TW201600500A - Oxime ester compound and a photopolymerizable composition comprising the same - Google Patents

Abstract

Disclosed herein is an oxime ester compound and a photopolymerizable composition comprising the same, more specifically, a photopolymerizable composition comprising photopolymerizable compound and photoinitiator, wherein the photoinitiator comprises oxime ester compound, and the photopolymerizable composition has an effect of excellent linearity pattern.

Description

An oxime ester compound and a photopolymerizable composition including the oxime ester compound

The present invention relates to an oxime ester compound and a photopolymerizable composition comprising the oxime ester compound, and more particularly, to a photopolymerizable composition comprising a photopolymerizable compound and a photoinitiator, wherein the light The starter includes an oxime ester compound.

The photoactive compound is a material which decomposes to generate chemically active atoms or molecules by absorbing light, and is widely used as a photoinitiator for various compositions such as photocurable inks, photosensitive printing plates, and photoresists.

Classical examples of known photoinitiators can be classified into various types such as acetophenone compounds, benzophenone compounds, triazine compounds, non-imidazole compounds, mercaptophosphine oxide compounds, and oxime ester compounds, of which hydrazine The ester compound has the advantage that, for example, absorption of ultraviolet light hardly exhibits color, high radical generation rate, excellent compatibility with the material of the photoresist composition, and stability.

In the case of a photoinitiator having an oxime ester compound, the absorption of the photoinitiator can be easily synthesized by introducing a suitable substituent into the compound. A variety of photoinitiators that can be adjusted in the area.

Since the oxime ester compound can polymerize and cure a polymerizable compound having an unsaturated bond by irradiating light of 365 nm to 435 nm to the photopolymerizable composition, it is used for a black matrix, a color filter, a column spacer. , a flexible insulating film, a photoresist composition for the overcoat layer.

Therefore, there is a continuing need for new photoinitiators to meet the industrial needs of various purposes, such as high sensitivity to long wavelength light such as 365 nm to 435 nm, good cure reactivity, ease of fabrication, due to high thermal stability. It is easy to handle and store, and has a satisfactory solubility in a solvent such as propylene glycol monomethyl ether acetate.

Conventionally known oxime ester compounds are the oxime ester compounds with p-dialkylaminobenzene in U.S. Patent 4,255,513, the acrylamide-substituted oxime ester compounds of U.S. Patent 4,202,697, and the benzophenones of U.S. Patent 4,590,145. An oxime ester compound or the like.

However, when a known oxime ester compound is used as a photoinitiator, the pattern shape defect of the printing process is caused by degradation due to light upon exposure to attach to the mask, and the yield is lowered.

Further, the decomposition temperature is lower than 240 ° C, and there is a problem that the adhesion of the photopolymerizable composition and the alkali resistance are lowered due to decomposition of the photoinitiator in the thermal curing step after the development process.

Therefore, there is a great need for an oxime ester compound having a novel structure and a photopolymerizable composition comprising the oxime ester compound having a novel structure which solves these problems.

(previous technical literature) (Patent Literature)

Patent Document 1: US Patent 4,255,513.

Patent Document 2: US Patent 4,202,697.

Patent Document 3: US Patent 4,590,145.

Accordingly, the present invention has been devised to solve the aforementioned problems, and an object of the present invention is to provide a novel structure of an oxime ester compound.

Further, another object of the present invention is to provide a photopolymerizable composition comprising a photopolymerizable compound and a photoinitiator, wherein the photopolymerizable composition has an excellent linear pattern by containing a novel structure of an oxime ester compound. The effect, and compatibility with other ingredients can be improved by good solubility.

In order to achieve the aforementioned object, an aspect of the invention provides an oxime ester compound represented by the following Chemical Formula 1:

Wherein R is a C1 to C20 alkyl group, and n is an integer of from 12 to 20.

Further, the invention provides a photopolymerizable composition comprising a photopolymerizable compound and a photoinitiator, wherein the photoinitiator comprises the oxime ester compound of the following Chemical Formula 1:

Wherein R is a C1 to C20 alkyl group, and n is an integer of from 12 to 20.

