KR20240058111A - Substrate with resin composition, light shielding film, and partition wall - Google Patents

Abstract

The purpose of the present invention is to provide a resin composition that can form a thick film partition that achieves both the non-adhesion of the film after prebaking and the heat resistance after curing at the designed linewidth of the photomask even during high exposure dose processing. The object of the present invention is a photo radical generator, a hindered phenol compound and/or a hindered amine compound, a polysiloxane containing a specific structure, a (meth)acrylic polymer containing a specific structure and/or a specific structure. It is a resin composition containing a cardo-based polymer, and can be achieved by a resin composition in which the ratio of the weight of the polysiloxane to the total weight of the (meth)acrylic polymer and the cardo-based polymer is 30/70 to 70/30.

Description

Substrate with resin composition, light shielding film, and partition wall

The present invention relates to a resin composition, a light-shielding film formed from the resin composition, and a barrier rib-equipped substrate having patterned barrier ribs.

In recent years, as a color display device with increased light utilization efficiency, a color display device including a light source, a wavelength conversion unit including a phosphor for wavelength conversion, a polarization separation means, and a polarization conversion means has been proposed (e.g., (see patent document 1). For example, a blue light source, a liquid crystal element, a phosphor that is excited by blue light and emits red fluorescence, a phosphor that is excited by blue light and emits green fluorescence, and a wavelength converter having a light scattering layer that scatters blue light. A color display device has been proposed (for example, see Patent Document 2).

However, color filters containing color conversion phosphors as described in Patent Documents 1 and 2 generate fluorescence in all directions, so light extraction efficiency is low and luminance is insufficient. In particular, in high-precision display devices called 4K and 8K, as the pixel size becomes smaller, the problem of luminance becomes more significant, and thus higher luminance is required.

In order to improve the luminance of a display device, it is effective to isolate the color conversion phosphor with a highly reflective partition. Additionally, in order to prevent color mixing of light between adjacent pixels, it is necessary to increase the light-shielding property of the partition. Therefore, there is a demand for a barrier material that has both high reflectivity and high light blocking properties.

Japanese Patent Publication No. 2000-131683 Japanese Patent Publication No. 2009-244383 Japanese Patent Publication No. 2000-347394 Japanese Patent Publication No. 2006-259421 International Publication No. 2020/008969

In order to form a partition that has both high reflectivity and high light-blocking properties, the inventors first studied a method of using a material in which a light-shielding pigment was added to a white partition material using a titanium oxide white pigment that exhibits high reflectivity. However, in this method, the entire exposure light is absorbed by the white pigment and the light-shielding pigment, the light does not reach the bottom of the film during exposure, and the problem of poor pattern processability has become apparent.

As described in Patent Documents 3 and 4, a technique for blackening by adding a specific metal compound and baking after pattern formation has been proposed. However, this blackening technology requires baking at 400°C or higher, and has the problem that light-shielding properties do not improve when heated at 250°C or lower.

Therefore, the inventors devised a design that transmits the exposure light during the pattern exposure process after film formation and heats the exposed film at a temperature of 120°C or more and 250°C or less to increase light blocking properties. Additionally, this can be achieved by using a resin composition containing a resin, an organometallic compound containing at least one metal selected from the group consisting of silver, gold, platinum, and palladium, a photopolymerization initiator or a quinonediazide compound, and a solvent. achieved (see patent document 5). In particular, it was found that using polysiloxane as a resin can form a partition wall with high heat resistance.

However, this technology had the problem that when polysiloxane was used as the resin, the film after prebaking was sticky, making it difficult to handle the substrate during processing. On the other hand, when using (meth)acrylic polymer and/or cardo-based polymer as the resin, the adhesion after prebaking is improved, but when forming a thick film partition of 10 ㎛ or more in height, a difference in curing degree occurs at the top and bottom of the film, resulting in curing. Later, it became clear that wrinkles were caused by stress differences. Additionally, the problem that partitions formed using (meth)acrylic polymers and/or cardo-based polymers have lower heat resistance and weather resistance than those using siloxane polymers has also become apparent.

In addition, in order to form a thick film barrier rib with a height of 10 μm or more, pattern processing may be performed at a high exposure dose of about 300 to 500 mJ/cm2. In this case, with respect to the line width design of the photomask, the line width of the formed barrier rib is greatly reduced. Another problem of thickening also became clear.

Therefore, the purpose of the present invention is to provide a resin composition that can form a thick film partition that achieves both the non-adhesion of the film after prebaking and the heat resistance after curing at the designed line width of the photomask even during high exposure dose processing.

As a result of intensive research, the inventors of the present application and others have found that a photo radical generator, a hindered phenol compound and/or a hindered amine compound, a polysiloxane containing a specific structure, a (meth)acrylic polymer and/or a specific structure, and/or It is a resin composition containing a cardo-based polymer containing a specific structure, and the ratio of the weight of the polysiloxane to the total weight of the (meth)acrylic polymer and the cardo-based polymer is 30/70 to 70/30. By forming a partition wall, The present invention was completed by discovering that a thick film partition that achieves both the non-stickiness of the film after prebaking and the heat resistance after curing can be formed within the designed linewidth of the photomask even during high exposure dose processing.

That is, the present invention provides the following.

[1] (i) a photo radical generator,

(ii) a polysiloxane comprising a structure having an aromatic ring represented by the following general formula (1) or (2) and a structure having a radical photopolymerizable group represented by the following general formula (3),

(iii) a (meth)acrylic polymer comprising a structure having an aromatic ring represented by the following general formula (4) and a structure having a radical photopolymerizable group represented by the following general formula (5) and/or the following general formula ( 6) Or a cardo-based polymer having a structure expressed by the following general formula (7) and a radical photopolymerizable group.

A resin composition containing, wherein the ratio of the weight of the polysiloxane to the total weight of the (meth)acrylic polymer and the cardo-based polymer is 30/70 to 70/30.

(In General Formulas (1) to (7), R ¹ and R ² each independently represent hydrogen, a hydroxy group, an alkoxy group, a group having a siloxane bond, or a monovalent organic group having 1 to 30 carbon atoms. R ³ and R ⁴ each independently represents hydrogen, a hydroxy group, or a monovalent organic group having 1 to 30 carbon atoms, and R ⁵ to R ⁷ each independently represent hydrogen, a monovalent organic group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an adjacent aryl group. R ⁸ represents ^hydrogen , a monovalent organic group having 1 to _{30 carbon} atoms, or ^an aryl _group having 6 to 20 carbon atoms. ₄ each independently represents an organic group having an aromatic ring, p, q, and r each independently represent an organic group having _a photo radical polymerizable group, and s is an integer of 0 to 2 _. a, b, c, d, e, f and g each independently represent an integer of 1 or more, and when a to e are 2 or more, a plurality of R ¹ , R ² , R ³ . R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ and Y ₂ may be the same or different.)

[2] The resin composition according to [1], wherein the hindered phenol compound is a hindered phenol compound having two or more hindered phenol groups in one molecule.

[3] The resin composition according to [1] or [2], wherein the hindered amine compound is a piperidine compound.

[4] The resin composition according to any one of [1] to [3], wherein the hindered amine compound is a piperidine compound having a photopolymerizable group.

[5] The weight average molecular weight of the polysiloxane is 5,000 to 300,000, and the repeating unit represented by the general formula (1) or (2) is 30 to 70 mol% among all repeating units of the polysiloxane, and the general formula (3) ) The resin composition according to any one of [1] to [4], containing 15 to 70 mol% of the repeating unit represented by ).

[6] The resin composition according to any one of [1] to [5], wherein the (meth)acrylic polymer and/or cardo-based polymer has a glass transition temperature of 60°C or higher.

[7] [1] to [6] further containing at least one of a white pigment, a light-shielding pigment, and an organometallic compound containing at least one metal selected from the group consisting of silver, gold, platinum, and palladium. The resin composition according to any one of the above.

[8] The resin composition according to any one of [1] to [7], containing an oxime ester compound and a phosphine oxide compound as the photo radical generator.

[9] The resin composition according to any one of [1] to [8], further containing a liquid-repellent compound having a photopolymerizable group.

[10] A light-shielding film formed by curing the resin composition according to any one of [1] to [9].

[11] A substrate with barrier ribs having barrier ribs patterned (A-1) with the resin composition according to any one of [1] to [9] on an underlying substrate, wherein the barrier ribs have a reflectance per 10 μm of thickness at a wavelength of 550 nm. A substrate with a partition having an OD value of 1.0 to 3.0 per 10 μm of thickness at 10% to 60% and a wavelength of 450 nm.

[12] The patterned barrier rib (A-1) contains a resin, a white pigment, and a light-shielding pigment, and the light-shielding pigment has a weight ratio of titanium nitride, zirconium nitride, carbon black, red pigment, and blue pigment of 20/ A pigment selected from 80 to 80/20 mixed pigments and particles containing at least one metal oxide or metal selected from the group consisting of palladium oxide, platinum oxide, gold oxide, silver oxide, palladium, platinum, gold, and silver. , a substrate with a partition described in [11].

[13] The barrier rib-equipped substrate according to [11] or [12], wherein the patterned barrier rib (A-1) further contains a hindered amine compound.

[14] Between the base substrate and the patterned barrier rib (A-1), there is also a patterned light-shielding barrier rib (A-2) having an OD value of 0.5 or more per 1.0 μm in thickness, of [11] to [13]. The board having a partition according to any one of the above.

[15] The substrate with a barrier rib according to any one of [11] to [14], which has a pixel layer further containing the color conversion light-emitting material (B) arranged and isolated by the patterned barrier rib (A-1).

[16] A display device having the barrier rib-equipped substrate according to any one of [11] to [15], and a light emission source selected from a liquid crystal cell, an organic EL cell, a mini LED cell, and a micro LED cell.

The resin composition of the present invention can form a fine thick film barrier rib pattern with excellent non-stickiness after prebaking and heat resistance after curing at the designed linewidth of the photomask even during high exposure dose processing.

1 is a cross-sectional view showing one aspect of the barrier rib-equipped substrate of the present invention having patterned barrier ribs.
Fig. 2 is a cross-sectional view showing one aspect of the barrier rib-equipped substrate of the present invention, which has patterned barrier ribs and pixels containing a color conversion light-emitting material.
Fig. 3 is a cross-sectional view showing one aspect of the barrier rib-equipped substrate of the present invention, which has a patterned barrier rib, a color conversion light-emitting material, and a light-shielding barrier rib.
Fig. 4 is a cross-sectional view showing one aspect of the barrier rib-equipped substrate of the present invention, which has patterned barrier ribs, a color conversion light-emitting material, and a color filter.
Fig. 5 is a cross-sectional view showing one aspect of the barrier rib-equipped substrate of the present invention, which has a patterned barrier rib, a color-converting light-emitting material, a light-shielding barrier rib, and a color filter.
Fig. 6 is a cross-sectional view showing one aspect of the barrier rib-equipped substrate of the present invention, which has patterned barrier ribs, a color conversion light emitting material, and a low refractive index layer.
Fig. 7 is a cross-sectional view showing one aspect of the barrier-equipped substrate of the present invention, which has patterned barrier ribs, a color conversion light-emitting material, a low refractive index layer, and an inorganic protective layer I.
Fig. 8 is a cross-sectional view showing one aspect of the barrier rib-equipped substrate of the present invention, which has patterned barrier ribs, a color conversion light-emitting material, a low refractive index layer, and an inorganic protective layer I.
Fig. 9 is a cross-sectional view showing one aspect of the barrier-equipped substrate of the present invention, which has patterned barrier ribs, a color-converting light-emitting material, a light-shielding barrier rib, a color filter, a low refractive index layer, and an inorganic protective layer I.
Fig. 10 is a cross-sectional view showing one aspect of the barrier rib-equipped substrate of the present invention having patterned barrier ribs, a color conversion light emitting material, a low refractive index layer, and an inorganic protective layer II.
Fig. 11 is a cross-sectional view showing one aspect of the barrier rib-equipped substrate of the present invention, which has patterned barrier ribs, a color conversion light-emitting material, a color filter, and an inorganic protective layer III and/or a yellow organic protective layer.
Fig. 12 is a cross-sectional view showing one aspect of the barrier rib-equipped substrate of the present invention, which has patterned barrier ribs, a color conversion light emitting material, an inorganic protective layer IV, and/or a yellow organic protective layer.
Fig. 13 is a cross-sectional view showing one aspect of the substrate with a barrier rib of the present invention, which has a patterned barrier rib and a pixel containing a light emission source selected from an organic EL cell, a mini LED cell, and a micro LED cell.
Fig. 14 is a cross-sectional view showing one aspect of a substrate with a barrier rib of the present invention, which has a patterned barrier rib, a color conversion light emitting material, and a pixel containing a light emitting light source selected from an organic EL cell, a mini LED cell, and a micro LED cell.
Fig. 15 is a cross-sectional view showing the configuration of a display device used for color mixing evaluation in the example.

Hereinafter, preferred embodiments of the resin composition, the light-shielding film formed from the resin composition, the manufacturing method of the light-shielding film, and the substrate with partitions according to the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and its purpose or use is Depending on the situation, it can be implemented with various changes. The resin composition of the present invention can be suitably used as a material for forming a partition wall blocking a color conversion phosphor or a light emitting light source selected from an organic EL cell, mini LED cell, or micro LED cell.

The resin composition of the present invention includes a photo radical generator, a hindered phenol compound and/or a hindered amine compound, a polysiloxane containing a specific structure, a (meth)acrylic polymer containing a specific structure, and/or a specific structure. It is preferable that it contains a cardo-based polymer, and that the ratio of the weight of the polysiloxane to the total weight of the (meth)acrylic polymer and the cardo-based polymer is 30/70 to 70/30.

The resin composition of the present invention preferably has negative photosensitivity when used for pattern formation of the partition (A-1) described later. In order to provide negative photosensitivity, the resin composition of the present invention preferably contains a photo radical generator. By containing a photo radical generator, it is possible to form partition walls with a high-precision pattern shape.

The photo radical generator may be any that decomposes and/or reacts upon irradiation of light (including ultraviolet rays and electron beams) to generate radicals. For example, α-aminoalkylphenone compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; 2,4,6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl ) -Phosphine oxide compounds such as phosphine oxide; 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], 1-phenyl-1,2-butadione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, ethanone-1- and oxime ester compounds such as [9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime). You may contain two or more of these.

Among these, in order to form a thick film partition, it is preferable to contain an oxime ester compound that is resistant to oxygen interference and is effective in surface hardening, and a phosphine oxide compound that is effective in bottom hardening in order to absorb longer wavelength light and generate radicals. The content of the photo radical generator in the resin composition of the present invention is preferably 0.01% by weight or more, and more preferably 1% by weight or more, based on the solid content, from the viewpoint of effectively promoting radical hardening. On the other hand, from the viewpoint of suppressing the elution of the remaining photo-radical generator, etc., the content of the photo-radical generator is preferably 20% by weight or less, and more preferably 10% by weight or less, based on the solid content.

The resin composition of the present invention preferably contains a hindered phenol compound and/or a hindered amine compound. By containing a hindered phenol compound and/or a hindered amine compound, it is possible to appropriately trap radicals, suppress overreaction, and suppress line width increase when forming a barrier pattern with a high exposure dose, allowing the photomask to maintain its designed line width. A fine barrier pattern can be formed.

The hindered phenol compound is preferably a hindered phenol compound having two or more hindered phenol groups in one molecule. Here, the hindered phenol group refers to a functional group including a structure having at least one t-butyl group at a carbon site adjacent to the carbon site where the hydroxyl group of the phenolic hydroxyl group is bonded. The hindered phenol group preferably has a structure in which t-butyl groups are located at two carbon sites adjacent to the carbon site where the hydroxyl group of the phenolic hydroxyl group is bonded. By having two or more hindered phenol groups in one molecule, the radical trap effect is appropriately limited, suppressing line width thickening when forming a barrier pattern with a high exposure dose, and forming a fine barrier pattern within the designed line width of the photomask. there is. It is more preferable to have 3 or more hindered phenol groups per molecule, and even more preferably to have 4 or more hindered phenol groups per molecule.

Examples of hindered phenol compounds include 3,5-di-t-butyl-4-hydroxytoluene, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, Hexamethylenebis[3(3,5-di-t-butyl-4-hydroxyphenylpropionate, thiodiethylenebis[3(3,5-di-t-butyl-4-hydroxyphenylpropionate) , ethylenebis(oxyethylene)bis(3-(5-t-butyl-4-hydroxy-m-tolyl)propionate, tris-(3,5-di-t-butyl-4-hydroxybenzyl) -Isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, pentaerythritol tetrakis(3-(3 ,5-di-t-butyl-4-hydroxyphenyl)propionate, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate , 2-[1-(2-hydroxy3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenylacrylate, 2,2'-methylenebis(6-t- Butyl-4-methylphenol or 4,4'-butylidenebis(6-t-butyl-3-methylphenol), 1,3,5-tris(3,5-di-t-butyl-4-hyde Roxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4,4',4"-(1-methylpropanyl-3-ylidene)tris (6-t-butyl-m-cresol), 6,6'-di-t-butyl-4,4'-butylidenedi-m-cresol, 3,9-bis-(2-(3-(3 -t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5]undecene, 1,3, Two or more types of these may be included, such as 5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene.

Among these, hexamethylenebis[3(3,5-di-t-butyl-4-hydroxyphenylpropionate, thiodiethylenebis[3(3,5- Di-t-butyl-4-hydroxyphenylpropionate, ethylenebis(oxyethylene)bis(3-(5-t-butyl-4-hydroxy-m-tolyl)propionate, tris-(3, 5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxy Benzyl)benzene, pentaerythritoltetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2-t-butyl-6-(3-t-butyl-2- Hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[1-(2-hydroxy3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenylacrylate Rate, 2,2'-methylenebis(6-t-butyl-4-methylphenol or 4,4'-butylidenebis(6-t-butyl-3-methylphenol), 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4,4',4" -(1-methylpropanyl-3-ylidene)tris(6-t-butyl-m-cresol), 6,6'-di-t-butyl-4,4'-butylidenedi-m-cresol, 3,9-bis-(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetra Oxaspiro[5,5]undecene, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene are preferred, 1, 3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, pentaerythritol tetrakis(3-(3,5-di-t-butyl) -4-hydroxyphenyl)propionate, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[1-(2 -hydroxy3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenylacrylate, 2,2'-methylenebis(6-t-butyl-4-methylphenol or 4 ,4'-Butylidenebis(6-t-butyl-3-methylphenol), 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3, 5-triazine-2,4,6(1H,3H,5H)-trione, 4,4',4"-(1-methylpropanyl-3-ylidene)tris(6-t-butyl-m -cresol) and 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene are more preferred.

