KR20160115636A

KR20160115636A - Novel para-vinylbenzene compound and photosensitive photoresist composition comprising the same

Info

Publication number: KR20160115636A
Application number: KR1020150076048A
Authority: KR
Inventors: 장화영; 현승학
Original assignee: 장화영
Priority date: 2015-03-27
Filing date: 2015-05-29
Publication date: 2016-10-06

Abstract

Provided is a photocurable composition including: (A) a photocurable compound; and (B) a para-vinylbenzene-containing monomer which is represented by chemical formula 1. In the chemical formula 1, X, Y, Z, and R0 are the same as defined in the present specification. According to the present invention, the photosensitive photoresist composition shows high photocurability.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound containing para-vinylbenzene, and a photosensitive photoresist composition using the compound. [0002]

A novel compound containing para-vinylbenzene, and a photosensitive photoresist composition using the same.

Column spacer, UV overcoat, R.G.B. A photoresist composition for forming an organic insulating film or the like included in a thin film display such as a color resist, a black matrix, a liquid crystal display element, and an OLED includes a binder resin, a photoinitiator, and a polyfunctional monomer having an ethylenic unsaturated bond.

In particular, thin film display devices, such as OLEDs, must be sealed to protect the sensitive components of the device from atmospheric gases (primarily oxygen or moisture).

One embodiment of the present invention provides a novel para-vinylbenzene containing compound.

Another embodiment of the present invention provides a photosensitive photoresist composition comprising para-vinylbenzene-containing monomers having the structure:

Another embodiment of the present invention provides an encapsulated device that is sealed with an organic protective layer formed of a photo-cured product of the photoresist composition.

In one embodiment of the present invention, there is provided a para-vinylbenzene containing compound having a structure represented by the following general formula (1).

&Lt; Formula 1 >

In this formula,

X and Y are each independently a single bond; C = N; CH = CH; Oxygen; sulfur; A substituted or unsubstituted alkyl group having 1-40 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7-40 carbon atoms, or a substituted or unsubstituted alkylaryl group having 7-40 carbon atoms Or a group selected from the group consisting of the following formulas (2) to (5)

Z is, independently of each other, C = N; CH = CH; Oxygen; sulfur; A substituted or unsubstituted alkyl group having 1-40 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7-40 carbon atoms, or a substituted or unsubstituted alkylaryl group having 7-40 carbon atoms Or a group selected from the group consisting of the following formulas (2) to (5)

&Lt; Formula 2 > < EMI ID =

&Lt; Formula 4 > < EMI ID =

In the above formula,

Each independently selected from the group consisting of absent or a group represented by the following formula (6)

(6)

m, n, p, q and r are each independently an integer of 0 to 10,

R0 and the substituent R are the same or different and each independently represents hydrogen, deuterium, fluoro, a substituted or unsubstituted alkyl group having 1-40 carbon atoms, a substituted or unsubstituted alkenyl group having 2-40 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3-40 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5-40 carbon atoms, a substituted or unsubstituted aryl group having 6-40 carbon atoms, a substituted or unsubstituted 7- to 40- A substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms, a substituted or unsubstituted arylvinyl group having 8 to 40 carbon atoms, a substituted or unsubstituted aryl acrylate group having 9 to 40 carbon atoms, An arylalkoxy group having 7 to 30 carbon atoms,

The substituent when substituted is a halogen, a hydroxy group, a nitro group, a cyano group, an imino group, an amino group, a vinyl group, an acrylate group, a carboxyl group, an alkyl group having 1-20 carbon atoms, an aryl group having 6-30 carbon atoms, A cycloalkyl group having 3 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, and combinations thereof,

The alkyl group, aryl group, cycloalkyl group, heteroaryl group and heterocycloalkyl group in the above substituents are CH ₃ ; -C (CH _{³⁾ 3;} -CH (CH ₃₎ _2; -CN; -OCH _3; -CH = CH ₂ ; -C? CH; -C (= O) CH = CH 2; -CH ₂ OC (= O) CH = CH ₂ ; Acrylate groups; A methacrylate group; A phenyl group, and a combination thereof, wherein the substituent is at least one substituent selected from the group consisting of a halogen atom,

* Denotes the connecting part.

The above-mentioned photosensitive photoresist composition comprising the novel para-vinylbenzene-containing compound has a high photo-curability, a low moisture permeability, and a low outgassing amount.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto.

