KR20140147426A - Photoactive compound, photosensitive resin composition comprising the photoactive compound, photosensitive material manufactured by using the photosensitive resin composition and display device having the photosensitive material - Google Patents
Photoactive compound, photosensitive resin composition comprising the photoactive compound, photosensitive material manufactured by using the photosensitive resin composition and display device having the photosensitive material Download PDFInfo
- Publication number
- KR20140147426A KR20140147426A KR1020130070653A KR20130070653A KR20140147426A KR 20140147426 A KR20140147426 A KR 20140147426A KR 1020130070653 A KR1020130070653 A KR 1020130070653A KR 20130070653 A KR20130070653 A KR 20130070653A KR 20140147426 A KR20140147426 A KR 20140147426A
- Authority
- KR
- South Korea
- Prior art keywords
- resin composition
- unsubstituted
- substituted
- photosensitive resin
- group
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133512—Light shielding layers, e.g. black matrix
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
Abstract
Description
The present invention relates to a photoactive compound, a photosensitive resin composition containing the same, a photosensitive material made of the photosensitive resin composition, and a display device including the same.
The photoactive compound is a substance that absorbs and decomposes light to generate chemically active atoms or molecules, and is widely used in photosensitive resin compositions and the like. Examples of such chemically active materials include acids, bases, and radicals. In particular, the photoactive compound in which a radical is generated can be used together with an acrylic group which causes a polymerization reaction together with a radical to improve the strength of a coated film.
On the other hand, the photosensitive resin composition is applied on a substrate to form a coating film, and after a specific portion of the coating film is exposed by light irradiation using a photomask or the like, the unexposed portion is removed by developing treatment to be used for forming a pattern . Since such a photosensitive resin composition can be cured by irradiation with light, it is used for photocurable ink, photosensitive printing plate, various photoresist, color filter photoresist for LCD, photoresist for resin black matrix, or transparent photoresist.
In addition, since the use of the LCD is becoming more and more diversified, the photosensitive resin composition is being used for constituting a liquid crystal display device such as a TV and a monitor in addition to the use of a conventional notebook computer and a mobile phone. In order to improve productivity and durability, There is an increasing demand for fast response and excellent mechanical properties. Recently, mobile products are demanding products that can realize fine patterns with high physical properties while requiring high resolution.
The present invention provides a photoactive compound containing a oxime ester group, a photosensitive resin composition containing the same, a photosensitive material made of the photosensitive resin composition, and a display device including the same.
An embodiment of the present invention provides a compound represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R1 is hydrogen; A substituted or unsubstituted C 1 ~ C 5 alkyl group; Or a substituted or unsubstituted C 2 -C 10 alkenyl group,
R2 is hydrogen; A substituted or unsubstituted C 1 ~ C 5 alkyl group; A substituted or unsubstituted C 2 -C 10 alkenyl group; A substituted or unsubstituted C 3 -C 10 cycloalkyl group; A substituted or unsubstituted C 7 -C 20 arylalkyl group; Or is an aryl group, a substituted or unsubstituted C 6 ~ C 20.
In addition, one embodiment of the present disclosure provides a photoinitiator comprising the compound.
In addition, one embodiment of the present invention provides a photosensitive resin composition comprising the photoinitiator.
In addition, one embodiment of the present invention provides a photosensitive material made of the photosensitive resin composition.
Further, one embodiment of the present invention provides a display device including the photosensitive material.
The photo-cured film or pattern using the photoinitiator according to one embodiment of the present invention has an advantage of good chemical resistance.
The photo-cured film or pattern using the photoinitiator according to one embodiment of the present invention is advantageous in that the defective rate of dropping out of the film or pattern is small.
The photoinitiator according to one embodiment of the present invention has an advantage that a high sensitivity characteristic and a fine pattern can be realized.
