KR102503806B1 - A photo sensitive resin composition, a display partition wall structure prepared using the composition, and a display devide comprising the same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for forming a barrier rib comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, which is prepared from the photosensitive resin composition. The cured film has a maximum transmittance of less than 10% at a wavelength of 450 nm or more and 470 nm or less, and a minimum transmittance of 30% or more at a wavelength of 620 nm or more and 660 nm or less. A barrier rib structure and a display device including the barrier rib structure are provided.

Description

Photosensitive resin composition, a display barrier rib structure manufactured using the same, and a display device including the same

The present invention relates to a photosensitive resin composition, a display partition structure manufactured using the same, and a display device including the same.

In general, a display including a color conversion panel using a blue light source forms a barrier between each color conversion pixel in order to prevent light blocking characteristics for blue used as a light source and color mixing of each color conversion pixel. Due to the conversion efficiency, the thickness of the color conversion pixel and the barrier rib is formed to a film thickness of about 7 μm to 15 μm.

When a photosensitive resin composition for a black matrix that is conventionally used to form a partition of a display including a color conversion panel using a blue light source is used, it is formed beyond the conventionally used film thickness of 1 μm to 1.5 μm. Since the thickness of the barrier rib is 7 μm to 15 μm, it is difficult to form a cured film of a forward taper because the thickness of the barrier rib is too thick, and there is a problem in that the barrier rib is made in a reverse taper shape. When the barrier rib is made in a reverse tapered shape, there is a problem in that the barrier rib pattern is lost because the contact area with the lower substrate is small. In addition, when the barrier rib is formed with the existing black matrix, coating is performed in the process and the pattern is processed through the exposure process. However, due to the black color in the exposure process, it is difficult to recognize the Align key located at the bottom and it is difficult to form a pattern in an accurate position. Because of this, there is a limit to using the existing black matrix material as a material for forming the barrier rib.

Also, among the conventional techniques, C.I. Pigment Red, C.I. Pigment Yellow and C.I. A technique of preparing a color photosensitive resin composition using Pigment Orange or the like and manufacturing a color filter is a technique commonly used. Also in this case, it is common that the film thickness used for manufacturing the color filter is about 2 μm to 3 μm. In addition, since the color filter technology uses a white light source as a light source and has the purpose of expressing light of a specific wavelength in combination with a color filter, it is a technology for luminance or color coordinates. It is different from the present technology used for the purpose of blocking the light source.

Korean Patent Laid-open Publication No. 10-2007-0094460 aims to provide a photosensitive resin composition for forming barrier ribs having excellent shape stability against heat, but as described above, barrier ribs are formed with a film thickness of about 7 μm to 15 μm. When the thickness is too thick, it is difficult to form a cured film of a forward taper, and the barrier rib is formed in a reverse taper shape.

KR 10-2007-0094460 A

The present invention is to improve the above-described conventional technical problems, and prevents reverse taper formation in a thick film after barrier rib formation, so that it is easy to form a forward taper that is advantageous in forming barrier ribs, and efficiently blocks blue light to achieve the purpose of a color conversion pixel. It is an object of the present invention to provide a photosensitive resin composition capable of improving light emitting characteristics of a display device including color conversion pixels.

In addition, an object of the present invention is to provide a display barrier rib structure manufactured using the photosensitive resin composition and a display device including the display barrier rib structure.

The present invention relates to a photosensitive resin composition for forming a barrier rib comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, which is prepared from the photosensitive resin composition. The cured film provides a photosensitive resin composition for barrier rib formation characterized in that the maximum transmittance is less than 10% at a wavelength of 450 nm or more and 470 nm or less, and the minimum transmittance is 30% or more at a wavelength of 620 nm or more and 660 nm or less.

In addition, the present invention provides a display barrier rib structure made of the photosensitive resin composition.

In addition, the present invention provides a display device including the display barrier rib structure.

The photosensitive resin composition of the present invention prevents formation of a reverse taper in a thick film after forming a barrier rib, so that it is easy to manufacture a barrier rib having a forward tapered shape, which is advantageous in forming the barrier rib, and provides an effect of efficiently blocking blue light.

In addition, the photosensitive resin composition contains C.I. Pigment Red, C.I. Pigment Yellow and C.I. It includes one or more species selected from the group consisting of Pigment Orange, and accordingly, the display barrier rib structure made of the photosensitive resin composition according to the present invention may be formed in a red color. The red-based display barrier rib structure can effectively absorb blue-based light and effectively transmit red-based light, thereby exhibiting excellent light-shielding properties in a display device using a blue light source and improving light emitting properties. to provide.