When light is irradiated to the oxime ester compound of the present invention having a novel structure, a long-chain alkyl radical is generated, and since the radical has a long length, the mobility of the radical is small, so that only light irradiation is performed. Curing occurs on the area, and finally the oxime ester compound of the present invention having a novel structure has excellent pattern linearity characteristics.

Further, the oxime ester compound of the present invention having a novel structure has excellent compatibility with other materials due to high solubility, and absorbs ultraviolet rays and hardly exhibits color, and therefore it is advantageous to use the composition for optical purposes.

Accordingly, the present invention provides a photopolymerizable composition comprising a photopolymerizable compound and a photoinitiator, wherein the photopolymerizable composition has excellent linearity by using a fluorenyl ester compound having a novel structure as a photoinitiator The effect of the pattern, and almost no color.

Fig. 1 is a 1H-NMR chart of the oxime ester compound of Chemical Formula 2 prepared in Preparation Example 1.

2 is a 1H-NMR chart of the oxime ester compound of Chemical Formula 4 prepared in Preparation Example 3.

The invention is described in detail below.

The present invention relates to an oxime ester compound represented by the following Chemical Formula 1:

Wherein R is a C1 to C20 alkyl group, and n is an integer of from 12 to 20.

In the oxime ester compound of Chemical Formula 1, it is preferred that R in Chemical Formula 1 is preferably a C1 or C6 alkyl group, and n is preferably an integer of from 12 to 20.

Further, the oxime ester compound of Chemical Formula 1 may be selected from one or more of the group consisting of Chemical Formula 2 to Chemical Formula 5 below, but is not limited thereto:

[Chemical Formula 5]

The oxime ester compound of the formula 1 of the present invention can be prepared according to the following steps: (1) a step of preparing a compound having a mercapto group by reacting diphenyl sulfide with an alkylcarbon ruthenium chloride; and (2) having a ruthenium a step of reacting a compound with nitrous acid to prepare a compound having a mercapto group; and (3) a step of reacting a compound having a mercapto group with an alkylcarbonium chloride to prepare an oxime ester compound of Chemical Formula 1, and in the following reaction formula The reaction mechanism is shown in 1.

Further, R and n of the oxime ester compound of Chemical Formula 1 are determined according to the alkyl group of the alkylcarbonium chloride of the step (1) and the step (3).

The oxime ester compound of Chemical Formula 1 of the novel compound of the present invention includes a diphenyl sulfide group. Therefore, when light is irradiated to the oxime ester compound of Chemical Formula 1, the photoreactivity of the oxime ester compound of Chemical Formula 1 is improved by energy transfer, and the optical efficiency can be maximized. In addition, due to its suction The ultraviolet light also hardly exhibits color, so it is advantageous to use the composition for optical purposes.

Therefore, in order to utilize the oxime ester compound of Chemical Formula 1, the present invention provides a photopolymerizable composition using the oxime ester compound of Chemical Formula 1 as a photoinitiator.

More specifically, the present invention provides a photopolymerizable composition comprising a photopolymerizable compound and a photoinitiator, wherein the photoinitiator comprises an oxime ester compound of the following Chemical Formula 1:

Wherein R is a C1 to C20 alkyl group, and n is an integer of from 12 to 20.

The type of the photopolymerizable compound is not particularly limited as a component for supplementing light efficiency and color change, but is preferably an acrylic oligomer having an ethylenically unsaturated bond.

The acrylic oligomer having an ethylenically unsaturated bond is a photocurable acrylic oligomer which can be subjected to a UV curing reaction by a chemical reaction of a monomer for introducing a precursor and an ethylenically unsaturated bond.

The acrylic oligomer precursor can be copolymerized with a (meth)acrylic monomer having a C1 to C14 alkyl group and a polymerizable monomer. The method of preparing the acrylic oligomer is not particularly limited, but an acrylic oligomer precursor can be prepared by a method conventionally used in the art, such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, and is preferably used. Overall aggregation.

