CN106200089B - Liquid crystal display device with a light guide plate - Google Patents
Liquid crystal display device with a light guide plate Download PDFInfo
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- CN106200089B CN106200089B CN201510397274.3A CN201510397274A CN106200089B CN 106200089 B CN106200089 B CN 106200089B CN 201510397274 A CN201510397274 A CN 201510397274A CN 106200089 B CN106200089 B CN 106200089B
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Abstract
The invention provides a liquid crystal display, comprising a thin film transistor on a lower substrate; a plurality of color filters on the thin film transistor and aligned to be spaced apart from each other; an insulating layer on the plurality of color filters; a light blocking layer on the insulating layer; a transparent layer having a convex surface and located on the light blocking layer; an upper substrate facing the lower substrate; and a liquid crystal layer interposed between the lower substrate and the upper substrate, wherein the light-blocking layer includes an organic black pigment, and a shape of the transparent layer having the convex surface is different from a shape of the light-blocking layer. The present invention can provide a liquid crystal display having excellent reliability.
Description
Cross Reference to Related Applications
The present application claims priority and benefit of korean patent application No. 10-2014-0161934 filed by the korean intellectual property office on 19/11/2014, which is incorporated herein by reference in its entirety.
Technical Field
The present invention relates to a liquid crystal display (L CD).
Background
A liquid crystal display (L CD) is one of the most widely used flat panel displays and is a display device that adjusts the amount of transmitted light by applying a voltage to electrodes formed by interposing a liquid crystal layer between two display panels and realigning liquid crystal molecules of the liquid crystal layer.
Specifically, the main structure is that a plurality of thin film transistors and pixel electrodes are aligned in a matrix form in one display panel (hereinafter, referred to as "thin film transistor array panel"), and red, green, and blue color filters are formed in the other display panel (hereinafter, referred to as "common electrode panel"), and the common electrode covers the front side thereof.
However, since the pixel electrodes and the color filters are formed in different display panels and it is difficult to precisely align therebetween, the liquid crystal display (L CD) may have an alignment error.
On the other hand, the light blocking layer is formed to be larger than a predetermined size in consideration of an alignment margin when the thin film transistor array panel and the common electrode group are aligned.
In addition, a liquid crystal layer space between two display panels is called a liquid crystal layer gap (cell gap), and the liquid crystal layer gap has an effect on overall operational characteristics (e.g., response speed, contrast ratio, viewing angle, luminance uniformity, etc.) of the liquid crystal display (L CD).
Therefore, there is an increasing demand for a liquid crystal display (L CD) that prevents the aperture ratio from deteriorating due to the increase in the size of the light blocking layer and maintains a uniform liquid crystal layer gap over the entire front side of the substrate.
Disclosure of Invention
One embodiment provides a liquid crystal display (L CD) having excellent reliability by simultaneously forming a light-blocking layer and a light-blocking layer having a shape different from that of a transparent layer.
One embodiment provides a liquid crystal display (L CD) including a thin film transistor on a lower substrate, a plurality of color filters on the thin film transistor and aligned to be spaced apart from each other, an insulating layer on the plurality of color filters, a light blocking layer on the insulating layer, a transparent layer on the light blocking layer and having a convex surface (covex), an upper substrate facing the lower substrate, and a liquid crystal layer interposed between the lower substrate and the upper substrate, wherein the light blocking layer includes an organic black pigment, and a shape of the transparent layer having a convex surface is different from a shape of the light blocking layer.
The organic black pigment may include a compound represented by the following chemical formula 1.
[ chemical formula 1]
In the chemical formula 1, the first and second,
R11to R20Independently hydrogen or substituted or unsubstituted C1 to C10 alkyl.
The transparent layer having the convex surface may cover all or a portion of the front surface of the light blocking layer.
The transparent layer may include a primary transparent layer and a secondary transparent layer.
The thickness of the primary transparent layer may be thicker than the thickness of the secondary transparent layer.
The primarily transparent layer may support a gap between the upper substrate and the lower substrate.
The liquid crystal display (L CD) may further include a pixel electrode between the insulating layer and the light blocking layer.
The liquid crystal display (L CD) may further include a common electrode interposed between the upper substrate and the liquid crystal layer.
The liquid crystal display (L CD) may also include a common electrode directly on the lower substrate.
The optical density of the light blocking layer may be about 1.0 or more than 1.0 greater than the optical density of the transparent layer.
The light blocking layer and the transparent layer may be manufactured by: coating the light blocking layer composition and drying it, coating the clear layer composition on the dried light blocking layer composition and drying it, and simultaneously exposing and developing the light blocking layer composition and the clear layer composition.
The light blocking layer composition may include a binder resin, a reactive unsaturated compound, a photopolymerization initiator, an organic black pigment, and a solvent.
The light blocking layer composition may include about 1 wt% to about 30 wt% of a binder resin; about 1% to about 20% by weight of a reactive unsaturated compound; about 0.05% to about 5% by weight of a photopolymerization initiator; about 1% to about 30% by weight of an organic black pigment, and the balance solvent.
The transparent layer composition may include an adhesive resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.
The transparent layer composition may further include a black pigment.
The transparent layer composition may include about 3 wt% to about 70 wt% of the binder resin; about 2 wt% to about 40 wt% reactive unsaturated compound; about 0.1 wt% to about 5 wt% of a photopolymerization initiator; and the balance solvent.
Other embodiments of the invention are included in the following detailed description.
A light-blocking layer and a light-blocking layer having a convex surface and a shape different from that of the transparent layer are simultaneously formed to provide a liquid crystal display (L CD) having excellent reliability.
Drawings
Fig. 1 to 4 are cross-sectional views of a liquid crystal display (L CD) according to an exemplary embodiment.
Fig. 5 is a schematic diagram illustrating a light blocking layer and a transparent layer structure in a conventional liquid crystal display (L CD).
Fig. 6 and 7 are schematic views illustrating a light blocking layer and a transparent layer structure in a liquid crystal display (L CD) according to an exemplary embodiment.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein. These exemplary embodiments disclosed in this specification are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.
In the drawings, the thickness of layers and regions are exaggerated for clarity. In addition, the layers and regions illustrated in the drawings are schematic in nature, and their shapes are not intended to illustrate the precise shape of a component of an object, and are not intended to limit the scope of the invention. It will be understood that when a layer is referred to as being "on" another layer or substrate, it can be directly on the other layer or substrate, or a third layer may be present therebetween. Like reference numerals refer to like elements throughout this specification.
