CN106200089B - LCD Monitor - Google Patents

Abstract

The present 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; and a plurality of color filters on the plurality of color filters an insulating layer; 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 interposing the lower substrate with the A liquid crystal layer between upper substrates, wherein the light blocking layer contains an organic black pigment, and the shape of the transparent layer having the convex surface is different from that of the light blocking layer. The present invention can provide a liquid crystal display with excellent reliability.

Description

LCD Monitor

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of Korean Patent Application No. 10-2014-0161934 filed in the Korean Intellectual Property Office on Nov. 19, 2014, the entire contents of which are incorporated herein by reference.

technical field

The present invention relates to a liquid crystal display (LCD).

Background technique

A liquid crystal display (LCD) 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 that interpose a liquid crystal layer between two display panels and make the liquid crystal The liquid crystal molecules of the layer are realigned and formed.

One of the currently used liquid crystal displays (LCDs) has a structure in which field generating electrodes are disposed in two display panels, respectively. 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"), while in another display panel (hereinafter referred to as "common electrode panel") ), red, green, and blue color filters are formed, and a common electrode covers the front side thereof.

However, such a liquid crystal display (LCD) may have alignment errors because pixel electrodes and color filters are formed in different display panels and it is difficult to precisely align therebetween. In order to solve this problem, a structure in which the color filter and the pixel electrode are formed on the same display panel (color filter on array, COA) is proposed.

On the other hand, considering the alignment limit when the thin film transistor array panel is aligned with the common electrode group, the formed light-blocking layer is larger than a predetermined size.

In addition, the liquid crystal layer space between the two display panels is called a liquid crystal layer gap (cell gap), and the liquid crystal layer gap affects the overall operating characteristics of the liquid crystal display (LCD) (such as response speed, contrast ratio, viewing angle, brightness uniformity, etc.) )influential. When the liquid crystal layer gap is not uniform, a uniform image is not displayed on the entire screen, resulting in image quality defects.

Therefore, there is an increasing need for a liquid crystal display (LCD) that prevents deterioration of the aperture ratio due to an increase in the size of the light blocking layer and maintains a uniform liquid crystal layer gap across the front side of the substrate.

SUMMARY OF THE INVENTION

One embodiment provides a liquid crystal display (LCD) 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 (LCD) comprising thin film transistors on a lower substrate; a plurality of color filters on the thin film transistors and aligned to be spaced apart from each other; an insulating layer on a color filter; 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 shape of the transparent layer having a convex surface is different from that of the light blocking layer.

The organic black pigment may contain a compound represented by Chemical Formula 1 below.

[Chemical formula 1]

In Chemical Formula 1,

R ¹¹ to R ²⁰ are independently hydrogen or substituted or unsubstituted C1 to C10 alkyl.

The transparent layer having the convex surface may cover all or a part of the front surface of the light blocking layer.

The transparent layer may include a primary transparent layer and an auxiliary transparent layer.

The thickness of the primary transparent layer may be thicker than the thickness of the auxiliary transparent layer.

The primary transparent layer may support the gap between the upper and lower substrates.

The liquid crystal display (LCD) may further include a pixel electrode between the insulating layer and the light blocking layer.

The liquid crystal display (LCD) may further include a common electrode interposed between the upper substrate and the liquid crystal layer.

Liquid crystal displays (LCDs) may also include a common electrode directly on the underlying substrate.

The optical density of the light blocking layer may be about 1.0 or greater than the optical density of the transparent layer.

The light-blocking layer and the transparent layer can be produced by applying the light-blocking layer composition and drying it, coating the transparent layer composition on the dried light-blocking layer composition and drying it, and simultaneously exposing and developing A light-blocking layer composition and a transparent layer composition.

The light blocking layer composition may contain 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% binder resin; about 1 wt% to about 20 wt% reactive unsaturated compound; about 0.05 wt% to about 5 wt% photopolymerization initiator; From about 1 wt% to about 30 wt% organic black pigment, and a balanced amount of solvent.

The transparent layer composition may contain a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.

The transparent layer composition may further contain a black pigment.

The transparent layer composition may comprise from about 3 wt% to about 70 wt% binder resin; from about 2 wt% to about 40 wt% reactive unsaturated compound; from about 0.1 wt% to about 5 wt% photopolymerization initiator; and Balanced amount of 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 (LCD) with excellent reliability.

Description of drawings

1 to 4 are cross-sectional views of a liquid crystal display (LCD) according to an exemplary embodiment.

FIG. 5 is a schematic diagram illustrating the structure of a light blocking layer and a transparent layer in a conventional liquid crystal display (LCD).

FIGS. 6 and 7 are schematic views illustrating structures of a light blocking layer and a transparent layer in a liquid crystal display (LCD) according to an exemplary embodiment.

Detailed ways

The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown. However, the present invention may 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 content will be thorough and complete, and will fully convey the ideals of the present invention to those skilled in the art.

In the drawings, the thicknesses of layers and regions are exaggerated for clarity. In addition, the layers and regions shown in the drawings are schematic in nature, and their shapes are not the exact shapes intended to illustrate the composition of objects, and are not intended to limit the scope of the present 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 also be present therebetween. The same reference numerals in the drawings refer to the same elements throughout this specification.

