TWI413861B - Negative photo sensitive resin composition, interlayer insulating film and forming method thereof - Google Patents

Abstract

Disclosed is a negative photosensitive resin composition comprised of (A) an annual olefin resin containing repeating units represented by a general formula (1) (where R1, R2, R3 and R4 each represent an independent substituent group chosen from: a hydrogen atom, an alkyl group having 1-15 carbon atoms, an alkenyl group with 2-20 carbon atoms, a cycloalkyl group with 5-15 carbon atoms, an aryl group with 6-20 carbon atoms or an alkoxy group with 1-20 carbon atoms; or a hydrolysable silyl group, an alkoxycarbonyl group with 2-20 carbon atoms, a trialkylsiloxy carbonyl group with 4-20 carbon atoms, an alkyl carbonyl oxy group with 2-20 carbon atoms, an alkenyl carbonyl oxy group with 3-20 carbon atoms and an oxetanyl group; attached directly or via and jointly with an oxygen atom, a nitrogen atom or a sulphur atom), (B) a polyfunctional acrylic monomer and (C) a photoinitiator.

Description

Negative film type photosensitive resin composition, interlayer insulating film and forming method thereof

The present invention relates to a negative-type photosensitive resin composition, an interlayer insulating film, and a method of forming the same.

In an electronic component such as a thin film transistor (hereinafter referred to as a "TFT") liquid crystal display device, a magnetic head device, an integrated circuit device, and a solid-state image sensor device, in order to insulate between wirings arranged in a layer shape, An interlayer insulating film is provided (see Patent Document 1). The material of the interlayer insulating film is preferably a material having a small number of steps for obtaining a necessary pattern shape and having sufficient flatness. Therefore, a negative-type photosensitive resin composition is widely used (see Patent Document 2).

[Previous Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2000-10089

Patent Document 2: Japanese Patent No. 3650985

In the above electronic component, the TFT liquid crystal display device is produced by forming a transparent electrode film on the interlayer insulating film and forming a liquid crystal alignment film on the transparent electrode film. At this time, since the interlayer insulating film is exposed to high temperature conditions in the step of forming the transparent electrode film, sufficient resistance to the high temperature condition is required.

In addition, in the TFT-type liquid crystal display device, the structure of the liquid crystal display element is complicated by various technologies such as large screen, high luminance, high definition, and high-speed response. Therefore, regarding the interlayer insulating film to be used, in terms of low dielectric constant, high light transmittance (>80%, λ=400 nm), etc., higher performance is required than before, and liquid crystal display is required. The structure of the component also has special requirements such as thick filming to about 50 μm.

However, in the negative-type photosensitive resin composition which is usually used in the formation of the interlayer insulating film, it is extremely difficult to achieve thick film formation, high light transmittance, and high resolution at the same time, and it is strongly required to develop a combination of the above characteristics. A negative-type photosensitive resin composition of the interlayer insulating film.

In view of the above, it is an object of the present invention to provide a negative-type photosensitive film capable of forming an interlayer insulating film which is sufficiently excellent in various properties such as resolution, transparency, heat resistance, heat discoloration resistance, and solvent resistance even when thickened. Resin composition. Further, an object of the present invention is to provide an interlayer insulating film formed of the above-described negative-type photosensitive resin composition and a method of forming the same.

The present invention provides a negative-type photosensitive resin composition comprising (A) a cyclic olefin resin comprising a repeating unit represented by the following formula (1), (B) a polyfunctional acrylic monomer, and (C) ) Photopolymerization initiator. In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and a ring having 5 to 15 carbon atoms. An alkyl group, an aryl group having 6 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, or a hydrolyzable alkylene group, an alkoxycarbonyl group having 2 to 20 carbon atoms, or a trialkyldecaneoxy group having 4 to 20 carbon atoms. The substituent in the carbonyl group, the alkylcarbonyloxy group having 2 to 20 carbon atoms, the alkenylcarbonyloxy group having 3 to 20 carbon atoms or the oxetanyl group may be directly or via an oxygen atom, a nitrogen atom or a sulfur atom. Connected to each other.

[Chemical 1]

The negative-type photosensitive resin composition having the above-described configuration can form an interlayer insulating film which is sufficiently excellent in various properties such as resolution, transparency, heat resistance, heat discoloration resistance, and solvent resistance, even if it is thick.

The cyclic olefin resin (A) preferably contains a structural unit represented by the above formula (1), and R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom.

Further, the (A) cyclic olefin resin preferably contains an alkylcarbonyl group represented by the above formula (1), and any one of R ¹ , R ² , R ³ and R ⁴ is a carbon number of 2 to 20 carbon atoms. A structural unit of an oxy group.