As used herein, when a specific definition is not otherwise provided, the term "alkyl" refers to C1 to C20 alkyl, the term "alkenyl" refers to C2 to C20 alkenyl, the term "cycloalkenyl" refers to C3 to C20 cycloalkenyl, the term "heterocycloalkenyl" refers to C3 to C20 heterocycloalkenyl, "aryl" refers to C6 to C20 aryl, the term "arylalkyl" refers to C6 to C20 arylalkyl, the term "alkylene" refers to C1 to C20 alkylene, the term "arylene" refers to C6 to C20 arylene, the term "alkylarylene" refers to C6 to C20 alkylarylene, the term "heteroarylene" refers to C3 to C20 heteroarylene, and the term "alkyleneoxy" refers to C1 to C20 alkyleneoxy.
As used herein, when a specific definition is not otherwise provided, the term "substituted" refers to a compound substituted with a substituent selected from the group consisting of: halogen (F, CI, Br, or I), hydroxyl, C1 to C20 alkoxy, nitro, cyano, amino, imino, azido, amidino, hydrazino, hydrazono, carbonyl, carbamoyl (carbamyl group), thiol, ester, ether, carboxyl, or a salt thereof, sulfonic acid, or a salt thereof, phosphoric acid, or a salt thereof, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C20 aryl, C3 to C20 cycloalkyl, C3 to C20 cycloalkenyl, C3 to C20 cycloalkynyl, C2 to C20 heterocycloalkyl, C2 to C20 heterocycloalkenyl, C2 to C20 heterocycloalkynyl, C3 to C20 heteroaryl, or a combination thereof.
As used herein, the term "hetero", when a specific definition is not otherwise provided, refers to a compound of formula containing at least one heteroatom selected from N, O, S and P.
As used herein, the term "combination" refers to mixing or copolymerization when a specific definition is not otherwise provided.
As used herein, a cationic-based cyclic (cardo-based) resin refers to a resin comprising at least one functional group selected from the following chemical formulae 2-1 to 2-11 in a main chain.
As used herein, unless a specific definition is otherwise provided, when a chemical bond is not drawn, a hydrogen atom is bonded at the position where the bond will occur.
A liquid crystal display (L CD) according to one embodiment includes a thin film transistor on a lower substrate, a plurality of color filters on the thin film transistor and aligned to be spaced apart from each other, an insulating layer on the plurality of color filters, a light blocking layer on the insulating layer, a transparent layer on the light blocking layer and having a convex surface, an upper substrate facing the lower substrate, and a liquid crystal layer interposed between the lower substrate and the upper substrate, wherein the light blocking layer includes an organic black pigment, and a shape of the transparent layer having a convex surface is different from a shape of the light blocking layer.
The light blocking layer and the transparent layer do not need to have the same thickness because they are different in shape. However, the light blocking layer and the transparent layer have different cross sections because they are different in shape.
Referring to fig. 5 below, a transparent layer having the same shape as that of the light blocking layer is disposed on the light blocking layer in the conventional liquid crystal display (L CD), however, referring to fig. 6 and 7 below, more than one transparent layer having a shape different from that of the light blocking layer is disposed on the light blocking layer in the liquid crystal display (L CD) according to an embodiment.
When the light blocking layer and the transparent layer in the liquid crystal display (L CD) have the shapes provided in fig. 6 below, a fine pattern can be advantageously formed by reducing the Critical Dimension (CD), and here, when the light blocking layer and the transparent layer in the liquid crystal display (L CD) have the shapes provided in fig. 7 below, the reliability can be improved.
Fig. 1 to 4 are cross-sectional views of a liquid crystal display (L CD) according to an exemplary embodiment.
Referring to fig. 1 to 4, a thin film transistor is located on a lower substrate 200. The thin film transistor may be composed of three terminals (a control terminal, an input terminal, and an output terminal) as a switch. The thin film transistor may include a gate electrode 111, a gate insulating layer 112, a semiconductor 113, a source electrode 114, a drain electrode 115, and a protective layer 116.
Specifically, a gate line and a gate electrode 111 including a storage electrode line are formed on the lower substrate 200.
The gate line may be more than one, and the gate electrode including the gate line may be more than one. The plurality of gate lines extend in a horizontal direction and transmit gate signals. A plurality of gate electrodes may be connected to each other and form one protruding portion.
The storage electrode line may be more than one, and mainly extend in a horizontal direction and transmit a predetermined voltage, such as a common voltage (Vcom), or the like.
A gate insulating layer 112 is formed on the gate electrode 111. The gate insulation layer 112 may comprise silicon nitride, silicon dioxide, or a combination thereof.
A semiconductor 113 is formed on the gate insulating layer 112, and the semiconductor 113 may be formed of amorphous silicon, crystalline silicon, or the like. The semiconductor 113 mainly extends in a vertical direction and may extend toward the plurality of gate electrodes.
More than one pair of ohmic contact elements (not shown) are formed on the semiconductor 113. The ohmic contact element may be formed of, for example, silicide or n + hydrogenated amorphous silicon doped with a high concentration of n-type impurities.
On the ohmic contact, a data conductor including a data line and a drain electrode 115 is formed.
The data lines transmit data signals and mainly extend in a vertical direction, and thus cross the gate lines. Each data line extends toward the gate electrode 111 and includes source electrodes 114 connected to each other.
On the thin film transistor, a plurality of color filters 110a, 110b, and 110c are disposed. The color filters 110a, 110b and 110c include red, green and blue filters spaced apart from each other. The color filters 110a, 110b and 110c are spaced apart from each other in the horizontal direction, but may be formed in stripes in the vertical direction.
An insulating layer 120 is disposed on the plurality of color filters 110a, 110b, and 110 c. The insulating layer 120 may be located in a space between adjacent color filters. The insulating layer 120 may be formed as an organic layer or an inorganic layer, but the inorganic layer may be more preferable. When the insulating layer 120 is formed as an organic layer, it is difficult to form one step by using a light-blocking layer and a transparent layer. In addition, the insulating layer 120 may not be patterned, and thus is partially patterned by a photolithography process, unlike an overcoat layer (over coating layer), which is baked immediately after being coated on the front side.
A light blocking layer 140 is disposed on the insulating layer 120, and a transparent layer 150 is disposed on the light blocking layer 140.
The liquid crystal display (L CD) may further include an auxiliary light-blocking layer (not shown) between the insulating layer 120 and the light-blocking layer 140.
The light-blocking layer 140 includes an organic black pigment to have a high optical density, and the organic black pigment may include a lactam-based organic black, such as a compound represented by the following chemical formula 1.
[ chemical formula 1]
In the chemical formula 1, the first and second,
R11to R20Independently hydrogen or substituted or unsubstituted C1 to C10 alkyl. For example, R11To R20May be hydrogen.
