KR20170009794A - Oxime ester compound and photosensitive resin composition containing the compound - Google Patents

Abstract

The present invention relates to an oxime ester compound represented by chemical formula 1, useful for a photoinitiator in a photo-crosslinking reaction. In chemical formula 1, R^1 represents a phenyl sulfide, diphenyl sulfoxide, diphenyl sulfone or carbazolyl group containing a group selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group and a cyano group; p is 0 or 1; R^2 represents H or a C1-C6 alkyl group, C4-C10 cycloalkyl group, or a linear or branched C1-C10 alkyl group non-substituted or substituted with a C6-C20 aryl group, or a phenyl group non-substituted or substituted with a C1-C6 alkyl group; and R^3 represents H, a C1-C6 alkyl group or phenyl group. The photosensitive resin composition comprising the oxime ester compound according to the present invention as a photoinitiator shows improved solubility and high sensitivity. The photoinitiator is very useful for a photosensitive resin composition, such as a black resist, color resist, overcoat, column spacer and an organic dielectric film of LCDs.

Description

Oxime ester compound and photosensitive resin composition containing the same [

     The present invention relates to a high-sensitivity photopolymerization initiator which is excellent in stability, developability and transmittance in the visible light region, is low in solubility, and particularly is activated by absorbing near ultraviolet rays efficiently such as 365 to 435 nm, and a photosensitive composition containing the same.

The LCD color filter is mainly made of color resist based on pigment dispersed millbase and is based on three colors of red, green and blue. , Liquid crystal display devices, and the like, and its application range is rapidly expanding. A color filter used for a color liquid crystal display device, an image pickup device, or the like is a device for uniformly applying a colored photosensitive resin composition containing a coloring agent corresponding to each color of red, green and blue on a substrate on which a black matrix is pattern- And then the coating film formed by heating and drying is exposed and developed, and if necessary, further heating and curing is repeated for each color to form pixels of each color.

The black matrix is located between the RGB patterns of the color filters and suppresses light interference from each pixel region, thereby contributing to improvement of contrast in a display device and good color development.

As a production method of a color filter using a conventional pigment, a dyeing method, an electrodeposition method, an ink jet method, a pigment dispersion method, and the like are known. In the case of the pigment dispersion method, a colored photosensitive composition in which a binder resin, a photopolymerization initiator, a photopolymerizable monomer or the like is added to a coloring composition in which a pigment is dispersed by a dispersing agent or the like is coated on a glass substrate and dried, The colored photosensitive resin composition is cured or softened. Next, a coloring pattern is formed by dissolving a portion that has not been cured or a softened portion in the developing process, and a step of fixing the coloring pattern onto the substrate through a heating process is repeated for each color to form a color filter.

The colored photosensitive resin composition used for forming a pixel of such a color filter is required to have sufficient resolution, adhesion with a substrate, and low development residue. In addition, it is required to improve the pixel formability such as sharpness of the pattern edge, that is, sufficient developing margin, that the residue is not formed in the removed portion in the developing process, that the removed portion has sufficient solubility, and the like. Particularly, in recent years, as the substrate becomes larger, the time required for the developing process becomes longer, and a colored photosensitive resin composition having a large developing margin is strongly demanded. When a colored photosensitive resin composition having a small developing margin is used, problems such as loss or erosion of a pixel occur particularly when a time is required for a developing process such as a color filter for a large screen.

In order to solve such a problem, an oxime ester compound is used as a photopolymerization initiator. However, when a pattern is formed using a colored photosensitive resin composition containing an oxime ester-based photopolymerization initiator, only the surface is cured, There is still a problem that sufficient straightness can not be obtained in the case of the above. In addition, although an excessive amount of initiator is used for high sensitivity, excessive use of an initiator causes a problem of insufficient resolution and low luminance. In recent years, as the number of production of liquid crystal display displays has increased, the production amount of color filters has also increased. From the viewpoint of productivity, the development of a photopolymerization initiator having excellent photosensitivity can realize sufficient sensitivity with a small amount, It is possible to increase the production amount.

Various oxime ester compound derivatives as a photopolymerization initiator which can be used as a photoinitiator in the above photosensitive resin composition are already known in Patent Documents 1 to 10 below.

[Patent Document 1] JP-A-2001-302871

[Patent Document 2] PCT W002 / 100903

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2004-534797

[Patent Document 4] JP-A-2005-025169

[Patent Document 5] JP-A-2005-242279

[Patent Document 6] Japanese Unexamined Patent Application Publication No. 2006-160634

[Patent Document 7] PCT W007 / 071497

[Patent Document 8] PCT W008 / 138733

[Patent Document 9] PCT W008 / 078686

[Patent Document 10] PCT W009 / 081483

In order to shorten the processing time, the photoresist compounds forming a pattern by UV curing by photocuring reaction are required to have a highly sensitive photoinitiator excellent in photoreactivity and a photoinitiator excellent in solubility and easy to handle. For example, in color resist applications, there is a need for resists that contain pigments dispersed with a high degree of technology for high color quality properties. As the pigment content increases, the hardening of the color resist becomes more difficult, and therefore, an initiator having a photosensitivity higher than that of a commonly used initiator is required. In addition, such photoinitiators are required to meet the high requirements for industry-related properties such as high solubility in organic solvents, thermal stability and storage stability.

It is an object of the present invention to provide an oxime ester photopolymerization initiator excellent in developability, adhesion, and alkali resistance, including a high sensitivity characteristic in which UV maximum absorption is efficiently absorbed by long wavelength light such as 365 nm to 410 nm, And an ester photopolymerization initiator compound.

The present inventors intend to achieve the above object by providing a photopolymerization initiator containing an oxime ester compound or an alpha-chitooloxime ester compound represented by the following general formula (1) as an active ingredient.

According to an aspect of the present invention, there is provided an oxime ester compound represented by the following formula (1).

[Chemical Formula 1]

(Wherein R ¹ is phenylsulfide, diphenylsulfoxide, diphenylsulfone or carbazolyl group containing a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group, and p is 0 or 1, and R ² is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms Or a phenyl group substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms, and R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

According to another aspect of the present invention, there is provided a composition comprising: (a) an ethylenically unsaturated photopolymerizable compound; And

(b) a photosensitive resin composition comprising the above oxime ester compound as a photoinitiator.

