KR20170003123A - Photosensitive double resin layer, black column spacer using the same, and color filter - Google Patents
Photosensitive double resin layer, black column spacer using the same, and color filter Download PDFInfo
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- KR20170003123A KR20170003123A KR1020150093375A KR20150093375A KR20170003123A KR 20170003123 A KR20170003123 A KR 20170003123A KR 1020150093375 A KR1020150093375 A KR 1020150093375A KR 20150093375 A KR20150093375 A KR 20150093375A KR 20170003123 A KR20170003123 A KR 20170003123A
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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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
- G03F7/027—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
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Abstract
Description
The present disclosure relates to a photosensitive double layer resin film, a black column spacer made using the same, and a color filter including the black column spacer.
The photosensitive resin composition is an indispensable material for the production of display devices such as color filters, liquid crystal display materials, organic light emitting devices, and display panel materials. For example, a color filter such as a color liquid crystal display requires a black matrix at a boundary portion between coloring layers such as red, green, and blue in order to enhance display contrast and coloring effect, The black matrix is mainly formed of a photosensitive resin composition.
In recent years, efforts have been made to use the black matrix material as a column spacer supporting between two TFTs and a C / F substrate existing between the liquid crystal layers, and the column spacer is referred to as a black column spacer.
In order to realize the function of the black column spacer, basic characteristics such as compression displacement, elastic recovery rate and breaking strength are required, and steps of a black column spacer pattern must be realized by adjusting the exposure amount using a mask.
However, since the conventional black column spacer is manufactured by applying, exposing, and developing one photosensitive resin composition, it is disadvantageous in the stepwise implementation, and further, the taper angle of the formed pattern is low, so that it is difficult to stably pattern the black column spacer.
Therefore, studies for developing a photosensitive resin film capable of overcoming the above problems are continuing.
One embodiment is to provide a photosensitive double-layer resin film having a small CD bias, a high taper angle of the pattern, and excellent chemical resistance.
Another embodiment is to provide a black column spacer made using the photosensitive double layer resin film.
Another embodiment is to provide a color filter including the black column spacer.
One embodiment comprises a first resin film obtained by applying and curing a first composition on a substrate and a second resin film obtained by applying and curing the second composition on the first resin film, A reactive unsaturated compound, a photopolymerization initiator, a pigment, and a solvent, wherein the second composition comprises an epoxy group-containing acrylic binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent, wherein the epoxy group is derived from an epoxy group- Wherein the epoxy group-derived monomer is contained in an amount of 5% by weight to 60% by weight based on the total amount of monomers constituting the epoxy group-containing acrylic binder resin in the second composition.
The epoxy group-derived monomer may be contained in an amount of 15% by weight to 45% by weight based on the total amount of the monomers constituting the epoxy group-containing acrylic binder resin in the second composition.
The epoxy group-derived monomer may be an acrylate monomer.
The epoxy group-derived monomer may be at least one of the compounds represented by the following formulas (1) to (3).
[Chemical Formula 1]
(2)
(3)
In the above Chemical Formulas 1 to 3,
R 1 to R 3 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L 9 to L 12 each independently represent a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group,
X is a substituted or unsubstituted C3 to C20 alicyclic ring or a substituted or unsubstituted C6 to C20 aromatic ring.
The epoxy group-containing acrylic binder resin may include a repeating unit represented by the following formula (5).
[Chemical Formula 5]
In Formula 5,
R 5 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
The epoxy group-containing acrylic binder resin may have a weight average molecular weight of 1,000 g / mol to 100,000 g / mol.
The epoxy group-containing acrylic binder resin may have a degree of dispersion of 1.0 to 3.0.
The reactive unsaturated compound in the second composition may comprise an acidic functional group.
The acid functional groups may include -COOH, -SO 3 H, -OSO 3 H, or a combination thereof.
The reactive unsaturated compound in the second composition may be represented by the following general formula (6) or (7).
[Chemical Formula 6]
(7)
In the above formulas (6) and (7)
R 11 and R 12 are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group,
L 1 to L 8 each independently represents a C1 to C10 alkylene group,
A represents a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C3 to C20 cycloalkenylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heteroarylene group to be.
The binder resin in the first composition may include a cadmium-based binder resin, an acrylic-based binder resin, or a combination thereof.
The weight ratio of the cationic binder resin to the acrylic binder resin may be 99: 1 to 50:50.
The pigment may comprise a black pigment.
The black pigment may include aniline black, perylene black, titanium black, cyanine black, lignin black, lactam-based organic black, RGB black, carbon black, or a combination thereof.
Wherein the first composition comprises 1 to 30% by weight of a binder resin, 1 to 20% by weight of a reactive unsaturated compound, 0.05 to 5% by weight of a photopolymerization initiator, %, Pigment dispersion 5% to 30% by weight, and solvent balance.
The second composition may include 1 wt% to 10 wt% of an epoxy group-containing acrylic binder resin, 1 wt% to 10 wt% of a reactive unsaturated compound, 0.1 wt% to 5 wt% of a photopolymerization initiator, and a remaining amount of a solvent.
The second composition may further comprise a pigment.
The first composition and the second composition may each independently include an additive of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine surfactant, a radical polymerization initiator, .
Another embodiment provides a black column spacer prepared by exposing and developing the photosensitive double layer resin film.
The pattern in the black column spacer may have a taper angle of 20 degrees or greater.
Another embodiment provides a color filter comprising the black column spacer.
Other aspects of the present invention are included in the following detailed description.
The photosensitive resin film according to one embodiment is composed of a double layer, and the composition constituting the upper layer of the double layer contains an epoxy group-containing acrylic binder resin in a specific amount, and has a small CD bias, a high taper angle of pattern, A black column spacer and a color filter including the black column spacer are provided.
1 to 7 are scanning electron microscope (SEM) photographs of a pattern in a black column spacer produced using the photosensitive double-layer resin films according to Examples 1 to 4 and Comparative Examples 1 to 3, respectively.
