TWI673569B - Photosensitive resin composition for interlayer insulating film, interlayer insulating film and production method thereof - Google Patents

Abstract

An object of the present invention is to provide a photosensitive resin composition for forming an interlayer insulating film, an interlayer insulating film, and a method for forming the interlayer insulating film.

Means for Solving the Problem The photosensitive resin composition for forming an interlayer insulating film of the present invention is a resin containing an alkali-soluble resin (A), a photosensitizer (B), a silane coupling agent (C), and a crosslinking agent (D) The photosensitive resin composition for forming an interlayer insulating film, wherein the crosslinking agent (D) is at least 1 selected from the group consisting of an oxetane-containing compound, an epoxy-containing compound, and a block isocyanate compound. Species.

Description

Photosensitive resin composition for forming interlayer insulating film, interlayer insulating film, and method for forming interlayer insulating film

The present invention relates to a method for forming a photosensitive resin composition for forming an interlayer insulating film, an interlayer insulating film, and an interlayer insulating film.

In recent years, the increase in the size and size of semiconductor devices has continued to develop, and further thinning and miniaturization of package substrates are required. Along with this, it is required to form an interlayer insulating film of a package substrate having a surface protection layer, an interlayer insulating film, or a redistribution layer of a semiconductor element with a material having more excellent electrical characteristics, heat resistance, and mechanical characteristics. .

Polyimide resin (hereinafter, referred to as "PI") or polybenzoxazole (hereinafter, referred to as "PBO") is a representative of a material that can satisfy such requirements, and has been reviewed, for example, for PI or PBO Use of photosensitive PI or photosensitive PBO that imparts light-sensitive properties. When these photosensitive resins are used, in addition to the advantages that the pattern forming steps are simplified and the tedious manufacturing steps can be shortened, they can be used as bases compared to the conventional introduction of carboxyl groups. The developed vinyl-based photosensitive resin is effective as the above-mentioned interlayer insulating film because it has high heat resistance and high insulation resistance (see, for example, Patent Documents 1 and 2).

On the other hand, photosensitive PI or photosensitive PBO is necessary for firing at high temperature (350 ~ 400 ° C), or the stability over time is not good, the number of formed resin films is reduced, and the solvent solubility is high. For lower issues.

On the other hand, an interlayer insulating film using a photosensitive acrylic resin having high heat resistance and good operability is proposed (Patent Document 3 and the like). However, the interlayer insulating film using the photosensitive acrylic resin still needs to be improved in terms of mechanical properties and the like.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-180472

[Patent Document 2] Japanese Patent Laid-Open No. 2007-031511

[Patent Document 3] Japanese Patent Laid-Open No. 2008-040183

The present invention is made in view of the foregoing circumstances, and an object thereof is to provide a photosensitive resin composition capable of forming an interlayer insulating film having good mechanical properties.

A first aspect of the present invention is a photosensitive resin composition for forming an interlayer insulating film, which contains an alkali-soluble resin (A), a photosensitizer (B), a silane coupling agent (C), and a crosslinking agent (D). The photosensitive resin composition for forming an interlayer insulating film is characterized in that the crosslinking agent (D) is at least one selected from the group consisting of an oxetane-containing compound, an epoxy-containing compound, and a block isocyanate compound. 1 species.

A second aspect of the present invention is an interlayer insulating film using the photosensitive resin composition for forming an interlayer insulating film in the first aspect described above.

A third aspect of the present invention is a method for forming an interlayer insulating film, comprising: using a photosensitive resin composition for forming an interlayer insulating film in the first aspect described above to form a photosensitive resin composition layer on a support; A step, a step of exposing the photosensitive resin composition layer, a step of developing the exposed photosensitive resin composition layer to form an interlayer insulating film pattern, and a step of heating and curing the interlayer insulating film pattern step.

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming an interlayer insulating film having good mechanical properties and the like.

[Best Mode for Carrying Out the Invention]

Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited in any way by the following embodiments. Within the scope of the purpose, appropriate changes can be added to implement.

感光 Photosensitive resin composition for interlayer insulation film formation≫

A first aspect of the present invention is a photosensitive resin composition for forming an interlayer insulating film, which contains an alkali-soluble resin (A), a photosensitizer (B), a silane coupling agent (C), and a crosslinking agent (D). The photosensitive resin composition for forming an interlayer insulating film is characterized in that the crosslinking agent (D) is at least one selected from the group consisting of an oxetane-containing compound, an epoxy-containing compound, and a block isocyanate compound. 1 species.

[Alkali soluble resin (A)]

As the alkali-soluble resin, any resin containing an alkali-soluble group having solubility in an alkali can be used.

As the alkali-soluble resin (A) (hereinafter referred to as "copolymer (A)"), for example, an acrylic resin can be suitably used.

As the acrylic resin, a constitutional unit (A1) represented by the general formula (a-1) or an alicyclic epoxy-based unit (A3) is preferred.

[Constituent unit (A1)]

The constituent unit (A1) is represented by the following general formula (a-1).

