KR20210106011A - Negative photosensitive resin composition - Google Patents

Abstract

[Problem] To provide a negative photosensitive resin composition capable of increasing the curing rate, making it possible to sufficiently harden the surface of the coating film by exposure from the back surface of the substrate even if the film thickness is 15 µm or more, and forming a fine transparent structure.
[Solution Means] The photosensitive resin composition containing the following component (A), component (B), component (C-1), component (C-2), and component (D). (A) component: alkali-soluble copolymer, (B) component: a compound having two or more at least one polymerizable group selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group and an allyl group, (C- 1) Component: It has an oxime ester group, and the extinction coefficient in methanol or acetonitrile in 365 nm is 5,000 ml/g*cm or more photoinitiator, (C-2) component: The extinction coefficient in methanol or acetonitrile in 365 nm is 100ml/g·cm or less of a photoinitiator, (D)component: a solvent.

Description

Negative photosensitive resin composition {NEGATIVE PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a negative photosensitive resin composition and a cured film obtained therefrom. In more detail, this invention relates to the photosensitive resin composition suitable for the use of a display material, its cured film, and various materials using this cured film.

It is known that the epoxy cation polymerization type UV-curable resin composition containing the epoxy compound and the photo-acid generator proposed as a negative type photosensitive resin composition has high transparency and can thicken film (for example, patent document 1).

Further, as a negative material capable of alkali development, a radical polymerization type negative material containing a polymer having an acryloyl group, a polyfunctional acryl monomer, and a photoradical initiator is known (for example, Patent Document 2).

On the other hand, although the resolution is high, it is known that a positive type material is difficult to thicken and transparency is also low (for example, patent document 3).

International Publication No. 2008/007764 Pamphlet Japanese Patent Laid-Open No. 2004-302389 Japanese Patent Laid-Open No. H8-339082

The photosensitive resin composition disclosed by the above-mentioned patent document 1 is easy to produce tackiness in a coating film before exposure after application|coating, and handling property is bad. In addition, since development with an aqueous alkaline solution cannot be performed, development with an organic solvent is essential. The alkali phenomenon seems to be feasible by introducing a carboxyl group into the polymer. In copolymerization of a monomer having an epoxy group and a monomer having a carboxyl group, the reaction between the epoxy group and the carboxyl group easily occurs during polymerization, making it difficult to control the synthesis of the polymer. In addition, even if the polymer is synthesized by controlling the reaction, the storage stability is low.

In addition, the negative type material described in Patent Document 2, which enables alkali development, has low curability in a thick film of 15 µm or more, and in the process of exposing from the back surface of the substrate, curing does not proceed sufficiently until it reaches the surface of the coating film, and a rectangular pattern was difficult to form. In addition, by adding an excessive amount of a photoradical initiator having a high extinction coefficient, even when exposed from the back surface of the substrate, it becomes possible to cure it to the surface.

From these points, there is a demand for a material that has high transparency, can develop in alkali, has high handleability even when forming a thick film, and has excellent curability.

The present invention has been made in view of the above circumstances, and even if the film thickness is 15 μm or more, not only has curability that can be cured with a small amount of exposure from the back surface of the substrate, but also has high transparency after curing and can form a fine transparent structure It is to provide a negative photosensitive resin composition.

As a result of intensive research conducted to solve the above problems, the present inventors, by using together photoinitiators having two different extinction coefficients as a photoinitiator, have good curability even at low exposure doses, can form patterns, and have excellent transparency. Photosensitive resin composition found that can be realized, and completed the present invention.

That is, it is related with the photosensitive resin composition containing the following (A) component, (B) component, (C-1) component, (C-2) component, and (D)component as a 1st viewpoint.

(A) component: alkali-soluble copolymer;

(B) component: the compound which has 2 or more of at least 1 sort(s) of polymeric group chosen from the group which consists of an acrylate group, a methacrylate group, a vinyl group, and an allyl group;

(C-1) component: a photoinitiator having an oxime ester group and having an extinction coefficient of 5,000 ml/g·cm or more in methanol or acetonitrile at 365 nm;

(C-2) component: the photoinitiator whose extinction coefficient in methanol or acetonitrile in 365 nm is 100 ml/g*cm or less;

(D) Component: Solvent.

As a 2nd viewpoint, it is related with the photosensitive resin composition of a 1st viewpoint which further contains a thiol compound as (E)component.

As a 3rd viewpoint, (A) component relates to the photosensitive resin composition of a 1st viewpoint or 2nd viewpoint which is an alkali-soluble copolymer whose number average molecular weights are 2,000-50,000 in polystyrene conversion.

As a fourth aspect, the alkali-soluble copolymer of component (A) is a copolymer generated by copolymerization of a monomer mixture comprising at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride and maleimide, It relates to the photosensitive resin composition in any one of a 1st viewpoint thru|or a 3rd viewpoint.

As a 5th viewpoint, content of (C-1) component is 0.3 mass part - 5 mass parts with respect to 100 mass parts of (A) component It relates to the photosensitive resin composition in any one of a 1st viewpoint - a 4th viewpoint. .

As a 6th viewpoint, content of (C-2) component is 0.5 mass part - 10 mass parts with respect to 100 mass parts of (A) component It relates to the photosensitive resin composition in any one of a 1st viewpoint - a 5th viewpoint. .

As a 7th viewpoint, content of (B) component relates to the photosensitive resin composition in any one of a 1st viewpoint - a 6th viewpoint whose content of (B) component is 10 mass parts - 150 mass parts with respect to 100 mass parts of (A) component.

As an 8th viewpoint, (C-1) component is a photoinitiator which has a carbazole structure, It is related with the photosensitive resin composition in any one of a 1st viewpoint to a 7th viewpoint.

As a 9th viewpoint, (C-2) It is related with the photosensitive resin composition in any one of 1st viewpoint - 8th viewpoint whose component is a photoinitiator which has a hydroxyl group.

As a 10th viewpoint, it is related with the photosensitive resin composition in any one of a 1st viewpoint thru|or a 9th viewpoint which further contains surfactant as (F)component.

As an 11th viewpoint, it is related with the cured film obtained using the photosensitive resin composition in any one of a 1st viewpoint - a 10th viewpoint.

