KR102613079B1 - Oxime ester compound and photosensitive resin composition containing the compound - Google Patents

Abstract

The present invention provides an oxime ester compound represented by the following formula (1), which is useful as a photoinitiator in a photocrosslinking reaction.

(Wherein, R ¹ is 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 cyano group, and p is is 0 or 1, and R ² is a hydrogen atom; or a straight-chain or branched alkyl group with 1-10 carbon atoms substituted or unsubstituted with an alkyl group with 1-6 carbon atoms, a cycloalkyl group with 4-10 carbon atoms, or an aryl group with 6-20 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 photosensitive resin composition containing the oxime ester compound according to the present invention as a photoinitiator has improved solubility and excellent sensitivity. These photoinitiators are very useful in photosensitive resin compositions such as LCD black resist, color resist, overcoat, column spacer, and organic insulating film.

Description

Oxime ester compound and photosensitive resin composition containing the same {Oxime ester compound and photosensitive resin composition containing the compound}

The present invention relates to a highly sensitive photopolymerization initiator that has excellent stability, developability, and transmittance in the visible light region, has low sublimation properties, and is particularly activated by efficiently absorbing near-ultraviolet rays of 365 to 435 nm, and a photosensitive composition containing the same.

The LCD color filter is mainly made of color resist based on a pigment-dispersed millbase, and uses three basic colors: red, green, and blue, and is used as an imaging device. , It is widely used in liquid crystal displays, etc., and its application range is rapidly expanding. Color filters used in color liquid crystal displays, imaging devices, etc. are usually made by uniformly applying a colored photosensitive resin composition containing colorants corresponding to each color of red, green, and blue onto a substrate on which a black matrix pattern is formed by spin coating. After drying by heating, the formed coating film is exposed, developed, and further heated and hardened as necessary, and the process is repeated for each color to form pixels of each color.

The black matrix is located between the RGB patterns of the color filter and contributes to improving contrast and obtaining good color development in the display device by suppressing light interference from each pixel area.

Conventional methods for manufacturing color filters using pigments include dyeing, electrodeposition, inkjet, and pigment dispersion methods. In the case of the pigment dispersion method, a colored photosensitive resin composition photosensitized by adding a binder resin, a photopolymerization initiator, a photopolymerizable monomer, etc. to a colored composition in which the pigment is dispersed by a dispersant, etc. is coated on a glass substrate, dried, and then the pattern is exposed to light. Cures or softens the colored photosensitive resin composition. Next, a colored pattern is formed by dissolving the part that was not hardened or softened in the development process, and the process of fixing the colored pattern on the substrate through a heating process is repeated for each color to form a color filter.

Colored photosensitive resin compositions used to form pixels of such color filters are required to have characteristics such as sufficient resolution, adhesion to the substrate, and low development residue. In addition, it is required that no residue is generated in the removed area during the development process, that the removed area has sufficient solubility, and that pixel formation properties such as sharpness of the pattern edge are improved, that is, a sufficient development margin is required. In particular, in recent years, as substrates have become larger, the time required for the development process has become longer, and there is a strong demand for colored photosensitive resin compositions with a large development margin. If a colored photosensitive resin composition with a small development margin is used, problems such as loss or erosion of pixels may occur, especially in cases where the development process requires time, such as a color filter for a large screen.

To solve this problem, an oxime ester-based compound is used as a photopolymerization initiator. However, if a pattern is formed using a colored photosensitive resin composition containing an oxime ester-based photopolymerization initiator, only the surface is cured, and the pattern after development is still left. There remains a problem of not being able to achieve sufficient straightness. In addition, an excessive amount of initiator is used to achieve high sensitivity, but the use of an excessive amount of initiator causes problems of insufficient resolution and reduced luminance. Recently, as the production number of liquid crystal displays has increased, the production of color filters has also been increasing. From a productivity perspective, the development of a photopolymerization initiator with excellent light sensitivity can achieve sufficient sensitivity with a small amount, resulting in cost savings and excellent sensitivity, thereby reducing the exposure amount. It can be lowered and production can be increased.

Various oxime ester compound derivatives as photopolymerization initiators that can be used as photoinitiators in the photosensitive resin composition are already known in the following Patent Documents 1 to 10.

[Patent Document 1] Japanese Patent Publication 2001-302871

[Patent Document 2] PCT W002/100903

[Patent Document 3] Japanese Patent Publication 2004-534797

[Patent Document 4] Japanese Patent Publication 2005-025169

[Patent Document 5] Japanese Patent Publication 2005-242279

[Patent Document 6] Japanese Patent Publication 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

Photoresist compounds that form patterns through photocuring reaction by UV irradiation require highly sensitive photoinitiators with excellent photoreactivity and photoinitiators with excellent solubility that are easy to manufacture and handle in order to shorten the process time. For example, in color resist applications, resists containing pigments dispersed with advanced technology are required for high color quality characteristics. As the pigment content increases, curing of the color resist becomes more difficult, so an initiator with higher photosensitivity than commonly used initiators is required. Additionally, these photoinitiators are required to meet high requirements for industrially relevant properties such as high solubility in organic solvents, thermal stability, and storage stability.