Further, the present invention may use any solvent which is usually used during the polymerization, and polymerization initiators such as azos, peroxides, acetals, redoxs, and hemiacetals may be used.

The alkyl group of the (meth)acrylic monomer having a C1 to C14 alkyl group includes an aliphatic group and an aromatic group, and the monomer includes methyl (meth)acrylate, ethyl (meth)acrylate, N-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-butyl (meth)acrylate, tert-butyl (meth)acrylate, (A) Isobutyl acrylate, amyl (meth)acrylate, ethylhexyl (meth)acrylate, ethyl butyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid Octyl ester, decyl (meth) acrylate, isodecyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate and (methyl) Dodecyl acrylate and the like. The foregoing monomers may be used singly or in combination of two or more.

Specific examples of the polymerizable monomer may, for example, be a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, or 2-hydroxyl (meth)acrylate. Butyl ester, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropanediol (meth) acrylate And 4-hydroxybutyl vinyl ether or the like; and a monomer having a carboxyl group such as (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, and the like; and the like. The polymerizable monomers may be used singly or in combination of two or more.

There are no special types of monomers used to introduce ethylenically unsaturated single bonds. It is preferred to use an isocyanate monomer having an isocyanate group and a double bond in one molecule, and an example thereof may be 2-isocyanatoethyl (meth)acrylate.

The method for producing the photocurable acrylic oligomer is not particularly limited, and the photocurable acrylic oligomer is preferably used as a photopolymerizable compound. Specifically, for example, the photocurable acrylic oligomer can be produced by the following steps: producing a precursor; adding 0.5 to 20 parts by weight with respect to 100 parts by weight of the acrylic oligomer precursor prepared as described above The isocyanate monomer and 0.001 to 0.5 part by weight of the catalyst are allowed to react. The kind of the catalyst is not particularly limited as long as the catalyst can promote the reaction of the isocyanate group with the hydroxyl group or the carboxyl group contained in the acrylic oligomer precursor, and for example, an organotin compound, an organic silver compound or a mixture thereof can be used.

The weight average molecular weight (polystyrene conversion, Mw) of the photopolymerizable compound measured by gel permeation chromatography (GPC) may be 200,000 to 1,000,000.

Further, the photoinitiator is characterized by containing an oxime ester compound represented by the following Chemical Formula 1:

Wherein R is a C1 to C20 alkyl group, and n is an integer of from 12 to 20.

Among the oxime ester compounds of Chemical Formula 1, R in Chemical Formula 1 is preferred. It is a C1 or C6 alkyl group, and n is preferably an integer of 12 to 20.

Further, the oxime ester compound of Chemical Formula 1 may be selected from one or more of the group consisting of Chemical Formula 2 to Chemical Formula 5 below, but is not limited thereto:

Since n is an integer of from 12 to 20, the oxime ester compound of Chemical Formula 1 used as a photoinitiator in the photopolymerizable composition of the present invention has a long alkyl chain. Therefore, when light is irradiated to the oxime ester compound of Chemical Formula 1, a long-chain alkyl radical is generated, and since the radical has a long length, the mobility of the radical is small, so that it is only on the region irradiated with light. Curing occurs. Therefore, if an oxime ester compound containing the chemical formula 1 is used as the light By forming a pattern of the photopolymer composition of the starting agent, excellent pattern linearity can be ensured.

The photoinitiator is contained in an amount of from 0.01 to 10 parts by weight based on 100 parts by weight of the solid of the photopolymerizable compound. If the content is less than 0.01 part by weight, the degree of overall curing of the photopolymerizable composition is lowered. If the content is more than 10 parts by weight, the transmittance of ultraviolet light is lowered, so that there is a problem that the degree of solidification in the deep portion is lowered.

Further, the photopolymerizable composition of the present invention may further include a solvent, and the solvent conventionally used in the photopolymerizable composition may be used in the present invention without any particular limitation as long as the solvent effectively dissolves the photopolymerizable composition. Other components contained therein, and specifically, ethers, aromatic hydrocarbons, ketones, alcohols, esters or guanamines and the like are preferably used.