As a twelfth viewpoint, it relates to the cured film obtained by exposing the coating film on the light-transmitting base material which consists of the photosensitive resin composition in any one of a 1st viewpoint to a 10th viewpoint from the surface opposite to the coating-film surface of this base material.

As a 13th viewpoint, it relates to the interlayer insulating film for liquid crystal displays which consists of the cured film as described in an 11th viewpoint or a 12th viewpoint.

As a 14th viewpoint, it is related with the optical filter which consists of a cured film as described in an 11th viewpoint or a 12th viewpoint.

According to the present invention, as a photoinitiator of a radical curing type negative resist composition, an oxime ester photoinitiator having an extinction coefficient of 5,000 ml/g cm or more in methanol or acetonitrile at 365 nm and methanol or acetonitrile at 365 nm By using a mixture of photoinitiators having an extinction coefficient of 100 ml/g cm or less, the curing rate by exposure is increased, and even if the film thickness is 15 μm or more, it becomes possible to sufficiently harden the surface of the coating film by exposure from the back surface of the substrate. A transparent structure may be formed.

The photosensitive resin composition of this invention is the photosensitive resin composition containing the following (A) component, (B) component, (C-1) component, (C-2) component, and (D)component.

(A) component: alkali-soluble copolymer;

(B) component: the compound which has 2 or more of at least 1 sort(s) of polymeric group chosen from the group which consists of an acrylate group, a methacrylate group, a vinyl group, and an allyl group;

(C-1) component: a photoinitiator having an oxime ester group and having an extinction coefficient of 5,000 ml/g·cm or more in methanol or acetonitrile at 365 nm;

(C-2) component: the photoinitiator whose extinction coefficient in methanol or acetonitrile in 365 nm is 100 ml/g*cm or less;

(D) Component: Solvent.

<(A) component>

Component (A) is an alkali-soluble polymer, and is a copolymer generated by copolymerization of a monomer mixture containing a monomer having an alkali-soluble group and other monomers (hereinafter, simply referred to as a copolymer of component (A)).

(A) Although the copolymer of component should just be a copolymer which has such a structure, it does not specifically limit about the kind, etc. of skeleton of the main chain of polymer|macromolecule which comprises a copolymer, and a side chain.

However, if the copolymer of component (A) has an excessive number average molecular weight of more than 50,000, the developability of the unexposed portion is lowered, whereas if the number average molecular weight is too small, the curing of the exposed portion is insufficient. A component may elute at the time of image development. Therefore, as a copolymer of (A) component, it is preferable to select the copolymer which has a number average molecular weight in the range of 2,000-50,000. In the present specification, the number average molecular weight and the weight average molecular weight described later are all measured in terms of polyester by gel permeation chromatography (GPC).

As a monomer which has an alkali-soluble group, the monomer which has a carboxyl group, a phenolic hydroxyl group, an acid anhydride group, and a maleimide group is mentioned.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate. , N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, 4-vinylbenzoic acid, etc. are mentioned.

Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide, and the like. can be heard

As a monomer which has an acid anhydride group, maleic anhydride, itaconic anhydride, etc. are mentioned, for example.

As a monomer which has a maleimide group, maleimide, the above-mentioned N-(carboxyphenyl) maleimide, N-(hydroxyphenyl) maleimide, etc. are mentioned, for example.

It is preferable that it is a copolymer obtained by copolymerizing the monomer mixture containing at least 1 sort(s) selected from the group which consists of acrylic acid, methacrylic acid, maleic anhydride, and maleimide among these monomers which have an alkali-soluble group.

Moreover, in this invention, when obtaining the said copolymer, the monomer which has the said alkali-soluble group and the other monomer copolymerizable are used together.

Specific examples of such other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, N-substituted maleimide compounds, acrylonitrile compounds, acrylamide compounds, methacrylamide compounds, styrene compounds, and vinyl compounds. .

Hereinafter, although the specific example of the said other monomer is given, it is not limited to these.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, phenoxy. Ethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2 -Ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl- 8-tricyclodecyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, diethylene glycol monoacrylate, Caprolactone 2-(acryloyloxy)ethyl ester, poly(ethylene glycol)ethyl ether acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, acryloyl Ethyl isocyanate, 8-ethyl-8- tricyclodecyl acrylate, glycidyl acrylate, etc. are mentioned.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate. acrylate, phenyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2- Methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adaman Tyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 2-hydroxyethyl methacrylate, 2 -Hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2- (methacryloyloxy) ethyl ester , poly(ethylene glycol) ethyl ether methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, methacryloylethyl isocyanate, and 8-ethyl- 8-tricyclodecyl methacrylate glycidyl methacrylate etc. are mentioned.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether. can be heard

As said styrene compound, styrene, methylstyrene, chlorostyrene, bromostyrene etc. are mentioned, for example.

Examples of the N-substituted maleimide compound include N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

As said acrylonitrile compound, acrylonitrile etc. are mentioned, for example.

The method for obtaining the copolymer of component (A) used in the present invention is not particularly limited, but, for example, a monomer mixture containing the monomer having an alkali-soluble group and the other monomer, and, if necessary, a polymerization initiator or the like. In a solvent, it is obtained by carrying out polymerization reaction under the temperature of 50-110 degreeC. At this time, the solvent used will not be specifically limited if it melt|dissolves the monomer and other monomers which have an alkali-soluble group, and the copolymer of (A) component. As a specific example, the solvent described in the solvent of (D)component mentioned later is mentioned.

The alkali-soluble copolymer obtained in this way is in the state of the solution melt|dissolved in the solvent normally.

In addition, the solution of the copolymer of component (A) obtained as described above is charged under stirring with diethyl ether or water to reprecipitate, and the resulting precipitate is filtered and washed, then under normal pressure or reduced pressure, at room temperature or By heat-drying, it can be set as the powder of the said copolymer. By this operation, the polymerization initiator and unreacted monomer coexisting with the copolymer can be removed, and as a result, a purified copolymer powder can be obtained. What is necessary is just to melt|dissolve the obtained powder again in a solvent and just to perform the said operation repeatedly, when it cannot fully refine|purify by one operation.