The present invention provides a negative-type photosensitive resin composition for forming an interlayer insulating film, which comprises irradiating at least a part of a film formed of the negative-type photosensitive resin composition with ultraviolet rays having a wavelength of 400 nm or less A step of.

Further, the negative-type photosensitive resin composition of the present invention preferably further contains (D) an alkali-soluble resin.

The present invention provides an interlayer insulating film formed of the negative-type photosensitive resin composition described above.

The present invention provides a method of forming an interlayer insulating film, comprising the steps of: irradiating at least a portion of a film formed of the negative-type photosensitive resin composition; developing the film after irradiation; and developing The above film is calcined to form an interlayer insulating film.

[Effects of the Invention]

According to the present invention, it is possible to provide a negative-type photosensitive resin composition which can form an interlayer insulating film which is sufficiently excellent in various properties such as resolution, transparency, heat resistance, heat-resistant discoloration property, and solvent resistance, even if it is thick.

Hereinafter, preferred embodiments of the present invention will be described in detail.

The negative-type photosensitive resin composition of the present embodiment contains (A) a cyclic olefin resin, (B) a polyfunctional acrylic monomer, and (C) a photopolymerization initiator. Each component will be described in detail below.

- (A) cyclic olefin resin -

The (A) cyclic olefin resin of the present embodiment is a polymer having a repeating unit represented by the following general formula (1).

[Chemical 2]

R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 5 to 15 carbon atoms, or carbon. An aryl group of 6 to 20 or an alkoxy group having 1 to 20 carbon atoms, or a hydrolyzable alkylene group, an alkoxycarbonyl group having 2 to 20 carbon atoms, a trialkyldecyloxycarbonyl group having 4 to 20 carbon atoms, or carbon The alkylcarbonyloxy group having 2 to 20 carbon atoms, the alkenylcarbonyloxy group having 3 to 20 carbon atoms, and the substituent in the oxetanyl group may be bonded to each other directly or via an oxygen atom, a nitrogen atom or a sulfur atom.

More preferably, each of R ¹ , R ² , R ³ and R ^{4 is} independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 15 carbon atoms. Or a substituent in an alkoxy group having 6 to 20 carbon atoms and an alkylcarbonyloxy group having 2 to 20 carbon atoms. According to the above configuration, the effect of improving the solubility in various solvents is obtained.

Specific examples of the hydrolyzable alkylene group include a trimethoxydecyl group and a methyldimethoxydecyl group.

Specific examples of the alkylcarbonyloxy group having 2 to 20 carbon atoms include a methyl ester, a third butyl ester, a 2-ethylhexyl ester, a benzyl ester, a cyclopentyl ester, a cyclohexyl ester, and an allyl ester. Among the alkylcarbonyloxy groups, a methyl ester, a benzyl ester or the like is particularly preferably used in terms of heat resistance.

The (A) cyclic olefin resin used in the present embodiment preferably contains the above formula by 1 mol% or more based on the total amount of the structural unit of the formula (1) in the cyclic olefin. (1) The structural unit represented by R ¹ , R ² , R ³ and R ⁴ is a hydrogen atom, and more preferably contains 10 mol% or more. When the ratio is 1 mol% or more, the heat resistance of the obtained negative-type photosensitive resin composition tends to be improved. Further, the above ratio is preferably 60 mol% or less, more preferably 50 mol% or less. When the ratio is 60 mol% or less, the solubility in the solvent for preparing the negative-type photosensitive resin composition tends to increase.

The (A) cyclic olefin resin used in the present embodiment is preferably represented by the above formula (1), based on the total amount of the structural unit of the formula (1) in the cyclic olefin, and containing 1 mol% or more. Further, any one of R ¹ , R ² , R ³ and R ⁴ is a structural unit of an alkylcarbonyloxy group having 2 to 20 carbon atoms, more preferably 10 mol% or more. When the ratio is 1 mol% or more, there is a tendency that the solubility in the solvent for preparing the negative-type photosensitive resin composition is improved. The above ratio is preferably 60 mol% or less, more preferably 50 mol% or less. When the ratio is 60 mol% or less, the effect of improving the heat resistance of the obtained negative-type photosensitive resin composition tends to be obtained.

The above (A) cyclic olefin resin can be produced by subjecting a monomer represented by the following formula (2) to a solvent in the presence of a metal catalyst.

[Chemical 3]

(A) Examples of the solvent used in the production of the cyclic olefin resin include aliphatic hydrocarbons such as pentane, hexane, and heptane, and alicyclic hydrocarbons such as cyclohexane. , aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as dichloromethane, chloroform, and chlorobenzene, nitromethane, and nitrate Nitrogen-containing hydrocarbons such as nitrobenzene and acetonitrile, and ethers such as diethyl ether, dioxane, and tetrahydrofuran. These solvents may be used alone or in combination of two or more.

