TW202035470A - 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 provides a photosensitive resin composition, a display partition wall structure manufactured by the photosensitive resin composition, and a display device including the display partition wall structure, wherein the photosensitive resin composition for forming partition wall is characterized by including (A) a colorant, (B) an alkali-soluble resin, (C) a polymerizable compound, (D) a photo-polymerization initiator, and (E) a solvent; a cured film made by the aforementioned photosensitive resin composition has a maximum transmittance at a wavelength of between 450nm and 470nm of 10% or less, and a minimum transmittance at a wavelength of between 620nm and 660nm of 30% or more. The photosensitive resin composition of the present invention provides an effect of preventing the formation of a reverse tapered shape in the thick film after the partition wall is formed, facilitating the production of the partition wall having a forward tapered shape that is advantageous for forming the partition wall; moreover, it can effectively block blue lights.

Description

Photosensitive resin composition, display partition structure and display device

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

Generally speaking, in a display including a color conversion panel that uses a blue light source, in order to realize the light-shielding characteristic of the blue used as the light source and prevent the color mixing of each color conversion element, a partition is formed between each color conversion element , Due to the conversion efficiency of the color conversion element, the thickness of the color conversion element and the partition wall is formed with a film thickness of about 7㎛ ~ 15㎛.

If the conventionally used photosensitive resin composition for black matrix (Black Matrix) is used to form the partition wall of a display including a color conversion panel using a blue light source, the thickness of the film will be 1㎛ ~ 1.5㎛ more than the film thickness used in the past. The thickness of the partition wall film is 7㎛ ~ 15㎛, so there is a problem that the thickness of the partition wall is too thick and the tapered shape of the partition wall is difficult to form a cured film of a forward tapered shape, but the partition wall is made in a reverse tapered shape. If the partition wall is made in a reverse tapered shape, the contact area with the lower substrate is small, and therefore there is a problem that the partition wall pattern is lost. In addition, if the partition wall is formed by the conventional black matrix, the process needs to be coated and the pattern is formed by the exposure process. However, in the exposure process, there is an Align key located at the lower part that is difficult to identify because the color is black. ), it is difficult to form a pattern at the correct position, so there is a limitation when using conventional black matrix materials as a material for forming partition walls.

In addition, in the prior art, the technique of producing a color photosensitive resin composition using C.I. Pigment Red, C.I. Pigment Yellow, C.I. Pigment Orange, etc., to produce a color filter is a generally used technique. In this case, the thickness of the film used to manufacture the color filter is generally 2㎛~3㎛. In addition, in the color filter technology, a white light source is used as the light source, and its purpose is to present light of a specific wavelength by combining with the color filter. Therefore, there is a difference from this technology for brightness and color coordinates. In the present invention, the combination of blue Color is used as the target light source, and the partition wall material is used to achieve the purpose of blocking the light source.

Korean Laid-open Patent No. 10-2007-0094460 aims to provide a photosensitive resin composition for forming partition walls that is excellent in shape stability against heat. However, the actual situation is that the same as the above-mentioned problem, it is about 7㎛ ~ 15㎛ In the case where the film thickness forms the partition wall, the problem that the thickness of the partition wall is too thick and the tapered shape of the partition wall is not easy to form a forward-tapered cured film, but the partition wall is formed in a reverse tapered shape.

Prior art literature

Patent literature

Korean Published Patent No. 10-2007-0094460

Problems to be solved

In order to improve the above-mentioned problems of the prior art, the object of the present invention is to provide a photosensitive resin composition that prevents the formation of a reverse tapered shape in a thick film after the partition wall is formed, and facilitates the formation of a forward tapered shape that facilitates the formation of the partition wall, and is effective The purpose of blocking blue light and implementing color conversion primitives can improve the light-emitting characteristics of a display device including the color conversion primitives.

In addition, an object of the present invention is to provide a display partition wall structure manufactured using the above-mentioned photosensitive resin composition and a display device including the display partition wall structure.

The way to solve the problem

The present invention provides a photosensitive resin composition for forming partition walls, comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. The cured film made of the 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.

In addition, the present invention provides a display partition wall structure manufactured from the above-mentioned photosensitive resin composition.

In addition, the present invention provides a display device including the above-mentioned display partition structure.

Invention effect

The photosensitive resin composition of the present invention provides an effect of preventing the formation of a reverse tapered shape in the thick film after the partition wall is formed, facilitating the production of a partition wall having a forward tapered shape favorable for the formation of the partition wall, and effectively blocking blue light.