1 is a diagram showing transmittance spectra of patterned cured films prepared using photosensitive resin compositions according to Example 1 and Comparative Example 1 of the present invention.
2 is an image of a cross-section of a cured film prepared with a film thickness of 2 μm using the photosensitive resin composition according to Examples 1 to 3 and Comparative Example 1 of the present invention and determining the minimum pattern forming mask size.
3 is a cross-section of a cured film prepared with a film thickness of 10 μm using the photosensitive resin composition according to Examples 1 to 3 and Comparative Example 1 of the present invention and an image for determining the minimum pattern forming mask size.
4 is a view of a method for measuring the taper angle of the photosensitive resin composition according to Examples 1 to 17 and Comparative Examples 1 to 5 of the present invention.

The present invention relates to a photosensitive resin composition for forming a barrier rib comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, which is prepared from the photosensitive resin composition. The cured film has a maximum transmittance of less than 10% at a wavelength of 450 nm or more and 470 nm or less, and a minimum transmittance of 30% or more at a wavelength of 620 nm or more and 660 nm or less. A barrier rib structure and a display device including the barrier rib structure are provided.

Preferably, the cured film made of the photosensitive resin composition has a maximum transmittance of less than 8% at a wavelength of 450 nm to 470 nm, and a minimum transmittance of 35% at a wavelength of 620 nm to 660 nm when the thickness of the cured film is 7 to 15 μm. % or more, more preferably, the maximum transmittance at a wavelength of 450 nm or more and 470 nm or less may be less than 5%, and the minimum transmittance may be 40% or more at a wavelength of 620 nm or more and 660 nm or less.

In one embodiment, the cured film is characterized in that the ratio of transmittance A to transmittance B is 10 or more when the maximum transmittance is A at a wavelength of 450 nm or more and 470 nm or less, and the minimum transmittance is B at a wavelength of 620 nm or more and 660 nm or less. Accordingly, there is an advantage in blocking the blue series and advantageous in recognizing the Align key in the exposure process.

When the cured film satisfies the specific transmittance condition in the above-described specific wavelength range, it is possible to efficiently block blue-based light generated from the rear surface, which is excellent in a display device using a blue light source including the cured film as a partition wall structure. It exhibits light-shielding properties and can provide an effect of improving light-emitting properties.

The photosensitive resin composition according to the present invention is C.I. Pigment Red, C.I. Pigment Yellow and C.I. Including at least one member selected from the group consisting of pigment orange, a red-based barrier rib structure is formed, thereby efficiently blocking blue light.

In a quantum dot display, quantum dots located in each pixel are converted into respective colors by electric or blue light to realize an image. In terms of preventing color mixing of green pixels, there is a technical difference from a color filter that implements color by transmitting light of a specific wavelength using a white light source generated from the rear.

In addition, conventionally used barrier rib structures are generally formed in black, but it is difficult to form a cured film of a forward taper in a thick film, and there are problems in that a reverse taper occurs, and it is difficult to recognize the Align key located at the bottom when forming a pattern, resulting in an accurate location. There is a problem in that it is difficult to form a pattern on, and there is a limit to its use as a material for forming a partition wall structure.

In the present invention, forward taper means a case where the taper angle is 90 ° or less, and reverse taper can be understood to mean a case where the taper angle exceeds 90 °.

The display device according to the present invention includes a display barrier rib structure manufactured using the photosensitive resin composition, and thus, light emitting characteristics of the display device may be improved.

In addition, the photosensitive resin composition according to the present invention forms a red-based barrier rib structure, and when forming a cured film in a thick film thereafter, the formation of a reverse taper can be prevented, and thus the forward taper can be easily formed.

Among the forward-tapered diaphragm structures thus formed, the higher the taper angle, the better the aperture ratio. The taper angle may be 50° or more and 90° or less, and more preferably 70° or more and 90° or less.

Hereinafter, the present invention will be described in detail.

<Photosensitive Resin Composition>

The photosensitive resin composition according to the present invention includes (A) a colorant, (B) an alkali-soluble resin, (C) a polymerizable compound, (D) a photopolymerization initiator and (E) a solvent, and the (A) colorant is C.I. Pigment Red, C.I. Pigment Yellow and C.I. It may include at least one selected from the group consisting of Pigment Orange.

The photosensitive resin composition according to the present invention can be characterized in that it is used for forming barrier ribs in a display device using a blue light source.

(A) colorant

The colorant is C.I. Pigment Red, C.I. Pigment Yellow and C.I. It may include at least one selected from the group consisting of pigment orange, and accordingly, the display barrier rib structure made of the photosensitive resin composition according to the present invention may be formed in a red color. The red-based display barrier rib structure can absorb blue-based light and transmit red-based light, thereby exhibiting excellent light blocking characteristics and improving light emitting characteristics in a display device using a blue light source.