The problem to be solved by the present invention is to provide an oxime ester photopolymerization initiator and alpha-chito-oxime that have high sensitivity properties that enable UV maximum absorption by efficiently absorbing light of long wavelengths such as 365 nm to 410 nm and are activated, while also having excellent developability, adhesion, and alkali resistance. The object is to provide a photoinitiator containing an ester photopolymerization initiator compound.

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

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

[Formula 1]

(Wherein, R ¹ is 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 cyano group, and p is is 0 or 1, and R ² is a hydrogen atom; or a straight-chain or branched alkyl group with 1-10 carbon atoms substituted or unsubstituted with an alkyl group with 1-6 carbon atoms, a cycloalkyl group with 4-10 carbon atoms, or an aryl group with 6-20 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, (a) an ethylenically unsaturated photopolymerizable compound; and

(b) A photosensitive resin composition containing the above-described oxime ester compound as a photoinitiator is provided.

The oxime ester compound of the present invention has a high transmittance in the visible light region, excellent residual film rate and chemical resistance, and has a very high radical generation efficiency for bright lines such as 365 nm (i line), making it useful as a highly sensitive photopolymerization initiator for photosensitive resin compositions. You can use it. According to the present invention, high-quality black matrices, color filters, column spacers, insulating films, photocrosslinkable films, etc. can be manufactured using the photosensitive composition described above.

The purpose of the present invention is to provide a photopolymerization initiator that is activated by efficiently absorbing light of long wavelengths such as 365 nm or 405 nm.

The oxime ester compound of the present invention is a new compound represented by the above formula (1). The oxime ester compound contains geometric isomers due to the double bond of the oxime, but these are not distinguished.

That is, in this specification, the compound represented by the formula (1) and the compounds represented by the following formulas (2) and (3), which are preferred forms of the compounds described later, represent a mixture of both or one of the two, and represent isomers. It is not limited to structure.

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

[Formula 1]

In the formula (1), R ¹ is phenyl sulfide or diphenyl sulfoxide, or diphenyl sulfone or carbazolyl group, including a group selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group and cyano group. .

R ² is a hydrogen atom; or a linear or branched alkyl group having 1 to 10 carbon atoms 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 it is 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 The substituents of phenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, or carbazolyl group are not particularly limited as long as they do not impair the purpose of the present invention. Examples of preferable substituents include amino groups substituted with 1 or 2 organic groups, morpholin-1-yl group and piperazin-1-yl group, halogen, nitro group, and cyano group.

Among R ¹ , since the photosensitive resin composition has very excellent sensitivity, a group represented by the following formula (2) or (3) is preferable, a group represented by the following formula (2) is more preferable, and a group represented by the following formula (2) is preferred. As a group, it is preferable that X is a sulfoxide, and even more preferably, it is a sulfone.

When forming a pattern using a photosensitive resin composition, coloring is likely to occur in the pattern due to heating in the post-bake process during pattern formation. However, in the case of using an oxime ester compound represented by the formula (1) in which R ¹ is a group represented by the formula (2) and Coloration of the pattern can be suppressed.

In formula (2), R ⁴ , R ⁵ , and R ⁶ are each independently 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, is sulfur, sulfoxide or sulfone.

When R ⁴ , R ⁵ , and R ⁶ in the formula (2) are each independently an organic group, they can be selected from various organic groups as long as they do not impair the purpose of the present invention. In Formula (2), when R ⁴ , R ⁵ , and R ⁶ are organic groups, preferred examples include an alkoxy group having 1 to 6 carbon atoms; Saturated aliphatic acyl group having 2 to 7 carbon atoms; Alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; 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; Morpholine-1-yl; A benzoyl group substituted by a group selected from the group consisting of piperazin-1-yl group, phenyl group, and nitrophenyl group; Mono alkylamino group having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholine-1-yl; or piperazine-1-yl group.

Among R ⁴ , benzoyl group; Naphthenoyl group; Alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholine-1-yl; piperazine-1-yl group; and a benzoyl group substituted by a group selected from the group consisting of a phenyl group; nitro group; Alternatively, a cyano group is more preferable.

In Formula (2), the bonding position of R ⁴ is preferably the para position with respect to the bond where the phenyl group to which R ⁴ is bonded is bonded to sulfur atom sulfoxide or sulfone, and the bonding position of R ⁵ and R ⁶ is the ortho position. It is desirable to be

When R ¹ is a carbazolyl group (Formula (3)) The nitrogen atom R ⁷ on the carbazolyl group is an alkoxyalkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, an aminoalkyl group with 1 to 20 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms. am. A preferred example of R ⁷ is: Examples include an alkoxyalkyl group with 1 to 20 carbon atoms, an aryl alkyl group with 7 to 30 carbon atoms, or an aminoalkyl group with 1 to 20 carbon atoms, especially among 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 is a cyano group, a nitro group, a halogen, an amino group having 1 to 10 carbon atoms substituted with 1 or 2 organic groups, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted 2 to 10 carbon atoms group. It is a heterocyclic group of 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.

