KR20090007578A - Polymer and photosensitive resin composition comprising the same - Google Patents

Abstract

Disclosed is a polymer having a repeat unit represented by the general formula (1) and a repeat unit represented by the general formula (3).

Description

POLYMER AND PHOTOSENSITIVE RESIN COMPOSITION COMPRISING THE SAME

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a polymer of a closed ring polyimide for use in an interlayer insulating film (passivation film), a surface protective film (overcoating film), an insulating film for a high-density packaging substrate of a semiconductor device, and a photosensitive resin composition containing the same. More specifically, the present invention provides a surface protective film, an interlayer insulating film, and an insulating film for a high-density mounting substrate, which have high solubility in a general solvent, enable high film thickness coating and alkali development, and attain a high resolution cured product. It relates to a polymer of a closed ring-based polyimide suitable for use, and a photosensitive resin composition containing the same.

Background Art Conventionally, polyimide resins having excellent heat resistance, mechanical properties, and the like are widely used for surface protective films and interlayer insulating films used in semiconductor devices of electronic devices. Moreover, with the high integration of a semiconductor element, the photosensitive polyimide-type resin which gave photosensitive property for the improvement of film formation precision is proposed variously, and the side chain polymerizable negative photosensitive polyimide is used abundantly.

For example, Patent Document 1 below describes a photosensitive composition using an aromatic polyimide precursor having an acrylic side chain. However, this photosensitive composition has a problem that it is difficult to cope with a high film thickness due to the problem of light transmittance and a large residual stress after curing. Furthermore, there was a problem with the environment or safety for the solvent phenomenon. Moreover, since it is necessary to use the organic solvent as a developing solution, development of the radiation-sensitive resin composition of alkali developing type is desired.

In order to solve these problems, many proposals have been made conventionally. For example, the following patent documents 2 and 3 propose a positive photosensitive polyimide composition which is alkali developable. However, the applicability of these photosensitive polyimide compositions is not necessarily good, and it is difficult to cope with a high film thickness of 15 µm or more, for example. There is also a problem that it is difficult to obtain a sufficiently high resolution. For this reason, there is a problem that it is difficult to cope with the use of the surface protective film, the interlayer insulating film, or the insulating film for a high-density mounting substrate which requires high film thickness coating and high resolution. In addition, many patents have been filed, but it is difficult to sufficiently satisfy the required characteristics due to high integration, thinning, and the like of semiconductor devices.

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

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

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

<Start of invention>

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art, and its object is to obtain a cured product having high solubility in a general solvent, high film thickness coating and alkali development, and high resolution. It is possible to provide a polymer of a closed ring-based polyimide suitable for a surface protective film, an interlayer insulating film, and an insulating film for a high density mounting substrate, and a photosensitive resin composition containing the same.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said subject, the present inventors discovered that the said subject can be achieved by the following structures, and came to complete this invention.

That is, according to this invention, the polymer and photosensitive resin composition shown below are provided.

[1] A polymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (3).

(In Formula 1, X represents a tetravalent aromatic or aliphatic hydrocarbon group, A represents a divalent group represented by the following formula (2))

(In Formula 2, R ¹ represents a divalent group, R ² 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 2, n ¹ and n ² At least one is at least one, and at least one of R ² is a hydrogen atom)

(In Formula 3, X represents a tetravalent aromatic or aliphatic hydrocarbon group, B represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a divalent group represented by the following Formula 4.)

(In Formula 4, Z represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms)

[2] The polymer according to the above [1], wherein X in the formulas (1) and (3) is a tetravalent aliphatic hydrocarbon group.

[3] (A) Photosensitive resin composition containing the polymer as described in said [1] or [2], (B) photo-acid generator, and (C) crosslinking agent.

[4] The photosensitive resin composition according to the above [3], further containing a phenol resin.

[5] The photosensitive resin composition according to the above [3] or [4], wherein the crosslinking agent (C) has an alkoxyalkylated amino group.

The polymer of the novel closed ring-based polyimide of the present invention and the photosensitive resin composition containing the same have high solubility in a general solvent, enable high film thickness coating and alkali development, and at the same time obtain a cured product having high resolution. The film exhibits an effect suitable for the use of a protective film, an interlayer insulating film, and an insulating film for a high density mounting substrate.

1: is a schematic cross section of the semiconductor element which has the insulated resin layer formed using the photosensitive resin composition of this invention.

It is a schematic cross section of the semiconductor element which has the insulated resin layer formed using the photosensitive resin composition of this invention.

Explanation of the sign

1: substrate

2: metal pad

3: insulation film

4: metal wiring

5: insulation film

Best Mode for Carrying Out the Invention

Best Modes for Carrying Out the Invention Best Modes for Carrying Out the Invention Hereinafter, the best embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. It is to be understood that modifications, improvements, and the like, as appropriate, fall within the scope of the present invention.