In addition, the above-mentioned photosensitive resin composition contains one or more selected from the group consisting of CI pigment red (Pigment Red), CI pigment yellow (Pigment Yellow), and CI pigment orange (Pigment Orange) as a colorant, whereby the present invention The display partition wall structure manufactured from the photosensitive resin composition of may be formed of a red color. The red-based display partition wall structure can effectively absorb blue-based light and effectively transmit red-based light. Therefore, in a display device using a blue light source, it exhibits excellent light-shielding characteristics and provides an effect of improving light-emitting characteristics.

The present invention provides a photosensitive resin composition for forming barrier ribs, a display barrier rib structure manufactured from the photosensitive resin composition, and a display device including the display barrier rib structure, and the photosensitive resin composition for forming barrier ribs is characterized by including (A) colorant, (B) alkali-soluble resin, (C) polymerizable compound, (D) photopolymerization initiator, and (E) solvent. The cured film made from the above-mentioned photosensitive resin composition has a thickness of 450 nm or more and 470 nm or less The maximum transmittance in wavelengths is less than 10%, and the minimum transmittance in wavelengths from 620 nm to 660 nm is 30% or more.

Preferably, the cured film made from the above-mentioned photosensitive resin composition may have a maximum transmittance of less than 8% at a wavelength of 450nm or more and 470nm and less than 8% when the thickness of the cured film is 7 to 15㎛, and at a wavelength of 620nm or more and 660nm or less The minimum transmittance in can be 35% or more, more preferably the maximum transmittance in wavelengths above 450nm and 470nm can be less than 5%, and the minimum transmittance in wavelengths above 620nm and 660nm can be 40% or more

In one embodiment, the above-mentioned cured film is characterized in that when the maximum transmittance in a wavelength of 450 nm or more and 470 nm or less is set to A, and the minimum transmittance in a wavelength of 620 nm to 660 nm or less is set to B, the transmittance is B The ratio to the transmittance A is 10 or more, thus, it has the advantages of favoring the blue color blocking and identifying the alignment mark in the exposure process.

When the cured film satisfies the specific transmittance conditions in the specific wavelength range, it can effectively block the blue light generated on the back surface. Therefore, in a display device using a blue light source including the cured film as a barrier rib structure , Can exhibit excellent light-shielding characteristics, and provide the effect of improving light-emitting characteristics.

The photosensitive resin composition of the present invention contains one or more of the group consisting of C.I. Pigment Red, C.I. Pigment Yellow, and C.I. Pigment Orange as the colorant, and can form a red partition wall structure, thereby effectively blocking blue light.

The quantum dot display is the quantum dots located in each pixel are converted into each color by electricity or blue light to realize the image. The partition structure used for this will block the blue light source on the back and prevent the red and blue emitted from each pixel. The mixing of color and green light is technically different from a color filter that uses a white light source emitted from the back and transmits light of a specific wavelength to achieve color.

In addition, the barrier rib structure used in the past is generally formed in black, and it is difficult to form a forward-tapered cured film when the film is thick, resulting in a reverse-tapered shape, and it is difficult to identify the alignment mark located at the lower part when the pattern is formed. The problem of forming a pattern at the correct position has a limitation in the material used as a barrier rib structure.

In the present invention, the meaning of forward taper can be understood as the case where the taper angle is less than 90°, and the meaning of reverse taper can be understood as the case where the taper angle is greater than 90°.

The display device of the present invention includes a display partition wall structure manufactured using the above-mentioned photosensitive resin composition, and thereby the light-emitting characteristics of the display device can be improved.

In addition, the photosensitive resin composition of the present invention forms a red-based partition wall structure, and when a cured film is formed as a thick film thereafter, it can prevent the formation of an inverse cone shape, and therefore has the advantage of being easy to form a forward cone shape.

In the forward-tapered partition wall structure formed in this way, the larger the taper angle, the more improved the aperture ratio. The taper angle is preferably 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 of the present invention contains (A) a colorant, (B) an alkali-soluble resin, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, and the (A) colorant may contain One or more selected from the group consisting of CI Pigment Red (Pigment Red), CI Pigment Yellow (Pigment Yellow) and CI Pigment Orange (Pigment Orange).

The photosensitive resin composition of the present invention can be characterized by being used for forming partition walls of a display device using a blue light source.