The photosensitive resin composition containing the compound according to the present invention is excellent in sensitivity due to efficient absorption of a UV light source, and can achieve a fine pattern with excellent residual ratio, mechanical strength, heat resistance, chemical resistance, and resistance to development. Therefore, the photosensitive resin composition according to the present invention is advantageous for the development of products such as color filter photoresists for liquid crystal display elements, photoresists for resin black matrix, and column spacers.
Hereinafter, the present invention will be described in detail.
1. Compound
An embodiment of the present invention provides a compound represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R1 is hydrogen; A substituted or unsubstituted C 1 ~ C 5 alkyl group; Or a substituted or unsubstituted C 2 -C 10 alkenyl group,
R2 is hydrogen; A substituted or unsubstituted C 1 ~ C 5 alkyl group; A substituted or unsubstituted C 2 -C 10 alkenyl group; A substituted or unsubstituted C 3 -C 10 cycloalkyl group; A substituted or unsubstituted C 7 -C 20 arylalkyl group; Or is an aryl group, a substituted or unsubstituted C 6 ~ C 20.
In one embodiment of the present disclosure, R 1 may be a substituted or unsubstituted C 1 -C 5 alkyl group.
In one embodiment of the present disclosure, R 2 may be a substituted or unsubstituted C 1 -C 5 alkyl group.
In the present specification, the alkyl group may be linear or branched and may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like, but is not limited thereto.
In the present specification, the alkenyl group may be linear or branched and includes, for example, a butenyl group; Pentenyl; Or an alkenyl group to which an aryl group such as a stilbenyl group or a styrenyl group is bonded, but is not limited thereto.
In the present specification, the cycloalkyl group is a monocyclic or polycyclic aliphatic ring group consisting only of carbon and hydrogen. Examples thereof include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, and the like.
In the present specification, the aryl group is a monocyclic or polycyclic aromatic ring group. Examples thereof include, but are not limited to, a phenyl group, a naphthyl group, an anthracene group, a biphenyl group, a phenanthrene group, a pyrenylene group, and a fluorene group.
In the present specification, the arylalkyl group is an alkyl group to which an allyl group is connected.
One embodiment of the present disclosure provides a photoinitiator comprising the compound.
In one embodiment of the present invention, the maximum absorption wavelength (? Max) of the photoinitiator may be from 330 nm to 360 nm. In this case, there is an advantage that the ultraviolet rays can be effectively reacted upon exposure.
In the above formula (1), R 2 is a moiety in which radicals, which are active species, are decomposed at the time of exposure, and is preferably a methyl group or a phenyl group, although the structure is not particularly limited. The methyl group or the phenyl group has a simple structure and is good in motion and can improve the photo-initiating efficiency.
In the above formula (1), R 1 is preferably a methyl group or a heptyl group.
Due to such a structural feature, the compound according to the present invention has high sensitivity, high solubility and characteristics such as low volatility as compared with a photoactive compound containing oxime ester disclosed in the prior art and is used as a photoinitiator in a photosensitive resin composition Sensitivity, chemical resistance, resistance to developing, hardenability and high-temperature process characteristics can be improved.
The method for producing the compound represented by the formula (1) according to the present invention is not particularly limited, but it can be produced by the following method.
[Reaction Scheme 1]
2. Photosensitive resin composition
The present invention provides a photosensitive resin composition comprising the compound represented by Formula 1 as a photoinitiator.
The photosensitive resin composition of the present invention may further include an alkali-soluble binder resin, a polymerizable compound having an ethylenically unsaturated bond, and a solvent.
The amount of the compound represented by the formula (1) is not particularly limited, but is preferably 0.1 to 5% by weight based on the total weight of the photosensitive resin composition. If it is less than 0.1% by weight, sufficient sensitivity may not be obtained, and if it exceeds 5% by weight, UV light may not be delivered to the bottom due to high UV absorption.