1. (A) Polymer:

The polymer (A) of the present invention includes a repeating unit represented by Formula 1 and a repeating unit represented by Formula 3. This will be described in detail below.

X in the said Formula (1) is a tetravalent aromatic hydrocarbon group or tetravalent aliphatic hydrocarbon group, Preferably it is a tetravalent aliphatic hydrocarbon group. Specific examples of the tetravalent aromatic hydrocarbon group include tetravalent groups in which four hydrogens of the parent skeleton of the aromatic hydrocarbon are substituted.

As an aromatic hydrocarbon group, the group shown below is mentioned, for example.

Examples of the tetravalent aliphatic hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an alkyl alicyclic hydrocarbon group. More specifically, the tetravalent group in which four hydrogens of the backbone of a linear hydrocarbon group, an alicyclic hydrocarbon, or an alkyl alicyclic hydrocarbon is substituted is mentioned. Moreover, these tetravalent aliphatic hydrocarbon groups may be what contains an aromatic ring in at least one part of the structure. Here, as a chain hydrocarbon, ethane, n-propane, n-butane, n-pentane, n-hexane, n-octane, n-decane, n-dodecane, etc. are mentioned. Moreover, as an alicyclic hydrocarbon, a monocyclic hydrocarbon group, a bicyclic hydrocarbon group, a tricyclic or more hydrocarbon, etc. are mentioned specifically ,.

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, bicyclo [3.1.1] hept-2-ene, bicyclo [2.2.2] octane, bicyclo [2.2.2] Oct-7-ene etc. are mentioned. Further, tricyclic or higher hydrocarbons include tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [5.2.1.0 ^2,6 ] dec-4-ene, adamantane, tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecane and the like.

As an alkyl alicyclic hydrocarbon, what substituted the said alicyclic hydrocarbon by alkyl groups, such as a methyl group, an ethyl group, a propyl group, and a butyl group, is mentioned. More specifically, methylcyclopentane, 3-ethyl-1-methyl-1-cyclohexene, 3-ethyl-1-cyclohexene, etc. are mentioned. Moreover, as a tetravalent aliphatic hydrocarbon group which contains an aromatic ring in at least one part of its structure, it is preferable that the number of the aromatic rings contained in one molecule is three or less, and it is especially preferable that it is one. More specifically, 1-ethyl-6-methyl-1,2,3,4-tetrahydronaphthalene, 1-ethyl-1,2,3,4-tetrahydronaphthalene, etc. are mentioned.

Preferred nuclei of tetravalent groups as X include n-butane, cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, bicyclo [2.2.2] oct-7 -Ene, tetracyclo [6.2.1.1 ^{3,6.0 2,7} ] dodecane, methylcyclopentane, etc. are mentioned.

More preferred as X

to be.

In addition, particularly preferred as X

, Most preferred

to be. These X can be used individually by 1 type or in combination of 2 or more type.

A in Formula 1 is a divalent group represented by Formula 2 above. In addition, R <^1> in the said General formula (2) is a divalent group. As an example of R <^1> , an oxygen atom, a sulfur atom, a sulfone group, a carbonyl group, a methylene group, an alkylene group (except methylene group), a dimethyl methylene group, a bis (trifluoromethyl) methylene group, etc. are mentioned.

R ² in Formula 2 independently represents a hydrogen atom, an acyl group or an alkyl group. Preferred acyl groups include formyl group, acetyl group, propionyl group, butyroyl group, isobutyroyl group and the like, and preferred alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group and n. -Butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, etc. are mentioned. In addition, at least one of R ² is a hydrogen atom. Further, the formula (2) of n ¹ and n ² is an integer from 0 to 2, and at least one of n ¹ and n ² is 1 or more.

Preferred as A

to be. Moreover, what is more preferable as A is

to be.

X in the said Formula (3) is a tetravalent aromatic hydrocarbon group or tetravalent aliphatic hydrocarbon group. X in this general formula (3) is the same as X in the said general formula (1), and the same thing is mentioned as a preferable example.

B in Formula 3 is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a divalent group represented by Formula 4. Specifically, the substituted or unsubstituted alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 4 or more carbon atoms. As a C4 or more alkylene group, For example, C4 alkylene groups, such as a 1, 4- butylene group; C5 alkylene groups, such as a 1, 5- pentylene group; Alkylene groups having 6 carbon atoms such as 2-methyl-1,5-pentylene group and 1,6-hexylene group; And an alkylene group having 7 to 20 carbon atoms such as a 1,10-decylene group and a 1,12-dodecylene group. Among them, an alkylene group having 6 or more carbon atoms is preferable, and an alkylene group having 7 to 20 carbon atoms is more preferable because of the solubility of the polymer in the solvent.

