reaction. The heating imidization reaction is usually carried out by heating a synthesis solution of polyamic acid at 120 to 210 ° C .;! To 16 hours. If necessary, water in the system is removed using an azeotropic solvent such as toluene or xylene. The reaction may be performed while

In the present invention, “/ (A) polyimide resin” conceptually includes a “polyimide precursor” that finally becomes (A) a polyimide resin by heat treatment after exposure and development. That is, the photosensitive resin composition of the present invention may contain a polyimide precursor instead of (A) the polyimide resin or together with (A) the polyimide resin. Specific examples of the polyimide precursor include the above-described polyamic acid obtained by reacting the monomer (4) and the monomer (5), a compound obtained by esterifying the power of polyamic acid and rubonic acid. For example, a compound obtained by esterifying a carboxylic acid of a polyamic acid can be obtained by converting, for example, a half ester obtained by reacting a monomer (4) with an alcohol into (i) an acid chloride with thionyl chloride and the like. 5) Reaction is performed, or (ii) conversion into an active ester compound with bis (1H-benzotriazolyl) carbonate or the like and further reaction with the monomer (5). This polyamide precursor can be imidized by heat treatment after exposure and development to obtain (A) a polyimide resin in situ.

[0081] (A) Polystyrene resin weight average molecular weight (hereinafter also referred to as "Mw") measured by gel permeation chromatography (GPC) is usually about 2,000-500,000. Yes, the preferred <is about 3,000-250,000. When the Mw force is 000 or less, sufficient mechanical properties as an insulating film tend not to be obtained. On the other hand, when the Mw is 500,000 or more, the photosensitive resin composition obtained by using this (A) polyimide resin tends to have poor solubility in a solvent or a developer.

[0082] (Other resins)

In the photosensitive resin composition of the present invention, other resins other than the above-mentioned (A) polyimide resin (hereinafter referred to as “(Α ′) resin”) may be used as long as the effects of the present invention are not impaired. Can be further added. The type of (Α ′) resin that can be contained is not particularly limited, but is preferably alkali-soluble, and further contains an alkali-soluble resin having a phenolic hydroxyl group (hereinafter also referred to as “phenol resin”). It is more preferable because the resolution becomes good.

[0083] Examples of the resin having a phenolic hydroxyl group that can be contained include nopolac resin, polyhydroxystyrene and a copolymer thereof, and phenol-xylylene glycol dimethyl. Examples thereof include an ether condensation resin, a creso-l-xylylene glycol dimethyl ether condensation resin, and a phenol-dicyclopentaene condensation resin.

[0084] Specific examples of nopolac resins include phenol / formaldehyde condensed nopolac resins, talesol / formaldehyde condensed nopolac resins, phenol-naphthol / formaldehyde condensed nopolac resins, and the like.

[0085] The nopolac resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst. Examples of the phenols used in this case include phenol, o crezo monore, m crezo monore, p crezo monore, o echino refenonore, m- echenore enoenore, p echino leenore, o Butinolephenol, m Butinoleenole, p-Butylphenol, 2, 3 Xylenol, 2,4 Xylenol, 2,5 Xylenol, 2, 6 Xylenol, 3, 4 Xylenol, 3, 5 , 5 trimethenourenore, 3,4,5-trimethylphenol, force teconore, resorcinol, pyrogallol, α-naphthol, / 3-naphthol and the like. Examples of aldehydes include formaldehyde, paraformaldehyde, acetoaldehyde, and benzaldehyde.

[0086] Monomers other than hydroxystyrene constituting the copolymer of polyhydroxystyrene are not particularly limited. Specifically, styrene, indene, ρ methoxystyrene, p-n-butoxystyrene, p-tert-butoxy Styrene derivatives such as styrene, p-acetoxystyrene, and p-hydroxy-a-methylstyrene; (meth) acrylic acid, methyl (meth) ate acrylate, ethyl (meth) acrylate, n propyl (meth) acrylate, isopropyl ( (Meth) acrylate, n-butyl (meth) acrylate, sec butyl (meth) acrylate, (meth) acrylic acid derivatives such as butyl (meth) acrylate; methyl butyl ether, ethyl vinyl etherate, n butinorevininore Vinenore Etheno, such as Ethenore, Tebutinorevininore Ethenore And acid anhydride derivatives such as maleic anhydride and itaconic anhydride.

[0087] The content of the resin having a phenolic hydroxyl group is preferably 0 to 90% by mass with respect to 100% by mass of the total of (A) the polyimide resin and the resin having a phenolic hydroxyl group, and 5 to 80% by mass. It is particularly preferable to set the content to 10 to 70% by mass.