The oxime ester compound of the present invention has high transmittance in a visible light region, excellent residual film ratio and chemical resistance, and has a very high radical generation efficiency against a bright line such as 365 nm (i line), which is useful as a highly sensitive photopolymerization initiator of a photosensitive resin composition Can be used. According to the present invention, a high quality black matrix, a color filter, a column spacer, an insulating film, and a photoconductive coating film can be manufactured using the photosensitive composition described above.

An object of the present invention is to provide a photopolymerization initiator which is activated by efficiently absorbing light of a long wavelength such as 365 nm or 405 nm.

The oxime ester compound of the present invention is a novel compound represented by the above formula (1). The oxime ester compound has a geometric isomer of a oxime double bond, but does not distinguish them.

That is, in the present specification, the compound represented by the formula (1) and the compound represented by the following formula (2) or (3), which is a preferred form of the compound described below, represent a mixture or both of them, It is not limited to the structure.

Hereinafter, the oxime ester compound of the present invention and a photopolymerization initiator containing the compound as an active ingredient will be described in detail.

[Chemical Formula 1]

In the above formula (1), R ¹ is phenylsulfide or diphenylsulfoxide, or diphenylsulfone or carbazolyl group, which comprises a group selected from the group consisting of monovalent organic groups, amino groups, halogens, nitro groups and cyano groups .

R ² is a hydrogen atom; A straight chain or branched chain alkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; Or a phenyl group substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms.

R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

p is 0 or 1;

In R ¹ , Phenyl sulfide or diphenyl sulfoxide, or a substituent group having a diphenyl sulfone or carbazolyl group is not particularly limited within the scope of not impairing the object of the present invention. Examples of preferred substituents include an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group.

R ¹ is preferably a group represented by the following formula (2) or (3), more preferably a group represented by the following formula (2) and more preferably a group represented by the following formula (2) from the viewpoint of the excellent sensitivity of the photosensitive resin composition As a group, it is preferable that X is a sulfoxide, and still more preferable is a sulfone.

In the case of forming a pattern using a photosensitive resin composition, the pattern tends to be colored by heating in a post-baking step at the time of pattern formation. However, when the oxime ester compound represented by the formula (1) wherein R ¹ is a group represented by the above formula (2) and X is a sulfur atom or a sulfoxide or a sulfone is used as a photopolymerization initiator in the photosensitive resin composition, It is possible to suppress the coloring of the pattern due to the etching.

In formula (2), R ⁴ , R ⁵ and R ⁶ each independently represent a monovalent organic group, an alkylamino group having 1 to 20 carbon atoms, a halogen, a nitro group, a cyano group, or a substituted or unsubstituted aryl group, X Is sulfur, sulfoxide or sulfone.

When R ⁴ , R ⁵ , and R ⁶ in the formula (2) are each independently an organic group, various organic groups can be selected within the range not impairing the object of the present invention. In the formula (2), when R ⁴ , R ⁵ and R ⁶ are organic groups, preferable examples thereof include an alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthenoyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; An alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholin-1-yl group; A benzoyl group substituted by a group selected from the group consisting of a piperazin-1-yl group, a phenyl group and a nitrophenyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholin-1-yl group; Or a piperazin-1-yl group.

R ⁴ is a benzoyl group; A naphthenoyl group; An alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholin-1-yl group; Piperazin-1-yl group; A benzoyl group substituted by a group selected from the group consisting of a phenyl group; A nitro group; Or a cyano group is more preferable.

Location to combine the R ⁴ position for coupling is about the coupling hand is a phenyl group which R ⁴ bonds in combination with a sulfur atom sulfoxide or sulfone, preferably a para-position and R ^5, R ⁶ in the general formula (2) include ortho position .

When R ¹ is a carbazolyl group (formula (3)) The nitrogen atom R ⁷ on the carbazolyl group may be substituted with an alkoxyalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms to be. As a preferable example of R ⁷ , There may be mentioned an aminoalkyl group having 1 to 20 carbon atoms alkoxyalkyl group, an arylalkyl group having a carbon number of 7 to 30 or 1 to 20 carbon atoms of, especially from R ⁷ An alkoxyalkyl group having 1 to 20 carbon atoms is preferable, and an alkoxyalkyl group having 1 to 6 carbon atoms is more preferable.

R ⁸ represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted naphthyl group substituted with a halogen atom, 20, or a thiophenecarbonyl group.

As R ⁸ , among these groups, a thiophenecarbonyl group is preferable, and a cyano group and a nitro group are particularly preferable.

R ⁸ When the phenyl group, naphthyl group and heterocyclic group have a substituent, the number of the substituent is not limited within the range not impairing the object of the present invention, but is preferably 1 to 4. The substituent may be an alkyl group having 1 to 6 carbon atoms.

R ³ in the formula (1) is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R ³ is preferably a methyl group or an ethyl group, and more preferably a methyl group.

When p is 0 in the above formula (1), the method of synthesizing the oxime ester compound of the present invention represented by the present invention is not particularly limited, but it can be produced, for example, by the following method according to the following Reaction Scheme 1. Specifically, an aromatic compound represented by the following formula (1-1) is acylated by a Friedel-Crafts reaction using a halocarbonyl compound represented by the following formula (1-2) ), Obtaining a ketone compound through an oxidation reaction using a ketone compound (1-4) to obtain a sulfone compound, oxysifying the resulting sulfone compound with a hydroxyamine to obtain an oxime compound represented by the following formula (1-5) (R ₃ CO) ₂ O) represented by the following formula (1-6) or an acid halide (R ₃ COHal, Hal is a halogen atom) represented by the following formula (1-6) is reacted with the obtained oxime compound To obtain an oxime ester compound represented by the following formula (1-8). Hal in the following formula (1-2) is a halogen atom and is a group represented by the following formulas (1-1), (1-2), (1-3), (1-4) 8), R ¹ , R ² , and R ³ are the same as in the formula (1).