Z in Formula 4 is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms. Specifically, the substituted or unsubstituted alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 3 or more carbon atoms. As a C3 or more alkylene group, For example, C3-C5 alkylene groups, such as a 1, 3- propylene group, a 2, 2- dimethyl propylene group, a 1, 4- butylene group, and a 1, 5- pentylene group; Alkylene groups having 6 carbon atoms such as 2-methyl-1,5-pentylene group and 1,6-hexylene group; And an alkylene group having 7 to 20 carbon atoms such as a 1,10-decylene group and a 1,12-dodecylene group.

More preferred as a divalent group represented by the formula (4)

to be.

The polymer (A) is usually a monomer represented by the following formula (5) (hereinafter also referred to as "monomer (5)"), a monomer represented by the following formula (6) (hereinafter also referred to as "monomer (6)"), and the following formula The monomer represented by 7 (henceforth "monomer (7)") can be made to react in a polymerization solvent, a polyamic acid is synthesize | combined, and it can obtain by carrying out imidation reaction further. In general, the following two kinds of methods are known for synthesizing the polyamic acid, and any method may be synthesized. That is, after (i) monomer (6) and monomer (7) are dissolved in a polymerization solvent, the method of making monomer (5) react, (ii) monomer (5) is dissolved in a polymerization solvent, and then monomer (7) Is reacted and the monomer (6) is further reacted.

Further, the formula (5) in X is the formula (6) in the R ^1, R ² the same as X in the formula (1), and, n ^1, and n ² is R ¹ in the second formula, R ^2, n ^1, and n ² And B in the formula (7) is the same as B in the formula (3).

As a polymerization solvent, Usually, aprotic solvents, such as N, N- dimethylformamide, N, N- dimethylacetamide, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, and dimethyl sulfoxide; Protic solvents such as metacresol are used. If necessary, methanol, ethanol, propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 2- (2-methoxyethoxy) ethanol and 2- (2-ethoxyethoxy) ethanol Alcohol solvents; Ether solvents such as diglyme and triglyme; Aromatic hydrocarbon solvents, such as toluene and xylene, can be added.

As for the imidation reaction, although heat imidation reaction and chemical imidation reaction are known normally, it is preferable to synthesize | combine (A) polymer by a heat imidation reaction. Heat imidation reaction is normally performed by heating the synthetic solution of polyamic acid at 120-210 degreeC for 1 to 16 hours. Moreover, if necessary, reaction can be performed, removing water in a system using azeotropic solvents, such as toluene and xylene.

The polystyrene reduced weight average molecular weight (hereinafter also referred to as "Mw") of the polymer (A) measured by gel permeation chromatography (GPC) is usually about 2,000 to 500,000, preferably about 3,000 to 200,000. When Mw is less than 2,000, there exists a tendency for mechanical characteristics not sufficient as an insulating film to be obtained. On the other hand, when Mw exceeds 500,000, there exists a tendency for the solubility to a solvent and a developing solution of the photosensitive resin composition obtained using this (A) polymer to run short.

The proportion of the monomer (5) in the total monomer (monomer (5) + monomer (6) + monomer (7)) of the polymer (A) is usually 40 to 60 mol%, preferably 45 to 55 mol% All. When the ratio of the monomer (5) which occupies for all the monomers is less than 40 mol% or exceeds 60 mol%, there exists a tendency for the molecular weight of the (A) polymer obtained to fall. In addition, the ratio of the monomer (6) with respect to the sum total of the monomer (6) and the monomer (7) is 10-99 mol% normally, Preferably it is 20-95 mol%, More preferably, it is 30-90 mol%. .

2. Photosensitive Resin Composition:

Next, the photosensitive resin composition of this invention is demonstrated. The photosensitive resin composition of this invention contains the above-mentioned (A) polymer, (B) photoacid generator, and (C) crosslinking agent. This will be described in detail below.

((B) photoacid generator)

The photoacid generator (B) contained in the photosensitive resin composition of this invention is a compound which generate | occur | produces an acid by irradiation of a radiation (henceforth "exposure"). Examples of the (B) photoacid generator having such properties include photoacid generators of chemical amplification systems such as iodonium salt compounds, sulfonium salt compounds, sulfone compounds, sulfonic acid ester compounds, halogen-containing compounds, sulfonimide compounds and diazomethane compounds; Naphthoquinone diazide (NQD) type photoacid generators, such as a diazo ketone compound, are mentioned.

As the iodonium salt compound, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium nonafluorobutanesulfonate, diphenyl iodonium pyrenesulfonate, diphenyl iodonium dodecylbenzenesulfonate, diphenyl Phenyl iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluorobutanesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, etc. are mentioned.

Examples of the sulfonium salt compound include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium naphthalenesulfonate, and 4-hydroxyphenylbenzyl Methylsulfonium p-toluenesulfonate, 4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4,7-di-n-butoxy-1-naphthyltetrahydrothiopheniumtrifluoromethane Sulfonate, 4,7-di-n-hydroxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium Hexafluoro phosphate, 4-n-butoxy-1- naphthyl tetrahydrothiophenium trifluoromethanesulfonate, etc. are mentioned.