(A) Colorant

The colorant may contain one or more selected from the group consisting of C.I. Pigment Red, C.I. Pigment Yellow, and C.I. Pigment Orange, whereby the display partition wall structure manufactured from the photosensitive resin composition of the present invention can be formed in a red color. The red-based display partition wall structure can absorb blue-based light and transmit red-based light, thereby exhibiting excellent light-shielding characteristics in a display device using a blue light source, and improving light-emitting characteristics.

The aforementioned CI Pigment Red can be selected from CI 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, 270, and 272,

The aforementioned CI Pigment Yellow can be selected from CI Pigment Yellow 11, 13, 20, 24, 31, 53, 83, 86, 93, 94, 95, 99, 108, 109, 110, 117, 125, 128, 129, 138 More than one in the group consisting of, 139, 147, 148, 150, 151, 154, 155, 166, 167, 173, 180, 185 and 199,

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

Preferably, the aforementioned C.I. Pigment Red may be one or more selected from the group consisting of C.I. Pigment Red 177, 179, 254, 264 and 269,

The aforementioned C.I. Pigment Yellow may be one or more selected from the group consisting of C.I. Pigment Yellow 138, 139, 150 and 185,

The aforementioned C.I. Pigment Orange may be one or more selected from the group consisting of C.I. Pigment Orange 64 and 71.

In addition, the present invention has a feature that even if it does not contain a black colorant, it can effectively block blue light. For this reason, the above-mentioned coloring agent of the present invention preferably does not contain a black coloring agent, but if necessary, it may contain up to 20% by weight relative to the total weight of the coloring agent. If the colorant contains the black colorant excessively, the inverse taper may be generated due to insufficient deep curing during the exposure process, and there is a problem that the luminous efficiency of the display is reduced due to the decrease in reflectivity, which is not good. Specifically, the above-mentioned black coloring agent may include black organic/inorganic pigments (Pigment) and dyes (Dye) such as carbon black, titanium black, aniline black, internal amide black and perylene black, and it can be understood to also include The coloring agent can show the concept of a black combination.

The content of the colorant may be 1 to 30% by weight, preferably 3 to 20% by weight, relative to the total weight of the solid content in the photosensitive resin composition. When the content of the colorant is within the above range, the light-shielding characteristics against blue light can be improved, and the light-emitting characteristics of the display device can be improved.

In one embodiment, the colorant may include one or more selected from the group consisting of the CI pigment red (Pigment Red), the CI pigment yellow (Pigment Yellow), and the CI pigment orange (Pigment Orange). The total weight of the agent, the content of the CI Pigment Red (Pigment Red) may be 50% by weight or more. When the content of the above-mentioned C.I. Pigment Red is within the above-mentioned range, the transmittance at a wavelength of 660 nm or more is high, and the alignment mark located at the lower part can be easily recognized during the exposure process, which is preferable.

In the present invention, the total weight of solids in the photosensitive resin composition means the total weight of the remaining components after excluding the solvent of the photosensitive resin composition.

(B) Alkali solubility Resin

The alkali-soluble resin has reactivity and alkali solubility by the action of light or heat, and functions as a dispersion medium of solid components including the colorant. As long as it functions as a binder resin, it can be selected and used without particular restrictions. A resin well known in the art.

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

Examples of the above-mentioned unsaturated carboxyl group-containing monomers include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated tricarboxylic acids, and other unsaturated carboxylic acids having one or more carboxyl groups in the molecule. For example, as the above-mentioned unsaturated Monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc. can be used. The above-mentioned carboxyl group-containing monomers can be used alone or in combination of two or more.

Examples of other monomers copolymerizable with the above-mentioned carboxyl group-containing monomer include aromatic vinyl compounds; unsaturated carboxylic acid esters; unsaturated carboxylic acid aminoalkyl esters; unsaturated carboxylic acid glycidyl esters; carboxylates Acid vinyl esters; Unsaturated ethers; Vinyl cyanide compounds; Unsaturated amides; Unsaturated imines; Aliphatic conjugated dienes; and polystyrene, polymethyl acrylate, polymethyl Macromonomers having monoacrylic acid groups or monomethacrylic acid groups at the ends of polymer branches such as methyl acrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. These monomers can be used individually or in mixture of two or more types.

In an embodiment, the alkali-soluble resin may be a copolymer represented by the following Chemical Formula 1.