(A) The catalyst (E) used in the polymerization of the cyclic olefin resin is preferably at least coordinated to a transition metal selected from the group consisting of Group 8, element 9, and Group 10 elements of the periodic table. A cyclopentadienyl complex of a ligand. Specific examples thereof include iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), and platinum (Pt). Among these metals, preferred ones are cobalt, nickel, palladium, and platinum from the viewpoint of improving the polymerization activity of the catalyst, and palladium is particularly preferably used.

The promoter (F) used in the polymerization of the cyclic olefin resin (A) is preferably a promoter which promotes dissociation of the ligand forming the complex of the catalyst (E). For example, an ionic compound obtained by combining a non-coordinating anion and a cation exemplified below can be mentioned.

Examples of the non-coordinating anion include tetra(phenyl)borate, tetrakis(fluorophenyl)borate, tetrakis(difluorophenyl)borate, and tetrakis(trifluorophenyl). Borate, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(tetrafluoromethylphenyl)borate, tetra(tolyl)borate, Tetrakis(xylyl)borate, (triphenyl, pentafluorophenyl) borate, [tris(pentafluorophenyl), phenyl]borate and tridecahydro-7,8 -Tridecahydride-7, 8-dicarbaundecaborate.

Examples of the above cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a transition metal ferrocene (ferrocenium). ) cations and the like.

Specific examples of the carbonium cation include a trisubstituted carbonium cation such as a triphenylcarbonium cation and a trisubstituted phenylcarbenium cation. Specific examples of the trisubstituted phenylcarbenium cation include a tri(methylphenyl)carbonium cation and a tris(dimethylphenyl)carbonium cation.

Specific examples of the ammonium cation include trialkyl ammonium cations such as trimethyl ammonium cation, triethyl ammonium cation, tripropyl ammonium cation, tributyl ammonium cation, and tri(n-butyl) ammonium cation. , N,N-diethyl anilinium cations and N,N-dialkylanilinium cations such as N,N-2,4,6-pentamethylanilinium cation, and a dialkylammonium cation such as an (isopropyl)ammonium cation or a dicyclohexylammonium cation.

Specific examples of the phosphonium cation include a triphenylphosphonium cation, a tris(methylphenyl)phosphonium cation, and a triarylsulfonium cation such as a tris(dimethylphenyl)phosphonium cation.

The above ionic compound is, for example, trityl tetra(pentafluorophenyl)borate, triphenylcarbonium tetra(fluorophenyl)borate, N,N-dimethylanilinium tetra(pentafluorophenyl)borate and 1,1'-dimethylferrocene tetrakis(pentafluorophenyl)borate 1,1'-dimethylferrocenium tetra(pentafluorophenyl)borate.

In the present embodiment, the ratio of the catalyst (E) to the promoter (F) varies depending on various conditions, and therefore cannot be determined in a general manner. However, it is generally preferred to use the catalyst E/catalyst F (Mo The ear ratio is 1/0.1 to 1/10000, more preferably 1/0.5 to 1/5000, and still more preferably 1/1 to 1/2000.

The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the (A) cyclic olefin resin of the present embodiment is preferably 2 × 10 ³ to 2 × 10 ⁵ , more preferably 2 × 10 ⁴ to 1.8 ×. 10 ⁵ . When Mw is less than 2 × 10 ³ , the obtained film tends to have heat resistance and surface hardness. On the other hand, when the Mw exceeds 2 × 10 ⁵ , the developability and the solubility in the solvent for preparing the photosensitive resin composition tend to decrease.

- (B) Polyfunctional acrylic monomer -

In the (B) polyfunctional acrylic monomer of the present embodiment, a difunctional or higher polyfunctional (meth) acrylate is used. Specific examples thereof include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and pentaerythritol. Acrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylol Methane tetraacrylate, tetramethylol methane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,3,5-tripropylene decyl hexahydro- Triazine (1,3,5-triacryloyl hexahydro-s-triazine), 1,3,5-trimethylpropenyl hexahydro-s-triazine, tris(hydroxyethylpropenyl)trimeric isocyanate (tris) (hydroxyethylacryloyl)isocyanurate), tris(hydroxyethylmethacryloyl)trimeric isocyanate, triacryloyl formal, trimethyl propylene phthalate Formaldehyde, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol Dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 2-hydroxy propanediol diacrylate, 2-hydroxypropanediol dimethacrylate Ester, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropyl glycol diacrylate, isopropyl glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate Ester, N, N'-bis(acryloyl)cysteine, N,N'-bis(methacryloyl)cysteine, thio Thiodiglycol diacrylate, thiodiethanol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate, bisphenoxy Bisphenoxy ethanol fluorene diacrylate, bisphenoxyethanol oxime dimethacrylate, diallyl bisphenol A, o-diallyl bisphenol A, maleic acid Diallyl maleate and triallyl trimellitate. The effect of increasing the mechanical strength is obtained by using a difunctional or higher polyfunctional (meth) acrylate.