[0088] Further, the photosensitive resin composition of the present invention includes the above-mentioned resin having a phenolic hydroxyl group. In addition to the above, a phenolic low molecular weight compound can be contained. Specific examples of phenolic low molecular weight compounds that can be contained include 4,4'-dihydroxydiphenyl methane, 4,4'-dihydroxydiphenyl ether, tris (4-hydroxyphenol) methane, 1,1- Bis (4-hydroxyphenyl) -1-1-phenylethane, Tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) 1-methylethynole] benzene, 1,4-bis [1- (4-Hydroxyphenyl) mono 1-methylethynole] benzene, 4, 6-bis [14-hydroxyphenyl) 1 methylethyl] 1,3-dihydroxybenzene, 1,1-bis (4-hydroxy 1) 1- [4— {1- (4-hydroxyphenyl) 1 1-methinoretinole} fenenore] ethane, 1, 1, 2, 2, 2 tetra (4-hydroxyphenenole) ethane, etc. Raco Leave with a force S.

[0089] The content ratio of the phenolic low molecular weight compound is (A) 100 parts by mass of a polyimide resin (provided that (Α ') resin is further contained, the sum of (Α) polyimide resin and (Α') resin) 100 to 100 parts by mass is preferable with respect to 100 parts by mass), more preferably 5 to 40 parts by mass, and even more preferably 5 to 40 parts by mass.

[0090] ((B) Photoacid generator)

The photoacid generator (i) contained in the photosensitive resin composition of the present invention is a compound that generates an acid upon irradiation with radiation (hereinafter also referred to as “exposure”). (I) Photoacid generators having such properties include chemical amplification of ododonium salt compounds, sulfonium salt compounds, sulfone compounds, sulfonic acid ester compounds, halogen-containing compounds, sulfonimide compounds, diazomethane compounds, etc. Photoacid generators based on naphthoquinonediazide (NQD) such as diazoketone compounds.

[0091] Examples of the iodine salt compound include diphenyl trifluoromethane sulfonate, diphenyl benzoyl benzoate, diphen nitro sulfonate sulfonate Honate, diphenenoredo de nore benzene sulphonate, diphene enore hexahexafluoroantimonate, bis (4 t butylphenol) odon tritrifluoromethanesulfonate, bis (4 t butylphenol) ) Iodonium nonafluorobutane sulfonate, bis (4t butylphenol) oddonum camphor sulfonate, bis (4t butylphenyl) odonium p toluenesulfonate, etc. The power S

[0092] Examples of sulfonium salt compounds include triphenylsulfonium trifluoromethanesulfonate, triphenylenosnorephonium nonafnorebutansnorephonate, and triphenylenoresnorephonium mumphfer. Sulfonate, triphenylsulfonium naphthalenesulfonate, 4-hydroxyphenyl.benzyl.methylsulfonium p-toluenesulfonate, 4- (phenylphenol) phenyl'diphenylsulfonium hexafluorophosphate, 4, 7 —G

4,7 di n hydroxy 1 naphthyltetrahydrothiofluorotrifluoromethane sulphonate, 4,7 di n-butoxy 1 naphthinoletetrahydrothiohexafluorophosphate, 4- n-butoxy 1 naphthyl tetrahydrothiophene Examples thereof include nimutrifluormethanesulfonate.

[0093] Examples of the sulfone compound include β-ketosulfone, βsulfonylsulfone, and a-diazo compounds thereof. More specifically, mention may be made of phenacylphenylsulfone, mesitylphenacylsulfone, bis (phenylsulfoninole) methane, 4-trisphenacylsulfone, and the like.

[0094] Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, imino sulfonate, and the like. More specifically, benzoin tosylate, pyrogallol tristrifluormethane sulfonate, pyrogallol methanesulfonic acid triester, nitrobenzil 9,10 diethoxyanthracene 2-sulfonate, α-methylol benzoin tosylate, α— Examples include methylophone and a-methylolbenzoindodecyl sulfonate.

[0095] Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, and the like. Preferable examples of halogen-containing compounds include 1, 1-bis (4 chlorophenenole) -1, 2, 2, 2 trichloroethane, phenenole bis (trichloromethyl) s triazine, 4- Methoxyphenyl monobis (trichloromethyl) —s triazine, styryl monobis (trichloromethyl) s triazine, 4-methoxystyryl monobis (trichloromethyl) s triazine, naphthyl monobis (trichloromethyl) s Lyazine and s-triazine derivatives represented by the following general formula (12).