In this invention, the polymerization solution of the said (A) alkali-soluble copolymer may be used as it is, or the powder may be re-dissolved in the solvent of (D)component mentioned later, for example, and you may use it as a state of a solution.

On the other hand, as copolymerization ratio of a monomer, it is preferable to set it as alkali-soluble monomer/other monomer =5-50 mass parts/50-95 mass parts. When the copolymerization ratio of the alkali-soluble monomer is too small, the unexposed portion does not dissolve in the developer and tends to cause a residual film or residue. In addition, when there is too much copolymerization ratio of an alkali-soluble monomer, sclerosis|hardenability of an exposed part may be insufficient, and a pattern may not be formed.

<(B) component>

(B) A component is a compound which has two or more polymeric groups. The compound having two or more polymerizable groups as used herein means a compound having two or more polymerizable groups in one molecule and in which these polymerizable groups are at the molecular terminal. The polymerizable group means an acrylate group, a methacrylate group, a vinyl group or an allyl group, and the component (B) targets a compound having two or more of at least one group.

The compound which has two or more polymeric groups which is this (B) component WHEREIN: Compatibility with each component is favorable in the solution of the negative photosensitive resin composition of this invention, and from a viewpoint of not affecting developability, weight Compounds having an average molecular weight of 1,000 or less are preferred.

Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate. , pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane tetraacrylic Rate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,3,5-triacryloylhexahydro-S-triazine, 1,3,5- Trimethacryloyl hexahydro-S-triazine, tris (hydroxyethyl acryloyl) isocyanurate, tris (hydroxyethyl methacryloyl) isocyanurate, triacryloyl formal, tri Methacryloyl formal, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethanediol diacrylate, ethanediol diacrylate Methacrylate, 2-hydroxypropanediol diacrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropylene glycol diacrylate, isopropylene glycol Dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N,N'-bis(acryloyl)cysteine, N,N'-bis(methacryloyl)cysteine, thiodiglycol Diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate , bisphenoxyethanol fluorene diacrylate, bisphenoxyethanol fluorenedi methacrylate, diallyl ether bisphenol A, o-diallyl bisphenol A, diallyl maleate, triallyl trimellitate, and the like. have.

The polyfunctional acrylate compound can be easily obtained as a commercial item, and specific examples thereof include, for example, KAYARAD (registered trademark) T-1420, KAYARAD DPHA, KAYARAD DPHA-2C, KAYARAD D-310, KAYARAD D. -330, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD DN-0075, KAYARAD DN-2475, KAYARAD R-526, KAYARAD NPGDA, KAYARAD PEG400DA, KAYARAD MANDA, KAYARAD R 167, KAYARAD HX-220, KAYARAD HX620, KAYARAD R-551, KAYARAD R-712, KAYARAD R-604, KAYARAD R-684, KAYARAD GPO-303, KAYARAD TMPTA, KAYARAD THE-330, KAYARAD TPA-320, KAYARAD TPA -330, KAYARAD PET-30, KAYARAD RP-1040 (above, manufactured by Nippon Kayaku Co., Ltd.); ARONIX (registered trademark) M-210, ARONIX M-208, ARONIX M-211B, ARONIX M-215, ARONIX M-220, ARONIX M-225, ARONIX M-270, ARONIX M-240, ARONIX M- 6100, ARONIX M-6250, ARONIX M-6500, ARONIX M-6200, ARONIX M-309, ARONIX M-310, ARONIX M-321, ARONIX M-350, ARONIX M-360, ARONIX M-313, ARONIX M- 315, ARONIX M-306, ARONIX M-303, ARONIX M-452, ARONIX M-408, ARONIX M-403, ARONIX M-400, ARONIX M-402, ARONIX M-405, ARONIX M-406, ARONIX M- 450, ARONIX M-460, ARONIX M-510, ARONIX M-520, ARONIX M-1100, ARONIX M-1200, ARONIX M-6100, ARONIX M-6200, ARONIX M-6250, ARONIX M-6500, ARONIX M- 7100, ARONIX M8030, ARONIX M8060, ARONIX M8100, ARONIX M8530, ARONIX M-8560, ARONIX M9050 (above, manufactured by Toagosei Co., Ltd.); VISCOAT 295, VISCOAT 300, VISCOAT 360, VISCOAT GPT, VISCOAT 3PA, VISCOAT 400, VISCOAT 260, VISCOAT 312, VISCOAT 335HP, VISCOAT 700 (above, manufactured by Osaka Organic Chemical Industry Ltd.); A-200, A-400, A-600, A-1000, A-B1206PE, ABE-300, A-BPE-10, A-BPE-20, A-BPE-30, A-BPE-4, A- BPEF, A-BPP-3, A-DCP, A-DOD-N, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, A-PTMG- 65, A-9300, A-930-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD- TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, 9PG, 701A, 1206PE, NPG, NOD-N, HD-N, DOD-N, DCP, BPE-1300N, BPE-900, BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, 1G (above, manufactured by Shin Nakamura Chemical Co., Ltd.); LIGHTESTER EG, LIGHTESTER 2EG, LIGHTESTER 3EG, LIGHTESTER 4EG, LIGHTESTER 9EG, LIGHTESTER 14EG, LIGHTESTER 1.4BG, LIGHTESTER NP, LIGHTESTER 1.6HX, LIGHTESTER 1.9ND, LIGHTESTER G-101P, LIGHTESTER G-201P, LIGHTESTER G-201P M, LIGHTESTER BP-2EMK, LIGHTESTER BP-4EM, LIGHTESTER BP-6EM, LIGHTESTER TMP, LIGHTACRYLATE 3EG-A, LIGHTACRYLATE 4EG-A, LIGHTACRYLATE 9EG-A, LIGHTACRYLATE 14EG-A, LIGHTACRYLATE PTMGA-250, LIGHTACRYLATE NP-A, LIGHTACRYLATE MPD-A, LIGHTACRYLATE 1.6HX-A, LIGHTACRYLATE 1.9ND-A, LIGHTACRYLATE MOD-A, LIGHTACRYLATE DCP-A, LIGHTACRYLATE BP-4PA, LIGHTACRYLATE BA-134, LIGHTACRYLATE BP-10EA, LIGHTACRYLATE BP- A, LIGHTACRYLATE G-201P, LIGHTACRYLATE TMP-A, LIGHTACRYLATE TMP-3EO-A, LIGHTACRYLATE TMP-6EO-3A, LIGHTACRYLATE PE-3A, LIGHTACRYLATE PE-4A, LIGHTACRYLATE DPE-6A, EPOXYESTER 70PA (epoxiestel) , EPOXYESTER 200PA, EPOXYESTER 80MFA, EPOXYESTER 3002M, EPOXYESTER 3002A, EPOXYESTER 3000MK, EPOXYESTER 3000A, EPOXYESTER EX-0205, AH-600, AT-600, UA-306H, U A-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 (manufactured by Kyoeisha Chemical Co., Ltd.); EBECRYL (registered trademark) TPGDA, EBECRYL 145, EBECRYL 150, EBECRYL PEG400DA, EBECRYL 11, EBECRYL HPNDA, EBECRYL PETIA, EBECRYL PETRA, EBECRYL TMPTA, EBECRYL TMPTA, EBECRYL 140 EBECRY EBRYL 204, EBECRYL 205, EBECRYL 210, EBECRYL 215, EBECRYL 220, EBECRYL 6202, EBECRYL 230, EBECRYL 244, EBECRYL 245, EBECRYL 264, EBECRYL 265, EBECRYL 284 , EBECRYL 1259, EBECRYL KRM8200, EBECRYL 4820, EBECRYL 4858, EBECRYL 5129, EBECRYL 8210, EBECRYL 8301, EBECRYL 8307, EBECRYL 8402, EBECRYL 8405, EBECRYL 77 KRM8296; EBECRYL 812, EBECRYL 1830, EBECRYL 846, EBECRYL 851, EBECRYL 852, EBECRYL 853, EBECRYL 1870, EBE CRYL 884, EBECRYL 885, EBECRYL 600, EBECRYL 605, EBECRYL 645, EBECRYL 648, EBECRYL 860, EBECRYL 1606, EBECRYL 3500, EBECRYL 3608, Allnex Ltd.); SR212, SR213, SR230, SR238F, SR259, SR268, SR272, SR306H, SR344, SR349, SR508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S, SR9003, CD9043, SR9045, SR9209, SR205, SR9209, SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD541, CD542, SR603, SR644, SR9036, SR351S, SR368, SR415, SR444, SR454, SR49, SR492, SR499, CD492, SR CD9021, SR9035, SR350, SR295, SR355, SR399, SR494, SR9041 (made by Sartomer), etc. are mentioned.