As a sulfone compound, (beta) -keto sulfone, (beta) -sulfonyl sulfone, these (alpha)-diazo compounds, etc. are mentioned. More specifically, phenacyl phenyl sulfone, mesityl phenacyl sulfone, bis (phenyl sulfonyl) methane, 4-trisphenacyl sulfone, etc. are mentioned.

Alkyl sulfonic acid ester, haloalkyl sulfonic acid ester, aryl sulfonic acid ester, imino sulfonate etc. are mentioned as a sulfonic acid ester compound. More specifically, benzointosylate, pyrogallol tristrifluoromethanesulfonate, pyrogallol methanesulfonic acid triester, nitrobenzyl-9,10- diethoxyanthracene-2-sulfonate, α-methylol benzo intosyl The rate, the (alpha)-methylol benzoin octane sulfonate, the (alpha)-methylol benzoin trifluoromethane sulfonate, the (alpha)-methylol benzo indodecyl sulfonate, etc. are mentioned.

As a halogen containing compound, a haloalkyl group containing hydrocarbon compound, a haloalkyl group containing heterocyclic compound, etc. are mentioned. Specific examples of the preferred halogen-containing compound include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, phenyl-bis (trichloromethyl) -s-triazine and 4-methoxy Phenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, 4-methoxystyryl-bis (trichloromethyl) -s-triazine, naphthyl And s-triazine derivatives represented by the following general formula (8), such as -bis (trichloromethyl) -s-triazine and the like.

In said Formula (8), R <^3> represents a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 alkoxyl group, Y represents a halogen atom, Q represents an oxygen atom, or a sulfur atom.

The s-triazine derivative represented by the formula (8) has a wide absorption in the g-, h-, and i-ray regions, and has a higher acid generating efficiency than other radiation-sensitive acid generators having other triazine skeletons. Insulated hardened | cured material with a high film rate can be obtained. In the above formula (8), examples of the alkyl group having 1 to 4 carbon atoms represented by R ³ are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl And the like 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. In addition, it is preferable that R <^3> in the said Formula (8) is a hydrogen atom or a C1-C4 alkyl group, and it is more preferable that it is a hydrogen atom, a methyl group, or an ethyl group.

In the above formula (8), the halogen atom represented by Y is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom. In addition, Q in the formula (8) is more preferably an oxygen atom.

Specific examples of the s-triazine derivative represented by the formula (8) include 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine (Q = O , R ³ = H, Y = Cl), 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine (Q = O, R ³ = CH ₃ , Y = Cl). In addition, these s-triazine derivatives can be used individually by 1 type or in combination of 2 or more types.

As the sulfonimide compound, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide , N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like Can be mentioned.

Bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane etc. are mentioned as a diazomethane compound.

Moreover, as a diazo ketone compound, a 1, 3- diketo-2- diazo compound, a diazo benzoquinone compound, a diazonaphthoquinone compound, etc. are mentioned. As a specific example of a preferable diazo ketone compound, the 1, 2- naphthoquinone diazide- 4-sulfonic acid ester compound of phenols is mentioned.

Among the above-mentioned compounds, sulfonium salt compounds, sulfone compounds, halogen-containing compounds, diazoketone compounds, sulfonimide compounds and diazomethane compounds are preferable, and sulfonium salt compounds and halogen-containing compounds are more preferable. Especially preferred are 4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4,7 -Di-n-hydroxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium hexafluorophosphate, 4 -n-butoxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl)- s-triazine, 4-methoxystyryl-bis (trichloromethyl) -s-triazine. In addition, these (B) photo-acid generators can be used individually by 1 type or in combination of 2 or more type.

(B) The content rate of a photo-acid generator is 100 mass parts of (A) polymers (However, when it contains another polymer other than (A) polymers, the total of 100 masses of (A) polymers and other polymers) To parts), usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass. If it is less than 0.1 mass part, there exists a possibility that it may become difficult to fully produce the chemical change by the catalysis of the acid generate | occur | produced by exposure. On the other hand, when it exceeds 20 mass parts, application | coating nonuniformity may arise at the time of apply | coating the photosensitive resin composition, and there exists a possibility that the insulation after hardening may fall.

((C) crosslinking agent)

(C) A crosslinking agent is a compound which forms the bond with compound composition and other crosslinking agent molecules, such as resin, by the action of a heat and an acid. As a specific example of (C) crosslinking agent, the polyfunctional (meth) acrylate compound, an epoxy compound, the hydroxymethyl group substituted phenol compound, the compound which has an alkoxyalkylated amino group, etc. are mentioned. 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 type.

Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin 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, neopentylglycol di ( Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocy And the like can be press-rate di (meth) acrylate.

As an epoxy compound, a novolak-type epoxy resin, a bisphenol-type epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, etc. are mentioned.

As the hydroxymethyl group-substituted phenolic compound, 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, 3,5-dihydroxymethyl-4-methoxytoluene [2,6 -Bis (hydroxymethyl) -p-cresol].

