KR20150086050A - Novel sulfonylimide salt compouds, preparation thereof, photosensitive resin composition and adhesive composition having the same - Google Patents

Novel sulfonylimide salt compouds, preparation thereof, photosensitive resin composition and adhesive composition having the same Download PDF

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Publication number
KR20150086050A
KR20150086050A KR1020140006184A KR20140006184A KR20150086050A KR 20150086050 A KR20150086050 A KR 20150086050A KR 1020140006184 A KR1020140006184 A KR 1020140006184A KR 20140006184 A KR20140006184 A KR 20140006184A KR 20150086050 A KR20150086050 A KR 20150086050A
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Prior art keywords
chemical formula
group
compound
carbon atoms
pattern
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KR1020140006184A
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Korean (ko)
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최한영
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동우 화인켐 주식회사
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Priority to KR1020140006184A priority Critical patent/KR20150086050A/en
Priority to CN201480073414.5A priority patent/CN106414318A/en
Priority to JP2016546052A priority patent/JP2017508723A/en
Priority to PCT/KR2014/010941 priority patent/WO2015108271A1/en
Publication of KR20150086050A publication Critical patent/KR20150086050A/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
    • C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors

Abstract

The present invention relates to a novel sulfonylimide salt compound, a photo acid generator and a photosensitive resin composition including the same and, more specifically, a photosensitive resin composition, which includes a sulfonylimide salt compound denoted by chemical formula 1 and accordingly has good photosensitivity, thereby significantly increasing a curing rate.

Description

TECHNICAL FIELD The present invention relates to a novel sulfonylimide salt compound, a process for producing the same, and a photoacid generator and a photosensitive resin composition containing the same. BACKGROUND ART [0002]

The present invention relates to a photosensitive resin composition comprising a sulfonylimide salt compound.

The photosensitive resin is a representative functional polymer material practically used in production of various precision electronic and information industrial products and is currently being used for the production of high-tech industries, especially semiconductors and displays. Generally, a photosensitive resin means a polymer compound in which a chemical change of a molecular structure occurs within a short period of time by light irradiation, and a change in physical properties such as solubility, coloring, and curing for a specific solvent occurs. By using a photosensitive resin, fine precision processing is possible, energy and raw materials can be largely reduced as compared with a thermal reaction process, and work can be performed quickly and accurately in a small installation space, , Photocurable surface coating materials, and so on.

Among them, in the display field, the photosensitive resin composition is used for forming various photo-curing patterns such as a photoresist, an insulating film, a protective film, a color filter, a black matrix, and a column spacer. Specifically, the photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photo-curable pattern. In order to improve the process yield and improve the physical properties of the application object in this process, a photosensitive resin having a high sensitivity A composition is required.

Korean Patent Publication No. 2008-0046560 discloses a photosensitive resin composition containing a separate adhesion enhancer, but fails to solve the problem of high sensitivity.

Korean Patent Publication No. 2008-0046560

The present invention provides a sulfonylimide salt compound and a photoacid initiator containing the sulfonylimide salt compound, which can improve the photosensitivity and cure rate when used in a photosensitive resin composition.

1. A sulfonylimide salt compound represented by the following formula (1): < EMI ID =

[Chemical Formula 1]

Figure pat00001

(Wherein Y & lt ; + & gt ; is a compound represented by the following formula (2) or (3)

(2)

Figure pat00002

(3)

Figure pat00003

R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group,

Figure pat00004
,
Figure pat00005
, A linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group or an alkylcarbonyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms, or R 4 and R 5 To form a ring having 4 to 6 carbon atoms,

The aryl group may be substituted to share one bond with the bonded benzene ring,

R 1 , R 2 , R 3 , R 4 and R 5 may each independently be substituted at least once in one ring and may be different substituents when substituted one or more times.

2. The compound according to 1 above, wherein the compound of formula 2 is selected from the group consisting of compounds represented by the following formulas 4 to 11:

[Chemical Formula 4]

Figure pat00006

[Chemical Formula 5]

Figure pat00007

[Chemical Formula 6]

Figure pat00008

(7)

Figure pat00009

[Chemical Formula 8]

Figure pat00010

[Chemical Formula 9]

Figure pat00011

[Chemical formula 10]

Figure pat00012

(11)

Figure pat00013
.