The C.I. Pigment Red is C.I. Pigment Red 9, 97, 81, 105, 122, 123, 144, 149, 150, 155, 166, 168, 171, 175, 176, 177, 179, 180, 185, 192, 202, 208, 209, 214 , 215, 216, 220, 222, 224, 242, 254, 255, 264, 269, at least one selected from the group consisting of 270 and 272,

The C.I. Pigment Yellow is C.I. Pigment Yellow 11, 13, 20, 24, 31, 53, 83, 86, 93, 94, 95, 99, 108, 109, 110, 117, 125, 128, 129, 138, 139, 147, 148, 150 , 151, 154, 155, 166, 167, 173, 180, 185 and at least one selected from the group consisting of 199,

The C.I. Pigment Orange is C.I. It may be at least one selected from the group consisting of Pigment Orange 13, 15, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71.

Preferably, the C.I. Pigment Red is C.I. At least one selected from the group consisting of Pigment Red 177, 179, 254, 264 and 269,

The C.I. Pigment Yellow is C.I. At least one selected from the group consisting of Pigment Yellow 138, 139, 150 and 185,

The C.I. Pigment Orange is C.I. It may be at least one selected from the group consisting of Pigment Orange 64 and 71.

In addition, the present invention is characterized in that it can have an effect of efficiently blocking blue-based light without including a black colorant. Therefore, the colorant of the present invention preferably does not contain a black colorant, but may contain up to 20% by weight based on the total weight of the colorant, if necessary. If the colorant contains an excessive amount of the black colorant, reverse taper may occur due to lack of deep curing in an exposure process, and luminous efficiency of the display may decrease due to a decrease in reflectance, which is not preferable. Specifically, the black colorant may include black organic/inorganic pigments (pigments) and dyes (dyes) such as carbon black, titanium black, aniline black, lactam black, and perylene black. It can be understood as a concept that includes even combinations that can represent.

The colorant may be included in an amount of 1 to 30% by weight, preferably 3 to 20% by weight, based on the total weight of solids in the photosensitive resin composition. When the colorant is included within the above range, light blocking properties for blue light may be improved, and light emitting properties of the display device may be improved.

In one embodiment, the colorant is the C.I. Pigment Red and the C.I. Pigment Yellow and the C.I. It may include at least one selected from the group consisting of Pigment Orange, and the C.I. The content of Pigment Red may be 50% by weight or more. The C.I. When the content of Pigment Red is included within the above range, the transmittance is high at a wavelength of 660 nm or more, so it is preferable to easily recognize the Align key located at the lower part in the exposure process.

In the present invention, the total weight of the solid content in the photosensitive resin composition means the total weight of the components other than the solvent of the photosensitive resin composition.

(B) alkali soluble resin

The alkali-soluble resin has reactivity and alkali solubility by the action of light or heat, acts as a dispersion medium for solids including the coloring agent, and resins known in the art are selected and used without particular limitation as long as they perform the function of a binder resin. can

Specifically, the alkali-soluble resin is preferably a copolymer of an unsaturated carboxyl group-containing monomer and another monomer copolymerizable therewith.

Examples of the unsaturated carboxyl group-containing monomer include unsaturated carboxylic acids having at least one carboxyl group in a molecule such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids. For example, as the unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid may be used. The carboxyl group-containing monomers may be used alone or in combination of two or more.

Other monomers copolymerizable with the carboxyl group-containing monomer include aromatic vinyl compounds; unsaturated carboxylic acid esters; unsaturated carboxylic acid aminoalkyl esters; unsaturated carboxylic acid glycidyl esters; carboxylic acid vinyl esters; unsaturated ethers; vinyl cyanide compounds; unsaturated amides; unsaturated imides; aliphatic conjugated dienes; And polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, and polysiloxane have a monoacryloyl group or a monomethacryloyl group at the end of the polymer branched chain. The macromonomers which have, etc. are mentioned. These monomers can be used individually or in mixture of 2 or more types, respectively.

For example, the alkali-soluble resin may be a copolymer represented by Formula 1 below.

[Formula 1]

In Formula 1,

X is a group represented by the following formula (2),

Y is maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl end methylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride A residue excluding the carboxylic acid anhydride group (-CO-O-CO-) from the contained dicarboxylic acid anhydride,

Z is a residue obtained by removing two carboxylic acid anhydride groups from tetracarboxylic dianhydrides such as pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenylethertetracarboxylic dianhydride.

[Formula 2]

In Formula 2, * is a bonding hand.

The alkali-soluble resin may be included in an amount of 20 to 70% by weight, preferably 30 to 60% by weight, based on the total weight of solids in the photosensitive resin composition. When the alkali-soluble resin is included within the above range, it is easy to form a cured film due to sufficient solubility in the developing solution, and film reduction of the pixel portion of the exposed area is prevented during development, so that the omission of the non-pixel portion becomes good. do.

(C) polymerizable compound

The polymerizable compound is a compound that can be polymerized by light and heat, and as long as it can be polymerized by light and heat, polymerizable compounds known in the art may be selected and used without particular limitation. Specifically, monofunctional monomers, Bifunctional monomers, other polyfunctional monomers, and the like can be used.