[Reaction Scheme 1]

When p is 0 in the above formula (1), the method of synthesizing the oxime ester compound of the present invention represented by the present invention is not particularly limited, but it can be produced, for example, by the following method according to the following Reaction Scheme 1. Specifically, a sulfone compound is obtained through an oxidation reaction using a ketone compound represented by the following formula (2-1) with (1-4), and the resulting sulfone compound is oximized in the presence of a base (NaOMe) or hydrochloric acid (HCl) Reacting a ketooxime ester compound represented by the following formula (2-4) with an RONO (R is an alkyl group having 1 to 6 carbon atoms) represented by the following formula (2-3) and an acid anhydride represented by the following formula (2-5) (R ₃ CO) ₂ O) or an acid halide (R ₃ COHal, Hal is a halogen atom) represented by the following formula (2-6) can be reacted to obtain an oxime ester compound represented by the following formula (2-7). Hal in the following formula (2-6) is a halogen atom and R ¹ , R ² , and R ^{3 in the} following formulas (2-1), (2-4), (2-5) Is the same as in the formula (1).

[Reaction Scheme 2]

More specifically, among the oxime ester compounds represented by the above formula (1), particularly preferred compounds are 2-1 to 2-41 of the following formula (2).

Specific examples of the oxime ester compound of the present invention represented by the above formula (1) include the following 2-1 to 2-41 compounds. However, the present invention is not limited to the following compounds.

(2)

       2-1 2-2 2-3

      2-4 2-5 2-6

      2-7 2-8 2-9

      2-10 2-11 2-12

      2-13 2-14 2-15

         2-16 2-17 2-18

          2-19 2-20 2-21

          2-22 2-23 2-24

             2-25 2-26

           2-27

          2-30 2-31 2-32

          2-33 2-34 2-35

         2-36 2-37 2-38

2-39 2-40 2-41

2-39 2-40 2-41

The oxime ester compound of the present invention is useful as a photopolymerization initiator of a polymerizable compound having an ethylenic unsaturated bond.

Next, the photosensitive composition of the present invention will be described.

The photopolymerizable compound contained in the photosensitive resin composition according to the present invention is not particularly limited and conventionally known photopolymerizable compounds can be used. Among them, a photopolymerization initiator containing the oxime ester compound of the present invention as an effective component and a resin or monomer having an ethylenically unsaturated bond are preferable, and a combination thereof is more preferable. By combining a resin having an ethylenic unsaturated group and a monomer having an ethylenic unsaturated group, it is possible to improve the curability of the photosensitive resin composition and facilitate pattern formation.

The polymerizable compound having an ethylenically unsaturated bond is not particularly limited and those conventionally used in the photosensitive composition may be used. Examples of the polymerizable compound include ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, Unsaturated aliphatic hydrocarbons such as tetrafluoroethylene; (Meth) acrylic acid,? -Chloroacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic acid, crotonic acid, isocrotonic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl acrylate, Ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, acrylamide, methacrylate, Methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, - ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, ethylene glycol di Acrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol Acrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, tetramethylol propane tetraacrylate, tetramethylol propane tetramethacrylate, tetramethylol propane tetramethacrylate, tetramethylol propane tetramethacrylate, Pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacryl Monomers and oligomers such as acrylate, diacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and cardoepoxy diacrylate; A polyester (meth) acrylate obtained by reacting a (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyvalent alcohol with a monovalent base or a polyvalent base acid, a polyester (meth) acrylate obtained by reacting a polyol group with a compound having two isocyanate groups, ) Polyurethane (meth) acrylate obtained by reacting acrylic acid; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, (Meth) acrylate resins obtained by reacting an epoxy resin such as a cydyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin, and a dihydroxybenzene type epoxy resin with (meth) acrylic acid. Further, a resin obtained by reacting the epoxy (meth) acrylate resin with a polybasic acid anhydride can be used. These photopolymerizable compounds may be cardade resins. Among them, oxime ester compounds of the present invention may be added to esters of polyfunctional (meth) acrylates, unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols having a mono (meth) acryloyl group of a polymer having a carboxyl group and a hydroxyl group at both terminals A photopolymerization initiator containing an effective component is suitable. These polymerizable compounds may be used singly or as a mixture of two or more, or in the case of mixing two or more of them, they may be copolymerized in advance and used as a copolymer.

As the polymerizable compound having an ethylenically unsaturated bond, the photosensitive composition of the present invention can be used as an alkali developing photosensitive resin composition by using an alkali developing compound having an ethylenic unsaturated bond. Examples of the alkali developing compound having an ethylenically unsaturated bond include a copolymer of an acrylate ester, a polyphenylmethane type epoxy resin having a phenol and / or cresol novolak resin, a polyfunctional epoxy group, an epoxy compound, and the like, with an unsaturated monobasic acid And a resin obtained by reacting polybasic acid anhydride with a polybasic acid anhydride can be used.

The mass average molecular weight of the resin having an ethylenically unsaturated bond is preferably from 1,000 to 40,000. By setting the mass average molecular weight to 1000 or more, it is preferable because heat resistance and film strength can be obtained. The weight average molecular weight is preferably 4000 or less, because good developability can be obtained. The alkali developing compound having an ethylenically unsaturated bond preferably contains 0.2 to 1.0 equivalent of an unsaturated group.

The acid value of the resin having an ethylenically unsaturated bond is preferably in the range of 10 to 150 mg KOH / g, more preferably 70 to 110 mg KOH / g in terms of resin solid content. When the acid value is 10 mg KOH / g or more, sufficient solubility in a developing solution can be obtained, which is preferable. The acid value of 150 mg KOH / g or less is preferable because sufficient curability can be obtained and the surface property can be improved.

Examples of the unsaturated monobasic acid acting on the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, and hydroxyethyl methacrylate maleate. Hydroxyethyl methacrylate maleate, hydroxypropyl methacrylate maleate, dicyclopentadiene maleate, and the like.

Examples of the polybasic acid anhydrides which can be reacted with the unsaturated monobasic acid after the action of the unsaturated monobasic acid may include biphenyltetracarboxylic anhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellitic anhydride, Anhydrides, 2,2'-3,3'-benzophenonetetracarboxylic anhydride, ethylene glycol bisanhydrotrimellitate, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and anhydrous methyl hymeic acid.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows. That is, an epoxy adduct having a structure in which the carboxyl group of the unsaturated monobasic acid is added in an amount of 0.1 to 1.0 per one epoxy group of the epoxy compound, wherein the amount of the acid anhydride of the polybasic acid anhydride Is 0.1 to 1.0 in terms of the structure.