The transparent layer having the convex surface may cover all or a portion of the front surface of the light blocking layer.
For example, referring to fig. 6 below, the transparent layer having a convex surface in the liquid crystal display (L CD) according to one exemplary embodiment covers a portion of the front side of the light blocking layer, and referring to fig. 7 below, the transparent layer having a convex surface in the liquid crystal display (L CD) according to the exemplary embodiment covers the entire front side of the light blocking layer.
The transparent layer may be disposed on the front side of the light blocking layer by a photo halftone (photo halftone) process as described below.
The transparent layer may include a primary transparent layer 152 and a secondary transparent layer 153, and here, the primary transparent layer and the secondary transparent layer are independently present, e.g., a side of the primary transparent layer or the like is not in contact with a side of the secondary transparent layer or the like.
The light blocking layer and the transparent layer are simultaneously formed as described below, and here, the primary transparent layer may have a role of a spacer that supports a space between the upper substrate and the lower substrate, and the secondary transparent layer may have a role of a secondary spacer that assists the primary transparent layer and supports a space between the upper substrate and the lower substrate. Thus, the primary transparent layer having the spacer function may be thicker than the secondary transparent layer having the secondary spacer function. In this way, when the transparent layers are formed separately as the primary transparent layer and the secondary transparent layer, the primary transparent layer supports the secondary transparent layer even when the buffer effect is deteriorated, and thus structural stability can be ensured.
On the other hand, a pixel electrode 130 including an auxiliary pixel electrode may be formed on the insulating layer 120. The auxiliary pixel electrodes may be spaced apart from each other at intervals of the plurality of gate lines and disposed at the top and bottom of each gate line, respectively, and thus adjacent to each other in a column direction. The auxiliary pixel electrode may have an overall quadrangular shape.
On the upper substrate 300, for example, between the upper substrate 300 and the liquid crystal layer 160, a common electrode 170 may be formed, and between the common electrode 170 and the liquid crystal layer 160, an alignment layer (not shown) may be formed. The common electrode 170 may transmit a common voltage.
The common electrode 170 may be directly formed on the lower substrate 200 instead of the upper substrate 300, and a patterned electrode may be used instead of the common electrode 170.
The liquid crystal layer 160 has negative dielectric anisotropy, and when there is no electric field, liquid crystal molecules of the liquid crystal layer 160 are aligned with their long axes perpendicular to the surfaces of the two substrates (upper and lower substrates). The liquid crystal layer 160 includes an alignment aid including a reactive mesogen (mesogen), and the liquid crystal molecules may have a pretilt angle and a long axis thereof substantially parallel to a length direction of the pixel electrode 130. The alignment aid may be included in the alignment layer rather than the liquid crystal layer.
On the other hand, the structure of the thin film transistor described with reference to fig. 1 to 4 is only an example and may be modified to include various structures of the thin film transistor structure.
The light blocking layer and the transparent layer may be formed by: coating and drying the light blocking layer composition, drying and coating the clear layer composition on the dried light blocking layer composition, and simultaneously exposing and developing the dried light blocking layer composition and the clear layer composition.
The exposure may be performed by using a halftone mask. The halftone mask may include a region transmitting about 100% of light during exposure, a region transmitting about 25% to about 35% of light during exposure, a region transmitting about 15% to about 25% of light during exposure, and a region transmitting about 0% of light during exposure, but the structure of the halftone mask is not limited thereto.
Because the clear layer composition and the light blocking layer composition are simultaneously exposed and developed after the clear layer composition is applied to achieve the spacers and steps on the light blocking layer composition and to achieve optical density without exposing and developing the light blocking layer composition, the difference between the optical density of the light blocking layer per 1 micron and the optical density of the clear layer per 1 micron is greater than or equal to about 1.0. For example, the difference between the optical density of the light blocking layer per 1 micron and the optical density of the transparent layer per 1 micron may be greater than or equal to about 1.0, such as about 1.5.
Specifically, the light-blocking layer and the transparent layer on the light-blocking layer can be manufactured as follows.
(1) Coating and film formation
The light blocking layer composition is coated on a substrate subjected to a predetermined pre-treatment such as a glass substrate or an IZO substrate to have a desired thickness using a spin coating method or a slit coating method, a roll coating method, a screen printing method, an applicator method, etc., followed by heating the coated substrate at a temperature ranging from about 70 ℃ to about 100 ℃ for about 1 minute to about 10 minutes to remove the solvent. Next, the transparent layer composition was coated and heated (dried) using the same method to obtain a film.
(2) Exposure method
After placing a mask including a half-tone portion for providing a light-blocking layer pattern and a full-tone portion for providing a transparent layer pattern, the resultant film is irradiated with active rays of about 200 nm to about 500 nm to form a desired pattern. The irradiation is performed by using a light source such as a mercury lamp, a metal halide lamp, an argon laser, or the like having a low pressure, a high pressure, or an ultrahigh pressure. X-rays, electron beams, and the like may also be used as appropriate.
When a high-pressure mercury lamp is used, the exposure process uses a light dose (using a 365 nm sensor) of, for example, about 500 mj/cm or less than 500 mj/cm. However, the light dose may vary depending on the kinds of the respective components of the black photosensitive resin composition, the combination ratio thereof, and the dry film thickness.
(3) Development
After the exposure process, the exposed film is developed by dissolving and removing unnecessary portions other than the exposed portions using an alkaline aqueous solution, thereby forming an image pattern.
(4) Post-treatment
The developed image pattern can be heated again, thereby achieving excellent qualities of heat resistance, light resistance, close contact characteristics, crack resistance, chemical resistance, high strength, storage stability, and the like.
Hereinafter, the light blocking layer composition and the transparent layer composition are described.
The light-blocking layer composition includes a binder resin, a reactive unsaturated compound, a photopolymerization initiator, an organic black pigment, and a solvent.
The light-blocking layer composition may further contain a color calibration agent such as an anthraquinone-based pigment, a perylene-based pigment, a phthalocyanine-based pigment, an azo-based pigment, or the like.
The organic black pigment may be used together with a dispersant for dispersion. Specifically, the pigment may be surface-pretreated with a dispersant, or the pigment and the dispersant may be added together during preparation of the light-blocking layer composition.
The dispersant may be a nonionic dispersant, an anionic dispersant, a cationic dispersant, or the like. Specific examples of the dispersant may be polyalkylene glycol or an ester thereof, polyoxyalkylene (polyoxyalkylenes), polyol ester alkylene oxide addition product (polyhydric alcohol ester alkylene oxide addition product), alcohol alkylene oxide addition product (alcohol alkylene oxide addition product), sulfonate, carboxylate, alkylamide alkylene oxide addition product (alkyl amide alkylene oxide addition product), alkylamine, and the like, and they may be used alone or in a mixture of two or more.