[0096] [Chemical 24]

[0097] In the general formula (12), R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyl group having! To 4 carbon atoms, Y represents a halogen atom, Q represents an oxygen atom, Or a sulfur atom is shown.

[0098] The s-triazine derivative represented by the general formula (12) has wide absorption in the g-line, h-line, and i-line regions, and is a general radiation-sensitive acid having another triazine skeleton. As a result, it is possible to obtain an insulating cured product having higher acid generation efficiency and higher residual film ratio than the generator. In the general formula (12), the alkyl group having 1 to 4 carbon atoms represented by R includes methyl group, ethyl group, n propyl group, isopropyl group, n butyl group, iso butyl group, A sec butyl group, a tert butyl group, etc. can be mentioned. Examples of the alkoxyl group having 1 to 4 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group and the like. R in the general formula (12) is more preferably a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0099] In the general formula (12), the halogen atom represented by Y is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. S is preferable, and a chlorine atom is more preferable. Furthermore, Q in the general formula (12) is more preferably an oxygen atom.

[0100] Specific examples of the s-triazine derivative represented by the general formula (12) include 2- [2- (furanyl) yl]-4, 6 bis (trichloromethyl) s triazine ( Q = 〇, R = H, Y = C1), 2— [2— (5 Methylfuran-2-inole) etul] — 4, 6 Bis (trichloromethinole) s Triazine (Q = 〇, R = CH, Y = C1) etc. Power S In addition,

Three

These S-triazine derivatives may be used alone or in combination of two or more. And force S.

[0101] Examples of the sulfonimide compounds include N— (trifluoromethylsulfonyloxy) succinimide, N (trifluoromethylsulfonyloxy) phthalimide, N (trifluoromethylsulfonyloxy) diphenylmaleimide, N (Trifluoromethylsulfonyloxy) Bicyclo [2.2.1] hept-5ene 2,3 dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like.

[0102] Diazomethane compounds include bis (trifluoromethylsulfonyl) diazomethane and bis

(Cyclohexinoresnorehoninole) diazomethane, bis (phenenolesnorehoninole) diazomethane, etc.

[0103] Examples of the diazo ketone compound include 1,3-diketo 2-diazo compound, diazobenzoquinone compound, diazonaphthoquinone compound and the like. Specific examples of preferred diazoketone compounds include 1,2-naphthoquinone diazide 4 sulfonate compounds of phenols.

Of the above-mentioned compounds, sulfonium salt compounds, sulfone compounds, halogen-containing compounds, diazoketone compounds, sulfonimide compounds, and diazomethane compounds are preferred. Sulfonium salt compounds and halogen-containing compounds are more preferred. . Particularly preferred are 4 (phenylthio) phenyl'diphenylsulfonium hexafluorophosphate, 4 phonate, 4,7 dihydroxy 1 naphthyltetrahydrothiophenetrifluoromethanesulfonate, 4, 7 Di n-butoxy 1 naphthyltetrahydrothiohexafluorophosphate, 4-n-butoxy 1 naphthyltetrahydrothiophene trifluoromethanesulfonate, 4-methoxyphenyl bis (trichloromethyl) —s triazine, styryl mono Bis (trichloromethyl) s triazine, 4-methoxystyryl bis (trichloromethyl) s triazine. These (B) photoacid generators can be used singly or in combination of two or more.

[0105] The content ratio of (B) photoacid generator is (A) 100 parts by mass of polyimide resin (provided that (Α ') resin is further contained, (Α) polyimide resin and (Α') resin) To 100 parts by mass) is usually from 0 .;! To 20 parts by mass, preferably from 0.5 to 10 parts by mass. Less than 1 part by mass In some cases, it may be difficult to cause sufficient chemical changes due to the catalytic action of the acid generated by exposure. On the other hand, if it exceeds 20 parts by mass, there is a risk of uneven coating when the photosensitive resin composition is applied, or the insulation after curing may be reduced.

[0106] ((C) Crosslinking agent)

(C) The crosslinking agent is a compound that forms a bond with a compounded composition such as a resin or other crosslinking agent molecules by the action of heat or acid. Specific examples of the (C) crosslinking agent include polyfunctional (meth) acrylate compounds, epoxy compounds, hydroxymethyl group-substituted phenol compounds, and compounds having an alkoxyalkylated amino group. Of these, compounds having an alkoxyalkylated amino group are preferred. In addition, these (C) crosslinking agents can be used individually by 1 type or in combination of 2 or more types.