3. The compound according to claim 1, wherein the compound of formula (3) is a sulfonylimide salt compound selected from the group consisting of compounds represented by the following formulas (12) to (30)

[Chemical Formula 12]

Figure pat00014

[Chemical Formula 13]

Figure pat00015

[Chemical Formula 14]

Figure pat00016

[Chemical Formula 15]

Figure pat00017

[Chemical Formula 16]

Figure pat00018

[Chemical Formula 17]

Figure pat00019

[Chemical Formula 18]

Figure pat00020

[Chemical Formula 19]

Figure pat00021

[Chemical Formula 20]

Figure pat00022

[Chemical Formula 21]

Figure pat00023

[Chemical Formula 22]

Figure pat00024

(23)

Figure pat00025

≪ EMI ID =

Figure pat00026

(25)

Figure pat00027

(26)

Figure pat00028

(27)

Figure pat00029

(28)

Figure pat00030

[Chemical Formula 29]

Figure pat00031

(30)

Figure pat00032
.

4. A sulfonylimide salt compound represented by the general formula (1) above is prepared by reacting a compound represented by the following general formula (31) with a compound represented by the following general formula (32) or (33) :

(31)

Figure pat00033

(32)

Figure pat00034

(33)

Figure pat00035

(Wherein Z is a monovalent cation, W is a halogen atom,

R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group,

Figure pat00036
,
Figure pat00037
, A linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group or an alkylcarbonyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms, or R 4 and R 5 To form a ring having 4 to 6 carbon atoms,

The aryl group may be substituted to share one bond with the bonded benzene ring,

R 1 , R 2 , R 3 , R 4 and R 5 may each independently be substituted at least once in one ring and may be different substituents when substituted one or more times.

5. A photoacid generator comprising a sulfonylimide salt compound of any one of the above 1 to 3.

6. A photosensitive resin composition comprising the photoacid generator and the photopolymerizable compound of the above 5.

7. The photosensitive resin composition according to 6 above, wherein the sulfonylimide salt compound is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the photopolymerizable compound.

8. A photocurable pattern produced from the photosensitive resin composition of the above 6.

9. The electrophotographic photoreceptor according to the above 8, wherein the photocurable pattern is selected from the group consisting of an adhesive layer, an array planarizing film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a color filter pattern, a black matrix pattern, a column spacer pattern and a black column spacer .

10. An image display apparatus comprising the photocuring pattern of the above 9.

The sulfonylimide salt compound of the present invention imparts excellent photosensitivity to the photosensitive resin composition and can significantly improve the curing rate.

The present invention relates to a sulfonylimide salt compound which contains a novel sulfonylimide salt compound and exhibits excellent photosensitivity when used in a photosensitive resin composition, thereby remarkably improving the curing rate.

Hereinafter, the present invention will be described in detail.

<Sulfonylimide salt compound>

The sulfonylimide salt compound of the present invention is represented by the following formula (1).

[Chemical Formula 1]

Figure pat00038

Wherein Y &lt; + &gt; is a compound represented by the following formula (2) or (3);

(2)

Figure pat00039

(3)

Figure pat00040

R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group,

Figure pat00041
,
Figure pat00042
, A linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group or an alkylcarbonyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms, or R 4 and R 5 And R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom or a halogen atom, May be substituted at least once in one ring and may be different substituents when substituted one or more times.

The sulfonylimide salt compound represented by the formula (1) according to the present invention can be used as a photoacid generator, and when it is used in a photosensitive resin composition, it exhibits excellent photosensitivity and the curing rate can be remarkably improved.

More specifically, the anionic compound of the sulfonylimide salt compound includes an electron-withdrawing substituent, thereby increasing the cationic property to the nitrogen atom, thereby stabilizing the anionic part of the compound and at the same time increasing the activity of the cationic part Can be increased. It is considered that the cationic part with increased activity increases the photosensitivity of the photosensitive resin composition in the exposure step and significantly improves the curing rate.

In the sulfonylimide salt compound represented by the above formula (1), specific examples of the compound of the formula (2) include the compounds represented by the following formulas (4) to (11).

[Chemical Formula 4]

Figure pat00043

[Chemical Formula 5]

Figure pat00044

[Chemical Formula 6]

Figure pat00045

(7)

Figure pat00046

[Chemical Formula 8]

Figure pat00047

[Chemical Formula 9]

Figure pat00048

[Chemical formula 10]

Figure pat00049

(11)

Figure pat00050
.

In the sulfonylimide salt compound represented by the formula (1), the compound represented by the formula (3) is a compound represented by the following formulas (12) to (30).