In the photosensitive composition according to the present invention, the alkali-soluble resin binder may contain a monomer having an acid functional group, a copolymer thereof with a copolymerizable monomer, or a polymer reaction of the copolymer and an ethylenically unsaturated compound containing an epoxy group ≪ / RTI >
Non-limiting examples of the monomer including the acid group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprenesulfonic acid, styrenesulfonic acid, 5-norbornene- (Meth) acryloyloxy) ethyl phthalate, mono-2 - ((meth) acryloyloxy) ethyl succinate, omega -carboxylic polycaprolactone mono Group.
Non-limiting examples of the monomer copolymerizable with the monomer including the acid group include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy- Acrylate, 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl (Meth) acrylate, (Meth) acrylates such as methoxy ethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, poly (ethylene glycol) Acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) (Meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, methyl? -Hydro (Meth) acrylate, dicyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, ethylcyclohexylmethyl acrylate, Pentenyl (meth) acrylate, dicyclopentanyl oxyethyl (meth) acrylate, and dicyclopentenyl oxyethyl (meth) unsaturated carboxylic acid ester selected from the group consisting of acrylates;
Aromatic vinyls selected from the group consisting of styrene,? -Methylstyrene, (o, m, p) -vinyltoluene, (o, m, p) -methoxystyrene, and (o, m, p) -chlorostyrene;
Unsaturated ethers selected from the group consisting of vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether;
N-vinyl tertiary amines selected from the group consisting of N-vinyl pyrrolidone, N-vinyl carbazole, and N-vinyl morpholine;
Unsaturated imides selected from the group consisting of N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, and N-cyclohexylmaleimide;
Maleic anhydrides such as maleic anhydride or methyl maleic anhydride;
Unsaturated glycidyl compounds selected from the group consisting of allyl glycidyl ether, glycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate; And mixtures thereof.
The alkali-soluble binder resin used in the present invention has an acid value of about 30 to 300 KOH mg / g, a weight average molecular weight of 1,000 to 200,000, and more preferably a molecular weight of 5,000 to 100,000.
The polymerizable compound having an ethylenically unsaturated bond is selected from the group consisting of ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, trimethylolpropane di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2-trisacryloyloxymethyl ethyl phthalic acid, propylene glycol di (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (metha) A compound obtained by esterifying an alcohol with an?,? - unsaturated carboxylic acid;
A compound obtained by adding (meth) acrylic acid to a compound containing a glycidyl group such as trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct;
ester compounds of a compound having a hydroxyl group or an ethylenic unsaturated bond such as a phthalic acid diester of? -hydroxyethyl (meth) acrylate and a toluene diisocyanate adduct of? -hydroxyethyl (meth) acrylate with a polyvalent carboxylic acid (Meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and polyisocyanate. Examples of the compound having an ethylenically unsaturated bond include allyl glycidyl ether, glycidyl 1-hexene-2-methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, Or more;
(Meth) acrylic acid alkyl ester selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; And
And 9,9'-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. However, it is not limited to these compounds and compounds known in the art can be used .
In some cases, silica dispersions can be used for these compounds. For example, there are Nanocryl XP series (0596, 1045, 21/1364) and Nanopox XP series (0516, 0525) manufactured by Hanse Chemie.
In the photosensitive resin composition according to the present invention, non-limiting examples of the solvent include methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol di But are not limited to, ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, Ethylcellosolve acetate, methyl cellosolve acetate, butyl acetate, and dipropylene glycol monomethyl ether. The solvent is preferably selected from the group consisting of glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, And the like.
The photosensitive resin composition of the present invention contains 0.1 to 5% by weight of the compound represented by the formula (1), 0.5 to 50% by weight of a polymerizable compound having an ethylenically unsaturated bond, 1 to 50% by weight of an alkali soluble binder resin and 10 to 95% %.
The photosensitive composition according to the present specification may further include at least one additive such as a second photoactive compound, a curing accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, a filler, and a surfactant in addition to the above components.