As used herein, the term " substituted ", unless otherwise defined, means that at least one hydrogen atom in the chemical structure or compound is replaced by a halogen, a hydroxy group, An alkenyl group having 1-10 carbon atoms, an alkynyl group having 1-10 carbon atoms, an alkyl group having 1-10 carbon atoms, an alkoxy group having 1-20 carbon atoms, an aryl group having 6-40 carbon atoms, a cycloalkyl group having 3-40 carbon atoms, A heteroaryl group having 1 to 30 carbon atoms, or a heterocycloalkyl group having 2 to 30 carbon atoms.

In the present specification, "a combination thereof" means that two or more substituents are condensed and connected or joined together.

In the structural formulas of the present specification, "*" means a part connected to a chemical formula.

"Hetero" as used herein means that the carbon atom in the formula structure or compound is substituted with at least one atom selected from the group consisting of B, N, O, S and P.

In another embodiment of the present invention, there is provided a compound comprising a novel para-vinylbenzene having the structure of Formula 1:

&Lt; Formula 1 >

In this formula,

&Lt; Formula 2 > < EMI ID =

&Lt; Formula 4 > < EMI ID =

In the above formula,

(6)

m, n, p, q and r are each independently an integer of 0 to 10,

* Denotes the connecting part.

The para-vinylbenzene-containing compound may be any one of compounds represented by the following formulas (7) to (17).

&Lt; Formula 7 > < EMI ID =

&Lt; Formula 10 > < EMI ID =

&Lt; Formula 13 > < EMI ID =

&Lt; Formula 16 > < EMI ID =

In the above formulas (7) to (17)

X, Y, Z and R < 0 > are as defined in formula (1).

The para-vinylbenzene-containing compound can be specifically represented by any one of the following compounds 1 to 72, but is not limited thereto.

A method for synthesizing monomers containing para-vinylbenzene having the structure of the above formula (1) can be found in the following reaction scheme 1.

[Reaction Scheme 1]

X, Y, Z and R0 are the same as defined in Formula 1,

Wherein Q is MgCl or MgBr.

The reaction scheme 1 shows a synthesis mechanism of a part of the monomers including para-vinylbenzene having the structure of the formula (1). However, those skilled in the art can appropriately substitute para-vinylbenzene, It can be easily understood that the monomer containing it can be synthesized.

The novel para-vinylbenzene-containing compound can be used as a photoresist material for forming a pattern by light such as ultraviolet rays and UV light contained in a photoresist composition. Specifically, the novel para-vinylbenzene-containing compound is used in a photo-curing composition used as a sealing material for various electronic devices, and can improve the sealing effect and is used as a photo-crosslinking agent for a photoresist for LCD and OLED So that the outgassing and moisture absorption rate can be reduced, and the life and performance can be improved.

In another embodiment of the present invention, there is provided a photosensitive photoresist composition comprising 1 to 99.5 parts by weight of a polymerizable compound comprising the para-vinylbenzene-containing compound and 0.1 to 40 parts by weight of a photoinitiator.

In another embodiment of the present invention, a photosensitive photoresist composition containing 1 to 99.5 parts by weight of a polymerizable compound containing the para-vinylbenzene-containing compound, 0.1 to 70 parts by weight of a photocurable compound, and 0.1 to 30 parts by weight of a photoinitiator Lt; / RTI >

In another embodiment of the present invention, 1 to 99.5 parts by weight of a polymerizable compound comprising the para-vinylbenzene-containing compound, 0 to 50 parts by weight of an acrylic polymer or an acrylic polymer having an acryl unsaturated bond in a side chain, a photoinitiator 0.01 To 30 parts by weight of a photoresist composition and a solvent.

In another embodiment of the present invention, there is provided a photoresist composition comprising 1 to 99.5 parts by weight of a polymerizable compound comprising a compound containing para-vinylbenzene, 0.1 to 80 parts by weight of a photocurable compound, acrylic resin having acrylic unsaturated bonds in an acrylic polymer or side chain 0 to 40 parts by weight of a polymer, 0.1 to 30 parts by weight of a photoinitiator and a solvent.