As used herein, when no specific definition is otherwise provided, the term "alkyl" refers to C1 to C20 alkyl, the term "alkenyl" refers to C2 to C20 alkenyl, and 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, and the term "arylalkyl" refers to C6 to C20 Arylalkyl, the term "alkylene" refers to a C1 to C20 alkylene group, the term "arylene" refers to a C6 to C20 arylene group, and the term "alkylarylene" refers to a C6 to C20 arylene group C20 alkylarylene, the term "heteroarylene" refers to a C3 to C20 heteroarylene, and the term "alkyleneoxy" refers to a C1 to C20 alkyleneoxy group.

As used herein, when no specific definition is 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), hydroxy, C1 to C20 alkanes, in place of at least one hydrogen Oxy group, nitro group, cyano group, amino group, imino group, azide group, amidino group, hydrazine group, hydrazino group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or Its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C20 aryl, C3 to C20 cycloalkyl, C3 to C20 ring alkenyl, C3 to C20 cycloalkynyl, C2 to C20 heterocycloalkyl, C2 to C20 heterocycloalkenyl, C2 to C20 heterocycloalkynyl, C3 to C20 heteroaryl, or combinations thereof.

As used herein, when no specific definition is otherwise provided, the term "hetero" refers to compounds of the formula that contain at least one heteroatom selected from N, O, S, and P.

As used herein, when no specific definition is otherwise provided, the term "combination" refers to mixing or copolymerization.

As used herein, the cardo-based resin refers to a resin containing at least one functional group selected from the following Chemical Formulae 2-1 to 2-11 in the main chain.

As used herein, unless a specific definition is provided otherwise, when chemical bonds are not drawn, hydrogen atoms are bonded at positions where bonding would occur.

A liquid crystal display (LCD) 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; on the plurality of color filters an insulating layer; 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 interposing the lower substrate with the The liquid crystal layer between the upper substrates, wherein the light blocking layer contains an organic black pigment, and the shape of the transparent layer having the convex surface is different from that of the light blocking layer.

The light blocking layer and the transparent layer do not need to have the same thickness because they have different shapes. However, the light-blocking layer and the transparent layer have different cross-sections because they have different shapes.

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 a conventional liquid crystal display (LCD). However, referring to FIGS. 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 a liquid crystal display (LCD) according to one embodiment.

When the light blocking layer and the transparent layer in the liquid crystal display (LCD) have the shapes provided in FIG. 6 below, fine patterns can be advantageously formed by reducing the critical dimension (CD), and here, when the liquid crystal display (LCD) ), the reliability can be improved when the light blocking layer and the transparent layer have the shapes provided in Figure 7 below.

1 to 4 are cross-sectional views of a liquid crystal display (LCD) according to an exemplary embodiment.

Referring to FIGS. 1 to 4 , thin film transistors are located on the lower substrate 200 . The thin film transistor can be composed of three terminals (control terminal, input terminal and 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, gate lines and gate electrodes 111 including storage electrode lines are formed on the lower substrate 200 .

There may be more than one gate line, and there may be more than one gate electrode including the gate line. A plurality of gate lines extend in the 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 extends in a horizontal direction and transmits a predetermined voltage, such as a common voltage (Vcom) and the like.

A gate insulating layer 112 is formed on the gate electrode 111 . The gate insulating layer 112 may include 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 extends mainly in the vertical direction and may extend out 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 contacts, data conductors including data lines and drain electrodes 115 are formed.

The data lines transmit data signals and extend mainly in the 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, color filters 110b, and color filters 110c are arranged. The plurality of color filters 110a, 110b, and 110c include red filters, green filters, and blue filters spaced apart from each other. The plurality of color filters 110a, 110b, and 110c are spaced apart from each other in the horizontal direction, respectively, but may be formed in stripes in the vertical direction.

The insulating layer 120 is disposed on the plurality of color filters 110a, the color filters 110b, and the color filters 110c. The insulating layer 120 may be located in the space between adjacent color filters. The insulating layer 120 may be formed as an organic layer or an inorganic layer, but an inorganic layer may be preferred. 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. Additionally, the insulating layer 120 may not be patterned, and thus partially patterned by a photolithographic process, unlike an overcoating layer, which is baked immediately after being coated on the front side.

The light blocking layer 140 is disposed on the insulating layer 120 , and the transparent layer 150 is disposed on the light blocking layer 140 .

The liquid crystal display (LCD) may further include an auxiliary light blocking layer (not shown) between the insulating layer 120 and the light blocking layer 140 . Here, the auxiliary light blocking layer may be located in a space between adjacent color filters.

The light blocking layer 140 includes an organic black pigment to have 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 Chemical Formula 1,

R ¹¹ to R ²⁰ are independently hydrogen or substituted or unsubstituted C1 to C10 alkyl. For example, R ¹¹ to R ²⁰ can be hydrogen.

The transparent layer having the convex surface may cover all or a part of the front surface of the light blocking layer.