The compound which has two or more of these polymeric groups can be used 1 type or in combination of 2 or more type.

It is preferable that content of (B) component in the negative photosensitive resin composition of this invention is 10-150 mass parts with respect to 100 weight part of (A) component, More preferably, it is 20-120 mass parts, Especially Preferably it is 30-110 mass parts. (B) When there is too little ratio of content of a component, even if an exposure part becomes insufficient hardening and pattern formation does not do it, even if it did, it may become a film|membrane with low reliability. Moreover, when this ratio is excessive, adhesion may generate|occur|produce in the coating film after prebaking, or an unexposed part may become poor dissolution at the time of image development.

<(C)component>

(C) Component is a photoinitiator, In this invention, the photoinitiator which has two types of different (gram) extinction coefficient of following (C-1) and (C-2) is used.

<(C-1) component>

(C-1) A component has an oxime ester group and is a photoinitiator whose extinction coefficient in methanol in 365 nm or acetonitrile is 5,000 ml/g*cm or more. Specifically, it has an oxime ester group and a light absorption site|part, and the compound whose extinction coefficient in methanol or acetonitrile in 365 nm is 5,000 ml/g*cm or more is mentioned.

As said oxime ester group, group represented by following formula (1) is mentioned, for example.

[Formula 1]

(Wherein, R ¹ represents a phenyl group, a straight chain, branched or cyclic alkyl group having 1 to 10 carbon atoms or a benzyl group, and R ² represents a hydrogen atom, a straight chain, branched or cyclic C 1 to 10 alkyl group or a phenyl group. , the broken line indicates the number of bonds.)

Examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, 1-adamantyl group, etc. are mentioned.

As the light absorbing moiety, a group selected from a phenyl group, a phenylthiophenyl group, an N-alkylcarbazole group, a naphthyl group, a coumarin group, an alkoxyphenyl group, a phenylalkoxyphenyl group, and a phenoxyalkoxyphenyl group, a benzoyl group, a naphthylcarbonyl group, etc. It is preferable that the group having a benzoyl structure is substituted. In addition, a phenyl group, a phenylthio group, a diphenylamino group, etc. may be substituted in the said structure.

(C-1) As a component, for example, the oxime ester group represented by the said Formula (1) is a phenyl group, a phenylthiophenyl group, N-alkylcarbazole group, a naphthyl group in a light absorption site|part via a single bond or a carbonyl group. , a compound bonded to a group selected from a coumarin group, an alkoxyphenyl group, a phenylalkoxyphenyl group, and a phenoxyalkoxyphenyl group is preferable.

As a specific example of this (C-1) component, For example, 1-(4-phenylthiophenyl)-1,2-octanedione-2-(O-benzoyloxime), ethanone (ethanone),1- [9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), (E)-4-(4(4-(diphenylamino)benzoyl) )benzyloxy)benzaldehyde-O-acetyloxime, (E)-4-(4,8-dimethoxy-1-naphthoyl)benzaldehyde-O-acetyloxime, 1-(9-propyl-9H-carbazole-3 -yl)butane-1,3-dione-1-(O-acetyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]butane-1,3 -dione-1-(O-acetyloxime) etc. are mentioned.

The photoinitiator of the component (C-1) can be easily obtained as a commercial product (photopolymerization initiator), and specific examples thereof include, for example, IRGACURE (registered trademark) OXE01, IRGACURE (registered trademark) OXE02 (above, BASF). corporation), ADEKA OPTOMER (adeka optomer) N-1919, ADEKA ARKLS (adeka a cruise) NCI-831, ADEKA ARKLS NCI-930 (above, manufactured by ADEKA Corporation), and the like.

Even if the photoinitiator of these (C-1) component is used independently, it is also possible to use 2 or more types together.