The photo-curable compound may be a vinyl group, an acrylate group, a methacrylate-containing monomer, or an oligomer having 2 to 30 monomers polymerized therein,

The monomer may be a halogen, a hydroxyl group, a nitro group, a cyano group, an imino group, an amino group, an amidino group, a vinyl group, an acrylate group, a hydrazine group, a hydrazone group, Substituted or unsubstituted with at least one substituent selected from the group consisting of a cycloalkyl group having from 3 to 30 carbon atoms, a heteroaryl group having from 3 to 30 carbon atoms, a heterocycloalkyl group having from 2 to 30 carbon atoms,

The alkyl group, aryl group, cycloalkyl group, heteroaryl group and heterocycloalkyl group in the substituent group may be any of alkyl group, aryl group, cycloalkyl group, heteroaryl group and heterocycloalkyl group as CH ₃ ; -C (CH _{3) 3;} -CH (CH ₃₎ _2; -CN; -OCH _3; -CH = CH ₂ ; -C? CH; -C (= O) CH = CH 2; -COC (= O) CH = CH 2; Acrylate groups; A methacrylate group; A phenyl group, and a combination thereof. The present invention also provides a photosensitive photoresist composition, which is further substituted or unsubstituted by at least one secondary substituent selected from the group consisting of a phenyl group and a combination thereof.

More specifically, the photo-curing compound is a (meth) acrylate having an alkyl group of 1-30 carbon atoms, a di (meth) acrylate of 2-30 carbon atoms, a tri (meth) acrylate of 3-30 carbon atoms, Tetra (meth) acrylate, and combinations thereof. &Lt; IMAGE >

The photoinitiator may include, without limitation, conventional photopolymerization initiators capable of carrying out a photo-curable reaction. For example, the photopolymerization initiator may include triazine, acetophenone, benzophenone, thioxanthone, benzoin, phosphorus, oxime, or a mixture thereof. Examples of triazine derivatives include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxysti (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) -4,6- (Piperonyl) -6-triazine, 2,4- (trichloromethyl (4'-methoxystyryl) -6-triazine or mixtures thereof.

Examples of the acetophenone-based solvents include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloro 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2,2'-dichloroacetophenone, Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, or mixtures thereof.

Examples of the benzophenone-based compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-dichlorobenzo Phenone, 3,3'-dimethyl-2-methoxybenzophenone, or a mixture thereof.

Examples of thioxanthone include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone or And mixtures thereof.

The benzoin group may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal or a mixture thereof.

Phosphorous can be bisbenzoylphenylphosphine oxide, benzoyldiphenylphosphine oxide or mixtures thereof.

The oxime system was prepared by reacting 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (o-acetyloxime) 2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, or mixtures thereof.

The photoinitiator may be contained in the photosensitive photoresist composition in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the photocurable compound (A) / (B) monomers containing para-vinylbenzene of the general formula (1) in the photosensitive photoresist composition. Within the above range, photopolymerization can sufficiently take place at the time of exposure, and the transmittance can be prevented from being lowered due to the unreacted initiator remaining after the photopolymerization. Preferably 0.4 to 11 parts by weight.

The photosensitive photoresist composition may further include at least one coloring material selected from the group consisting of red, green, blue, black and white.

Further, the coloring material refers to a compound which appears as red, green, blue, black and white in the visible light and UV region.

In another embodiment of the present invention, there is provided an organic film formed from a photosensitive photoresist composition comprising the para-vinylbenzene-containing compound.

In another embodiment of the present invention, there is provided an apparatus comprising the organic film.

In another embodiment of the present invention, there is provided an apparatus for applying a film formed from a photoresist composition as an encapsulant.

The device may be a flexible organic light emitting device, an organic light emitting device (OLED), a solar cell, a lighting device, a TFT-LCD, a color filter, a metal sensor pad, a microdisk laser, an integrated circuit, , A charge coupled device, an organic integrated circuit (O-IC), a light emitting polymer, an organic thin film transistor (O-TFT), an organic light emitting transistor (O-LET) or an organic field effect transistor (O-FET).

Hereinafter, examples and comparative examples of the present invention will be described. The following embodiments are only examples of the present invention, and the present invention is not limited to the following embodiments.

(Example)

Synthesis Example 1: Preparation of compound [13]

A compound containing para-vinylbenzene represented by the above-mentioned compound 13 was prepared according to the following Reaction Scheme 2.