Included in R ⁸ When the phenyl group, naphthyl group and heterocyclic group have a substituent, the number of substituents is not limited as long as it does not impair the purpose 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 for synthesizing the oxime ester compound of the present invention is not particularly limited, but can be prepared by the following method according to [Scheme 1] below, for example. Specifically, an aromatic compound represented by the following formula (1-1) is acylated using a halocarbonyl compound represented by the following formula (1-2) by the Friedel-Crafts reaction (1-3) ) is obtained, the ketone compound is oxidized using (1-4) to obtain a sulfone compound, and the obtained sulfone compound is oximed with hydroxyamine to produce an oxime compound represented by the following formula (1-5). and reacting the obtained oxime compound with an acid anhydride ((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). The oxime ester compound represented by the following formula (1-8) can be obtained. In addition, Hal in the following formula (1-2) is a halogen atom and has the following formulas (1-1), (1-2), (1-3), (1-4), (1-5), (1- In 8), R ¹ , R ² , and R ³ are the same as in formula (1).

[Scheme 1]

When p is 0 in the above formula (1), the method for synthesizing the oxime ester compound of the present invention is not particularly limited, but can be prepared by the following method according to [Scheme 1] below, for example. Specifically, a ketone compound represented by the following formula (2-1) is oxidized using (1-4) to obtain a sulfone compound, and the obtained sulfone compound is oximed in the presence of a base (NaOMe) or hydrochloric acid (HCl). RONO (R is an alkyl group having 1 to 6 carbon atoms) represented by the following formula (2-3) is reacted to produce a ketoxime ester compound represented by the following formula (2-4) and an acid anhydride represented by the following formula (2-5) (R ₃ CO) ₂ O) or an acid halide represented by the following formula (2-6) (R ₃ COHal, Hal is a halogen atom) can be reacted to obtain an oxime ester compound represented by the following formula (2-7). In addition, Hal in the following formula (2-6) is a halogen atom, and in the following formulas (2-1), (2-4), (2-5), (2-6), R ¹ , R ² , R ³ is the same as Chemical Formula (1).

[Scheme 2]

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

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

[Formula 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 2-28 2-29

2-30 2-31 2-32

2-33 2-34 2-35

2-36 2-37 2-38

2-39 2-40 2-41

The oxime ester compound of the present invention is useful as a photopolymerization initiator for polymerizable compounds having an ethylenically 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 active ingredient and a resin or monomer having an ethylenically unsaturated bond are preferable, and it is more preferable to combine them. By combining a resin having an ethylenically unsaturated group and a monomer having an ethylenically unsaturated group, the curability of the photosensitive resin composition can be improved and pattern formation can be facilitated.

The polymerizable compound having the ethylenically unsaturated bond is not particularly limited, and those used in conventional photosensitive compositions can be used. For example, ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, Unsaturated aliphatic hydrocarbons such as tetrafluoroethylene; (meth)acrylic acid, α-chloroacrylic acid, itagonic acid, maleic acid, fumaric acid, maleic acid, crotonic acid, isocrotonic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl acrylate, 2-hydroxyethyl meth. Crylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, acrylic acid amide, meta Crylic acid amide, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2 -Ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate , tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate Rate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate Late, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardoepoxydi Monomers and oligomers such as acrylates; After reacting polyester (meth)acrylate, which is obtained by reacting (meth)acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol and a monobasic acid or polybasic acid, and a compound having a polyol group and two isocyanate groups, (meth) ) 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, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polygly. and epoxy (meth)acrylate resin obtained by reacting epoxy resins such as cidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, and dihydroxybenzene type epoxy resin with (meth)acrylic acid. Furthermore, a resin obtained by reacting the epoxy (meth)acrylate resin with a polybasic acid anhydride can be used. These photopolymerizable compounds may be cardo-based resins. Among these, the oxime ester compounds of the present invention are mixed with polyfunctional (meth)acrylates having mono(meth)acryloyl groups of polymers having carboxyl groups and hydroxyl groups at both ends, unsaturated monobasic acids, and esters of polyhydric alcohols or polyphenols. A photopolymerization initiator used as an active ingredient is suitable. These polymerizable compounds may be used individually or in combination of two or more types, and when two or more types are used in combination, they may be copolymerized in advance and used as a copolymer.

Additionally, as the polymerizable compound having an ethylenically unsaturated bond, an alkali-developable compound having an ethylenically unsaturated bond can be used to make the photosensitive composition of the present invention an alkali-developable photosensitive resin composition. Examples of the alkali-developable compounds having the ethylenically unsaturated bond include copolymers of acrylic acid esters, phenol and/or cresol noblock resins, polyphenyl methane type epoxy resins having a polyfunctional epoxy group, and epoxides such as epoxy compounds and unsaturated monobasic acids. A resin obtained by reacting with a polybasic acid anhydride can be used.