It is preferable that content of (C-1) component in the negative photosensitive resin composition of this invention is 0.3 mass part - 5 mass parts with respect to 100 mass parts of (A) component, More preferably, 0.5 mass part - 4 is the mass part. When the ratio of this (C-1) component is less than 0.3 mass part, when the coating film which apply|coated this resin composition on a base material is exposed from the back surface of this base material as mentioned later, until it reaches the surface of a coating film Sclerosis|hardenability of may fall, and when this ratio is excessive than 5 mass parts, the transmittance|permeability of a cured film may fall, or when exposing from the back surface of a base material, sclerosis|hardenability of the surface may fall.

<(C-2) component>

(C-2) A component is a photoinitiator whose extinction coefficient in methanol or acetonitrile in 365 nm is 100 ml/g*cm or less. (C-2) As a component, it is preferable, for example to have a hydroxyl group.

As a specific example of such (C-2) component, 1-hydroxy-cyclohexyl-phenyl- ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy -2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, phenyl glyoxylic acid methyl ester (fenyl glyoxylic acid methyl ester), 2 -oxy-2-phenylacetic acid 2-[2-hydroxy-ethoxy]ethyl ester etc. are mentioned.

The photoinitiator of the component (C-2) can be easily obtained as a commercial product (photopolymerization initiator), and specific examples thereof include, for example, IRGACURE (registered trademark) 2959, IRGACURE (registered trademark) 754, IRGACURE (registered trademark) 184, DAROCURE MBF, and DAROCURE 1173 (above, manufactured by BASF Corporation).

Even if the photoinitiator of these (C-2) component is used independently, it is also possible to use 2 or more types together.

It is preferable that content of (C-2) component in the negative photosensitive resin composition of this invention is 0.5 mass part - 10 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 1 mass part - 7 mass parts is the mass part. When the ratio of this (C-2) component is less than 0.5 mass part, sclerosis|hardenability of the surface may fall, and when this ratio is excessive than 10 mass parts, the transmittance|permeability of a cured film falls, or a residue in an unexposed part may occur.

<(D)component: solvent>

The solvent of (D)component used for this invention melt|dissolves (A)component, (B)component, and (C)component, and (E)component, (F)component etc. which are mentioned later added as needed It dissolves, and if it is a solvent which has such a solubility, the kind, structure, etc. are not specifically limited.

As a solvent of such (D)component, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl- 2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2-hydroxyethyl propionate, 2-hydroxy-2-methylpropionate ethyl, ethoxyethyl acetate, ethyl hydroxyacetate, 2 -Hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate , ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

These solvents can be used individually by 1 type or in combination of 2 or more types.

Among the solvents of these (D)components, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, etc. are preferable from a viewpoint that the coating film property is favorable and safety is high. These solvents are generally used as solvents for photoresist materials.

<(E) component>

(E) A component is a thiol compound. In the negative photosensitive resin composition of the present invention, for the purpose of improving the curing rate, the negative photosensitive resin composition may further contain a thiol compound unless the effect of the present invention is impaired.

(E) Although it does not restrict|limit especially as a thiol compound of a component, For example, 1-hexanethiol, 1-heptanethiol, 1-octanethiol, 1-nonanethiol, 1-decanethiol, 1-undecanethiol , 1-dodecanthiol, 1-octadecanethiol, 2-mercaptobenzothiazole, 6-methyl-2-mercaptobenzothiazole, 5-chloro-2-mercaptobenzothiazole, 2-naphthalenethiol, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercaptobenzimidazole, 2-mercaptobenzooxazole, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, trimethylol Propane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutanate), 1,4-bis (3-mercaptobutyryl) and oxy)butane and 1,3,5-tris[2-(3-sulfanylbutanoyloxy)ethyl]-1,3,5-triazinane-2,4,6-trione.

The thiol compound which is these (E)component can be used individually by 1 type or in combination of 2 or more types.

Among the thiol compounds that are these (E) components, pentaerythritol tetrakis (3-mercaptobutanate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris[2-( 3-sulfanylbutanoyloxy)ethyl]-1,3,5-triazinane-2,4,6-trione is preferred from the viewpoint of high storage stability of the negative photosensitive resin solution and obtaining sufficient curability. do.

When a thiol compound is used, the content is 0.01-10 mass parts based on 100 mass parts of (A) component, Preferably it is 0.03-5 mass parts. (E) Even if the usage-amount of the thiol compound of a component sets to excessive quantity, pattern resolution may fall. When too little, the effect of sclerosis|hardenability improvement may not be expressed.

<(F) component>

(F) A component is surfactant. In the negative photosensitive resin composition of this invention, for the purpose of improving the applicability|paintability, unless the effect of this invention is impaired, surfactant can be contained further.

(F) Although it does not restrict|limit especially as surfactant of component, For example, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned. As this kind of surfactant, commercial items, such as the Sumitomo 3M Limited make, the DIC Corporation make, or AGC Seimi Chemical Co., Ltd. make, can be used, for example. Since these commercial items can be obtained easily, they are suitable. Specific examples thereof include PolyFox (polyfox) PF-136A, 151, 156A, 154N, 159, 636, 6320, 656, 6520 (manufactured by Omnova), MEGAFAC (registered trademark) R30, R08, R40, R41, R43, F251 , F477, F552, F553, F554, F555, F556, F557, F558, F559, F560, F561, F562, F563, F565, F567, F570 (manufactured by DIC Corporation), FC4430, FC4432 (manufactured by Sumitomo 3M Limited), ASAHI GUARD (Asa-d) (registered trademark) AG710, SURFLON (sau-fron) (registered trademark) S-386, S-611, S-651 (manufactured by AGC Seimi Chemical Co., Ltd.), FTERGENT (fta-gent) (trademark) Fluorine surfactants, such as FTX-218, DFX-18, 220P, 251, 212M, 215M (made by Neos Co., Ltd.); BYK-300, 302, 306, 307, 310, 313, 315, 320, 322, 323, 325, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455( BYK Chemie Japan made by KK), SH3746, SH3749, SH3771, SH8400, SH8410, SH8700, SF8428 (manufactured by Toray Dow Corning Silicone Co., Ltd.), KF-351, KF-352, KF-353, KF-354L, KF and silicone-based surfactants such as -355A, KF-615A, KF-945, KF-618, KF-6011, and KF-6015 (manufactured by Shin-Etsu Chemical Co., Ltd.).