In order to improve the developability of the alkali developable photosensitive resin composition having an ethylenically unsaturated bond in order to improve the developability of the (colored) alkali developable photosensitive resin composition of the present invention by adjusting the acid value, the ethylenically unsaturated bond , A monofunctional or polyfunctional epoxy compound can also be used.

The acid value of the resin having an ethylenically unsaturated bond is preferably in the range of 10 to 150 mg KOH / g, more preferably in the range of 70 to 110 mg KOH / g, in terms of the solid content of the resin, and the amount of the monofunctional or polyfunctional epoxy compound Is satisfied.

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, undecyl glycidyl ether, allyl glycidyl ether , Propylglycidyl ether, phenylglycidyl ether, benzylglycidyl ether, p-cumylglycidyl ether, triglycidyl ether, styrene oxide, pinenoxide, and methylstyrene oxide. .

As the polyfunctional epoxy compound, use of at least one selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers is preferable because a colored colored alkali-developable photosensitive resin composition having better characteristics can be obtained. In addition, phenol novolak type epoxy compounds, biphenyl novolak type epoxy compounds, cresol novolak type epoxy compounds, bisphenol A novolak type epoxy compounds, dicyclopentadiene novolak type epoxy compounds; Epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclo-nucleic acid carboxylate, and 3,4-epoxycyclovinylmethyl-3,4-epoxycyclonucleic acid carboxylate. Epoxy compounds; Glycidyl esters such as phthalic acid diglycidyl ester and dimer glycidyl ester; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxy compounds such as dicyclopentadiene oxide; Naphthalene type epoxy compounds, and triphenylmethane type epoxy compounds.

The photosensitive resin composition may contain a known photopolymerization initiator other than the oxime ester compound represented by the formula (1), if necessary. Specific examples of known photopolymerization initiators include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert- Benzophenone such as benzophenone, 2-chlorobenzophenone and p, p'-bisdimethylaminobenzophenone, benzophenone such as benzophenone, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin Benzoin ethers such as isobutyl ether and the like, benzyl dimethyl ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, , Anthraquinones such as 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, Organic peroxides such as menthol oxide and the like, (O-chlorophenyl) -4,5-di (m-methoxyphenyl) -4,5-dihydroxybenzoimidazole, 2-mercaptobenzooxazole and 2-mercaptobenzothiazole, -Imidazolyl dimer and the like, triazine compounds such as p-methoxy triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl- (Trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6- (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl ] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenol) ethenyl] Azine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s- And the like, such as butane -1-amino-on ketone-having a halomethyl group triazine compound, 2-benzyl-1- (4-morpholinophenyl). Among them, it is particularly preferable to use an oxime-based photopolymerization initiator in terms of sensitivity. These photopolymerization initiators may be used alone or in combination of two or more.

In the case where the photosensitive composition contains a photopolymerization initiator other than the compound represented by the formula (1), the content of the other photopolymerization initiator is not particularly limited within the range not hindering the object of the present invention. In this case, the content of the other photopolymerization initiator is typically 50 parts by weight or less, more preferably 30 parts by weight or less, and particularly preferably 10 parts by weight or less, based on the total amount of the photopolymerization initiator contained in the photosensitive resin composition. The amount of the oxime ester compound of the present invention added is preferably 1 to 70 parts by weight, more preferably 1 to 50 parts by weight, and most preferably 5 to 30 parts by weight, based on 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond Wealth. Within the above range, it is possible to obtain sufficient heat resistance and chemical resistance, and at the same time to improve the coating film forming ability and to suppress the photo-curing failure.

The photosensitive resin composition (particularly, the alkaline developable photosensitive resin composition) of the present invention may further contain a coloring agent to form a colored photosensitive composition. By including the colorant, it is preferably used for forming a color filter of a liquid crystal display, for example. Further, the photosensitive resin composition according to the present invention is preferably used for forming a black matrix in a color filter of a display device, for example, by including a light-shielding agent as a coloring agent.

The coloring agent contained in the photosensitive resin composition according to the present invention is not particularly limited, and for example, a compound classified as a pigment in a color index (CI) (The Society Oders and Color Company) It is preferable to use one having the following color index (CI) number attached thereto.

Examples of yellow pigments that can be preferably used include C.I. Pigment Yellow 12, 13, 14, 17, 20, 24, 55, 83, 86, 93, 109, 110, 117, 125, 137, 139, 147, 148, 153, 154, 166, And 185, respectively.

Examples of orange pigments that can be preferably used include C.I. Pigment Orange 36, 43, 51, 55, 59, 61, 63, 64, 71 and 73.

Examples of red pigments which can be preferably used include C.I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 245, 254, 255, 264 And 265, respectively.

Examples of purple pigments which can be preferably used include C.I. Pigment Violet 19, 23, 29, 30, 37, 40, 50.

Examples of blue pigments which can be preferably used include C.I. Pigment Blue 15, 15: 1, 15: 4, 15: 6, 16, 22, 60, 64 and 66.

Examples of pigments of other colors which can be preferably used are C.I. Pigment Green 7, 36, C.I. Pigment Brown 23, 25, 26, C.I. Pigment Black 7 and the like. Examples of known pigments include cationic dyes such as nitroso compounds, sinin, xanthene, oxazine, thiazine, diarylmethane, triarylmethane and pyrylium, merocyanine, coumarin, indigo, aromatic amines, Examples of the dyes include neutral dyes such as phthalocyanine, azo, quinone and thioxanthine sensitive dyes and dyes such as benzophenones, acetophenones, benzoins, thioxanthones, anthraquinones, imidazoles, biimidazoles, coumarins, And compounds such as tolumarines, triphenylphyryliums, triazines, benzoic acid, and the like.

When a colorant is used as the light shielding agent, it is preferable to use a black pigment as the light shielding agent. Examples of the black pigment include various pigments without discrimination of organic matters or inorganic substances such as metal oxides, complex oxides, metal sulfides, metal sulfates or metal carbonates such as carbon black, titanium black, copper, iron, manganese, cobalt and silver. Among them, it is preferable to use carbon black that has a high light shielding property.

As the carbon black, known carbon black such as channel black, furnace black, thermal black and lamp black can be used, but it is preferable to use channel black having excellent light shielding properties.