The mass average molecular weight of the resin having an ethylenically unsaturated bond is preferably 1,000 to 40,000. It is preferable that the mass average molecular weight is 1000 or more because good heat resistance and film strength can be obtained. Moreover, it is preferable to set the mass average molecular weight to 4000 or less because good developability can be obtained. In addition, the alkali-developable compound having an ethylenically unsaturated bond preferably contains 0.2 to 1.0 equivalents of unsaturated groups.

The acid value of the resin having the ethylenically unsaturated bond is preferably in the range of 10 to 150 mg KOH/g, more preferably 70 to 110 mg KOH/g, based on the resin solid content. It is preferable that the acid value is 10 mg KOH/g or more because sufficient solubility in the developing solution is obtained. Also, setting the acid value to 150 mg KOH/g or less is preferable because sufficient curability can be obtained and surface properties can be improved.

Examples of the unsaturated monobasic acid that acts on the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate and maleate. Hydroxymethacrylate/malate, hydroxypropyl methacrylate/malate, dicyclopentadiene/malate, etc. can be mentioned.

In addition, polybasic acid anhydrides used after reacting the unsaturated monobasic acid include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellitic anhydride, and pyrodellic acid. Anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, methyl hymic anhydride, etc. are mentioned.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid, and the polybasic acid anhydride is preferably as follows. That is, in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, the acid anhydride of the polybasic acid anhydride is added to one hydroxyl group of the epoxy adduct. It is desirable to have a ratio of 0.1 to 1.0 structures.

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

The acid value of the resin having the ethylenically unsaturated bond is preferably in the range of 10 to 150 mg KOH/g, more preferably 70 to 110 mg KOH/g, and the amount of monofunctional or polyfunctional epoxy compound used is within the range of the acid value. It is desirable to select to satisfy .

Examples of the monofunctional epoxy compounds include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, undecyl glycidyl ether, and allyl glycidyl ether. , propargyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, p-cumyl glycidyl ether, triglycidyl ether, styrene oxide, pinen oxide, methyl styrene oxide, etc. .

As the above-mentioned polyfunctional epoxy compound, it is preferable to use at least one selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers because a colored alkali-developable photosensitive resin composition with even better properties can be obtained. In addition, phenol noblock-type epoxy compounds, biphenyl noblock-type epoxy compounds, cresol noblock-type epoxy compounds, bisphenol A noblock-type epoxy compounds, and dicyclopentadiene noblock-type epoxy compounds; Alicyclics such as 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclonucleic acid carboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclonucleic acid carboxylate, etc. Formula epoxy compound; 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; Deoxy compounds such as dicyclopentadienoxide; Naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, etc. can be used.

The photosensitive resin composition may, if necessary, contain a known photopolymerization initiator other than the oxime ester compound represented by the formula (1). Specific examples of known photopolymerization initiators include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylaceto. Acetophenones such as phenone, benzophenones such as benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin. Benzoin ethers such as isobutyl ether, benzyl dimethyl ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, etc. sulfur compounds, anthraquinones such as 2-ethylanthraquinone, octamethyl anthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, Organic peroxides such as menperoxide, thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole, and 2-(o-chlorophenyl)-4 , imidazolyl compounds such as 5-di(m-methoxyphenyl)-imidazolyl dimer, triazine compounds such as p-methoxytriazine, and 2,4,6-tris(trichloromethyl) -s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis (trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4 -diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenol)ethenyl]-4,6 -bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)- Trees having a halomethyl group such as 4,6-bis(trichloromethyl)-s-triazine and 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine and aminoketones such as azine compounds and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1one. Among these, it is particularly preferable to use an oxime-based photopolymerization initiator in terms of sensitivity. These photopolymerization initiators can be used individually or in combination of two or more types.

When the photosensitive composition contains a photopolymerization initiator other than the oxime ester compound represented by the formula (1), the content of the other photopolymerization initiator is not particularly limited as long as it does not impair the object of the present invention. In this case, the content of the other photopolymerization initiator is typically preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and especially preferably 10 parts by weight or less, relative to the total amount of photopolymerization initiators contained in the photosensitive resin composition. The addition amount of the oxime ester compound of the present invention 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. It is wealth. By keeping it within the above range, sufficient heat resistance and chemical resistance can be obtained, while the coating film forming ability can be improved and photocuring defects can be suppressed.

The photosensitive resin composition (especially 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 example, for forming a color filter for a liquid crystal display. Additionally, the photosensitive resin composition according to the present invention contains a light-shielding agent as a colorant, and is therefore preferably used for forming a black matrix in a color filter of a display device, for example.

The colorant contained in the photosensitive resin composition according to the present invention is not particularly limited, but includes, for example, a compound classified as a pigment in the color index (C.I.; The Society of Dyers and Colourist), specifically. It is preferable to use those with the same color index (C.I.) number below.

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, 168, 175, 180 and 185.

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 that 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.