Examples of the compound having an alkoxyalkylated amino group include a plurality of active methylol groups in one molecule such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, and (poly) methylolated urea. As a nitrogen-containing compound which has, the compound etc. which one or more of the hydrogen atoms of the hydroxyl group of this methylol group were substituted by alkyl groups, such as a methyl group and a butyl group, etc. are mentioned. Moreover, although the compound which has the alkoxyalkylated amino group may be the mixture which mixed several substituted compounds, and the thing containing the oligomer component formed by partial self-condensation exists, these can also be used.

More specific examples of the compound having an alkoxyalkylated amino group include compounds represented by the following formulas (9) to (15).

In addition, the compound represented by the said General formula (9) (hexakis (methoxymethyl) melamine) is marketed as a brand name "Cymel 300" (made by Cytec Industries). In addition, the compound (tetrakis (butoxymethyl) glycoluril) represented by the formula (11) is commercially available under the trade name "Cymel 1170" (manufactured by Cytec Industries, Inc.).

Examples of the compound having an alkoxyalkylated amino group include hexakis (methoxymethyl) melamine (formula (9)), tetrakis (methoxymethyl) glycoluril (formula (12)), and tetrakis (butoxymethyl) glycoluril (Formula 11) is particularly preferred, and hexakis (methoxymethyl) melamine (Formula 9) is most preferred.

The content rate of (D) crosslinking agent is suitably set so that the film formed by the photosensitive resin composition may become the quantity which hardens enough. Specifically, the content ratio of the crosslinking agent (D) is based on 100 parts by mass of the polymer (A), provided that the polymer (A) is polymer and the other polymer in total when other polymers other than the polymer (A) are further contained. It is 5-50 mass parts normally with respect to 100 mass parts), Preferably it is 10-40 mass parts. If it is less than 5 mass parts, there exists a possibility that the solvent resistance and plating liquid resistance of the insulating layer obtained may become inadequate. On the other hand, when it exceeds 50 mass parts, there exists a possibility that the developability of the thin film formed by the photosensitive resin composition may become inadequate.

(Other polymers (resin))

The photosensitive resin composition of this invention can further contain other polymers (resin) other than the above-mentioned (A) polymer as needed in the range which does not impair the effect of this invention. Although the "other polymer (resin)" which can be contained is not specifically limited, It is preferable that it is alkali-soluble, and also to contain alkali-soluble resin (henceforth "phenol resin") which has a phenolic hydroxyl group is resolvable. Since it becomes favorable, it is more preferable.

Examples of the phenol resin that may be contained include novolak resins, polyhydroxystyrenes and copolymers thereof, phenol-xylylene glycol dimethyl ether condensation resins, cresol-xylylene glycol dimethyl ether condensation resins and phenol-dicyclopentadiene condensation resins. Etc. can be mentioned.

Specific examples of the novolak resins include phenol / formaldehyde condensation novolac resins, cresol / formaldehyde condensation novolac resins, and phenol-naphthol / formaldehyde condensation novolac resins.

Novolak resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst. As phenols used at this time, for example, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p -Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xyl Phenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like. Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

Although monomers other than hydroxystyrene which comprise the copolymer of polyhydroxy styrene are not specifically limited, Specifically, styrene, indene, p-methoxy styrene, p-butoxy styrene, p-acetoxy styrene, p-hydride Styrene derivatives such as oxy-α-methylstyrene; (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth (Meth) acrylic acid derivatives such as) acrylate and t-butyl (meth) acrylate; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether and t-butyl vinyl ether; Acid anhydride derivatives, such as maleic anhydride and itaconic anhydride, are mentioned.

The content ratio of the phenol resin is preferably 0 to 90 parts by mass, more preferably 5 to 80 parts by mass, and particularly preferably 10 to 70 parts by mass based on 100 parts by mass of the total amount of the (A) polymer and the phenol resin. Do. If it is less than 5 mass parts, there exists a tendency for the effect of containing this phenol resin to become difficult to be exhibited. On the other hand, when it exceeds 90 mass parts, there exists a tendency for the mechanical strength of a film | membrane to fall.

In addition, the photosensitive resin composition of this invention can contain a phenolic low molecular weight compound other than the phenol resin mentioned above. As a specific example of the phenolic low molecular weight compound which can be contained, 4,4'- dihydroxy diphenylmethane, 4,4'- dihydroxy diphenyl ether, tris (4-hydroxyphenyl) methane, 1,1- Bis (4-hydroxyphenyl) -1-phenylethane, tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4 -Bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene , 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1,2,2-tetra (4 -Hydroxyphenyl) ethane and the like.