The types of the monofunctional monomer, the bifunctional monomer, and the polyfunctional monomer are not particularly limited. For example, as the polyfunctional monomer, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri( meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol Penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like can be used.

The amount of the polymerizable compound may be included in an amount of 5 to 50% by weight, preferably 10 to 40% by weight, based on the total weight of the solid content in the photosensitive resin composition. When the polymerizable compound is included within the above range, it is preferable in terms of strength or smoothness of the pixel unit.

(D) photopolymerization initiator

As the photopolymerization initiator, photopolymerization initiators known in the art may be selected and used without particular limitation. For example, acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, biimidazole-based compounds and the like can be used.

For example, o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one may be used as the oxime-based compound, and Ciba's OXE-01 and OXE-02 are typical commercial products. .

The photopolymerization initiator may be used alone or in combination of two or more.

The photopolymerization initiator may be included in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on the total weight of solids in the photosensitive resin composition. When the photopolymerization initiator is included within the above range, the photopolymerization reaction rate is appropriate, thereby preventing an increase in the total process time and preventing deterioration of physical properties of the final cured film due to photoreaction.

The photosensitive resin composition according to the present invention may further include a photopolymerization initiation auxiliary agent in addition to the photopolymerization initiator. In the case of using a photopolymerization initiation auxiliary agent together with the photopolymerization initiator, the photosensitive resin composition becomes more sensitive and productivity is improved, so it is preferable.

The photopolymerization initiation aid is a compound used to accelerate the polymerization of the polymerizable compound polymerization initiated by the photopolymerization initiator, and one or more compounds selected from the group consisting of amines and carboxylic acid compounds may be preferably used. .

The photopolymerization initiation aid may be included in an amount of more than 0 mol and less than 10 mol, preferably 0.01 mol to 5 mol, based on 1 mol of the photopolymerization initiator. When the photopolymerization initiation auxiliary agent is included within the above range, the photopolymerization efficiency can be improved and the productivity improvement effect can be expected.

(E) Solvent

The solvent is not particularly limited, and various organic solvents known in the field of photosensitive resin compositions may be used.

내지 200

인 유기 용제를 사용할 수 있고, 보다 바람직하게는 알킬렌글리콜알킬에테르아세테이트류, 케톤류, 3-에톡시프로피온산 에틸이나, 3-메톡시프로피온산 메틸 등의 에스테르류를 사용할 수 있으며, 더욱 바람직하게는 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 시클로헥사논, 3-에톡시프로피온산 에틸, 3-메톡시프로피온산 메틸 등을 사용할 수 있다. 상기 용제는 각각 단독으로 또는 2종류 이상 혼합하여 사용할 수 있다.The solvent preferably has a boiling point of 100 in terms of application and drying properties.

to 200

Phosphorus organic solvents can be used, more preferably alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate or methyl 3-methoxypropionate can be used, more preferably propylene Glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like can be used. These solvents may be used alone or in combination of two or more.

The amount of the solvent may be 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the photosensitive resin composition. When the solvent is included within the above content range, the effect of improving the coating property when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), an inkjet, or the like It is desirable because it provides

heat curing agent

The photosensitive resin composition according to the present invention may further include a heat curing agent if necessary, and when the heat curing agent is further included, when forming a cured product using the photosensitive resin composition, deep curing of the cured product or mechanical curing of the cured product is performed. strength can be improved.

The thermal curing agent may be selected from the group consisting of, for example, monofunctional alicyclic epoxy resins, silane-modified epoxy resins, and novolak-type epoxy resins.

The amount of the thermal curing agent may be included in an amount of 0.05 to 10% by weight, preferably 0.1 to 10% by weight, based on the total weight of the solid content in the photosensitive resin composition. When the thermal curing agent is included within the above range, there are advantages in that chemical resistance is improved and heat resistance and development speed may be improved.

additive

The photosensitive resin composition according to the present invention may further include additives as needed, and the type of the additive may be determined according to the needs of the user, and is not particularly limited in the present invention, but, for example, fillers, High molecular compounds, surfactants, adhesion accelerators, antioxidants, aggregation inhibitors and the like are exemplified.

The antioxidant may include, for example, at least one selected from the group consisting of phosphorus-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants. It is possible to suppress the occurrence of yellowing that may be caused by The antioxidant may include at least one selected from the group consisting of a phenol-based compound, a phosphorus-based compound, and a sulfur-based compound, which is a phenolic-phosphorus compound, a phenolic-sulfur compound, a phosphorus-sulfur compound, or a phenolic-phosphorus compound. -Can be used in combination with sulfur-based compounds.

The antioxidant may be included in an amount of 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the total weight of solids in the photosensitive resin composition. When the antioxidant is included within the above range, it is preferable in terms of solving the problem of lowering the luminous intensity, and there is an advantage in that it is possible to prevent aging due to heat and to preserve the color during post-baking during the process of forming a cured product. .