[Reaction Scheme 2]

Preparation of intermediate compound [13-3]

64 mL (64 mmol) of the compound [13-2] (1M in diethyl ether) was added to a 0.5 L reaction flask under nitrogen atmosphere and 10 g (40 mol) of the compound [46-1] diluted by mixing with 0.1 L of diethyl ether Drop it. After completion of the reaction, the temperature is lowered to 0 to 4 ° C, 57 ml of a 5% sulfuric acid solution is slowly added, and 57 ml of ethyl acetate is added thereto and stirred. The organic layer was separated and washed with purified water 5 times, then the water was removed and the filtrate was concentrated under reduced pressure. This mixture was purified by column chromatography to give 7.1 g (53%) of the intermediate compound [13-3].

MS / FAB, C ₂₄ H ₃₄ O = 338, found m / z = 339 (M ⁺ )

Preparation of intermediate compound [13-4]

In a 1 L reaction flask, 7.1 g (21 mmol) of the intermediate compound [13-3], 0.07 L of acetic acid and 0.2 mL of concentrated sulfuric acid as a catalyst were added under nitrogen atmosphere and stirred at 100 占 폚. After completion of the reaction, the temperature is lowered and the reaction is terminated by slowly adding distilled water at 0 to 4 ° C. Then, 0.3 L of ethyl acetate is added and stirred. The organic compounds were separated and washed with 1N NaOH aqueous solution to pH 8. The water was removed and concentrated under reduced pressure. The organic solvent was removed to obtain 5.9 g (87%) of intermediate compound [13-4].

MS / FAB, C ₂₄ H ₃₂ = 320, found m / z = 320 (M ⁺ )

Preparation of intermediate compound [13-5]

In a 1 L reaction flask, 0.13 L of ethyl acetate and 20 mL of methanol are added to 5.9 g (18 mmol) of the intermediate compound [13-4] in a nitrogen atmosphere and the mixture is stirred. Add 2 g of 10% Pd / C (10% palladium on activated charcoal) and slowly stir the hydrogen gas in the reaction solvent. After completion of the reaction, the reaction mixture was filtered through silica gel, and the organic solvent was concentrated under reduced pressure to obtain 5.4 g (94%) of intermediate compound [13-5].

MS / FAB, C ₂₄ H ₃₄ = 322, found m / z = 323 (M ⁺ )

Preparation of intermediate compound [13-7]

In a 0.5 L reaction flask, 42 mL of dichloromethane was placed in a nitrogen atmosphere, and then 7.3 g (55 mmol) of aluminum chloride was added at 0 ° C. and 5.6 g (55 mmol) of the compound [13-6] -5] is dissolved in 9 mL of dichloromethane and then slowly added dropwise. After confirming the completion of the reaction, slowly pour the reaction solution into 0.1 L of a 10% aqueous sulfuric acid solution, terminate the reaction, add dichloromethane and stir. The organic layer is separated, the water is removed, and the filtrate is concentrated under reduced pressure. This mixture was purified by column chromatography to obtain 5.4 g (80%) of Intermediate Compound [13-7].

_{MS / FAB, C 28 H 38} O 2 = 406, found m / z = 406 (M +)

Preparation of intermediate compound [13-8]

In a 1 L reaction flask, 5.4 g (13 mmol) of the intermediate compound [13-7] and 0.2 L of methanol are placed under a nitrogen atmosphere, and 2 g (48 mmol) of sodium borohydride is slowly added at 0 to 4 ° C. The temperature is slowly raised to room temperature and stirring is continued for 3 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove the organic solvent. The concentrate was diluted with 0.1 L of dichloromethane, washed with saturated brine, and then the organic layer was separated, washed with water several times to neutralize , And the organic layer was separated and concentrated under reduced pressure to give 5.2 g (95%) of intermediate compound [13-8].

_{MS / FAB, C 28 H 42} O 2 = 410, found m / z = 411 (M +)

Preparation of compound [13]

In a 0.5 L reaction flask, 0.06 L of dimethyl sulfoxide was added to and dissolved in 5.2 g (13 mmole) of the intermediate compound [13-8] in a nitrogen atmosphere, 0.3 g (2 mmol) of zinc chloride was added at 70 to 90 ° C, Acetic acid (TFA) (1 mL) is slowly added dropwise, and the mixture is refluxed and stirred. After completion of the reaction, the reaction mixture was cooled to room temperature and poured into ice water. Ethyl acetate was added to extract the organic layer. The organic layer was separated, the water was removed, and the filtrate was concentrated under reduced pressure. This mixture was purified by column chromatography to give 1.5 g (31%) of the desired compound [13].