A hindered amine compound refers to a compound having at least one hindered amino group in the molecule. The hindered amino group is preferably a functional group having a secondary or tertiary amine structure bonded to two quaternary carbons. The hindered amine compound is preferably a piperidine compound. By containing the piperidine compound, the radical trap effect is appropriately limited, suppressing line width thickening when forming a barrier pattern with a high exposure dose, and forming a fine barrier pattern within the designed line width of the photomask. It is more preferable that it is a piperidine compound having a 2,2,6,6-tetramethylpiperidine structure.

As a hindered amine compound, for example, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxy Phenyl]methyl]butylmalonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, methyl-1,2,2,6,6-pentamethyl-4-p. Peridyl sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, decane bisate The reaction product of (2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester with 1,1-dimethylethylhydroperoxide and octane, tetrakis(1,2,2 ,6,6-pentamethyl-4-pyridyl)butane-1,2,3,4-tetracarboxylate or tetrakis(2,2,6,6-tetramethyl-4-pyridyl)butane-1 , 2,3,4-tetracarboxylate, etc. can be mentioned.

Among these, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl, which are piperidine compounds having a photopolymerizable group. Methacrylates are preferred. By using a piperidine compound having a photopolymerizable group, a radical reaction progresses while trapping radicals, and curing of the bottom portion of the film can be further advanced. In this case, in the partition (A-1) containing the photocured product of the negative photosensitive resin composition, the photopolymerizable group may be photopolymerized.

The content of the hindered phenol compound and/or the hindered amine compound in the resin composition of the present invention is preferably 0.050% by weight or more, and more preferably 0.070% by weight or more, based on the solid content, from the viewpoint of suppressing line thickness. On the other hand, from the viewpoint of efficiently advancing the radical reaction, the content of the hindered phenol compound and/or the hindered amine compound is preferably 5.0% by weight or less, and more preferably 3.0% by weight or less, based on the solid content. In particular, when using a hindered phenol compound, since the radical trapping effect is large, the solid content is more preferably 0.10% by weight or more and 0.50% by weight or less. Additionally, when using a piperidine compound having a photopolymerizable group as the hindered amine compound, the content is more preferably 0.10% by weight or more and 2.5% by weight or less from the viewpoint of promoting curing of the film bottom.

The resin composition of the present invention contains polysiloxane as a resin. Polysiloxane has the function of improving crack resistance, weather resistance, and heat resistance of the partition wall. The content of polysiloxane in the solid content of the resin composition is preferably 10% by weight or more, and more preferably 15% by weight or more, from the viewpoint of improving the crack resistance of the partition during heat treatment. On the other hand, from the viewpoint of improving light resistance, the content of polysiloxane in the solid content of the resin composition is preferably 55% by weight or less, and more preferably 50% by weight or less. Here, solid content means all components included in the resin composition excluding volatile components such as solvents. The amount of solid content can be determined by heating the resin composition and measuring the remaining content after evaporating the volatile components.

Polysiloxane is a hydrolyzed/dehydrated condensate of organosilane. Polysiloxane includes a structure having an aromatic ring represented by the following general formula (1) or (2) and a structure having a radical photopolymerizable group represented by the following general formula (3). It may also include other repeating units.

(In general formulas (1) to (3), R ¹ and R ² each independently represent hydrogen, a hydroxy group, an alkoxy group, a group having _a siloxane bond, or _a monovalent organic group having 1 to 30 carbon atoms. and X ₃ represents _an organic group having an aromatic ring, and a, b, and c each independently represent an integer of 1 or more. R ¹ , R ² , X ₁ , X ₂ , X ₃ and Y ₁ may be the same or different.)

The “group having a siloxane bond” represented by R ¹ or R ² refers to a “-Si-O-Si-” bond generated by condensation of silanol groups. The functional group bonded to the Si atom of the binding site is not particularly limited. As the “monovalent organic group having 1 to 30 carbon atoms” represented by R ¹ or R ² , an alkyl group (including straight-chain and branched alkyl groups) having 1 to 6 carbon atoms is preferable. Preferred specific examples thereof include methyl group, ethyl group, n-propyl group, and isopropyl group. As the “organic group having an aromatic ring” represented by X ₁ , X ₂ or X ₃ , an aromatic hydrocarbon group having 6 to 15 carbon atoms is preferable. Preferred specific examples thereof include phenyl group, benzyl group, styryl group, naphthyl group, and biphenyl group.

As the “radical photopolymerizable group” represented by Y ₁ , an ethylenically unsaturated group is preferable, and a functional group containing a methacryl group and/or an acrylic group is more preferable. Preferred specific examples thereof include 3-methacryloxypropyl group and 3-acryloxypropyl group.

Wherein a, b and c each independently represent an integer of 1 or more, a is preferably 10 to 60, more preferably 20 to 55, and b is preferably 10 to 60, more preferably 20 to 55. , c is preferably 5 to 60, more preferably 10 to 50.

By including a repeating unit derived from an alkoxysilane compound containing an organic group having an aromatic ring represented by General Formula (1) or (2), the Tg of the polysiloxane can be improved and the non-stickiness after prebaking can be improved. .

Among all repeating units in polysiloxane, it is preferable to contain 20 to 80 mol% of repeating units represented by general formula (1) or (2). By containing 20 mol% or more of the repeating unit represented by General Formula (1) or (2), the non-stickiness after prebaking can be further improved. The content of the repeating unit represented by General Formula (1) or (2) is more preferably 25 mol% or more, and even more preferably 30 mol% or more. On the other hand, by containing 80 mol% or less of the repeating unit represented by General Formula (1) or (2), thermal condensation of siloxane in the film can be carried out efficiently and the degree of curing of the film can be improved. The content of the repeating unit represented by General Formula (1) or (2) is more preferably 75 mol% or less, and even more preferably 70 mol% or less.

Among alkoxysilane compounds containing an organic group having an aromatic ring represented by General Formula (1) or (2), a bifunctional alkoxysilane compound containing two organic groups having an aromatic ring represented by General Formula (2) is derived. It is desirable to include repeating units. By including a repeating unit derived from a bifunctional alkoxysilane compound represented by General Formula (2), excessive thermal polymerization (condensation) of polysiloxane due to heating can be suppressed, and crack resistance of the partition can be improved.

By containing 10 mol% or more of the repeating unit represented by General Formula (2), crack resistance can be further improved. The content of the repeating unit represented by General Formula (2) is more preferably 15 mol% or more, and still more preferably 20 mol% or more. On the other hand, by including 80 mol% or less of the repeating unit represented by General Formula (2), the molecular weight of the polysiloxane can be sufficiently increased during polymerization, and coatability can be improved. The content of the repeating unit represented by General Formula (2) is more preferably 70 mol% or less.

In addition, the polysiloxane contains a repeating unit derived from an alkoxysilane compound containing an organic group having a photo radical polymerizable group represented by the general formula (3), so that a cross-linking reaction proceeds in the exposed area by radicals generated from the photo radical generator. Thus, the degree of curing of the exposed area can be increased.

Of all the repeating units in polysiloxane, it is preferable to contain 10 to 80 mol% of the repeating unit represented by general formula (3). By containing 10 mol% or more of the repeating unit represented by General Formula (3), radical crosslinking between polysiloxanes in the film can be carried out efficiently, and the degree of curing of the film can be improved. The content of the repeating unit represented by General Formula (3) is more preferably 12 mol% or more, and still more preferably 15 mol% or more. On the other hand, by including 80 mol% or less of the repeating unit represented by General Formula (3), excessive radical crosslinking of polysiloxane can be suppressed and the crack resistance of the partition can be improved. The content of the repeating unit represented by General Formula (3) is more preferably 75 mol% or less, and even more preferably 70 mol% or less.

Other repeating units that may be included in polysiloxane include repeating units derived from alkoxysilane compounds containing organic groups having cyclic ether groups such as epoxy groups and/or oxetanyl groups, and alkoxysilane compounds containing organic groups having alkyl groups having 1 to 30 carbon atoms. a repeating unit derived from an alkoxysilane compound, a repeating unit derived from an alkoxysilane compound containing an organic group having an acid anhydride, and a repeating unit derived from an alkoxysilane compound containing an organic group having a fluorine group. These do not have to be included, and if they are included, the content is preferably 80 mol% or less, more preferably 70 mol% or less, of the total repeating units.

The repeating units represented by the general formulas (1), (2), and (3) are derived from alkoxysilane compounds represented by the following general formulas (8), (9), and (10), respectively. That is, the polysiloxane containing repeating units represented by the general formulas (1), (2), and (3) includes an alkoxysilane compound represented by the following general formulas (8), (9), and (10). It can be obtained by hydrolyzing and polycondensing an alkoxysilane compound. Additionally, other alkoxysilane compounds may be used.

In the general formulas ⁽ 8), ₍ 9) and (10), R ¹ , R ₂ , X _{1 ,} , R ¹ , R ² , X ₁ , X ₂ , X ₃ and Y ₁ represent the same groups. R ⁹ may be the same or different and represents a monovalent organic group with 1 to 20 carbon atoms, and is preferably an alkyl group with 1 to 6 carbon atoms. In addition, in general formulas (8), (9) and (10), a notation such as “-(OR ⁹ ) ₂ ” means that two “-(OR ⁹ )” are bonded to a Si atom.

Examples of the alkoxysilane compound represented by general formula (8) include phenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilantolyltrimethoxysilane, biphenyltrimethoxysilane, Aromatic ring-containing alkoxy such as 3-trimethoxysilylpropylphthalic anhydride, 3-triethoxysilylpropylphthalic anhydride, phenylmethyldimethoxysilane, phenylethyldimethoxysilane, phenylpropyldimethoxysilane, and styryltrimethoxysilane. Silane compounds can be mentioned. You may use two or more of these.

Examples of the alkoxysilane compound represented by general formula (9) include diphenyldimethoxysilane, 1-naphthylphenyldimethoxysilane, tolylphenyldimethoxysilane, biphenylphenyldimethoxysilane, and 1-naphthyltolyldimethyl. Alkoxysilane compounds containing two aromatic rings, such as toxysilane and 1-naphthylbiphenyldimethoxysilane, can be mentioned. You may use two or more of these.

Among these, diphenyldimethoxysilane, diphenyldiethoxysilane, styryltrimethoxysilane, and styryltriethoxysilane are preferred from the viewpoint of crack resistance and non-stickiness.

Examples of the alkoxysilane compound represented by general formula (10) include vinyl trimethoxysilane, allyl trimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane, vinylmethyldimethoxysilane, styrylmethyldimethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ -Alkoxysilane compounds containing a radical photopolymerizable group such as acryloylpropylmethyldimethoxysilane can be mentioned. You may use two or more of these. Among these, from the viewpoint of photopolymerization reactivity, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-methacryloylpropyltrimethoxysilane, and γ-methacryloylpropyl Methyldimethoxysilane is preferred.

In addition, since the styryl group is a radically photopolymerizable group and is also an aromatic group, it is an alkoxysilane compound represented by general formula (10), containing a styryl group such as styryltrimethoxysilane or styryltriethoxysilane. When using an alkoxysilane compound, it is not necessary to include an alkoxysilane compound other than this represented by general formula (8) or (9). That is, if the polysiloxane contains a structure represented by the general formula (3) and a styryl group, it does not need to contain the structure represented by the general formula (1) or (2). Similarly, when an alkoxysilane compound containing a styryl group such as styryltrimethoxysilane or styryltriethoxysilane is used as the alkoxysilane compound represented by general formula (8), in addition to this, it is expressed by general formula (10) It is not necessary to include any alkoxysilane compounds. That is, if the polysiloxane contains a structure represented by the general formula (1) and has a styryl group, it does not need to contain the structure represented by the general formula (3). In this case, the content of the repeating unit containing a structure having a styryl group is preferably 12 mol% or more, and more preferably 15 mol% or more, from the viewpoint of improving non-stickiness after prebaking. On the other hand, from the viewpoint of suppressing excessive radical crosslinking of polysiloxane and improving the crack resistance of the partition, the content of the repeating unit containing a structure having a styryl group is more preferably 70 mol% or less, and 60 mol% or less. It is more desirable.

Other alkoxysilane compounds include, for example, dimethyldimethoxysilane, ethylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4- Epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylethyldimethoxysilane, 3-dimethylmethoxysilylpropylsuccinic anhydride, 3-dimethylethoxysilylpropylsuccinic anhydride, trifluoro Bifunctional alkoxy compounds such as propylmethyldimethoxysilane and trifluoropropylethyldimethoxysilane; Methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- trifunctional alkoxysilane compounds such as ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane; 3-Glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-ethyl-3 Alkoxysilane compounds containing an epoxy group or an oxetane group such as -{[3-(trimethoxysilyl)propoxy]methyl}oxetane; 3-Trimethoxysilylpropionic acid, 4-trimethoxysilylbutyric acid, 5-trimethoxysilylvaleric acid, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-trimethoxy Carboxyl group-containing alkoxysilane compounds such as silylpropylcyclohexyldicarboxylic anhydride and 3-trimethoxysilylpropylphthalic anhydride; Alkoxysilane compounds containing fluorine groups such as trifluoropropyltrimethoxysilane and perfluoropentyltrimethoxysilane; tetrafunctional alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, and silicate 51 (tetraethoxysilane oligomer); Monofunctional alkoxysilane compounds such as trimethylmethoxysilane and triphenylmethoxysilane can be mentioned. You may use two or more of these.

As other alkoxysilane compounds, it is preferable to contain at least one carboxyl group-containing alkoxysilane compound. By containing an alkoxysilane compound containing a carboxyl group, the solubility of the unexposed area is improved, and resolution can be improved during pattern processing.

From the viewpoint of applicability, the weight average molecular weight (Mw) of polysiloxane is preferably 1,000 or more, and more preferably 2,000 or more. From the viewpoint of non-stickiness, 5,000 or more is more preferable. On the other hand, from the viewpoint of developability, the Mw of polysiloxane is preferably 500,000 or less, and more preferably 300,000 or less. Here, the Mw of polysiloxane in the present invention refers to the polystyrene conversion value measured by gel permeation chromatography (GPC). The measurement method is as described in the examples described later.

Polysiloxane can be obtained by hydrolyzing the above-mentioned organosilane compound and then subjecting the hydrolyzate to a dehydration condensation reaction in the presence of a solvent or without a solvent.

Various conditions for hydrolysis can be set according to physical properties suitable for the intended use, taking into account the reaction scale, size and shape of the reaction vessel, etc. Examples of various conditions include acid concentration, reaction temperature, reaction time, etc.

For the hydrolysis reaction, an acid catalyst such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyhydric carboxylic acid or its anhydride, or ion exchange resin can be used. Among these, an acidic aqueous solution containing an acid selected from formic acid, acetic acid and phosphoric acid is preferable.

When an acid catalyst is used in the hydrolysis reaction, the amount of the acid catalyst added is preferably 0.05 parts by weight or more, based on 100 parts by weight of the total alkoxysilane compounds used in the hydrolysis reaction, from the viewpoint of making the hydrolysis progress more quickly. , 0.1 parts by weight or more is more preferable. On the other hand, from the viewpoint of appropriately controlling the progress of the hydrolysis reaction, the amount of acid catalyst added is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the total alkoxysilane compound. Here, the total amount of alkoxysilane compounds means the amount including all of the alkoxysilane compound, its hydrolyzate, and its condensate. The same applies below.

The hydrolysis reaction can be performed in a solvent. The solvent can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the resin composition.

When a solvent is produced through a hydrolysis reaction, it is also possible to perform hydrolysis without a solvent. When used in a resin composition, it is also preferable to adjust the resin composition to an appropriate concentration by further adding a solvent after completion of the hydrolysis reaction. In addition, it is also possible to distill or remove all or part of the produced alcohol, etc., by heating and/or under reduced pressure after hydrolysis, and then add a suitable solvent.

Examples of the dehydration condensation reaction include a method of heating the silanol compound solution obtained by the hydrolysis reaction of the organosilane compound as it is. The heating temperature is preferably 50°C or higher and the boiling point or lower of the solvent, and the heating time is preferably 1 to 100 hours. Additionally, in order to increase the degree of polymerization of polysiloxane, reheating or addition of a base catalyst may be performed. Additionally, depending on the purpose, after the dehydration condensation reaction, an appropriate amount of the resulting alcohol or the like may be distilled and removed under heating and/or reduced pressure, and then a suitable solvent may be added.

The resin composition of the present invention is a (meth)acrylic polymer comprising as a resin a structure having an aromatic ring represented by the general formula (4) and a structure having a radical photopolymerizable group represented by the general formula (5). , and/or a cardo-based polymer having a structure represented by the general formula (6) or the general formula (7) and a radical photopolymerizable group. (Meth)acrylic polymer and/or cardo-based polymer have the function of improving non-stickiness after prebaking. The content of (meth)acrylic polymer and/or cardo-based polymer in the solid content of the resin composition is preferably 10% by weight or more, and more preferably 15% by weight or more, from the viewpoint of improving non-stickiness after prebaking. On the other hand, from the viewpoint of improving the heat resistance of the partition, the content of (meth)acrylic polymer and/or cardo-based polymer in the solid content of the resin composition is preferably 55% by weight or less, and more preferably 50% by weight or less.

As the (meth)acrylic polymer, one obtained by radical polymerization of a (meth)acrylic compound and/or a styrene compound is preferable. There are no particular restrictions on the catalyst for radical polymerization, and azo compounds such as azobisisobutyronitrile and organic peroxides such as benzoyl peroxide are generally used.

Conditions for radical polymerization can be set appropriately; for example, a (meth)acrylic compound and/or a styrene compound and a radical polymerization catalyst are added to the solvent, and the inside of the reaction vessel is sufficiently purged with nitrogen by bubbling or reduced pressure degassing. Afterwards, it is preferable to react at 60 to 110°C for 30 to 300 minutes. Additionally, chain transfer agents such as thiol compounds may be used as needed.