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

Examples of blue pigments that 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 that can be preferably used include C.I. Pigment Green 7, 36, C.I. Pigment Brown 23, 25, 26, C.I. Black pigments such as Pigment Black 7 can be mentioned. Known pigments include, for example, nitroso compounds, cyanine, xanthene, oxazine, thiazine, diarylmethane, cationic dyes such as trialrylmethane and pyrylium, merocyanine, coumarin, indigo, aromatic amines, Neutral dyes such as phthalocyanine, azo, quinone, and thioxanthene photosensitive dyes, and benzophenones, acetophenones, benzoins, thioxanthons, anthraquinones, imidazoles, biimidazoles, coumarins, and ketones. It may further include compounds such as tocoumarins, triphenylpyryliums, triazines, and benzoic acid.

When the colorant is used as a light-blocking agent, it is preferable to use a black pigment as the light-blocking agent. Black pigments include various pigments regardless of whether they are organic or inorganic, such as carbon black, titanium black, copper, iron, manganese, cobalt, silver, metal oxides, complex oxides, metal sulfides, metal sulfates, or metal carbonates. Among these, it is preferable to use carbon black as it has high light-shielding properties.

As carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, but it is preferable to use channel black, which has excellent light blocking properties.

Since resin carbon black has lower conductivity than carbon black without resin coating, when used as a black matrix for liquid crystal display elements such as liquid crystal displays, it produces low current leakage and highly reliable low power consumption displays. can do. Additionally, in order to adjust the color tone of carbon black, the above-mentioned organic pigments may be appropriately added as auxiliary pigments.

In order to uniformly disperse the above coloring agent in the photosensitive resin composition, a dispersing agent may be additionally used. As such a dispersant, it is preferable to use a polymer dispersant of polyethyleneimine, urethane resin, or acrylic resin. In particular, when using carbon black as a colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant. In addition, the inorganic pigment and the organic pigment may be used alone or in combination of two or more types, but when used together, it is preferable to use the organic pigment in the range of 10 to 80 parts by weight based on 100 parts by weight of the total amount of the inorganic pigment and the organic pigment. It is more preferable to use it in the range of ~40 parts by weight.

The amount of colorant used in the photosensitive resin composition may be appropriately determined depending on the use of the photosensitive resin composition, but for example, when the total solid content of the photosensitive resin composition is 100 parts by weight, 5 to 70 parts by weight is preferable and 25 to 60 parts by weight is more preferable. desirable. It is preferable that the above range is used because the black mattress or each colored layer can be formed in the desired pattern.

In particular, when forming a black matrix using a photosensitive resin composition, it is desirable to adjust the amount of light-shielding agent in the photosensitive resin composition so that the OD value per 1 μm film of the black matrix is 4 or more. If the OD value per 1 μm of film in a black matrix is 4 or more, sufficient display contrast can be obtained when used in the black matrix of a liquid crystal display. The colorant is preferably dispersed at an appropriate concentration using a dispersant to form a dispersion and then added to the photosensitive resin composition.

Various additives may be added to the photosensitive resin composition according to the present invention as needed. Specifically, solvents, sensitizers, curing accelerators, photocrosslinking agents, photosensitizers, dispersing aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerates, thermal polymerization inhibitors, antifoaming agents, surfactants, etc. are exemplified.

Solvents used in the photosensitive resin composition according to the present invention include, for example, ethylene glycol monoether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethyl glycol monomethyl ether. , (poly)alkylene glycol monoalkyl ethers such as diethylene 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 such as toluene and xylene; Amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide can be mentioned. These solvents may be used individually, or two or more types may be used in combination.

Among the above solutions, propylene glycol monomethyl ether, ethylene glycol 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 has excellent solubility in the photopolymerizable compound described above and the oxime ester photopolymerization initiator of the present invention and can improve the dispersibility of the colorant component described above. Propylene glycol monomethyl ether acetate, 3- It is particularly preferred to use methoxybutylacetate. The solvent may be appropriately determined depending on the use of the photosensitive resin composition, but as an example, the solvent may be used in an amount of 50 to 900 parts by weight based on 100 parts by weight of the total solid content of the photosensitive resin composition.

Examples of thermal polymerization lubricant used in the photosensitive resin composition according to the present invention include hydroquinone and hydroquinone monoethyl ether. Antifoaming agents include silicone-based and fluorine-based compounds, and surfactants include anionic, cationic, and non-ionic compounds. Compounds such as ionic compounds can be exemplified.

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

According to the present invention, a substrate having a column spacer, a black matrix, a color filter, an organic insulating film, and a film formed by coating the same are provided from such a photosensitive resin composition, wherein the film is a polarizer used in a plasma display panel and a liquid crystal display. It may be used as the surface of a sunglasses lens, a prescription eyeglass lens, a camera finder lens, an instrument cover, an automobile glass, a tram glass, a luminance enhancing film, or an optical waveguide film.

Substrates include, for example, glass substrates, silicon substrates, flexible substrates, and substrates with flat surfaces such as polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamideimide substrates, polyimide substrates, aluminum substrates, GaAs substrates, etc. can be mentioned.