The front side of the light blocking layer may refer to the side surface of the light blocking layer in contact with the transparent layer. For example, referring to FIG. 6 below, a transparent layer having a convex surface in a liquid crystal display (LCD) according to an exemplary embodiment covers a portion of the front side of the light blocking layer, and referring to FIG. 7 below, in accordance with the exemplary embodiment The transparent layer having the convex surface in the liquid crystal display (LCD) of 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 process as described below.

The transparent layer may include the main transparent layer 152 and the auxiliary transparent layer 153, and here, the main transparent layer and the auxiliary transparent layer exist independently, for example, the sides of the main transparent layer and the like are not in contact with the sides and the like of the auxiliary transparent layer.

The light blocking layer and the transparent layer are simultaneously formed as described below, and here, the main transparent layer may have the role of a spacer supporting the space between the upper substrate and the lower substrate, and the auxiliary transparent layer may have the function of helping the main transparent layer And the role of the auxiliary spacer that supports the space between the upper substrate and the lower substrate. Therefore, the primary transparent layer having the function of a spacer may be thicker than the auxiliary transparent layer having the function of an auxiliary spacer. In this way, when the transparent layer is separately formed as the main transparent layer and the auxiliary transparent layer, the main transparent layer supports the auxiliary transparent layer even when the buffering 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 by the interval of a plurality of gate lines and disposed on the top and bottom of each gate line, respectively, and thus adjacent to each other in the column direction. The auxiliary pixel electrode may have an overall quadrangular shape.

On the upper substrate 300, eg, 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 liquid crystal molecules of the liquid crystal layer 160 are aligned with their long axes perpendicular to the surfaces of the two substrates (the upper and lower substrates) when there is no electric field. The liquid crystal layer 160 includes an alignment aid, and the alignment aid includes reactive mesogens, and the liquid crystal molecules may have a pretilt angle and a long axis thereof is substantially parallel to the length direction of the pixel electrode 130 . The alignment aid may be included in the alignment layer instead of the liquid crystal layer.

On the other hand, the structures of thin film transistors described with reference to FIGS. 1 to 4 are merely examples and may be modified to include various structures of thin film transistor structures.

The light-blocking layer and the transparent layer may be formed by applying and drying the light-blocking layer composition, drying and coating the transparent layer composition on the dried light-blocking layer composition, and simultaneously exposing and developing the dried light-blocking layer composition Layer composition and transparent layer composition.

Exposure can be done by using a halftone mask. The halftone mask may include areas that transmit about 100% light during exposure, areas that transmit about 25% to about 35% light during exposure, areas that transmit about 15% to about 25% light during exposure, and During the period, about 0% of the light is transmitted, but the structure of the halftone mask is not limited to these.

Because the transparent layer composition and the light-blocking layer composition are exposed and developed at the same time after the transparent layer composition is applied, so as to realize the spacers and steps on the light-blocking layer composition, and the light-blocking layer composition is not exposed and developed. The optical density is obtained in the case of , so the difference between the optical density per 1 micron of the light blocking layer and the optical density per 1 micron of the transparent layer is greater than or equal to about 1.0. For example, the difference between the optical density per 1 micron of the light blocking layer and the optical density per 1 micron of the transparent layer may be greater than or equal to about 1.0, eg, 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 predetermined pre-treated substrate such as a glass substrate or an IZO substrate using a spin coating method or a slit coating method, a roller coating method, a screen printing method, an applicator method, etc. to a desired thickness, then the coated substrate is heated at a temperature in the range of about 70°C to about 100°C 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

After placing a mask including a halftone portion for providing a light blocking layer pattern and a fulltone portion for providing a transparent layer pattern, the resulting film is irradiated with an active ray of about 200 nm to about 500 nm to form a desired pattern. Irradiation is carried out by using light sources such as mercury lamps, metal halide lamps, argon lasers, etc. with low pressure, high pressure or ultra-high pressure. X-rays, electron beams, etc. may also be used as appropriate.

When using a high pressure mercury lamp, the exposure process uses, for example, a light dose of about 500 mJ/cm 2 or less (using a 365 nm sensor). However, the amount of light may vary depending on the kind of each component 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 using an alkaline aqueous solution by dissolving and removing unnecessary parts other than the exposed parts, thereby forming an image pattern.

(4) Post-processing

The developed image pattern can be reheated to achieve excellent quality such as heat resistance, light resistance, close contact characteristics, crack resistance, chemical resistance, high strength, storage stability, etc.

Hereinafter, the light-blocking layer composition and the transparent layer composition are described.

The light-blocking layer composition contains a binder resin, a reactive unsaturated compound, a photopolymerization initiator, an organic black pigment, and a solvent.

The light-blocking layer composition may further include color calibration agents such as anthraquinone-based pigments, perylene-based pigments, phthalocyanine-based pigments, azo-based pigments, and the like.

Organic black pigments can be used with dispersants for dispersion. Specifically, the pigment may be surface-pretreated with a dispersant, or the pigment and dispersant may be added together during the preparation of the light blocking layer composition.