Resin carbon black has a lower conductivity than carbon black without resin coating, and therefore, when used as a black matrix for a liquid crystal display device such as a liquid crystal display, manufacture a display with low current consumption with low current leakage and high reliability can do. Further, the organic pigment may be suitably added as an auxiliary pigment in order to adjust the color tone of the carbon black.

In order to uniformly disperse the colorant in the photosensitive resin composition, a dispersant may be further used. As such a dispersing agent, it is preferable to use a polymeric dispersant of a polyethylene imine type, a urethane resin type or an acrylic resin type. Particularly when carbon black is used as a coloring agent, it is preferable to use an acrylic resin-based dispersing agent as a dispersing agent. The inorganic pigments and the organic pigments may be used alone or in combination of two or more. When used in combination, the organic pigments are preferably used in an amount of 10 to 80 parts by weight based on 100 parts by weight of the total of the inorganic pigments and the organic pigments, To 40 parts by weight.

The amount of the colorant to be used in the photosensitive resin composition may be appropriately determined depending on the use of the photosensitive resin composition. For example, when the total solid content of the photosensitive resin composition is 100 parts by weight, the amount is preferably 5 to 70 parts by weight, more preferably 25 to 60 parts by weight desirable. By setting the thickness within the above range, a black matrix or each coloring layer can be formed with a desired pattern, which is preferable.

Particularly, in the case of forming a black matrix using a photosensitive resin composition, it is preferable to adjust the amount of the light shielding agent in the photosensitive resin composition so that the OD value per 1 mu m of the black matrix coating is 4 or more. When the OD value per 1 m of the coating film in the black mattress is 4 or more, sufficient display contrast can be obtained when the black matrix is used for a black matrix of a liquid crystal display. The colorant is preferably added to the photosensitive resin composition after preparing a dispersion in which the colorant is dispersed at a suitable concentration using a dispersant.

Various additives may be added to the photosensitive resin composition according to the present invention as necessary. Specifically, examples thereof include a solvent, a sensitizer, a curing accelerator, a photocrosslinking agent, a photosensitizer, a dispersing aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an antiperspirant, a thermal polymerization inhibitor, a defoaming agent and a surfactant.

Examples of the solvent used in the photosensitive resin composition according to the present invention include ethylene glycol monoether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethyl glycol monomethyl ether (Poly) alkylene glycol monoalkyl ethers such as diethyl glycol monoethyl ether, diethylene glycol monoethyl ether and diethylene glycol mono-n-ether; (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and propylene glycol monoethyl ether acetate; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Methyl ethyl ketone; Cyclohexanone, 2-heptanone; Ketones such as 3-heptanone; Other esters such as methyl 2-hydroxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate and ethyl ethoxyacetate; Aromatic hydrocarbons of toluene, xylenes; Amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

Among these solutions, propylene glycol monomethyl ether, ethyleneglycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3- Methoxybutyl acetate is preferred because it is highly soluble in the above-mentioned photopolymerizable compound and the oxime ester photopolymerization initiator of the present invention, and the dispersibility of the above-mentioned colorant component can be improved, and propylene glycol monomethyl ether acetate, 3- Particularly preferred is the use of methoxybutyl acetate. The solvent may be appropriately determined according to the use of the photosensitive resin composition, but is, for example, 50 to 900 parts by weight based on 100 parts by weight of the total solid content of the photosensitive resin composition.

Examples of the thermo-polymerizable paper-feeding agent used in the photosensitive resin composition according to the present invention include hydroquinone, hydroquinone monoethyl ether, and the like. Examples of the defoaming agent include silicone compounds and fluorine compounds. Surfactants include anionic, cationic, Ionic system, and the like.

The photosensitive resin composition according to the present invention is prepared by mixing all of the above components with a stirrer. And may be filtered using a filter so that the prepared photosensitive resin composition is uniform.

According to the present invention, there is provided a substrate having a column spacer, a black matrix, a color filter, an organic insulating film, and a film formed from such a photosensitive resin composition by coating such a photosensitive resin composition. The film is used for a plasma display panel, A sunglass lens, a spectacle lens with a frequency, a finder lens for a camera, a cover for a meter, a glass for an automobile, a glass for a train, a brightness enhancement film, or an optical waveguide film.

As the substrate, for example, a glass substrate, a silicon substrate, or a flexible substrate, a substrate having a flat surface such as a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, .

The method of applying the photosensitive resin composition on the substrate is not particularly limited and it is possible to apply the coating method using a coater such as a spin coating method, a casting method, a roll coating method, a slit & spin coating method, The coating method can be applied on a substrate or the like.

The applied photosensitive composition is dried to form a coating film. The drying method is not particularly limited and includes, for example, ① drying in a hot plate at a temperature of 80 to 120 캜, preferably 90 to 100 캜 for 60 to 120 seconds, ② a method of allowing to stand at room temperature for several hours to several days, (3) a method of removing volatile components such as solvents by putting them in a hot air heater or an infrared heater for several tens of minutes to several hours. Thus, a layer made of the solid content of the photosensitive composition is formed on a substrate or the like. Then, a layer of the solid content of the photosensitive composition is exposed, for example, the active energy ray can be selectively irradiated through a photomask. As the exposure light source, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp and the like are suitable. A laser beam or the like can also be used as an active energy ray for exposure. In addition, electron beams,? Rays,? Rays,? Rays, X rays, neutron rays, etc. can be used. The active energy ray is irradiated through a photomask, wherein the photomask is, for example, provided with a light-shielding layer on the surface of the glass plate to sandwich an active energy ray. The portion of the glass plate where the light-shielding layer is not provided is a light-transmitting portion through which the active energy ray passes. The photosensitive composition is exposed in a pattern according to the pattern of the light-transmitting portion, An irradiation area is generated. The amount of energy to be irradiated differs depending on the composition of the photosensitive composition, but is preferably about 30 to 2000 mJ / cm 2, for example.

As described above, when the photosensitive resin composition according to the present invention is used, the productivity of the liquid crystal display panel can be improved because the sensitivity is excellent.