In the case of additives whose content is not exemplified among the above additives, those skilled in the art can appropriately add and use them within a range that does not impair the effect of the present invention. For example, the additive may be used in an amount of 0.05 to 10% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the photosensitive resin composition, but is not limited thereto.

The photosensitive resin composition of the present invention may be prepared by a conventional method known in the art, and is not particularly limited in the present invention, but may be prepared by, for example, the following method.

A colorant is previously mixed with a solvent and dispersed using a bead mill or the like until the average particle diameter of the colorant is about 200 nm or less. At this time, a pigment (pigment) dispersant is used as needed, and some or all of the alkali-soluble resin may be blended. To the resulting dispersion, the remainder of the alkali-soluble resin, the polymerizable compound and photopolymerization initiator, and if necessary, additional additives are added, and then, if necessary, additional solvents are further added to a predetermined concentration to obtain the desired photosensitive resin composition.

< Display bulkhead structure and display device >

In addition, the present invention provides a display partition structure including a color conversion panel made of the photosensitive resin composition according to the present invention and a display device including the same.

In a display including a color conversion panel, since each pixel is driven to form an image, a thin film transistor for driving each pixel is formed, an insulating film is additionally formed due to the shape of the transistor, and then the pixel and the pixel are formed. A color conversion panel partition wall structure is formed. When the color conversion panel barrier rib structure is formed using the photosensitive resin composition of the present invention, color mixing of pixels of the display is prevented and it is advantageous to form a microcured film, and thus has the advantage of implementing a high-quality image.

The display device may include a liquid crystal display device, an organic light emitting diode, a flexible display, and the like, but is not limited thereto, and all display devices known in the field applicable thereto may be exemplified.

The color conversion panel barrier rib structure may be manufactured by coating the photosensitive resin composition of the present invention described above on a substrate, photocuring and developing to form a cured film.

First, the photosensitive resin composition of the present invention is applied onto a substrate and then heated and dried to remove volatile components such as a solvent to obtain a smooth cured film.

As the coating method, for example, spin coating, casting coating, roll coating, slit and spin coating, or slit coating may be used. After application, heat drying (prebaking) or drying under reduced pressure is followed by heating to volatilize volatile components such as solvents. Here, the heating temperature is usually 70 to 150°C and preferably 80 to 130°C. The cured film obtained in this way is irradiated with ultraviolet rays through a mask for forming a cured film of a target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel light rays are uniformly irradiated to the entire exposure area and accurate positioning of the mask and the substrate is performed. When irradiated with ultraviolet rays, the portion irradiated with ultraviolet rays is cured.

As the ultraviolet rays, g-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm), and the like may be used. The irradiation amount of ultraviolet rays can be appropriately selected as needed, and is not limited thereto in the present invention. When the photocured cured film is contacted with a developing solution to dissolve the unexposed portion and developed, a cured film shape of a target pattern can be formed.

The cured film shape obtained in this way can be hardened through a post-curing process, and the heating temperature is usually 150 to 250°C, preferably 180 to 230°C. The heating time is usually 5 to 30 minutes, preferably 15 to 20 minutes. The cured film thickness after heating and drying is usually about 7 to 15 μm.

Hereinafter, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are only examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention has been indicated in the claims, and furthermore contains all changes within the meaning and range equivalent to the written claims. In the following Examples and Comparative Examples, "%" and "parts" indicating content are based on mass unless otherwise specified.

Synthesis Example 1: Synthesis of alkali-soluble resin (B-1)

In a four-necked flask, 235 g (epoxy equivalent 235 g/eq) of a bisphenol fluorene type epoxy monomer represented by the following formula 2-1, 110 mg of tetramethylammonium chloride, and 100 2,6-di-tertbutyl-4-methylphenol mg and 72.0 g of acrylic acid were dissolved by heating from 90°C to 100°C while blowing air at a rate of 25 ml/min.

[Formula 2-1]

Next, while the solution was in a cloudy state, the temperature was slowly raised to 120°C to dissolve completely. At this time, stirring was continued while confirming that the solution gradually became transparent. Heating and stirring were continued for about 12 hours until the acid value was less than 1.0 mgK0H/g. Then, it cooled to room temperature, and the bisphenol fluorene type epoxy acrylate represented by the following general formula (1-1) which was colorless and transparent and was solid was obtained.

[Formula 1-1]

Thereafter, 600 g of propylene glycol monoethyl ether acetate (PGMEA) was added to 307.0 g of the bisphenol fluorene type epoxy acrylate thus obtained and dissolved, followed by 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide. After mixing, it was made to react at 110 degreeC to 115 degreeC for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90°C for 6 hours to obtain a cardo-based binder resin. At this time, the disappearance of the acid anhydride group was confirmed by IR spectrum, and it was confirmed that the prepared cardo-based binder resin had a weight average molecular weight of 3,300 g/mol and an acid value of 123 mgKOH/g.