[Chemical formula 1]

In the above chemical formula 1, X is a group represented by the following chemical formula 2, Y is from maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethyl tetrahydrophthalic anhydride, The residue of dicarboxylic acid anhydride contained in chlorosonic acid anhydride, methyltetrahydrophthalic anhydride, and glutaric anhydride after excluding the carboxylic acid anhydride group (-CO-O-CO-), Z is a residue obtained by excluding two carboxylic anhydride groups from tetracarboxylic dianhydrides such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, and diphenyl ether tetracarboxylic dianhydride.

[Chemical formula 2]

In the above chemical formula 2, * is a bonding bond.

The content of the alkali-soluble resin may be 20 to 70% by weight, and preferably 30 to 60% by weight, relative to the total weight of the solid content in the photosensitive resin composition. When the content of the alkali-soluble resin is within the above-mentioned range, the solubility in the developer is sufficient to easily form a cured film, which prevents the film of the image element part of the exposed part from being reduced during development, and the peeling property of the non-image element part becomes better , Therefore preferred.

(C) Polymeric compound

The above-mentioned polymerizable compound is a compound that can be polymerized by light and heat. As long as it is a compound that can be polymerized by light and heat, polymerizable compounds known in the art can be selected and used without particular limitation. Specifically, a monofunctional monomer can be used. , Difunctional monomers, other multifunctional monomers, etc.

The types of the monofunctional monomer, the difunctional monomer, and the polyfunctional monomer are not particularly limited. For example, as the polyfunctional monomer, trimethylolpropane tri(meth)acrylate and ethoxy are used. Trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, two Pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa (Meth)acrylate etc.

The content of the polymerizable compound may be 5 to 50% by weight, preferably 10 to 40% by weight, relative to the total weight of the solid content in the photosensitive resin composition. When the content of the polymerizable compound is within the above range, it is preferable from the viewpoint of the strength or smoothness of the image element portion.

(D) Photopolymerization initiator

The above-mentioned photopolymerization initiators can be selected and used without particular restrictions on photopolymerization initiators known in the art. For example, acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, and biimidazole-based compounds can be used.

For example, as the above-mentioned oxime compound, o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like can be used. As a commercially available product, a representative example is Ciba's OXE- 01, OXE-02.

The aforementioned photopolymerization initiators can be used alone or in combination of two or more.

The content of the photopolymerization initiator may be 0.01 to 10% by weight, preferably 0.01 to 5% by weight, relative to the total weight of the solid content in the photosensitive resin composition. In the case where the content of the photopolymerization initiator is within the above range, the photopolymerization reaction rate is appropriate to prevent an increase in the overall process time and prevent a decrease in the physical properties of the final cured film caused by the photoreaction, which is preferable.

The photosensitive resin composition of the present invention may additionally contain a photopolymerization initiation assistant to the above-mentioned photopolymerization initiator. When the above-mentioned photopolymerization initiator and the photopolymerization initiation auxiliary agent are used at the same time, the photosensitive resin composition has higher sensitivity and improved productivity, which is preferable.

The photopolymerization initiation assistant is a compound used to promote polymerization of a polymerizable compound that is polymerized by the photopolymerization initiator, and preferably one or more compounds selected from the group consisting of amines and carboxylic acid compounds can be used.

The content of the photopolymerization initiation assistant per 1 mol of the photopolymerization initiator may be generally greater than 0 mol and 10 mol or less, and preferably may be 0.01 mol to 5 mol. When the content of the photopolymerization initiation assistant is within the above range, the photopolymerization efficiency is 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 can be used.

From the viewpoint of coating properties and drying properties, it is preferable to use organic solvents with a boiling point of 100°C to 200°C for the above solvents, and more preferably to use alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy groups. Esters such as ethyl propionate or methyl 3-ethoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropane Ethyl acid, methyl 3-ethoxypropionate, etc. The above-mentioned solvents can be used individually or in combination of two or more.

The content of the solvent may be 60 to 90% by weight, preferably 70 to 85% by weight, relative to the total weight of the photosensitive resin composition. When the content of the above solvent is within the above content range, when using a roll coater, spin coater, slit spin coater, slit coater (sometimes called die coater), inkjet When a coating device such as a printer performs coating, it provides an effect of improving coating properties, which is preferable.

Thermal curing agent

The photosensitive resin composition of the present invention may further include a thermosetting agent as necessary. When the above-mentioned thermosetting agent is further included, when the photosensitive resin composition is used to form a cured product, the deep curing or curing of the cured product can be improved. The mechanical strength of the object.