The ethers include, for example, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; diethylene glycol dialkyl ether For example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc.; ethylene glycol alkyl ether acetate, such as methyl 赛路苏Acetate, ethyl stilbene acetate, etc.; and alkylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, Methoxybutyl acetate, methoxypentyl acetate, and the like.

The aromatic hydrocarbons include, for example, benzene, toluene, xylene, mesitylene, and the like.

The ketones include, for example, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, and the like.

Alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, and the like.

The ester includes, for example, an ester such as ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate or methyl 3-methoxypropionate; and a cyclic ester such as γ-butyrolactone.

In terms of drying and coating properties of the solvent, it is more preferred to use an organic solvent having a boiling point of from 100 ° C to 200 ° C, and examples of such a solvent include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and cyclohexanone. Ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate and the like.

The foregoing solvents may be used singly or in combination of two or more.

Further, the photopolymerizable composition of the present invention may further include known additives such as a color former, an alkali-soluble resin, a surfactant, and the like.

The photopolymerizable composition of the present invention is suitable for a wide range of uses. For example, the photopolymerizable composition of the present invention can be applied to printing inks, decorative materials, coating materials, tackifiers/adhesives or the like, and since it is difficult to be perceived by absorbing ultraviolet light, It is used as a composition for an optical image display device requiring transparency.

Preferred embodiments are provided below to better understand the present invention. While the preferred embodiment of the present invention has been disclosed, it will be understood by those of ordinary skill in the art that various modifications can be made without departing from the scope and spirit of the invention Modify, add, and replace.

(Example)

Preparation Example 1. Preparation of an oxime ester compound of Chemical Formula 2

1-1. Preparation of a compound having a mercapto group

20 g (107.5 mmol) of diphenyl sulfide was added to a mixed solution of 100 g of dichloroethane and 21.7 g (163 mmol) of aluminum chloride, and then 17.4 g (107.5 mmol) at a temperature lower than 6 ° C Xinzhi chlorine is added to the aforementioned solution. Subsequently, the reaction liquid was stirred for 1 hour, and then it was placed in ice water, and oil-water separation was carried out by adding ethyl acetate.

Thereafter, the organic layer was separated by washing with water, anhydrous magnesium sulfate was added to the organic layer and dried, and then solvent was removed from the organic layer to obtain 26.3 g of a compound having a mercapto group.

The obtained compound having a mercapto group was analyzed by 1 H-NMR, and it was confirmed to have the structure of the following chemical formula 6, and the spectrum is as follows.

¹ H-NMR (CDCl ₃ , ppm): 2.01 (t, 3H), 2.55 (m, 10H), 3.65 (s, 2H), 7.00 (t, 1H), 7.07 (t, 2H), 7.20 (d, 2H), 7.32 (d, 2H), 7.66 (d, 2H).

1-2. Preparation of a compound having a mercapto group

5.4 g (52 mmol) of nitrosoisobutyl ester was added to 13 g (47.4 mmol) of the compound having a mercapto group of Chemical Formula 6 prepared in the above Preparation Example 1-1, 3.6 g (35 mmol) of concentrated hydrochloric acid, and 50 g of After the mixed solution of methylformamide, the mixture was stirred at room temperature for 3.5 hours.

Subsequently, by adding ethyl acetate and water to the reaction mixture The oil-water separation was carried out, followed by washing the separated organic layer with water.

Thereafter, hexane was added to the separated organic layer to precipitate a solid, the organic layer was filtered, and the obtained solid was dried under reduced pressure to give 10.6 g of a compound having a mercapto group.

The obtained compound having a mercapto group was analyzed by 1 H-NMR to determine the structure, and it was confirmed to have the structure of the following Chemical Formula 7, and the spectrum was as follows.