The exposed film is developed with a developing solution to be patterned into a desired shape. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. Examples of the developing solution include organic solvents such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts. By the development after the exposure, the unirradiated area not irradiated with the active energy ray in the photosensitive composition layer is removed. On the other hand, the active energy irradiation area remains as a pattern. Post-baking is preferably performed at about 200 to 250 DEG C with respect to the pattern after development.

The formed pattern can be suitably used, for example, as a pixel or a black matrix of a color filter in a display device such as a liquid crystal display or the like. Such a color filter or a display device using the color filter is also one of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples.

[Example 1]

Synthesis of Formula 2-1

Stage 1 synthesis:

Synthesis of 4- (4- (phenylthio) phenyl) morpholine

10.0 g (41.4 mmol) of 4- (4- (bromophenyl) was dissolved in dry dimethylacetamide And dissolved at < RTI ID = 0.0 > 23 C < 1.7 g (41.4 mmol) of triethylamine were added, and the mixture was stirred for 8 hours at a reaction temperature of 50 캜. The temperature of the reactor was lowered to 23 ° C, and 50 ml of water was added to terminate the reaction. 70 ml of ethyl acetate was added to the reaction mixture. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by a rotary evaporator. The solvent was separated and purified by column chromatography to obtain 10.0 g (yield: 90%) of the target compound 4- (4- (phenylthio) phenyl) .

^{1 H-NMR (ppm):} δ 3.18 (t, 4H), 3.65 (t, 4H), 6.56 (d, 2H), 7.19-7.25 (m, 5H), 7.41 (d, 2H)

Two-step synthesis:

Synthesis of 1- (4 - ((4-mololenophenyl) thio) phenyl) -2- (O-tolyl) ethanone

10.0 g (36.8 mmol) of 4- (4- (phenylthio) phenyl) morpholine was dissolved in dry dichloromethane The reaction was cooled to < RTI ID = 0.0 > 0 C < 5.0 g (36.8 mmol) was slowly added thereto. To this was added slowly 6.2 g (36.8 mmol) of tolylacetyl chloride at 0 < 0 > C. After stirring for 8 hours and washing with 50 mL of water, the organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography to obtain 1- (4- (Yield: 70%) of the title compound was obtained in the form of a white solid.

^{1 H-NMR (ppm):} δ 2.34 (s, 3H), 3.18 (t, 4H), 3.65 (t, 3H), 4.14 (s, 2H), 6.56 (d, 2H), 7.14 (m, 1H) , 7.23 (d, 2H), 7.34 (d, IH), 7.40 (d, 2H), 7.52

Three-step synthesis:

Synthesis of 1- (4 - ((4-mololenophenyl) sulfonyl) phenyl) -2- (O-tolyl) ethanone

10.0 g (36.8 mmol) of 4- (4- (phenylthio) phenyl) morpholine was dissolved in dry dichloromethane The reaction was cooled to 0 < 0 > C and then 5.8 g (36.8 mmol) of 3-chlorobenzoic acid was added slowly. After stirring for 5 hours and washing with 50 mL of water, the organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography to obtain 1- (4- Sulfonyl) phenyl) -2- (O-tolyl) ethanone (yield: 80%).

^{1 H-NMR (ppm):} δ 2.34 (s, 3H), 3.18 (t, 4H), 3.65 (t, 3H), 4.14 (s, 2H), 6.93 (d, 2H), 7.14 (m, 1H) 2H), 7.20 (d, 2H), 7.40 (d, 2H)

Four-step synthesis:

Synthesis of ( E ) -2- (hydroxyimino) -1- (4 - ((4 -morpholinophenyl) sulfonyl) phenyl) -2- (O-tolyl) ethanone

10.0 g (21.5 mmol) of 1- (4 - ((4-morpholinophenyl) sulfonyl) phenyl) -2- (O-tolyl) ethanone was added to a three necked flask under nitrogen atmosphere and dissolved in 10 mL of dimethylformamide The reactor was cooled and sodium methoxide (1.2 g, 21.5 mmol) was added at 0 ° C. 2.5 g (21.5 mmol) of isoamyl nitrite was added dropwise to the reaction mixture, the mixture was heated to 23 占 폚 and stirred for 5 hours. The reactor was cooled and 20 mL of distilled water was added to terminate the reaction, and 50 mL of ethyl acetate was added to extract it. The organic layer was separated, dried over anhydrous magnesium sulfate, and distilled under reduced pressure to obtain the target compound ( E ) -2- (hydroxyimino) -1- (4- (4 -morpholinophenyl) sulfonyl) (Yield: 50%) of the title compound (O-tolyl) ethane.

^{1 H-NMR (ppm):} δ 2.0 (s, OH), 2.48 (s, 3H), 3.18 (t, 4H), 3.65 (t, 3H), 6.56 (d, 2H), 7.23-7.33 (m, 5H), 7.60 (d, 2H), 7.69-7.28 (m, 3H)

Five-step synthesis:

Synthesis of ( E ) -2- (acetoxyimino) -1- (4 - ((4-morpholinophenyl) sulfonyl) phenyl) -2- (O-tolyl) ethanone

( E ) -2- (hydroxyimino) -1- (4- (4-morpholinophenyl) sulfonyl) phenyl) -2- (O-tolyl ) Ethanol 5.0 g (10.8 mmol) was dissolved in 10 mL of dichloromethane, 1.1 g (10.8 mmol) of triethylamine was added, and 0.8 g (10.8 mmol) of acetyl chloride was slowly added dropwise. The mixture was stirred at 0 ° C for 3 hours, and 50 mL of water was added to the reaction solution, and the organic layer was washed twice. The organic layer was separated, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to obtain the target compound ( E ) -2- (acetoxyimino) -1- (4- ((4 -morpholinophenyl) thio) O-tolyl) ethanone (yield: 85%).

^{1 H-NMR (ppm):} δ 2.28 (s, 3H), 2.48 (s, 3H), 3.18 (t, 4H), 3.65 (t, 3H), 6.56 (d, 2H), 7.23-7.33 (m, 5H), 7.60 (d, 2H), 7.69-7.28 (m, 3H)

[Example 2]

Synthesis of Formula 2-2

The procedure of Example 1 was repeated except for changing 10.0 g of 4- (4- (phenylthio) phenyl) morpholine to 10 g of (4-nitrophenyl) (4- (phenylthio) To obtain 5.6 g of the oxime ester compound.