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

The content of the thermosetting agent may be 0.05 to 10% by weight, and preferably 0.1 to 10% by weight, relative to the total weight of the solid content in the photosensitive resin composition. In the case where the content of the thermal curing agent is within the above-mentioned range, there are advantages in that chemical resistance is improved, and heat resistance and development speed can be improved.

additive

The photosensitive resin composition of the present invention may further contain additives as required. The types of the additives may be determined according to the needs of users. There is no particular limitation in the present invention. Fillers, other polymer compounds, surfactants, Adhesion promoter, antioxidant, anticoagulant, etc.

The antioxidant may include, for example, one or more selected from the group consisting of phosphorous antioxidants, sulfur antioxidants, and phenolic antioxidants. In this case, it is possible to suppress the color change phenomenon that may occur at high temperatures during the manufacturing process or display production Later, yellowing may be caused by the light source. The antioxidant may include one or more selected from the group consisting of phenol-based compounds, phosphorus-based compounds, and sulfur-based compounds, and they may be phenol-based-phosphorus-based compounds, phenol-based-sulfur-based compounds, phosphorus-based-sulfur-based compounds, Or it can be used as a combination of phenol-phosphorus-sulfur compounds.

The content of the antioxidant may be 0.1 to 30% by weight, and preferably 0.5 to 20% by weight, relative to the total weight of the solid content in the photosensitive resin composition. When the content of the antioxidant is within the above range, it is preferable from the viewpoint of solving the problem of the decrease in luminous intensity, and it has the effect of preventing the aging caused by heat during post-baking in the process of forming the cured product, and the effect of maintaining the color can be expected advantage.

Among the above-mentioned additives, additives whose contents are not exemplified can be appropriately added by those skilled in the art within a range that does not impair the effects of the present invention. For example, with respect to the total weight of the photosensitive resin composition, the above-mentioned additives may be used at 0.05 to 10% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, but it is not limited thereto.

The photosensitive resin composition of the present invention can be produced by a usual method known in the art, and is not particularly limited in the present invention. As an example, it can be produced by the following method.

The colorant is mixed with a solvent in advance, and dispersed by a bead mill or the like until the average particle diameter of the colorant becomes 200 nm or less. At this time, a pigment dispersant is used as necessary, and part or all of the alkali-soluble resin may be blended. To the resulting dispersion, add the remaining alkali-soluble resin, polymerizable compound, photopolymerization initiator, and additional additives as needed, and then add additional solvents as needed to achieve a predetermined concentration to obtain the target photosensitive resin combination.

> Display next-wall structure and display device >

In addition, the present invention provides a display partition structure including a color conversion panel manufactured from the photosensitive resin composition of the present invention, and a display device including the display partition structure.

The display including the color conversion panel forms an image by driving each picture element, thus forming a thin film transistor for driving each picture element, and further forming an insulating film based on the shape of the transistor, and then forming a color to distinguish the picture element and the picture element The structure next to the conversion panel. If the photosensitive resin composition of the present invention is used to form the color conversion panel partition wall structure, it has the following advantages: preventing the color mixing of the picture elements of the display and facilitating the formation of a fine cured film, thereby enabling high-quality images to be realized.

As the display device, a liquid crystal display device, an organic light emitting diode, a flexible display, etc. can be cited, but it is not limited to this, and all applicable display devices known in the art can be exemplified.

The color conversion panel partition wall structure can be manufactured by applying the above-mentioned photosensitive resin composition of the present invention on a substrate, and performing photocuring and development to form a cured film.

First, after coating the photosensitive resin composition of the present invention on a substrate, it is heated and dried to remove volatile components such as a solvent, and a smooth cured film is obtained.

As the coating method, for example, it can be implemented by spin coating, flexible coating method, roll coating method, slit spin coating, or slit coating method. After coating, heat drying (pre-baking) or reduced-pressure drying is followed by heating to volatilize volatile components such as solvents. Among them, the heating temperature is usually 70 to 150°C, preferably 80 to 130°C. The cured film obtained in this way is irradiated with ultraviolet rays through the mask for forming the cured film of the bullseye pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper in order to irradiate the entire exposure part with uniform parallel light, and to perform precise position alignment of the mask and the substrate. If ultraviolet rays are irradiated, the parts irradiated with ultraviolet rays are cured.