[In the foregoing general formula, R represents a hydrogen atom or a methyl group, and Ra ⁰¹ represents a hydrogen atom or an organic group having a hydroxyl group]

In the general formula (a-1), R represents a hydrogen atom or a methyl group.

In the general formula (a-1), Ra ⁰¹ represents a hydrogen atom or an organic group having a hydroxyl group.

Here, the organic group includes, for example, a branched, linear, or cyclic alkyl group, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, and an arane which may have a substituent. Or a heteroaralkyl group which may have a substituent, Ra ⁰¹ has at least one hydroxyl group in this structure. The carbon number of the organic group is preferably 1-20, and more preferably 6-12. If the carbon number is large, it is preferable in terms of storage stability or lower dielectric constant of the interlayer insulating layer, and if the carbon number is small, the resolution is superior.

However, as the constituent unit (A1), if Ra ⁰¹ is a hydrogen atom, methacrylic acid or acrylic acid is selected, which is effective in improving the alkali developability of the copolymer, but in terms of storage stability, as The constituent unit (A1) is preferably an organic group having the above-mentioned hydroxyl group.

As a preferable example of the constituent unit (A1), a constituent unit represented by the following general formula (a-1-1) can be exemplified.

[In the foregoing general formula, R represents a hydrogen atom or a methyl group, Ya ⁰¹ represents a single bond or an alkylene group having 1 to 5 carbon atoms, Ra ⁰⁰¹ represents an alkyl group having 1 to 5 carbon atoms, and a represents 1 to 1 An integer of 5, b is an integer of 0 or 1 to 4, and a + b is 5 or less. Still, if there are more than 2 Ra ⁰⁰¹ , these Ra ⁰⁰¹ may be different from each other or may be the same]

In the general formula (a-1-1), R may be a hydrogen atom or a methyl group, and a methyl group is preferred.

In addition, Ya ⁰¹ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms. Specific examples are: methylene, ethylene, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neo Dentyl etc. Among them, a single bond, methylene, and ethylene are preferred.

Ya ⁰¹ is preferably a single bond in terms of improving alkali solubility and further improving heat resistance when used as an interlayer insulating film.

Here, a is an integer of 1 to 5, but in terms of the effect of the present invention or the point that it is easy to manufacture, a is preferably 1. In addition, when the bonding position of the hydroxyl group in the benzene ring is based on the carbon atom bonded to Ya ⁰¹ as the reference (1-position), it is preferable that the bond is at the 4-position.

Ra ⁰⁰¹ is a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, and the like. Among them, a methyl group or an ethyl group is preferred in terms of ease of production.

Here, b is an integer of 0 or 1 to 4. However, from the viewpoint of the effect of the present invention or the point that it is easy to manufacture, b is preferably 0.

Specific examples of the constituent unit (A1) include o-hydroxyphenyl (meth) acrylate, m-hydroxyphenyl (meth) acrylate, p-hydroxyphenyl (meth) acrylate, and (formyl) (Meth) acrylic acid o-hydroxymethyl acrylate, m-hydroxymethyl methacrylate, p-hydroxymethyl methacrylate, o-hydroxyphenylethyl (meth) acrylate, m -Hydroxyphenylethyl ester, p-hydroxyphenylethyl (meth) acrylate, etc., preferably p-hydroxyphenyl (meth) acrylate or p-hydroxybenzyl (meth) acrylate, especially P-hydroxyphenyl (meth) acrylate is preferred.

The content ratio of the aforementioned constituent unit (A1) in the copolymer is preferably 10 to 70 mol%. Furthermore, 15 to 60 mole% is more preferable, and 20 to 50 mole% is most preferable.

[Unit containing alicyclic epoxy group (A3)]

The unit (A3) containing an alicyclic epoxy group is not particularly limited as long as it is a structural unit derived from a compound having an alicyclic epoxy group and a vinylic double bond in the structure. The carbon number of the alicyclic group of the alicyclic epoxy group is preferably about 5 to 10. By the copolymer of the present invention Having a unit (A3) containing an alicyclic epoxy group, it is not necessary to add a low-molecular weight cross-linking component that causes out gas to the photosensitive resin composition, and at the same time, the heat resistance can be improved.

The specific alicyclic epoxy group-containing unit (A3) may be derived from a polymerizable unsaturated compound containing an alicyclic epoxy group represented by the following general formulae (1) to (31), for example.

In the formula, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a divalent hydrocarbon group having 1 to 8 carbons, R ⁶ represents a divalent hydrocarbon group having 1 to 20 carbons, and R ⁴ , R ⁵ and R ⁶ are Can be the same or different, w is an integer from 0 to 10.

Among these, the general formulae (1) to (6), (14), (16), (18), (21), (23) to (25), (30) are preferable. Furthermore, the general formulae (1) to (6) are preferred.

The content ratio of the alicyclic epoxy-containing unit (A3) in the copolymer is preferably 5 to 40 mole%. Furthermore, 10 to 30 mole% is more preferable, and 15 to 25 mole% is most preferable. When the content ratio is 10 mol% or more, the heat resistance or adhesion of the interlayer insulating film can be improved, and when it is less than 40 mol%, the dielectric constant of the interlayer insulating film can be suppressed from being low.