The above polyfunctional acrylic monomer can be easily obtained as a commercially available product, and examples thereof include Kyarad T-1420, Kyarad DPHA, Kyarad DPHA-2C, Kyarad D-310, Kyarad D-330, Kyarad DPCA-20, and Kyarad DPCA. -30, Kyarad DPCA-60, Kyarad DPCA-120, Kyarad DN-0075, Kyarad DN-2475, Kyarad R-526, Kyarad NPGDA, Kyarad PEG400DA, Kyarad MANDA, Kyarad R-167, Kyarad HX-220, Kyarad HX620, Kyarad R-551, Kyarad R-712, Kyarad R-604, Kyarad R-684, Kyarad GPO-303, Kyarad TMPTA, Kyarad THE-330, Kyarad TPA-320, Kyarad TPA-330, Kyarad PET-30, Kyarad RP -1040 (above manufactured by Nippon Kayaku Co., Ltd.); Aronix M-210, Aronix M-240, Aronix M-6200, Aronix M-305, Aronix M-309, Aronix M-400, Aronix M-402, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-1310, Aronix M-1600, Aronix M-1960, Aronix M-8100, Aronix M-8530, Aronix M-8560, Aronix M-9050 (manufactured by Toagosei Co., Ltd.); Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 3PA, Viscoat 400, Viscoat 260, Viscoat 312 and Viscoat 335HP (above manufactured by Osaka Organic Chemical Industry Co., Ltd.). In addition, these polyfunctional acrylic monomers may be used alone or in combination of two or more.

Among these polyfunctional acrylic monomers, in terms of solubility and transparency in the developer, it is particularly preferably dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Methacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, and pentaerythritol dimethacrylate.

-(C) Photopolymerization initiator -

The (C) photopolymerization initiator of the present embodiment includes a photosensitive radical polymerization initiator. Examples of the photosensitive radical polymerization initiator include α-diketones such as benzil and diacetyl, and acyloins such as benzoin. Acylin methylether, benzoin ether and acyloin ether, thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonate Acid, benzophenone, 4,4'-bis(dimethylamino)benzophenone, and benzophenone such as 4,4'-bis(diethylamino)benzophenone Class, acetophenone, p-dimethylamino acetophenone, α,α'-dimethoxyethoxy benzophenone (α,α'-dimethoxy acetoxy) Benzophenone), 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl(4-(methylthio)phenyl)-2-morpholine 2-methyl(4-(methylthio)phenyl)-2-morpholino-1-propanone) and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl) ) - acetophenones such as butan-1-one, quinones such as anthraquinone and 1,4-naphthoquinone, phenacyl ch Loride), tribromomethyl phenyl sulfone and tris(trichloromethyl)-s-triazine, etc., 2,4,6-trimethyl 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentyl Peroxides such as phosphine oxide and bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, and peroxides such as di-t-butyl peroxide Wait. By using a photosensitive radical polymerization initiator, the effect of improving the sensitivity of the negative-type photosensitive resin composition is obtained.

Commercial products of such photosensitive radical polymerization initiators include, for example, Irgacure-184, Irgacure-369, Irgacure-500, Irgacure-651, Irgacure-907, Irgacure-1700, Irgacure-819, Irgacure- 124, Irgacure-1000, Irgacure-2959, Irgacure-149, Irgacure-1800, Irgacure-1850, Irgacure-OXE-01, Darocur-1173, Darocur-1116, Darocur-2959, Darocur-1664, Darocur-4043 (above Ciba Specialty Chemicals, Inc.; Kayacure-DETX, Kayacure-MBP, Kayacure-DMBI, Kayacure-EPA, Kayacure-OA (manufactured by Nippon Kayaku Co., Ltd.); Lucirintpo (manufactured by BASF Co., Ltd.); Vicure-10 , Vicure-55 (above manufactured by STAUFFER Co. LTD); Trigonal P1 (manufactured by AKZO Co. LTD); Sandoray 1000 (manufactured by SANDOZ Co. LTD); DEAP (manufactured by APJOHN Co. LTD); Quantacure-PDO, Quantacure-ITX And Quantacure-EPD (above manufactured by WARDBLEKINSOP Co. LTD). In addition, by using these photosensitive radical polymerization initiators together with a photosensitizing agent, it is possible to obtain a high-sensitivity negative-plate type photosensitive resin composition which is less deactivated by oxygen.