As the above-mentioned ultraviolet rays, g-line (wavelength: 436 mm), h-line, i-line (wavelength: 365 mm), etc. can be used. The irradiation amount of ultraviolet rays can be appropriately selected according to needs, and is not limited in the present invention. If the cured film that has completed the photocuring is brought into contact with the developer to dissolve the non-exposed part and develop, the cured film shape of the bullseye pattern can be formed.

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

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 shown in the scope of patent application, and includes the meaning equivalent to the description in the scope of patent application and all modifications within the scope. In addition, in the following examples and comparative examples, "%" and "parts" indicating the content are quality standards unless specifically mentioned.

Synthesis example 1 ：Alkali-soluble resin (B-1) Synthesis

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

[Chemical formula 2-1]

Next, the solution was gradually heated to 120°C in a cloudy state to dissolve. At this time, the stirring was continued while confirming that the solution gradually became transparent. The heating and stirring were continued for about 12 hours until the acid value was less than 1.0 mgKOH/g. After that, it was cooled to room temperature to obtain a colorless, transparent and solid bisphenol fluorene type epoxy acrylate represented by the following Chemical Formula 1-1.

[Chemical formula 1-1]

Then, 600 g of propylene glycol monoethyl ether acetate (PGMEA) was added to 307.0 g of the bisphenol fluorene epoxy acrylate obtained as above to dissolve, and 80.5 g of benzophenone tetracarboxylic dianhydride and tetraethyl bromide were mixed. 1g of ammonium chloride, react at 110°C to 115°C 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 adhesive resin. At this time, the disappearance of the acid anhydride group was confirmed by IR spectrum, and it was confirmed that the produced 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 ：Alkali-soluble resin (B-2) Synthesis

Prepare a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction tube. As a monomer dropping funnel, add 3,4-epoxytricyclodecane-8-yl (meth)acrylate and 3,4-epoxytricyclodecane-9-yl (meth)acrylate 40 parts by weight of a mixture of 50:50 molar ratio, 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyl toluene, tert-butylperoxy-2-ethylhexanoate 4 parts by weight, 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) were stirred and prepared. Here, 6 parts by weight of n-dodecyl mercaptan and 24 parts by weight of PGMEA are added to the chain transfer agent dropping tank and stirred for preparation. Then, 395 parts by weight of PGMEA was added to the flask, and after replacing the atmosphere in the flask with nitrogen from air, the temperature of the flask was increased to 90°C while stirring. After that, the dropwise addition of the monomer and the chain transfer agent was started. During the dropwise addition, each was carried out for 2 hours while maintaining 90°C. After 1 hour, the temperature was increased to 110°C and maintained for 5 hours to obtain a resin with 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 by the GPC method using an HLC-8120GPC (manufactured by Tosoh Corporation) device.

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

Example and comparison Example of production of photosensitive resin composition

The resin compositions of Production Example 1 and Production Example 2 were produced according to Table 1 below.

[Table 1] (unit weight%) Alkali-soluble resin Photopolymerizable compound Photopolymerization initiator Thermal curing agent Dispersant Antioxidants Solvent Manufacturing example 1 B-2 11.8 7.87 1 0.59 0.85 0.97 76.92 Manufacturing example 2 B-1 11.8 7.87 1 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) Thermal curing agent: epoxy resin (ESCN 195XL, manufactured by Sumitomo Chemical Co., Ltd.) Dispersant: DISPERBYK-110 (BYK) Oxidizing agent: Sumilizer GP (manufactured by Sumitomo Chemical) (E) Solvent: propylene glycol monomethyl ether acetate (PGMEA)

According to Table 2 below, a pigment was added to the above-mentioned Production Example 1 and Production Example 2 to produce a photosensitive resin composition.

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

Test example

(1) Transmission measurement

The 5cm×5cm glass substrate (Corning) was washed with neutral detergent and water and dried. The photosensitive resin compositions of the examples and the comparative examples were spin-coated on the glass substrate so that the final film thickness became 10 mm, respectively, and pre-baked at 100° C. and dried for 2 minutes to remove the solvent. Then, a mask containing a line/gap pattern of 1 to 100㎛ and a pattern of 20㎜×20㎜ was exposed with an exposure amount of 50mJ/cm2, and the non-exposed part was removed with an aqueous alkali solution. The produced cured film was subsequently fired at 230°C for 20 minutes to produce a cured film of a partition pattern.