[Chemical Formula 12]

Figure pat00051

[Chemical Formula 13]

Figure pat00052

[Chemical Formula 14]

Figure pat00053

[Chemical Formula 15]

Figure pat00054

[Chemical Formula 16]

Figure pat00055

[Chemical Formula 17]

Figure pat00056

[Chemical Formula 18]

Figure pat00057

[Chemical Formula 19]

Figure pat00058

[Chemical Formula 20]

Figure pat00059

[Chemical Formula 21]

Figure pat00060

[Chemical Formula 22]

Figure pat00061

(23)

Figure pat00062

&Lt; EMI ID =

Figure pat00063

(25)

Figure pat00064

(26)

Figure pat00065

(27)

Figure pat00066

(28)

Figure pat00067

[Chemical Formula 29]

Figure pat00068

(30)

Figure pat00069
.

&Lt; Preparation of sulfonylimide salt compound >

The sulfonylimide salt compound represented by the formula (1) of the present invention is prepared by reacting a compound represented by the following formula (31) with a compound represented by the following formula (32) or (33).

(31)

Figure pat00070

(32)

Figure pat00071

(33)

Figure pat00072

In the formula, Z is a monovalent cation, and examples thereof include a sodium ion and a potassium ion, W is a halogen atom, and the other substituents are the same as those described above.

First, the compound of formula (30) and the compound of formula (31) or (32) are dissolved in a solvent, respectively, and stirred at room temperature for 30 minutes to 4 hours to react. The solvent used in the reaction is not particularly limited as long as it can dissolve the reactants, preferably distilled water. In the above reaction step, a catalyst may be further added if necessary.

Thereafter, a solvent may be added to the mixed solution and mixed, followed by extracting the product. The above step may be carried out by sufficiently mixing the product so that the product is dissolved in the organic solvent and can be separated from the unreacted product, and then extracting only the organic layer. If the solvent used in the step is soluble in the product, And is preferably toluene.

Finally, a step of subjecting the extracted organic layer to a vacuum distillation may be carried out to remove an organic solvent and a reaction residue to obtain a final product.

&Lt;

The present invention also provides a photoacid generator comprising the sulfonylimide salt compound. As described above, the sulfonylimide salt compound of the present invention imparts excellent photosensitivity to the photosensitive resin composition and can significantly improve the curing rate, and thus can be usefully used as a photoacid generator.

<Photosensitive resin composition>

The present invention also provides a photosensitive resin composition comprising a photoacid generator and a photopolymerizable compound according to the present invention.

The photoacid generator of the present invention can sensitize the photosensitive resin composition as described above to significantly improve the curing rate.

The content of the photoacid generator is not particularly limited and may be 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the photopolymerizable compound. When it is contained within the above range, the sensitivity is improved, the exposure time is shortened and the fishy property is improved, and the strength of the formed pattern and the smoothness of the surface can be improved. When the photoacid generator is contained in an amount of 10 parts by weight or more, the pattern hardening ratio may be improved, but the color of the pattern may change slightly after curing by absorbing a part of visible light.

The photopolymerizable compound of the present invention is not particularly limited as long as it is curable with the photoacid generator of the present invention, and may be, for example, an epoxy compound, an oxetane compound, or a vinyl ether compound, preferably an epoxy compound.

Specific examples of the epoxy compound include a monofunctional epoxy compound, a bifunctional epoxy compound, a trifunctional epoxy compound and a tetrafunctional epoxy compound, and preferably a monofunctional epoxy compound and a bifunctional epoxy compound It is good. These may be used alone or in combination of two or more.

Specific examples of the monofunctional epoxy compound include glycidylphenyl ether and 1,2-epoxyethylbenzene. The bifunctional epoxy compound is 3,4-epoxycyclohexylmethyl-3 ', 4'- Epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'- epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified, 4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate 4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), (3,4-epoxycyclohexylmethyl) ether of tylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxycyclohexahydrophthalate, di-2-ethylhexyl epoxycyclohexahydrophthalate . These may be used alone or in combination of two or more.

Specific examples of the oxetane-based compound include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) (Methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) 4-trifluoromethyloxetane, etc. These may be used alone or in combination of two or more.

Specific examples of the monomer capable of synthesizing the vinyl ether-based resin include styrene, vinyltoluene, methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, Benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether. These may be used alone or in combination of two or more.

The photosensitive resin composition of the present invention may further contain additives such as a colorant, a silane coupling agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an antiflocculant as necessary.

In addition, the photosensitive resin composition of the present invention may further comprise an alkali-soluble resin or the like as needed, and may be used as a composition capable of developing after curing. As the alkali-soluble resin, an alkali-soluble resin used in the art can be used without any particular limitation. In this case, it may further include an appropriate solvent used in the art.

<Light curing pattern>

An object of the present invention is to provide an image display device including the photo-curable pattern made of the photosensitive resin composition and the photo-curable pattern.