[0107] Examples of the polyfunctional (meth) atalylate compound include trimethylolpropane tri (meth) atrelate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth). Atalylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate , Ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neo Pentyl glycol di (meth) atari , Diethylene dalcol di (meth) acrylate, triethylene dalcol di (meth) acrylate, dipropylene dalcol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meta) ) Attaching talates, etc.

[0108] Examples of the epoxy compound include nopolac type epoxy resin, bisphenol type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin and the like.

[0109] Hydroxymethyl group-substituted phenolic compounds include 2 hydroxymethyl-4,6 dimethylphenol, 1,3,5-trihydroxymethylbenzene, 3,5-dihydroxymethyl 4-methoxytoluene [2,6 bis ( Hydroxymethyl) p cresol].

[0110] Compounds having an alkoxyalkylated amino group include (poly) methylolation A nitrogen-containing compound having a plurality of active methylol groups in one molecule, such as melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, (poly) methylol urea, and the like Examples include a compound in which at least one hydrogen atom of the hydroxyl group of the group is substituted with an alkyl group such as a methyl group or a butyl group. The compound having an alkoxyalkylated amino group may be a mixture in which a plurality of substituted compounds are mixed, and some of them contain an oligomer component that is partially self-condensed. Power S can be.

[0111] More specific examples of the compound having an alkoxyalkylated amino group include compounds represented by the following formulas (13) to (19).

[0112] [Chemical 25]

(H ₃ COH ₂ C) ₂ N

(1 3) (1 4)

(1 5) (1 6)

(1 7) (1 8)

(1 9)

[0113] The compound represented by the formula (13) (hexamethoxymethylmelamine) is commercially available under the trade name “Symel 300” (manufactured by Cytec Industries). Further, the compound represented by the formula (15) (tetrabutoxymethyldaryl alcohol) is commercially available under the trade name “Cymel 1170” (manufactured by Cytec Industries).

[0114] Examples of the compound having an alkoxyalkylated amino group include hexamethoxymethyl melamine (formula (13)), tetramethoxymethyl darryluril (formula (16)), tetrabutoxymethyl dallicol. Ryl (formula (15)) is particularly preferred, and hexamethoxymethylmelamine (formula (13)) is most preferred! /.

[0115] (C) The content of the crosslinking agent is such that the film formed by the photosensitive resin composition is sufficiently cured. The amount is appropriately set so as to be an amount to be adjusted. Specifically, the content ratio of (C) crosslinking agent is (A) 100 parts by mass of a polyimide resin (provided that (Α ′) resin is further contained, (Α) polyimide resin and (Α ′) It is usually 5 to 50 parts by mass, preferably 10 to 40 parts by mass with respect to 100 parts by mass of the resin). If it is less than 5 parts by mass, the resulting insulating layer may have insufficient solvent resistance and plating solution resistance. On the other hand, if it exceeds 50 parts by mass, the developability of the thin film formed by the photosensitive resin composition may be insufficient.

[0116] (Compound (D))

The chemical structure of the compound (D) contained in the photosensitive resin composition of the present invention is represented by the general formula (1). Here, R ¹ in the general formula (1) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R ² in the general formula (1),

And R ⁴ are each independently an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. (D) Preferred examples of the compound include orthoformate esters such as trimethyl orthoformate, triethyl orthoformate, and tripropyl orthoformate.

[0117] When the photosensitive resin composition of the present invention contains the compound (D), the viscosity of the photosensitive resin composition is difficult to change. Therefore, the photosensitive resin composition of the present invention is stable and easy to use even after being stored for a long period of time, and is excellent in storage stability.

[0118] The content ratio of the compound (D) is 100 parts by mass of (A) polyimide resin (provided that (Α ') resin is further contained, the total of (Α) polyimide resin and (Α') resin is 100) To 100 parts by mass, preferably 0.1 to 100 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 0.5 to 10 parts by mass. When the amount is less than 1 part by mass, the viscosity of the photosensitive resin composition tends to change. On the other hand, if it exceeds 100 parts by mass, the applicability tends to deteriorate.

[0119] (Solvent)

In the photosensitive resin composition of the present invention, in order to improve the handleability and to adjust the viscosity and storage stability, the organic resin is used as necessary within a range not impairing the effects of the present invention. The solvent can be contained. The type of solvent that can be contained is not particularly limited, but for example, aprotic such as Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, Ν-methyl-2-pyrrolidone, γ-butyrolataton, dimethyl sulfoxide, etc. Solvent: A phenolic protic solvent such as metataresole is preferably used.