The dispersing agent may be a nonionic dispersing agent, an anionic dispersing agent, a cationic dispersing agent, or the like. Specific examples of the dispersing agent may be polyalkylene glycol or its ester, polyoxyalkylene, polyhydric alcohol ester alkylene oxide addition product, alcohol epoxy Alkyl alkylene oxide addition product, sulfonate, sulfonate, carboxylate, carboxylate, alkyl amide alkylene oxide addition product, alkyl amine, etc., And they can be used alone or in a mixture of two or more.

Commercially available examples of the dispersant may include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-160 manufactured by BYK Co., Ltd., Germany 163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000 or DISPERBYK-2001; EFKA-47 manufactured by EFKA Chemicals Co. , EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400 or EFKA-450; Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000 or Solsperse 28000; or PB711 or PB821 manufactured by Ajinomoto Inc.

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 within the range is included, the light-blocking layer composition has improved dispersion characteristics.

Organic black pigments can be pretreated with water-soluble inorganic salts and wetting agents. When the organic black pigment is pretreated, the average particle size of the organic black pigment becomes finer.

Pretreatment can 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°C to about 100°C, and the filtration 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, and the like, but are not limited to these. Wetting agents can uniformly mix and pulverize pigments with water-soluble inorganic salts. Examples of humectants include alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether (diethylene glycolmonomethylether), etc., and alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerine polyethylene glycol), etc. These can 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 %, eg, about 2 wt % to about 20 wt %, based on the total amount of the light blocking layer composition. Resolution and pattern linearity are improved when pigments within the stated range are included.

In some embodiments, the light blocking layer composition may comprise about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, Organic black pigments in an amount of 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30% by weight. Furthermore, according to some embodiments of the present invention, the amount of organic black pigment can range from about any of the foregoing amounts to about any of the foregoing amounts.

The binder resin may include a cationic ring-based binder resin, an acryl-based binder resin, or a combination thereof.

The binder resin may be a cationic ring type binder resin. When the binder resin is a cation-based ring-based binder resin, the light-blocking layer composition containing the cation-based ring-based binder resin has excellent developability and sensitivity during photocuring, and thus has excellent fine pattern formation ability. Specifically, when the cationic ring-based adhesive resin is used, the reliability of a liquid crystal display (LCD) can be ensured.

The cationic ring-based binder resin may contain repeating units represented by the following Chemical Formula 2.

[Chemical formula 2]

In Chemical Formula 2,

R ¹ and R ² are independently a hydrogen atom or a substituted or unsubstituted (meth)acryloyloxy alkyl group,

R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and

Z ¹ is a single bond, O, CO, SO ₂ , CR ⁷ R ⁸ , SiR ⁹ R ¹⁰ (wherein R ⁷ to R ¹⁰ are independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or by One of the linking groups represented by one of the following Chemical Formulae 2-1 to 2-11.

[Chemical formula 2-1]

[Chemical formula 2-2]

[Chemical formula 2-3]

[Chemical formula 2-4]

[Chemical formula 2-5]

In Chemical Formula 2-5,

R ^a is a hydrogen atom, ethyl, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH=CH ₂ or phenyl.

[Chemical formula 2-6]

[Chemical formula 2-7]

[Chemical formula 2-8]

[Chemical formula 2-9]

[Chemical formula 2-10]

[Chemical formula 2-11]

Z ² is an acid dianhydride residual group,

m1 and m2 are each independently an integer in the range 0 to 4, and

n is an integer in the range 1 to 30.

The cationic ring-based binder resin may contain a functional group represented by the following Chemical Formula 3 at at least one of the two terminals.

[Chemical formula 3]

In Chemical Formula 3,

Z ³ is represented by the following Chemical Formulas 3-1 to 3-7.

[Chemical formula 3-1]

In Chemical Formula 3-1, R ^b and R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.

[Chemical formula 3-2]

[Chemical formula 3-3]

[Chemical formula 3-4]

[Chemical formula 3-5]

In Chemical Formula 3-5, R ^d is O, S, NH, substituted or unsubstituted C1-C20 alkylene, C1-C20 alkylamino, or C2-C20 alkenylamino.

[Chemical formula 3-6]

[Chemical formula 3-7]

The cationic ring-based binder resin can be prepared, for example, by mixing at least two of the following: a fluorine-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)fluoro(9,9- bis(4-oxiranylmethoxyphenyl)fluorine), etc.; anhydride compounds such as benzene tetracarboxylic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride dianhydride), benzophenonetetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic acid dianhydride, perylene tetracarboxylic acid dianhydride , tetrahydrofuran tetracarboxylic acid dianhydride (tetrahydrofuran tetracarboxylic aciddianhydride), tetrahydrophthalic anhydride (tetrahydrophthalic anhydride), etc.; glycol compounds, such as ethylene glycol, propylene glycol, polyethylene glycol, etc.; alcohol compounds, such as methanol, ethanol , propanol, n-butanol, cyclohexanol, benzyl alcohol, etc.; solvent compounds, such as propylene glycol methylethylacetate (propylene glycol methylethylacetate), N-methylpyrrolidone (N-methylpyrrolidone), etc.; phosphorus compounds , such as triphenylphosphine, etc.; and amine or ammonium salt compounds, such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride (benzyltriethylammonium chloride) etc.