The photocurable pattern made of the photosensitive resin composition has excellent adhesion to a base material. As a result, it can be used in various patterns such as an adhesive layer, an array planarizing film, a protective film, an insulating film pattern, and the like in an image display device, and can be used as a photoresist, a color filter, a black matrix, a column spacer pattern, But is not limited thereto.

The image display device having such a photo-curing pattern may include a liquid crystal display device, an OLED, a flexible display, and the like, but is not limited thereto, and all image display devices known in the art that can be applied are exemplified.

The photo-curing pattern can be produced by applying the above-described photosensitive resin composition of the present invention onto a substrate and forming a photo-curable pattern (after the development step if necessary).

First, a photosensitive resin composition is coated on a substrate and then heated and dried to remove a volatile component such as a solvent to obtain a smooth coated film.

The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coating method, a slit coating method or the like. After application, heating and drying (prebaking), or drying under reduced pressure, volatile components such as solvents are volatilized. Here, the heating temperature is usually 70 to 200 占 폚, preferably 80 to 130 占 폚. The thickness of the coating film after heat drying is usually about 1 to 8 mu m. Ultraviolet rays are applied to the thus obtained coating film through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and accurately align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.

The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto. If desired, the coating film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, and a desired pattern shape can be formed.

The developing method may be any of a liquid addition method, a dipping method, and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or an organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like.

These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkali developer is preferably 0.01 to 10% by weight, and more preferably 0.03 to 5% by weight.

The surfactant in the alkali developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. Each of these surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight. After development, it may be washed with water and, if necessary, subjected to post-baking at 150 to 230 ° C for 10 to 60 minutes.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Synthetic example  1: Synthesis of photoacid generator

1-1: Mine Generator  Synthesis of a-1

[Reaction Scheme 1]

Figure pat00073

A solution in which fluorosulfonylimide potassium salt (32.9 g, 0.15 mol) of fluorosulfonylimide potassium salt (32.9 g, 0.15 mol) dissolved in distilled shoe was added was added Triphenylsulfonium Bromide (34.3 g, 0.1 mol) After stirring the mixture for a time, the mixture was extracted with toluene (200 mL), and the toluene layer was distilled under reduced pressure to remove the solvent to obtain 44.0 g of a-1. Using an element analyzer (Flash EA 1112, Thermo Electron Scientific Instrument) Analysis confirmed that it was a-1.

Elemental analysis data: C, 48.71; H, 3.43; N, 3.12; 0, 14.49; S, 21.67

1-2: Mines Generator  Synthesis of a-2

[Reaction Scheme 2]

Figure pat00074

A solution of fluorosulfonylimide potassium salt (32.9 g, 0.15 mol) obtained by dissolving fluorosulfonylimide potassium salt (32.9 g, 0.15 mol) in a distillation shoe was added to the solution, and 2 After stirring the mixture for a time, the mixture was extracted with toluene (200 mL), and the toluene layer was distilled under reduced pressure to remove the solvent to obtain a-2 (45.9 g). Using an element analyzer (Flash EA 1112, Thermo Electron Scientific Instrument) It was confirmed that it was a-2.

Elemental analysis data: C, 31.22; H, 2.18; N, 3.06; O, 13.99; S, 13.92

Example  And Comparative Example

Photocurable compositions were prepared with the components and contents in Table 1 below.

division
(g) The photoacid generator (A) The photopolymerizable compound (B) Example 1 a-1 One b-1 100 Example 2 a-2 One b-1 100 Example 3 a-1 One b-2 100 Example 4 a-1 6 b-1 100 Example 5 a-1 12 b-1 100 Comparative Example 1 a-3 One b-1 100 Comparative Example 2 a-4 One b-1 100 Comparative Example 3 a-3 One b-2 100 A: photoacid generator
a-1 and a-2: The photoacid generator of Synthesis Example 1
a-3:

Figure pat00075
(Aldrich)
a-4:
Figure pat00076
(Aldrich)

b-1:
Figure pat00077
(TCL)
b-2:
Figure pat00078
(TCL)

Experimental Example

(1) Curing rate (reaction rate) Evaluation test

The photosensitive resin compositions of the prepared examples and comparative examples were coated on a glass plate with a thickness of 10 m using a Meyer bar, exposed to light of 100 mJ / cm 2 using a high-pressure mercury lamp, heated at 80 ° C for 10 minutes, A portion of the cured film was taken, dissolved in a CDCl3 solvent, subjected to NMR analysis, and the content of the remaining epoxy group was analyzed to calculate the reaction rate and recorded in Table 2.

The reaction rate was calculated as ((epoxy content before exposure - epoxy content after exposure) / epoxy content before exposure x 100.