¹ H-NMR (CDCl ₃ , ppm): 2.01 (t, 3H), 2.65 (m, 8H), 3.25 (t, 2H), 7.02 (t, 1H), 7.09 (t, 2H), 7.18 (d, 2H), 7.31 (d, 2H), 7.62 (d, 2H) 12.8 (s, 1H).

1-3. Preparation of an oxime ester compound of Chemical Formula 2

4 g (13.2 mmol) of the mixed solution of the thiol-containing compound of Chemical Formula 7 prepared in Preparation Example 1-2, 2.1 g (27 mmol) of pyridine, and 12 g of dimethylformamide was maintained at -10 ° C or below. Medium, and 3.7 g (15 mmol) of tetradecyl chloride was added dropwise to the mixed solution.

Subsequently, after the mixed solution was stirred at 5 ° C for 2 hours, ethyl acetate and water were added to the solution for oil-water separation, and the separated organic layer was washed with water.

Thereafter, anhydrous magnesium sulfate was added to the organic layer and dried, and then the solvent was removed from the organic layer to obtain 3.5 g of an oxime ester compound.

The obtained oxime ester compound was analyzed by 1H-NMR to determine the knot. The structure was confirmed to have the following chemical formula 2, the spectrum thereof is shown in Fig. 1, and the elemental analysis results thereof are as follows.

Elemental analysis: C, 74.21; H, 9.02; N, 2.38; S, 5.45.

Preparation Example 2. Preparation of an oxime ester compound of Chemical Formula 3

4 g (13.2 mmol) of a mixed solution of a compound having a mercapto group prepared in Preparation Example 1-2, 2.1 g (27 mmol) of pyridine, and 12 g of dimethylformamide was maintained at -10 ° C or below, and 5.4 g (15 mmol) of ruthenium chloride was added dropwise to the mixed solution.

Subsequently, after the mixed solution was stirred at 5 ° C for 2 hours, ethyl acetate and water were added to the solution for oil-water separation, and the separated organic layer was washed with water.

Thereafter, anhydrous magnesium sulfate was added to the organic layer and dried, and then the solvent was removed from the organic layer to obtain 3.5 g of an oxime ester compound.

The obtained oxime ester compound was analyzed by an elemental analyzer to determine the structure, and it was confirmed to have the structure of the following Chemical Formula 3, and the elemental analysis results were as follows.

Elemental analysis: C, 76.27; H, 9.97; N, 2.04; S, 4.71.

Preparation Example 3. Preparation of an oxime ester compound of Chemical Formula 4

3-1. Preparation of compounds having mercapto groups

20 g (107.5 mmol) of diphenyl sulfide was added to a mixed solution of 100 g (1 mol) of dichloroethane and 21.7 g (163 mmol) of aluminum chloride, and then 9.94 g (at a temperature lower than 6 ° C) 107.5 mmol) of propional chloride was added to the aforementioned solution.

Subsequently, the reaction liquid was stirred for 1 hour, and then it was placed in ice water, and oil-water separation was carried out by adding ethyl acetate.

Thereafter, the separated organic layer was washed with water, anhydrous magnesium sulfate was added to the organic layer and dried, and then solvent was removed from the organic layer to obtain 248 g of a compound having a mercapto group.

The structure of the obtained compound having a mercapto group is the following Chemical Formula 8:

3-2. Preparation of compounds having mercapto groups

5.4 g (52 mmol) of isobutyl nitrite was added to 13 g (47.4 mmol) of the compound having a mercapto group of Chemical Formula 8 prepared in Preparation Example 3-1, 3.6 g (35 mmol) of concentrated hydrochloric acid, and 50 g of dimethyl group. After the mixed solution of formamide was stirred, the mixture was stirred at room temperature for 3.5 hours.

Subsequently, oil-water separation was carried out by adding ethyl acetate and water to the reaction mixture, followed by washing the separated organic layer with water.

Thereafter, hexane was added to the separated organic layer to precipitate a solid, the organic layer was filtered, and the obtained solid was dried under reduced pressure, followed by 251 g. a compound having a mercapto group.