The content rate of a phenolic low molecular weight compound is 100 mass parts of (A) polymers (However, when it contains another polymer other than (A) polymers, a total of 100 mass parts of (A) polymers and other polymers). It is preferable to use 0-100 mass parts, It is more preferable to use 1-60 mass parts, It is especially preferable to use 5-40 mass parts. If it is less than 1 mass part, there exists a tendency for the effect of containing this phenolic low molecular weight compound to become difficult to be exhibited. On the other hand, when it exceeds 100 mass parts, there exists a tendency for the mechanical strength of a film | membrane to fall.

(solvent)

In order that the photosensitive resin composition of this invention may improve the handleability, or to adjust a viscosity and storage stability, an organic solvent can be included as needed in the range which does not impair the effect of this invention. Although the kind of solvent which can be contained is not specifically limited, For example, N, N- dimethylformamide, N, N- dimethylacetamide, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, dimethyl Aprotic solvents such as sulfoxide; Phenolic protic solvents such as methacresol are preferably used.

Further, the photosensitive resin composition of the present invention includes propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, aliphatic alcohols, lactic acid esters, and aliphatic carbons instead of or with the solvent. Organic solvents, such as acid ester, alkoxy aliphatic carboxylic acid ester, and ketone, can be contained.

As propylene glycol monoalkyl ethers, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc. are mentioned. As propylene glycol dialkyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, etc. are mentioned.

As propylene glycol monoalkyl ether acetates, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc. are mentioned. Examples of the aliphatic alcohols include 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 4-methyl-2-pentanol, 1-hexanol, and the like.

As lactic acid ester, methyl lactate, ethyl lactate, n-propyl lactic acid, isopropyl lactate, etc. are mentioned. Examples of the 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 and isobutyl propionate. Can be.

Examples of the alkoxy aliphatic carboxylic acid esters include methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate. Moreover, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone, cyclohexanone, etc. are mentioned as ketones.

Among these solvents, ethyl lactate, 2-heptanone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and butyl acetate are preferable, and ethyl lactate and propylene glycol monomethyl ether are particularly preferable. These solvents can be used individually by 1 type or in combination of 2 or more type. In addition, a solvent is used normally so that the content rate of the sum total of components other than a solvent may be 1-60 mass%.

(Other additives)

The photosensitive resin composition of this invention can contain other additives, such as a basic compound, an adhesion | attachment adjuvant, and surfactant, as needed in the range which does not impair the effect of this invention.

(Basic compound)

Examples of the basic compound include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, Trialkylamines such as tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine, n-dodecyldimethylamine and nitrogen-containing heterocyclic compounds such as pyridine, pyridazine and imidazole; Can be mentioned. Content of a basic compound is 5 mass parts or less normally with respect to 100 mass parts of (A) polymers, Preferably it is 3 mass parts or less. When content of a basic compound exceeds 5 mass parts with respect to 100 mass parts of (A) polymers, there exists a possibility that a photo-acid generator may not fully function.

(Adhesive aid)

The photosensitive resin composition of this invention can also contain an adhesion | attachment adjuvant in order to improve adhesiveness with a board | substrate. As the adhesion aid, a functional silane coupling agent is effective. Here, a functional silane coupling agent means the silane coupling agent which has reactive substituents, such as a carbonyl group, methacryloyl group, an isocyanate group, and an epoxy group. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-glycidoxypropyltrimethoxy Silane, (beta)-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned. It is preferable to make content of an adhesion | attachment adjuvant into 10 mass parts or less with respect to 100 mass parts of (A) polymers.

(Surfactants)

The photosensitive resin composition of this invention can also contain surfactant for the purpose of improving various characteristics, such as applicability | paintability, antifoaming property, and leveling property. As surfactant, For example, BM-1000, BM-1100 (above, BM Chemi Corporation), Megapack F142D, East F172, East F173, East F183 (above, Dai Nippon Ink Chemical Industries, Ltd.), Florad FC-135, East FC-170C, East FC-430, East FC-431 (above, Sumitomo 3M Corporation), Suplon S-112, East S-113, East S-131, East S-141, East Fluorine-based interfaces sold under the trade names S-145 (above, manufactured by Asahi Glass Co., Ltd.), SH-28PA, Copper-190, Copper-193, SZ-6032, SF-8428 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.). Active agents can be used. It is preferable to make content of surfactant into 5 mass parts or less with respect to 100 mass parts of (A) polymers.

The photosensitive resin composition which is embodiment of this invention can be used especially suitably as a surface protective film, an interlayer insulation film material, etc. of a semiconductor element. The photosensitive resin composition of embodiment of this invention is coated to a support body (copper foil with resin, a silicon wafer, an alumina substrate, etc. with a copper clad laminated board, a metal sputtering film, etc.), and it dries to volatilize a solvent etc., and forms a coating film. Then, it exposes through a desired mask pattern, and heat-processes (henceforth this heat-processing is called "PEB"), and promotes reaction of a phenol ring and a crosslinking agent. Subsequently, a desired pattern can be obtained by developing with alkaline developing solution and dissolving and removing an unexposed part. Moreover, a cured film can be obtained by heat processing in order to express insulating film characteristics.