_{MS / FAB, C 28 H 38} = 374, found m / z = 374 (M +)

Synthesis Example 2: Preparation of compound [46]

The compound containing para-vinylbenzene represented by the above-mentioned compound 46 was prepared according to the following reaction scheme 3.

[Reaction Scheme 3]

Preparation of intermediate compound [46-3]

In a 0.5 L reaction flask, 75 mL of dichloromethane was placed in a nitrogen atmosphere, 14 g (100 mmol) of aluminum chloride was added at 0 to 4 ° C and 10 g (100 mmol) of the compound [13-6] 1] are dissolved in 15 mL of dichloromethane and then slowly added dropwise. After confirmation of the completion of the reaction, the reaction solution is slowly poured into 0.1 L of a 10% aqueous sulfuric acid solution at 0 to 10 ° C, the reaction is terminated, and dichloromethane is added thereto and stirred. The organic layer is separated, the water is removed, and the filtrate is concentrated under reduced pressure. This mixture was purified by column chromatography (EA: Hex = 1: 2) to prepare 11 g (90%) of intermediate compound [46-3].

_{MS / FAB, C 28 H 28} O 3 = 412, found m / z = 412 (M +)

Preparation of intermediate compound [46-4]

In a 1 L reaction flask, 11 g (26 mmol) of the intermediate compound [46-3] and 0.4 L of methanol are placed under a nitrogen atmosphere, and 4 g (97 mmol) of sodium borohydride is slowly added at 0 to 4 ° C. The temperature is slowly raised to room temperature and stirring is continued for 3 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove the organic solvent. The resulting concentrate was diluted with 0.1 L of chloroform, washed with saturated brine, and then the organic layer was separated, washed again five times with neutral water , And the organic layer was separated and concentrated under reduced pressure to prepare 11 g (97%) of the intermediate compound [46-4].

_{MS / FAB, C 28 H 34} O 3 = 418, found m / z = 418 (M +)

Preparation of compound [46]

In a 0.5 L reaction flask, 0.1 L of dimethyl sulfoxide was added to and dissolved in 11 g (26 mmole) of the intermediate compound [46-4] in a nitrogen atmosphere, and then 0.6 g (4 mmol) of zinc chloride was added at 70 to 90 ° C and trifluoroacetic acid (TFA) is slowly added dropwise, and the mixture is stirred under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature and poured into ice water. Ethyl acetate was added to extract the organic layer. The organic layer was separated, the water was removed, and the filtrate was concentrated under reduced pressure. This mixture was purified by column chromatography (MC / n-Hx = 1/19) to give 3 g (35%) of the target compound [46].

_{MS / FAB, C 28 H 28} = 364, found m / z = 364 (M +)

Synthesis Example 3: Preparation of compound [71]

A compound containing para-vinylbenzene represented by the above-described compound 71 was prepared according to the following Reaction Scheme 4. [

[Reaction Scheme 4]

Preparation of intermediate compound [71-1]

19 g (67 mmol) of the intermediate compound [46-1] was dissolved in 0.1 L of dichloromethane, and 10 g (56 mmol) of N-bromosuccinimide was dissolved in 0.1 L of dichloromethane, slowly dropped at 0 to 4 ° C, Stir time. The reaction solution was poured into purified water, and the solid was filtered, recrystallized from dichloromethane and methanol, and purified by column chromatography to obtain 7 g (34%) of intermediate compound [71-1].

_{MS / FAB, C 22 H 21} Br = 365, found m / z = 365 (M +)

Preparation of intermediate compounds [71-2], [71-3] and [71-4]

(88%) of Intermediate Compound [71-2] and intermediate compound [71] were obtained in the same manner as in the synthesis of Intermediate Compounds [13-7], [13-8] and [13] -3] and 2.3 g of the intermediate compound [71-4].