Non-limiting examples of the second photoactive compound include 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl ) -6-triazine, 2,4-trichloromethyl- (phenylonyl) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) , 2,4-trichloromethyl- (4'-ethylbiphenyl) - (2-methoxyphenyl) propanoic acid, A triazine-based compound selected from the group consisting of 6-triazine, and 2,4-trichloromethyl- (4'-methylbiphenyl) -6-triazine;
Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, and 2,2'-bis (2,3-dichlorophenyl) Imidazole compounds selected from the group consisting of 5,5'-tetraphenylimidazole;
2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- (4-methylthiophenyl) -2-morpholinocyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, (Irgacure-907), and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Based compound;
O-acyloxime compounds such as Irgacure OXE 01 and Irgacure OXE 02 from Ciba Geigy;
Benzophenone compounds such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone;
Thioxanthone compounds selected from the group consisting of 2,4-diethylthioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, and diisopropylthioxanthone;
2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and bis (2,6-dichlorobenzoyl) propylphosphine A phosphine oxide-based compound selected from the group consisting of oxides;
(Diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl- Benzoyl-7-methoxy-coumarin, and 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-Cl ] -Benzopyrano [6,7,8-ij] -quinolizine-11-one.
Examples of the curing accelerator include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercaptan-1,3,4-thiadiazole, 2- (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis Trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris Trimethylolethane tris (3-mercaptopropionate), and the like, but the present invention is not limited thereto and may include those known in the art.
Examples of the thermal polymerization inhibitor include p-anisole, hydroquinone, pyrocatechol, t-butyl catechol, N-nitrosophenylhydroxyamine ammonium salt, N-nitrosophenylhydroxy Amine aluminum salt, and phenothiazine, but it is not limited thereto and may include those known in the art.
Other plasticizers, adhesion promoters, fillers, surfactants, and the like may be used as well as any compounds that can be included in conventional photosensitive resin compositions.
When the other components are added to the photosensitive resin composition of the present invention, it is preferable that the second photoactive compound is contained in an amount of 0.1 to 5% by weight and the other additives are contained in an amount of 0.01 to 5% by weight.
The photosensitive resin composition according to the present invention can be used for a roll coater, a curtain coater, a spin coater, a slot die coater, various printing or deposition, Lt; / RTI > support.
It is also possible to apply it onto a support such as a film and then transfer it to another support or coat it on a first support, transfer it to a blanket or the like, and transfer it to a second support again.
Examples of the light source for curing the photosensitive resin composition of the present invention include mercury vapor arc, carbon arc or Xe arc which emits light having a wavelength of 250 to 450 nm.
The photosensitive resin composition according to the present invention can be used as a light-sensitive material for forming a black matrix of a thin-film transistor liquid crystal display (TFT LCD) or an organic light-emitting diode, , A photosensitive material for overcoat layer formation, a column spacer photosensitive material, a photocurable coating material, a photocurable ink, a photocurable adhesive, a printing plate, a photosensitive material for a printing wiring board, and a photosensitive material for a plasma display panel (PDP) There is no restriction.
As typical examples of the photoinitiator used in the photosensitive resin composition, various kinds of acetophenone derivatives, benzophenone derivatives, nonimidazole derivatives, acylphosphine oxide derivatives, triazine derivatives, oxime ester derivatives and the like are known. In the case of the acetophenone derivative, a fine pattern can be realized, but the sensitivity is insufficient and physical properties such as residual film ratio, mechanical strength, heat resistance, chemical resistance and resistance to development are lowered.
Existing oxime ester derivatives have high sensitivity and show excellent physical properties but CD Bias is large and it is difficult to realize fine pattern.
Therefore, there is a need for the development of a photoactive compound which is a photoinitiator capable of realizing a fine pattern while exhibiting high sensitivity characteristics, and a photosensitive resin composition containing the same.