[Constituent unit (A2)]

Moreover, it is preferable that the said copolymer has the structural unit (A2) represented by general formula (a-2).

[R represents a hydrogen atom or a methyl group, and Rb represents a hydrocarbon group]

Examples of the Rb hydrocarbon group include a branched, linear, or cyclic alkyl group, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. The carbon number of the hydrocarbon group is preferably from 1 to 20. Further, as the branched or linear alkyl group, 1 to 12 carbon atoms are preferred, and 1 to 6 carbon atoms are most preferred. As the cyclic alkyl group, 6 to 20 carbon atoms are preferred, and 6 to 12 carbon atoms are preferred. For the best. The aryl group which may have a substituent or the aralkyl group which may have a substituent is preferably 6 to 20 carbon atoms, and most preferably 6 to 12 carbon atoms. When the carbon number is 20 or less, the alkali resolvability is sufficient, and when the carbon number is 1 or more, the dielectric constant of the interlayer insulating film is preferably reduced.

Specific examples of the constituent unit (A2) include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, pentyl acrylate, ethylhexyl acrylate, octyl acrylate, and acrylic acid. t-octyl linear or branched alkyl acrylates; cyclohexyl acrylate, dicyclopentyl acrylate, 2-methylcyclohexyl acrylate, isobornyl acrylate, etc. Esters; derivatives of benzyl acrylate, aryl acrylates (such as phenyl acrylate), and the like.

Or can be exemplified by methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t- Linear or branched alkyl methacrylates such as butyl ester, amyl methacrylate, hexyl methacrylate, octyl methacrylate, etc .; cyclohexyl methacrylate, dicyclopentyl methacrylate, Alicyclic methacrylic acid alkyl esters such as 2-methylcyclohexyl methacrylate, isobornyl methacrylate, etc .; benzyl methacrylate, aryl methacrylate (e.g. phenyl methacrylate, methyl methacrylate) Derived from cresyl methacrylate, naphthyl methacrylate, etc.).

By introducing the above-mentioned constituent unit (A2) into the copolymer, the dissolution rate of the copolymer can be adjusted. As the constituent unit (A2), especially those derived from a monomer having an alicyclic group, It is preferable in terms of reducing the dielectric constant.

The content ratio of the constituent unit (A2) in the copolymer is preferably 5 to 50 mole%.

[Constituent unit (A4)]

Moreover, the said copolymer may contain the structural unit (A4) other than the structural unit (A1)-(A3) in the range which does not contravene the objective of this invention. This structural unit is not particularly limited as long as it is a structural unit derived from a compound having an ethylenic double bond. Examples of such a constituent unit include constituent units selected from, for example, acrylamide, methacrylamide, allyl compounds, vinyl ethers, vinyl esters, and styrenes.

Specific examples of acrylamide include acrylamide and N-alkyl acrylamide (The carbon number of the alkyl group is preferably 1 to 10, and examples thereof include methyl, ethyl, and propyl. , Butyl, t-butyl, heptyl, octyl, cyclohexyl, hydroxyethyl, benzyl, etc.), N-arylpropenamide (as aryl, such as phenyl, tolyl, nitrophenyl , Naphthyl, hydroxyphenyl, etc.), N, N-dialkylpropenamide (the carbon number of the alkyl group is preferably 1 to 10), N, N-arylpropenamide (as aryl, (For example, phenyl), N-methyl-N-phenylacrylamidonium, N-hydroxyethyl-N-methacrylamidoamine, N-2-acetamidoethyl-N-acetamidopropene Lamine.

Specific examples of the methacrylamide include methacrylamide and N-alkylmethacrylamine (preferably a carbon number of 1 to 10 as the alkyl system, for example: Ethyl, ethyl, t-butyl, ethylhexyl Group, hydroxyethyl, cyclohexyl, etc.), N-arylmethacrylamide (as aryl, there is phenyl, etc.), N, N-dialkylmethacrylamide (as alkyl, there is ethyl Group, propyl, butyl, etc.), N, N-diarylmethacrylamide (as aryl, there is phenyl, etc.), N-hydroxyethyl-N-methylmethacrylamide, N -Methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide.

As allyl compounds, specifically, allyl esters (e.g., allyl acetate, allyl hexanoate, allyl octoate, allyl laurate, allyl palmitate, allyl stearate) Propyl ester, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxy ethanol, and the like.

Specific examples of the vinyl ethers include alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, and ethoxyethyl Vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethyl ether Aminoamino ethyl vinyl ether, diethyl amino ethyl vinyl ether, butyl amino ethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ether (e.g. vinyl Phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthryl ether, etc.).

Specific examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl hexanoate, and vinyl chloroacetate. Dichloroacetic acid Vinyl Ester, Vinyl Methoxy Acetate, Vinyl Butoxy Ethyl Acetate, Vinyl Phenyl Acetate, Vinyl Acetate, Vinyl Lactate, -β-Phenyl Butyric Acid Vinyl, Vinyl Benzoate Acid vinyl ester, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthalate.