Figs. 8 to 14 are views showing CD of the photosensitive double-layer resin film according to Examples 1 to 4 and Comparative Examples 1 to 3, respectively, measured with a 3-D profiler.
Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.
Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group Quot; means a C3 to C20 heterocycloalkenyl group, "an aryl group" means a C6 to C20 aryl group, an "arylalkyl group" means a C6 to C20 arylalkyl group, Refers to a C 1 to C 20 alkylene group, "arylene group" refers to a C6 to C20 arylene group, "alkylarylene group" refers to a C6 to C20 alkylarylene group, "heteroarylene group" refers to a C3 to C20 hetero Quot; means an arylene group, and the "alkoxysilylene group" means a C1 to C20 alkoxysilylene group.
Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, An ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1-C10 alkyl group, a C1- A C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkyl group, To C20 heterocycloalkenyl groups, C2 to C20 heterocycloalkynyl groups, C3 to C20 heteroaryl groups, or combinations thereof.
Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S, and P is included in the formula.
&Quot; (Meth) acrylic acid "refers to both" acrylic acid "and" methacrylic acid " "It means both are possible.
"Combination" as used herein, unless otherwise specified, means mixing or copolymerization.
Unless otherwise specified herein, an unsaturated bond includes not only multiple bonds between carbon-carbon atoms but also other molecules such as carbonyl bonds, azo bonds, and the like.
As used herein, the cadmium resin means a resin in which at least one functional group selected from the group consisting of the following formulas (8-1) to (8-11) is included in the main backbone of the resin.
Also, unless otherwise specified herein, "*" means the same or different atom or moiety connected to the formula.
The photosensitive resin film according to an embodiment includes a first resin film and a second resin film. For example, the photosensitive resin film may be a double layer composed of the first resin film and the second resin film. The first resin film is formed by applying a first composition onto a substrate and then curing, and the second resin film is formed by applying the second composition onto the first resin film and curing the same. The first composition includes a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a pigment, and a solvent, and the second composition includes an epoxy group-containing acrylic binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.
The optical density per 1 mu m of the first resin film may be larger than the optical density per 1 mu m of the second resin film by 0.4 or more, for example, 1.0 or more, such as 1.5 or more. In general, a photosensitive resin film for manufacturing a black column spacer is formed as a single layer, and therefore imperfect steps are required to be realized. However, since the photosensitive resin film according to one embodiment is composed of the first resin film including, for example, the first composition for obtaining the optical density and the second resin film including the spacer and the second composition for realizing the step difference , Sensitivity and developability can be easily controlled, so that a desired level difference can be obtained. Furthermore, since the surface of the first resin film can be hardened by the light transmitted through the second resin film, which may have optical density lower by 0.4 or more per 1 m than the first resin film at the intermediate position of the photosensitive resin film, A very improved result in terms of the developing margin can be obtained.
The photosensitive double-layer resin film including the first resin film and the second resin film provides a black column spacer through exposure, development, curing, or the like.
On the other hand, the photosensitive resin film formed by applying and curing (prebaking) the first composition, applying and curing (prebaking) the second composition thereon, and exposing, developing, and curing (postbaking) , The taper angle of the pattern is smaller than that of the photosensitive resin film formed by applying, exposing, developing, and curing (postbaking) the first composition, applying, exposing, developing, and curing The stable patterning may be difficult.
However, the photosensitive double-layered resin film according to one embodiment contains an epoxy group-containing acrylic binder resin in the second composition, and the epoxy group in the epoxy group-containing acrylic binder resin is the total amount of the monomers constituting the epoxy group- By weight, and 5% by weight to 60% by weight, so that the taper angle of the pattern can be increased and stable patterning becomes possible. Further, the CD bias can be lowered to less than 10 탆 and the chemical resistance can be improved.
Hereinafter, the first resin film will be described in detail.
The first resin film is formed by applying a first composition on a substrate and curing the first composition, and the first composition includes a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a pigment, and a solvent.
Since the first resin film should have a high optical density, the pigment may include a black pigment. The black pigment may be an inorganic black pigment, an organic black pigment or a combination thereof such as aniline black, perylene black, titanium black, cyanine black, lignin black, lactam-based organic black, RGB black, carbon black, . ≪ / RTI > Specifically, the black pigment may include an inorganic black pigment and an organic black pigment, the inorganic black pigment may be carbon black, and the organic black pigment may be a lactam-based organic black represented by the following formula (A).
(A)
The RGB black refers to a pigment in which at least two or more kinds of colored pigments such as a red pigment, a green pigment, a blue pigment, a violet pigment, a yellow pigment, and a purple pigment are mixed to form a black color.
When the black pigment contains carbon black, it is excellent in light shielding property, surface smoothness, dispersion stability, compatibility with the binder resin, and the like. On the other hand, when the black pigment is used, it may be used in combination with a color correcting agent such as an anthraquinone pigment, a perylene pigment, a phthalocyanine pigment or an azo pigment.
A dispersing agent may be used together to disperse the pigment. Specifically, the pigment may be surface-treated in advance with a dispersant, or a dispersant may be added together with the pigment when the first composition is prepared.
As the dispersing agent, a nonionic dispersing agent, an anionic dispersing agent, a cationic dispersing agent and the like can be used. Specific examples of the dispersing agent include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, Alkylamido alkylene oxide adducts, and alkylamines. These may be used singly or in combination of two or more thereof.
DISPERBYK-161, DISPERBYK-160, DISPERBYK-161, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-160 and DISPERBYK-160 of BYK Co., -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 and the like; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400 and EFKA-450 of EFKA Chemical Co., Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 from Zeneka; Or Ajinomoto's PB711 and PB821.
The dispersant may be included in an amount of 0.1 to 15% by weight based on the total weight of the first composition. When the dispersing agent is contained within the above range, the dispersibility of the first composition is excellent, and thus the stability, developability and patternability of the black column spacer are excellent.