The weight average molecular weight of the cationic ring-based binder resin is about 500 to about 50,000 g/mol, eg, about 1,000 to about 30,000 g/mol. When the weight average molecular weight of the cationic ring-based binder resin is within the range, patterns can be formed well without loss of film thickness during development.

The acryl-based binder resin is a copolymer of a first ethylenic 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 %, eg, about 10 wt % to about 40 wt %, based on the total amount of the acryl-based resin.

The second ethylenically unsaturated monomer can be an aromatic vinyl compound, such as styrene, α-methyl styrene, vinyl toluene, vinyl benzyl methyl ether, etc.; an unsaturated carboxylate compound, such as (methyl styrene) 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, etc.; unsaturated carboxylic acid amino alkyl ester compounds, such as (methyl) 2-aminoethyl acrylate, 2-dimethylaminoethyl (meth)acrylate, etc.; carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl benzoate, etc.; unsaturated carboxylic acid glycidyl ester ) compounds, such as glycidyl (meth)acrylate, etc.; vinyl cyanide compounds, such as (meth)acrylonitrile, etc.; unsaturated amide compounds, such as (meth)acrylamide, etc.; and the like. These can be used alone or in a mixture of two or more.

Specific examples of the acryl-based resin may be methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, methacrylic acid/benzyl methacrylate/methyl methacrylate 2-hydroxyethyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, etc., but not limited to these. These can 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, eg, 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 properties.

The acid value of the acryl-based resin may be about 15 mg KOH/gram to about 150 mg KOH/gram, eg, about 80 mg KOH/gram to about 130 mg KOH/gram. 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 acryl-based binder resin, the (weight) ratio of the cationic ring-based binder resin to the acryl-based binder resin in the first composition may be about 99:1 to About 50:50.

In some embodiments, the mixture of the cationic ring-based binder resin and the acryl-based binder resin may comprise 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% by weight of the cationic ring-based adhesive resin. Furthermore, 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 cationic ring-based binder resin and acryl-based binder resin may comprise 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% by weight of the acryl-based adhesive resin. Furthermore, 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 amount of the acryl-based binder resin contained exceeds the amount 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 %, eg, about 2 wt % to about 20 wt %, based on the total amount of the light blocking layer composition. Specifically, the cationic ring-based adhesive resin may be contained in an amount of about 1 wt % to about 20 wt % based on the total amount of the light-blocking layer composition, and about Acryloyl-based adhesive resin in an amount of 1 wt% to about 20 wt%. When the binder resin within the range is included, excellent resolution can be achieved.

In some embodiments, the light blocking layer composition may comprise about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, Binding resin in an amount of 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 wt%. Furthermore, according to some embodiments of the present invention, the amount of binding 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 an oligomer and may be a monofunctional or polyfunctional ester of (meth)acrylic acid containing at least one ethylenically unsaturated double bond.

The reactive unsaturated compound has an ethylenically unsaturated double bond, and thus, can cause sufficient polymerization during exposure during pattern formation and form a pattern having excellent heat resistance, light resistance, and chemical resistance.

The reactive unsaturated compound may be, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate Esters, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate Acrylates, Bisphenol A Di(meth)acrylate, Pentaerythritol Di(meth)acrylate, Pentaerythritol Tri(meth)acrylate, Pentaerythritol Tetra(meth)acrylate, Pentaerythritol Hex(meth)acrylate, Dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylic acid Esters, ethylene glycol monomethyl ether (meth)acrylate, trimethylol propane tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate Ester (tris(meth)acryloyloxyethyl phosphate), novolac epoxy(meth)acrylate, or a combination thereof.

(东亚合成化学工业有限公司(Toagosei Chemistry IndustryCo.，Ltd.))；KAYARAD

(日本化药有限公司(Nippon Kayaku Co.，Ltd.))；

(大阪有机化学工业有限公司(Osaka Organic Chemical Ind.，Ltd.))等。双官能(甲基)丙烯酸酯的实例可包含Aronix

(东亚合成化学工业有限公司)、KAYARAD

(日本化药有限公司)、

V-335

(大阪有机化学工业有限公司)等。三官能(甲基)丙烯酸酯的实例可包含Aronix

(东亚合成化学工业有限公司)、KAYARAD

(日本化药有限公司)、

(大阪有机化学工业有限公司)等。这些可单独使用或以两种或超过两种的混合物形式使用。Commercially available examples of reactive unsaturated compounds are as follows. Monofunctional (meth)acrylates can contain Aronix

(Toagosei Chemistry Industry Co., Ltd.); KAYARAD

(Nippon Kayaku Co., Ltd.);

(Osaka Organic Chemical Ind., Ltd.) and the like. Examples of difunctional (meth)acrylates may include Aronix

(Toa Synthetic Chemical Industry Co., Ltd.), KAYARAD

(Nihon Kayaku Co., Ltd.),

V-335

(Osaka Organic Chemical Industry Co., Ltd.) and so on. Examples of trifunctional (meth)acrylates may include Aronix

(Toa Synthetic Chemical Industry Co., Ltd.), KAYARAD

(Nihon Kayaku Co., Ltd.),

(Osaka Organic Chemical Industry Co., Ltd.) and so on. These can be used alone or in a mixture of two or more.