[0120] Further, in the photosensitive resin composition of the present invention, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates instead of or together with the above solvents. Organic solvents such as alcohols, aliphatic alcohols, lactic acid esters, aliphatic carboxylic acid esters, alkoxy aliphatic sulfonic acid esters, and ketones.

[0121] Examples of the propylene glycol monoalkyl ethers include propylene glycol monomethylenoate, propylene glycol monomethenoate ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like. Examples of the propylene glycol dialkyl ethers include propylene glycol jet nole etherate, propylene glycol nole propenolate nole, propylene glycol nole di ether ether and the like.

[0122] Examples of the propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropino oleate acetate, propylene glycol mono butyl ether acetate and the like. Can be mentioned. Examples of aliphatic alcohols include 1-butanol, 2-butanol, 1-pentanol mononole, 2-pentanol mononole, 4-methyl-2-pentanol, 1-hexanol and the like.

[0123] Examples of the lactic acid esters include methyl lactate, ethyl acetate, n-propyl lactate, and isopropyl lactate pills. Examples of aliphatic carboxylic acid esters include n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate, etc. I'll do it.

[0124] Examples of the alkoxy aliphatic carboxylic acid esters include methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate. Examples of ketones include 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone, cyclohexanone, and the like.

[0125] Of these solvents, ethyl lactate, 2-heptanone, cyclohexanone, propylene glycol Monoethyl methinoreateolate, propyleneglycolole methinoreteate acetate, butyl acetate is preferred, and propylene glycol monomethyl ether is particularly preferred. These solvents can be used alone or in combination of two or more. The solvent is usually used so that the total content of components other than the solvent is !!-60 mass%.

[0126] (Other additives)

The photosensitive resin composition of the present invention may contain other additives such as a basic compound, an adhesion aid, and a surfactant as necessary, as long as the effects of the present invention are not impaired. Touch with S.

[0127] (Basic compounds)

Examples of the basic compound include triethylamine, tree n-propylamine, tree n-butylamine, tree n-pentylamine, tree n-hexylamine, tree n-heptylamine, tree n-year-old cutinoleamine, tree n-noninoleamine, tree Examples thereof include trialkylamines such as n-decinoleamine, tri-n-dodecylamine, and n-dodecyldimethylamine, and nitrogen-containing heterocyclic compounds such as pyridine, pyridazine and imidazole. The content of the basic compound is usually 5 parts by mass or less, preferably 3 parts by mass or less with respect to 100 parts by mass of the (A) polyimide resin. If the content of the basic compound is more than 5 parts by mass with respect to 100 parts by mass of the (A) polyimide resin, the photoacid generator may not function sufficiently.

[0128] (Adhesion aid)

The photosensitive resin composition of the present invention may contain an adhesion assistant in order to improve adhesion to the substrate. A functional silane coupling agent is effective as the adhesion assistant. Here, the functional silane coupling agent refers to a silane coupling agent having a reactive substituent such as a carbonyl group, a methacryloyl group, an isocyanate group, or an epoxy group. Specific examples include trimethoxysilylbenzoic acid, _Ί -methacryloxypropyltrimethoxylane, _{vinyltriacetoxysilane} , _{butyltrimethoxysilane} , γ-isocyanatopropyltriethoxyhexyl) ethyltrimethoxysilane and the like. be able to. The content of the adhesion assistant is preferably 10 parts by mass or less with respect to 100 parts by mass of (ii) polyimide resin. [0129] (Surfactant)

The photosensitive resin composition of the present invention may contain a surfactant for the purpose of improving various properties such as coating properties, defoaming properties, and leveling properties. Surfactants include, for example, BM-1000, BM-1100 (above, manufactured by BM Chemi Co., Ltd.), MegaFuck F142D, F172, F173, F183 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC-135, FC-170C, FC-430, FC-431 (Sumitomo 3EM), Surflon S-112, S-113, S-131, S-141, S- 145 (above, manufactured by Asahi Glass Co., Ltd.), SH-28PA, i-190, ibid-193, SZ-6032, SF-8428 (above, made by Toray Dow Cowing Silicone), etc. Surfactants can be used. The content of the surfactant is preferably 5 parts by mass or less with respect to 100 parts by mass of the (A) polyimide resin.