The pigment may be used by pretreatment using a water-soluble inorganic salt and a wetting agent. When the pigment is used by the pretreatment, the average particle diameter of the pigment can be made smaller.
The pretreatment may be performed by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained in the kneading step.
The kneading may be carried out at a temperature of 40 to 100 DEG C, and the filtration and washing may be performed by washing the inorganic salt with water, etc., followed by filtration.
Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride and potassium chloride. The wetting agent acts as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed to easily pulverize the pigment. Examples of the wetting agent include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and the like Alkylene glycol monoalkyl ethers; And alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol and the like. These may be used singly or in combination of two or more thereof.
Specifically, the pigment may be used in the form of a pigment dispersion including the dispersant and a solvent described later, and the pigment dispersion may include a solid pigment, a dispersant, and a solvent. At this time, the solid pigment may be included in an amount of 8 to 30% by weight based on the total weight of the pigment dispersion. The pigment dispersion may be included in an amount of 5% by weight to 30% by weight, such as 5% by weight to 20% by weight, for example, 5% by weight to 10% by weight based on the total weight of the first composition. When the pigment dispersion is contained within the above range, the resolution and the linearity of the pattern are excellent.
The binder resin may include a cadmium binder resin, an acrylic binder resin, or a combination thereof.
When the binder resin includes a cadmium binder resin, the first composition is excellent in developability, sensitivity in photo-curing is good, fine patterning property is excellent, and reliability of the black column spacer can be secured.
The cadmium binder resin may include a repeating unit represented by the following formula (8).
[Chemical Formula 8]
In Formula 8,
R 21 And R 22 are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,
R 23 And R 24 are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,
Z 1 is a single bond, O, CO, SO 2 , CR 7 R 8 , SiR 9 R 10 , wherein R 7 To R < 10 > each independently represents a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group), or a linking group represented by the following general formulas (8-1) to (8-11)
[Formula 8-1]
[Formula 8-2]
[Formula 8-3]
[Formula 8-4]
[Formula 8-5]
(In the formula 8-5,
R a is a hydrogen atom, an ethyl group, C 2 H 4 Cl, C 2 H 4 OH, CH 2 CH═CH 2 , Or a phenyl group.)
[Formula 8-6]
[Formula 8-7]
[Formula 8-8]
[Formula 8-9]
[Chemical Formula 8-10]
[Formula 8-11]
Z 2 is an acid anhydride residue,
m1 and m2 are each independently an integer of 0 to 4;
The cadmium-based binder resin may include a functional group represented by the following formula (9) in at least one of the two terminals.
[Chemical Formula 9]
In the above formula (9)
Z 3 can be represented by the following general formulas (9-1) to (9-7).
[Formula 9-1]
(In the above formula (9-1), R b And R c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.
[Formula 9-2]
[Formula 9-3]
[Formula 9-4]
[Formula 9-5]
(Wherein R d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 alkylamine group, or a substituted or unsubstituted C2 to C20 alkenyl group Phenylethyl group.
[Formula 9-6]
[Formula 9-7]
Examples of the cationic binder resin include fluorene-containing compounds such as 9,9-bis (4-oxiranylmethoxyphenyl) fluorene; Benzene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride , Tetrahydrofuran tetracarboxylic acid dianhydride, tetrahydrophthalic anhydride and the like; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol and benzyl alcohol; Propylene glycol methyl ethyl acetate, and N-methyl pyrrolidone; Phosphorus compounds such as triphenylphosphine; And an amine or an ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, or the like.
The weight average molecular weight of the cationic binder resin may be from 500 g / mol to 50,000 g / mol, such as from 1,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the cadmium binder resin is within the above range, the pattern can be formed well without residue during the production of the black column spacer, a good pattern can be obtained without loss of film thickness during development.
The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer, and is a resin containing at least one acrylic repeating unit.
The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and combinations thereof.
The first ethylenically unsaturated monomer may be included in an amount of 5% by weight to 50% by weight, for example, 10% by weight to 40% by weight based on the total amount of the acrylic resin.
The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These may be used singly or in combination of two or more.
Specific examples of the acrylic binder resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer Methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, but are not limited thereto, and they may be used alone or in combination of two or more.
The weight average molecular weight of the acrylic binder resin may be from 3,000 g / mol to 150,000 g / mol, such as from 5,000 g / mol to 50,000 g / mol, such as from 7,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the acrylic binder resin is within the above range, physical and chemical properties of the first composition are excellent, viscosity is appropriate, and adhesion to the substrate is excellent when the black column spacer is produced.
The acid value of the acrylic binder resin may be from 15 mgKOH / g to 150 mgKOH / g, such as from 80 mgKOH / g to 130 mgKOH / g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.
The binder resin in the first composition may include a cadmium-based binder resin, an acrylic-based binder resin, or a combination thereof. That is, when the cationic binder resin and the acrylic-based binder resin are mixed and used as the binder resin in the first composition, the content (weight) ratio between the cationic binder resin and the acrylic-based binder resin in the first composition is 99: 1 to 50:50.
If the content of the acrylic binder resin in the first composition exceeds the content of the cadmium binder resin, the chemical resistance and the reliability may be deteriorated.
The binder resin may be contained in an amount of 1% by weight to 30% by weight, for example, 3% by weight to 20% by weight, for example, 3% by weight to 15% by weight based on the total amount of the first composition. When the binder resin is contained within the above range, superior sensitivity, developability, resolution, and straightness of the pattern can be obtained.
The reactive unsaturated compound may be monomers or oligomers, and monofunctional or polyfunctional esters of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be used.
By having the ethylenically unsaturated double bond, the reactive unsaturated compound can form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern formation step.
The reactive unsaturated compound may be, for example, at least one selected from the group consisting of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth) Acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, or a combination thereof.