Commercially available examples of dispersants may include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000 or DISPERBYK-2001, EFKA-47EA, EFKA-48, EFKA-49, EFEFKA-100, EFKA-400 or EFKA-450, manufactured by Zeeka Co., Inc. (Zenekanech Co., 5000, Solsperse-200, Solerspace, SolisP 5000, Solisbee-40, Solisbee-200, Solispex-200, SolisPBP-200, SolisP-5000, SolisP-200, Solisps-102, Solisps-5000, Solisps-200, Solisk-200, Solisps-200.
The dispersant may be included in an amount of about 0.1 wt% to about 15 wt% based on the total amount of the light-blocking layer composition. When the dispersant is included within the range, the light blocking layer composition has improved dispersion characteristics.
The organic black pigment may be pretreated with a water-soluble inorganic salt and a wetting agent. When the organic black pigment is pretreated, the average particle diameter of the organic black pigment becomes finer.
The pretreatment may be performed by kneading the pigment with a water-soluble inorganic salt and a wetting agent, followed by filtering and washing the kneaded pigment.
The kneading may be performed at a temperature of about 40 ℃ to about 100 ℃, and the filtering and washing may be performed by filtering the pigment after washing off the inorganic salt with water or the like.
Examples of the water-soluble inorganic salt may be sodium chloride, potassium chloride, etc., but are not limited thereto. The wetting agent allows the pigment to be uniformly mixed with the water-soluble inorganic salt and pulverized. Examples of the wetting agent include alkylene glycol monoalkyl ethers (alkylene glycol monoalkyl ethers), such as ethylene glycol monoethyl ether (ethylene glycol monoethyl ether), propylene glycol monomethyl ether (propylene glycol monomethyl ether), diethylene glycol monomethyl ether (diethylene glycol monomethyl ether), and the like, and alcohols, such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol polyethylene glycol (glycerol polyethylene glycol), and the like. These may be used alone or in a mixture of two or more.
The organic black pigment may be included in an amount of about 1 wt% to about 30 wt%, for example about 2 wt% to about 20 wt%, based on the total amount of the light-blocking layer composition. When the pigment is contained in the range, resolution and pattern linearity are improved.
In some embodiments, the light blocking layer composition may include an organic black pigment in an amount of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 weight%. Further, according to some embodiments of the present invention, the amount of the organic black pigment may range from about any of the foregoing amounts to about any of the foregoing amounts.
The binder resin may comprise a cationic ring-type binder resin, an acryl-type binder resin, or a combination thereof.
When the binder resin is an alicyclic binder resin, the light-blocking layer composition comprising the alicyclic binder resin has excellent developability and sensitivity during photocuring and thus has excellent fine pattern formation ability, in particular, when an alicyclic binder resin is used, the reliability of a liquid crystal display (L CD) can be ensured.
The cationic ring-type binder resin may include a repeating unit represented by the following chemical formula 2.
[ chemical formula 2]
In the chemical formula 2, the first and second organic solvents,
R1and R2Independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,
R3and R4Each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and
Z1is a single bond, O, CO, SO2、CR7R8、SiR9R10(wherein R is7To R10Independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or a linking group represented by one of the following chemical formulae 2-1 to 2-11.
[ chemical formula 2-1]
[ chemical formula 2-2]
[ chemical formulas 2-3]
[ chemical formulas 2-4]
[ chemical formulas 2 to 5]
In the chemical formula 2-5, the metal oxide,
Rais hydrogen atom, ethyl, C2H4Cl、C2H4OH、CH2CH＝CH2Or a phenyl group.
[ chemical formulas 2 to 6]
[ chemical formulae 2 to 7]
[ chemical formulas 2 to 8]
[ chemical formulas 2 to 9]
[ chemical formulas 2-10]
[ chemical formulas 2 to 11]
Z2An acid dianhydride residual group (acid dianhydride residual group),
m1 and m2 are each independently an integer in the range of 0 to 4, an
n is an integer in the range of 1 to 30.
The cationic cyclic binder resin may include a functional group represented by the following chemical formula 3 at least one of both ends.
[ chemical formula 3]
In the chemical formula 3, the first and second,
Z3represented by the following chemical formulas 3-1 to 3-7.
[ chemical formula 3-1]
In chemical formula 3-1, RbAnd RcEach independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, ester group, or ether group.
[ chemical formula 3-2]
[ chemical formulas 3-3]
[ chemical formulas 3-4]
[ chemical formulas 3-5]
In chemical formula 3-5, RdO, S, NH, substituted or unsubstituted C1 to C20 alkylene, C1 to C20 alkylamino, or C2 to C20 alkenylamino.
[ chemical formulas 3-6]
[ chemical formulas 3 to 7]
The cationic ring-type binder resin may be prepared, for example, by mixing at least two of the following: fluorine-containing compounds such as 9, 9-bis (4-oxiranylmethoxyphenyl) fluorine (9, 9-bis (4-oxiranylmethoxyphenyl) fluoride) and the like; anhydride compounds such as benzene tetracarboxylic acid dianhydride (naphthalene tetracarboxylic acid dianhydride), naphthalene tetracarboxylic acid dianhydride (naphthalene tetracarboxylic acid dianhydride), biphenyl tetracarboxylic acid dianhydride (biphenyltetracarboxylic acid dianhydride), benzophenone tetracarboxylic acid dianhydride (benzophenone tetracarboxylic acid dianhydride), pyromellitic acid dianhydride, cyclobutanetetracarboxylic acid dianhydride (cyclobutane tetracarboxylic acid dianhydride), perylene tetracarboxylic acid dianhydride (perylene tetracarboxylic acid dianhydride), tetrahydrofuran tetracarboxylic acid dianhydride (tetrahydrofuran tetracarboxylic acid dianhydride), tetrahydrophthalic acid anhydride (tetrahydrophthalic anhydride), and the like; glycol compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and the like; alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, benzyl alcohol and the like; solvent compounds such as propylene glycol methyl ethyl acetate (propylethylene glycol methyl acetate), N-methylpyrrolidone (N-methylpyrrolidinone), etc.; phosphorus compounds such as triphenylphosphine, etc.; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride (benzytriethyllammonium chloride), and the like.
The weight average molecular weight of the cationic ring-type binder resin is from about 500 to about 50,000 g/mole, for example from about 1,000 to about 30,000 g/mole. When the weight average molecular weight of the cationic ring-based binder resin is within the range, a pattern can be well formed without losing the film thickness during development.