[0130] The photosensitive resin composition according to an embodiment of the present invention can be suitably used particularly as a surface protective film or an interlayer insulating film material of a semiconductor element. The photosensitive resin composition of the embodiment of the present invention is applied to a support (a copper foil with resin, a copper wafer with a copper clad laminate, a silicon wafer with a metal sputtered film, an alumina substrate, etc.) and dried to remove a solvent or the like Volatilizes to form a coating film. Thereafter, exposure is performed through a desired mask pattern, and heat treatment (hereinafter, this heat treatment is referred to as “PEB”) is performed to promote the reaction between the phenol ring and the crosslinking agent. Subsequently, development with an alkaline developer can dissolve and remove the unexposed areas, thereby obtaining a desired pattern. Furthermore, a hard film can be obtained by performing a heat treatment in order to develop the insulating film characteristics.

[0131] As a method for applying the photosensitive resin composition to the support, for example, a coating method such as a dubbing method, a spray method, a bar coating method, a roll coating method, or a spin coating method can be used. The coating thickness can be appropriately controlled by adjusting the coating means and the solid content concentration and viscosity of the composition solution. After coating, a pre-beta treatment is usually performed to evaporate the solvent. The conditions vary depending on the composition of the photosensitive resin composition, the film thickness used, etc. Usually 70 to 150 ° C, preferably 80 to 140 ° C, and about 1 to 60 minutes.

[0132] Examples of radiation used for exposure include low-pressure mercury lamp, high-pressure mercury lamp, and metal harassment. Examples thereof include ultraviolet rays such as id lamp, g-line and i-line, electron beam, and laser beam. Exposure light amount is suitably selected according to the light source and the resin film thickness and the like to be used, for example, when irradiated with ultraviolet rays from a high pressure mercury lamp, the resin thickness of 10 to 50 111, typically at about 100~5000mJ / cm ² is there.

[0133] After the exposure, PEB is performed to promote the curing reaction between the phenol ring and the (C) crosslinking agent by the generated acid. PEB conditions vary depending on the composition of the photosensitive resin composition and the film thickness used, etc. Usually 70 to 150 ° C, preferably 80 to 140 ° C, and! To 60 minutes. Thereafter, development is performed with an alkaline developer, and a desired pattern is formed by dissolving and removing unexposed portions. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. The development conditions are usually 20 to 40 ° C;! To 10 minutes.

[0134] Examples of the alkaline developer include alkaline compounds such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, choline, and the like; Examples thereof include an alkaline aqueous solution dissolved in water. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution. After developing with an alkaline developer, wash with water and dry.

[0135] Furthermore, in order to sufficiently develop the characteristics as an insulating film after development, the film can be sufficiently cured by heat treatment. Although such curing conditions are not particularly limited, depending on the use of the cured product, the photosensitive resin composition is cured by heating at a temperature of 100 to 400 ° C for about 30 minutes to 10 hours. be able to. In addition, heating can be performed in multiple stages in order to sufficiently advance the curing or to prevent deformation of the obtained pattern shape. For example, when performing in two stages, the first stage is heated at a temperature of 50 to 200 ° C. for about 5 minutes to 2 hours, and further in the second stage at a temperature of 100 to 400 ° C. for 10 minutes to Heat for about 10 hours to harden.

[0136] Under such curing conditions, a hot plate, oven, infrared furnace, microwave oven, or the like can be used as the heating equipment.

[0137] Next, a semiconductor element using the photosensitive resin composition of the embodiment of the present invention is illustrated. This will be explained by the surface. As shown in FIG. 1, a patterned insulating film 3 is formed on a substrate 1 on which a patterned metal pad 2 is formed using the photosensitive resin composition of the present embodiment. Next, if the metal wiring 4 is formed so as to be connected to the metal pad 2, the semiconductor element can be obtained with the force S.

Further, as shown in FIG. 2, a patterned insulating film 5 may be formed on the metal wiring 4 by using the photosensitive resin composition of the present embodiment. Thus, if the photosensitive resin composition which is this embodiment is used, the semiconductor element which has the insulating resin layer formed of this photosensitive resin composition can be obtained.

Example

[0139] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. The methods for measuring and evaluating various physical properties are shown below.

[0140] [Molecular weight (Mw)]: GPC column (TSKgel a ~ M, 1 TSKgel a-2500) manufactured by Tosoh Corporation, flow rate: 1.0 ml / min, elution solvent: N, N —Dimethylformamide, column temperature: Measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under analytical conditions of 35 ° C.