Among the above-mentioned photosensitive radical polymerization initiators, α, α'-dimethoxyacetoxy group is particularly preferable in terms of solubility in a photosensitive resin composition preparation liquid and transparency after exposure. Benzophenone, 2-methyl(4-(methylthio)phenyl)-2-morpholinyl-1-propanone and 2-methyl(4-(methylthio)phenyl)-2- Morpholinyl-1-propanone.

-(D) alkali soluble resin -

The alkali-soluble resin of the present embodiment is a linear organic high molecular polymer, and has at least one base which promotes alkali solubility from a molecule (preferably a molecule mainly composed of an acrylic copolymer or a styrene copolymer). An alkali-soluble resin of a group (for example, a carboxyl group, a phosphate group, a sulfonic acid group, etc.) is suitably selected. Among them, a resin which is soluble in an organic solvent and can be developed with a weak aqueous alkali solution is particularly preferred.

When the alkali-soluble resin is produced, for example, a method by a known radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical polymerization initiator, and the kind of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, or can be experimentally set. condition.

The linear organic high molecular polymer is preferably a polymer having a carboxylic acid in its side chain. For example, Japanese Patent Laid-Open No. Sho 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese Patent Publication No. Sho 58-12577, Japanese Patent Publication No. Sho 54-25957, Japanese Patent Laid-Open No. 59-53836 The methacrylic acid copolymer, the acrylic copolymer, the itaconic acid copolymer, the butenoic acid copolymer, the maleic acid copolymer, and the partially esterified cis-form described in each of the publications of JP-A-59-71048 a butenedioic acid copolymer, an acidic cellulose derivative having a carboxylic acid in a side chain, a polymer having an acid anhydride added to a polymer having a hydroxyl group, and the like, and further having a (meth) propylene fluorene in a side chain. The base polymer is a preferred polymer.

Among these polymers, a multicomponent copolymer comprising a benzyl (meth)acrylate/(meth)acrylic copolymer and a benzyl (meth)acrylate/(meth)acrylic acid/other monomer is particularly preferred. In addition, a polymer obtained by copolymerizing 2-hydroxyethyl methacrylate or the like may be mentioned as a useful polymer. The polymer can be used in admixture in any amount.

In addition to the above, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, acrylic acid, as described in JP-A-7-140654 2-Hydroxy-3-phenoxypropyl ester/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/ Methyl methacrylate/methacrylic acid copolymer and 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer.

Regarding the specific structural unit of the (D) alkali-soluble resin, a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith is particularly preferred. Examples of the other monomer copolymerizable with the above (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, and a vinyl compound. Among them, the hydrogen atom of the alkyl group and the aryl group may be substituted by a substituent.

Specific examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. Butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl acrylate , toluene acrylate, naphthalene acrylate and cyclohexyl acrylate.

Further, examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, and N-vinyl pyrrolidone (N-vinyl pyrrolidone). ), tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH ₂ =CR ⁵ R ⁶ [wherein R ⁵ represents a hydrogen atom or a carbon number of 1 ～5 alkyl, R ⁶ represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms] and CH ₂ =C(R ⁵ )(COOR ⁷ ) [wherein R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R ⁷ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. These other monomers which can be copolymerized may be used alone or in combination of two or more.

Preferred other copolymerizable monomers are selected from the group consisting of CH ₂ =CR ⁵ R ⁶ , CH ₂ =C(R ⁵ )(COOR ⁷ ), phenyl (meth)acrylate, benzyl (meth)acrylate, and At least one of styrene is particularly preferably CH ₂ =CR ⁵ R ⁶ and/or CH ₂ =C(R ⁵ )(COOR ⁷ ).

- Preparation of Negative Film Type Photosensitive Resin Composition -

The negative-type photosensitive resin composition of the present embodiment is prepared by mixing the components of the above (A) cyclic olefin resin, (B) polyfunctional acrylic monomer, and (C) photopolymerization initiator. The negative-type photosensitive resin composition is suitably dissolved in a suitable solvent and used in a solution state. For example, a negative film in a solution state can be prepared by mixing (A) a cyclic olefin resin, (B) a polyfunctional acrylic monomer, (C) a photopolymerization initiator, and optionally other formulation agents in a predetermined ratio. A photosensitive resin composition.