(F) Surfactant of component can be used individually by 1 type or in combination of 2 or more types.

When surfactant is used, the content is 0.01-1 mass part based on 100 mass parts of (A) component, Preferably it is 0.02-0.8 mass part. (F) Even if the usage-amount of surfactant of component sets to quantity exceeding 1 mass part, the said applicability|paintability improvement effect becomes dull and it becomes uneconomical. When it is 0.01 mass part or less, the effect of an applicability|paintability improvement may not be expressed.

<Other Additives>

Further, the negative photosensitive resin composition of the present invention may contain, if necessary, a sensitizer, a chain transfer agent, a crosslinking agent, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, or a polyvalent agent, as long as the effects of the present invention are not impaired. It may contain dissolution accelerators, such as a phenol and polyhydric carboxylic acid.

<Negative photosensitive resin composition>

The negative photosensitive resin composition of this invention has the alkali-soluble polymer of (A) component, the compound which has two or more polymeric groups of (B) component, and the oxime ester group of (C-1) component, methanol in 365 nm A photoinitiator having an extinction coefficient of 5,000 ml/g·cm or more in medium or acetonitrile, and a photoinitiator having an extinction coefficient in methanol or acetonitrile at 365 nm of component (C-2) of 100 ml/g·cm or less as component (D) It is a composition which melt|dissolved in the solvent of and can further contain 1 or more types of the thiol compound of (E) component, surfactant of (F) component, and other additives as needed, respectively.

Among these, the preferable example of the negative photosensitive resin composition of this invention is as follows.

[1]: Based on 100 mass parts of (A) component, 10-150 mass parts (B) component, 0.3 mass part - 5 mass parts (C-1) component, 0.5 mass part - 10 mass parts (C-2) ) component, and the negative photosensitive resin composition in which these components were melt|dissolved in the solvent of (D)component.

[2]: The composition of said [1] WHEREIN: The negative photosensitive resin composition which further contains 0.01-10 mass parts of (E) component based on 100 mass parts of (A) component.

[3]: The composition of the said [1] or [2] WHEREIN: The negative photosensitive resin composition which further contains 0.01-1 mass part of (F) component based on 100 mass parts of (A) component.

Although the ratio of the solid content in the negative photosensitive resin composition of this invention is not specifically limited as long as each component is melt|dissolving in the solvent uniformly, For example, it is 1-80 mass %, For example, 5- 70 mass %, or 10-60 mass %. Here, solid content means what removed the solvent of (D)component from all the components of a negative photosensitive resin composition.

Although the preparation method of the negative photosensitive resin composition of this invention is not specifically limited, As the preparation method, for example, the copolymer of (A) component is melt|dissolved in the solvent of (D) component, and (B) ) A method of mixing the compound having two or more polymerizable groups of the component, the photoinitiator of the component (C-1), and the photoinitiator of the component (C-2) in a predetermined ratio to obtain a uniform solution, or A suitable step WHEREIN: The method of adding and mixing the thiol compound of (E)component, surfactant of (F)component, and other additives as needed is mentioned.

In preparation of the negative photosensitive resin composition of this invention, the polymerization solution of the copolymer of (A) component obtained by the polymerization reaction in the solvent of (D)component can be used without refinement|purification as it is. In this case, when the (B) component, (C-1) component, (C-2) component, etc. are added to the polymerization solution of the (A) component in the same manner as above to make a uniform solution, for the purpose of adjusting the concentration ( D) The solvent of the component may be additionally added. At this time, the solvent of (D) component used in the formation process of the copolymer of (A) component and the solvent of (D) component used for concentration adjustment at the time of preparation of the negative photosensitive resin composition may be the same , may be different.

And it is preferable to use, after filtering the solution of the prepared negative photosensitive resin composition using the filter etc. whose pore diameter is about 0.2 micrometer.

<Paint film and cured film>

The negative photosensitive resin composition of the present invention is a semiconductor substrate (eg, a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate , ITO substrate, etc.) or film substrate (e.g., triacetyl cellulose (TAC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET) film, acrylic film, polyimide On a resin film such as mid), etc., the coating film is formed by rotating application, drip application, roll application, slit application, rotary application following the slit, inkjet application, etc., and then pre-drying with a hot plate or oven, etc. can do. Thereafter, by heat-treating this coating film, a negative photosensitive resin film is formed.

As the conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected within the range of a temperature of 70°C to 150°C and a time period of 0.3 to 60 minutes are employed. The heating temperature and heating time are preferably 80°C to 120°C, and 0.5 to 10 minutes.

Moreover, the film thickness of the negative photosensitive resin film formed from the negative photosensitive resin composition is, for example, 0.1-50 micrometers, for example, is 0.5-40 micrometers, Furthermore, it is 1-30 micrometers, for example.

The negative photosensitive resin film formed from the negative photosensitive resin composition of the present invention is contained in the negative photosensitive resin film when exposed to light such as _{ultraviolet rays, ArF, KrF, or F 2 laser light using a mask having a predetermined pattern.} By the action of radicals generated from the photoinitiator of the component (C-1) and the component (C-2) used, the exposed portion of the film is insoluble in the alkaline developer.

In addition, when the negative photosensitive resin film of the present invention is formed on a light transmissive substrate, not only exposure from the upper portion of the surface of the substrate on which this resin film (coating film) is formed, but also the surface on which this resin film (coating film) is formed Even if it exposes through a mask etc. from the surface on the opposite side to (coating-film surface), an exposure part turns into hardened|cured material which is fully insoluble in an alkaline developing solution.

After that, development is performed using an alkaline developer. Thereby, the unexposed part of the negative photosensitive resin film is removed, and the relief in pattern shape is formed.

Examples of the alkaline developer that can be used include an aqueous solution of an alkali metal hydroxide such as sodium carbonate, potassium carbonate, potassium hydroxide and sodium hydroxide, an aqueous solution of quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline and alkaline aqueous solutions such as aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine. Moreover, surfactant etc. can also be added to these developing solutions.