When the (meth)acrylic polymer has an ethylenically unsaturated bond, for example, as the (meth)acrylic polymer, a (meth)acrylic compound and/or a styrene compound is radically polymerized, followed by glycidyl having an ethylenically unsaturated double bond group. It is preferable to obtain it by addition reaction of a compound. There is no particular limitation on the catalyst used for the addition reaction of the glycidyl compound having an ethylenically unsaturated double bond group, and known catalysts can be used, for example, dimethylaniline, 2,4,6-tris(dimethylaminomethyl) Amino-based catalysts such as phenol and dimethylbenzylamine, tin-based catalysts such as tin(II) 2-ethylhexanoate and dibutyltin laurate, titanium-based catalysts such as titanium(IV) 2-ethylhexanoate, and triphenylphos. Phosphorus-based catalysts such as pins and chromium-based catalysts such as chromium acetylacetonate and chromium chloride are used. Among these, when used simultaneously with polysiloxane, a phosphorus-based catalyst is preferable from the viewpoint of improving the storage stability of polysiloxane.

The (meth)acrylic polymer used in the resin composition of the present invention includes a structure represented by the following general formula (4) and a structure represented by the following general formula (5). Other structures may be included.

(In general formulas (4) and (5), R ³ and R ⁴ each independently represent hydrogen, a hydroxy group, or a monovalent organic group having 1 to 30 carbon atoms. X ₄ represents an organic group having an aromatic ring. Y ₂ d and e each independently represent an integer of 1 or more, and when d and e are 2 or more, each of R ³ , R ⁴ , X ₄ and Y ₂ may be the same. It can be done.)

The “monovalent organic group having 1 to 30 carbon atoms” represented by R ³ or R ⁴ is preferably an alkyl group (including straight-chain and branched alkyl groups) having 1 to 6 carbon atoms. Preferred specific examples thereof include methyl group, ethyl group, n-propyl group, and isopropyl group.

The “organic group having an aromatic ring” represented by X ₄ is preferably an aromatic hydrocarbon group having 6 to 15 carbon atoms. Preferred specific examples thereof include phenyl group, benzyl group, styryl group, naphthyl group, and biphenyl group.

As the “organic group having a radical photopolymerizable group” represented by Y ₂ , an ethylenically unsaturated group is preferable, and a functional group containing a methacryl group and/or an acrylic group is more preferable. Preferred specific examples thereof include functional groups obtained by adding glycidyl methacrylate and/or glycidyl acrylate to a carboxylic acid group.

d and e each independently represent an integer of 1 or more, but d is preferably 10 to 60, more preferably 20 to 50, and e is preferably 5 to 60, more preferably 10 to 50.

The repeating unit represented by general formula (4) is derived from a (meth)acrylic acid compound and/or a styrene compound containing an organic group having an aromatic ring. Non-stickiness can be improved by containing an organic group having an aromatic ring.

Of all the repeating units in the (meth)acrylic polymer, it is preferable to contain 10 to 80 mol% of the repeating unit represented by the general formula (4). By containing 10 mol% or more of the repeating unit represented by General Formula (4), the non-adhesiveness of the film after prebaking can be improved. The content of the repeating unit represented by General Formula (4) is more preferably 15 mol% or more, and still more preferably 20 mol% or more. On the other hand, by including 80 mol% or less of the repeating unit represented by General Formula (4), the degree of curing of the partition can be improved. The content of the repeating unit represented by General Formula (4) is more preferably 75 mol% or less, and even more preferably 70 mol% or less.

Examples of (meth)acrylic acid compounds containing an organic group having an aromatic ring include phenyl (meth)acrylate, benzyl (meth)acrylate, tolyl (meth)acrylate, naphthyl (meth)acrylate, etc. there is. Examples of styrene compounds include p-methylstyrene, o-methylstyrene, m-methylstyrene, and α-methylstyrene. Among these, styrene is preferable. By copolymerizing styrene, the heat resistance and heat-and-moisture resistance of the resulting cured film are improved.

The repeating unit represented by General Formula (5) preferably has an ethylenically unsaturated group as a photo-radical polymerizable group. By containing an ethylenically unsaturated group as a radical photopolymerizable group, a crosslinking reaction proceeds in the exposed area with radicals generated from the photoradical generator, and the degree of curing of the exposed area can be increased.

Of all the repeating units in the (meth)acrylic polymer, it is preferable to contain 10 to 80 mol% of the repeating unit represented by General Formula (5). By containing 10 mol% or more of the repeating unit represented by General Formula (5), radical crosslinking between resins in the film can be carried out efficiently, and the degree of curing of the film can be improved. The content of the repeating unit represented by General Formula (5) is more preferably 15 mol% or more, and still more preferably 20 mol% or more. On the other hand, by including 80 mol% or less of the repeating unit represented by General Formula (5), excessive radical crosslinking of the (meth)acrylic polymer can be suppressed and the crack resistance of the partition can be improved. The content of the repeating unit represented by General Formula (5) is more preferably 75 mol% or less, and even more preferably 70 mol% or less.

Examples of ethylenically unsaturated groups include vinyl group, allyl group, acrylic group, and methacryl group. As a method of adding such a side chain to an acrylic (co)polymer, a general method is to add an ethylenically unsaturated compound or (meth)acrylic acid chloride having a glycidyl group to the carboxylic acid group of the acrylic (co)polymer as described above. am. In addition, a compound having an ethylenically unsaturated group can also be added using isocyanate. Examples of the ethylenically unsaturated compounds, acrylic acid, or methacrylic acid chloride having a glycidyl group herein include glycidyl (meth)acrylate, α-ethylglycidyl (meth)acrylate, and α-n- (meth)acrylate. Propylglycidyl, (meth)acrylic acid α-n-butylglycidyl, (meth)acrylic acid 3,4-epoxybutyl, (meth)acrylic acid 3,4-epoxyheptyl, (meth)acrylic acid α-ethyl-6, 7-Epoxyheptyl, allyl glycidyl ether, vinyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o- Vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-di Glycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5- Triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, 2,4,6-triglycidyloxymethylstyrene, acrylic acid chloride, meta Crylic acid chloride, etc. can be mentioned.

As other repeating units in the (meth)acrylic polymer, those containing a carboxyl group and/or an acid anhydride group are preferable. By containing a carboxyl group and/or an acid anhydride group, the solubility contrast between exposed and unexposed areas increases, and the resolution at which pattern processing is possible improves. Examples of (meth)acrylic compounds containing a carboxyl group and/or an acid anhydride group include (meth)acrylic acid, (meth)acrylic anhydride, itaconic acid, itaconic anhydride, mono(2-acryloyloxyethyl) succinic acid, and monophthalic acid (2). -acryloyloxyethyl), tetrahydrophthalic acid mono(2-acryloyloxyethyl), etc. You may use two or more of these.

Other repeating units in the (meth)acrylic polymer do not need to be included, and if included, their content is preferably 90 mol% or less, more preferably 80 mol% or less, of all repeating units.

The weight average molecular weight (Mw) of the (meth)acrylic polymer is not particularly limited, but is preferably 2,000 or more and 200,000 or less in terms of polystyrene as measured by gel permeation chromatography (GPC). By setting Mw in the above range, good application characteristics are obtained, and the solubility of the unexposed area in the developer solution during pattern formation also becomes good.

The (meth)acrylic polymer used in the resin composition of the present invention may be synthesized and used as in the synthesis example described later, or a commercially available product may be used. Commercially available (meth)acrylic polymers include, for example, AX3-BX-TR-101, AX3-BX-TR-102, AX3-BX-TR-106, AX3-BX-TR-107, and AX3-BX-TR. -108, AX3-BX-TR-109, AX3-BX-TR-110, AX3-RD-TR-501, AX3-RD-TR-502, AX3-RD-TR-503, AX3-RD-TR-504 , AX3-RD-TR-103, AX3-RD-TR-104 (brand name, manufactured by Nippon Shokubai Co., Ltd.), SPCR-10X, SPCR-10P, SPCR-24X, SPCR-18X, SPCR-215X (brand name, Examples include Showa Denko Co., Ltd.) and X-4007 (brand name, Nichiyu Co., Ltd.). Among these, SPCR-10X, SPCR-10P, SPCR-24X, SPCR-18X, and SPCR-215X, which have an aromatic group and a photo-radical polymerizable group, are preferable. You may use two or more types of these.

The cardo-based polymer used in the resin composition of the present invention contains a structure represented by the following general formula (6) or the following general formula (7) and a radical photopolymerizable group. Other structures may be included.

(In general formulas (6) and (7), R ⁵ to R ⁷ are hydrogen, a monovalent organic group with 1 to 30 carbon atoms, an aryl group with 6 to 20 carbon atoms, or a ring formed between adjacent R ⁵ to R ⁷ is oriented. R ⁸ represents a ring group, a monovalent organic group having 1 to 30 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and s is an integer of 1 to 2. f to g each independently represent an integer of 1 or more. When f to g is 2 or more, a plurality of R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different.

Here, the “monovalent organic group having 1 to 30 carbon atoms” is preferably an alkyl group (including straight-chain and branched alkyl groups) having 1 to 6 carbon atoms. Preferred specific examples thereof include methyl group, ethyl group, n-propyl group, and isopropyl group. Additionally, as the “aryl group having 6 to 20 carbon atoms,” an aromatic hydrocarbon group having 6 to 15 carbon atoms is preferable. Preferred specific examples thereof include phenyl group, benzyl group, styryl group, naphthyl group, and biphenyl group. Additionally, from the viewpoint of ease of synthesis, R ⁵ , R ⁶ and R ⁷ are preferably hydrogen, and R ⁸ is preferably a phenyl group.

f and g each independently represent an integer of 1 or more, but f is preferably 2 to 60, more preferably 3 to 50, and e is preferably 2 to 60, more preferably 3 to 50.

As the “photo radical polymerizable group” contained in the cardo-based polymer, an ethylenically unsaturated group is preferable. By containing an ethylenically unsaturated group as a radical photopolymerizable group, a crosslinking reaction proceeds in the exposed area with radicals generated from the photoradical generator, and the degree of curing of the exposed area can be increased.

Examples of ethylenically unsaturated groups include vinyl group, allyl group, styryl group, acrylic group, and methacryl group. Functional groups including a styryl group, methacryl group, and acrylic group are preferred. Preferred examples include functional groups obtained by adding glycidyl methacrylate and/or glycidyl acrylate to a carboxylic acid group.

The cardo-based polymer used in the resin composition of the present invention preferably contains an alkali-soluble group as “other structure.” As the alkali-soluble group, one containing a carboxyl group and/or an acid anhydride group is preferable. By containing a carboxyl group and/or an acid anhydride group, the solubility contrast between exposed and unexposed areas increases, and the resolution at which pattern processing is possible improves.

The weight average molecular weight (Mw) of the cardo-based polymer is not particularly limited, but is preferably 2,000 or more and 200,000 or less in terms of polystyrene as measured by gel permeation chromatography (GPC) described later. By setting Mw in the above range, good application characteristics are obtained, and the solubility of the unexposed area in the developer solution during pattern formation also becomes good.

The cardo-based polymer used in the resin composition of the present invention may be synthesized and used, or a commercially available product may be used. Commercially available cardo-based polymers include, for example, "Ogsol" (registered trademark) CR-TR, CR-TR2, CR-TR3, CR-TR4, CR-TR5, CR-TR6 (trade name, Osaka Gas Chemical) (manufactured by Nippon Corporation), INR-16 (brand name, manufactured by Nagase Chemtex Co., Ltd.), V-259ME (brand name, manufactured by Shin-Niptetsu Sumikin Kagaku Co., Ltd.), WR-301 (brand name, manufactured by ADEKA Co., Ltd.) ), etc. Among these, V-259ME and WR-301, which contain a structure represented by the general formula (6) or (7) and a radical photopolymerizable group and an alkali-soluble group, are preferable. You may use two or more types of these.

The resin composition of the present invention preferably contains, as a resin, the total weight of the above-mentioned polysiloxane and the above-mentioned (meth)acrylic polymer and cardo-based polymer in a ratio of 30/70 to 70/30. By containing it in this ratio, it is possible to achieve both the high heat resistance derived from polysiloxane and the non-stickiness of the film after prebaking derived from (meth)acrylic polymer and/or cardo-based polymer. The ratio of the weight of polysiloxane to the total weight of the (meth)acrylic polymer and cardo-based polymer is more preferably 35/65 to 65/35, and still more preferably 40/60 to 60/40.

The (meth)acrylic polymer and/or cardo-based polymer preferably has a glass transition temperature of 60°C or higher. By having a high glass transition temperature, the non-stickiness of the film after prebaking can be improved. 65°C or higher is more preferable. The glass transition temperature can be measured as described in the Examples described later.

It is preferable that the resin composition of the present invention further contains a white pigment. The white pigment has the function of further improving the reflectance of the partition. Examples of white pigments include titanium dioxide, zirconium oxide, zinc oxide, barium sulfate, and complex compounds thereof. You may contain two or more of these. Among these, titanium dioxide is preferable because it has a high reflectivity and is easy to use industrially. The crystal structure of titanium dioxide is classified into anatase type, rutile type, and brookite type. Among these, rutile-type titanium oxide is preferable because of its low photocatalytic activity.

The white pigment may be subjected to surface treatment. Surface treatment with a metal oxide containing a metal selected from Al, Si, and Zr is preferable and can improve the light resistance and heat resistance of the formed barrier rib. From the viewpoint of further improving the reflectance of the partition, the average primary particle diameter of the white pigment is preferably 100 to 500 nm, and more preferably 150 nm to 350 nm. Here, the average primary particle diameter of the white pigment can be measured by laser diffraction using a particle size distribution measuring device (N4-PLUS; manufactured by Beckman Coulter Co., Ltd.).

Titanium dioxide pigments preferably used as white pigments include, for example, R960; CR-97, manufactured by DuPont Co., Ltd. (rutile type, SiO ₂ /Al ₂ O ₃ treated, average primary particle size 210 nm); and Ishihara Sangyo Co., Ltd. (rutile type, Al ₂ O ₃ /ZrO ₂ treatment, average primary particle diameter 250 nm). You may contain two or more of these. From the viewpoint of further improving the reflectance, the content of the white pigment in the resin composition is preferably 10% by weight or more in solid content, and more preferably 15% by weight or more. On the other hand, from the viewpoint of improving the surface smoothness of the partition, the content of the white pigment is preferably 60% by weight or less in the solid content, and more preferably 55% by weight or less.

The resin composition of the present invention also contains a light-shielding pigment and/or an organometallic compound containing at least one metal selected from the group consisting of silver, gold, platinum, and palladium (hereinafter referred to as an “organometallic compound”) It is preferable to contain ). Light-shielding pigments and organometallic compounds have the function of further improving the light-shielding properties of the partition.

The light-shielding pigment preferably contains a black pigment from the viewpoint of improving light-shielding properties.

Examples of black pigments include black organic pigments, mixed-color organic pigments, and black inorganic pigments. Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone-based pigments. These may be coated with resin.

Examples of mixed-color organic pigments include those obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, magenta, and cyan, and producing pseudo-blackening. Among these, a mixed pigment of a red pigment and a blue pigment is preferable from the viewpoint of achieving both an appropriately high OD value and pattern processability. The weight ratio of the red pigment and the blue pigment in the mixed pigment is preferably 20/80 to 80/20, and more preferably 30/70 to 70/30. Specific examples of representative pigments are expressed by color index (CI) numbers as follows. Examples of red pigments include Pigment Red (hereinafter abbreviated as PR)9, PR177, PR215, PR254, etc. You may contain two or more of these. Examples of blue pigments include Pigment Blue (hereinafter abbreviated as PB) 15, PB15:4, and PB15:6. You may contain two or more of these.

Examples of the black inorganic pigment include graphite; Fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, gold, platinum, and palladium; metal oxide; metal complex oxides; metal sulfides; metal nitride; metal oxynitride; Metal carbides, etc. can be mentioned. You may contain two or more of these.

Among the above black pigments, pigments selected from titanium nitride, zirconium nitride, carbon black, and mixed pigments with a weight ratio of red pigment and blue pigment of 20/80 to 80/20 are preferable because they have high light-shielding properties.

From the viewpoint of improving light-shielding properties, the content of the light-shielding pigment in the resin composition is preferably 0.01% by weight or more in solid content, and more preferably 0.05% by weight or more. On the other hand, from the viewpoint of stably forming a fine thick film partition pattern, the content of the light-shielding pigment is preferably 5% by weight or less, and more preferably 3% by weight or less, based on the solid content.

In addition, the resin composition of the present invention may contain other light-shielding pigments other than black pigments in order to improve light-shielding properties at specific wavelengths. Other light-shielding pigments include, for example, red pigments, blue pigments, purple pigments, green pigments, and yellow pigments. You may contain two or more of these.

The organometallic compound decomposes and aggregates in the exposure process and/or the heating process when forming the pattern of the barrier rib (A-1), which will be described later, to form black particles or yellow particles. It has the function of improving optical properties (OD value). Since the OD value is low before exposure and increases after pattern formation, the exposed light can be sufficiently transmitted to the bottom in the exposure process to cause photocuring or photodecomposition. In order to form a partition (A-1) with a high OD value, if the pattern is formed using a resin composition containing a large amount of light-shielding pigment in advance, photocuring at the bottom is likely to be insufficient. As a result, the shape of the obtained partition A-1 tends to be inversely tapered. When a pattern is formed using the resin composition of the present invention containing the above-mentioned organometallic compound, the bottom portion is sufficiently photocured, and the taper angle can be easily set to a preferable range described later.

Examples of the organometallic compound include silver-containing organometallic compounds such as silver neodecanoate, silver octylate, and silver salicylate; Organometallic compounds containing gold such as chloro(triphenylphosphine)gold; Organometallic compounds containing platinum, such as bis(acetylacetonato)platinum and dichlorobis(triphenylphosphine)platinum; and organometallic compounds containing bis(acetylacetonato)palladium and dichlorobis(triphenylphosphine)palladium. You may contain two or more of these.

Among these, if it contains an organometallic compound containing silver such as neodecanoic acid, silver octylate, or silver salicylate, it decomposes and agglomerates in the exposure process and/or heating process to produce nano silver particles and turn yellow.

On the other hand, organometallic compounds containing platinum such as bis(acetylacetonato)platinum; When an organometallic compound containing palladium, such as bis(acetylacetonato)palladium, is contained, it decomposes and aggregates in the exposure process and/or the heating process to produce palladium oxide and turn black.