As a method of coating a photosensitive resin composition to a support body, coating methods, such as an immersion method, the spraying method, the bar coating method, the roll coating method, or the spin coating method, can be used, for example. In addition, application | coating thickness can be suitably controlled by adjusting solid content concentration and a viscosity of a coating means and a composition solution. After coating, a prebaking process is normally performed in order to volatilize a solvent. Although the conditions differ according to the compounding composition, film thickness, etc. of a photosensitive resin composition, they are about 70 to 150 degreeC normally, Preferably it is about 1 to 60 minutes at 80 to 140 degreeC.

As radiation used for exposure, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, ultraviolet rays, such as g rays and i rays, an electron beam, a laser beam, etc. are mentioned, for example. Although the exposure amount is suitably selected according to the light source, resin film thickness, etc. to be used, For example, when irradiating an ultraviolet-ray from a high pressure mercury lamp, when the resin film thickness is 10-50 micrometers, it is about 100-5000 mJ / cm <^2> normally.

After exposure, PEB is performed to accelerate the curing reaction between the phenol ring and the crosslinking agent (C) caused by the generated acid. Although conditions of PEB differ according to the compounding composition, film thickness, etc. of a photosensitive resin composition, they are about 70 to 150 degreeC normally, Preferably it is about 1 to 60 minutes at 80 to 140 degreeC. Then, it develops with alkaline developing solution, and forms a desired pattern by melt | dissolving and removing an unexposed part. As a developing method in this case, the shower developing method, the spray developing method, the immersion developing method, the puddle developing method, etc. are mentioned. Developing conditions are about 1 to 10 minutes at 20-40 degreeC normally.

As said alkaline developing solution, the alkaline aqueous solution which melt | dissolved alkaline compounds, such as sodium hydroxide, potassium hydroxide, aqueous ammonia, tetramethylammonium hydroxide, and choline, in water so that a density | concentration may be about 1-10 mass% is mentioned, for example. . A suitable amount of water-soluble organic solvents, such as methanol and ethanol, surfactant, etc. can also be added to the said alkaline aqueous solution, for example. After developing with an alkaline developer, the solution is washed with water and dried.

Moreover, it can fully harden by heat processing in order to fully express the characteristic as an insulating film after image development. Although such curing conditions are not particularly limited, the photosensitive resin composition can be cured by heating at a temperature of 100 to 400 ° C. for about 30 minutes to 10 hours depending on the use of the cured product. Moreover, in order to fully advance hardening or to prevent deformation | transformation of the obtained pattern shape, you may heat in multiple steps. For example, in the case of performing in two steps, in the first step, it is heated at a temperature of 50 to 200 ° C. for about 5 minutes to 2 hours, and in the second step, it is heated at a temperature of 100 to 400 ° C. for about 10 minutes to 10 hours. It can also harden.

If it is such hardening conditions, a hotplate, oven, an infrared furnace, a microwave oven, etc. can be used as a heating installation.

Next, the semiconductor element using the photosensitive resin composition of embodiment of this invention is demonstrated by drawing. As shown in FIG. 1, the patterned insulating film 3 is formed on the board | substrate 1 in which the patterned metal pad 2 was formed using the photosensitive resin composition of this embodiment. Next, when the metal wiring 4 is formed so that it may connect with the metal pad 2, a semiconductor element can be obtained.

In addition, as shown in FIG. 2, the patterned insulating film 5 can also be formed on this metal wiring 4 using the photosensitive resin composition of this embodiment. Thus, when the photosensitive resin composition which is this embodiment is used, the semiconductor element which has the insulated resin layer formed by this photosensitive resin composition can be obtained.

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In addition, "part" and "%" in an Example and a comparative example are a mass reference | standard unless there is particular notice. In addition, the measuring method of various physical properties and the evaluation method of various characteristics are shown below.

[Molecular weight (Mw)]: Flow rate: 1.0 ml / min, elution solvent: N, N-dimethylformamide, column using a GPC column (1 TSKgel α-M, 1 TSKgel α-2500) manufactured by Tosoh Corporation Temperature: It measured by the gel permeation chromatography (GPC) which makes monodisperse polystyrene the standard by the analysis conditions of 35 degreeC.

[Mixability]: When each component was mixed at the composition ratio shown in Table 3 below, the case of becoming a "good", translucent or opaque solution was defined as "defect" when the solution became a transparent and uniform solution.

[Coating property]: The 6-inch silicon wafer was spin-coated with the photosensitive resin composition, and it heated at 110 degreeC for 3 minutes on the hotplate, and produced the 20 micrometer-thick uniform coating film. Defects such as cracks in the coating film were "good" and deficient defects such as cracks were "good".