Examples of commercially available products of the above reactive unsaturated compounds are as follows. The (meth) acrylic acid is one example of a polyfunctional ester, doah Gosei cultivating the T (weeks)社of Aronix M-101 ®, copper or the like M-111 ®, the same M-114 ®; KAYARAD TC-110S ® and TC-120S ® from Nihon Kayaku Co., Ltd.; Osaka yukki cultivate may be a T (weeks)社of V-158 ®, V-2311 ® and the like. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei cultivating the T (weeks)社of Aronix M-210 ®, copper or the like M-240 ®, the same M-6200 ®; KAYARAD HDDA ® , HX-220 ® and R-604 ® from Nihon Kayaku Corporation; Osaka yukki cultivating and the like T (weeks)社of V-260 ®, V-312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei the cultivating T (weeks)社of Aronix M-309 ®, the same M-400 ®, the same M-405 ®, the same M-450 ®, Dong M -7100 ® , copper M-8030 ® , copper M-8060 ® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ®, copper DPCA-20 ®, ® copper -30, -60 ® copper, copper ® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ®, copper ® -300, -360 ® copper, copper -GPT ®, copper -3PA ®, and the like copper -400 ®. These products may be used alone or in combination of two or more.
The reactive unsaturated compound may be treated with an acid anhydride so as to give better developing properties.
The reactive unsaturated compound may be included in an amount of 1 wt% to 20 wt%, for example, 1 wt% to 10 wt% based on the total amount of the first composition. When the reactive unsaturated compound is contained in the above range, the pattern is formed with sufficient curing during exposure in the pattern formation process, and thus the pattern is excellent in heat resistance, light resistance, chemical resistance, and resolution and adhesion.
As the photopolymerization initiator, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, or a combination thereof may be used.
Examples of the acetophenone compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt Dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.
Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.
Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone and the like.
Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.
Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) - 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-1-yl) -Bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like. .
Examples of the oxime compounds include O-acyloxime compounds, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- -9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl- Can be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- 2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione -1-one oxime-O-acetate, 1- (4-phenylsulfanylphenyl) -butan-1-one oxime- O-acetate and the like can be used.
The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a nonimidazole compound in addition to the above compounds.
The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy.
Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate and the like .
The photopolymerization initiator may be included in an amount of 0.05 wt% to 5 wt%, for example, 0.1 wt% to 5 wt% with respect to the total amount of the first composition. When the photopolymerization initiator is contained within the above range, the photopolymerization initiator sufficiently undergoes curing during exposure in the pattern formation step to obtain excellent reliability, and is excellent in pattern heat resistance, light resistance, chemical resistance, resolution and adhesion, It is possible to prevent a decrease in transmittance caused by the zero.
The solvent may be a pigment dispersion containing the pigment, the binder resin, the reactive unsaturated compound, and a material having compatibility with the photopolymerization initiator but not reacting with the binder resin.
Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol dimethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate, and the like, and also include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, And high boiling solvents such as ethyl acetate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.
Of these, glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether and ethylene glycol diethyl ether are preferably used in consideration of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.
The solvent may be included in an amount of 30% by weight to 90% by weight based on the total amount of the first composition. When the solvent is included within the above range, the first composition has an appropriate viscosity, and thus the processability of the black column spacer is excellent.
Meanwhile, the first composition may further include additives such as malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.
The silane-based coupling agent may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group in order to improve adhesion with a substrate.
Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. These may be used singly or in combination of two or more.
The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the first composition. When the silane coupling agent is included in the above range, the adhesion and storage stability are excellent.
The first composition may further contain a surfactant, for example, a fluorine-based surfactant, in order to improve coatability and prevent defect formation, if necessary.
The fluorine is a surfactant, the BM Chemie社BM-1000 ®, BM-1100 ® , and the like; Mecha Pack F 142D ® , copper F 172 ® , copper F 173 ® , copper F 183 ®, etc. manufactured by Dainippon Ink & Chemicals Incorporated; Sumitomo M. (Note)社Pro rod FC-135 ®, the same FC-170C ®, copper FC-430 ®, the same FC-431 ®, and the like; Asahi Grass Co., Saffron S-112 ® of社, such S-113 ®, the same S-131 ®, the same S-141 ®, the same S-145 ®, and the like; Toray Silicone ® (Note)社SH-28PA, the same -190 ®, may be used a fluorine-containing surfactants commercially available under the name such as copper -193 ®, SZ-6032 ®, SF-8428 ®.
The surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the first composition. When the surfactant is contained within the above range, coating uniformity is ensured, no staining occurs, and wetting to an IZO substrate or a glass substrate is excellent.
In addition, the first composition may contain a certain amount of other additives such as an antioxidant, a stabilizer and the like within a range that does not impair the physical properties.
Hereinafter, the second resin film will be described in detail.
The second resin film is formed by applying a second composition on the first resin film and curing the second resin film, and the second composition includes an epoxy group-containing acrylic binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.
The epoxy group in the epoxy group-containing acrylic binder resin is derived from an epoxy group-derived monomer, and the epoxy group-derived monomer is contained in an amount of 5 to 60% by weight based on the total amount of the monomers constituting the epoxy group-containing acrylic binder resin in the second composition. Thereby, the formed pattern can maintain a high taper angle of 20 DEG or more. When the epoxy-derived monomer is contained in an amount of less than 5% by weight based on the total amount of the monomers constituting the epoxy group-containing acrylic binder resin in the second composition, the taper angle of the formed pattern is lowered to less than 20 占 and stable patterning is difficult. , The CD bias becomes large and stable patterning becomes difficult.
For example, the epoxy group-derived monomer may be used in an amount of 10 to 45% by weight, for example, 15 to 45% by weight, such as 15 to 30% by weight, based on the total amount of monomers constituting the epoxy- .
For example, the epoxy group-derived monomer may be an acrylate monomer.