Specific examples of the styrenes include styrene and alkylstyrene (for example, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropyl Styrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, ethyl (Methoxymethylstyrene, etc.), alkoxystyrene (e.g. methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogenated styrene ( E.g. chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo -4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.). Moreover, acrylonitrile, methacrylonitrile, etc. can also be mentioned.

As the other constituent unit, it is preferable to select a derivative derived from a monomer having an alicyclic group, from the viewpoint of reducing the dielectric constant of the interlayer insulating film.

In the present invention, the copolymer (A) is preferably composed of the aforementioned constituent units (A1), (A2), and (A3).

The mass average molecular weight (Mw: measured value of polystyrene conversion by gel permeation chromatography (GPC)) of the copolymer (A) is preferably 2,000 to 50,000, and more preferably 5,000 to 30,000. By combining the molecules When the amount is set to 2000 or more, it can be easily formed into a film. In addition, by setting the molecular weight to 50,000 or less, moderate alkali solubility can be obtained.

The above-mentioned copolymer can be produced by a known radical polymerization. That is, a polymerizable monomer derived from the aforementioned constituent units (A1) to (A3) and a well-known free-radical polymerization initiator are dissolved in a polymerization solvent and then produced by heating and stirring.

Furthermore, the alkali-soluble resin (A) may contain one or more other copolymers in addition to the copolymers of the above-mentioned constituent units (A1) to (A3). This copolymer is more preferably 0 to 50 parts by mass, and still more preferably 0 to 30 parts by mass with respect to 100 parts by mass of the copolymer (A). The mass average molecular weight (Mw: measured value of polystyrene conversion by gel permeation chromatography (GPC)) of the copolymer is preferably 2,000 to 50,000, and more preferably 5,000 to 30,000.

[Photosensitizer (B)]

The photosensitive agent (B) in the present invention is not particularly limited as long as it is a compound that can be used as a photosensitive component, but a compound containing a quinonediazide group can be exemplified as a preferable example.

Specific examples of the compound containing a quinonediazide group include a phenol compound (also referred to as a compound containing a phenolic hydroxyl group), and a completely or partially esterified product with a naphthoquinonediazidesulfonic acid compound.

Specific examples of the phenol compound include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone; (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylbenzene) Phenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylbenzene Phenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) 2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3 -Hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4 -Dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) ) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methyl) Phenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane, 4,4 '-[(3,4 -Dihydroxyphenyl) methylene] bis (2-cyclohexyl-5-methylphenol ) And other trisphenol compounds;

2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol, 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methyl Linear 3-core phenolic compounds such as phenol; 1,1-bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2, 5-dimethyl-3- (4-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane, bis [2,5-dimethyl-3- (4-hydroxybenzyl) -4 -Hydroxyphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-bis Methyl-4-hydroxyfluorenyl) -4-hydroxy-5-ethylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxy Sulfenyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4-hydroxy-5-ethylphenyl] methane , Bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3- (2-hydroxy-5-methyl Methylfluorenyl) -5-methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy-5-methylfluorenyl) -5-methylphenyl] methane, bis [2,5- Linear tetranuclear phenolic compounds such as dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane; 2,4-bis [2-hydroxy-3- (4- Hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3- (4-hydroxybenzyl) -5-methylfluorenyl] -6-ring Linear pentamers of hexylphenol, 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4-methylphenol, etc. Linear polyphenol compounds such as phenol compounds;

Bis (2,3, -trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2- (2 , 3,4-trihydroxyphenyl) -2- (2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ', 4 '-Dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- (3' -Fluoro-4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) ) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4'-hydroxy-3 ', 5'-dimethylphenyl) propane And other bisphenol-type compounds; 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- ( Multinuclear branched compounds such as 3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene; 1,1 -A condensed phenol compound such as bis (4-hydroxyphenyl) cyclohexane. These can be separate or grouped Use 2 or more types together.

Examples of the naphthoquinonediazidesulfonic acid compound include naphthoquinone-1,2-diazide-5-sulfonic acid and naphthoquinone-1,2-diazide-4-sulfonic acid.

In addition, other compounds containing a quinonediazide group may include, for example, ortho benzo quinonediazide, ortho-naphthoquinonediazide, ortho-anthraquinonediazide or o-naphthoquinonediazide These nuclear substituted derivatives of sulfonates and the like. Further, o-quinonediazide sulfonyl chloride, and compounds having a hydroxyl group or an amine group (for example, phenol, p-methoxyphenol, dimethylphenol, hydroquinone, and bisphenol A) can be used. , Naphthol, Catechol, Pyrogallol, Pyrogallol Monomethyl Ether, Pyrogallol-1,3-Dimethyl Ether, Gallic Acid, Esterification or Ether Residual Reaction products such as converted gallic acid, aniline, p-aminodiphenylamine, etc.). These systems can be used alone or in combination of two or more.