Intermediate compound [71-2]: MS / FAB, C ₂₆ H ₂₅ BrO ₂ = 499, found m / z = 499 (M ⁺

Intermediate compound [71-3]: MS / FAB, C ₂₆ H ₂₉ BrO ₂ = 453, found m / z = 453 (M ⁺

Intermediate compound [71-4]: MS / FAB, C ₂₆ H ₂₅ Br = 445, found m / z = 445 (M ⁺

Preparation of compound [71]

(5 mmol) of the intermediate compound [71-4], 0.4 g (6 mmol) of the compound [71-5], 0.8 g (9 mmol) of sodium tert-butoxide and 20 mL of toluene were added to a 0.1 L reaction flask under a nitrogen atmosphere, Lt; / RTI > The mixture was cooled to room temperature, and 50 mL of distilled water and 50 mL of ethyl acetate were added to separate layers, and the obtained organic layer was distilled under reduced pressure. This mixture was purified by column chromatography to give 3 g (80%) of the desired compound [71].

MS / FAB, C ₅₄ H ₅₆ N ₂ = 733, found m / z = 733 (M ⁺ ).

Examples 1 to 9 and Comparative Examples 1 to 3

(A) a photo-curing compound, (B) a monomer containing para-vinylbenzene of the formula (1) (unused in Comparative Examples 1-3) and (c) a photopolymerization initiator according to the composition shown in the following Table 2 Composition (unit: parts by weight) was put into a 125 ml brown polypropylene bottle and mixed for 3 hours using a shaker to prepare a photo-curable composition.

Specific specifications of the photocurable compound (A) used in Examples 1 to 9 and Comparative Examples 1 to 3, the monomer (B) containing para-vinylbenzene of Chemical Formula 1 and the photoinitiator (C) are as follows.

(A) Photo-curing compound (manufactured by Aldrich):

(a1) hexyl acrylate

(a2) hexanediol diacrylate

(a3) pentaerythritol tetraacrylate

(B) Monomers comprising para-vinyl benzene of formula (1)

(b1) The monomer (b1) prepared in Synthesis Example 1

(b2) The monomer prepared in Synthesis Example 2

(b3) The monomer prepared in Synthesis Example 3

(C) Photoinitiator (BASF):

(c1) Darocur TPO

(c2) Irgacure 907

(c3) OXE-01

Property evaluation method

1: Evaluation of outgassing amount

The photocurable composition was applied on a glass substrate by spraying and irradiated at 100 mW / cm < ² > for 10 seconds to be UV-cured to obtain an organic protective layer specimen of 20 cm x 20 cm x 3 m (width x length x thickness). For the specimen, use a GC / MS instrument (Perkin Elmer Clarus 600). (Flow rate: 1.0 mL / min, average velocity = 32 cm / s) as a mobile phase using a DB-5 MS column (length: 30 m, diameter: 0.25 mm, , The split ratio is 20: 1, the temperature condition is kept at 40 占 폚 for 3 minutes, then the temperature is raised at a rate of 10 占 폚 / min, and then the temperature is maintained at 320 占 폚 for 6 minutes. The adsorbent was Tenax GR (5% phenylmethylpolysiloxane), the glass size was 20 cm x 20 cm, the collecting container was Tedlar bag, the collection temperature was 90 ° C, the collection time was 30 minutes, the N2 purge flow rate was 300 mL / . As a standard solution, a calibration curve is prepared at 150 ppm, 400 ppm, and 800 ppm of a toluene solution in n-hexane, and R2 value is obtained as 0.9987. The above conditions are summarized in Table 1 below.

[Table 1]

The outgassing amount evaluation results are shown in Table 3 below.

2: Evaluation of moisture permeability

Evaluation of water vapor transmission rate: A moisture permeability meter (PERMATRAN-W 3/33, MOCON) was used. The photocurable composition was applied by spraying on an Al sample holder and irradiated at 100 mW / cm < ² > for 10 seconds to UV cure to form a cured specimen of 5 mu m thick. The moisture permeability was measured for 24 hours at 37.8 ° C and 100% relative humidity using a moisture permeability meter (PERMATRAN-W 3/33, MOCON) for a film thickness of 5 μm.

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

3: Evaluation of light curing rate

Sight rate was determined the intensity of the absorption peak in the FT-IR 1635cm ^-1 vicinity using a (NICOLET 4700, Thermo Co.) (C = C), 1510cm -1 vicinity (CH) with respect to the photocurable composition. A photocurable composition is applied on a glass substrate by spraying and irradiated at 100 mW / cm < ² > for 10 seconds to be UV-cured to obtain a specimen of 20 cm x 20 cm x 3 mu m (width x length x thickness). Obtain a cured film, and by using the FT-IR (NICOLET 4700, Thermo Co.) to measure the intensity of the absorption peak in the vicinity of 1635cm ^-1 (C = C), 1510cm ^-1 vicinity (CH).