[0141] [Mixability]: When each component is mixed in the composition ratio shown in Table 3, it is “good” when it becomes a transparent and uniform solution, and “bad” when it becomes a translucent or opaque solution. "

[0142] [Applicability]: A photosensitive resin composition was spin-coated on a 6-inch silicon wafer and heated on a hot plate at 110 ° C. for 3 minutes to prepare a uniform coating film having a thickness of 20 πι. A coating film with defects such as cracks was evaluated as “bad”, and a crack without defects such as cracks was determined as “good”.

[Resolution]: First, a silicon wafer on which a coating film was formed was obtained by the same procedure as in the applicability evaluation test. The obtained silicon wafer was exposed using an aligner (MA-150 manufactured by Suss Microtec). The exposure was performed by irradiating ultraviolet rays from a high-pressure mercury lamp through a pattern mask. The ultraviolet rays were irradiated so that the exposure amount at a wavelength of 350 nm was 1000 to 5000 mj / cm ² . Then, expose the exposed silicon wafer with a hot plate. 110 ° C, 3 minutes heating (PEB), 60 seconds at 23 ° C using a 2-38 mass ^_0/0 tetramethylammonium Niu arm hydroxide key side solution and immersion development. After immersion development, the dimensions of the square hole pattern formed on the silicon wafer (coating film) without any residue as measured by the pattern mask were measured. The minimum dimension among the measured dimensions was defined as “resolution m)”. When the measured resolution was 50 am or less, it was evaluated as “good”, and when it was above 50 am, it was evaluated as “bad”. Table 3 shows the resolution measurement and evaluation results.

[Change in viscosity with time]: The prepared photosensitive resin composition was stored at room temperature for 7 days. The viscosity before storage (mPa's) was measured using an E-type viscometer, and the rate of change in viscosity before and after storage was calculated by the following equation.

"Viscosity change rate (%)" = (viscosity after storage (mPa · s)) / (viscosity before storage (mPa · s)) X 10 o-ioo

[0145] (Synthesis example 1)

In a separable flask with a volume of 500 mL, 1, 2, 1-bis (3-amino-4-hydroxyphenyl) 1, 1, 1, 1, 3, 3, 3-hexafluoropropane (monomer “ΜΑ— 1 )) 41 · lg (50 mol%), 1,10-decylenediamine (monomer “ΜΒ-1”) 19.4 g (50 mol%), and N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”) 195 g added. After each monomer was dissolved by stirring at room temperature, 44.5 g (100 mol%) of 1,2,3,4-butanetetracarboxylic dianhydride (monomer “MC-2”) was charged. After stirring at 120 ° C for 5 hours under nitrogen, the temperature was raised to 180 ° C and dehydration was performed for 5 hours. After completion of the reaction, the reaction mixture was poured into water, and the product was reprecipitated, filtered and vacuum dried to obtain 91 g of polymer (A-1). The molecular weight Mw of the obtained polymer (A-1) was 23100. In addition, IR analysis was performed and it was confirmed that there was an absorption of l YScnT ¹ indicating imide.

[0146] (Synthesis Examples 2 and 3)

Polymers (A-2) and (A-3) were obtained in the same manner as in Synthesis Example 1 except that the respective monomers and NMP were blended according to the blending recipe shown in Table 1. Table 1 shows the yield (g) and molecular weight Mw of the obtained polymer. Moreover, it was confirmed by IR analysis that any of the obtained polymers had absorption of YScn ¹ indicating imide. The structures of the monomers used in Synthesis Examples;! To 3 are shown below. [0147] [Chemical 26]

MA-

[0148] [Chemical 27]

MB-1

MB-2

[0149] [Chemical 28]

MC— 1 MC- 2

[0150] [Table 1]

(Synthesis Example 4: Resin having a phenolic hydroxyl group (P-1))

m-Talesol and p-Talesol were mixed at a molar ratio of 60:40, and formalin was added thereto, followed by condensation by a conventional method using a oxalic acid catalyst, and a weight average molecular weight (Mw) of 8 700. Cresol nopolac resin (Pl) was obtained. The OH equivalent of this resin was 122 g / eq.

[0152] (Example 1)

100 parts of the polymer obtained in Synthesis Example 1 (A-1), 1 part of a photoacid generator (B-1), 30 parts of a crosslinking agent (C1), 5 parts of a compound (D-1), and a solvent ( A photosensitive resin composition (Example 1) was obtained by mixing 220 parts of ethyl lactate (EU), and the evaluation of the mixing property of the obtained photosensitive resin composition was “good”. The evaluation of “good” and the patterning property was “good.” The change with time in viscosity was 0%.