The negative-type photosensitive resin composition of the present embodiment is contained in an amount of 10 parts by weight to 150 parts by weight, more preferably 40 parts by weight to 120 parts by weight, based on 10 parts by weight of the (A) cyclic olefin resin. (B) A polyfunctional acrylic monomer. When the (B) polyfunctional acrylic monomer is less than 10 parts by weight, sufficient photosensitivity may not be obtained. On the other hand, in the case of more than 150 parts by weight, the breaking strength tends to decrease. Further, (C) a photopolymerization initiator is contained in a proportion of preferably from 1 part by weight to 40 parts by weight, more preferably from 3 parts by weight to 35 parts by weight. When the (C) photopolymerization initiator is less than 1 part by weight, heat resistance, surface hardness, and chemical resistance tend not to be obtained. On the other hand, in the case of more than 40 parts by weight, the transparency tends to decrease.

The solvent used in the preparation of the negative-type photosensitive resin composition of the present embodiment is a component obtained by dissolving (A) a cyclic olefin resin, (B) a polyfunctional acrylic monomer, and (C) a photopolymerization initiator. A solvent that does not react with each component. Specific examples thereof include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, methyl cellosolve acetate and ethyl cellosolve acetate. Glycol alkyl ether acetate such as ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether and diethylene glycol diethyl ether Propylene glycol monoalkyl ethers such as diethylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol Propylene glycol alkyl ether acetate such as butyl ether acetate, propylene glycol alkyl ether propionate such as propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate, toluene And aromatic hydrocarbons such as xylene, ketones such as methyl ethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone, and methyl acetate, ethyl acetate, propyl acetate, acetic acid Butyl ester, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, hydroxyl Methyl acetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropane Esters such as propyl acrylate, methyl 3-hydroxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate.

Among these solvents, propylene glycol alkyl ether acetates, propylene glycol alkyl ether acetates, and aromatic hydrocarbons are preferably used in terms of solubility, reactivity with each component, and ease of formation of a coating film.

Further, a high boiling point solvent may be used in combination with the above solvent. Examples of the high-boiling solvent which can be used in combination include N-methyl formamide, N, N-dimethyl formamide, and N-methylformamide. (N-methyl formanilide), N-methyl acetamide, N, N-dimethyl acetamide, N-methylpyrrolidone (N- Methyl pyrrolidone), dimethyl sulfoxide, benzyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid , 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate , γ-butyrolactone, ethylene carbonate, propylene carbonate and phenyl cellosolve acetate. The negative-type photosensitive resin composition of the present embodiment may contain other components than the above, as needed, within the range not impairing the object of the present invention.

The negative-type photosensitive resin composition prepared in the above manner can be used by filtration using a micropore filter having a pore diameter of about 0.2 μm to 0.5 μm.

- Method of forming interlayer insulating film -

The method of forming the interlayer insulating film of the present embodiment includes at least the following steps. (1) a step of forming a film of the negative-type photosensitive resin composition on a substrate; (2) a step of irradiating at least a part of the film with light (in the case where "exposure" is present); (3) after exposing a step of developing the film; and 4) a step of forming the interlayer insulating film by firing the developed film (hereinafter, "baking").

Here, the term "light" as used in the present embodiment means light including ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, gamma rays, synchrotron light, and proton beams.

Hereinafter, these steps will be described in detail.

- (1) Step -

In the step (1), the negative-type photosensitive resin composition is preferably formed into a liquid composition, a film is formed on the surface of the substrate, and the solvent is removed by prebaking to form a negative-type photosensitive resin composition. Membrane.

Examples of the type of the substrate that can be used include a glass substrate, a germanium wafer, and a substrate on which various metals are formed on the surfaces of the substrates. The film formation method of the composition solution is not particularly limited, and a method of coating is preferred. The coating method may be an appropriate method such as a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, or an inkjet method.

The pre-baking conditions vary depending on the type and use ratio of the constituent components of the negative-type photosensitive resin composition, and can be, for example, 30 to 15 minutes at 60 to 130 °C. The film thickness of the film formed is preferably from 5 μm to 20 μm in terms of prebaking.

- (2) Step -

In the step (2), at least a portion of the formed film is exposed. In this case, when only a part of the above film is exposed, exposure is usually performed via a photomask having a pattern of a predetermined shape.

Examples of the light used for the exposure include ultraviolet rays such as i-line (wavelength 365 nm), far ultraviolet rays such as KrF excimer lasers and ArF excimer lasers, X-rays such as synchrotron light, and charged particle beams such as electron beams. Among these lights, ultraviolet rays are preferable, ultraviolet rays having a wavelength of 400 nm or less are more preferable, and ultraviolet rays containing i-lines are more preferable. The exposure amount is preferably set to about 50 J/m ² to 10000 J/m ² .

- (3) Step -

In the step (3), the exposed film is developed to remove the unexposed portion to form a pattern having a predetermined shape.