These quinonediazide-containing compounds are prepared in a suitable solvent such as dioxane in the presence of a base such as triethanolamine, carbonate, bicarbonate, or the like. Condensation of quinone-1,2-diazide-5-sulfonyl chloride or naphthoquinone-1,2-diazide-4-sulfonyl chloride can be made by full or partial esterification.

As the component (B), a non-benzophenone-based compound containing a quinonediazide group is preferably used, and a polynuclear branched compound is more preferably used. The compound having a phenolic hydroxyl group preferably has a gram absorbency index of 1 or less at a wavelength of 350 nm. As a result, the photosensitive resin composition can not only obtain higher sensitivity, but also transmittance (transmittance) when used as an interlayer insulating film. Clarity). Furthermore, it is more preferable that the compound containing a phenolic hydroxyl group has a decomposition temperature of 300 ° C or higher. This ensures the transparency of the interlayer insulating film.

As such a component (B), a compound containing a quinonediazide group is preferable, and a naphthoquinonediazide sulfonate is particularly preferable. Among them, 4,4 '-[(3,4-dihydroxyphenyl) methylene] bis (2-cyclohexyl-5-methylphenol), 1- [1- (4-hydroxyphenyl) can be suitably used. ) Isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene and other naphthoquinonediazide sulfonates.

(B) The content of the component is preferably 10 to 40% by mass, and more preferably 15 to 30% by mass relative to the total solid content. By setting the content of the component (B) to 10% by mass or more, the resolution can be improved. In addition, after the pattern is formed, the pattern film can be reduced in weight. In addition, by setting the content of the component (B) to 40% by mass or less, appropriate sensitivity or transmittance can be imparted.

[Silane coupling agent (C)]

The photosensitive resin composition for forming an interlayer insulating film of the present invention contains a silane coupling agent (C). The photosensitive resin composition for forming an interlayer insulating film of the present invention, by containing the silane coupling agent (C), can not only improve the adhesion between the film and the substrate formed by the photosensitive resin composition of the present invention, but also adjust the adhesion. Properties of a film formed from the photosensitive resin composition of the present invention.

Specific examples of the silane coupling agent (C) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-shrinkage. Glyceryloxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacrylic acid Propylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxy Silane, vinyltrialkoxysilane. Among these, γ-glycidoxypropyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane is more preferable, and γ-glycidoxypropyltriol Alkoxysilane is more preferred, and 3-glycidoxypropyltrimethoxysilane is even more preferred. These systems can be used alone or in combination of two or more.

When the silane coupling agent is contained, the content is preferably 0.01 to 10% by mass, more preferably 0.1 to 2% by mass, and most preferably 0.2 to the total solid content of the photosensitive resin composition of the present invention. 1.5% by mass. When it is contained in the range as described above, it is preferable to improve the adhesion between the pattern formed by the photosensitive resin composition of the present invention and the substrate.

[Crosslinking agent (D)]

The photosensitive resin composition for forming an interlayer insulating film of the present invention contains a crosslinking agent (D). The crosslinking agent (D) is at least one selected from the group consisting of an oxetane-containing compound, an epoxy group-containing compound, and a block isocyanate compound.

The photosensitive resin composition for forming an interlayer insulating film of the present invention has a crosslinking density increased by containing a crosslinking agent (D), and the layer of the present invention is used. The interlayer insulating film formed by the photosensitive resin composition for forming an interlayer insulating film not only improves the elasticity, but also has a higher elongation at break, so it is considered to be superior in mechanical properties. It is considered that the mechanical properties of the interlayer insulating film formed using the photosensitive resin composition for forming an interlayer insulating film of the present invention are equal to or better than those obtained when a polyimide resin is used.

[Compound containing oxetane, compound containing epoxy group]

Examples of the compound having an oxetanyl group or an epoxy group include styrene oxide, phenyl glycidyl ether, 0-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, and cinnamic acid. Glyceryl ester, methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, glycidyl, N-glycidyl Glyceryl phthalimide, 1,3-dibromophenyl glycidyl ether, CELLOXIDE 2000 (manufactured by Daicel Chemical Industry Co., Ltd.), oxetanol, and the like. As specific examples of the oxetane-containing compound, ARON OXT OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toa Kosei Co., Ltd.) can be used. As specific examples of the epoxy group-containing compound, epoxy resin EXA4850-150 and epoxy resin EXA4850-1000 (both manufactured by DIC Corporation) can be used.

[Block isocyanate compound]

The block isocyanate compound used in the present invention, the block isocyanate used in the present invention is inert at ordinary temperature, and is heated to oxime Blocking agents such as diketones, diketones, phenols, caprolactams, etc. will dissociate and regenerate isocyanate-based compounds. The block isocyanate compound may be used singly or in combination of two or more kinds.