The reactive unsaturated compound can 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 %, eg, about 1 wt % to about 10 wt %, based on the total amount of the light blocking layer composition. When the reactive unsaturated compound within the range is included, the reactive unsaturated compound is sufficiently cured during exposure for pattern formation to improve reliability.

In some embodiments, the light blocking layer composition may comprise about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, Reactive unsaturated compound in an amount of 19 or 20% by weight. Furthermore, according to some embodiments of the present invention, the amount of reactive unsaturated compound can range from about any of the foregoing amounts to about any of the foregoing amounts.

The photopolymerization initiator can be a photopolymerization initiator commonly used in photosensitive resin compositions, such as acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and benzoin-based compounds , oxime compounds, etc.

Examples of acetophenone compounds may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methyl 2-hydroxy-2-methylpropinophenone, p-t-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2' -Dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinoprop-1-one (2-methyl-1-( 4-(methylthio)phenyl)-2-morpholinopropan-1-one), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.

Examples of benzophenone compounds may be benzophenone, benzoylbenzoate, methyl benzoyl benzoate, 4-phenylbenzophenone (4- phenylbenzophenone), hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4, 4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc.

Examples of thioxanthone compounds may be thioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethylthioxanthone, 2,4-diisoxanthone Propyl thioxanthone, 2-chlorothioxanthone, etc.

Examples of the benzoin-based compound may be benzoin, benzoin methyl ether, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethylketal, and the like.

Examples of triazine compounds may be 2,4,6-trichloro-s-triazine (2,4,6-trichloro-s-triazine), 2-phenyl-4,6-bis(trichloromethyl) )-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxy Naphthyl)-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)-s-triazine Methyl)-6-styryl-s-triazine, 2-(naphthol 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy Naphthol 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-sunenyl-s-triazine, 2-4- Bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine and the like.

Examples of oxime-based compounds may be O-acyloxime-based compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2- Octanedione (2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octandione), 1-(O-acetyloxime)-1-[9-ethyl-6-( 2-Methylbenzoyl)-9H-carbazol-3-yl]ethanone (1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3- yl]ethanone), O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one (O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one), etc. Specific examples of the O-acyl oxime compound may be 1,2-octandione (1,2-octandione), 2-dimethylamino-2-(4-methylbenzyl)-1-(4-methylbenzyl)- Lin-4-yl-phenyl)-butan-1-one (2-dimethylamino-2-(4-methylbenzyl)-l-(4-morpholin-4-yl-phenyl)-butan-1-one), 1 -(4-phenylsulfanyl phenyl)-butane-1,2-dione 2-oxime-O-benzoate (1-(4-phenylsulfanyl phenyl)-butane-1,2-dione2-oxime-O -benzoate), 1-(4-phenylsulfanyl phenyl)-octane-1,2-dione 2-oxime-O-benzoate (1-(4-phenylsulfanyl phenyl)-octane-1,2 -dione 2-oxime-O-benzoate), 1-(4-phenylsulfanyl phenyl)-octan-1-one oxime-O-acetate (1-(4-phenylsulfanyl phenyl)-octan-1-one oxime-O-acetate), 1-(4-phenylsulfanyl phenyl)-butan-1-one oxime-O-acetate (1-(4-phenylsulfanyl phenyl)-butan-1-one oxime-O- acetate) or a combination thereof.

In addition to the compounds, the photopolymerization initiator may further include carbazole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazo-based compounds, imidazole-based compounds, biimidazole-based compounds based) compounds, etc.

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 glycolbis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, di- Pentaerythritol tetrakis-3-mercapto propionate, etc. (dipentaerythritoltetrakis-3-mercapto propionate).

The photopolymerization initiator may be included in an amount of about 0.05 wt % to about 5 wt %, eg, about 0.1 wt % to about 5 wt %, based on the total amount of the light blocking layer composition. When the photopolymerization initiator within the range is contained, excellent reliability can be ensured due to sufficient curing during exposure during pattern formation.

In some embodiments, the light blocking layer composition may comprise 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 Photopolymerization initiator in an amount of 5% by weight. Furthermore, according to some embodiments of the present invention, the amount of photopolymerization initiator may range from about any of the foregoing amounts to about any of the foregoing amounts.