The method of applying the photosensitive resin composition on the substrate is not particularly limited, and includes known methods such as spin coating, casting, roll coating, slit & spin coating, and spinless coater. It can be applied on a substrate, etc. using a suitable coating method.

The applied photosensitive composition is dried to form a coating film. The drying method is not particularly limited, and examples include ① drying on a hot plate at a temperature of 80 to 120°C, preferably 90 to 100°C for 60 to 120 seconds, ② leaving at room temperature for several hours to several days, ③ A method of removing volatile components such as solvents by using a warm air heater or an infrared heater for tens of minutes to several hours can be used. In this way, a layer made of solid content of the photosensitive composition is formed on a substrate or the like. Next, the layer consisting of solid content of the photosensitive composition is exposed, for example, by selectively irradiating active energy rays through a photomask. Suitable exposure light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, and metal halide lamps. In addition, laser beams, etc. can be used as active energy rays for exposure. In addition, electron beams, α-rays, β-rays, γ-rays, X-rays, and neutron rays can also be used. Active energy rays are irradiated through a photomask, where the photomask is, for example, a light-shielding layer installed on the surface of a glass plate to block the active energy rays. The part of the glass plate where the light-shielding layer is not installed is a light-transmitting part through which active energy rays pass, and the photosensitive composition is exposed in a pattern according to the pattern of this light-transmitting part, resulting in unirradiated areas not irradiated with active energy rays and areas irradiated with active energy rays. An investigation area is created. The amount of energy to be irradiated varies depending on the composition of the photosensitive composition, but is preferably about 30 to 2000 mJ/cm2, for example.

As already explained, using the photosensitive resin composition according to the present invention has excellent sensitivity, so the productivity of the liquid crystal display panel can be improved.

The film after exposure is developed with a developing solution and patterned into a desired shape. The developing method is not particularly limited, and for example, immersion method, spray method, etc. can be used. Examples of developing solutions include organic solutions such as monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. Unirradiated areas in the photosensitive composition layer that are not irradiated with active energy rays are removed due to the post-exposure phenomenon. Meanwhile, the active energy ray irradiation area remains as is and forms a pattern. It is preferable to post-bake the pattern after development at about 200 to 250°C.

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

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

[Example 1]

Synthesis of Formula 2-1

Step 1 synthesis:

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

10.0 g (41.4 mmol) of 4-(4-(bromophenyl) was dried in dimethylacetamide under a nitrogen atmosphere. Dissolve in 20mL and store at 23℃ sodium hydroxide. 1.7 g (41.4 mmol) was added and the reaction temperature was set to 50°C and stirred for 8 hours. The temperature of the reactor was lowered to 23°C, 50 ml of water was added to terminate the reaction, and 70 ml of ethyl acetate was added thereto for extraction. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed using a rotary evaporator. After separation and purification by column chromatography, 10.0 g (yield: 90%) of the target compound 4-(4-(phenylthio)phenyl)morpholine was obtained. got it

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)

Step 2 synthesis:

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

10.0 g (36.8 mmol) of 4-(4-(phenylthio)phenyl)morpholine was dried in dichloromethane under a nitrogen atmosphere. Dissolve in 20mL, cool the reaction to 0℃, and add aluminum trichloride. 5.0g (36.8mmol) was slowly added. Here, 6.2 g (36.8 mmol) of tolylacetyl chloride was slowly added dropwise at 0°C. After stirring for 8 hours, adding 50 mL of water and washing, the organic layer was separated, dried over anhydrous magnesium sulfate, filtered, the solvent was removed using a rotary evaporator, and the target compound 1-(4-((4-mol) was purified by column chromatography. 11.8 g of polynophenyl)thio)phenyl)-2-(O-tolyl)ethanone (yield: 70%) was obtained.

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, 1H), 7.40 (d, 2H), 7.52 (d, 2H), 7.74 (d, 2H)

3-step synthesis:

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

10.0 g (36.8 mmol) of 4-(4-(phenylthio)phenyl)morpholine was dried in dichloromethane under a nitrogen atmosphere. After dissolving in 20 mL and cooling the reactant to 0°C, 5.8 g (36.8 mmol) of 3-chlorobenzoic acid was slowly added. After stirring for 5 hours, adding 50 mL of water and washing, the organic layer was separated, dried over anhydrous magnesium sulfate, filtered, the solvent was removed using a rotary evaporator, and the target compound 1-(4-((4-mol) was purified by column chromatography. 12.8 g of polynophenyl)sulfonyl)phenyl)-2-(O-tolyl)ethanone (yield: 80%) was obtained.