Here, as the isocyanate compound, a known one may be used, and examples thereof include aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate, and dicyclohexylmethane diisocyanate. Alicyclic diisocyanates such as isocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated phenylene diisocyanate, hydrogenated tolyl diisocyanate, tolyl diisocyanate, 4,4'- Diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthyl diisocyanate, phenylene diisocyanate, benzylamine diisocyanate, p-phenyl diisocyanate, naphthyl diisocyanate And other aromatic diisocyanates, dicyclohexylmethane-4,4'-diisocyanate, biuret bodies, isocyanurate bodies, adducts of trimethylolpropane, and the like. Among them, aliphatic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, alicyclic diisocyanates such as dicyclohexyl diisocyanate, isophorone diisocyanate, tolyl diisocyanate, and Aromatic diisocyanates such as toluidine diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, and naphthyl diisocyanate, biuret bodies, isocyanurates, and trimethylol Adducts such as propane are preferred. Among them, the adducts are the adducts of aliphatic diisocyanate and trimethylolpropane, the biuret system is the reaction product of hexamethylene diisocyanate and water or tertiary alcohol, and the isocyanurate The system is preferably a trimer of hexamethylene diisocyanate.

The block agent is added to a polyisocyanate group and is stable at normal temperature. However, if the block agent is heated to a temperature above the dissociation temperature, it will be liberated and an isocyanate group compound will be formed. Specific examples of the blocking agent include lactam compounds such as γ-butyrolactam, ε-caprolactam, γ-valprolactam, and prolactam, and methyl ethyl ketone. Oxime, methyl isoamyl ketoxime, methyl isobutyl ketoxime, formamidine oxime, acetamoxime, acetamoxime, diethylammonium oxime, benzophenone oxime, cyclohexanone oxime, etc. Oxime compounds, monocyclic phenol compounds such as phenol, cresol, catechol, nitrophenol, polycyclic phenol compounds such as 1-naphthol, methanol, ethanol, isopropanol, tert-butanol, trimethylol Alcohol compounds such as propane, 2-ethylhexyl alcohol, ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, alkyl malonate, Reactive methylene compounds such as alkyl esters, alkyl acetoacetates, ethyl acetone, and the like. The blocking agent may be used alone or in combination of two or more.

The block isocyanate compound can be produced by reacting an isocyanate compound with a blocking agent. The reaction between the isocyanate compound and the blocking agent is, for example, in a solvent (1.4 dioxane, acetic acid cellosolve, etc.) that does not have active hydrogen, under heating at about 50 to 100 ° C and according to the needs in the block The presence of the catalyst was carried out. The use ratio of the isocyanate compound and the blocking agent is not particularly limited, but the equivalent ratio of the isocyanate group to the blocking agent in the isocyanate compound is preferably 0.95: 1.0 to 1.1: 1.0, and more preferably 1: 1.05 to 1.15. As the block catalyst system, well-known ones can be used, and examples thereof include metal alkoxides such as sodium methoxide, sodium ethoxide, sodium phenate, potassium methoxide, tetramethylammonium, tetraethylammonium, and tetrabutylammonium. Alkyl ammonium hydroxide Compounds, organic weak salts such as acetates, caprylates, myristic salts, benzoates, and the like, alkali metal salts of alkyl carboxylic acids such as acetic acid, hexanoic acid, caprylic acid, and myristic acid. The block catalyst system may be used singly or in combination of two or more kinds.

As the block isocyanate compound, a commercially available product can be used. As specific examples of commercially available products, TPA-B80E (trade name: Asahi Kasei Corporation, isocyanate type), 17B-60P (trade name: Asahi Kasei Corporation, biuret type), E402-B80B ( Trade name: Asahi Kasei Co., Ltd., additive type) and so on. The content of the block isocyanate compound is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, and most preferably 10 to 40% by mass relative to the total solid content of the photosensitive resin composition of the present invention.

In the present invention, it is preferable to use a block isocyanate compound as the crosslinking agent (D) from the viewpoint of improving the mechanical characteristics of the interlayer insulating film. Among the block isocyanate compounds, an adduct-type block isocyanate compound is preferably used. When an adduct-type block isocyanate compound is used, the content of the adduct-type block isocyanate compound is preferably 10 to 40% by mass relative to the entire solid content of the photosensitive resin composition of the present invention. It is more preferably 15 to 25% by mass. By setting it as the said range, in addition to the improvement of the mechanical characteristic of an interlayer insulation film, heat resistance can also be provided.

[Organic solvent (S)]

The photosensitive resin composition according to the present invention can improve coating In order to adjust the viscosity or adjust the viscosity, it is preferable to contain an organic solvent (S).

Examples of the (S) component include benzene, toluene, xylene, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, and cyclohexane. Alcohol, ethylene glycol, diethylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 3-methoxybutyl ester (MA), 3-methoxybutanol (BM), 3-methyl-3-methoxy Butyl ester, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether propionate, propylene glycol monomethyl ether propionate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, or a mixture thereof Wait. Among them, it is preferable to use PGME, PGMEA, MA, or a mixed solvent of PGME and PGMEA, a mixed solvent of MA and BM, and the like.

The amount of the organic solvent (S) used is not particularly limited, and it is appropriately set in accordance with the thickness of the coating film within a concentration that can be applied to the substrate. Specifically, it is preferable that the solid content concentration of the photosensitive resin composition is 10 to 50% by mass, and it is particularly preferred to use it within a range of 15 to 35% by mass.