The photosensitive resin composition containing the compound according to the present invention is excellent in sensitivity due to efficient absorption of a UV light source, and has excellent residual film ratio, mechanical strength, heat resistance, chemical resistance and resistance to developing. In addition, CD Bias (Critical Dimension of the actual pattern) has a small feature. Therefore, the photosensitive resin composition according to the present invention is advantageous for the development of products such as a color filter photoresist for a liquid crystal display element, a photoresist for a resin black matrix, and a column spacer.
There is provided a photosensitive material produced from the photosensitive resin composition according to the present specification.
More specifically, the present invention provides a photosensitive material in the form of a thin film or a pattern formed by applying the photosensitive resin composition of the present invention onto a substrate by an appropriate method.
The coating method is not particularly limited, but a spray method, a roll coating method, a spin coating method, or the like can be used, and generally, a spin coating method is widely used. After the coating film is formed, a part of the residual solvent may be removed under reduced pressure as occasion demands.
A display device including the photosensitive material according to the present invention is provided.
The display device may be a plasma display panel (PDP), a light emitting diode (LED), an organic light emitting diode (OLED), a liquid crystal display (LCD) A liquid crystal display (LCD), and a cathode ray tube (CRT).
One embodiment of the present invention relates to a method of manufacturing a photosensitive resin composition comprising the steps of: 1) applying a photosensitive resin composition having a photoinitiator containing a compound represented by Formula 1 on a substrate to form a film; And
And 2) irradiating light onto the film.
In the method of manufacturing a photosensitive material according to an embodiment of the present invention, the light for curing the photosensitive resin composition in the step 2) may be a mercury vapor arc, a carbon arc, Xe Arcs, and the like.
The method of applying the composition to the substrate is not particularly limited, and a method generally used in the art can be employed.
After the photosensitive resin composition is applied, a pattern can be formed.
The method for forming the pattern is not particularly limited, and a method generally used in the art can be employed. For example, a patterned photoresist can be formed on the substrate by exposure and development using a photomask.
In the method of manufacturing a photosensitive material according to an embodiment of the present invention, the step of pre-baking the coated photosensitive resin composition may further include a step of pre-baking the applied photosensitive resin composition.
In the method of manufacturing a photosensitive material according to an embodiment of the present invention, the method may further include post-baking after forming the film or pattern.
The methods and conditions of the pre-bake and post-bake are not particularly limited, and the methods and conditions commonly used in the art can be employed.
3. Example
The present specification will be described in more detail by way of the following examples. It is to be understood, however, that the embodiments are illustrative of the present specification and the scope of the present invention is not limited thereto.
[Example]
[Synthesis Example 1]
1) Synthesis of structural formula 1
Phenylacetic acid (10 g, 0.0734 mol) was dissolved in acetic anhydride (37 g, 0.367 mol) at room temperature and stirred in a nitrogen atmosphere for several minutes. The reaction was initiated by adding 1-methylimidazole as a catalyst thereto, and the reaction was allowed to proceed for 12 hours. Water was then added to hydrolyze the acetic anhydride.
The mixture was extracted with ethyl acetate and the organic layer was washed with saturated aqueous sodium hydrogen carbonate solution, dehydrated with magnesium sulfate and concentrated.
Thereafter, the concentrated residue was purified by column (eluent: hexane / ethyl acetate (9/1)) to obtain the compound of formula 1.
Yield: 67% (6.6g), 1H NMR (500 MHz, CDCl 3, ppm): 7.35-7.32 (2H, t, Ar), 7.28-7.26 (1H, t, Ar), 7.21-7.20 (2H, d , Ar), 3.69 (2H, s, CH 2), 2.15 (3H, s, CH 3)
2) Synthesis of structural formula 2
A solution of the compound of the above structural formula 1 (4 g, 0.0298 mol) in methylene chloride was cooled with ice and then sulfuryl chloride (4.7 g, 0.0357 mol) was dissolved in methylene chloride ) Was added dropwise over 5 minutes.