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) , 7.40 (d, 2H), 7.65 (d, 2H), 6.93 (d, 2H), 8.11 (d, 2H), 8.17 (d, 2H)

Step 4 synthesis:

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

Add 10.0 g (21.5 mmol) of 1-(4-((4-morpholinophenyl)sulfonyl)phenyl)-2-(O-tolyl)ethanone to a three-necked flask under a nitrogen atmosphere and dissolve in 10 mL of dimethylformamide. The reactor was cooled and 1.2 g (21.5 mmol) of sodium methoxide was added at 0°C. 2.5 g (21.5 mmol) of isoamylnitrite was added dropwise to this reaction, then the temperature was raised to 23°C and stirred for 5 hours. The reactor was cooled, 20 mL of distilled water was added to terminate the reaction, and 50 mL of ethyl acetate was added and extracted. The organic layer was separated, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to obtain the target compound ( E )-2-(hydroxyimino)-1-(4-((4-morpholinophenyl)sulfonyl)phenyl)-2-. 5.3 g (O-tolyl)ethanone (yield: 50%) was obtained.

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)

5-step synthesis:

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

Under a nitrogen atmosphere, the internal temperature was lowered to 0°C or lower, and ( E )-2-(hydroxyimino)-1-(4-((4-morpholinophenyl)sulfonyl)phenyl)-2-(O-tolyl) ) 5.0 g (10.8 mmol) of ethanone 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 to wash the organic layer twice. The organic layer was separated, dried over anhydrous magnesium sulfate, and distilled under reduced pressure to obtain the target compound ( E )-2-(acetoxyimino)-1-(4-((4-morpholinophenyl)thio)phenyl)-2-( 4.6 g (yield; 85%) of O-tolyl)ethanone was obtained.

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 same experiment as in Example 1 was performed except that 10.0 g of 4-(4-(phenylthio)phenyl)morpholine was replaced with 10 g of (4-nitrophenyl)(4-(phenylthio)phenyl)methanone, resulting in Formula 2-2. 5.6 g of the oxime ester compound was obtained.

[Example 3]

Synthesis of Formula 2-4

An oxime having the structure of Formula 2-2 was obtained in the same manner as in Example 1 except that 10.0 g of 4-(4-(phenylthio)phenyl)morpholine was replaced with 10 g of N,N-diethyl-4-(phenylthio)aniline. 6.2 g of ester compound was obtained.

[Example 4]

Synthesis of Formula 2-8

An oxime having the structure of Formula 2-2 was performed in the same manner as in Example 1 except that 10.0 g of 4-(4-(phenylthio)phenyl)morpholine was replaced with 9.6 g of (2,4-dinitrophenyl)(phenyl)sulfane. 5.3 g of ester compound was obtained.

[Example 5]

Synthesis of Formula 2-12

The same experiment as Example 1 was performed except that 10.0 g of 4-(4-(phenylthio)phenyl)morpholine was replaced with 10 g of (4-(phenylthio)phenyl)(thiophen-2-yl)methanone, and Formula 2 was obtained. 5.5 g of oxime ester compound of -2 structure was obtained.

[Example 6]

Synthesis of Formula 2-19

The same experiment as in Example 1 was performed except that 10.0 g of 4-(4-(phenylthio)phenyl)morpholine was replaced with 8.5 g of 1-methyl-2-((4-nitrophenyl)sulfonyl)benzene, resulting in Formula 2- 6.5 g of oxime ester compound of structure 2 was obtained.

[Example 7]

Preparation of transparent resist composition

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

[Formula 2-2]

[Example 8]

Black resist composition preparation

For 10 g of acrylic copolymer, 13.6 g of dipentaerythritol hexaacrylate, 2.0 g of the photoinitiator of Chemical Formula 2-1, 48 g of Pigment Black 7, and 25 g of propylene glycol monoethyl ether were added and stirred well to obtain a black resist composition.

[Example 9]

Manufacture of red color resist composition

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

[Example 10]

Preparation of transparent resist composition

For 17g of acrylic copolymer, 13.6g of dipentaerythritol hexaacrylate, 1.5g of photoinitiator of Chemical Formula 2-2, and 67g of propylene glycol monoethyl ether were added and stirred well to obtain a transparent resist composition.

[Formula 2-2]

[Example 11]

Black resist composition preparation

For 10 g of acrylic copolymer, 13.6 g of dipentaerythritol hexaacrylate, 2.0 g of the photoinitiator of Chemical Formula 2-2, 48 g of Pigment Black 7, and 25 g of propylene glycol monoethyl ether were added and stirred well to obtain a black resist composition.

[Example 12]

Red resist composition preparation

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

[Comparative Example 1]

Preparation of transparent resist composition

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

[Formula A]

[Comparative Example 2]

Black resist composition preparation

For 10 g of acrylic copolymer, 13.6 g of dipentaerythritol hexaacrylate, 2.0 g of photoinitiator of formula A, 48 g of Pigment Black 7, and 25 g of propylene glycol monoethyl ether were added and stirred well to obtain a black resist composition.

[Comparative Example 3]

Preparation of red color resist composition

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

[Comparative Example 4]

Preparation of transparent resist composition

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

[Formula B]

[Comparative Example 5]

Black resist composition preparation

For 10 g of acrylic copolymer, 13.6 g of dipentaerythritol hexaacrylate, 2.0 g of photoinitiator of the following formula B, 48 g of Pigment Black 7, and 25 g of propylene glycol monoethyl ether were added and stirred well to obtain a black resist composition.