The epoxy content before and after the exposure was calculated from the NMR integral of the phenyl group in the molecule and the integral of the epoxy in the spectrum.

(2) Color evaluation after curing

The hue of the pattern produced in Experimental Example (1) was visually observed and evaluated according to the following criteria.

◎: No change in color was observed with naked eyes

○: slight visibility was observed in the area where the color change was very small by the naked eye

△: Change of color in the naked eye is weakly recognized over a certain range.

X: Changes in color visually confirmed throughout the entire range.

division Evaluation of hardening rate After curing
Color evaluation Example 1 91 ◎ Example 2 93 ◎ Example 3 92 ◎ Example 4 96 ○ Example 5 99 △ Comparative Example 1 78 ◎ Comparative Example 2 81 ◎ Comparative Example 3 79 ◎

The compositions of Examples 1 to 3 were excellent in the curing rate, and no color change of the pattern was confirmed.

The compositions of Examples 4 and 5 contained a slight amount of the photoacid generator, so that the color change was slightly observed, but still excellent results were obtained and the curing rate was further improved.

However, the compositions of Comparative Examples 1 to 3 showed a very low curing rate.

Claims (10)

A sulfonylimide salt compound represented by the following formula (1): &lt; EMI ID =
[Chemical Formula 1]
Figure pat00079

(Wherein Y & lt ; + & gt ; is a compound represented by the following formula (2) or (3)
(2)
Figure pat00080

(3)
Figure pat00081

R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group,
Figure pat00082
,
Figure pat00083
, A linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group or an alkylcarbonyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms, or R 4 and R 5 To form a ring having 4 to 6 carbon atoms,
The aryl group may be substituted to share one bond with the bonded benzene ring,
R 1 , R 2 , R 3 , R 4 and R 5 may each independently be substituted at least once in one ring and may be different substituents when substituted one or more times.
The compound of claim 1, wherein the compound of formula (2) is selected from the group consisting of compounds represented by the following formulas (4) to (11):
[Chemical Formula 4]
Figure pat00084

[Chemical Formula 5]
Figure pat00085

[Chemical Formula 6]
Figure pat00086

(7)
Figure pat00087

[Chemical Formula 8]
Figure pat00088

[Chemical Formula 9]
Figure pat00089

[Chemical formula 10]
Figure pat00090

(11)
Figure pat00091
.
The compound of claim 1, wherein the compound of formula (3) is a sulfonylimide salt compound selected from the group consisting of compounds represented by the following formulas (12) to (30)
[Chemical Formula 12]
Figure pat00092

[Chemical Formula 13]
Figure pat00093

[Chemical Formula 14]
Figure pat00094

[Chemical Formula 15]
Figure pat00095

[Chemical Formula 16]
Figure pat00096

[Chemical Formula 17]
Figure pat00097

[Chemical Formula 18]
Figure pat00098

[Chemical Formula 19]
Figure pat00099

[Chemical Formula 20]
Figure pat00100

[Chemical Formula 21]
Figure pat00101

[Chemical Formula 22]
Figure pat00102

(23)
Figure pat00103

&Lt; EMI ID =
Figure pat00104

(25)
Figure pat00105

(26)
Figure pat00106

(27)
Figure pat00107

(28)
Figure pat00108

[Chemical Formula 29]
Figure pat00109

(30)
Figure pat00110
.
The sulfonylimide salt compound represented by the formula (1) of claim 1 is prepared by reacting a compound represented by the following formula (31) with a compound represented by the following formula (32) or (33)
(31)
Figure pat00111

(32)
Figure pat00112

(33)
Figure pat00113

(Wherein Z is a monovalent cation, W is a halogen atom,
R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group,
Figure pat00114
,
Figure pat00115
, A linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group or an alkylcarbonyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms, or R 4 and R 5 To form a ring having 4 to 6 carbon atoms,
The aryl group may be substituted to share one bond with the bonded benzene ring,
R 1 , R 2 , R 3 , R 4 and R 5 may each independently be substituted at least once in one ring and may be different substituents when substituted one or more times.
A photoacid generator comprising the sulfonylimide salt compound of any one of claims 1 to 3.
A photosensitive resin composition comprising the photoacid generator and the photopolymerizable compound of claim 5.
The photosensitive resin composition according to claim 6, wherein the sulfonylimide salt compound is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the photopolymerizable compound.
A photocurable pattern produced from the photosensitive resin composition of claim 6.
The photocurable pattern according to claim 8, wherein the photocurable pattern is selected from the group consisting of an adhesive layer, an array planarizing film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a color filter pattern, a black matrix pattern, a column spacer pattern and a black column spacer.
9. An image display device comprising the photocurable pattern of claim 9.

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