The acryl-based adhesive resin is a copolymer of a first ethylenic (ethylene) unsaturated monomer and a second ethylenic unsaturated monomer copolymerizable therewith, and is a resin including at least one acryl-based repeating unit.
The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group. Examples of monomers include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or combinations thereof.
The first ethylenically unsaturated monomer may be included in an amount of about 5 wt% to about 50 wt%, for example about 10 wt% to about 40 wt%, based on the total amount of the acryl-based resin.
The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α -methylstyrene, vinyltoluene, vinylbenzyl methyl ether and the like, an unsaturated carboxylic acid ester compound such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate and the like, an unsaturated carboxylic acid aminoalkyl ester compound such as 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate and the like, a carboxylic acid vinyl ester compound such as vinyl acetate, vinyl benzoate and the like, an unsaturated carboxylic acid glycidyl ester compound such as glycidyl (meth) acrylate and the like, a vinyl cyanide compound such as (meth) acrylonitrile and the like, an unsaturated amide compound such as (meth) acrylamide and the like, and these may be used alone or in a mixture of more than two kinds.
Specific examples of the acryl-based resin may be, but are not limited to, 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, and the like. These may be used alone or in a mixture of two or more.
The weight average molecular weight of the acryl-based resin is about 3,000 g/mole to about 150,000 g/mole, for example about 5,000 g/mole to about 50,000 g/mole or about 7,000 g/mole to about 30,000 g/mole. When the weight average molecular weight of the acryl-based resin is within the range, the light blocking layer composition may have excellent physical and chemical characteristics.
The acid number of the acryl-based resin may be about 15 mg KOH/g to about 150 mg KOH/g, for example about 80 mg KOH/g to about 130 mg KOH/g. When the acid value of the acryl-based resin is within the range, the pixel pattern may have excellent resolution.
When the cationic ring-based binder resin is mixed with the acrylic-based binder resin, the ratio (by weight) of the cationic ring-based binder resin to the acrylic-based binder resin in the first composition may be about 99: 1 to about 50: 50.
In some embodiments, the mixture of the male-ring-based adhesive resin and the acrylic-based adhesive resin may include the male-ring-based adhesive resin in an amount of about 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99 wt%. Further, according to some embodiments of the present invention, the amount of the cationic ring-based binder resin may range from about any of the foregoing amounts to about any of the foregoing amounts.
In some embodiments, the mixture of the cationic ring-based adhesive resin and the acryl-based adhesive resin may include the acryl-based adhesive resin in an amount of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 wt%. Further, according to some embodiments of the present invention, the amount of the acryl-based adhesive resin may range from about any of the foregoing amounts to about any of the foregoing amounts.
When the acryl-based binder resin is included in an amount exceeding that of the cationic ring-based binder resin, chemical resistance and reliability may be deteriorated.
The binder resin may be included in an amount of about 1 wt% to about 30 wt%, for example about 2 wt% to about 20 wt%, based on the total amount of the light blocking layer composition. Specifically, the cationic ring-based binder resin may be included in an amount of about 1% by weight to about 20% by weight based on the total amount of the light-blocking layer composition, and the acryl-based binder resin may be included in an amount of about 1% by weight to about 20% by weight based on the total amount of the light-blocking layer composition. When the binder resin is contained within the range, excellent resolution can be achieved.
In some embodiments, the light blocking layer composition may include the binder resin in an amount of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 wt%. Further, according to some embodiments of the present invention, the amount of the binder resin may range from about any of the foregoing amounts to about any of the foregoing amounts.
The reactive unsaturated compound may be a monomer or oligomer and may be a monofunctional or multifunctional ester of (meth) acrylic acid comprising at least one ethylenically unsaturated double bond.
The reactive unsaturated compound has an ethylenically unsaturated double bond, and therefore, sufficient polymerization can be caused during exposure in the pattern forming process and a pattern having excellent heat resistance, light resistance, and chemical resistance is formed.
The reactive unsaturated compound may be, for example, 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, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol hexa, Bisphenol a epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloxyethyl phosphate, novolac epoxy (meth) acrylate, or combinations thereof.
Commercially available examples of reactive unsaturated compounds are as follows. The monofunctional (meth) acrylate may comprise Aronix
(Toagosei Chemistry industry Co., Ltd., &lTtT transformation = L "&gTt L &lTt/T &gTt td.); KAYARAD
(Nippon Kayaku Co., L td.);
(Osaka Organic Chemical Ind., L td.) examples of difunctional (meth) acrylates may include Aronix
(Toyata chemical industries, Ltd.), KAYARAD
(Nippon Chemicals Co., Ltd.),
V-335
(Osaka organic chemical industries, Ltd.), and the like. Examples of trifunctional (meth) acrylates may include Aronix
(Toyata chemical industries, Ltd.), KAYARAD
(Nippon Chemicals Co., Ltd.),
(Osaka organic chemical industries, Ltd.), and the like. These may be used alone or in a mixture of two or more.
The reactive unsaturated compound may be treated with an acid anhydride to improve developability.
The reactive unsaturated compound may be included in an amount of about 1 wt% to about 20 wt%, for example about 1 wt% to about 10 wt%, based on the total amount of the light-blocking layer composition. When the reactive unsaturated compound is contained within the range, the reactive unsaturated compound is sufficiently cured during exposure for pattern formation to improve reliability.
In some embodiments, the light blocking layer composition may include the reactive unsaturated compound in an amount of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 wt%. Further, according to some embodiments of the present invention, the amount of the reactive unsaturated compound may range from about any of the foregoing amounts to about any of the foregoing amounts.
The photopolymerization initiator may be any one commonly used in photosensitive resin compositions, for example, acetophenone compounds, benzophenone compounds, thioxanthone-based compounds, benzoin compounds, oxime compounds, and the like.
Examples of the acetophenone-based compound may be 2, 2 ' -diethoxyacetophenone (2, 2 ' -diethoxyacetophenone), 2 ' -dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone (2-hydroxy-2-methylpropiophenone), p-tert-butyltrichloroacetophenone (p-t-butyltrichloroacetophenone), p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2' -dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one (2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and the like.
Examples of the benzophenone-based compound may be benzophenone, benzoyl benzoate (benzoyl benzoate), methyl benzoyl benzoate (methyl benzoyl benzoate), 4-phenylbenzophenone (4-phenylbenzophenone), hydroxybenzophenone, acrylated benzophenone, 4 ' -bis (dimethylamino) benzophenone, 4 ' -bis (diethylamino) benzophenone, 4 ' -dimethylaminobenzophenone, 4 ' -dichlorobenzophenone, 3 ' -dimethyl-2-methoxybenzophenone, and the like.