The photo-curing rate is calculated according to the following formula (1).

Photocuring rate (%) = | 1- (A / B) | x 100

In the formula 1, A is the ratio of the intensity of the absorption peak of 1635cm ^-1 in the vicinity of the intensity of the absorption peak in the vicinity of 1510cm ^-1 for the cured film, B is in the vicinity of 1510cm ^-1 for the photocurable composition Of the absorption peak at around 1635 cm < ^-1 >

The evaluation results of the photo-curing rate are shown in Table 2 below.

[Table 2]

As shown in Table 2, the outgassing amounts in the outgassing evaluations of Examples 1 to 9 according to the embodiment of the present invention were significantly lower than those of Comparative Examples 1 to 3, and the coating film formed of the photo- Was significantly lower than that of Comparative Examples 1 to 3. In addition, the photocurable compositions of Examples 1 to 9 according to the embodiments of the present invention were higher than those of the photocurable compositions of Comparative Examples 1 to 3. On the other hand, the photocurable compositions of Comparative Examples 1 to 3, which do not contain monomers containing para-vinylbenzene of the above formula (1), have a photo-curability ratio in comparison with the photocurable compositions of Examples 1 to 9 according to the embodiment of the present invention It was confirmed that it was low, the moisture permeability was high, and the amount of outgas was high, which was inferior, and the effect of the present invention could not be realized.

Although the preferred embodiments of the present invention have been described in detail, the scope of the present invention is not limited thereto

Claims

A compound comprising para-vinylbenzene having the structure of Formula (1).
&Lt; Formula 1 >

In this formula,
X and Y are each independently a single bond; C = N; CH = CH; Oxygen; sulfur; A substituted or unsubstituted alkyl group having 1-40 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7-40 carbon atoms, or a substituted or unsubstituted alkylaryl group having 7-40 carbon atoms Or a group selected from the group consisting of the following formulas (2) to (5)
Z is, independently of each other, C = N; CH = CH; Oxygen; sulfur; A substituted or unsubstituted alkyl group having 1-40 carbon atoms, a substituted or unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7-40 carbon atoms, or a substituted or unsubstituted alkylaryl group having 7-40 carbon atoms Or a group selected from the group consisting of the following formulas (2) to (5)

&Lt; Formula 2 >< EMI ID =

&Lt; Formula 4 >< EMI ID =

In the above formula,
Each independently selected from the group consisting of absent or a group represented by the following formula (6)
(6)

m, n, p, q and r are each independently an integer of 0 to 10,
R0 and the substituent R are the same or different and each independently represents hydrogen, deuterium, fluoro, a substituted or unsubstituted alkyl group having 1-40 carbon atoms, a substituted or unsubstituted alkenyl group having 2-40 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3-40 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5-40 carbon atoms, a substituted or unsubstituted aryl group having 6-40 carbon atoms, a substituted or unsubstituted 7- to 40- A substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms, a substituted or unsubstituted arylvinyl group having 8 to 40 carbon atoms, a substituted or unsubstituted aryl acrylate group having 9 to 40 carbon atoms, An arylalkoxy group having 7 to 30 carbon atoms,
The substituent when substituted is a halogen, a hydroxy group, a nitro group, a cyano group, an imino group, an amino group, a vinyl group, an acrylate group, a carboxy group, an alkyl group having 1-20 carbon atoms, an aryl group having 6-30 carbon atoms, A cycloalkyl group having 3 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, and combinations thereof,
The alkyl group, aryl group, cycloalkyl group, heteroaryl group and heterocycloalkyl group in the above substituents are CH ₃ ; -C (CH _{³⁾ 3;} -CH (CH ₃₎ _2; -CN; -OCH _3; -CH = CH ₂ ; -C? CH; -C (= O) CH = CH 2; -CH ₂ OC (= O) CH = CH ₂ ; Acrylate groups; A methacrylate group; A phenyl group, and a combination thereof, wherein the substituent is at least one substituent selected from the group consisting of a halogen atom,
* Denotes the connecting part.