The developing solution used for development is preferably: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, and N-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperididine, 1,8- Diazabicyclo[5,4,0]-7-undecene (1,8-diazabicyclo[5,4,0]-7-undecene) and 1,5-diazabicyclo[4,3,0 An aqueous solution of a basic compound such as -5-decene (1,5-diazabicyclo[4,3,0]-5-nonene). A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous solution of the basic compound in an appropriate amount.

In the present embodiment, when the negative-type photosensitive resin composition does not contain an insoluble component such as a filler or a pigment, various organic solvents in which the constituent components are dissolved may be used as the developer.

The development method may be a suitable method such as a liquid pool method, a dipping method, a shaking dipping method, or a shower method.

The development time varies depending on the compounding composition of the negative-type photosensitive resin composition, and can be, for example, 30 seconds to 300 seconds. In addition, since the negative-type photosensitive resin composition for forming the interlayer insulating film has been used for more than 20 seconds from the optimum conditions, the formed pattern is defective in peeling, and the development time must be strictly controlled. However, in the case of the negative-type photosensitive resin composition of the present invention, even if the excess time from the optimum development time is 30 seconds or more, a favorable pattern can be formed and the product yield can be improved.

- (4) Step -

In the step (4), the developed film is post-exposed as needed, and then baked by a heating means such as a hot plate or an oven to cure the film to form an interlayer insulating film. Examples of the light used for the post-exposure include ultraviolet rays such as i-line (wavelength 365 nm), far-ultraviolet rays such as KrF excimer lasers and ArF excimer lasers, X-rays such as synchrotron light, and charged particle beams such as electron beams.

Among these lights, ultraviolet rays are preferable, ultraviolet rays having a wavelength of 400 nm or less are more preferable, and ultraviolet rays containing i-lines are more preferable. The exposure amount of the post-exposure is preferably set to 50 J/m ² to 10000 J/m ² . The baking conditions vary depending on the type and use ratio of the constituent components of the negative-type photosensitive resin composition, the desired pattern shape, and the heating device to be used, but in the case of a hot plate, for example, 150 ° C to 240 10 ° to 30 minutes at ° C, and in the case of an oven, for example, from 150 ° C to 240 ° C for 30 minutes to 90 minutes. Further, at the time of baking, a stage baking method in which heat treatment is performed twice or more may be employed.

As described above, the target interlayer insulating film can be formed on the substrate. The obtained interlayer insulating film is excellent in various properties such as resolution, transparency, heat resistance, heat discoloration resistance, and solvent resistance, and can be used, for example, in various liquid crystal display elements including TFT liquid crystal display elements. Electronic components such as magnetic head elements, integrated circuit elements, and solid-state imaging elements. Further, according to the method for forming an interlayer insulating film of the present embodiment, an interlayer insulating film having excellent characteristics can be easily formed with high product yield.

[Example]

The invention is more specifically illustrated by the following examples, but the invention is not limited to the examples.

(Example 1)

- Preparation of Negative Film Type Photosensitive Resin Composition -

10 g of Aronix M-305 (manufactured by Toagosei Co., Ltd., trade name) as (B) polyfunctional acrylic monomer was dissolved in 36.4 g of toluene, and then R ¹ and R ² were added to the obtained solution. A monomer in which R ⁴ is a hydrogen atom and R ³ is a methyl ester group and a monomer in which R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom is copolymerized in a ratio of 1:1 (mole ratio) (A) 1 g of a cyclic olefin resin, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one as a (C) photopolymerization initiator (Ciba Specialty Manufactured by Chemicals, trade name: IRGACURE-907) 0.6 g, and then filtered using a membrane filter having a pore size of 0.5 μm to prepare a negative-type photosensitive resin having a solid content of 30% by weight (wt%) in a solution state. (S-1).

- Formation of interlayer insulating film -

The negative-type photosensitive resin composition (S-1) was applied onto a glass substrate using a table coater, and then prebaked in an explosion-proof dryer at 80 ° C for 10 minutes to form a coating film. Next, the coating film was exposed to ultraviolet light having a wavelength of 365 nm at a cumulative exposure amount of 100 mJ/cm ² via a mask having a pattern having a predetermined shape. Then, using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, immersing and developing at 25 ° C for 5 minutes, and then washing with pure water for 1 minute, thereby removing unnecessary portions, and obtaining a patterned film.

Next, the obtained patterned film was baked in an oven at 200 ° C for 30 minutes to be hardened, whereby an interlayer insulating film having a film thickness of 50 μm having a specific pattern shape was obtained.

-Evaluation-

Next, evaluation was performed in the following manner. The evaluation results are shown in Table 1 together with the film thickness of the interlayer insulating film (the same applies hereinafter).