Synthesis Example 2: Synthesis of alkali-soluble resin (B-2)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared. As a monomer loading lot, a mixture 40 in which 3,4-epoxytricyclodecan-8-yl(meth)acrylate and 3,4-epoxytricyclodecan-9-yl(meth)acrylate were mixed at a molar ratio of 50:50 parts by weight, 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyltoluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) Stirring was prepared by adding. 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added to the chain transfer agent dropping tank to prepare stirring. Thereafter, 395 parts by weight of PGMEA was added to the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring. Dropwise addition of monomer and chain transfer agent was then started. Dropping proceeded for 2 hours while maintaining 90 ° C. After 1 hour, the temperature was raised to 110 ° C. and maintained for 5 hours to obtain a resin having a solid acid value of 100 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 17,000, and the molecular weight distribution (Mw/Mn) was 2.3.

The weight average molecular weight (Mw) of the alkali-soluble resin was measured using the GPC method, and an HLC-8120GPC (manufactured by Tosoh Co., Ltd.) was used.

Measurement conditions were used by connecting TSK-GELG4000HXL and TSK-GELG2000HXL columns in series, and the temperature of the column was set to 40 °C. Tetrahydrofuran was used as a mobile phase solvent and measured while flowing at a flow rate of 1.0 mL/min. The concentration of the measurement sample was 0.6% by weight, the injection amount was 50 μL, and the analysis was performed using an RI detector. TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, and A-500 (manufactured by Tosoh Co., Ltd.) were used as standard materials for calibration, and the weight average molecular weight of the alkali-soluble resin obtained under the above conditions was measured. did

Preparation of photosensitive resin compositions according to Examples and Comparative Examples

Resin compositions of Preparation Examples 1 and 2 were prepared according to Table 1 below.

(Unit: % by weight) alkali soluble resin photopolymerizable compound photopolymerization initiator heat curing agent dispersant antioxidant solvent Preparation Example 1 B-2 11.8 7.87 One 0.59 0.85 0.97 76.92 Preparation Example 2 B-1 11.8 7.87 One 0.59 0.85 0.97 76.92

(B) Alkali-soluble resin: B-1: Alkali-soluble resin of Synthesis Example 1

B-2: Alkali-soluble resin of Synthesis Example 2

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate (Kayarad DPHA, Nippon Chemical Co., Ltd.)

(D) Photopolymerization initiator: Irgacure OXE01 (manufactured by Basf)

Heat curing agent: Epoxy resin (ESCN 195XL, manufactured by Sumitomo Chemical Co., Ltd.)

Dispersant: DISPERBYK-110 (BYK)

Antioxidant: Sumilizer GP (made by Sumitomo Chemical)

(E) solvent: propylene glycol monomethyl ether acetate (PGMEA)

According to Table 2 below, a photosensitive resin composition was prepared by adding a pigment (pigment) to Preparation Example 1 and Preparation Example 2.

pigment (pigment) Pigment content resin composition Resin composition content Example 1 Red 177 2.5 Preparation Example 1 97.5 Example 2 Red 179 2.5 Preparation Example 1 97.5 Example 3 Red 179 2.5 Preparation Example 2 97.5 Example 4 Red 254 2.5 Preparation Example 1 97.5 Example 5 Red 264 2.5 Preparation Example 1 97.5 Example 6 Red 269 2.5 Preparation Example 1 97.5 Example 7 Yellow 138 2.5 Preparation Example 1 97.5 Example 8 Yellow 139 2.5 Preparation Example 1 97.5 Example 9 Yellow 150 2.5 Preparation Example 1 97.5 Example 10 Yellow 185 2.5 Preparation Example 1 97.5 Example 11 Orange 64 2.5 Preparation Example 1 97.5 Example 12 Orange 71 2.5 Preparation Example 1 97.5 Example 13 Red 179/Yellow 138 1.75 / 0.75 Preparation Example 1 97.5 Example 14 Red 179 / Orange 64 2.0 / 0.5 Preparation Example 1 97.5 Example 15 Red 179 / Orange 64 1.5/1.0 Preparation Example 1 97.5 Comparative Example 1 Black 7 15 Preparation Example 1 97.5 Comparative Example 2 organic black 15 Preparation Example 1 97.5 Comparative Example 3 Green 36 15 Preparation Example 1 97.5 Comparative Example 4 Blue 15:6 15 Preparation Example 1 97.5 Comparative Example 5 Blue 15:6 / Green 36 1.25 / 1.25 Preparation Example 1 97.5

test example

(1) Measurement of permeability

A 5cmХ5cm glass substrate (Corning Co.) was washed with neutral detergent and water and then dried. Each of the photosensitive resin compositions according to Examples and Comparative Examples was spin-coated on the glass substrate to a final film thickness of 10 μm, pre-baked at 100° C., and dried for 2 minutes to remove the solvent. Thereafter, a mask including a line/space pattern of 1 to 100 μm and a 20 mmХ20 mm pattern was exposed at an exposure amount of 50 mJ/cm ² , and the unexposed portion was removed using an alkaline aqueous solution. The prepared cured film was then fired at 230° C. for 20 minutes to prepare a barrier rib pattern cured film.