After completion of the dropwise addition, the mixture was stirred at 0 ° C for 2 hours and then at room temperature for one day. The solvent was removed in vacuo and the residue was purified by column (eluent: hexane / ethyl acetate (9/1)) to give the compound of formula 2.
Yield: 100% (5g), 1H NMR (500 MHz, CDCl 3, ppm): 7.43-7.37 (5H, m, Ar), 5.34 (1H, s, CH), 2.22 (3H, s, CH 3)
3) Synthesis of structural formula 3
A solution of the compound of formula 2 (5 g, 0.0296 mol) in acetone at 5-10 ° C was added to a suspension of potassium ethyl xanthogenate (4.8 g, 0.0296 mol) in acetone over 15 minutes. The mixture was stirred at 10 [deg.] C for 2 hours. The solvent was then evaporated and water was added. The brown solution was extracted with ethyl acetate.
The residue was purified by column (eluent: hexane / ethyl acetate (9/1)) to obtain the compound of the structural formula 3. The obtained residue was purified by silica gel column chromatography.
Yield: 98% (7.4g), 1H NMR (500 MHz, CDCl 3, ppm): 7.37-7.33 (5H, m, Ar), 5.61 (1H, s, CH), 4.62-4.58 (2H, q, CH 2 CH 3), 2.27 (3H , s, CH 3), 1.41-1.38 (3H, t, CH 2 CH 3)
4) Synthesis of structural formula 4
To an ice cold suspension of the compound of formula 3 (7.4 g, 0.0290 mol) and hydroxylamine hydrochloride (2.2 g, 0.0320 mol) in methanol was added pyridine (2.8 g, 0.0362 mol) And then reacted. The solvent was removed in vacuo and the residue dissolved in ethyl acetate. The organic layer was washed with 1N hydrochloric acid, dehydrated with magnesium sulfate, and then concentrated to obtain the compound of formula 4.
Yield: 95% (7.4 g), 1H NMR (500 MHz, DMSO d6, ppm): 11.12 (1H, s, NOH), 7.40-7.35 (4H, m, Ar), 7.32-7.28 ), 5.57 (1H, s, CH), 4.56-4.51 (2H, q, CH 2 CH 3), 1.73 (3H, s, CH 3), 1.30-1.27 (3H, t, CH 2 CH 3)
5) Synthesis of structural formula 5
The solution obtained by dissolving potassium hydroxide (1.7 g, 0.0311 mol) in water was cooled with ice, and a solution obtained by dissolving 2.1 g (0.0077 mol) of the compound of formula (4) in methylene chloride was added thereto. Lt; 0 > C for 2 hours.
Afterwards, further water was added to separate the phases, the aqueous phase was washed twice with hexane and acidified to pH 2 with concentrated hydrochloric acid. The water layer was extracted five times with ethyl acetate. Thereafter, the organic layer was dehydrated with magnesium sulfate, and the solvent was removed in a vacuum to obtain the compound of the structural formula 5.
Yield: 94% (1.6g), 1H NMR (500 MHz, DMSO d6, ppm): 12.36 (1H, s, NOH), 7.50-7.40 (5H, m, Ar), 2.29 (3H, s, CH 3)
6) Synthesis of structural formula 6
A suspension of the compound of formula 5 (1.6 g, 0.0071 mol) and potassium carbonate (2.9 g, 0.0213 mol) in acetone was stirred at room temperature for 10 minutes and acetyl chloride (0.6 g, 0.0078 mol) And the mixture was stirred at room temperature for 2 hours. The solid was then filtered off and the filtrate was concentrated in vacuo.
The residue was dissolved in ethyl acetate and washed with water. The organic layer was dehydrated with magnesium sulfate and then concentrated to half. Thereafter, the filtrate was diluted with hexane, the precipitate was filtered out, and this was dried to obtain Compound 1 of Structural Formula 6.