The epoxy group-derived monomer may be at least one of the compounds represented by the following formulas (1) to (3). For example, the epoxy group-inducing monomer may include a compound represented by the following formula (1), a compound represented by the following formula (2), a compound represented by the following formula (3), or a combination thereof.
[Chemical Formula 1]
(2)
(3)
In the above Chemical Formulas 1 to 3,
R 1 to R 3 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L 9 to L 12 each independently represent a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group,
X is a substituted or unsubstituted C3 to C20 alicyclic ring or a substituted or unsubstituted C6 to C20 aromatic ring.
For example, the epoxy group-derived monomer may be at least one selected from the group consisting of glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxybutyl (meth) Acrylate glycidyl ether, or combinations thereof, but is not limited thereto.
The epoxy group-containing acrylic binder resin may further include a repeating unit represented by the following formula (5).
[Chemical Formula 5]
In Formula 5,
R 5 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
When the epoxy group-containing acrylic binder resin further contains the repeating unit represented by the above formula (5), the chemical resistance is excellent.
The epoxy group-containing acrylic binder resin may have a weight average molecular weight of 1,000 g / mol to 100,000 g / mol, for example, 2,000 g / mol to 50,000 g / mol. When the weight average molecular weight of the epoxy group-containing acrylic binder resin is within the above range, the physical properties of the black column spacer, such as chemical resistance and development margin, can be further optimized.
The epoxy group-containing acrylic binder resin may have a degree of dispersion of 1.0 to 3.0, such as 1.5 to 3.0, for example, 2.0 to 2.5. When the degree of dispersion of the epoxy group-containing acrylic binder resin is within the above range, the development margin and physical properties of the formed spacer are excellent. The degree of dispersion means a value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).
Since the second composition is intended to realize spacers and steps and does not necessarily require a high optical density, the pigment (particularly the pigment dispersion containing the pigment) of the constituents of the first composition is not necessarily contained in the composition . That is, the second composition may further comprise a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent, or, if necessary, the second composition may also include a pigment (specifically, a pigment dispersion containing a pigment). In addition, the second composition may further comprise additives described for the first composition.
The second composition may contain the same constituents as those of the first composition except for the epoxy group-containing acrylic binder resin and the reactive unsaturated compound. However, in this case, the content of each component of the first composition and the second composition may be different, so that the optical density per 1 μm of the first composition and the second composition may be different.
Therefore, the photopolymerization initiator, the pigment (specifically, the pigment dispersion including the pigment), the solvent, and the additive, etc. constituting the second composition for forming the second resin film are not limited to those described for the first composition for forming the first resin film . ≪ / RTI >
The optical density per 1 mu m of the second resin film may be lower than the optical density per 1 mu m of the first resin film by 0.4 or more, for example, 1.0 or more, such as 1.5 or more.
The epoxy group-containing acrylic binder resin in the second composition may be contained in an amount of 1 to 10% by weight, for example, 3 to 10% by weight based on the total amount of the second composition. When the epoxy group-containing acrylic binder resin is contained within the above range, excellent sensitivity, developability, resolution, and straightness of pattern can be obtained.
The reactive unsaturated compound in the second composition may contain an acidic functional group, unlike the reactive unsaturated compound in the first composition.
The acid functional groups may include -COOH, -SO 3 H, -OSO 3 H, or a combination thereof, such as -COOH.
For example, the reactive unsaturated compound in the second composition may include a functional group derived from a dibasic acid at the terminal. In this case, there is an excellent effect of increasing the taper angle of the reactive unsaturated compound containing no functional group.
The dibasic acids include, for example, monophthalate, monosuccinate, oxalic acid, malonic acid, naphthalenedicarboxylic acid, quinolinic acid, and the like, but are not limited thereto.
For example, the reactive unsaturated compound in the second composition may be represented by the following formula (6) or (7).
[Chemical Formula 6]
(7)
In the above formulas (6) and (7)
R 11 and R 12 are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group,
L 1 to L 8 each independently represents a C1 to C10 alkylene group,
A represents a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C3 to C20 cycloalkenylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heteroarylene group to be.
In addition, since the reactive unsaturated compound in the second composition has an ethylenically unsaturated double bond, sufficient polymerization can be caused during exposure in the pattern formation step, and a pattern excellent in heat resistance, light resistance, and chemical resistance can be formed.
The content of the reactive unsaturated compound in the second composition may be the same as that described for the reactive unsaturated compound in the first composition, except for the above-mentioned contents.
The reactive unsaturated compound in the second composition may be included in an amount of 1 wt% to 10 wt%, for example, 3 wt% to 7 wt% with respect to the total amount of the second composition. When the reactive unsaturated compound is contained within the above range, the pattern formation process sufficiently cures upon exposure to light, thereby providing excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, and excellent resolution and adhesion.
The photopolymerization initiator in the second composition may be included in an amount of 0.1 wt% to 5 wt%, for example, 0.1 wt% to 3 wt% with respect to the total amount of the second composition. When the photopolymerization initiator is contained within the above range, it is possible to obtain sufficient reliability due to sufficient curing during exposure in the pattern formation step, to have excellent heat resistance, light resistance and chemical resistance, excellent resolution and adhesion, It is possible to prevent the transmittance from being lowered.
The solvent in the second composition may be contained in an amount of from about 40% by weight to about 95% by weight based on the total amount of the second composition. When the solvent is contained within the above range, the second composition has an appropriate viscosity, and therefore, the black column spacer is excellent in the fairness in manufacturing the black column spacer. However, the solvent of the second composition may be lower in solubility (lower) than the solvent of the first composition. For example, the solvent of the first composition may be PGMEA, PGME, EDM (ethylene glycol dimethyl ether), 3-MBA, EEP, and the solvent of the second composition may be PGMEA, 3-MBA, n-butyl acetate, , n-hexyl acetate, and the like, but are not limited thereto.
Another embodiment provides a black column spacer prepared by exposing and developing the above-mentioned photosensitive resin film, for example, exposure, development, and curing.