Using a UV-Vis spectrophotometer, the transmittance for each wavelength of the 20㎜Х20㎜ patterned cured film manufactured to the thickness of 10㎛ was measured, and the maximum transmittance at 450nm or more and 470nm or less (A) wavelength and 620nm or more The ratio of the minimum transmittance at a wavelength of 660 nm or less (B) and the transmittance (A) to the transmittance (B) was calculated as (B)/(A) and shown in Table 3 below, and in Example 1 and Comparative Example 1 The transmittance spectrum of the barrier rib pattern cured film prepared using the photosensitive resin composition according to FIG. 1 is shown in FIG.

(2) Tapered shape measurement

Device Used: Electron Microscope (SEM, Scanning Electron Microscope, SU-8200, Hitachi)

Acceleration voltage: 15 kV

Observation magnification: Х 5.0 k

In order to determine the taper shape of the barrier rib pattern as a forward taper or a reverse taper, a cross section of the cured film was measured with an electron microscope. The cured film sample of the barrier rib pattern for electron microscope measurement was prepared in the same way as in (1) transmittance measurement, but the film thickness was uniformly prepared with a cured film having a thickness of 2 μm and 10 μm, respectively, and the manufacturing process was used for analysis of the cured film of the barrier rib pattern obtained through removal of the solvent through heat drying after coating, exposure, development, and heat drying at 220 ° C., a cross-sectional sample was prepared, and the results are shown in FIGS. 2 and 3. In the case of the measuring method, forward taper and reverse taper were distinguished as shown in FIG. 4, and the taper angle was measured and entered in Table 3 below.

(3) Evaluation of minimum formation mask size of cured film

Patterns can be formed according to the size of the portion formed with a line / space pattern of 1 to 100 μm in the barrier rib pattern cured film having a thickness of 10 μm prepared using the photosensitive resin composition prepared according to the above Examples and Comparative Examples, The minimum mask size that can be formed varies depending on the composition. For example, in FIG. 3, in the case of Example 1, in the case of the number 18, the pattern was not formed, but in the case of the number 19, the pattern was formed, so 19 is written. 3, the minimum forming mask size of Example 1 is 19 μm, Example 2 is 10 μm, Example 3 is 8 μm, and Comparative Example 1 is 50 μm. In the case of a low number, since it is possible to form a narrower barrier rib, it is advantageous in manufacturing a display including a color conversion pixel. The minimum formation mask size of the cured film prepared using the photosensitive resin composition according to Examples and Comparative Examples was measured and shown in Table 3 below.

(1) Permeability (2) Taper shape (taper angle °) (3) Minimum forming mask size (μm) (A) (B) (B)/(A) 2㎛ thickness 10㎛ thickness Example 1 2.99 95.98 32.1 Forward taper(32) Sun Taper(38) 19 Example 2 0.01 88.62 8862.0 Forward Taper(49) Sun Taper(69) 10 Example 3 0.01 88.59 8859.0 Net taper(56) Sun Taper(73) 8 Example 4 0.37 97.56 263.7 Forward taper (44) Stern taper(57) 9 Example 5 0.11 90.93 826.6 Stern taper(35) Net taper (45) 22 Example 6 7.57 95.17 12.6 Sun Taper(33) Forward taper (44) 20 Example 7 0.00 99.16 - Forward Taper(41) Sun Taper(63) 9 Example 8 0.01 93.71 9371.0 Sun Taper(38) Net taper (45) 22 Example 9 0.01 96.49 9649.0 Forward taper (42) Sun Taper(66) 20 Example 10 0.01 97.39 9739.0 Stern taper(35) Net taper(43) 30 Example 11 0.01 43.66 4366.0 Forward taper(44) Stern taper(62) 8 Example 12 0.00 81.56 - Forward taper(32) Net taper (48) 28 Example 13 0.00 87.2 - Net taper(43) Sun Taper(65) 10 Example 14 0.00 76.64 - Stern taper(47) Sun Taper(68) 7 Example 15 0.00 70.65 - Stern taper(46) Sun Taper(68) 8 Comparative Example 1 0.42 0.51 1.2 Sun Taper(89) Reverse Taper(151) 50 Comparative Example 2 0.03 0.11 3.7 Sun Taper(87) Reverse Taper(152) 12 Comparative Example 3 6.05 0.06 0.0 Forward Taper(52) Reverse Taper(147) 20 Comparative Example 4 70.34 0.44 0.0 Stern taper(55) Reverse Taper(157) 24 Comparative Example 5 45.98 0.93 0.0 Sun Taper(63) Reverse Taper(139) 26

The result of *(B)/(A) is rounded to two decimal places.