Among these, from the viewpoint of further improving the OD value, bis(acetylacetonato)palladium is preferable for neodecanoic acid.

In the resin composition of the present invention, the content of the organometallic compound in the solid content is preferably 0.2 to 5% by weight. By setting the content of the organometallic compound to 0.2% by weight or more, the OD value of the obtained partition can be further improved. The content of the organometallic compound is more preferably 0.5% by weight or more. On the other hand, the reflectance can be further improved by setting the content of the organometallic compound to 5% by weight or less.

The resin composition of the present invention preferably further contains a coordination compound having a phosphorus atom (hereinafter sometimes referred to as a “coordination compound”). The coordinating compound coordinates with the organometallic compound in the resin composition, improves the solubility of the organometallic compound in the solvent, promotes decomposition of the organometallic compound, and can further improve the OD value of the obtained barrier rib. Examples of the coordination compound include triphenylphosphine, tri-t-butylphosphine, trimethylphosphine, tricyclohexylphosphine, and tris(O-tolyl)phosphine. You may contain two or more of these. The content of the coordination compound in the resin composition of the present invention is preferably 0.5 to 3.0 molar equivalents relative to the organometallic compound.

It is preferable that the resin composition of the present invention further contains a photopolymerizable compound. The photopolymerizable compound in the present invention refers to a compound having two or more ethylenically unsaturated double bonds in the molecule. By containing a photopolymerizable compound, a radical crosslinking reaction occurs with the (meth)acrylic group in the resin, and the degree of curing of the film can be improved. Considering the ease of radical polymerization, it is preferable that the photopolymerizable compound has a (meth)acrylic group.

Examples of photopolymerizable compounds include 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, Pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol Heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol Nonamethacrylate, tetrapentaerythritol decamethacrylate, etc. can be mentioned. You may contain two or more of these.

The content of the photopolymerizable compound in the resin composition of the present invention is preferably 1% by weight or more based on the solid content from the viewpoint of effectively promoting radical hardening. On the other hand, from the viewpoint of suppressing excessive reaction of radicals and improving resolution, the content of the photopolymerizable compound is preferably 50% by weight or less based on the solid content.

The resin composition of the present invention preferably contains a liquid-repellent compound having a photopolymerizable group. A liquid-repellent compound is a compound that imparts the property (liquid-repellent performance) of repelling water or organic solvents to a resin composition. There is no particular limitation as long as the compound has these properties, but specifically, a compound having a fluoroalkyl group is preferably used. By containing a liquid-repellent compound, liquid-repellent performance can be imparted to the top of the partition after forming the partition A-1 described later. Thereby, for example, when forming a pixel containing the color conversion light emitting material (B) described later, color conversion light emitting materials with different compositions can be easily separately applied to each pixel.

A liquid-repellent compound refers to a compound having a fluoroalkyl or fluoroalkyl group at the terminal, main chain, and/or side chain. The liquid-repellent compound contained in the resin composition of the present invention is more preferably a liquid-repellent compound having a photopolymerizable group because it can form a firm bond with the resin. Examples of the liquid-repelling compound having a photopolymerizable group include "Megapac" (registered trademark) RS-72-A, RS-75-A, RS-56, RS-90 (trade name, manufactured by DIC Co., Ltd.), etc. can be mentioned. In addition, in this case, the photopolymerizable group may be photopolymerized in the partition (A-1) containing the photocured product of the negative photosensitive resin composition.

From the viewpoint of improving the liquid-repellent performance of the partition and improving inkjet applicability, the content of the liquid-repellent compound in the resin composition is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, based on the solid content. On the other hand, from the viewpoint of improving compatibility with the resin or white pigment, the content of the liquid-repelling compound is preferably 10% by weight or less, and more preferably 5% by weight or less, based on the solid content.

Additionally, the resin composition of the present invention may contain a surfactant, an adhesion improving agent, etc., as needed. By containing a surfactant in the resin composition of the present invention, flow properties during application can be improved. Surfactants include, for example, "Megapac" (registered trademark) F445, F470, F475, F477 (trade name, DIC Co., Ltd.), NBX-15, FTX-218 (trade name, Neos Co., Ltd.) (a) fluorine-based surfactants such as; Silicone-based surfactants such as “BYK” (registered trademark)-333, 352, and 301 (above, brand name, manufactured by Big Chemi Japan Co., Ltd.); polyalkylene oxide-based surfactant; and poly(meth)acrylate-based surfactants. You may contain two or more of these.

By containing an adhesion improving agent in the resin composition of the present invention, adhesion to the underlying substrate is improved, and a highly reliable partition can be obtained. Examples of adhesion improving agents include alicyclic epoxy compounds and silane coupling agents. Among these, alicyclic epoxy compounds are preferable from the viewpoint of heat resistance. Examples of alicyclic epoxy compounds include 3',4'-epoxycyclohexymethyl-3,4-epoxycyclohexanecarboxylate, 1,2-bis(hydroxymethyl)-1-butanol, and 2,2-bis(hydroxymethyl)-1-butanol. -Epoxy-4-(2-oxiranyl)cyclohexane adduct, ε-caprolactone modified 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate, 1,2-epoxy- 4-vinylcyclohexane, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) formula ε-caprolactone, 3,4-epoxycyclohexylmethyl methacrylate, 1,4-cyclohexanedicarboxylic acid dicarboxylic acid Glycidyl, 1,4-cyclohexanedimethanol diglycidyl ether, etc. are mentioned. You may contain two or more of these.

From the viewpoint of further improving adhesion to the underlying substrate, the content of the adhesion improving agent in the resin composition of the present invention is preferably 0.1% by weight or more, and more preferably 1% by weight or more, based on the solid content. On the other hand, from the viewpoint of pattern processability, the content of the adhesion improving agent is preferably 20% by weight or less, and more preferably 10% by weight or less based on the solid content.

It is preferable that the resin composition of the present invention further contains a solvent. The solvent has the function of adjusting the viscosity of the resin composition to a range suitable for application and improving the uniformity of the partition. As a solvent, it is preferable to combine a solvent whose boiling point under atmospheric pressure exceeds 150°C and is 250°C or lower, and a solvent whose boiling point is 150°C or lower. Examples of solvents include alcohols such as isopropanol and diacetone alcohol; Glycols such as ethylene glycol and propylene glycol; Ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclopentanone; Amides such as dimethylformamide and dimethylacetamide; Acetates such as propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate can be mentioned. You may contain two or more of these. Among these, from the viewpoint of applicability, it is preferable to combine diacetone alcohol as a solvent with a boiling point under atmospheric pressure of more than 150°C and 250°C or less, and propylene glycol monomethyl ether as a solvent with a boiling point of 150°C or less.

The content of the solvent can be arbitrarily set depending on the application method, etc. For example, when forming a film by spin coating, the solvent content is generally set to 50% by weight or more and 95% by weight or less in the resin composition.

The resin composition of the present invention can be produced, for example, by mixing the above-described photo radical generator, polysiloxane, (meth)acrylic polymer and/or cardo-based polymer, and other components as needed.

Next, the light-shielding film of the present invention will be described. The light-shielding film of the present invention is obtained by curing the resin composition of the present invention described above. The light-shielding film of the present invention can be suitably used as a light-shielding pattern in an OGS type touch panel, such as a decorative pattern for a cover base material, in addition to the partition A-1 described later. The thickness of the light-shielding film is preferably 10 μm or more.

Next, the method for manufacturing a light-shielding film of the present invention will be explained with an example. The method for producing a light-shielding film of the present invention includes a film forming process of applying the resin composition of the present invention onto a base substrate and drying it to obtain a dried film, an exposure process of pattern exposing the obtained dried film, and a developing solution-soluble portion of the dried film after exposure. It is desirable to have a developing process for dissolving and removing the film and a heating process for curing the dried film after development by heating it.

Examples of the application method of the resin composition in the film forming process include a slit coating method and a spin coating method. Examples of drying devices include hot air ovens and hot plates. The drying time is preferably 80 to 120°C, and the drying time is preferably 1 to 15 minutes.

The exposure process is a process in which necessary parts of the dried film are photocured by exposure, or unnecessary parts of the dried film are photodecomposed, and any part of the dried film is made soluble in a developer. In the exposure process, exposure may be carried out through a photomask having a predetermined opening, or an arbitrary pattern may be drawn directly using a laser beam or the like without using a photomask.

As an exposure apparatus, a proximity exposure machine is mentioned, for example. As the actinic light irradiated in the exposure process, ultraviolet rays are preferable. Moreover, examples of the light source include high-pressure mercury lamps, ultra-high pressure mercury lamps, halogen lamps, etc., and ultra-high pressure mercury lamps are preferable. Exposure conditions can be appropriately selected depending on the thickness of the dry film to be exposed. In general, it is preferable to use an ultra-high pressure mercury lamp with an output of 1 to 100 mW/cm2 and expose at an exposure dose of 1 to 10,000 mJ/cm2.

In the development process, the portion soluble in the developer of the dried film after exposure is removed by dissolving with the developer, and only the portion insoluble in the developer remains, and the dried film is patterned in an arbitrary pattern shape (hereinafter referred to as the pattern before heating). This is the process of obtaining. Examples of the pattern shape include shapes such as grid shape, stripe shape, and hole shape. Examples of the development method include an immersion method, a spray method, and a brush method.

As a developing solution, a solvent capable of dissolving unnecessary parts in the dried film after exposure can be appropriately selected, and an aqueous solution containing water as a main component is preferable. For example, when the resin composition contains a polymer having a carboxyl group, an aqueous alkaline solution is preferable as the developing solution. Examples of the aqueous alkaline solution include inorganic aqueous alkali solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, and calcium hydroxide; and organic alkaline aqueous solutions such as tetramethylammonium hydroxide. Among these, from the viewpoint of improving resolution, potassium hydroxide aqueous solution or tetramethylammonium hydroxide aqueous solution is preferable. Additionally, from the viewpoint of improving resolution, the developer may contain a surfactant. The development temperature is preferably 20 to 50°C to facilitate process management. The heating process is a process of heating and hardening the pattern before heating formed in the developing process. Examples of heating devices include hot plates and ovens. The heating temperature is preferably 250°C or lower from the viewpoint of suppressing the occurrence of cracks in the film being heated. The heating time is preferably 15 minutes to 2 hours. When the resin composition of the present invention contains the above-mentioned organometallic compound, the heating temperature is preferably 150°C or higher from the viewpoint of further improving the OD value.

Next, the substrate with partitions of the present invention will be described. The substrate with a barrier rib of the present invention has a barrier rib (hereinafter sometimes referred to as “partition wall (A-1)”) formed in the (A-1) pattern on an underlying substrate. The base substrate has a function as a support in the substrate with partitions. When the partition has a pixel containing a color-converting light-emitting material described later, it has a function of suppressing color mixing of light between adjacent pixels.

In the barrier-equipped substrate of the present invention, the barrier rib (A-1) preferably has a reflectance of 10% to 60% per 10 μm of thickness at a wavelength of 550 nm and an OD value of 1.0 to 3.0 per 10 μm of thickness at a wavelength of 450 nm. do. By setting the reflectance to 10% or more and the OD value to 3.0 or less, (A-1) the luminance of the display device can be improved using reflection from the side of the partition. On the other hand, by setting the reflectance at a wavelength of 550 nm to 60% or less and the OD value at a wavelength of 450 nm to 1.0 or more, transmitted light through the partition A-1 can be suppressed and color mixing of light between adjacent pixels can be suppressed.

Fig. 1 shows a cross-sectional view of one aspect of the barrier rib-equipped substrate of the present invention, which has patterned barrier ribs. It has a partition wall (2) patterned on the base substrate (1).

<Substrate>

Examples of the base substrate include a glass plate, a resin plate, and a resin film. As a material for the glass plate, alkali-free glass is preferable. Preferred materials for the resin plate and resin film include polyester, (meth)acrylic polymer, transparent polyimide, and polyethersulfone. The thickness of the glass plate and the resin plate is preferably 1 mm or less, and is preferably 0.8 mm or less. The thickness of the resin film is preferably 100 μm or less.

<Bulkhead (A-1)>

The barrier rib (A-1) preferably has a reflectance of 10% to 60% per 10 μm of thickness at a wavelength of 550 nm and an OD value of 1.0 to 3.0 per 10 μm of thickness at a wavelength of 450 nm. Here, the thickness of the partition A-1 refers to the height of the partition A-1 and/or the width of the partition A-1. The height of the partition A-1 refers to the length of the partition A-1 in a direction perpendicular to the base substrate (height direction). In the case of the substrate with a partition shown in FIG. 1, the height of the partition 2 is expressed by symbol H. In addition, the width of the partition A-1 refers to the length of the partition A-1 in a direction parallel to the underlying substrate. In the case of the substrate with a barrier rib shown in FIG. 1, the width of the barrier rib 2 is expressed by symbol L. Additionally, in this specification, “height” may be referred to as “thickness.”

In the present invention, it is believed that the reflectance on the side of the partition contributes to improving the luminance of the display device, and the light blocking property contributes to suppressing color mixing. On the other hand, since the reflectance and OD value per thickness are considered to be the same regardless of the height direction or the width direction, in the present invention, attention is paid to the reflectance and OD value per thickness of the partition. As will be described later, the thickness (height) of the partition A-1 is preferably 0.5 to 100 μm, and the width is preferably 1 to 100 μm. Therefore, in the present invention, 10 μm was selected as a representative value of the thickness of the partition A-1, and attention was paid to the reflectance and OD value per 10 μm of thickness. If the reflectance per 10 μm thickness of the barrier rib A-1 at a wavelength of 550 nm is less than 10%, visible light reflection from the side of the barrier rib becomes small, and the luminance of the display device becomes insufficient. The reflectance per 10 μm of thickness at a wavelength of 550 nm is preferably 10% or more, more preferably 20% or more, and still more preferably 30% or more.

The OD value per 10 μm thickness of the barrier rib (A-1) at a wavelength of 450 nm is preferably 1.0 or more, more preferably 1.5 or more, and even more preferably 2.0 or more. The higher the OD value per 10 μm of thickness at a wavelength of 450 nm, the greater the light blocking ability of the side of the partition, thereby preventing color mixing between adjacent pixels and improving the contrast of the display device. If the OD value per 10 μm of the thickness of the barrier rib (A-1) at a wavelength of 450 nm is less than 1.0, blue excitation light leaks to adjacent pixels, thereby causing a pixel containing a color conversion light-emitting material (B) described later between the barrier ribs. In this case, light is emitted within the pixel and color mixing occurs.

The reflectance per 10 μm thickness at a wavelength of 550 nm of the barrier rib (A-1) was measured from the upper surface of the barrier rib (A-1) with a thickness of 10 μm using a spectrophotometer (e.g., CM-2600d manufactured by Konica Minolta Co., Ltd.) ) can be used to measure by SCI mode. However, in cases where a sufficient area for measurement cannot be secured or a measurement sample with a thickness of 10 ㎛ cannot be collected, and when the composition of the partition A-1 is known, it is the same as that of the partition A-1. A solid film with a thickness of 10 μm may be produced, and the reflectance per 10 μm thickness may be obtained by similarly measuring the reflectance of the solid film instead of the partition (A-1). For example, using the material from which the barrier rib (A-1) was formed, a solid film was produced under the same processing conditions as for forming the barrier rib (A-1) except that the thickness was set to 10 μm and the pattern was not formed, For the obtained solid film, the reflectance may be similarly measured from the upper surface.

The OD value per 10 μm thickness at a wavelength of 450 nm of the barrier rib (A-1) was measured using an optical densitometer (e.g., U-4100 manufactured by Hitachi High-Tech Science) from the upper surface for the barrier rib (A-1) with a thickness of 10 μm. The intensity of incident light and transmitted light can be measured and calculated using the following formula (1). However, in cases where a sufficient area for measurement cannot be secured, or when a measurement sample with a thickness of 10 μm cannot be collected, or when the composition of the partition (A-1) is known, as in the measurement of reflectance, the partition ( The OD value per 10 μm thickness may be obtained by producing a 10 μm thick solid film of the same composition as A-1) and measuring the OD value similarly for the solid film instead of the partition (A-1).

OD value = log10(I ₀ /I) … (One)

I ₀ : Incident light intensity

I: Transmitted light intensity

In addition, as a means for bringing the reflectance and OD value into the above range, for example, making the partition A-1 have a preferable composition described later, etc.

The taper angle of the partition A-1 is preferably 45° to 110°. The taper angle of the partition wall (A-1) refers to the angle formed by the side and bottom sides of the partition wall cross section. In the case of the substrate with a barrier rib shown in FIG. 1, the taper angle of the barrier rib 2 is expressed by symbol θ. By setting the taper angle to 45° or more, the difference between the widths of the upper and lower portions of the partition A-1 becomes small, and the width of the partition A-1 can be easily formed in a desirable range described later. The taper angle is more preferably 70° or more. On the other hand, by setting the taper angle to 110° or less, when forming a pixel containing the color conversion light emitting material (B) described later by inkjet application, ink agglomeration can be suppressed and inkjet coating properties can be improved. Here, ink agglomeration refers to a phenomenon in which ink passes over the partition and mixes into adjacent pixel parts. The taper angle is more preferably 95° or less. The taper angle of the partition A-1 was determined by examining an arbitrary cross section of the partition A-1 using an optical microscope (FE-SEM (for example, S-4800 manufactured by Hitachi Ltd.)). , It can be obtained by observing at an acceleration voltage of 3.0 kV and a magnification of 2,500 times, and measuring the angle formed by the side and bottom sides of the cross section of the partition A-1.

In addition, as a means for adjusting the taper angle of the partition A-1 to the above range, for example, the partition A-1 is formed with a preferable composition described later, or formed using the resin composition of the present invention described above. Things can be mentioned.

The thickness of the partition A-1 is preferably larger than the thickness of the pixel when the partition-equipped substrate has a pixel containing the color conversion light emitting material (B) described later. Specifically, the thickness of the partition A-1 is preferably 0.5 μm or more, and more preferably 10 μm or more. On the other hand, from the viewpoint of more efficiently extracting light emission from the bottom of the pixel, the thickness of the partition A-1 is preferably 100 μm or less, and more preferably 50 μm or less. In addition, the width of the partition A-1 is preferably sufficient to further improve luminance by utilizing light reflection from the side of the partition and to further suppress color mixing of light in adjacent pixels due to light leakage. Specifically, the width of the partition is preferably 1 μm or more, and more preferably 5 μm or more. On the other hand, from the viewpoint of further improving luminance by securing a large light-emitting area of the pixel, the width of the partition A-1 is preferably 100 μm or less, and more preferably 50 μm or less.