The pattern in the black column spacer may have a taper angle of 20 DEG or more, for example, 20 DEG or more and 60 DEG or less.
The black column spacer manufacturing method is as follows.
(1) Coating and Film Formation Step
The first composition is coated on a substrate such as a glass substrate or an IZO substrate subjected to a predetermined pretreatment to a desired thickness using a spin, slit coat method, roll coating method, screen printing method, applicator method, And then heated at 70 DEG C to 100 DEG C for 1 minute to 10 minutes to remove the solvent to form a first resin film. Thereafter, the second composition is applied and cured on the first resin film in the same manner. Thus, a photosensitive double-layered resin film according to one embodiment is formed.
(2) Exposure step
In order to form a pattern necessary for the obtained photosensitive double-layer resin film, a mixed mask consisting of a half tone portion for implementing a black matrix pattern and a full tone portion for implementing a column spacer pattern is interposed, and then an active line of 200 nm to 500 nm is irradiated. As the light source used for the irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, and the like can be used.
The exposure dose differs depending on the kind of each component of the composition, the blending amount, and the dried film thickness, but is 500 mJ / cm 2 (according to the 365 nm sensor) or less when high pressure mercury lamp is used.
(3) Development step
As a developing method, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution as a developing solution following the above-described exposure step, so that only the exposed portion is left to form a pattern.
(4) Post-treatment step
There is a post-heating process for obtaining an image pattern obtained by development in the above process, in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability.
Another embodiment provides a color filter comprising the black column spacer.
Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.
( Example )
(Photosensitive Double layer Resin film Produce)
Example One
The following compositions were used to prepare the first composition in the composition shown in Table 1 below and the second composition in the composition shown in Table 2 below. The first composition is coated on a substrate such as a glass substrate or an IZO substrate to a thickness of 2.0 탆 and then dried and cured by a VCD process or the like for 1 minute to 10 minutes to form a second composition having a thickness of 1.5 탆 And then cured for 1 minute to 10 minutes to prepare a photosensitive double-layered resin film according to Example 1 composed of two layers.
Specific methods of preparing the first composition and the second composition are as follows. After dissolving the photopolymerization initiator in the solvent, the mixture was thoroughly stirred at room temperature for 30 minutes or more, and then binder resin and reactive unsaturated compound were added thereto, followed by stirring at room temperature for about 1 hour. Subsequently, the other additives were added to the resulting solution, and the mixture was stirred for about 10 minutes. Then, the pigment dispersion was added thereto and stirred at room temperature for 2 hours or more (in the case of the second composition, the step of adding pigment dispersion may be omitted). The product was then filtered three times to remove impurities, thereby preparing the first composition and the second composition, respectively.
(In Table 1, the lactam-based organic black is represented by the following formula (A).
(A)
Epoxy group-containing acrylic binder resin ( BCS94 , Samsung SDI) Synthetic example
In a 1 L three-necked flask, 210 g of propylene glycol acetate is added, and the mixture is purged with nitrogen while maintaining 85 ° C. Further, 25.0 g of glycidyl methacrylate, 25.0 g of acrylic acid, 55.0 g of benzylmethacrylate, 20.0 g of hydroxyl methacrylate and 12.0 g of styrene were added to a 500 mL beaker, and 7.5 g of dimethyl 2,2'-azobis (2-methylpropionate) And the mixture is stirred to dissolve. The dissolved and dissolved solution was dropped into another three-necked flask for 3 hours, followed by further reaction for 3 hours to terminate the reaction.
The measured weight average molecular weight is 15,000 g / mol and the dispersity (PDI) is 2.5.
Example 2
A photosensitive double-layer resin film according to Example 2 was prepared in the same manner as in Example 1 except that the second composition was prepared using the following components in the compositions shown in Table 3 below.
Epoxy group-containing acrylic binder resin ( BCS95 , Samsung SDI) Synthetic example
In a 1 L three-necked flask, 210 g of propylene glycol acetate is added, and the mixture is purged with nitrogen while maintaining 85 ° C. 35.0 g of glycidyl methacrylate, 25.0 g of acrylic acid, 45.0 g of benzylmethacrylate, 20.0 g of hydroxyl methacrylate and 12.0 g of styrene were added to a 500 mL beaker, and 7.5 g of dimethyl 2,2'-azobis (2-methylpropionate) And the mixture is stirred to dissolve. The dissolved and dissolved solution was dropped into another three-necked flask for 3 hours, followed by further reaction for 3 hours to terminate the reaction.
The measured molecular weight is 15,000 g / mol and the dispersity (PDI) is 2.5.
Example 3
The following compositions were prepared in the same manner as in Example 1 except that the first composition was prepared in the composition shown in Table 4 below and the second composition was prepared in the composition shown in Table 5 below. To prepare a photosensitive double-layered resin film.
(In Table 4, the lactam-based organic black is represented by the following formula (A).
(A)
Epoxy group-containing acrylic binder resin ( BCS89 , Samsung SDI) Synthetic example
In a 1 L three-necked flask, 210 g of propylene glycol acetate is added, and the mixture is purged with nitrogen while maintaining 85 ° C. 20.0 g of Cyclomer M-100 (DAICEL), 18.0 g of acrylic acid, 27.0 g of benzylmethacrylate, 30.0 g of N-phenylmaleimide and 6.0 g of styrene were added to a 500 mL beaker, followed by the addition of dimethyl 2,2'-azobis 2-methylpropionate), and dissolve by stirring. The solution, which is dissolved by stirring, is dropped into a three-necked flask for 3 hours and then reacted for further 3 hours to terminate the reaction.
The measured weight average molecular weight is 15,000 g / mol and the dispersity (PDI) is 2.5.
Example 4
A photosensitive double-layered resin film according to Example 4 was prepared in the same manner as in Example 3, except that the second composition was prepared in the composition shown in the following Table 6 using the following components.