Referring to Table 3, the barrier rib pattern cured film prepared using the photosensitive resin composition according to the embodiment has a maximum transmittance of less than 10%, specifically less than about 8%, at a wavelength of 450 nm or more and 470 nm or less, and is 640 nm or more and 660 nm It can be seen that the minimum transmittance at the wavelength below is 30% or more, specifically, about 40% or more, and blue light is absorbed and effectively blocked, while red light is not absorbed. Accordingly, when a barrier rib pattern cured film of a display device using a blue light source is formed using the photosensitive resin composition according to the present invention, light loss may be prevented and light emitting properties may be improved.

In particular, the barrier rib patterns made of the photosensitive resin composition according to Examples 7 and 12 to 15 did not transmit light at all at a wavelength of 450 nm or more and 470 nm or less, and it was confirmed that they had a very good blue light source blocking effect as a display barrier rib structure. .

On the other hand, the barrier rib pattern cured films prepared using the photosensitive resin compositions according to Comparative Examples 1 to 3 have a maximum transmittance of less than 1% at wavelengths of 640 nm or more and 660 nm or less, as well as wavelengths of 450 nm or more and 470 nm or less, and not only blue light. In addition, red light is also absorbed and blocked, and the cured film of the barrier rib pattern prepared using the photosensitive resin composition according to Comparative Examples 4 to 5 has a maximum transmittance of more than 40% at a wavelength of 450 nm or more and 470 nm or less, and is 640 nm or more and 660 nm. Since the minimum transmittance at the wavelength below is less than about 1.5%, blue light is transmitted without absorption, and red light is absorbed and blocked, so when applying the barrier rib pattern cured film to a display device using a blue light source, Loss of light may occur and thus light emitting characteristics may be deteriorated.

In addition, referring to FIG. 1, it can be seen that the transmittance spectrum of the cured film of the barrier rib pattern prepared using the photosensitive resin composition according to Example 1 and Comparative Example 1 is satisfied. In the case of Example 1, the transmittance value described above is satisfied, In the case of Comparative Example 1, it can be confirmed that the transmittance value described above is not satisfied.

Referring to FIGS. 2 and 3 and Table 3, it can be seen that both barrier ribs manufactured using the photosensitive resin compositions according to Examples and Comparative Examples have a forward taper (angle of 90° or less) when the film thickness is 2 μm. can However, when the same photosensitive resin composition is used to form a thickness of 10 μm, the barrier rib formed using the photosensitive resin composition according to the embodiment is prevented from forming a reverse taper when forming a cured film in a thick coating film, in other words , It can be confirmed that a forward taper is formed, but it can be confirmed that a reverse taper (angle greater than 90°) is formed when a cured film is formed on a barrier rib formed using the photosensitive resin composition according to Comparative Example.

Claims (7)

(A) a colorant, (B) an alkali-soluble resin, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a photosensitive resin composition for partition formation containing a solvent,
The alkali-soluble resin (B) is a cardo-based binder resin,
The cured film made of the photosensitive resin composition has a maximum transmittance of less than 10% at a wavelength of 450 nm or more and 470 nm or less, and a minimum transmittance of 30% or more at a wavelength of 620 nm or more and 660 nm or less,
The cured film is photosensitive for barrier rib formation, characterized in that the ratio of transmittance A to transmittance B is 10 or more when the maximum transmittance is A at a wavelength of 450 nm or more and 470 nm or less, and the minimum transmittance is B at a wavelength of 620 nm or more and 660 nm or less. resin composition. delete The method of claim 1,
The (A) colorant is at least one selected from the group consisting of CI Pigment Red, CI Pigment Yellow, and CI Pigment Orange, photosensitive resin for forming barrier ribs. composition. The method of claim 1,
The photosensitive resin composition is a photosensitive resin composition for forming barrier ribs, characterized in that for forming barrier ribs of a display device using a blue light source. The method of claim 1,
With respect to the total weight of the solid content of the photosensitive resin composition,
1 to 30% by weight of the (A) colorant;
20 to 70% by weight of the (B) alkali-soluble resin;
5 to 50% by weight of the (C) polymerizable compound;
(D) 0.01 to 10% by weight of the photopolymerization initiator; and
The photosensitive resin composition for forming partition walls, comprising 60 to 90% by weight of (E) a solvent based on the total weight of the photosensitive resin composition. A display barrier rib structure made of the photosensitive resin composition for forming barrier ribs according to any one of claims 1 and 3 to 5. A display device comprising the display barrier rib structure of claim 6 .

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