Examples of the thioxanthone-based compound may be thioxanthone, 2-methylthioxanthone (2-methylthioxanthene), isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.
Examples of the benzoin-based compound may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.
Examples of triazines are 2, 4, 6-trichloro-s-triazine (2, 4, 6-trichlororo-s-triazine), 2-phenyl-4, 6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4 ' -dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4 ' -methoxynaphthyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-biphenyl-4, 6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphthol 1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol 1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2-4-bis (trichloromethyl) -6-sunflower-yl-s-triazine, 2-4-bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine and the like.
Examples of the oxime compound may be O-acyloxime (O-acyloxime-based) compounds, 2- (O-benzoyl oxime) -1- [4- (phenylthio) phenyl ] -1, 2-octanedione (2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl ] -1, 2-octanedione), 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone (1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylphenyloxy) -9H-carbazol-3-yl ] ethanone), O-ethoxycarbonyl- α -oxyamino-1-phenylpropan-1-one (O-ethoxycarbonyl- α -oxyphenone-1-phenyl-1-one) (O-ethoxycarbonyl- α -phenoxyimine-1-phenylpropane-1-one) (O-phenoxyketone-364-phenyloxime-4- (1-phenylthiophenyl) -1- [4- (2-phenylthiobutyryl) -1-2-oxomethyl-2-1-phenyloxime-4- (2-phenylthiophenyl) -1- (1-phenylthiobenzone-4-2-oxoethyl-2-1-phenyloxime) -1- (1-4-phenylthiobenzone-4-2-oxomethyl-2-oxoketone), and the like compounds may be mentioned in combination.
The photopolymerization initiator may further include, in addition to the above-mentioned compounds, carbazole-based compounds, diketone-based compounds, sulfonium borate-based (sulfonium borate-based) compounds, diazonium-based compounds, imidazole-based compounds, bisimidazole-based (bisimidazole-based) compounds, and the like.
The photopolymerization initiator may be used together with a photosensitizer capable of causing a chemical reaction by absorbing light and becoming excited and then transferring its energy.
Examples of the photosensitizer may be tetraethylene glycol bis-3-mercaptopropionate (tetraethylene glycol bis-3-mercapto propionate), pentaerythritol tetrakis-3-mercaptopropionate (pentaerythritoltetrakis-3-mercapto propionate), dipentaerythritol tetrakis-3-mercaptopropionate, and the like (dipentaerythritoltetrakis-3-mercapto propionate).
The photopolymerization initiator may be included in an amount of about 0.05% by weight to about 5% by weight, for example about 0.1% by weight to about 5% by weight, based on the total amount of the light-blocking layer composition. When the photopolymerization initiator is contained in the range, since curing is sufficiently performed during exposure in the pattern forming process, excellent reliability can be secured.
In some embodiments, the light blocking layer composition may include a photopolymerization initiator in an amount of about 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, or 5 wt%. Further, according to some embodiments of the present invention, the amount of the photopolymerization initiator may range from about any one of the foregoing amounts to about any one of the foregoing amounts.
The solvent is a material that is compatible with, but not reactive with, the pigment, the binder resin, the reactive unsaturated compound, and the photopolymerization initiator.
Examples of the solvent may include alcohols such as methanol, ethanol, and the like; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran and the like; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like; ethylene glycol ethyl ether such as methyl ethylene glycol ethyl ether, ethyl ethylene glycol ethyl ether, diethyl ethylene glycol ethyl ether and the like; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and the like; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate and the like; aromatic hydrocarbons such as toluene, xylene, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-acetone, methyl-n-butanone, methyl-n-pentanone, 2-heptanone, and the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, and the like; lactates such as methyl lactate, ethyl lactate, and the like; alkyl oxyacetates such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, etc.; alkyl alkoxyacetates such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and the like; alkyl 3-oxopropionates such as methyl 3-oxopropionate, ethyl 3-oxopropionate, etc.; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-oxopropionates such as methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, etc.; alkyl 2-alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-oxo-2-methylpropionates such as methyl 2-oxo-2-methylpropionate, ethyl 2-oxo-2-methylpropionate and the like; mono-oxo-monocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, and the like; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, 2-hydroxy-3-methyl butyrate, and the like; or ketoesters such as ethyl pyruvate and the like. In addition, high boiling point solvents such as N-methylformamide, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, ethyl benzyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ -butyrolactone, ethylene carbonate, propylene carbonate, phenyl ethylene glycol ethyl acetate, and the like can also be used.
In view of mutual solubility and reactivity, it is preferable to use glycol ethers such as ethylene glycol monoethyl ether and the like; ethylene glycol alkyl ether acetates such as ethyl ethylene glycol ethyl acetate and the like; esters such as 2-hydroxyethyl propionate and the like; carbitols such as diethylene glycol monomethyl ether and the like; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate and the like.
The solvent is used in a balanced amount, for example, from about 40% to about 90% by weight based on the total amount of the light-blocking layer composition. When the solvent within the range is included, the light-blocking layer has an appropriate viscosity resulting in improved processability.
In some embodiments, the light blocking layer composition may include a solvent in an amount of about 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, or 90 weight percent. Further, according to some embodiments of the invention, the amount of solvent may range from about any of the foregoing amounts to about any of the foregoing amounts.
The light blocking layer composition may further include an additive such as malonic acid, 3-amino-1, 2-propanediol, a silane-based 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, an epoxy group, or the like, to improve the close contact characteristics with the substrate.
Examples of the silane-based coupling agent may include trimethoxysilylbenzoic acid (trimethyoxysilicic acid), gamma-methacryloxypropyltrimethoxysilane (gamma-methacryloxypropyltrimethoxysilane), vinyltriacetoxysilane (vinyl triacetoxysilane), vinyltrimethoxysilane (vinyl trimethyoxysilane), gamma-isocyanatopropyltriethoxysilane (gamma-isocyanatopropylthiosilane), gamma-glycidoxypropyltrimethoxysilane (gamma-glycidoxypropyltrimethoxysilane), β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane (β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and the like, these may be used alone or in a mixture of two or more.
The silane-based coupling agent may be included in an amount of about 0.01 parts by weight to 10 parts by weight based on 100 parts by weight of the light-blocking layer composition.
In addition, the light blocking layer composition may further include a surfactant (e.g., a fluorine-based surfactant) to improve coating characteristics and prevent defects when necessary.