The para-vinylbenzene-containing compound may be any one of compounds represented by the following formulas (7) to (17).
&Lt; Formula 7 >< EMI ID =

&Lt; Formula 10 >< EMI ID =

&Lt; Formula 13 >< EMI ID =

&Lt; Formula 16 >< EMI ID =

In the above formulas (7) to (17)
X, Y, Z and R < 0 > are as defined in formula (1).

The method according to claim 1,
The para-vinylbenzene-containing compound is represented by any one of the following compounds 1 to 72
Para-vinylbenzene.

1 to 99.5 parts by weight of a polymerizable compound comprising a compound containing para-vinylbenzene according to any one of claims 1 to 3 and 0.1 to 40 parts by weight of a photoinitiator.

1 to 99.5 parts by weight of a polymerizable compound containing a compound containing para-vinylbenzene according to any one of claims 1 to 3, 0.1 to 70 parts by weight of a photocurable compound and 0.1 to 30 parts by weight of a photoinitiator Resist composition.

1 to 99.5 parts by weight of a polymerizable compound comprising a compound containing para-vinylbenzene according to any one of claims 1 to 3, 0 to 50 parts by weight of an acrylic polymer or an acrylic polymer having an acryl unsaturated bond in a side chain, 0.01 to 30 parts by weight and a solvent.

1 to 99.5 parts by weight of a polymerizable compound comprising a compound containing para-vinylbenzene according to any one of claims 1 to 3, 0.1 to 80 parts by weight of a photo-curable compound, 0.1 to 80 parts by weight of an acrylic polymer having an acrylic unsaturated bond 0 to 40 parts by weight of an acrylic polymer, 0.1 to 30 parts by weight of a photoinitiator and a solvent.

The method as claimed in claim 5,
The photocurable compound may be a vinyl group, an acrylate group, or a methacrylate-containing monomer, or an oligomer obtained by polymerizing 2-30 of the monomers,
The monomer may be a halogen, a hydroxyl group, a nitro group, a cyano group, an imino group, an amino group, an amidino group, a vinyl group, an acrylate group, a hydrazine group, a hydrazone group, Substituted or unsubstituted with at least one substituent selected from the group consisting of a cycloalkyl group having from 3 to 30 carbon atoms, a heteroaryl group having from 3 to 30 carbon atoms, a heterocycloalkyl group having from 2 to 30 carbon atoms,
The alkyl group, aryl group, cycloalkyl group, heteroaryl group and heterocycloalkyl group in the substituent group may be any of alkyl group, aryl group, cycloalkyl group, heteroaryl group and heterocycloalkyl group as CH ₃ ; -C (CH _{3) 3;} -CH (CH ₃₎ _2; -CN; -OCH _3; -CH = CH ₂ ; -C? CH; -C (= O) CH = CH 2; -COC (= O) CH = CH 2; Acrylate groups; A methacrylate group; A phenyl group, and a combination thereof. The photoresist composition of claim 1, wherein the photoresist composition is a photoresist composition.

The method according to claim 5, 7, and 8,
(Meth) acrylate having a C 1-30 alkyl group, a di (meth) acrylate having a carbon number of 2-30, a tri (meth) acrylate having a carbon number of 3-30, a tetra (Meth) acrylate, and combinations thereof.

The method according to any one of claims 4 to 9,
The photosensitive photoresist composition further comprises at least one colorant selected from the group consisting of red, green, blue, black and white, wherein the colorant is selected from the group consisting of a visible photoresist and a photosensitive photoresist visible in UV at red, green, blue, Composition.

An organic film formed from a photosensitive photoresist composition comprising a compound comprising para-vinylbenzene according to any one of claims 1 to 4.

An apparatus comprising an organic film according to claim 11.

An apparatus for applying a film formed from a photosensitive photoresist composition comprising a para-vinylbenzene-containing compound according to any one of claims 1 to 4 as an encapsulating material.

The method according to claim 12 or 13,
The device may be a flexible organic light emitting device, an organic light emitting device (OLED), a solar cell, a lighting device, a TFT-LCD, a color filter, a metal sensor pad, a microdisk laser, an integrated circuit, , A charge coupled device, an organic integrated circuit (O-IC), a light emitting polymer, an organic thin film transistor (O-TFT), an organic light emitting transistor (O-LET) or an organic field effect transistor (O-FET).