The UV-Vis spectrophotometer was used to measure the transmittance based on different wavelengths of the 20mm×20mm pattern cured film made with a thickness of 10㎛, and the maximum transmission in the wavelength below 450nm and 470nm (A) The minimum transmittance and the minimum transmittance in the wavelength of 620nm above 660nm below (B) and the ratio of transmittance (B) to transmittance (A) calculated according to (B)/(A) are shown in Table 3 below. The transmittance spectrum of the cured film of the partition pattern produced from the photosensitive resin composition of Example 1 and Comparative Example 1 is shown in Figure 1.

(2) Cone shape measurement

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

Accelerating voltage: 15kV

Observation magnification: × 5.0k

In order to judge the tapered shape of the partition wall pattern according to the forward and reverse tapered shapes, the cross section of the cured film was measured with an electron microscope. The cured film sample of the partition wall pattern used for the electron microscope measurement was manufactured by the same method as the method in the above (1) Transmittance measurement, and the cured film was manufactured uniformly with a film thickness of 2㎛ and 10㎛ respectively, In the manufacturing process, the cured film of the partition pattern obtained by the removal of the solvent by heating and drying after coating, exposure, development, and then heating and drying at 220°C/20min was used for analysis to prepare a cross-sectional sample. The results are shown in No. 2 Figure and Figure 3. As for the measurement method, as shown in Figure 4, the taper angle was measured after distinguishing the forward taper and the reverse taper, and described in Table 3 below.

(3) Evaluation of the minimum formed mask size of the cured film

The pattern can be formed according to the size of the part formed by the line/space pattern of 1 to 100㎛ in the 10㎛ thickness of the barrier rib pattern cured film manufactured using the photosensitive resin composition manufactured according to the above-mentioned examples and comparative examples. The minimum mask size that can be formed will vary. For example, in Figure 3, regarding Example 1, in the case of the digit 18, no pattern is formed, and in the case of the digit 19, since the pattern is formed, it is marked as 19. In Figure 3, the minimum mask size of Example 1 is 19㎛, Example 2 is 10㎛, Example 3 is 8㎛, and Comparative Example 1 is 50㎛. In the case of decimal places, a narrower partition wall can be formed, which is beneficial to the manufacture of displays containing color conversion pixels. The minimum formation mask size of the cured film produced was measured using the photosensitive resin composition of an Example and a comparative example, and is shown in Table 3 below.

[table 3] (1) Transparency (2) Cone shape (cone angle °) (3) The minimum mask size (㎛) (A) (B) (B)/(A) 2㎛ thickness 10㎛ thickness Example 1 2.99 95.98 32.1 Forward taper (32) Forward taper (38) 19 Example 2 0.01 88.62 8862.0 Forward cone (49) Forward cone (69) 10 Example 3 0.01 88.59 8859.0 Forward taper (56) Forward cone (73) 8 Example 4 0.37 97.56 263.7 Forward taper (44) Forward taper (57) 9 Example 5 0.11 90.93 826.6 Forward taper (35) Forward cone (45) twenty two Example 6 7.57 95.17 12.6 Forward cone (33) Forward taper (44) 20 Example 7 0.00 99.16 - Forward cone (41) Forward cone (63) 9 Example 8 0.01 93.71 9371.0 Forward taper (38) Forward cone (45) twenty two Example 9 0.01 96.49 9649.0 Forward taper (42) Forward cone (66) 20 Example 10 0.01 97.39 9739.0 Forward taper (35) Forward cone (43) 30 Example 11 0.01 43.66 4366.0 Forward taper (44) Forward cone (62) 8 Example 12 0.00 81.56 - Forward taper (32) Forward taper (48) 28 Example 13 0.00 87.2 - Forward cone (43) Forward cone (65) 10 Example 14 0.00 76.64 - Forward taper (47) Forward taper (68) 7 Example 15 0.00 70.65 - Forward cone (46) Forward taper (68) 8 Comparative example 1 0.42 0.51 1.2 Forward cone (89) Inverted cone (151) 50 Comparative example 2 0.03 0.11 3.7 Forward taper (87) Inverted cone (152) 12 Comparative example 3 6.05 0.06 0.0 Forward taper (52) Inverted cone (147) 20 Comparative example 4 70.34 0.44 0.0 Forward cone (55) Inverted cone (157) twenty four Comparative example 5 45.98 0.93 0.0 Forward cone (63) Inverted cone (139) 26 *The result of (B)/(A) is rounded to two decimal places.