Examples of the fluorine-based surfactant may be commercial fluorine-based surfactants, for example
And
(BM Chemie Inc.)); MEGAFACE F
F
F
And F
Dainippon Ink chemical industry Co., Ltd (Dainippon Ink Kagaku Kogyo Co., L td.); FU L ORAD
FULORAD
FULORAD
And FU L ORAD
(Sumitomo 3M Co., Ltd.; SURF L ON.); Sumitomo 3M Co., L td.))
SURFLON
SURFLON
SURFLON
And SURF L ON
(Asahi Glass Co., L td.); and
and
and the like (Toray Silicone Co., L td.).
The surfactant may be used in an amount of about 0.001 parts by weight to 5 parts by weight based on 100 parts by weight of the light blocking layer composition.
In addition, other additives such as an antioxidant, a stabilizer, and the like may be contained in predetermined amounts unless these may deteriorate the characteristics of the light-blocking layer composition.
The transparent layer composition may include an adhesive resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.
The transparent layer composition achieves spacers and steps but does not necessarily require high optical density, and therefore does not include organic black pigments. In other words, the transparent layer composition may include a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent, or may further include an organic black pigment, if necessary. In addition, the transparent layer composition may further include additives described for the light blocking layer composition.
The respective components consisting of the binder resin, the reactive unsaturated compound, the photopolymerization initiator, the organic black pigment and the solvent contained in the transparent layer composition are the same as those described in the light-blocking layer composition.
The binder resin included in the transparent layer composition may be included in an amount of about 3 wt% to about 70 wt%, for example about 3 wt% to about 60 wt%, of the total amount of the transparent layer composition. When the binder resin is contained within the range, excellent resolution can be obtained.
In some embodiments, the transparent layer composition may include the adhesive resin in an amount of about 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70 weight%. Further, according to some embodiments of the present invention, the amount of the binder resin may range from about any of the foregoing amounts to about any of the foregoing amounts.
The reactive unsaturated compound included in the transparent layer composition may be included in an amount of about 2 wt% to about 40 wt%, for example about 3 wt% to about 30 wt%, of the total amount of the transparent layer composition. When the reactive unsaturated compound is contained in the range, the transparent layer composition is sufficiently cured during exposure of the pattern forming process, ensuring excellent reliability.
In some embodiments, the transparent layer composition may include the reactive unsaturated compound in an amount of about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 weight%. Further, according to some embodiments of the present invention, the amount of the reactive unsaturated compound may range from about any of the foregoing amounts to about any of the foregoing amounts.
The photopolymerization initiator may be included in an amount of about 0.1% by weight to about 5% by weight, for example about 0.2% by weight to about 5% by weight, based on the total amount of the transparent layer composition. When the photopolymerization initiator is contained in the range, the transparent layer composition is sufficiently cured during exposure of the pattern forming process, obtaining excellent reliability.
In some embodiments, the transparent layer composition may include a photopolymerization initiator in an amount of about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, or 5 wt%. Further, according to some embodiments of the present invention, the amount of the photopolymerization initiator may range from about any one of the foregoing amounts to about any one of the foregoing amounts.
The solvent is included in a balance, for example, in an amount of about 40 wt% to about 90 wt% based on the total amount of the transparent layer composition. When the solvent is included within the range, the transparent layer composition has an appropriate viscosity, providing excellent processability.
In some embodiments, the light blocking layer composition may include a solvent in an amount of about 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, or 90 weight percent. Further, according to some embodiments of the invention, the amount of solvent may range from about any of the foregoing amounts to about any of the foregoing amounts.
The solubility of the solvent of the transparent layer composition may be lower than that of the light blocking layer composition. For example, the solvent of the light blocking layer composition may include PGMEA, PGME, EDM, 3-MBA, EEP, etc., and the solvent of the transparent layer composition may include PGMEA, 3-MBA, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, etc., but the present invention is not limited thereto.
Hereinafter, the present invention is described in more detail with reference to examples. However, these examples are not to be construed in any way as limiting the scope of the invention.
(preparation of light-blocking layer and clear layer)
Preparation examples 1 to 3
Each of the light blocking layer compositions and transparent layer compositions according to preparation examples 1 to 3 was prepared by using the following components in the following compositions provided in tables 1 to 3 below.
Specifically, a photopolymerization initiator is dissolved in a solvent, the solution is sufficiently stirred at room temperature for 30 minutes or more, a binder resin and a reactive unsaturated compound are sequentially added thereto, and the mixture is stirred at room temperature for about 1 hour. Subsequently, other additives are added to the stirred solution, the mixture is stirred for about 10 minutes, then the pigment is added thereto, and the obtained mixture is stirred at room temperature for 2 hours or more. Then, the product was filtered three times to remove impurities therein, and a light-blocking layer composition and a transparent layer composition were obtained.
Preparation example 1: preparation of light-blocking layer composition
(Table 1)
(Unit: gram)
Preparation example 2: preparation of clear layer composition
(Table 2)
(Unit: gram)
Preparation example 3: preparation of clear layer composition
(Table 3)
(Unit: gram)
(production of light-blocking layer and transparent layer)
Preparation of example 4
(1) The light-blocking layer composition of preparation example 1 was coated on a pretreated IZO substrate to a thickness of 1.5 μm using a spin coating method or a slit coating method, a roll coating method, a screen printing method, using an applicator, etc., and dried by heating a hot plate at 70 to 100 ℃ for 1 to 10 minutes to remove the solvent therein.
(2) The transparent layer composition of preparation example 2 was coated on the dried light-blocking layer composition film using the same method as in item (1), and dried to obtain a two-layer film.
(3) A mask including a half-tone portion (transmitting 15% to 70% of light) for forming a light-blocking layer pattern and a full-tone area portion (transmitting 100% of light) for forming a transparent layer pattern was placed on the two-layer film, and the front side was exposed to actinic rays of 200 nm to 500 nm using an exposer (oxtail (ushioc inc.) motor co. As a light source in irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon laser, or the like can be used, and X-rays, electron beams, or the like can also be used as necessary. The exposure dose may vary depending on the kind of components in the composition, the amount to be mixed, and the film thickness during drying, but may be less than or equal to 500 mj/cm when a high-pressure mercury lamp is used (by using a 365 nm sensor).
(4) The exposed layer was developed with a 0.2 wt% aqueous solution of potassium hydroxide (KOH) by using a developer (SVS corporation, SSP-200), unnecessary regions were dissolved and removed and the exposed regions were left, and thus a pattern was formed.
(5) The image pattern obtained by development was heated in an oven at 230 ℃ for 30 minutes, and a sample including a light-blocking layer and a transparent layer formed on the light-blocking layer was manufactured.