The partition A-1 has a repeating pattern of a predetermined number of pixels according to the screen size of the image display device. The number of pixels in an image display device is, for example, 4000 horizontally and 2000 vertically. The number of pixels affects the resolution (detail) of the displayed image. Therefore, it is necessary to form a number of pixels according to the required image resolution and the screen size of the image display device, and it is desirable to determine the pattern formation dimensions of the partition in accordance with this.

The partition (A-1) preferably contains resin, white pigment, and light-shielding pigment. The resin has the function of improving the crack resistance and light resistance of the partition. The white pigment has the function of further improving the reflectance of the partition. The light-shielding pigment has the function of controlling the OD value and suppressing color mixing of light in adjacent pixels.

The resin, white pigment, and light-shielding pigment are the materials constituting the resin composition and are as described above. From the viewpoint of improving light-shielding properties, the light-shielding pigment preferably contains at least one type of pigment selected from black pigment, red pigment, blue pigment, purple pigment, and yellow pigment. Among these, it is preferable to contain a black pigment and/or a yellow pigment from the viewpoint of suppressing color mixing of light in adjacent pixels.

The black pigment is the same as previously described as a material constituting the resin composition.

Yellow pigments include, for example, yellow organic pigments such as Pigment Yellow (hereinafter abbreviated as PY) PY137, PY138, PY139, PY150, PY166, PY168, and PY185, and metal fine particles such as nano silver particles and nano gold particles. ; metal oxide; metal complex oxides; metal sulfides; metal nitride; metal oxynitride; Examples include yellow inorganic pigments such as metal carbides.

Among these, light-shielding pigments include titanium nitride, zirconium nitride, carbon black, mixed pigments with a weight ratio of red pigment and blue pigment of 20/80 to 80/20, and palladium oxide, from the viewpoint of suppressing color mixing of light in adjacent pixels. It is preferable to contain at least one type of pigment selected from particles containing metal or at least one type of metal oxide selected from the group consisting of platinum, gold oxide, silver oxide, palladium, platinum, gold, and silver.

It is preferable that the partition wall (A-1) further contains a hindered amine compound. By containing a hindered amine compound, the weather resistance of the partition can be improved. The partition wall (A-1) is a material constituting the resin composition and is as described above. The hindered amine compound may be immobilized on the resin by reacting with a photopolymerizable group in the molecule.

The content of the hindered amine compound in the partition (A-1) is preferably 0.005% by weight or more, and more preferably 0.008% by weight or more from the viewpoint of further improving weather resistance. On the other hand, from the viewpoint of improving the surface hardenability of the partition, the content of the hindered amine compound in the partition (A-1) is preferably 5.0% by weight or less, and more preferably 3.0% by weight or less.

It is preferable that the partition wall (A-1) further contains a liquid-repellent compound. By containing a liquid-repellent compound, liquid-repellent performance can be imparted to the partition A-1. For example, when forming pixels containing the color conversion light-emitting material (B) described later, each pixel has a different composition. Color conversion luminescent materials can be easily differentiated and applied. The liquid-repellent compound is as described above as a material constituting the resin composition.

The surface contact angle of the partition (A-1) with respect to propylene glycol monomethyl ether acetate is preferably 10° or more, and is 20° from the viewpoint of improving inkjet applicability and facilitating separate application of the color conversion light-emitting material. More is more preferable, and 40 degrees or more is even more preferable. On the other hand, from the viewpoint of improving the adhesion between the partition and the underlying substrate, the surface contact angle of the partition A-1 is preferably 70° or less, and more preferably 60° or less. Here, the surface contact angle of the partition A-1 can be measured for the upper part of the partition based on the wettability test method for the substrate glass surface specified in JIS R3257 (date of establishment: 1999/04/20). Additionally, as a method of adjusting the surface contact angle of the partition A-1 to the above range, for example, a method of using the above-mentioned liquid-repellent compound can be mentioned.

As a method of pattern forming the partition A-1 on the base substrate, the photosensitive paste method is preferable because the pattern shape can be easily adjusted. Methods for patterning partitions by the photosensitive paste method include, for example, an application step of applying the above-described resin composition onto a base substrate and drying it to obtain a dried film, and exposing the obtained dried film to a pattern according to a desired pattern shape. A method comprising an exposure process, a development process of dissolving and removing the developer-soluble portion of the dried film after exposure, and a heating process of curing the partition walls after development is preferable. The resin composition preferably has negative photosensitivity. Pattern exposure may be done through a photomask having a predetermined opening, or an arbitrary pattern may be drawn directly using a laser beam or the like without using a photomask. Additionally, when the barrier-equipped substrate has a color filter and/or a light-shielding barrier A-2, which will be described later, the barrier rib A-1 is similarly patterned on the color filter and/or a light-shielding barrier A-2. can be formed. Each process is the same as previously described as the manufacturing method of the light-shielding film.

The barrier-equipped substrate of the present invention further includes a pixel (hereinafter sometimes referred to as “pixel (B)”) containing the color-converting light-emitting material (B) arranged and isolated by the barrier rib (A-1). It is desirable to have it. The pixel B has a function of enabling color display by converting at least a part of the wavelength range of incident light and emitting emitted light of a different wavelength range from the incident light.

Fig. 2 shows a cross-sectional view of one aspect of the barrier rib-equipped substrate of the present invention, which has patterned barrier ribs A-1 and pixels B. On the base substrate 1, it has a patterned partition wall 2, and pixels 3 are arranged in an area isolated by the partition wall 2. The color conversion material preferably contains a phosphor selected from inorganic phosphors and organic phosphors.

The substrate with a barrier rib of the present invention can be used as a display device, for example, by combining a backlight that emits blue light, a liquid crystal formed on a TFT, and a pixel (B). In this case, the area corresponding to the red pixel preferably contains a red phosphor that is excited by blue excitation light and emits red fluorescence. Similarly, the area corresponding to the green pixel preferably contains a green phosphor that is excited by blue excitation light and emits green fluorescence. It is preferable that the area corresponding to the blue pixel does not contain phosphor.

The inorganic phosphor is preferably one that emits light in each color, such as green or red, by blue excitation light, that is, that is excited by excitation light with a wavelength of 400 to 500 nm and has an emission spectrum peak in the region of 500 to 700 nm. do. Examples of such inorganic phosphors include YAG-based phosphors, TAG-based phosphors, sialon-based phosphors, Mn ⁴⁺ -containing activated fluoride complex phosphors, and inorganic semiconductors called quantum dots. Among these, quantum dots are preferable. Since quantum dots have a smaller average particle diameter compared to other phosphors, the surface of the pixel B can be smoothed and light scattering on the surface can be suppressed, so that light extraction efficiency can be further improved and luminance can be further improved.

Examples of materials for quantum dots include group II-IV, group III-V, group IV-VI, and group IV semiconductors. Such inorganic semiconductors include, for example, Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, Examples include GaSb, InN, InP, InAs, InSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, and CdSe. You may use two or more of these.

As an organic phosphor, it is preferable to emit light of each color, such as green or red, by blue excitation light. As a phosphor emitting red fluorescence, a pyromethene derivative having a basic skeleton represented by the following structural formula (11), and a pyromethene derivative having a basic skeleton represented by the following structural formula (12) as a phosphor emitting green fluorescence, etc. You can. Other examples include perylene-based derivatives, porphyrin-based derivatives, oxazine-based derivatives, and pyrazine-based derivatives that emit red or green fluorescence depending on the selection of the substituent. You may contain two or more of these. Among these, pyromethene derivatives are preferable because of their high quantum yield. Pyromethene derivatives can be obtained, for example, by the method described in Japanese Patent Application Laid-Open No. 2011-241160.

Since the organic phosphor is soluble in solvents, a pixel (B) of a desired thickness can be easily formed. From the viewpoint of improving color characteristics, the thickness of the pixel B is preferably 0.5 μm or more, and more preferably 1 μm or more. On the other hand, the thickness of the pixel B is preferably 30 μm or less, and more preferably 20 μm or less, from the viewpoint of thinning of the display device and curved surface processability.

The size of each pixel B is generally about 20 to 200 μm.

It is preferable that the pixels B are arranged and separated by the partition A-1. By providing a partition between pixels, diffusion and color mixing of emitted light can be further suppressed.

As a method of forming the pixel B, for example, a method of filling a space isolated by the partition A-1 with a coating liquid containing a color conversion light emitting material (hereinafter referred to as a color conversion light emitting material coating liquid) can be cited. there is. The color conversion luminescent material coating solution may further contain a resin or a solvent.

Methods for filling the color-converting light-emitting material coating solution include photolithography and inkjet, but the inkjet coating method is preferable from the viewpoint of easily separately applying different types of color-converting light-emitting material to each pixel.

<Light-shading bulkhead (A-2)>

The barrier rib-equipped substrate of the present invention is provided between the base substrate and the patterned barrier rib (A-1), and (A-2) a patterned barrier wall (hereinafter referred to as a "light-shielding barrier") having an OD value of 0.5 or more per 1.0 μm in thickness. It is preferable to have (sometimes described as “(A-2)”). By having the light-shielding partition A-2, light-shielding properties are improved, light leakage of the backlight in the display device is suppressed, and a clear image with high contrast can be obtained.

Fig. 3 shows a cross-sectional view showing one aspect of the substrate with a barrier rib of the present invention having a light-shielding barrier rib. It has a partition 2 and a light-shielding partition 4 patterned on a base substrate 1, and pixels 3 are arranged in areas isolated by the partition 2 and the light-shielding partition 4.

The light-shielding partition (A-2) has an OD value of 0.5 or more per 1.0 μm of thickness. Here, the thickness of the light-shielding partition A-2 is preferably 0.5 to 10 μm, as will be described later. In the present invention, 1.0 μm was selected as a representative value of the thickness of the light-shielding partition A-2, and attention was paid to the OD value per 1.0 μm of thickness. By setting the OD value per 1.0 μm of thickness to 0.5 or more, light blocking properties can be further improved and a clearer image with higher contrast can be obtained. On the other hand, the OD value per 1.0㎛ thickness is preferably 4.0 or less, and pattern processability can be improved. The OD value of the light-shielding partition A-2 can be measured similarly to the OD value of the partition A-1 described above.

From the viewpoint of improving light-shielding properties, the thickness of the light-shielding partition A-2 is preferably 0.5 μm or more, and more preferably 1.0 μm or more. On the other hand, from the viewpoint of improving flatness, the thickness of the light-shielding partition A-2 is more preferably 5 μm or less. In addition, the width of the light-shielding partition A-2 is preferably approximately the same as that of the partition A-1 described above.

The light-shielding partition (A-2) preferably contains resin and a light-shielding pigment. The resin has the function of improving the crack resistance and light resistance of the partition. The light-shielding pigment has the function of absorbing incident light and reducing emitted light. The resin and light-shielding pigment can be materials similar to those described above as materials constituting the resin composition.

As a method of pattern forming the light-shielding barrier rib (A-2) on the base substrate, for example, using the photosensitive material described in Japanese Patent Application Laid-Open No. 2015-1654, the photosensitive barrier rib (A-2) can be formed similarly to the barrier rib (A-1) described above. A method of forming a pattern by the paste method is preferable.

In addition, the substrate with a partition of the present invention preferably has a color filter (hereinafter sometimes referred to as a “color filter”) with a thickness of 1 to 5 μm between the base substrate and the pixel B. . A color filter can improve the color purity of a display device by transmitting visible light in a specific wavelength range and changing the transmitted light to a desired color. By setting the thickness of the color filter to 1 μm or more, color purity can be further improved. On the other hand, brightness can be further improved by setting the thickness to 5 μm or less.

Fig. 4 shows a cross-sectional view of one aspect of the substrate with a partition of the present invention having a color filter. It has a partition 2 and a color filter 5 patterned on a base substrate 1, and has a pixel 3 on the color filter 5.

Examples of color filters include color filters using pigment-dispersed materials in which pigments are dispersed in photoresists, which are used in flat panel displays such as liquid crystal displays. In addition, the color filters may be stacked separately from the pixel B containing the color conversion light-emitting material, or may be stacked integrally.

The substrate with a barrier rib of the present invention preferably has a color filter with a thickness of 1 to 5 μm between the base substrate and the pixel B and separated by a light-shielding barrier wall. Fig. 5 shows a cross-sectional view of one aspect of a substrate with a barrier rib of the present invention having a color filter isolated by a light-shielding barrier rib. It has a color filter (5) isolated by a light-shielding partition (4) formed in a pattern on an underlying substrate (1), and has a partition (2) and a pixel (3) thereon.

The substrate with a partition of the present invention has a low refractive index layer (hereinafter referred to as “low refractive index layer (C)”) on the top or bottom of the pixel (B) and (C) having a refractive index of 1.20 to 1.35 at a wavelength of 550 nm. It is desirable to have ). By having the low refractive index layer (C), light extraction efficiency can be further improved and the luminance of the display device can be further improved.

Fig. 6 shows a cross-sectional view of one aspect of the barrier rib-equipped substrate of the present invention having a low refractive index layer. It has partitions 2 and pixels 3 patterned on a base substrate 1, and also has a low refractive index layer 6 on these.

In a display device, from the viewpoint of appropriately suppressing light reflection of the backlight and efficiently entering light into the pixel B, the refractive index of the low refractive index layer C is preferably 1.20 or more, and more preferably 1.23 or more. . On the other hand, from the viewpoint of improving luminance, the refractive index of the low refractive index layer (C) is preferably 1.35 or less, and more preferably 1.30 or less. Here, the refractive index of the low refractive index layer (C) can be measured by irradiating light with a wavelength of 550 nm from the direction perpendicular to the cured film surface under atmospheric pressure and 20°C using a prism coupler.

The low refractive index layer (C) can be formed as in Examples 72 to 74, for example, using the low refractive index layer forming material obtained in Preparation Example 6 described later. The thickness of the low refractive index layer (C) is preferably 0.1 μm or more, and more preferably 0.5 μm or more, from the viewpoint of covering the level difference of the pixel (B) and suppressing the occurrence of defects. On the other hand, the thickness of the low refractive index layer (C) is preferably 20 μm or less, and more preferably 10 μm or less, from the viewpoint of reducing stress that causes cracks in the low refractive index layer (C).

In addition, the substrate with a partition of the present invention preferably has an inorganic protective layer I with a thickness of 50 to 1,000 nm on the low refractive index layer (C). By having the inorganic protective layer I, it becomes difficult for moisture in the air to reach the low refractive index layer (C), thus suppressing refractive index fluctuations in the low refractive index layer (C) and suppressing luminance deterioration.

7 and 8 show cross-sectional views of one aspect of the barrier rib-equipped substrate of the present invention having a low refractive index layer and an inorganic protective layer (I). It has partitions 2 and pixels 3 patterned on a base substrate 1, and has a low refractive index layer 6 and an inorganic protective layer (I) 7 on or below them.

The substrate with a partition of the present invention preferably has the low refractive index layer (C) between the pixel (B) and the color filter, and further has a layer of 50 to 1,000 nm in thickness on the low refractive index layer (C). It is desirable to have an inorganic protective layer (I). By having the low refractive index layer (C) between the pixel (B) and the color filter, the effect of improving light extraction of emitted light is increased, and the luminance of the display is improved.

Fig. 9 shows a cross-sectional view of one aspect of the substrate with a barrier rib of the present invention, which has the low refractive index layer and the inorganic protective layer (I) between the pixel (B) and the color filter. It has a color filter (5) isolated by a light-shielding partition (4) on the base substrate (1), a low refractive index layer (6) and an inorganic protective layer (I) (7) thereon, and a partition pattern formed thereon. (2) and pixel (3).

In addition, the substrate with a partition of the present invention preferably has an inorganic protective layer (II) with a thickness of 50 to 1,000 nm between the pixel (B) and the low refractive index layer (C). By having the inorganic protective layer (II), it becomes difficult for the raw materials forming the pixel (B) to move from the pixel (B) to the low refractive index layer, thereby suppressing refractive index fluctuations in the low refractive index layer (C) and reducing luminance deterioration. can be suppressed.

Fig. 10 shows a cross-sectional view of one aspect of the barrier rib-equipped substrate of the present invention having a low refractive index layer and an inorganic protective layer (II). It has partitions 2 and pixels 3 patterned on a base substrate 1, and also has an inorganic protective layer (II) 8 and a low refractive index layer 6 on these.

In addition, the substrate with a partition of the present invention preferably has an inorganic protective layer (III) and/or a yellow organic protective layer with a thickness of 50 to 1,000 nm between the color filter and the pixel (B). By having the inorganic protective layer (III), it becomes difficult for the forming material of the color filter to reach the pixel (B) containing the color-converting light-emitting material from the color filter, so that the pixel (B) containing the color-converting light-emitting material Deterioration in luminance can be suppressed. Additionally, by having a yellow organic protective layer, blue leakage light that is not completely converted by the pixel B containing the color conversion light-emitting material can be cut, thereby improving color reproducibility.

Fig. 11 shows a cross-sectional view of one aspect of the barrier rib-equipped substrate of the present invention, which has a color filter and an inorganic protective layer (III) and/or a yellow organic protective layer. It has a barrier rib 2 and a color filter 5 patterned on a base substrate 1, and has an inorganic protective layer (III) and/or a yellow organic protective layer 9 thereon, and a barrier rib 2 thereon. It has pixels 3 arranged in isolation.

In addition, the substrate with a partition of the present invention preferably has an inorganic protective layer (IV) and/or a yellow organic protective layer with a thickness of 50 to 1,000 nm on the base substrate. The inorganic protective layer (IV) and/or the yellow organic protective layer acts as a refractive index adjustment layer, so that light emitted from the pixel (B) can be extracted more efficiently, and the luminance of the display device can be further improved. Additionally, the yellow organic protective layer can improve color reproducibility by cutting blue leakage light that has not been completely converted by the pixel (B) containing the color conversion light-emitting material.