Epoxy group-containing acrylic binder resin ( BCS90 , Samsung SDI) Synthetic example
In a 1 L three-necked flask, 210 g of propylene glycol acetate is added, and the mixture is purged with nitrogen while maintaining 85 ° C. 20.0 g of Cyclomer M-100 (DAICEL), 18.0 g of acrylic acid, 22.0 g of benzylmethacrylate, 35.0 g of N-phenylmaleimide and 6.0 g of styrene were added to a 500 mL beaker, and dimethyl 2,2'-azobis 2-methylpropionate), and dissolve by stirring. The solution, which is dissolved by stirring, is dropped into a three-necked flask for 3 hours and then reacted for further 3 hours to terminate the reaction.
The measured molecular weight is 13,000 g / mol and the dispersity (PDI) is 2.3.
Comparative Example One
A photosensitive double-layered resin film according to Comparative Example 1 was prepared in the same manner as in Example 1 except that the second composition was prepared using the following components as shown in Table 7 below.
Acrylic binder resin ( BCS47 , Samsung SDI) Synthetic example
In a 1 L three-necked flask, 210 g of propylene glycol acetate is added, and the mixture is purged with nitrogen while maintaining 85 ° C. After addition of 18.0 g of acrylic acid, 42.0 g of benzylmethacrylate, 35.0 g of N-phenylmaleimide and 6.0 g of styrene, 7.5 g of dimethyl 2,2'-azobis (2-methylpropionate) as a photopolymerization initiator was added to a 500 mL beaker, . The solution, which is dissolved by stirring, is dropped into a three-necked flask for 3 hours and then reacted for further 3 hours to terminate the reaction.
The measured molecular weight is 14,000 g / mol and the dispersity (PDI) is 2.3.
Comparative Example 2
A photosensitive double-layered resin film according to Comparative Example 2 was prepared in the same manner as in Example 1, except that the second composition was prepared in the composition shown in Table 8 below using the following components.
The epoxy group-containing acrylic binder resin A Synthetic example
In a 1 L three-necked flask, 210 g of propylene glycol acetate is added, and the mixture is purged with nitrogen while maintaining 85 ° C. After addition of 4 g of glycidyl methacrylate, 25.0 g of acrylic acid, 46 g of benzylmethacrylate, 13 g of hydroxyl methacrylate and 12.0 g of styrene, 7.5 g of dimethyl 2,2'-azobis (2-methylpropionate) as a photopolymerization initiator was added to a 500 mL beaker Dissolve by stirring. The dissolved and dissolved solution was dropped into another three-necked flask for 3 hours, followed by further reaction for 3 hours to terminate the reaction.
The measured weight average molecular weight is 13500 g / mol and the dispersity (PDI) is 2.3.
Comparative Example 3
A photosensitive double-layered resin film according to Comparative Example 3 was prepared in the same manner as in Example 3, except that the second composition was prepared in the composition shown in the following Table 9 using the following components.
Of the epoxy group-containing acrylic binder resin B Synthetic example
In a 1 L three-necked flask, 210 g of propylene glycol acetate is added, and the mixture is purged with nitrogen while maintaining 85 ° C. Next, 90 g of Cyclomer M-100 (DAICEL), 18.0 g of acrylic acid, 5 g of benzylmethacrylate, 30.0 g of N-phenylmaleimide and 6.0 g of styrene were added to a 500 mL beaker, and dimethyl 2,2'-azobis methylpropionate), and dissolve by stirring. The solution, which is dissolved by stirring, is dropped into a three-necked flask for 3 hours and then reacted for further 3 hours to terminate the reaction.
The measured weight average molecular weight is 17,000 g / mol and the dispersity (PDI) is 2.5.
Rating 1: Taper Evaluation of angle and CD bias
The photosensitive double-layer resin films prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were exposed at 50 mJ using a photomask with an exposure machine (Ushio, HB-50110AA). Subsequently, the substrate was developed with a 0.2 wt% aqueous solution of potassium hydroxide (KOH) for 150 seconds using a developing machine (SVS, SSP-200) and hard-baked or post-baked in an oven at 230 캜 for 30 minutes. And the patterned specimen was obtained. The taper angle of the black column spacer pattern of the patterned specimen was measured using a scanning electron microscope (SEM). In addition, the pattern of the sample was measured using a 3D measuring instrument (nanoview, nanosystem), and the CD bias of the black column spacer was measured. (CD bias was measured at a mask of 10 탆). The measurement results are shown in Table 10 and Figs. 1 to 7.
Through Table 10 and Figs. 1 to 7, it can be seen that the second composition comprises a reactive unsaturated compound containing an acidic functional group and an acrylic binder resin containing an epoxy group, and the epoxy group-derived monomer Of Examples 1 to 4 containing 5% by weight to 60% by weight of the polyimide precursor were superior to the Comparative Examples 1 to 3 in the straightness of the pattern and at 20 ° or more suitable for the compression characteristics and recovery rate of the column spacer It can be confirmed that stable patterning is possible with a taper angle.
Evaluation 2: Chemical resistance evaluation
After coating the photosensitive double-layer resin films prepared in Examples 1 to 4 and Comparative Examples 1 to 3, exposure energy of half tone region was exposed (25% energy of full tone region) Thereby preparing a photosensitive resin film. The final thickness of the double-layer photosensitive resin film is 2 탆, cut into a size of 3 × 3 cm, immersed in 2 ml NMP, and left in an oven at 100 ° C. for 10 minutes. Then, the NMP was measured using HPLC, and the peak areas were added together to measure the chemical resistance. The results are shown in Table 11 below.