The solvent is a material 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, etc.; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, tetrahydrofuran, etc.; glycol ethers such as ethylene glycol monomethyl ether, ethyl ether Glycol monoethyl ether, etc; Alcohol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, etc.; propylene glycol alkane ether acetates, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc.; 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, etc.; saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate , n-butyl acetate, isobutyl acetate, etc.; lactate, such as methyl lactate, ethyl lactate, etc.; alkyl oxyacetate, such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate Esters, etc.; alkyl alkoxyacetates, such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; 3- Alkyl oxypropionate, such as methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.; alkyl 3-alkoxypropionate, such as methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-oxypropionate, such as methyl 2-oxypropionate , ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.; alkyl 2-alkoxypropionate, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate Esters, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-oxy-2-methylpropionate, such as methyl 2-oxy-2-methylpropionate , 2-Oxy-2-methylpropionic acid ethyl ester, etc; -Methyl methylpropionate, 2-ethoxy-2-methylpropionate ethyl ester, etc.; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyacetate ethyl ester, 2-hydroxy-3-methyl methyl butyrate, etc.; or ketoester, such as ethyl pyruvate, etc. In addition, high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide can also be used Amide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzene acetate Methyl ester, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylethylene glycol ethyl ether, etc.

In view of mutual solubility and reactivity, glycol ethers, such as ethylene glycol monoethyl ether, etc.; glycol alkyl ether acetates, such as ethyl glycol ethyl acetate, etc.; esters, such as 2-hydroxy propionate ethyl ester, etc.; carbitol, such as diethylene glycol monomethyl ether, etc.; propylene glycol alkyl ether acetate, 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, about 40 wt % to about 90 wt % based on the total light blocking layer composition. When the solvent within the range is contained, the light-blocking layer has an appropriate viscosity resulting in improved workability.

In some embodiments, the light blocking layer composition may comprise about 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, A solvent in an amount of 83, 84, 85, 86, 87, 88, 89 or 90 wt%. Furthermore, according to some embodiments of the present invention, the amount of solvent can range from about any of the foregoing amounts to about any of the foregoing amounts.

The light-blocking layer composition may further include additives such as malonic acid, 3-amino-1,2-propanediol, silane-based coupling agents, leveling agents, fluorine-based surfactants, radical polymerization initiators, or combinations thereof.

The silane-based coupling agent may have reactive substituents such as vinyl groups, carboxyl groups, methacryloxy groups, isocyanate groups, epoxy groups, etc., to improve the intimate contact characteristics with the substrate.

Examples of the silane-based coupling agent may include trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyl triacetoxysilane ), vinyl trimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl)ethyltrimethoxysilane (β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane) and the like. These can 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 contain a surfactant (eg, a fluorine-based surfactant) to improve coating characteristics and prevent defects if necessary.

和

(BM化学公司(BM Chemie Inc.))；MEGAFACE F

F

F

以及F

大日本油墨化学工业株式会社(Dainippon Ink Kagaku Kogyo Co.，Ltd.))；FULORAD

FULORAD

FULORAD

以及FULORAD

(住友3M株式会社(Sumitomo 3M Co.，Ltd.))；SURFLON

SURFLON

SURFLON

SURFLON

以及SURFLON

(朝日玻璃株式会社(Asahi Glass Co.，Ltd.))；以及

以及

等(东丽硅酮株式会社(Toray Silicone Co.，Ltd.))。Examples of fluorine-based surfactants can be commercial fluorine-based surfactants such as

and

(BM Chemie Inc.); MEGAFACE F

F

F

and F

Dainippon Ink Kagaku Kogyo Co., Ltd.; FULORAD

FULORAD

FULORAD

and FULORAD

(Sumitomo 3M Co., Ltd.); SURFLON

SURFLON

SURFLON

SURFLON

and SURFLON

(Asahi Glass Co., Ltd.); and

as well as

etc. (Toray Silicone Co., Ltd.).

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, predetermined amounts of other additives such as antioxidants, stabilizers, and the like may be included unless these may deteriorate the properties of the light-blocking layer composition.

The transparent layer composition may contain a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.

The clear layer composition achieves spacers and steps but not necessarily high optical density, and therefore does not contain organic black pigments. In other words, the transparent layer composition may contain a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent, or may further contain an organic black pigment if necessary. In addition, the transparent layer composition may further contain the additives described for the light blocking layer composition.

Each component 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 is the same as that 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 %, eg, about 3 wt % to about 60 wt %, based on the total amount of the transparent layer composition. When the binder resin within the range is included, excellent resolution can be obtained.

In some embodiments, the transparent layer composition may comprise 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 wt% amount of adhesive resin. Furthermore, according to some embodiments of the present invention, the amount of binding 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 %, eg, about 3 wt % to about 30 wt %, based on the total amount of the transparent layer composition. When the reactive unsaturated compound within the range is contained, the transparent layer composition is sufficiently cured during exposure in the pattern forming process, ensuring excellent reliability.

In some embodiments, the transparent layer composition may comprise 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% by weight of the reactive unsaturated compound . Furthermore, according to some embodiments of the present invention, the amount of reactive unsaturated compound can 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 wt % to about 5 wt %, eg, about 0.2 wt % to about 5 wt %, based on the total amount of the transparent layer composition. When the photopolymerization initiator within the range is included, the transparent layer composition is sufficiently cured during exposure in the pattern forming process, and excellent reliability is obtained.

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% . Furthermore, according to some embodiments of the present invention, the amount of photopolymerization initiator may range from about any of the foregoing amounts to about any of the foregoing amounts.