Fig. 12 shows a cross-sectional view of one aspect of the substrate with a partition of the present invention having an inorganic protective layer (IV) and/or a yellow organic protective layer. It has an inorganic protective layer (IV) and/or a yellow organic protective layer 10 on the base substrate 1, and has partitions 2 and pixels 3 patterned thereon.

Materials constituting the inorganic protective layers (I) to (IV) include, for example, metal oxides such as silicon oxide, indium tin oxide, and gallium zinc oxide; metal nitrides such as silicon nitride; etc. can be mentioned. Among these, silicon nitride or silicon oxide is more preferable because it has low water vapor permeability and high permeability. The thickness of the inorganic protective layers (I) to (IV) is preferably 50 nm or more, and more preferably 100 nm or more from the viewpoint of sufficiently suppressing the penetration of substances such as water vapor. On the other hand, from the viewpoint of suppressing a decrease in transmittance, the thickness of the inorganic protective layers (I) to (IV) is preferably 800 nm or less, and more preferably 500 nm or less.

The yellow organic protective layer is obtained, for example, by pattern processing a resin composition containing a yellow pigment and a resin. The yellow pigment and resin can be materials similar to those described above as materials constituting the above-mentioned partition wall (A-1). As a method of forming a pattern of the yellow organic protective layer, a method of forming a pattern using a photosensitive paste method is preferable, similar to the above-mentioned partition (A-1).

As shown in Fig. 7, when forming the yellow organic protective layer 8 on the color filter 7, the yellow organic protective layer 8 may have a role as an overcoat layer that flattens each pixel of the color filter.

The barrier-equipped substrate of the present invention can also be used in a display device using mini or micro LEDs in which a plurality of LEDs corresponding to each pixel are arranged, separated by a barrier formed on the substrate. Each pixel can be turned on/off by turning the mini or micro LED on/off, and liquid crystal is not required. That is, the substrate with partitions of the present invention can be used not only for partitions separating each pixel, but also for partitions separating mini or micro LEDs in a backlight.

For example, the substrate with a partition of the present invention preferably has a light emission source selected from organic EL cells, mini LED cells, and micro LED cells on the base substrate. By blocking the light emitting light source selected from the organic EL cell, mini LED cell, and micro LED cell with a partition, color mixing between each pixel can be prevented and the display color purity of the display can be improved.

Fig. 13 shows a cross-sectional view of one aspect of a substrate with a partition of the present invention having a light emission source selected from an organic EL cell, a mini LED cell, and a micro LED cell. Between the partition walls 2 patterned on the base substrate 1, there is a light emitting light source 11 selected from organic EL cells, mini LED cells, and micro LED cells. In addition, the substrate with a partition of the present invention preferably has a pixel (B) on an emission light source selected from an organic EL cell, a mini LED cell, and a micro LED cell.

Fig. 14 shows a cross-sectional view of one aspect of the substrate with a barrier rib of the present invention having a light emission source and pixels selected from organic EL cells, mini LED cells, and micro LED cells. Between the partition walls 2 patterned on the base substrate 1, a light emitting light source 11 selected from an organic EL cell, mini LED cell, and micro LED cell is provided, and a pixel 3 is placed thereon.

Next, the display device of the present invention will be described. The display device of the present invention has the above-described partition-equipped substrate and a light-emitting source. As the luminescent light source, a luminescent light source selected from liquid crystal cells, organic EL cells, mini LED cells, and micro LED cells is preferable. Since it has excellent luminescence properties, an organic EL cell is more preferable as a luminescent light source. A mini LED cell refers to a cell in which a large number of LEDs with a vertical and horizontal length of approximately 100 μm to 10 mm are arranged. A micro LED cell refers to a cell in which a large number of LEDs with a vertical and horizontal length of less than 100 μm are arranged.

The method of manufacturing a display device of the present invention will be explained by taking an example of a display device having a substrate with a partition of the present invention and an organic EL cell. A photosensitive polyimide resin is applied onto a glass substrate, and an insulating film having an opening is formed using photolithography. After sputtering aluminum thereon, the aluminum is patterned by photolithography to form a back electrode layer containing aluminum in the opening without an insulating film. Subsequently, tris(8-quinolinolato)aluminum (hereinafter abbreviated as Alq3) was formed as an electron transport layer thereon by vacuum deposition, and then dicyanomethylene pyran, quinacridone, and 4, were added to Alq3 as an emitting layer. A white light-emitting layer doped with 4'-bis(2,2-diphenylvinyl)biphenyl is formed. Next, N,N'-diphenyl-N,N'-bis(α-naphthyl)-1,1'-biphenyl-4,4'-diamine is formed into a film as a hole transport layer by vacuum deposition. Finally, ITO is deposited as a transparent electrode by sputtering to produce an organic EL cell with a white light-emitting layer. A display device can be produced by opposing the above-mentioned barrier rib-equipped substrate and the organic EL cell obtained in this way and bonding them with a sealant.

Example

The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to these scopes. In addition, among the compounds used, the names of those for which abbreviations are used are shown below.

PGMEA: propylene glycol monomethyl ether acetate

DAA: diacetone alcohol

EDM: diethylene glycol ethyl methyl ether

BHT: Dibutylhydroxytoluene

The solid concentration of the polysiloxane solution in Synthesis Examples 1 to 6 and the (meth)acrylic polymer solution in Synthesis Examples 7 to 9 were determined by the following method. 1.5 g of polysiloxane solution or (meth)acrylic polymer solution was weighed in an aluminum cup and heated at 250°C for 30 minutes using a hot plate to evaporate the liquid. The weight of the solid content remaining in the aluminum cup after heating was measured, and the solid content concentration was determined from the ratio to the weight before heating.

The weight average molecular weight of the polysiloxane solution in Synthesis Examples 1 to 6 and the (meth)acrylic polymer solution in Synthesis Examples 7 to 9 were calculated in terms of polystyrene by the following method.

Device: GPC measuring device with RI detector manufactured by Waters (2695)

Column: PLgel MIXED-C column (manufactured by Polymer Laboratories, 300 mm) x 2 (connected in series)

Measurement temperature: 40℃

Flow rate: 1mL/min

Solvent: tetrahydrofuran (THF) 0.5% by mass solution

Standard material: polystyrene

Detection mode: RI

The content ratio of each repeating unit in polysiloxane in Synthesis Examples 1 to 6 was determined by the following method. The polysiloxane solution was injected into an NMR sample tube made of "Teflon" (registered trademark) with a diameter of 10 mm, and ²⁹ Si-NMR measurement was performed, and the Si derived from a specific organosilane relative to the integrated value of the entire Si derived from the organosilane was measured. The content ratio of each repeating unit was calculated from the ratio of the integral values of . ²⁹ Si-NMR measurement conditions are shown below.

Device: Nuclear magnetic resonance device (JNM-GX270; manufactured by Nippon Electronics Co., Ltd.)

Measurement method: gated decoupling method

Measured nuclear frequency: 53.6693MHz ( ²⁹ Si nuclei)

Spectral Width: 20000Hz

Pulse width: 12㎲ (45°pulse)

Pulse repetition time: 30.0 seconds

Solvent: Acetone-d6

Reference substance: tetramethylsilane

Measurement temperature: 23℃

Sample rotation speed: 0.0Hz

Synthesis Example 1 Polysiloxane (PSL-1) solution

In a 1000 ml three-necked flask, 117.76 g (0.525 mol) of styryltrimethoxysilane, 71.16 g (0.306 mol) of 3-methacryloxypropylmethyldimethoxysilane, and 3-(3,4-epoxycyclohexyl) 21.56 g (0.088 mol) of propyltrimethoxysilane, 78.89 g (0.656 mol) of dimethyldimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.180 g of BHT, and 251.60 g of PGMEA. g was added, and an aqueous phosphoric acid solution containing 3.353 g of phosphoric acid (1.0% by weight based on the input monomer) dissolved in 80.33 g of water was added over 30 minutes while stirring at 40°C. After that, the flask was immersed in an oil bath at 70°C and stirred for 60 minutes, and then the temperature of the oil bath was raised to 115°C over 30 minutes. 1 hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the solution was heated and stirred for 2 hours (internal temperature was 100 to 110°C) to obtain a polysiloxane solution. Additionally, during the temperature increase and heating and stirring, a mixed gas of 95 volume% nitrogen and 5 volume% oxygen was flowed at 0.05 liter/min. During the reaction, a total of 182.96 g of by-products, methanol and water, flowed out. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight, and a polysiloxane (PSL-1) solution was obtained. Additionally, the weight average molecular weight of the obtained polysiloxane (PSL-1) was 12,000. Additionally, in polysiloxane (PSL-1), styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane , the molar ratios of each repeating unit derived from 3-trimethoxysilylpropylsuccinic anhydride were 30 mol%, 17.5 mol%, 5 mol%, 37.5 mol%, and 10 mol%, respectively.

Synthesis Example 2 Polysiloxane (PSL-2) solution

In a 1000 ml three-necked flask, 198.29 g (0.831 mol) of phenyltrimethoxysilane, 71.16 g (0.306 mol) of 3-methacryloxypropylmethyldimethoxysilane, and 3-(3,4-epoxycyclohexyl)propyl 21.56 g (0.088 mol) of trimethoxysilane, 42.08 g (0.350 mol) of dimethyldimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.197 g of BHT, and 256.24 g of PGMEA. An aqueous phosphoric acid solution containing 3.455 g of phosphoric acid (1.0% by weight based on the input monomer) dissolved in 85.84 g of water was added over 30 minutes while stirring at 40°C. After that, the flask was immersed in an oil bath at 70°C and stirred for 60 minutes, and then the temperature of the oil bath was raised to 115°C over 30 minutes. 1 hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the solution was heated and stirred for 2 hours (internal temperature was 100 to 110°C) to obtain a polysiloxane solution. Additionally, during the temperature increase and heating and stirring, a mixed gas of 95 volume% nitrogen and 5 volume% oxygen was flowed at 0.05 liter/min. During the reaction, a total of 195.52 g of by-products, methanol and water, flowed out. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight, and a polysiloxane (PSL-2) solution was obtained. Additionally, the weight average molecular weight of the obtained polysiloxane (PSL-2) was 5,500. In addition, in polysiloxane (PSL-2), phenyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, The molar ratios of each repeating unit derived from 3-trimethoxysilylpropylsuccinic anhydride were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

Synthesis Example 3 Polysiloxane (PSL-3) solution

In a 1000 ml three-necked flask, 203.13 g (0.831 mol) of diphenyldimethoxysilane, 76.06 g (0.306 mol) of 3-methacryloxypropyltrimethoxysilane, and 3-(3,4-epoxycyclohexyl)propyl 21.56 g (0.088 mol) of trimethoxysilane, 42.08 g (0.350 mol) of dimethyldimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.475 g of BHT, and 308.45 g of PGMEA. An aqueous phosphoric acid solution containing 3.887 g of phosphoric acid (1.0% by weight based on the input monomer) dissolved in 76.39 g of water was added over 30 minutes while stirring at 40°C. After that, the flask was immersed in an oil bath at 70°C and stirred for 60 minutes, and then the temperature of the oil bath was raised to 115°C over 30 minutes. One hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the solution was heated and stirred for 2 hours (internal temperature was 100 to 110°C) to obtain a polysiloxane solution. Additionally, during the temperature increase and heating and stirring, a mixed gas of 95 volume% nitrogen and 5 volume% oxygen was flowed at 0.05 liter/min. During the reaction, a total of 173.99 g of by-products, methanol and water, flowed out. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight, and a polysiloxane (PSL-3) solution was obtained. Additionally, the weight average molecular weight of the obtained polysiloxane (PSL-3) was 6,000. In addition, in polysiloxane (PSL-3), diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, The molar ratios of each repeating unit derived from 3-trimethoxysilylpropylsuccinic anhydride were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

Synthesis Example 4 Polysiloxane (PSL-4) solution

In a 1000 ml three-necked flask, 186.45 g (0.831 mol) of styryltrimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and dimethyldimethoxysilane were added. Add 78.89 g (0.656 mol), 45.91 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.132 g of BHT, and 243.65 g of PGMEA, and while stirring at 40°C, 3.328 g of phosphoric acid (added to 85.84 g of water) An aqueous solution of phosphoric acid (1.0% by weight based on the monomer) was added over 30 minutes. After that, the flask was immersed in an oil bath at 70°C and stirred for 60 minutes, and then the temperature of the oil bath was raised to 115°C over 30 minutes. One hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the solution was heated and stirred for 2 hours (internal temperature was 100 to 110°C) to obtain a polysiloxane solution. Additionally, during the temperature increase and heating and stirring, a mixed gas of 95 volume% nitrogen and 5 volume% oxygen was flowed at 0.05 liter/min. During the reaction, a total of 195.52 g of by-products, methanol and water, flowed out. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight, and a polysiloxane (PSL-4) solution was obtained. Additionally, the weight average molecular weight of the obtained polysiloxane (PSL-4) was 15,000. Also in polysiloxane (PSL-4), styryltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. The molar ratios of each repeating unit derived were 47.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

Synthesis Example 5 Polysiloxane (PSL-5) solution

In a 1000 ml three-necked flask, 76.06 g (0.306 mol) of 3-methacryloxypropyltrimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and dimethyl Add 142.01 g (1.181 mol) of dimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 0.954 g of BHT, and 206.29 g of PGMEA, and add phosphoric acid to 76.39 g of water while stirring at 40°C. 2.855 g (1.0% by weight based on the monomer input) of dissolved phosphoric acid aqueous solution was added over 30 minutes. After that, the flask was immersed in an oil bath at 70°C and stirred for 60 minutes, and then the temperature of the oil bath was raised to 115°C over 30 minutes. 1 hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the solution was heated and stirred for 2 hours (internal temperature was 100 to 110°C) to obtain a polysiloxane solution. Additionally, during the temperature increase and heating and stirring, a mixed gas of 95 volume% nitrogen and 5 volume% oxygen was flowed at 0.05 liter/min. During the reaction, a total of 173.99 g of by-products, methanol and water, flowed out. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight, and a polysiloxane (PSL-5) solution was obtained. Additionally, the weight average molecular weight of the obtained polysiloxane (PSL-5) was 5,000. Also in polysiloxane (PSL-5), 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, 3-trimethoxysilyl The molar ratios of each repeating unit derived from propylsuccinic anhydride were 17.5 mol%, 5 mol%, 67.5 mol%, and 10 mol%, respectively.

Synthesis Example 6 Polysiloxane (PSL-6) solution

In a 1000 ml three-necked flask, 203.13 g (0.831 mol) of diphenyldimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and 78.89 mol of dimethyldimethoxysilane. g (0.656 mol), 45.91 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.312 g of BHT, and 275.12 g of PGMEA were added, and while stirring at 40°C, 3.495 g of phosphoric acid (input monomer) was added to 70.88 g of water. An aqueous solution of phosphoric acid (1.0% by weight) was added over 30 minutes. After that, the flask was immersed in an oil bath at 70°C and stirred for 60 minutes, and then the temperature of the oil bath was raised to 115°C over 30 minutes. One hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the solution was heated and stirred for 2 hours (internal temperature was 100 to 110°C) to obtain a polysiloxane solution. Additionally, during the temperature increase and heating and stirring, a mixed gas of 95 volume% nitrogen and 5 volume% oxygen was flowed at 0.05 liter/min. During the reaction, a total of 161.44 g of by-products, methanol and water, flowed out. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight, and a polysiloxane (PSL-6) solution was obtained. Additionally, the weight average molecular weight of the obtained polysiloxane (PSL-6) was 6,000. Also from polysiloxane (PSL-6), diphenyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride The molar ratios of each repeating unit were 47.5 mol%, 5 mol%, 37.5 mol%, and 10 mol%, respectively.

The compositions of Synthesis Examples 1 to 6 are summarized and shown in Table 1.

[Table 1]

Synthesis Example 7 Synthesis of (meth)acrylic polymer solution (PAL-1)

After adding 3.00 g of 2,2'-azobis(isobutyronitrile) and 50.0 g of PGMEA to a 500 mL flask, 30.0 g (0.349 mol) of methacrylic acid, 22.48 g (0.216 mol) of styrene, and tricyclo [5.2.1.02,6] 35.0 g (0.149 mol) of decan-8-yl methacrylate was added, stirred for a while at room temperature, the inside of the flask was replaced with nitrogen, and then heated and stirred at 70°C for 5 hours. Next, 15.00 g (0.106 mol) of glycidyl methacrylate, 1.00 g of triphenylphosphine, 0.200 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, heated and stirred at 90°C for 4 hours. , a (meth)acrylic polymer solution was obtained. PGMEA was added to the obtained (meth)acrylic polymer solution so that the solid content concentration was 40% by weight, thereby forming a (meth)acrylic polymer solution (PAL-1). The weight average molecular weight of the (meth)acrylic polymer was 16000.

Synthesis Example 8 Synthesis of (meth)acrylic polymer solution (PAL-2)

Add 3.00 g of 2,2'-azobis(isobutyronitrile) and 50.0 g of PGMEA to a 500 mL flask, then add 15.0 g (0.174 mol) of methacrylic acid and 38.06 g (0.216 mol) of benzyl methacrylate. , 32.80 g (0.149 mol) of tricyclodecanyl methacrylate was added, stirred for a while at room temperature, the inside of the flask was replaced with nitrogen, and then heated and stirred at 70°C for 5 hours. Next, 15.0 g (0.106 mol) of glycidyl methacrylate, 1 g of triphenylphosphine, 0.200 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, heated and stirred at 90°C for 4 hours, A (meth)acrylic polymer solution was obtained. PGMEA was added to the obtained (meth)acrylic polymer solution so that the solid content concentration was 40% by weight, thereby forming a (meth)acrylic polymer solution (PAL-2). The weight average molecular weight of the (meth)acrylic polymer was 25000.

Synthesis Example 9 Synthesis of (meth)acrylic polymer solution (PAL-3)

After adding 3.00 g of 2,2'-azobis(isobutyronitrile) and 50.0 g of PGMEA to a 500 mL flask, 30.0 g (0.349 mol) of methacrylic acid, tricyclo[5.2.1.02,6]decane- 116.98 g (0.498 mol) of 8-yl methacrylate was added, stirred for a while at room temperature, the inside of the flask was replaced with nitrogen, and then heated and stirred at 70°C for 5 hours. Next, 15.00 g (0.106 mol) of glycidyl methacrylate, 1.00 g of triphenylphosphine, 0.200 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, heated and stirred at 90°C for 4 hours. , a (meth)acrylic polymer solution was obtained. PGMEA was added to the obtained (meth)acrylic polymer solution so that the solid content concentration was 40% by weight, thereby forming a (meth)acrylic polymer solution (PAL-3). The weight average molecular weight of the (meth)acrylic polymer was 16000.