Yield: 75% (1.3g), 1H NMR (500 MHz, CDCl 3, ppm): 7.45-7.42 (2H, t, Ar), 7.41-7.38 (1H, t, Ar), 7.35-7.33 (2H, d , Ar), 2.47 (3H, s, CH 3), 2.25 (3H, s, CH 3)
[Example 1]
3 g of an alkali-soluble binder resin as a copolymer of 3 g of Pigment Blue 15: 6, 1 g of Pigment Violet 23, benzyl methacrylate / methacrylic acid (BzMA / MAA) (molar ratio: 70/30, Mw: 24,000) 4 g of dipentaerythritol hexaacrylate as a polymerizable compound having unsaturated bonds, 2 g of an acrylic dispersant as a dispersant as an additive, 0.2 g of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, F-475 (DaiNippon Ink , 0.5 g of the compound prepared in Example 1 as a photoinitiator and 65.75 g of propylene glycol monomethyl ether acetate as a solvent were mixed and the mixture was stirred for 5 hours to prepare a green photosensitive resin composition.
Next, the solution was filtered with a 5-micron filter, and the obtained photosensitive composition solution was spin-coated on glass, and then heat-treated at about 100 캜 for 2 minutes to form an equivalent film having a thickness of about 2.5 탆.
The film was exposed at a light exposure of 40 mJ / cm 2 under a high-pressure mercury lamp using a square pattern having a length of 300 탆 and a stripe pattern having a width of 20 탆, and then the pattern was exposed to a KOH alkali of pH 11.3 to 11.7 Developed with aqueous solution and washed with deionized water. This was heat-treated at 230 DEG C for about 30 minutes, and the CD and color of the pattern were measured.
[Comparative Example 1]
A photosensitive resin composition was prepared in the same manner as in Example 1, except that 0.5 g of the following compound 2 was used instead of the compound 1 shown in Table 1 as a photoinitiator.
[Comparative Example 2]
A photosensitive resin composition was prepared in the same manner as in Example 1, except that 0.5 g of the following compound 3 was used instead of the compound 1 in Table 1 as a photoinitiator.
[Experimental Example]
[Experimental Example 1]
The spectral values of the rectangular patterns produced in Example 1 and Comparative Examples 1 and 2 were measured, and then the spectral values were measured again by performing additional heat treatment at 230 ° C for 1 hour.
Then, the color difference (? Eab) before and after the additional heat treatment was calculated to evaluate the heat resistance, and it is shown in Table 2 below.
It can be said that the color difference is smaller in the case of Example 1 and therefore the heat resistance is more excellent.
[Experimental Example 2]
CD values of the linear patterns produced in Example 1 and Comparative Examples 1 and 2 were measured and are shown in Table 3 below.
In the case of Example 1, the CD Bias is as small as 5 占 퐉, and a fine pattern pattern is possible.
Claims (13)
[Chemical Formula 1]
In Formula 1,
R1 is hydrogen; A substituted or unsubstituted C 1 ~ C 5 alkyl group; Or a substituted or unsubstituted C 2 -C 10 alkenyl group,
R2 is hydrogen; A substituted or unsubstituted C 1 ~ C 5 alkyl group; A substituted or unsubstituted C 2 -C 10 alkenyl group; A substituted or unsubstituted C 3 -C 10 cycloalkyl group; A substituted or unsubstituted C 7 -C 20 arylalkyl group; Or is an aryl group, a substituted or unsubstituted C 6 ~ C 20.