As shown in Table 11 above, the second composition comprises a reactive unsaturated compound containing an acidic functional group and an epoxy group-containing acrylic binder resin, wherein the epoxy group-derived monomer is contained in an amount of 5 to 60% by weight based on the total amount of monomers constituting the acrylic- It can be confirmed that Examples 1 to 4, which are contained in terms of% by weight, are superior in chemical resistance as compared with Comparative Examples 1 and 2. Further, when a monomer such as N-phenylmaleimide is further used in addition to the epoxy group-derived monomer in the production of the binder resin, it is confirmed that the chemical resistance is further improved. In the case of Comparative Example 3, it was confirmed that the epoxy group-containing monomers were contained much more than in Examples 1 to 3 and Comparative Examples 1 and 2, and excellent effects were obtained in terms of chemical resistance.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.
Claims (20)
Wherein the first composition comprises a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a pigment, and a solvent,
Wherein the second composition comprises an epoxy group-containing acrylic binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent,
Wherein the epoxy group is derived from an epoxy group-derived monomer, and the epoxy group-derived monomer is contained in an amount of 5 to 60% by weight based on the total amount of the monomers constituting the epoxy group-containing acrylic binder resin in the second composition.
Photosensitive double layer resin film.
Wherein the epoxy group-derived monomer is contained in an amount of 15% by weight to 45% by weight based on the total amount of monomers constituting the epoxy group-containing acrylic binder resin in the second composition.
Wherein the epoxy group-derived monomer is an acrylate monomer.
Wherein the epoxy group-derived monomer is at least one of compounds represented by the following general formulas (1) to (3):
[Chemical Formula 1]
(2)
(3)
In the above Chemical Formulas 1 to 3,
R 1 to R 3 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L 9 to L 12 each independently represent a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group,
X is a substituted or unsubstituted C3 to C20 alicyclic ring or a substituted or unsubstituted C6 to C20 aromatic ring.
The epoxy-group-containing acrylic binder resin is a photosensitive double-layer resin film comprising a repeating unit represented by the following formula (5)
[Chemical Formula 5]
In Formula 5,
R 5 is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
Wherein the epoxy group-containing acrylic binder resin has a weight average molecular weight of 1,000 g / mol to 100,000 g / mol.
Wherein the epoxy group-containing acrylic binder resin has a degree of dispersion of 1.0 to 3.0.
Wherein the reactive unsaturated compound in the second composition comprises an acidic functional group.
The acidic functional group is -COOH, -SO 3 H, -OSO 3 H, or a double layer film photosensitive resin comprising a combination of the two.
The reactive unsaturated compound in the second composition is a photosensitive double layer resin film represented by the following formula 6 or 7:
[Chemical Formula 6]
(7)
In the above formulas (6) and (7)
R 11 and R 12 are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group,
L 1 to L 8 each independently represents a C1 to C10 alkylene group,
A represents a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C3 to C20 cycloalkenylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heteroarylene group to be.
Wherein the binder resin in the first composition comprises a cationic binder resin, an acrylic binder resin, or a combination thereof.
Wherein the weight ratio of the cationic binder resin to the acrylic binder resin is from 99: 1 to 50:50.
Wherein the pigment comprises a black pigment.
Wherein the black pigment includes aniline black, perylene black, titanium black, cyanine black, lignin black, lactam-based organic black, RGB black, carbon black, or a combination thereof.
Wherein the first composition comprises a pigment dispersion comprising the pigment,
The first composition comprises 1 to 30% by weight of a binder resin, 1 to 20% by weight of a reactive unsaturated compound, 0.05 to 5% by weight of a photopolymerization initiator, 5 to 30% by weight of a pigment dispersion, Wherein the photosensitive double-layered resin film comprises:
The second composition is a photosensitive double layer resin film comprising an epoxy group-containing acrylic binder resin in an amount of 1 to 10% by weight, a reactive unsaturated compound in an amount of 1 to 10% by weight, a photopolymerization initiator in an amount of 0.1 to 5% .
Wherein the second composition further comprises a pigment.
The first composition and the second composition may each independently include an additive of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine surfactant, a radical polymerization initiator, Containing photosensitive double-layer resin film.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180086156A (en) * | 2017-01-20 | 2018-07-30 | 동우 화인켐 주식회사 | A photo sensitive resin composition, a color filter comprising a black metrics, a column spacer or black column spacer prepared by using the composition, and a display devide comprising the color filter |
| KR20180114580A (en) * | 2017-04-10 | 2018-10-19 | 삼성디스플레이 주식회사 | Photosensitive resin composition, and electronic device comprising cured product of composition for forming pattern comprising the same |
| CN109659151A (en) * | 2019-01-17 | 2019-04-19 | 中南大学 | A method of different Carbon-based supercapacitor electrode materials are prepared by regulating and controlling lignin molecule amount |
Family Cites Families (2)
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|---|---|---|---|---|
| JP6164050B2 (en) * | 2013-11-01 | 2017-07-19 | コニカミノルタ株式会社 | Optical film, polarizing plate, manufacturing method thereof, and image display device |
| KR101474803B1 (en) * | 2014-03-27 | 2014-12-19 | 제일모직주식회사 | Method of manufacturing black column spacer, black column spacer, and color filter |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180086156A (en) * | 2017-01-20 | 2018-07-30 | 동우 화인켐 주식회사 | A photo sensitive resin composition, a color filter comprising a black metrics, a column spacer or black column spacer prepared by using the composition, and a display devide comprising the color filter |
| KR20190039048A (en) * | 2017-01-20 | 2019-04-10 | 동우 화인켐 주식회사 | A photo sensitive resin composition, a color filter comprising a black metrics, a column spacer or black column spacer prepared by using the composition, and a display devide comprising the color filter |
| KR20180114580A (en) * | 2017-04-10 | 2018-10-19 | 삼성디스플레이 주식회사 | Photosensitive resin composition, and electronic device comprising cured product of composition for forming pattern comprising the same |
| CN109659151A (en) * | 2019-01-17 | 2019-04-19 | 中南大学 | A method of different Carbon-based supercapacitor electrode materials are prepared by regulating and controlling lignin molecule amount |
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