The compositions of Synthesis Examples 7 to 9 are summarized and shown in Table 2.

[Table 2]

Synthesis Example 10 Green organic phosphor

3,5-dibromobenzaldehyde (3.0g), 4-t-butylphenylboronic acid (5.3g), tetrakis(triphenylphosphine)palladium (0) (0.4g) and potassium carbonate (2.0g) It was placed in a flask and purged with nitrogen. Degassed toluene (30 mL) and degassed water (10 mL) were added thereto, and the mixture was refluxed for 4 hours. The reaction solution was cooled to room temperature, separated into liquids, and the organic layer was washed with saturated saline solution. This organic layer was dried with magnesium sulfate, filtered, and the solvent was distilled off. The obtained reaction product was purified by silica gel column chromatography to obtain 3,5-bis(4-t-butylphenyl)benzaldehyde (3.5 g) as a white solid. Next, 3,5-bis(4-t-butylphenyl)benzaldehyde (1.5g) and 2,4-dimethylpyrrole (0.7g) were added to the flask, and dehydrated dichloromethane (200mL) and trifluoroacetic acid (1 drop) were added to the flask. ) was added and stirred for 4 hours under a nitrogen atmosphere. To this reaction mixture, a dehydrated dichloromethane solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.85 g) was added, and the mixture was stirred for further 1 hour. After completion of the reaction, boron trifluoride diethyl ether complex (7.0 mL) and diisopropylethylamine (7.0 mL) were added and stirred for 4 hours, and water (100 mL) was further added and stirred to separate the organic layer. . This organic layer was dried with magnesium sulfate, filtered, and the solvent was distilled off. The obtained reaction product was purified by silica gel column chromatography to obtain 0.4 g of green powder (yield 17%). The results of ¹ H-NMR analysis of the obtained green powder were as follows, and it was confirmed that the green powder obtained above was [G-1] represented by the following structural formula.

Synthesis Example 11 Red organic phosphor

A mixed solution of 300 mg of 4-(4-t-butylphenyl)-2-(4-methoxyphenyl)pyrrole, 201 mg of 2-methoxybenzoyl chloride, and 10 ml of toluene was heated at 120°C for 6 hours under a nitrogen stream. After cooling to room temperature, the solvent was evaporated. The obtained residue was washed with 20 ml of ethanol and dried under vacuum to obtain 260 mg of 2-(2-methoxybenzoyl)-3-(4-t-butylphenyl)-5-(4-methoxyphenyl)pyrrole. Then, 260 mg of 2-(2-methoxybenzoyl)-3-(4-t-butylphenyl)-5-(4-methoxyphenyl)pyrrole, 4-(4-t-butylphenyl)-2-(4 A mixed solution of 180 mg of -methoxyphenyl)pyrrole, 206 mg of methanesulfonic anhydride, and 10 ml of degassed toluene was heated at 125°C for 7 hours under a nitrogen stream. After cooling the reaction mixture to room temperature, 20 ml of water was added and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, evaporated, and vacuum dried to obtain a pyromethene body as a residue. Next, 305 mg of diisopropylethylamine and 670 mg of boron trifluoride diethyl ether complex were added to the obtained mixed solution of pyromethene body and 10 ml of toluene under a nitrogen stream, and the mixture was stirred at room temperature for 3 hours. 20 ml of water was added to this reaction mixture, and the mixture was extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, dried over magnesium sulfate, and then evaporated. After purification by silica gel column chromatography and vacuum drying, 0.27 g of red-purple powder was obtained (yield 70%). The results of ¹ H-NMR analysis of the obtained red-purple powder were as follows, and it was confirmed that the red-purple powder obtained above was [R-1] represented by the following structural formula.

Synthesis Example 12 Polysiloxane solution containing silica particles (LS-1)

In a 500ml three-necked flask, 0.05g (0.4mmol) of methyltrimethoxysilane, 0.66g (3.0mmol) of trifluoropropyltrimethoxysilane, and 0.10g (0.4mmol) of trimethoxysilylpropylsuccinic anhydride. , 7.97 g (34 mmol) of γ-acryloxypropyltrimethoxysilane and 224.37 g of an isopropyl alcohol dispersion of 15.6% by weight silica particles (IPA-ST-UP: manufactured by Nissan Chemical Industries, Ltd.) were added, and ethylene was added. 163.93 g of glycol mono-t-butyl ether was added. While stirring at room temperature, an aqueous phosphoric acid solution containing 0.088 g of phosphoric acid dissolved in 4.09 g of water was added over 3 minutes. After that, the flask was immersed in an oil bath at 40°C and stirred for 60 minutes, and then the temperature of the oil bath was raised to 115°C over 30 minutes. 1 hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the solution was heated and stirred for another 2 hours (internal temperature was 100 to 110°C) to obtain a silica particle-containing polysiloxane solution (LS-1). Additionally, nitrogen was fractionated at 0.05 l (liter)/during the temperature increase and heating and stirring. During the reaction, a total of 194.01 g of by-products, methanol and water, flowed out. The solid content concentration of the obtained silica particle-containing polysiloxane solution (LS-1) was 24.3% by weight, and the contents of polysiloxane and silica particles in the solid content were 15% by weight and 85% by weight, respectively. Of the polysiloxanes in the obtained silica particle-containing polysiloxane (LS-1), methyltrimethoxysilane, trifluoropropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, and γ-acryloxypropyltrimethoxysilane. The molar ratios of each repeating unit derived were 1.0 mol%, 8.0 mol%, 1.0 mol%, and 90.0 mol%, respectively.

Example 1 Resin composition for partition (P-1)

As a white pigment, 5.00 g of titanium dioxide pigment (R-960; manufactured by BASF Japan Co., Ltd. (hereinafter referred to as “R-960”)), and as a resin, 5.00 g of the polysiloxane (PSL-1) solution obtained in Synthesis Example 1. , 0.0188 g of titanium nitride as a light-shielding pigment was mixed and dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-1).

Next, 8.27 g of the pigment dispersion (MW-1), 2.83 g of the polysiloxane (PSL-1) solution, 4.48 g of the (meth)acrylic polymer (PAL-1) solution obtained in Synthesis Example 7, and ethanone as a photopolymerization initiator. , 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) ("Irgacure" (registered trademark) OXE-02, 0.155 g of BASF Japan Co., Ltd. (hereinafter referred to as “OXE-02”), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (“Irgacure” 819, BASF Japan Co., Ltd. ( Hereinafter, “IC-819”)) 0.258 g, as a hindered phenol compound, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6- Trimethylbenzene ("Adeka Step" (registered trademark) AO-330, manufactured by ADEKA Co., Ltd. (hereinafter referred to as "AO-330")) 0.0309 g, as a photopolymerizable compound, dipentaerythritol hexaacrylate ("KAYARAD") (Registered trademark) DPHA, manufactured by Shin Nippon Yakugyo Co., Ltd. (hereinafter referred to as “DPHA”), 2.063 g, a liquid-repellent compound, a photopolymerizable fluorine-containing compound (“Megapak” (registered trademark) RS-72A, 20% by weight PGMEA Diluted solution product, manufactured by DIC Co., Ltd. (hereinafter referred to as “RS-72A”)) 0.258 g, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("Celoxide" (registered Trademark) 2021P, manufactured by Daicel Co., Ltd. (hereinafter referred to as “Celoxide (registered trademark) 2021P”)) 0.021 g, and an acrylic surfactant (“BYK” (registered trademark) 352, manufactured by Big Chemi Japan Co., Ltd. (hereinafter referred to as “Celoxide (registered trademark) 2021P”)). 0.103 g of a 10% by weight diluted solution of PGMEA (equivalent to a concentration of 500 ppm) of "BYK-352") was dissolved in 0.513 g of solvent PGMEA and 1.65 g of DAA and stirred. The obtained mixture was filtered through a 5.0 μm filter to obtain a resin composition for partition walls (P-1).

Example 2 Resin composition for partition (P-2)

5.00 g of R-960 as a white pigment and polysiloxane (PSL-1) solution as a resin were mixed and dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-2). In addition, 0.103 g of bis(acetylacetonato)palladium as an organometallic compound and 0.089 g of triphenylphosphine as a coordination compound having a phosphorus atom (equimolar amount with respect to the organometallic compound) were dissolved in 1.726 g of DAA. Thus, an organometallic compound solution (OM-1) was obtained.

Instead of the pigment dispersion (MW-1), 8.25 g of the pigment dispersion (MW-2) was added, 1.92 g of the organometallic compound solution (OM-1), 2.61 g of the polysiloxane (PSL-1) solution, and (meth)acrylic A resin composition for a partition (P-2) was obtained in the same manner as in Example 1, except that 4.26 g of the polymer (PAL-1) solution and 0.701 g of PGMEA were added, and DAA was not added.

Example 3 Resin composition for partition (P-3)

As an organometallic compound, 0.103 g of silver neodecanoic acid was dissolved in 0.928 g of EDM to obtain an organometallic compound solution (OM-2). Instead of the organometallic compound solution (OM-1), 1.03 g of the organometallic compound solution (OM-2), 2.72 g of the polysiloxane (PSL-1) solution, 4.37 g of the (meth)acrylic polymer (PAL-1) solution, and PGMEA were used. A resin composition for partition walls (P-3) was obtained in the same manner as in Example 2, except that 1.366 g was added.

Examples 4 to 6 Resin compositions for partition walls (P-4) to (P-6)

A resin composition for partition (P-4) was produced in the same manner as in Example 1, except that the polysiloxane (PSL-2), (PSL-3), and (PSL-4) solutions were used instead of the polysiloxane (PSL-1) solution, respectively. To obtain (P-6).

Example 7 Resin composition for partition (P-7)

A resin composition for a partition (P-7) was obtained in the same manner as in Example 1, except that the (meth)acrylic polymer (PAL-2) solution was used instead of the (meth)acrylic polymer (PAL-1) solution.

Example 8 Resin composition for partition (P-8)

A resin composition for a partition (P-8) was obtained in the same manner as in Example 1, except that Cardo-based polymer V-259ME was used instead of the (meth)acrylic polymer (PAL-1) solution.

Example 9 Resin composition for partition (P-9)

A resin composition for a partition (P-9) was obtained in the same manner as in Example 1, except that Cardo-based polymer WR-301 was used instead of the (meth)acrylic polymer (PAL-1) solution.

Example 10 Resin composition for partition (P-10)

Instead of the hindered phenol compound AO-330, pentaerythritoltetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate ("Adekastab" (registered trademark) AO- A resin composition for partition walls (P-10) was obtained in the same manner as in Example 1, except that 60, manufactured by ADEKA Co., Ltd. (hereinafter referred to as “AO-60”)) was used.

Example 11 Resin composition for partition (P-11)

Instead of the hindered phenol compound AO-330, 6,6'-di-t-butyl-4,4'-butylidenedi-m-cresol ("Adeka Step" (registered trademark) AO-40, ADEKA Co., Ltd. ) A resin composition for partition walls (P-11) was obtained in the same manner as in Example 1, except that the agent (hereinafter referred to as "AO-40")) was used.

Example 12 Resin composition for partition (P-12)

Instead of the hindered phenol compound AO-330, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate ("Adekastab" (registered trademark) AO-50, ADEKA ( A resin composition for partition walls (P-12) was obtained in the same manner as in Example 1, except that Agent (hereinafter referred to as “AO-50”)) was used.

Example 13 Resin composition for partition (P-13)

Except that the added amount of the hindered phenol compound AO-330 was 0.0474 g, 2.81 g of polysiloxane (PSL-1) solution, 4.46 g of (meth)acrylic polymer (PAL-1) solution, and 0.538 g of PGMEA were added. , the resin composition for partition walls (P-13) was obtained in the same manner as in Example 1.

Example 14 Resin composition for partition (P-14)

Except that the added amount of the hindered phenol compound AO-330 was 0.330 g, 2.46 g of polysiloxane (PSL-1) solution, 4.10 g of (meth)acrylic polymer (PAL-1) solution, and 0.962 g of PGMEA were added. , the resin composition for partition walls (P-14) was obtained in the same manner as in Example 1.

Example 15 Resin composition for partition (P-15)

Except that the added amount of the hindered phenol compound AO-330 was 0.00516 g, 2.86 g of polysiloxane (PSL-1) solution, 4.51 g of (meth)acrylic polymer (PAL-1) solution, and 0.474 g of PGMEA were added. , the resin composition for partition walls (P-15) was obtained in the same manner as in Example 1.

Example 16 Resin composition for partition (P-16)

Except that the added amount of the hindered phenol compound AO-330 was 0.00309 g, 2.87 g of polysiloxane (PSL-1) solution, 4.51 g of (meth)acrylic polymer (PAL-1) solution, and 0.474 g of PGMEA were added. , the resin composition for partition walls (P-16) was obtained in the same manner as in Example 1.

Example 17 Resin composition for partition (P-17)

As a hindered amine compound, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate ("Adekastab" (registered trademark) LA-82, manufactured by ADEKA Co., Ltd. (hereinafter referred to as " Example 1, except that 0.103 g of "LA-82")) was added, 2.70 g of polysiloxane (PSL-1) solution, 4.35 g of (meth)acrylic polymer (PAL-1) solution, and 0.668 g of PGMEA were added. In the same manner as above, a resin composition for partition walls (P-17) was obtained.

Example 18 Resin composition for partition (P-18)

Instead of the hindered amine compound LA-82, 2,2,6,6-tetramethyl-4-piperidyl methacrylate ("Adeka Step" (registered trademark) LA-87, manufactured by ADEKA Co., Ltd. (hereinafter referred to as , “LA-87”)), a resin composition for partition walls (P-18) was obtained in the same manner as in Example 17, except that “LA-87”)) was used.

Example 19 Resin composition for partition (P-19)

Example, except that the hindered phenol compound AO-330 was not added, and 2.74 g of polysiloxane (PSL-1) solution, 4.39 g of (meth)acrylic polymer (PAL-1) solution, and 0.621 g of PGMEA were added. In the same manner as in 17, a resin composition for partition walls (P-19) was obtained.

Example 20 Resin composition for partition (P-20)

Instead of the hindered amine compound LA-82, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate ("Adekastab" (registered trademark) LA-72, ADEKA Co., Ltd. ) Agent (hereinafter referred to as "LA-72")) was used in the same manner as in Example 19 to obtain a resin composition for partition walls (P-20).

Example 21 Resin composition for partition (P-21)

A resin composition for a partition (P-21) was obtained in the same manner as in Example 19, except that 1,2,2,5,5-pentamethylpiperidine was used in place of the hindered amine compound LA-82.

Example 22 Resin composition for partition (P-22)

Except that the added amount of the hindered amine compound LA-82 was 0.248 g, 2.56 g of polysiloxane (PSL-1) solution, 4.71 g of (meth)acrylic polymer (PAL-1) solution, and 0.838 g of PGMEA were added. , the resin composition for partition walls (P-22) was obtained in the same manner as in Example 19.

Example 23 Resin composition for partition (P-23)

Except that the added amount of the hindered amine compound LA-82 was 0.371 g, 2.40 g of polysiloxane (PSL-1) solution, 4.05 g of (meth)acrylic polymer (PAL-1) solution, and 1.024 g of PGMEA were added. , the resin composition for partition walls (P-23) was obtained in the same manner as in Example 19.

Example 24 Resin composition for partition (P-24)

Except that the added amount of the hindered amine compound LA-82 was 0.0100 g, 2.86 g of polysiloxane (PSL-1) solution, 4.51 g of (meth)acrylic polymer (PAL-1) solution, and 0.482 g of PGMEA were added. , the resin composition for partition walls (P-24) was obtained in the same manner as in Example 19.

Example 25 Resin composition for partition (P-25)

Except that the amount of the hindered amine compound LA-82 added was 0.0039, 2.86 g of polysiloxane (PSL-1) solution, 4.51 g of (meth)acrylic polymer (PAL-1) solution, and 0.471 g of PGMEA were added. In the same manner as in Example 19, a resin composition for partition walls (P-25) was obtained.

Example 26 Resin composition for partition (P-26)

A resin composition for partition walls (P-26) was obtained in the same manner as in Example 1, except that the addition amount of IC-819 was 0.413 g and OXE-02 was not added.

Example 27 Resin composition for partition (P-27)

A resin composition for partition walls (P-27) was obtained in the same manner as in Example 1, except that the addition amount of OXE-02 was 0.413 g and IC-819 was not added.

Example 28 Resin composition for partition (P-28)

A resin composition for a partition (P-28) was prepared in the same manner as in Example 1, except that the addition amount of the polysiloxane (PSL-1) solution was 1.33 g and the addition amount of the (meth)acrylic polymer (PAL-1) solution was 5.98 g. got it

Example 29 Resin composition for partition (P-29)

A resin composition for a partition (P-29) was prepared in the same manner as in Example 1, except that the addition amount of the polysiloxane (PSL-1) solution was 4.73 g and the addition amount of the (meth)acrylic polymer (PAL-1) solution was 2.58 g. got it

Example 30 Resin composition for partition (P-30)

7.68g of polysiloxane (PSL-1) solution, 7.68g of (meth)acrylic polymer (PAL-1) solution, 0.123g of OXE-02, 0.205g of IC-819, 1.64g of DPHA, and RS-72A. 0.205 g, 0.016 g of Celoxide 2021P, 0.025 g of AO-330, and 0.103 g of a 10% by weight diluted solution of PGMEA of BYK-352 were dissolved in 0.619 g of solvent PGMEA and 2.214 g of DAA and stirred. The obtained mixture was filtered through a 5.0 μm filter to obtain a resin composition for partition walls (P-30).

Example 31 Resin composition for partition (P-31)

Without adding the organometallic compound solution (OM-1), the addition amount of the polysiloxane (PSL-1) solution was 2.85 g, the addition amount of the (meth)acrylic polymer (PAL-1) solution was 4.50 g, and the addition amount of PGMEA was 0.284 g. A resin composition for partition walls (P-31) was obtained in the same manner as in Example 2, except that the addition amount of DAA was changed to 1.86 g.