- Evaluation of resolution -

For the obtained interlayer insulating film, a mask pattern having a diameter of 50 μm was used to evaluate the resolution. The case where the 50 μm square hole pattern was analyzed was evaluated as good (A), and the case where the 50 μm square hole pattern could not be analyzed was evaluated as defective (B).

- Evaluation of transparency -

The continuous film portion of the obtained interlayer insulating film was evaluated by measuring the transmittance at a wavelength of 400 nm using a two-beam spectrophotometer U-2900 (manufactured by Hitachi, Ltd., trade name). When the transmittance exceeds 90%, it can be said that the transparency is good (A).

- Evaluation of heat resistance -

The obtained interlayer insulating film was heated in an oven at 220 ° C for 60 minutes, and the rate of change (%) of the film thickness before and after heating was measured using a digital scale manufactured by Mitutoyo [= (film thickness before heating - heating) The film thickness after the film) × 100 / film thickness before heating] was evaluated. When the rate of change is within 5%, it can be said that the heat resistance is good (A).

- Evaluation of heat-resistant discoloration -

Nitrogen rinsing was performed on an oven at 250 ° C, and the obtained interlayer insulating film was heated in the oven for 60 minutes, and then a continuous beam portion of the interlayer insulating film was used using a double beam spectrophotometer U-2900 (trade name, Hitachi Hitachi) Manufactured by the manufacturer to determine the transmittance at a wavelength of 400 nm. The rate of change (%) of the transmittance before and after heating [= (penetration before heating - transmittance after heating) × 100 / transmittance before heating] was evaluated. When the rate of change is within 5%, it can be said that the heat discoloration resistance is good (A).

- Evaluation of solvent resistance -

The glass substrate on which the interlayer insulating film was formed was immersed in N-methylpyrrolidone at 50 ° C for 15 minutes, and the change rate of the film thickness of the interlayer insulating film before and after the immersion was measured using a digital scale manufactured by Mitutoyo. (%) [= (film thickness after immersion - film thickness before immersion) × 100 / film thickness before immersion] was evaluated. When the rate of change is within ±10%, it can be said that the solvent resistance is good (A).

(Example 2)

In the example 1, a negative-type photosensitive solution in a solution state was prepared in the same manner as in Example 1 except that 10 g of Aronix M-305 was used instead of 10 g of Aronix M-402 (manufactured by Toagosei Co., Ltd., trade name). The resin composition (S-2) obtained an interlayer insulating film having a film thickness of 40 μm having a predetermined pattern shape. The evaluation results are shown in Table 1.

In any of the interlayer insulating films of Examples 1 and 2, it was confirmed that the film thickness was excellent, and the resolution, transparency, heat resistance, heat discoloration resistance, and solvent resistance were excellent.

Claims (7)

A negative-type photosensitive resin composition comprising: (A) a cyclic olefin resin comprising a repeating unit represented by the following formula (1): (wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a cycloalkyl group having 5 to 15 carbon atoms; An aryl group having 6 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, or a hydrolyzable alkylene group, an alkoxycarbonyl group having 2 to 20 carbon atoms, or a trialkyldecyloxycarbonyl group having 4 to 20 carbon atoms. a substituent having an alkylcarbonyloxy group having 2 to 20 carbon atoms, an alkenylcarbonyloxy group having 3 to 20 carbon atoms, and an oxetanyl group may be linked to each other directly or via an oxygen atom, a nitrogen atom or a sulfur atom. (B) a polyfunctional acrylic monomer; and (C) a photopolymerization initiator, wherein the above (A) cyclic olefin resin comprises the above formula (1), and R ¹ , R ² , Any one of R ³ and R ⁴ is a structural unit of an alkylcarbonyloxy group having 2 to 20 carbon atoms. The negative-type photosensitive resin composition according to claim 1, wherein the (A) cyclic olefin resin comprises the above formula (1), and R ¹ , R ² , R ³ and R ⁴ A structural unit that is a hydrogen atom. The negative-type photosensitive resin composition according to claim 1 or 2, which is used for a method for forming an interlayer insulating film, which comprises a film formed of the negative-type photosensitive resin composition At least a portion of the step of irradiating ultraviolet rays having a wavelength of 400 nm or less. The negative-type photosensitive resin composition according to the first or second aspect of the invention, further comprising (D) an alkali-soluble resin. An interlayer insulating film which is formed by the negative-type photosensitive resin composition according to any one of the above-mentioned items of the first aspect of the invention. A cured film which is formed from the negative-type photosensitive resin composition according to any one of claims 1 to 4. A method of forming an interlayer insulating film, comprising the step of irradiating at least a portion of a film formed of the negative-type photosensitive resin composition according to any one of claims 1 to 4; The film after the irradiation of light is developed; and the developed film is fired to form an interlayer insulating film.