With reference to Table 3 above, it can be confirmed that the cured film of the barrier rib pattern produced from the photosensitive resin composition of the example has a maximum transmittance of less than 10% at a wavelength of 450nm to 470nm, specifically less than 8%, 640nm The minimum transmittance in the above wavelengths below 660 nm is 30% or more, specifically about 40% or more, blue light is absorbed and effectively blocked, and red light is not absorbed. Thereby, when forming the cured film of the partition pattern of the display device using a blue light source using the photosensitive resin composition of this invention, the loss of light can be prevented and light emission characteristics can be improved.

In particular, it can be confirmed that the barrier rib pattern produced from the photosensitive resin composition of Examples 7, 12 to 15 does not transmit light at a wavelength of 450 nm to 470 nm, and has a very excellent blue color as a display barrier structure. Light blocking effect.

On the other hand, the cured film of the partition pattern manufactured using the photosensitive resin composition of Comparative Examples 1 to 3 not only has a wavelength of 450nm to 470nm but also has a maximum transmittance of less than 1% at a wavelength of 640nm to 660nm. It is blue light, and red light is also absorbed and blocked. The cured film of the partition pattern made from the photosensitive resin composition of Comparative Examples 4 to 5 has a maximum transmittance of more than 40 at a wavelength of 450nm to 470nm. %, the minimum transmittance in the wavelengths above 640nm and 660nm is less than 1.5%. Blue light is not absorbed but passes through, and red light is absorbed and blocked. Therefore, the cured film of the partition pattern is applied to the blue light source. In the case of a display device, loss of light occurs and the light-emitting characteristics are reduced.

In addition, referring to Fig. 1, it can be confirmed that the transmittance spectra of the cured film of the partition pattern produced using the photosensitive resin composition of Example 1 and Comparative Example 1. In the case of Example 1, it can be confirmed that the above transmittance is satisfied. However, in the case of Comparative Example 1, it can be confirmed that the above transmittance value is not satisfied.

With reference to Figures 2 and 3 and Table 3 above, it can be seen that in the case of a film thickness of 2㎛, the partition walls manufactured using the photosensitive resin compositions of the Examples and Comparative Examples all have a forward tapered shape (less than 90° angle). However, when the same photosensitive resin composition is used to form a thickness of 10 ㎛, the barrier ribs formed using the photosensitive resin composition of the examples can be confirmed to prevent reverse formation when a cured film is formed with the subsequent thick coating film. Tapered, in other words, formed a forward tapered shape, but the partition wall formed using the photosensitive resin composition of the comparative example formed a reverse tapered shape (angle greater than 90°) when the cured film was formed as a thick film later .

no

Fig. 1 is a graph showing the transmittance spectra of patterned cured films manufactured using the photosensitive resin compositions of Example 1 and Comparative Example 1 of the present invention. Figure 2 is an image judging the size of the mask formed by the cross section and the minimum pattern of a cured film manufactured with a thickness of 2 mm using the photosensitive resin composition of Examples 1 to 3 and Comparative Example 1 of the present invention. Figure 3 is an image judging the size of the mask formed by the cross-section and minimum pattern of the cured film manufactured with the photosensitive resin composition of Examples 1 to 3 of the present invention and Comparative Example 1 with a film thickness of 10 mm. Fig. 4 is a diagram about a method of measuring the taper angle of the photosensitive resin compositions of Examples 1 to 17 and Comparative Examples 1 to 5 of the present invention.

Claims (7)

A photosensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, The cured film produced from 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 photosensitive resin composition according to claim 1, wherein when the maximum transmittance in a wavelength of 450 nm or more and 470 nm or less is A, and the minimum transmittance in a wavelength of 620 nm or more and 660 nm or less is B, The ratio of the transmittance B to the transmittance A of the cured film is 10 or more. The photosensitive resin composition according to claim 1, wherein the (A) colorant is one or more selected from the group consisting of C.I. Pigment Red, C.I. Pigment Yellow, and C.I. Pigment Orange. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is used to form a partition wall of a display device using a blue light source. The photosensitive resin composition according to claim 1, wherein, relative to the total weight of the solid content of the photosensitive resin composition, it comprises: The (A) colorant is 1-30% by weight; The (B) alkali-soluble resin is 20 to 70% by weight; The (C) polymerizable compound is 5-50% by weight; The (D) photopolymerization initiator 0.01 to 10% by weight; and With respect to the total weight of the photosensitive resin composition, the (E) solvent contains 60 to 90% by weight. A display partition structure manufactured from the photosensitive resin composition according to any one of claims 1 to 5. A display device comprising the structure next to the display described in claim 6.

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