The structure of the obtained compound having a mercapto group is the following Chemical Formula 9:

3-3. Preparation of oxime ester compound of Chemical Formula 4

3.6 g (13.2 mmol) of a mixed solution of a mercapto group-containing compound of Chemical Formula 9 prepared in Preparation Example 3-2, 2.1 g (27 mmol) of pyridine, and 12 g of dimethylformamide was maintained at -10 ° C or below. In the state, 3.7 g (15 mmol) of tetradecyl chloride was added dropwise to the mixed solution.

Subsequently, after the mixed solution was stirred at 5 ° C for 2 hours, ethyl acetate and water were added to the solution to carry out oil-water separation, and the separated organic layer was washed with water.

Thereafter, anhydrous magnesium sulfate was added to the organic layer and dried, and then the solvent was removed from the organic layer to obtain 3.5 g of an oxime ester compound.

The obtained oxime ester compound was analyzed by 1H-NMR and an elemental analyzer, and it was confirmed to have the structure of the following Chemical Formula 4, and its spectrum is shown in Fig. 2, and the elemental analysis results thereof are as follows.

Elemental analysis: C, 72.32; H, 8.15; N, 2.93; S, 6.69.

Preparation Example 4. Preparation of an oxime ester compound of Chemical Formula 5

3.6 g (13.2 mmol) of a mixed solution of a compound having a mercapto group prepared in Preparation Example 3-2, 2.1 g (27 mmol) of pyridine, and 12 g of dimethylformamide was maintained at -10 ° C or below. And 5.4 g (15 mmol) of ruthenium chloride was added dropwise to the mixed solution.

Subsequently, after the mixed solution was stirred at 5 ° C for 2 hours, oil-water separation was carried out by adding ethyl acetate and water, and the separated organic layer was washed with water.

Thereafter, anhydrous magnesium sulfate was added to the organic layer and dried, and then the solvent was removed from the organic layer to obtain 3.5 g of an oxime ester compound.

The obtained oxime ester compound was analyzed by an elemental analyzer to determine the structure, and it was confirmed to have the structure of the following Chemical Formula 5, and the elemental analysis results were as follows.

Elemental analysis: C, 74.84; H, 9.31; N, 2.38; S, 5.41.

<Preparation of Photopolymerizable Composition>

Example 1.

By preparing 50 g of bisphenol A glycerol (1 glycerol/phenol) diacrylate of the following Chemical Formula 10 and 10 g of dipentaerythritol hexaacrylate as a photopolymerizable compound, 40 g of carbon black (colorant) as an additive, 3 g in preparation The oxime ester compound of Chemical Formula 2 prepared in Example 1 was added as a photoinitiator to 100 g of propylene glycol monomethyl ether acetate solvent, followed by stirring for 30 minutes. A photopolymerizable composition.

Example 2.

A photopolymerizable composition was prepared in the same manner as in the above Example 1 except that the oxime ester compound of Chemical Formula 3 prepared in Preparation Example 2 was used as a photoinitiator.

Example 3.

A photopolymerizable composition was prepared in the same manner as in the above Example 1 except that the oxime ester compound of Chemical Formula 4 prepared in Preparation Example 3 was used as a photoinitiator.

Example 4.

A photopolymerizable composition was prepared in the same manner as in the above Example 1 except that the oxime ester compound of Chemical Formula 5 prepared in Preparation Example 4 was used as a photoinitiator.

Comparative Example 1.

Photopolymerization was carried out in the same manner as in the foregoing Example 1, except that 2,4,6-trimethylbenzimidyldiphenylphosphine oxide (TPO, BASF Co.) was used as the photoinitiator. Composition.

Comparative Example 2.

In addition to OXE-01 (1,2-octane-diketone 1-[4-(phenylthio)phenyl]-2-O-benzoguanidinium, Ciba Inc.) was used as a photoinitiator Outside A photopolymerizable composition was prepared in the same manner as in the foregoing Example 1.

Comparative Example 3.