The solvent is included in a balanced amount, 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 within the range is contained, the transparent layer composition has an appropriate viscosity, providing excellent workability.

In some embodiments, the light blocking layer composition may comprise about 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, A solvent in an amount of 83, 84, 85, 86, 87, 88, 89 or 90 wt%. Furthermore, according to some embodiments of the present invention, the amount of solvent can 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 the solubility of the solvent 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-amyl acetate , n-hexyl acetate, etc., but the present invention is not limited to these.

Hereinafter, the present invention is explained in more detail with reference to Examples. However, these examples are not to be construed as limiting the scope of the present invention in any sense.

(Preparation of light blocking layer and transparent layer)

Preparation Examples 1 to 3

Each of the light-blocking layer compositions and the transparent layer compositions according to Preparation Examples 1 to 3 were prepared by using the following components in the following compositions provided in Tables 1 to 3 below.

Specifically, the photopolymerization initiator is dissolved in the solvent, the solution is fully stirred at room temperature for more than or equal to 30 minutes, the binder resin and the reactive unsaturated compound are sequentially added thereto, and the mixture is stirred at room temperature for about 1 Hour. Subsequently, other additives were added to the stirred solution, the mixture was stirred for about 10 minutes, then the pigment was added thereto, and the obtained mixture was stirred at room temperature for 2 hours or more. Next, the product was filtered three times to remove impurities therein to obtain a light-blocking layer composition and a transparent layer composition.

Preparation Example 1: Preparation of Light-Blocking Layer Composition

(Table 1)

(Unit: grams)

Preparation Example 2: Preparation of Transparent Layer Composition

(Table 2)

(Unit: grams)

Preparation Example 3: Preparation of Transparent Layer Composition

(table 3)

(Unit: grams)

(Manufacture of light blocking layer and transparent layer)

Preparation Example 4

(1) Coat the light-blocking layer composition of Preparation Example 1 to a thickness of 1.5 μm on the pretreated IZO substrate using a spin coating method or a slit coating method, a roll coating method, a screen printing method, an applicator, etc. , and dried by heating a hot plate at 70°C to 100°C for 1 minute 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 bilayer film.

(3) Placing a mask including a halftone portion (transmitting 15% to 70% of light) for forming a light-blocking layer pattern and a full-tone region portion (transmitting 100% light) for forming a transparent layer pattern on the double-layer film The front side was exposed by irradiating actinic rays of 200 nm to 500 nm using an exposure device (Ushio Inc., HB-50110AA). As the light source in the radiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon laser, etc. can be used, and if necessary, an X-ray, an electron beam, etc. can also be used. The exposure dose varies depending on the kinds of components in the composition, the mixing amounts, and the film thickness during drying, but can be less than or equal to 500 mJ/cm2 (by using a 365 nm sensor) when using a high pressure mercury lamp.

(4) By developing the exposed layer with a 0.2 wt % potassium hydroxide (KOH) aqueous solution using a developer (SVS Corporation, SSP-200), unnecessary areas are dissolved and removed and exposed areas are left, and thus a pattern is formed.

(5) The image pattern obtained by the development was heated in an oven at 230° C. for 30 minutes, and a sample including a light-blocking layer and a transparent layer formed on the light-blocking layer was produced.

Preparation Example 5

Samples were fabricated according to the same method as in Preparation Example 4, but 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 fabricated 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 Preparation Example 2 and Preparation Example 3 were prepared using a spin coater (Mikasa Co., Ltd., Opticoat MS-A150), respectively. Coated to a thickness of 1.5 μm on each 10 cm x 10 cm IZO substrate, soft baked (or pre-baked) on a hot plate at 80°C for 150 sec, and by using an exposure device (Yoshio Electric Co., Ltd., HB -50110AA) and the light mask were exposed at 50 mJ. Subsequently, the obtained organic coatings (SVS Corporation, SSP-200) were respectively developed in a 0.2 wt % potassium hydroxide (KOH) aqueous solution for 150 seconds, and hard-baked (or post-baked) at 230° C. in an oven for 30 s, respectively. minutes to obtain each patterned sample. The optical density of the samples was measured and is shown in Table 4 below.

(Table 4)

Preparation Example 1 Preparation Example 2 Preparation 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 x 1 cm, placed in a glass bottle containing 5 ml of NMP, left in a 100°C oven for 15 minutes, and checked for occurrence of Decolorization and results are shown in Table 5 below.

Decolorization measurement

X: No discoloration when inspected with the naked eye

O: Highly discolored when inspected with the naked eye

(table 5)

Preparation Example 4 Preparation Example 5 Comparative Preparation Example 1 depigmentation X X O

Referring to Table 5, Preparation Example 4 and Preparation Example 5 showed excellent solvent resistance compared with Comparative Preparation Example 1 and no discoloration.

While the present invention has been described in connection with what are presently considered to be the practicable exemplary embodiments, it is to be understood that the present invention is not limited to the disclosed embodiments, but on the contrary, the present invention is intended to cover the spirit and scope of the appended claims Various modifications and equivalent arrangements within. Therefore, the above-described embodiments should be understood to be exemplary and not to limit the present invention 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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