[Surfactant (E)]

The photosensitive resin composition for forming an interlayer insulating film of the present invention may contain a surfactant (E). Examples of the surfactant (E) include a polysiloxane-based surfactant and a fluorine-based surfactant.

Specifically, polysiloxane surfactants can be used: BYK-077, BYK-085, BYK-300, BYK- 301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK-354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK- 390 and so on.

As the fluorine-based surfactant, F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F of DIC (DaiNippon Ink & Chemicals) can be used. -444, F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482 , F-483, F-484, F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF -1126, TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, etc., but it is not limited to these.

When the aforementioned surfactant is contained, the content is preferably 0.01 to 10% by mass, more preferably 0.1 to 2% by mass, and most preferably 0.05 to the total solid content of the photosensitive resin composition of the present invention. 1.0% by mass. When it is contained in the range as mentioned above, it is preferable to improve the adhesiveness of the pattern formed with the photosensitive resin composition of this invention, and a board | substrate.

[other]

In addition, the photosensitive resin composition according to the present invention may contain a boundary. Various additives such as surfactants, sensitizers, and defoamers.

As the surfactant, a conventionally known one can be used, and examples thereof include anionic, cationic, and nonionic compounds. Specific examples include X-70-090 (trade name: manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like. By adding a surfactant, coating properties and flatness can be improved.

As the sensitizer, a conventionally known positive-type photoresist can be used. Examples thereof include compounds having a phenolic hydroxyl group having a molecular weight of 1,000 or less.

As the antifoaming agent, a conventionally known one can be used, and examples thereof include a polysiloxane compound and a fluorine compound.

The photosensitive resin composition related to the present invention can be mixed (dispersed and kneaded) using a mixer such as a roll mill, a ball mill, a sand mixer, etc., for example, (A) component, (B) component, (C) component, and (D) component According to need, it is filtered by a filter such as a 5 μm membrane filter and then modulated.

[Interlayer insulation film]

The present invention provides an interlayer insulating film using the photosensitive resin composition for forming an interlayer insulating film.

The interlayer insulating film according to the present invention can be suitably used as an interlayer insulating film provided in an electronic component such as a liquid crystal display element, a integrated circuit element, a solid-state imaging element, and the like to insulate wirings arranged in layers.

A method for forming an interlayer insulating film using the photosensitive resin composition according to the present invention will be described below.

[Formation method of interlayer insulation film]

First, on a support such as a substrate, a photosensitive resin composition according to the present invention is coated and dried using a spinner, a roll coater, a spray coater, a slit coater, or the like to form a photosensitive composition. Resin composition layer. Examples of the substrate include a wiring provided with a transparent conductive circuit and the like, and a glass plate provided with a black matrix, a color filter, and a polarizing plate as required.

As the method of drying, for example, (1) a method of drying a heating plate at a temperature of 80 to 120 ° C for 60 to 120 seconds, (2) a method of leaving it at room temperature for several hours to several days, and (3) Any method of removing the solvent after putting it in a warm air heater or an infrared heater for tens of minutes to several hours may be used. The film thickness of the photosensitive resin composition layer is not particularly limited, but is preferably about 1.0 to 5.0 μm.

Then, exposure is performed through a designated mask. This exposure is performed by irradiating active energy rays such as ultraviolet rays, excimer laser light, and the like. Examples of the light source of the active energy ray include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, and an excimer laser generating device. The amount of energy ray to be irradiated varies depending on the composition of the photosensitive resin composition, but it is preferably about 30 to 2000 mJ / cm ² .

Next, the exposed photosensitive resin composition layer is developed with a developing solution to form a pattern. Examples of the developing solution include an organic alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution or an inorganic alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium metasilicate, and sodium phosphate. Accordingly, an interlayer insulating film can be provided within a desired range. most Then, the aforementioned pattern is heat-hardened. As this heat-hardening temperature, it is more preferable to perform heat-hardening treatment under conditions of 300 ° C or lower, and it is more preferable to perform heat-hardening treatment under conditions of 250 ° C or lower.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

<< Preparation of photosensitive resin composition >>

The components shown in Tables 1 and 2 were mixed and dissolved in a mixed solvent of PGMEA / PGME = 60/40 to prepare a photosensitive resin composition. The solid content concentrations of Examples 1 to 11 and Comparative Example 1 were 20% by mass, and the solid content concentrations of Examples 12 to 22 and Comparative Example 2 were 40% by mass.

Each abbreviation in the said table has the following meanings. In addition, the numerical value in [] is a compounding quantity (mass part).