[Chemical Formula 1]
In Formula 1,
R1 is hydrogen; A substituted or unsubstituted C 1 ~ C 5 alkyl group; Or a substituted or unsubstituted C 2 -C 10 alkenyl group,
R2 is hydrogen; A substituted or unsubstituted C 1 ~ C 5 alkyl group; A substituted or unsubstituted C 2 -C 10 alkenyl group; A substituted or unsubstituted C 3 -C 10 cycloalkyl group; A substituted or unsubstituted C 7 -C 20 arylalkyl group; Or is an aryl group, a substituted or unsubstituted C 6 ~ C 20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130070653A KR20140147426A (en) | 2013-06-19 | 2013-06-19 | Photoactive compound, photosensitive resin composition comprising the photoactive compound, photosensitive material manufactured by using the photosensitive resin composition and display device having the photosensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130070653A KR20140147426A (en) | 2013-06-19 | 2013-06-19 | Photoactive compound, photosensitive resin composition comprising the photoactive compound, photosensitive material manufactured by using the photosensitive resin composition and display device having the photosensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20140147426A true KR20140147426A (en) | 2014-12-30 |
Family
ID=52676219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020130070653A KR20140147426A (en) | 2013-06-19 | 2013-06-19 | Photoactive compound, photosensitive resin composition comprising the photoactive compound, photosensitive material manufactured by using the photosensitive resin composition and display device having the photosensitive material |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20140147426A (en) |
-
2013
- 2013-06-19 KR KR1020130070653A patent/KR20140147426A/en not_active Application Discontinuation
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2397903B1 (en) | Photoactive compound and photosensitive resin composition containing the same | |
| KR101384431B1 (en) | Photoactive compound and photosensitive resin composition comprising the same | |
| KR20100050081A (en) | Photo-iniciative polymerizer comprising oxime ester with unsaturated double bonds and photosensative resin composition having the same | |
| JP5420527B2 (en) | Crosslinkable compound and photosensitive composition containing the same | |
| KR20120054540A (en) | Photoresist composition comprising acrylate-based compounds | |
| KR101048329B1 (en) | Urethane-based multifunctional monomer, a manufacturing method thereof and a photosensitive resin composition comprising the same | |
| KR101489067B1 (en) | Photoactive compound and photosensitive resin composition comprising the same | |
| KR101498776B1 (en) | New compound, photosensitive composition comprising the same and photosensitive material | |
| KR101355152B1 (en) | Photoinitiator and photoresist resin composition comprising the same | |
| KR101384478B1 (en) | Photoactive compound comprising phosphonate group and photosensitive resin composition comprising the same | |
| KR101273140B1 (en) | Acrylate-based compounds and the photoresist composition comprising the same | |
| JP5860993B2 (en) | Siloxane compound, photosensitive composition containing the same, and photosensitive material | |
| KR101623624B1 (en) | Photoactive compound, photosensitive resin composition comprising the photoactive compound, photosensitive material manufactured by using the photosensitive resin composition and display device having the photosensitive material | |
| KR20130091866A (en) | Photosensitive composition and photosensitive material manufactured using the same | |
| KR20140147426A (en) | Photoactive compound, photosensitive resin composition comprising the photoactive compound, photosensitive material manufactured by using the photosensitive resin composition and display device having the photosensitive material | |
| KR20120106408A (en) | Photoactive compound and photosensitive resin composition comprising the same | |
| KR20130135090A (en) | Photoactive compound and photosensitive resin composition comprising the same | |
| KR101546103B1 (en) | Photoactive compound containing a silyl group and photosensitive resin composition comprising the same | |
| KR101612586B1 (en) | Photoresist resin composition, photosensitive material manufactured by using the photoresist resin composition and display device having the same | |
| KR101747528B1 (en) | Indole-based compound, colorant composition comprising the same and resin composition comprising the same | |
| KR101261618B1 (en) | Crosslinkable compound and photosensitive composition comprising the same | |
| KR20140016151A (en) | Polymeric compound and photosensitive composition comprising the same | |
| KR101586517B1 (en) | Polymer and organic light-emitting apparatus using the same | |
| KR20130058191A (en) | Photosensitive resin composition and photosensitive material using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E601 | Decision to refuse application |