In addition to OXE-02 (1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-O-ethinyl-ethanone oxime, Ciba A photopolymerizable composition was prepared in the same manner as in the foregoing Example 1 except that it was used as a photoinitiator.

Test Example 1. Evaluation of pattern accuracy and linearity of photopolymerizable composition

Each of the photopolymerizable compositions of Examples 1 to 4 and Comparative Examples 1 to 3 was applied onto a glass substrate having a pure surface having a thickness of 1 mm by a spin coater to form a photopolymerizable composition film. The film thickness after drying was 1.0 μm, and the drying was performed at 100 ° C for 5 minutes.

A black matrix was formed by irradiating a photopolymerizable composition film with ultraviolet rays through a negative mask having a line width of 20 μm, followed by spray development in a 0.5 wt% aqueous sodium carbonate solution at 25 ° C for 60 seconds.

The formed black matrix was observed with a microscope, the accuracy of the pattern was measured, and the linearity of the line was evaluated, and the evaluation criteria were as follows.

<Evaluation criteria for accuracy>

Each value was obtained by subtracting 20 μm from the line width of the pattern film cured by using a negative mask having a line width of 20 μm.

When the value is small (5 μm or less), the accuracy is evaluated as high.

<Linear evaluation criteria>

During microscopic observation:

No slight bending or shedding was observed on the straight side of the pattern: ○ slight bending or shedding was observed, but only in a part was observed: Δ slight bending or shedding was observed in all the patterns: ×.

The accuracy and linear results of the pattern are shown in Table 1 below:

As can be seen from the results of the foregoing Table 1, the pattern of the black matrix prepared by the photopolymerizable compositions of Examples 1 to 4 using the oxime ester compound of the present invention as a photoinitiator was slightly increased in line width. And it showed excellent results in accuracy and linearity, and no bending or peeling was observed on the side of the straight line pattern.

However, for the pattern of the black matrix prepared by the photopolymerizable composition of Comparative Example 1 to Comparative Example 3 which is not used as the photoinitiator of the oxime ester of the compound of the present invention, the line width is remarkably increased, and in a straight line pattern Bending or peeling was observed on the side.

Therefore, it can be confirmed that the photopolymerizable composition using the oxime ester compound of the present invention as a photoinitiator has an excellent pattern linearity. Produce a more precise pattern effect.

Claims (10)

An oxime ester compound represented by the following Chemical Formula 1: Wherein R is a C1 to C20 alkyl group, and n is an integer of from 12 to 20. The oxime ester compound according to claim 1, wherein R in the chemical formula 1 is a C1 alkyl group or a C6 alkyl group. The oxime ester compound according to claim 1, wherein the aforementioned Chemical Formula 1 is one or more selected from the group consisting of Chemical Formula 2 to Chemical Formula 5: [Chemical Formula 5] A photopolymerizable composition comprising a photopolymerizable compound and a photoinitiator, wherein the photoinitiator comprises the oxime ester compound of the following Chemical Formula 1: Wherein R is a C1 to C20 alkyl group, and n is an integer of from 12 to 20. The photopolymerizable composition according to claim 4, wherein the photopolymerizable composition comprises an acrylic oligomer having an ethylenically unsaturated bond. The photopolymerizable composition according to claim 5, wherein the aforementioned acrylic oligomer having an ethylenically unsaturated bond has a GPC weight average molecular weight of 200,000 to 1,000,000. The photopolymerizable composition according to claim 4, wherein R in the above Chemical Formula 1 is a C1 alkyl group or a C6 alkyl group. The photopolymerizable composition according to claim 4, wherein the aforementioned Chemical Formula 1 is one or more selected from the group consisting of Chemical Formula 2 to Chemical Formula 5: [Chemical Formula 3] The photopolymerizable composition according to claim 4, wherein the photoinitiator is contained in an amount of from 0.01 to 10 parts by weight based on 100 parts by weight of the photopolymerizable compound. The photopolymerizable composition according to claim 4, wherein the photopolymerizable composition further comprises a solvent.