[Example 3]

Synthesis of 2-4

The experiment was carried out in the same manner as in Example 1 except that 10.0 g of 4- (4- (phenylthio) phenyl) morpholine was changed to 10 g of N, N-diethyl-4- (phenylthio) 6.2 g of esthetic compound was obtained.

[Example 4]

Synthesis of Formula 2-8

The procedure of Example 1 was repeated except that 10.0 g of 4- (4- (phenylthio) phenyl) morpholine was replaced by 9.6 g of (2,4-dinitrophenyl) (phenyl) 5.3 g of esthetic compound was obtained.

[Example 5]

Synthesis of Formula 2-12

The procedure of Example 1 was repeated except for changing 10.0 g of 4- (4- (phenylthio) phenyl) morpholine to 10 g of (4- (phenylthio) phenyl) (thiophen- -2 structure of oxime ester compound.

[Example 6]

Synthesis of Formula 2-19

The procedure of Example 1 was repeated except that 10.0 g of 4- (4- (phenylthio) phenyl) morpholine was changed to 8.5 g of 1-methyl-2- ((4-nitrophenyl) 2 < / RTI > structure of oxime ester compound.

[Example 7]

Preparation of transparent resist composition

13.6 g of dipentaerythritol hexaacrylate, 1.5 g of the photoinitiator of the above formula (2-1) and 67 g of propylene glycol monoethyl ether were added to 17 g of the acrylic copolymer and stirred well to obtain a transparent resist composition.

[Formula 2-2]

[Example 8]

Preparation of black resist composition

13.6 g of dipentaerythritol hexaacrylate, 2.0 g of the photoinitiator of Formula 2-1, 48 g of Pigment Black, and 25 g of propylene glycol monoethyl ether were added to 10 g of the acrylic copolymer, followed by well stirring to obtain a black resist composition.

[Example 9]

Preparation of Red Color Resist Composition

13.6 g of dipentaerythritol hexaacrylate, 1.5 g of the photoinitiator of Formula 2-1, 25 g of Pigment Red 192 and 49 g of propylene glycol monoethyl ether were added to 10 g of the acrylic copolymer, and the mixture was stirred well to obtain a red color resist composition.

[Example 10]

Preparation of transparent resist composition

13.6 g of dipentaerythritol hexaacrylate, 1.5 g of the photoinitiator of the above formula (2-2) and 67 g of propylene glycol monoethyl ether were added to 17 g of the acrylic copolymer and stirred well to obtain a transparent resist composition.

[Formula 2-2]

[Example 11]

Preparation of black resist composition

13.6 g of dipentaerythritol hexaacrylate, 2.0 g of the photoinitiator of Formula 2-2, 48 g of Pigment Black and 25 g of propylene glycol monoethyl ether were added to 10 g of the acrylic copolymer, and the mixture was stirred well to obtain a black resist composition.

[Example 12]

Red Resist Composition Manufacturing

13.6 g of dipentaerythritol hexaacrylate, 1.5 g of the photoinitiator of Formula 4-1, 25 g of Pigment Red 192, and 49 g of propylene glycol monoethyl ether were added to 10 g of the acrylic copolymer, and the mixture was stirred well to obtain a red color resist composition.

[Comparative Example 1]

Preparation of transparent resist composition

13.6 g of dipentaerythritol hexaacrylate, 1.5 g of the photoinitiator represented by the following formula (A) and 67 g of propylene glycol monoethyl ether were added to 17 g of the acrylic copolymer and stirred well to obtain a transparent resist composition.

(A)

[Comparative Example 2]

Preparation of black resist composition

13.6 g of dipentaerythritol hexaacrylate, 2.0 g of the photoinitiator of Formula A, 48 g of Pigment Black and 25 g of propylene glycol monoethyl ether were added to 10 g of the acrylic copolymer and stirred well to obtain a black resist composition.

[Comparative Example 3]

Preparation of Red Color Resist Composition

13.6 g of dipentaerythritol hexaacrylate, 1.5 g of the photoinitiator of the formula (A), 25 g of Pigment Red 192 and 49 g of propylene glycol monoethyl ether were added to 10 g of the acrylic copolymer and stirred well to obtain a red color resist composition.

[Comparative Example 4]

Preparation of transparent resist composition

13.6 g of dipentaerythritol hexaacrylate, 1.5 g of the photoinitiator represented by the following formula (B) and 67 g of propylene glycol monoethyl ether were added to 17 g of the acrylic copolymer and stirred well to obtain a transparent resist composition.

[Chemical Formula B]

[Comparative Example 5]

Preparation of black resist composition

13.6 g of dipentaerythritol hexaacrylate, 2.0 g of the photoinitiator of the following formula (B), 48 g of pigment black and 25 g of propylene glycol monoethyl ether were added to 10 g of the acrylic copolymer and stirred well to obtain a black resist composition.

[Chemical Formula B]

[Comparative Example 6]

Red Resist Composition Manufacturing

13.6 g of dipentaerythritol hexaacrylate, 1.5 g of the photoinitiator of the above formula (B), 25 g of Pigment Red 192 and 49 g of propylene glycol monoethyl ether were added to 10 g of the acrylic copolymer and stirred well to obtain a red color resist composition. The evaluation of the obtained photosensitive composition was carried out as follows.

[Test Example]

The photosensitive composition was applied to a spin coater at 800 to 900 rpm for 15 seconds and then dried on a hot plate at 90 DEG C for 100 seconds. Using a predetermined mask, the resist film was exposed as a light source using an ultra-high pressure mercury lamp, and then spin-developed in a 0.04% potassium hydroxide solution at 25 캜 for 60 seconds and then washed with water. After washing with water and drying, it was baked at 230 ° C for 40 minutes to obtain a pattern. The following evaluation was made on the obtained pattern. Table 1 shows photopolymerization initiators and various evaluation results using the respective photosensitive compositions.

(1) Adhesiveness

According to the test method of JIS D 0202, a cross-cut was performed in a lattice form on a coated film heated at 200 캜 for 30 minutes after development and then subjected to a peeling test with a cellophane tape to observe and evaluate the lattice-like peeling state . The number of lattices was not more than 95, the number of lattices was not more than 60, the number of lattices was more than 40, and the number of lattices was peeled x.