[Formula B]

[Comparative Example 6]

Red resist composition preparation

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

[Test example]

The photosensitive composition was applied on a spin coater at 800 to 900 rpm for 15 seconds and then dried on a hot plate at 90°C for 100 seconds. Using a predetermined mask, it was exposed using an ultra-high pressure mercury lamp as a light source, and then spin developed in 0.04% potassium hydroxide solution at 25°C 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 performed on the obtained pattern. Photopolymerization initiators using each photosensitive composition and various evaluation results are shown in Table 1.

(1) Adhesion

According to the test method of JIS D 0202, a grid-shaped crosscut was made on the coating film heated at 200°C for 30 minutes after exposure development, and then a peeling test was performed using cellophane tape, and the peeling state of the grid was observed and evaluated. . If there was no delamination of 95 or more lattices, it was evaluated as ○, if there was no delamination of 60 or more lattices, it was evaluated as △, and if delamination occurred of 40 or more lattices, it was evaluated as x.

(2) Alkali resistance

After development, the film was baked at 230°C for 30 minutes, and then the state was observed after immersing the film in a 5% NaOH aqueous solution for 24 hours, a 4% KOH aqueous solution at 50°C for 10 minutes, and a 1% NaOH aqueous solution at 80°C for 5 minutes. A case in which there was no change in appearance or peeling was evaluated as ○, a case in which lifting of the resist was observed was evaluated as △, and a case in which peeling of the resist was observed was evaluated as x.

(3) Sensitivity evaluation

Each of the above-formed photosensitive resin compositions was applied to a glass substrate (Eagle2000, manufactured by Samsung Corning) using a spin coater, and dried on a hot plate at 90°C for 1 minute. After drying, the film thicknesses of the black resist and transparent negative resist were measured with a probe-type film thickness meter (α-step 500 manufactured by KLA-Tencor) and were 1 micron and 5 microns, respectively. Next, this sample was exposed to high-pressure mercury or the like through a mask. Afterwards, a resist pattern was obtained by developing by spraying with a 0.04% potassium hydroxide aqueous solution. The appropriate exposure amount (mJ/cm ² ) that can form the same dimensions as a 40 micron mask pattern is indicated. In other words, a resist with a small exposure amount shows high sensitivity because pattern formation is possible even with a small amount of light energy.

(4) Whitening phenomenon

Each photosensitive resin composition including the synthesized photoinitiator was applied to a glass substrate using a spin coater. At this time, depending on the solubility of the photoinitiator, the case where crystals are generated during rotational application and the coated surface is very poor is indicated as When no crystals are formed and the surface is clean, it is indicated as ○.

These results are shown in Table 1 below.

No. photoinitiator Adhesion Alkali resistance Sensitivity
(mJ/cm2) Thin film characteristics (whitening phenomenon) Example 7 Formula 2-1 ○ ○ 30 ○ Example 8 Formula 2-1 ○ ○ 45 ○ Example 9 Formula 2-1 ○ ○ 40 ○ Example 10 Formula 2-2 ○ ○ 30 ○ Example 11 Formula 2-2 ○ ○ 45 ○ Example 12 Formula 2-2 ○ ○ 35 ○ Comparative Example 1 Formula A △ △ 100 ○ Comparative Example 2 Formula A X X 150 X Comparative Example 3 Formula 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-based compound and the alpha-chitoxime ester-based compound according to the present invention had excellent adhesion and alkali resistance, and there was no whitening of the thin film. In particular, it can be seen that the photosensitive resin composition using an alpha-kitoxime ester-based initiator as in Examples 7 to 12 has very excellent sensitivity that enables pattern formation with a low exposure dose of 30 to 45 mJ/cm ² . In addition, as can be seen in Table 1, the photosensitive composition using the oxime ester-based and alpha-chito-oxime ester-based photoinitiator according to the present invention has fast sensitivity, excellent photocuring, excellent adhesion to the substrate, and resistance to basic aqueous solutions. You can see that it is very excellent. In order to produce a photosensitive composition, it has excellent compatibility with binders and polyfunctional monomers having ethylenically unsaturated bonds, and has excellent solubility in organic solvents, so after forming a thin film, a photosensitive resin composition thin film with a very uniform surface is formed. Could.

Claims (9)

In the oxime ester compound represented by the following formula (1),

(Wherein, R ¹ is 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 cyano group, and p is is 0 or 1, and R ² is a hydrogen atom; or a straight-chain or branched alkyl group with 1-10 carbon atoms substituted or unsubstituted with an alkyl group with 1-6 carbon atoms, a cycloalkyl group with 4-10 carbon atoms, or an aryl group with 6-20 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 compound represented by Formula 1 is an oxime ester compound, characterized in that it is selected from compounds represented by Formula 2 below.
[Formula 2]

2-1 2-2
delete delete delete delete delete delete delete (a) ethylenically unsaturated photopolymerizable compound; and
(b) A photosensitive resin composition comprising at least one photoinitiator selected from the oxime ester compounds according to claim 1.