[Examples 2 to 6, comparative examples;! To 3]

A photosensitive resin composition (Examples 2 to 6 and Comparative Examples 1 to 3) was obtained in the same manner as in Example 1 except that the formulation shown in Table 2 was used. Table 3 shows the evaluation results of the mixing property, coating property, and patterning property of the obtained photosensitive resin composition, and the change with time of the viscosity. The meanings of the abbreviations in Table 2 are as shown below.

[0154] <Other resins>

P-1: Cresol nopolak resin obtained in Synthesis Example 4

P-2: Fenol xylylene alcohol dimethyl ether condensation resin (Mitsui Chemicals, trade name: Millex (registered trademark) XLC-3L)

[0155] <(B) Photoacid generator>

B—1: styryl monobis (trichloromethyl) s triazine

B-2: 4, 7 Di n-Butoxy 1 Naphthyltetrahydrothiophenetrifluoromethane sulfonate

B—3: 2— [2— (Franchi 2 Inole) Etul] — 4, 6 Bis (trichloromethyl) s— Triazine (trade name: TFE Triazine, manufactured by Sanwa Chemical Co., Ltd.)

B—4: 2— [2— (5 Methylfuran-2-inole) ethyl] —4,6 Bis (trichloromethyl) s Triazine (trade name: TME Triazine, manufactured by Sanwa Chemical Co., Ltd.)

<(C) Crosslinking agent (crosslinking agent having an alkoxyalkylated amino group)>

C-1: Hexamethoxymethylmelamine (Cytech Industries, trade name: Saimenole 300) C-2: Tetramethoxymethyl dalcoluril (Cytech Industries, trade name: Saimenole: 1174)

[0157] <(D) Compound>

D—1: Triethyl orthoformate

D-2: Trimethyl orthoformate

D—3: Tripropyl orthoformate

[0158] <Solvent>

EL: Ethyl lactate

PGMEA: Propylene glycol monoethyl ether acetate

[0159] [Table 2]

Resolution Viscosity change rate

Mixability Applicability

(i m) Rating (%)

Example 1 Good Good 40 Good 0

Example 2 Good Good 40 Good 0

Example 3 Good Good 40 Good 0

Example 4 Good Good 20 Good 0

Example 5 Good Good 30 Good 0

Example 6 Good Good 20 Good 0

Comparative Example 1 Good Good 40 Good 8

Comparative Example 2 Good Good 40 Good 5

Comparative Example 3 Good Good 40 Good 6 Industrial Applicability

The photosensitive resin composition of the present invention is suitable for use as a surface protective film, an interlayer insulating film, and an insulating film for high-density mounting substrates, and is extremely useful in industry.

Claims

Claims [1] (A) a polyimide resin, (B) a photoacid generator, (C) a crosslinking agent having an alkoxyalkylated amino group, and (D) a compound represented by the following general formula (1) The photosensitive resin composition containing these. [Chemical 1]

(In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R \ R ³ and R ⁴ independently of each other represent an alkyl group having! Show)

[2] The photosensitive resin composition according to [1], wherein R ¹ in the general formula (1) is a hydrogen atom or a methyl group.

[3] The photosensitive resin composition according to claim 1 or 2, wherein the compound (D) is an orthoformate ester.

[4] The photosensitive resin composition according to any one of claims 1 to 3, further comprising a resin having a phenolic hydroxyl group.

[5] The photosensitive resin composition according to [1] or [4], which is (A) polyimide resin strength alkali-soluble.

[6] The photosensitive resin composition according to any one of claims 1 to 5, wherein the (A) polyimide resin contains a repeating unit represented by the following general formula (2).

[Chemical 2]

(In the general formula (2), X represents a tetravalent aromatic or aliphatic hydrocarbon group, and Α represents a hydroxyl group. A divalent group having

7. The photosensitive resin composition according to claim 6, wherein X in the general formula (2) is a tetravalent aliphatic hydrocarbon group.

[8] The photosensitive resin composition according to claim 6 or 7, wherein A in the general formula (2) is a group represented by the following general formula (3).

[Chemical 3]

(In the general formula (3), R ⁵ is selected from the group consisting of a single bond, an oxygen atom, a sulfur atom, a sulfone group, a carboninole group, a methylene group, a dimethylmethylene group, and a bis (trifluoromethyl) methylene group. At least one group selected, R ⁶ independently of each other represents a hydrogen atom, an acyl group or an alkyl group, n ¹ and n ² represent an integer of 0 to 4, and n ¹ and n ² At least one is 1 or more and at least one of R ⁶ is a hydrogen atom)