(A) -1: The following polymer compound (A) -1

(A) -2: The following polymer compound (A) -2

(B) -1: Obtained by reacting 3 mol naphthoquinonediazide-5-sulfonate with respect to the following compound (B) -1

(B) -2: Obtained by reacting 2 mol of naphthoquinonediazide-5-sulfonate with respect to the following compound (B) -1

(C) -1: The following compound (C) -1

(D) -1: Oxetane cross-linking agent (manufactured by Toa Synthetic Co., Ltd., OXT-121)

(D) -2: Soft epoxy cross-linking agent

(Made by Dainippon Ink Chemical Industry Co., Ltd., EXA4850-150)

(D) -3: block isocyanate crosslinking agent isocyanate type

(Made by Asahi Kasei Chemicals, TPA-B80E)

(D) -4: block isocyanate crosslinking agent biuret type

(Made by Asahi Kasei Chemicals, 17B-60P)

(D) -5: Block isocyanate crosslinking agent adduct

(Made by Asahi Kasei Chemicals, E402-B80B)

(E) -1: Silicon-based surface conditioner (BYK Japan, BYK-310)

<Formation of photosensitive resin film>

Using a spin coater (TR25000: manufactured by Tokyo Induction Co., Ltd.), the photosensitive resin compositions prepared in the examples and comparative examples were coated on an 8-inch silicon substrate, and pre-treated at 115 ° C for 90 seconds. Bake to form a coating film with a thickness of 2.0 μm. Next, an i-ray stepper (product name: NSR-i 14E, manufactured by Nikon Corporation, NA = 0.50, σ = 0.64, Focus = 0 μm) was used, and the coating film was irradiated with ultraviolet rays. The exposure amount was set to 500 mJ / cm ² .

The exposed coating film was developed with a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 23 ° C for 60 seconds, and then subjected to heat at 100 ° C for 30 minutes, then at 120 ° C for 30 minutes, and then at 200 ° C for 60 minutes. Hardened.

The following evaluations were performed on each of the prepared photosensitive resin films. The results are shown in Tables 3 to 4.

[Tensile elongation, tensile strength, tensile elasticity]

The obtained photosensitive resin film was subjected to measurement of the breaking elongation, breaking strength, and tensile elastic modulus of the photosensitive resin using a universal material testing machine (TENSILON, manufactured by Orientec Co., Ltd.). Record the evaluation result of tensile elongation as “Elongation (%)”, the evaluation result of breaking strength as “Tensile strength (%)”, and the evaluation result of tensile elasticity as “Young modulus (Gpa)”. In Tables 3 ~ 4.

[Measurement of glass transition temperature]

The glass transition temperature (Tg) was measured by a differential scanning calorimeter (DSC; Differential Scanning Calorimeter).

[Evaluation of linear expansion coefficient (CTE)]

For a photosensitive resin film that is heat-cured at a specified temperature, The thermomechanical analysis device TMA / SS-7100 (manufactured by SII Nano Technology Co., Ltd.) was used to perform thermomechanical analysis under a load of 5 g, a heating rate of 10 ° C./min, and a nitrogen gas environment (flow rate of 20 ml / min), The measurement of the test piece elongation in the temperature range of 50 to 450 ° C can obtain the CTE of the photosensitive resin film at 100 to 300 ° C. The results are shown in Tables 3 to 4 as "CTE (-ppm / K)".

As shown by the above results, it was found that the photosensitive resin film formed using the photosensitive resin composition for forming an interlayer insulating film of the present invention has a high elongation at break and excellent mechanical properties.

Among them, the photosensitive resin films of Examples 8, 9, 19, and 20 using an adduct-type block isocyanate compound as the crosslinking agent (D) had good heat resistance in addition to mechanical properties.

Claims (7)

A photosensitive resin composition for forming an interlayer insulating film, comprising a photosensitive resin for forming an interlayer insulating film containing an alkali-soluble resin (A), a photosensitizer (B), a silane coupling agent (C), and a crosslinking agent (D). The resin composition is characterized in that the photosensitive agent (B) is a compound containing a quinonediazide group, and the crosslinking agent (D) is selected from the group consisting of an oxetane-containing compound, an epoxy-containing compound, and an intercalation compound. At least one group of the segmented isocyanate compounds. The photosensitive resin composition for forming an interlayer insulating film according to claim 1, wherein the alkali-soluble resin (A) contains a structural unit (A1) represented by the following general formula (a-1) or contains an alicyclic ring Unit of oxygen (A3), [In the foregoing general formula, R represents a hydrogen atom or a methyl group, and Ra ⁰¹ represents a hydrogen atom or an organic group having a hydroxyl group]. The photosensitive resin composition for forming an interlayer insulating film according to claim 1 or 2, wherein the crosslinking agent (D) is a block isocyanate compound. The photosensitive resin composition for forming an interlayer insulating film according to claim 3, wherein the block isocyanate compound is an adduct-type block isocyanate compound. An interlayer insulating film using the photosensitive resin composition for forming an interlayer insulating film according to any one of claims 1 to 4. A method for forming an interlayer insulating film, comprising: using a photosensitive resin composition for forming an interlayer insulating film as described in any one of claims 1 to 4 on a support to form a photosensitive resin composition layer; A step of exposing the photosensitive resin composition layer, a step of developing the exposed photosensitive resin composition layer to form an interlayer insulating film pattern, and a step of heating and curing the interlayer insulating film pattern. The method for forming an interlayer insulating film according to claim 6 is characterized in that the aforementioned heat-hardening treatment is performed at 300 ° C or lower.