(2) Alkali resistance

After development, the coating was baked for 30 minutes, and then the coating film was immersed in 5% NaOH aqueous solution for 24 hours, 4% KOH aqueous solution at 50 ° C for 10 minutes and 1% NaOH aqueous solution at 80 ° C for 5 minutes. ?, No appearance change, no peeling?, A resist peeling was observed?, And a resist peeling was observed was evaluated as x.

(3) Sensitivity evaluation

Each of the thus-formed photosensitive resin compositions was applied to a glass substrate (Eagle 2000, manufactured by Samsung Corning Incorporated) with a spin coater and dried on a hot plate at 90 캜 for 1 minute. The film thicknesses of the black resist and the transparent negative resist obtained by measurement with a probe-type film thickness meter (α-step 500, manufactured by KLA-Tencor Co., Ltd.) after drying were 1 micron and 5 micron, respectively. Then, this sample was exposed through a mask with high-pressure mercury or the like. Thereafter, the resist pattern was developed by a spray developing method using a 0.04% potassium hydroxide aqueous solution to obtain a resist pattern. (MJ / cm < ² >) capable of forming the same dimensions as the mask pattern of 40 microns. That is, a resist having a small exposure dose shows high sensitivity because a pattern can be formed even with a small light energy.

(4) Whitening phenomenon

Each of the photosensitive resin compositions comprising the synthesized photoinitiator was applied to a glass substrate with a spin coater. In this case, a case where crystals are formed upon spin coating according to the solubility of the photoinitiator and x is a case where the coated surface is very poor is denoted by " DELTA ", and crystals are formed during drying after the film is formed, When no crystals are formed and the surface is clean, it is indicated by & cir &

The results are shown in Table 1 below.

No. Photoinitiator Adhesiveness Alkali resistance Sensitivity
(mJ / cm2) Thin film characteristics (whitening phenomenon) Example 7 2-1 ○ ○ 30 ○ Example 8 2-1 ○ ○ 45 ○ Example 9 2-1 ○ ○ 40 ○ Example 10 2-2 ○ ○ 30 ○ Example 11 2-2 ○ ○ 45 ○ Example 12 2-2 ○ ○ 35 ○ Comparative Example 1 A △ △ 100 ○ Comparative Example 2 A X X 150 X Comparative Example 3 A △ △ 120 △ Comparative Example 4 Formula B △ △ 80 ○ Comparative Example 5 Formula B X X 120 X Comparative Example 6 Formula B △ △ 100 △

From the above results, it was found that the photosensitive composition containing the oxime ester compound and the alpha-chitooloxime ester compound according to the present invention had excellent adhesion and alkali resistance and no whitening of the thin film. In particular, as in Examples 7 to 12, it can be seen that the photosensitive resin composition using an alpha-chitoolime ester initiator has a very high sensitivity capable of forming a pattern at a low exposure amount such as 30 to 45 mJ / cm ² . Further, as shown in Table 1, the photosensitive composition using the oxime ester-based and alpha-chitoolime ester-based photoinitiators according to the present invention has excellent photosensitivity due to a high sensitivity and has excellent adhesion to substrates and resistance to basic aqueous solutions It is very good. In addition, since it is excellent in compatibility with a binder and a polyfunctional monomer having an ethylenic unsaturated bond and has excellent solubility in an organic solvent, a thin film of a photosensitive resin composition having a very uniform surface is formed after the formation of a thin film Could.

Claims (9)

An oxime ester compound represented by the following formula (1).

(Wherein R ¹ is phenylsulfide, diphenylsulfoxide, diphenylsulfone or carbazolyl group containing a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group, and p is 0 or 1, and R ² is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms Or a phenyl group substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms, and R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. The method according to claim 1,
Oxime ester compounds, characterized in that that to which the R ¹ represented by the formula (2) or (3).

(Wherein R ⁴ , R ⁵ and R ⁶ are each independently selected from the group consisting of a monovalent organic group, an alkylamino group having 1 to 20 carbon atoms, a halogen, a nitro group, a cyano group and an aryl group having a substituent, , Sulfoxide or sulfone.)

(R ⁷ represents a heterocyclic group having 1 to 20 alkoxy group, having 6 to 20 aryl group, having a carbon number of 7 to 30 arylalkyl group, or C 1 -C 20 aminoalkyl group, or 2 to 20 carbon atoms of the, R ⁸ A substituted or unsubstituted naphthyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C2-C20 alkynyl group, A heterocyclic group, or a thiophenecarbonyl group. The method of claim 2,
When R ⁴ , R ⁵ and R ⁶ are each independently a monovalent organic group, the organic group is an alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthenoyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; An alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholin-1-yl group; A benzoyl group substituted by a group selected from the group consisting of a piperazin-1-yl group, a phenyl group and a nitrophenyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholin-1-yl group; Or a piperazin-1-yl group. The method of claim 2,
R ⁴ is a benzoyl group; A naphthenoyl group; An alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholin-1-yl group; Piperazin-1-yl group; A benzoyl group substituted by a group selected from the group consisting of a phenyl group; A nitro group; Or a cyano group. The method according to claim 1,
Lies to the para position and the combination of R ^5, R ⁶ for bonding hands phenyl group is combined with X of the R ⁴ bonded to the combination of R ⁴ in the general formula (2) is an oxime, characterized in that ortho position Ester compound. The method of claim 2,
R ⁷ is an alkoxyalkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an aminoalkyl group having 1 to 20 carbon atoms. The method of claim 2,
And R < ⁸ > is a thiophenecarbonyl group, a cyano group or a nitro group. The method according to claim 1,
Wherein the compound represented by Formula 1 is selected from compounds represented by Formula 2 below.

(2)

2-1 2-2 2-3

2-4 2-5 2-6

2-7 2-8 2-9

2-10 2-11 2-12

2-13 2-14 2-15

2-16 2-17 2-18

2-19 2-20 2-21

2-22 2-23 2-24

2-25 2-26

2-27

2-30 2-31 2-32

2-33 2-34 2-35

2-36 2-37 2-38

2-39 2-40 2-41 (a) an ethylenically unsaturated photopolymerizable compound; And
(b) at least one photoinitiator selected from the oxime ester compounds according to any one of claims 1 to 8.