[Patternability]: Ultraviolet light from a high pressure mercury lamp through a pattern mask using an aligner (MA-150, manufactured by Suss Microtec), and an exposure amount of 1000 to 5000 mJ / cm ² at a wavelength of 350 nm. The wafer with a coating film obtained by the coating test was exposed so that it might become. Subsequently, it heated (PEB) for 3 minutes at 110 degreeC on the hotplate, and immersion developed at 23 degreeC for 60 second using 2.38 mass% tetramethylammonium hydroxide aqueous solution. The case where the pattern was formed according to the mask was "good", and the case where the pattern according to the mask was not formed was "bad".

Synthesis Example 1

41.1 g of 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (monomer "MA-1") in a 500 mL separation flask , 19.4 g of 1,10-decylenediamine (monomer “MB-1”) and 195 g of N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”) were added. After stirring at room temperature to dissolve each monomer, 44.5 g of 1,2,3,4-butanetetracarboxylic dianhydride (monomer "MC-2") was added thereto. After stirring for 5 hours at 120 degreeC under nitrogen, it heated up at 180 degreeC and dehydrated for 5 hours. After the reaction was completed, the reaction mixture was poured into water, and the product was reprecipitated, filtered, and vacuum dried to obtain 91 g of a polymer. The molecular weight Mw of the obtained polymer was 23100. In addition, IR analysis was carried out to confirm that there was absorption of 1778 cm ^-1 representing the imide.

Synthesis Examples 2 to 7

A polymer was obtained in the same manner as in Synthesis Example 1 described above except that each monomer and NMP were mixed in a molar ratio shown in Table 1 below and the mass shown in Table 2 below. The yield (g) and molecular weight Mw of the obtained polymer are shown in Table 2. Moreover, IR analysis confirmed that there was absorption of 1778 cm <^-1> which shows an imide also about any obtained polymer. In addition, the structure of the monomer used by each synthesis example is shown below.

(Example 1)

The photosensitive resin composition (execution) by mixing 100 parts by mass of the polymer obtained in Synthesis Example 1, 170 parts by mass of the solvent (ethyl lactate (EL)), 1.5 parts of the photoacid generator (B-1), and 15 parts of the crosslinking agent (C-1). Example 1) was obtained. The evaluation of the blendability of the obtained photosensitive resin composition was "good", the applicability | paintability evaluation was "good", and the evaluation of patterning property was "good".

(Examples 2 to 11, Comparative Example 1)

Photosensitive resin compositions (Examples 2-11 and Comparative Example 1) were obtained in the same manner as in Example 1, except that the formulations shown in Table 3 were used. Evaluation of the mixing property, applicability | paintability, and patterning property of the obtained photosensitive resin composition is shown in Table 4 below. In addition, the meaning of the symbol in Table 3 is as showing below.

(Phenolic resin)

P-1: cresol novolak resin (polystyrene conversion weight average molecular weight = 8,700) which consists of m-cresol / p-cresol = 60/40 (molar ratio)

P-2: Phenol xylylene glycol dimethyl ether condensation resin (Mitsui Chemical Industries, Ltd. make, brand name: Mirex (registered trademark) XLC-3L)

(solvent)

EL: ethyl lactate

(Mine generator)

B-1: styryl-bis (trichloromethyl) -s-triazine

B-2: 4,7-di-n-butoxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate

B-3: 2-2 [-(furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd., brand name: TFE-triazine)

B-4: 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd., trade name: TME-triazine )

(Bridge)

C-1: hexamethoxymethyl melamine (manufactured by Cytec Industries, trade name: Cymel 300)

C-2: tetramethoxymethylglycoluril (manufactured by Cytec Industries, trade name: Cymel 1174)

C-3: Japan epoxy resin company make, brand name: Epicoat (registered trademark) 828

The polymer of the present invention, and the photosensitive resin composition containing the same, are suitable for the use of a surface protective film, an interlayer insulating film, or an insulating film for a high-density mounting substrate, which is very advantageous industrially.

Claims (5)

A polymer comprising a repeating unit represented by the following formula (1), and a repeating unit represented by the following formula (3). <Formula 1>

(In Formula 1, X represents a tetravalent aromatic or aliphatic hydrocarbon group, A represents a divalent group represented by the following formula (2)) <Formula 2>

(In Formula 2, R ¹ represents a divalent group, R ² 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 2, n ¹ and n ² At least one is at least one, and at least one of R ² is a hydrogen atom) <Formula 3>

(In Formula 3, X represents a tetravalent aromatic or aliphatic hydrocarbon group, B represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a divalent group represented by the following Formula 4.) <Formula 4>

(In Formula 4, Z represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms) The polymer of claim 1 wherein X in Formulas 1 and 3 is a tetravalent aliphatic hydrocarbon group. (A) the polymer according to claim 1 or 2, (B) photoacid generator, and (C) crosslinking agent Photosensitive resin composition containing. The photosensitive resin composition of Claim 3 which further contains a phenol resin. The photosensitive resin composition of Claim 3 or 4 in which the said (C) crosslinking agent has the alkoxyalkylated amino group.

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