Among the above, 0.5 to 3% by mass aqueous solution of sodium carbonate, 0.01 to 0.5% by mass aqueous solution of potassium hydroxide, and 0.1 to 2.38% by mass aqueous solution of tetraethylammonium hydroxide are generally used as a developing solution for photoresists, and also in the photosensitive resin composition of the present invention. , it can develop favorably using this alkaline developing solution, without causing problems such as swelling.

In addition, as a developing method, any, such as a puddle method, a dipping method, a rocking|fluctuation immersion method, can be used. The developing time at this time is normally 15 to 180 second.

After development, the negative photosensitive resin film is washed with running water, for example, for 20 to 90 seconds, and then air dried using compressed air or compressed nitrogen or by spinning to remove moisture on the substrate. , and a patterned film is obtained.

Subsequently, with respect to this patterned film, post-baking for thermosetting or post-exposure for photocuring, specifically, heating using a hot plate, oven, etc., or exposure using an ultraviolet irradiation device Thereby, the film (cured film) which has the favorable relief pattern which improved heat resistance, transparency, planarity, low water absorption, chemical-resistance, etc. is obtained.

As a post-baking furnace, in general, at a heating temperature selected within a temperature range of 120° C. to 250° C., a method of processing for 1 to 30 minutes on a hot plate and 1 to 90 minutes for 1 to 90 minutes in an oven is adopted.

And the cured film which has the favorable pattern shape made into the objective by such a post-baking can be obtained.

As described above, by the negative photosensitive resin composition of the present invention, there is no adhesion before exposure, alkali development is possible, and even with a film thickness of about 15 μm, it is sufficiently sensitive and the film decrease in the exposed part is very small during development, and a fine pattern is formed. It is possible to form a coating film having Furthermore, this cured film is excellent in transparency, heat resistance, and solvent resistance. Therefore, it can be suitably used for various films in a liquid crystal display, an organic electroluminescent display, a touchscreen element, etc., for example, an interlayer insulating film, a protective film, an insulating film, an optical film, etc.

Example

Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these Examples.

[Abbreviations used in the examples]

The meanings of the abbreviations used in the following examples are as follows.

MAA: methacrylic acid

MMA: methyl methacrylate

AIBN: azobisisobutyronitrile

PRG1: ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (365 nm extinction coefficient: 7,749 ml/g cm in CH ₃ CN)

PRG2: 1-hydroxy-cyclohexyl-phenyl-ketone (365 nm extinction coefficient: 88.64 ml/g cm in MeOH)

PRG3: 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (365 nm extinction coefficient: 48.93 ml/g cm in MeOH)

PRG4: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (365 nm extinction coefficient: 73.88 ml/g cm in MeOH)

PRG5: phenylglyoxylic acid methyl ester (365 nm extinction coefficient: 38 ml/g cm in CH ₃ CN)

PRG6: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (365 nm extinction coefficient: 7,858 ml/g cm in MeOH)

PRG7: bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (365 nm extinction coefficient: 2,309 ml/g cm in MeOH)

PRG8: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (365nm extinction coefficient: 446.5ml/g cm in CH ₃ CN)

DPHA: dipentaerythritol penta and hexaacrylate

CTA: Showa Denko K.K. Karenz-MT (carenz-MT) (registered trademark) PE1 (product name) (compound name: pentaerythritol tetrakis (3-mercaptobutyrate))

PGME: propylene glycol monomethyl ether

[Measurement of number average molecular weight and weight average molecular weight]

The number average molecular weight and weight average molecular weight of the copolymer of component (A) obtained according to the following synthesis examples were measured by using Shimadzu Science Co., Ltd. GPC apparatus (columns KF803L and KF804L), and the elution solvent tetrahydrofuran at a flow rate of 1 mL It was measured under the condition that it was eluted by flowing into the column at a rate of /min (column temperature: 40°C). In addition, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

<Synthesis Example 1>

As a monomer component constituting the copolymer, MAA (30.0 g), MMA (120.0 g) is used, and AIBN (6.4 g) is used as a radical polymerization initiator, and by polymerizing them in a solvent PGME (290 g), Mn9, 700 and a copolymer solution (copolymer concentration: 35% by mass) of component (A) having a Mw of 21,500 was obtained (P1). On the other hand, the polymerization temperature was adjusted to a temperature of 60°C to 90°C.

<Examples 1 to 5 and Comparative Examples 1 to 7>

According to the composition shown in following Table 1, in the solution of (A) component, (B) component, (C-1) component, (C-2) component, the solvent of (D)component, and (E) component The negative photosensitive resin composition of each Example and each comparative example was prepared by mixing in a predetermined ratio, stirring at room temperature for 3 hours, and setting it as a uniform solution.

[Table 1]

About each negative photosensitive resin composition of the obtained Examples 1-5 and Comparative Examples 1-7, the measurement of the film thickness after prebaking, the residual film rate, the transmittance|permeability, and the pattern shape observation were respectively performed.

[Evaluation of the remaining film rate]

After apply|coating the negative photosensitive resin composition on alkali-free glass (substrate) using a spin coater, it prebaked on the hotplate at the temperature of 110 degreeC for 120 second, and formed the coating film (film thickness 20 micrometers). Using an ultraviolet irradiator PLA-600FA manufactured by Canon Inc., ultraviolet rays having a light intensity of 7.1 mW/cm ² at 365 nm were emitted from the surface (rear surface) opposite to the surface on which the coating film was formed of this substrate 25 mJ with respect to the coating film. /cm ² irradiated. After performing spray image development for 90 second with 2.0 mass % sodium hydrogencarbonate aqueous solution after that, the cured film was obtained by performing running water washing for 20 second with ultrapure water.

About what baked the produced cured film on the hotplate of 140 degreeC for 3 minutes (post-baking), the film thickness was measured using ^{Dektak 3 made from Vecco.} The remaining film ratio (%) was calculated as (film thickness after post-baking/film thickness after pre-baking) x 100.