Preparation of example 5
A sample was manufactured according to the same method as that of preparation example 4, except that the transparent layer composition of preparation example 3 was used instead of the transparent layer composition of preparation example 2.
Comparative preparation example 1
A sample was manufactured according to the same method as in preparation example 4, except that the light blocking layer composition of preparation example 1 was coated to a thickness of 3.0 micrometers, and the transparent layer composition of preparation example 2 was not used.
Evaluation 1: evaluation of optical Density (optical depth: OD)
The light-blocking layer composition prepared in preparation example 1 and the transparent layer composition prepared in each of preparation example 2 and preparation example 3 were coated to a thickness of 1.5 μm on each 10 cm × 10 cm IZO substrate using a spin coater (sankis corporation (Mikasa co., L td.), Opticoat MS-a150), soft-baked (or pre-baked) on a hot plate for 150 seconds at 80 ℃, and exposed to 50 mj by using an exposure machine (oxtail motor corporation, HB-50110AA) and a photomask, respectively, and then, the obtained organic coatings (SVS corporation, SSP-200) were developed in 0.2 wt% potassium hydroxide (KOH) aqueous solution for 150 seconds, and hard-baked (or post-baked) in an oven for 30 minutes at 230 ℃, to obtain each patterned sample.
(Table 4)
| Preparation of example 1 | Preparation of example 2 | Preparation of example 3 | |
| Optical Density (OD) | 2.2 | 0 | 0.3 |
Evaluation 2: solvent resistance
The samples according to preparation example 4, preparation example 5 and comparative preparation example 1 were cut into a size of 1 cm × 1 cm, placed in a glass bottle containing 5 ml of NMP, left to stand in an oven at 100 ℃ for 15 minutes, and examined whether discoloration occurred, and the results are shown in table 5 below.
Decolorization measuring method
X: no discoloration when examined by naked eyes
O: high decolorization upon visual inspection
(Table 5)
| Preparation of example 4 | Preparation of example 5 | Comparative preparation example 1 | |
| Decolorization of | X | X | O |
Referring to table 5, preparative example 4 and preparative example 5 showed superior solvent resistance and no discoloration compared to comparative preparative example 1.
While the invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. The above embodiments are therefore to be understood as illustrative and not restrictive in any way.
Claims (10)
1. A liquid crystal display, comprising:
a thin film transistor on the lower substrate;
a plurality of color filters on the thin film transistor and aligned to be spaced apart from each other;
an insulating layer on the plurality of color filters;
a light blocking layer on the insulating layer;
a transparent layer on the light blocking layer and having a convex surface;
an upper substrate facing the lower substrate; and
a liquid crystal layer interposed between the lower substrate and the upper substrate,
wherein the light-blocking layer contains an organic black pigment, and
the transparent layer having the convex surface has a shape different from that of the light blocking layer, the transparent layer having the convex surface covers all or a part of a front surface of the light blocking layer, and a cross-sectional shape different from that of the light blocking layer when the transparent layer covers all of the front surface of the light blocking layer,
wherein the light blocking layer and the transparent layer are manufactured by:
coating a light-blocking layer composition and drying the light-blocking layer composition,
coating a clear layer composition on the dried light blocking layer composition and drying the clear layer composition, and
simultaneously exposing and developing the light blocking layer composition and the transparent layer composition,
wherein the transparent layer composition comprises 3 to 70 wt% of a binder resin, 2 to 40 wt% of a reactive unsaturated compound, 0.1 to 5 wt% of a photopolymerization initiator, and the balance of a solvent,
wherein the light blocking layer composition includes 1 to 30 wt% of a binder resin, 1 to 20 wt% of a reactive unsaturated compound, 0.05 to 5 wt% of a photopolymerization initiator, 1 to 30 wt% of an organic black pigment, and the balance of a solvent.
2. The liquid crystal display of claim 1, wherein the organic black pigment comprises a compound represented by the following chemical formula 1:
[ chemical formula 1]
Wherein, in the above chemical formula 1,
R11to R20Independently hydrogen or substituted or unsubstituted C1 to C10 alkyl.
3. The liquid crystal display according to claim 1, wherein the transparent layer comprises a primary transparent layer and a secondary transparent layer.
4. The liquid crystal display according to claim 3, wherein the thickness of the primary transparent layer is thicker than the thickness of the secondary transparent layer.
5. The liquid crystal display according to claim 3, wherein the primarily transparent layer supports a gap between the upper substrate and the lower substrate.
6. The liquid crystal display defined in claim 1 further comprising a pixel electrode between the insulating layer and the light blocking layer.
7. The liquid crystal display according to claim 1, further comprising a common electrode interposed between the upper substrate and the liquid crystal layer.
8. The liquid crystal display of claim 1, further comprising a common electrode directly on the lower substrate.
9. The liquid crystal display according to claim 1, wherein the optical density of the light-blocking layer is 1.0 or more than 1.0 greater than the optical density of the transparent layer.
10. The liquid crystal display of claim 1 wherein the transparent layer composition further comprises a black pigment.
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| KR20140161934 | 2014-11-19 | ||
| KR10-2014-0161934 | 2014-11-19 | ||
| KR1020150082151A KR101788088B1 (en) | 2014-11-19 | 2015-06-10 | Liquid crystal display |
| KR10-2015-0082151 | 2015-06-10 |
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| KR102376292B1 (en) * | 2017-07-26 | 2022-03-18 | 삼성디스플레이 주식회사 | Display device |
| CN109085713A (en) * | 2018-07-25 | 2018-12-25 | 深圳市华星光电半导体显示技术有限公司 | A kind of display panel and preparation method thereof |
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| CN100437307C (en) * | 2003-03-17 | 2008-11-26 | 三星电子株式会社 | Panel for displaying device, manufacturing method thereof and liquid-crystal displaying device therewith |
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| TW594232B (en) * | 2002-11-26 | 2004-06-21 | Hannstar Display Corp | A method of utilizing dual-layer photoresist to form black matrix and spacers on a control circuit substrate |
| EP1780583B1 (en) * | 2004-07-14 | 2013-12-25 | Sharp Kabushiki Kaisha | Active matrix substrate and drive circuit thereof |
| KR101732197B1 (en) * | 2009-01-19 | 2017-05-02 | 바스프 에스이 | Black matrix for colour filters |
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| CN106200089A (en) | 2016-12-07 |
| KR101788088B1 (en) | 2017-10-19 |
| TW201619671A (en) | 2016-06-01 |
| TWI560502B (en) | 2016-12-01 |
| KR20160059939A (en) | 2016-05-27 |
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