[Evaluation of transmittance]

After the negative photosensitive resin composition was applied onto a quartz substrate using a spin coater, it was prebaked on a hot plate at a temperature of 110°C for 120 seconds to form a coating film (film thickness: 20 µm). ^{With respect to this coating film, 100 mJ/cm 2} of ultraviolet rays having ^{a light intensity of 7.1 mW/cm 2} at 365 nm was irradiated using an ultraviolet irradiation apparatus PLA-600FA manufactured by Canon Inc. About this cured film, the transmittance|permeability of the wavelength of 400 nm was measured using the ultraviolet-ray visible spectrophotometer (SIMADZU UV-2550 model made by Shimadzu Corporation).

[Evaluation of patterning]

A negative photosensitive resin composition was applied to a film thickness of 200 nm using a spin coater on an alkali-free glass (substrate) having a black 10 μm line & space formed thereon, and then prebaked on a hot plate at a temperature of 110° C. for 120 seconds. and a coating film was formed (film thickness: 20 µm). The light intensity at 365 nm was 7.1 mW/cm ^{2 using the UV irradiator PLA-600FA manufactured by Canon Inc. Ultraviolet rays were irradiated to the coating film by 100 mJ/cm 2} from the surface (rear surface) opposite to the surface on which the coating film was formed of the substrate. After that, spray development was performed for 90 seconds with a 2.0 mass % sodium carbonate aqueous solution, and then a pattern was formed by performing running water washing for 20 seconds with ultrapure water. About what baked the produced pattern on a 140 degreeC hotplate for 3 minutes, it observed with the scanning microscope (SEM), and confirmed the pattern shape. A case in which a rectangular shape with a period of 20 µm was produced was denoted by ○, a case in which a rectangular shape was produced but insufficient in film thickness (a film thickness of 14 µm or less) was denoted by Δ, and a case in which a rectangular shape was not produced was denoted by ×.

[Evaluation results]

The results of the above evaluation are shown in Table 2 below.

[Table 2]

As can be seen from the results shown in Table 2, all of the negative photosensitive resin compositions of Examples 1 to 5 have a high residual film ratio even at a low exposure dose, and a photoinitiator (C-2) having a small extinction coefficient at 365 nm is used in combination. It was confirmed that sclerosis|hardenability could be improved by doing this. Moreover, the transmittance|permeability after exposure was all very high, 90% or more, and high transparency was maintained even if it was a thick film (film thickness 20 micrometers). Furthermore, it was possible to form a pattern having a rectangular shape.

On the other hand, for Comparative Examples 1 to 4 using only a photoinitiator having a large extinction coefficient of 365 nm and Comparative Example 6 in which a photoinitiator having a relatively large extinction coefficient was used in combination, the remaining film rate was low at an exposure dose similar to the above Example, and the pattern (Rectangle) was produced, but the result was that the film thickness was reduced. Moreover, about Comparative Examples 1-3, the transmittance|permeability after exposure was also as low as 90 % or less. Furthermore, in Comparative Example 5 using only a photoinitiator having a small extinction coefficient at 365 nm, and Comparative Example 7 in which an initiator having a large extinction coefficient not containing an oxime ester group and a photoinitiator having a small extinction coefficient were used in combination, the transmittance is high, but exposure It melted in an alkaline developing solution later, sclerosis|hardenability was low, such as being set to 0, and the result that a pattern could not be formed was brought.

Industrial Applicability

The negative photosensitive resin composition according to the present invention is suitable as a material for forming cured films such as protective films, flattening films, and insulating films in various displays such as thin film transistor (TFT) liquid crystal display elements, organic EL elements, and touch panel elements. In particular, to form an interlayer insulating film of a TFT-type liquid crystal element, a protective film of a color filter, an array planarization film, an interlayer insulating film of a capacitive touch panel, an insulating film of an organic EL element, a structure sheet as an optical characteristic adjustment layer on the display surface, etc. It is also suitable as a material.

Claims (14)

The photosensitive resin composition containing the following (A) component, (B) component, (C-1) component, (C-2) component, and (D)component.
(A) component: alkali-soluble copolymer;
(B) component: the compound which has 2 or more of at least 1 sort(s) of polymeric group chosen from the group which consists of an acrylate group, a methacrylate group, a vinyl group, and an allyl group;
(C-1) component: It has an oxime ester group, and the extinction coefficient in methanol or acetonitrile in 365 nm is 5,000 ml/g*cm or more photoinitiator;
(C-2) component: the photoinitiator whose extinction coefficient in methanol or acetonitrile in 365 nm is 100 ml/g*cm or less;
(D) Component: Solvent.
According to claim 1,
(E) The photosensitive resin composition which further contains a thiol compound as a component.
3. The method of claim 1 or 2,
(A) The photosensitive resin composition whose number average molecular weight is an alkali-soluble copolymer of 2,000-50,000 in conversion of polystyrene.
4. The method according to any one of claims 1 to 3,
The photosensitive resin composition whose alkali-soluble copolymer of (A) component is a copolymer generated by copolymerization of the monomer mixture containing at least 1 sort(s) selected from the group which consists of acrylic acid, methacrylic acid, maleic anhydride, and maleimide.
5. The method according to any one of claims 1 to 4,
(C-1) The photosensitive resin composition whose content of a component is 0.3 mass parts - 5 mass parts with respect to 100 mass parts of (A) component.
5. The method according to any one of claims 1 to 4,
(C-2) The photosensitive resin composition whose content of a component is 0.5 mass parts - 10 mass parts with respect to 100 mass parts of (A) component.
7. The method according to any one of claims 1 to 6,
(B) The photosensitive resin composition whose content of a component is 10 mass parts - 150 mass parts with respect to 100 mass parts of (A) component.
8. The method according to any one of claims 1 to 7,
(C-1) The photosensitive resin composition whose component is a photoinitiator which has a carbazole structure.
9. The method according to any one of claims 1 to 8,
(C-2) The photosensitive resin composition whose component is a photoinitiator which has a hydroxyl group.
10. The method according to any one of claims 1 to 9,
(F) The photosensitive resin composition which further contains surfactant as a component.
The cured film obtained using the photosensitive resin composition in any one of Claims 1-10.
The cured film obtained by exposing the coating film on the transparent base material which consists of the photosensitive resin composition in any one of Claims 1-10 from the surface on the opposite side to the coating-film surface of this base material.
An interlayer insulating film for a liquid crystal display comprising the cured film according to claim 11 or 12.
The optical filter which consists of the cured film of Claim 11 or 12.