Example 32 Resin composition for partition (P-32)

0.20 g of titanium nitride as a light-shielding pigment and 7.00 g of polysiloxane (PSL-1) solution as a resin were mixed and dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-3). The pigment dispersion (MW-3) was 5.90 g, the polysiloxane (PSL-1) solution was 0.79 g, the (meth)acrylic polymer (PAL-1) solution was 6.54 g, OXE-02 was 0.108 g, and IC-819 was 0.180 g. g, 1.44 g of DPHA, 0.179 g of RS-72A, 0.014 g of Celoxide 2021P, 0.022 g of AO-330, and 0.103 g of a 10% by weight diluted solution of PGMEA of BYK-352 were dissolved in 1.804 g of solvent PGMEA and stirred. did. The obtained mixture was filtered through a 5.0 μm filter to obtain a resin composition for partition walls (P-32).

Example 33 Resin composition for partition (P-33)

4.00 g of the organometallic compound solution (OM-1), 6.21 g of the polysiloxane (PSL-1) solution, 6.21 g of the (meth)acrylic polymer (PAL-1) solution, 0.108 g of OXE-02, IC- 0.180g of 819, 1.44g of DPHA, 0.179g of RS-72A, 0.014g of Celoxide 2021P, 0.022g of AO-330, and 0.103g of 10% by weight diluted solution of PGMEA of BYK-352, and 2.03g of solvent PGMEA. It was dissolved and stirred. The obtained mixture was filtered through a 5.0 μm filter to obtain a resin composition for partition walls (P-33).

Example 34 Resin composition for partition (P-34)

Without adding the liquid-repellent compound RS-72A, the amount of polysiloxane (PSL-1) solution added was 2.67 g, the amount of (meth)acrylic polymer (PAL-1) solution added was 4.32 g, and the amount of PGMEA added was 0.830 g. Otherwise, the same procedure as in Example 2 was carried out to obtain a resin composition for partition walls (P-34).

Comparative Examples 1 to 2 Resin compositions for partition walls (P-35) to (P-36)

Resin compositions for partition walls (P-35) to (P-36) were prepared in the same manner as in Example 1, except that the polysiloxane (PSL-5) and (PSL-6) solutions were used instead of the polysiloxane (PSL-1) solution, respectively. got it

Comparative Example 3 Resin composition for partition (P-37)

A resin composition for a partition (P-37) was obtained in the same manner as in Example 1, except that the (meth)acrylic polymer (PAL-3) solution was used instead of the (meth)acrylic polymer (PAL-1) solution.

Comparative Example 4 Resin composition for partition (P-38)

A resin composition for a partition (P-38) was prepared in the same manner as in Example 1, except that the addition amount of the polysiloxane (PSL-1) solution was 0.590 g and the addition amount of the (meth)acrylic polymer (PAL-1) solution was 6.72 g. got it

Comparative Example 5 Resin composition for partition (P-39)

A resin composition for a partition (P-39) was prepared in the same manner as in Example 1, except that the addition amount of the polysiloxane (PSL-1) solution was 5.07 g and the addition amount of the (meth)acrylic polymer (PAL-1) solution was 2.24 g. got it

Comparative Example 6 Resin composition for partition (P-40)

A resin composition for a partition (P-40) was obtained in the same manner as in Example 1, except that the (meth)acrylic polymer (PAL-1) solution was not added and the addition amount of the polysiloxane (PSL-1) solution was changed to 7.31 g. .

Comparative Example 7 Resin composition for partition (P-41)

Mix 5.00g of R-960 as a white pigment, 5.00g of (meth)acrylic polymer (PAL-1) solution as a resin, and 0.0188g of titanium nitride as a light-blocking pigment, and disperse using a mill-type disperser filled with zirconia beads. A pigment dispersion (MW-4) was obtained.

8.27 g of pigment dispersion (MW-4) was added instead of pigment dispersion (MW-1), and 7.31 g of (meth)acrylic polymer (PAL-1) solution was added without adding polysiloxane (PSL-1) solution. Except this, a resin composition for partition walls (P-41) was obtained in the same manner as in Example 1.

Comparative Example 8 Resin composition for partition (P-42)

Example, except that the hindered phenol compound AO-330 was not added, and 2.87 g of polysiloxane (PSL-1) solution, 4.52 g of (meth)acrylic polymer (PAL-1) solution, and 0.467 g of PGMEA were added. In the same manner as in 1, a resin composition for partition walls (P-42) was obtained.

The compositions of Examples 1 to 34 and Comparative Examples 1 to 8 are summarized and shown in Tables 3-1 to 3-4.

[Table 3-1]

[Table 3-2]

[Table 3-3]

[Table 3-4]

Preparation Example 1 Color conversion luminescent material composition (CL-1)

Green quantum dot material (Lumidot 640 CdSe/ZnS, average particle diameter: 6.3 nm: manufactured by Aldrich) containing 20 parts by weight of a 0.5% by weight toluene solution, 45 parts by weight of DPHA, and "Irgacure" (registered trademark) 907 (BASF Japan (BASF Japan) 5 parts by weight of (manufactured by Co., Ltd.), 166 parts by weight of PGMEA solution of acrylic resin (SPCR-18 (trade name), manufactured by Showa Denko Co., Ltd.) and 97 parts by weight of toluene were mixed and stirred uniformly. dissolved. The obtained mixture was filtered through a 0.45 μm syringe filter to prepare a color conversion light-emitting material composition (CL-1).

Preparation Example 2 Color conversion luminescent material composition (CL-2)

A color conversion light-emitting material composition (CL- 2) was prepared.

Preparation Example 3 Color conversion luminescent material composition (CL-3)

A color conversion light emitting material composition (CL- 3) was prepared.

Preparation Example 4 Color filter forming material (CF-1)

90 g of C.I. Pigment Green 59, 60 g of C.I. Pigment Yellow 150, 75 g of polymer dispersant ("BYK" (registered trademark)-6919 (brand name) manufactured by Big Chemistry (hereinafter referred to as "BYK-6919")), binder resin ( A slurry was prepared by mixing 100 g of "Adeka Ackles" (registered trademark) WR301 (trade name) manufactured by ADEKA Co., Ltd. and 675 g of PGMEA. The beaker containing the slurry was connected to a dyno mill and a tube, and using zirconia beads with a diameter of 0.5 mm as a medium, dispersion treatment was performed for 8 hours at a circumferential speed of 14 m/s to produce Pigment Green 59 dispersion (GD-1). did.

Pigment Green 59 dispersion (GD-1) 56.54 g, acrylic resin ("Cyclomer" (registered trademark) P(ACA)Z250 (brand name) manufactured by Daicel Allnex Co., Ltd. (hereinafter referred to as "P(ACA)Z250 」)) 3.14 g, DPHA 2.64 g, photopolymerization initiator (“Optmer” (registered trademark) NCI-831 (trade name) manufactured by ADEKA Co., Ltd. (hereinafter “NCI-831”)) 0.330 g, surfactant ( 0.04 g of BYK" (registered trademark)-333 (brand name) manufactured by Big Chemistry (hereinafter referred to as "BYK-333")), 0.01 g of BHT as a polymerization inhibitor, and 37.30 g of PGMEA as a solvent were mixed to form a color filter. (CF-1) was produced.

Preparation Example 5 Resin composition for light-shielding partition

A slurry was prepared by mixing 150 g of carbon black (MA100 (brand name) manufactured by Mitsubishi Chemical Corporation), 75 g of polymer dispersant BYK-6919, 100 g of P(ACA)Z250, and 675 g of PGMEA. The beaker containing the slurry was connected to a dyno mill and a tube, and dispersion treatment was performed for 8 hours at a circumferential speed of 14 m/s using zirconia beads with a diameter of 0.5 mm as a medium to produce a pigment dispersion (MB-1).

56.54 g of pigment dispersion (MB-1), 3.14 g of P(ACA)Z250, 2.64 g of DPHA, 0.330 g of NCI-831, 0.04 g of BYK-333, 0.01 g of tertiary butylcatechol as a polymerization inhibitor, and 37.30 g of PGMEA was mixed to produce a resin composition for a light-shielding partition.

Preparation Example 6 Low refractive index layer forming material

5.350 g of the silica particle-containing polysiloxane solution (LS-1) obtained in Synthesis Example 12, 1.170 g of ethylene glycol mono-t-butyl ether, and 3.48 g of DAA were mixed, and then filtered through a 0.45㎛ syringe filter to obtain a low refractive index. Layer forming materials were prepared.

Preparation Example 7 Yellow organic protective layer forming material (YL-1)

150 g of C.I. Pigment Yellow 150, 75 g of polymer dispersant ("BYK" (registered trademark)-6919 (product name) manufactured by Big Chemistry (hereinafter referred to as "BYK-6919")), binder resin ("Adeka Ackles" (registered) A slurry was prepared by mixing 100 g of WR301 (trade name) manufactured by ADEKA Co., Ltd. and 675 g of PGMEA. The beaker containing the slurry was connected to a dyno mill and a tube, and using zirconia beads with a diameter of 0.5 mm as a medium, dispersion treatment was performed for 8 hours at a circumferential speed of 14 m/s to produce Pigment Yellow 150 dispersion (YD-1). did.

An organometallic compound solution prepared using 3.09g of Pigment Yellow 150 dispersion (YD-1), 23.54g of polysiloxane (PSL-1) solution as a resin, 6.02g of DPHA as a photopolymerizable compound, and silver neodecanoate as an organometallic compound. 6.02 g of (OM-2), 0.20 g of OXE-02 as a photopolymerization initiator, 0.40 g of IC-819, 0.060 g of IRGANOX (registered trademark) 1010, and 0.050 g of a 10% by weight diluted solution of PGMEA of BYK-352 (concentration (equivalent to 500 ppm) was dissolved in 61.15 g of solvent PGMEA and stirred. The obtained mixture was filtered through a 5.0 μm filter to obtain a yellow organic protective layer forming material (YL-1).

Examples 35 to 69, Comparative Examples 9 to 16

As a base substrate, a square alkali-free glass substrate (manufactured by AGC Techno Glass Co., Ltd., thickness 0.7 mm) with a side of 10 cm was used. The resin composition for partitions shown in Tables 4 to 5 was spin-coated thereon, dried at a temperature of 100°C for 3 minutes using a hot plate (product name SCW-636, manufactured by Dainippon Screen Seizo Co., Ltd.), and a dried film was formed. Produced. The produced dry film was exposed to light using a parallel light mask aligner (product name PLA-501F, manufactured by Canon Co., Ltd.), using an ultra-high pressure mercury lamp as a light source, through a photomask, and exposed to an exposure dose of 100 mJ/cm2 (g, h, and i lines). The exposure amount was calculated as i-line conversion value. After that, using an automatic developing device (“AD-2000 (brand name)” manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 100 seconds using a 0.045% by weight potassium hydroxide aqueous solution, followed by 30 seconds using water. rinsed. Additionally, using an oven (brand name IHPS-222, manufactured by Espec Co., Ltd.), heating was performed in the air at a temperature of 230°C for 30 minutes to form a partition wall with a height of 10 μm and a width of 20 μm on the glass substrate, with a short side of 80 μm. A partition formed in a grid-like pattern with a pitch of ㎛ and a long side of 280 ㎛ was formed.

The color conversion light-emitting material composition shown in Tables 4 and 5 was applied to the area isolated by the barrier of the obtained barrier-equipped substrate using an inkjet method under a nitrogen atmosphere, and dried at 100°C for 30 minutes to form a pixel with a thickness of 5.0 μm. was formed to obtain a substrate with partition walls having the configuration shown in FIG. 2 .

Example 70

As a base substrate, a square alkali-free glass substrate (manufactured by AGC Techno Glass Co., Ltd., thickness 0.7 mm) with a side of 10 cm was used. The light-shielding barrier forming material obtained in Preparation Example 5 was spin-coated on top of it, dried at a temperature of 100°C for 3 minutes using a hot plate (product name SCW-636, manufactured by Dainippon Screen Seizo Co., Ltd.), and a dried film was formed. Produced. The produced dry film was exposed using a parallel light mask aligner (product name PLA-501F, manufactured by Canon Co., Ltd.) through a photomask using an ultra-high pressure mercury lamp as a light source, and exposed to an exposure dose of 40 mJ/cm2 (g, h, i lines). exposed to light. After that, using an automatic developing device (“AD-2000 (brand name)” manufactured by Takizawa Sangyo Co., Ltd.), development was performed for 50 seconds with a 0.3% by weight tetramethylammonium aqueous solution, followed by development for 30 seconds using water. rinsed. In addition, using an oven (product name IHPS-222, manufactured by Espec Co., Ltd.), heating was performed in the air at a temperature of 230°C for 30 minutes, and an OD per 1.0 μm of thickness was formed on a glass substrate with a height of 2.0 μm and a width of 20 μm. A substrate with light-shielding partitions in which the partitions with a value of 2.0 were formed in a lattice pattern with a pitch of 40 µm on the short side and 280 µm on the long side was obtained.

Thereafter, by the same method as in Example 36, on the light-shielding partition, partitions with a height of 10 μm and a width of 20 μm were formed in the same grid pattern as the light-shielding partition with a pitch interval of 40 μm on the short side and 280 μm on the long side. A substrate with a partition formed as follows was obtained. The color conversion light-emitting material composition (CL-2) obtained in Preparation Example 2 was applied to the area isolated by the barrier of the obtained barrier-equipped substrate using an inkjet method under a nitrogen atmosphere, and dried at 100°C for 30 minutes. A pixel with a thickness of 5.0 μm was formed, and a substrate with a partition having the structure shown in FIG. 3 was obtained.

Example 71

Color filter forming material (CF-1) obtained by Preparation Example 4, obtained by the same method as Example 36, so that the film thickness after curing is 2.5 μm in the area isolated by the partition of the partition-equipped substrate before pixel formation. was applied and dried in vacuum. A photomask designed to expose the opening area of the substrate with a partition was exposed at an exposure dose of 40 mJ/cm2 (g, h, i lines). After developing with a 0.3% by weight tetramethylammonium aqueous solution for 50 seconds, heat curing was performed at 230°C for 30 minutes, and a color filter layer with a height of 2.5 μm, a short side of 40 μm, and a long side of 280 μm was formed in the area isolated by the partition. formed. Thereafter, the color conversion light-emitting material composition (CL-2) obtained in Preparation Example 2 was applied onto the color filter using an inkjet method under a nitrogen atmosphere, and dried at 100°C for 30 minutes to form a pixel with a thickness of 5.0 μm. was formed to obtain a substrate with partition walls having the configuration shown in FIG. 4 .

Example 72

The low-refractive-index layer forming material obtained in Preparation Example 6 was spin-coated on a barrier-walled substrate after forming pixels by the same method as in Example 36, using a hot plate (product name SCW-636, Dainippon Screen Seizo Co., Ltd. ) agent) was used and dried at a temperature of 100°C for 3 minutes to produce a dried film. Additionally, using an oven (brand name IHPS-222, manufactured by Espec Co., Ltd.), heating was performed in air at a temperature of 90°C for 30 minutes to form a low refractive index layer with a height of 1.0 μm and a refractive index of 1.25, as shown in Figure 6. A substrate with a partition having the configuration was obtained.

Example 73

On the low refractive index layer of the barrier rib-equipped substrate having the low refractive index layer obtained in Example 72, using a plasma CVD device (PD-220NL, manufactured by Samco Corporation), an inorganic protective layer I with a height of 50 to 1,000 nm was formed, A silicon nitride film with a film thickness of 300 nm was formed, and a substrate with partitions having the structure shown in FIG. 7 was obtained.

Example 74

As a base substrate, a square alkali-free glass substrate (manufactured by AGC Techno Glass Co., Ltd., thickness 0.7 mm) with a side of 10 cm was used. The light-shielding barrier forming material obtained in Preparation Example 5 was spin-coated thereon, dried at a temperature of 100°C for 3 minutes using a hot plate (product name SCW-636, manufactured by Dainippon Screen Seizo Co., Ltd.), and a dried film was formed. Produced. The produced dry film was subjected to photomask using a parallel light mask aligner (product name PLA-501F, manufactured by Canon Co., Ltd.) using an ultra-high pressure mercury lamp as a light source, and an exposure dose of 40 mJ/cm2 (g, h, i lines) was applied. exposed to light. Afterwards, using an automatic developing device (“AD-2000 (brand name)” manufactured by Takizawa Sangyo Co., Ltd.), development was performed for 50 seconds with a 0.3% by weight tetramethylammonium aqueous solution, followed by development with water for 30 seconds. rinsed. Additionally, using an oven (brand name IHPS-222, manufactured by Espec Co., Ltd.), heating was performed in the air at a temperature of 230°C for 30 minutes, and a layer of 2.0 μm in height, 20 μm in width, and 1.0 μm in thickness was placed on a glass substrate. A substrate with light-shielding partitions was obtained, in which partitions with an OD value of 2.0 were formed in a lattice pattern with a pitch of 40 µm on the short side and 280 µm on the long side.

Thereafter, the color filter forming material (CF-1) obtained in Preparation Example 4 was applied to the area isolated by the light-shielding partition so that the film thickness after curing was 2.5 μm, and dried in vacuum. A photomask designed to expose the opening area of the substrate with a partition was exposed at an exposure dose of 40 mJ/cm2 (g, h, i lines). After developing with a 0.3% by weight tetramethylammonium aqueous solution for 50 seconds, heat curing was performed at 230°C for 30 minutes, and a color filter layer with a height of 2.5 μm, a short side of 40 μm, and a long side of 280 μm was formed in the area isolated by the partition. formed.

Thereafter, the low refractive index layer forming material obtained in Preparation Example 6 was spin-coated and dried at a temperature of 90°C for 2 minutes using a hot plate (product name SCW-636, manufactured by Dainippon Screen Seizo Co., Ltd.). A dry membrane was produced. Additionally, using an oven (brand name IHPS-222, manufactured by Espec Co., Ltd.), it was heated in air at a temperature of 90°C for 30 minutes to form a low refractive index layer with a height of 1.0 μm and a refractive index of 1.25.

Afterwards, a silicon nitride film with a thickness of 300 nm corresponding to the inorganic protective layer I with a height of 50 to 1,000 nm was formed on the low refractive index layer using a plasma CVD device (PD-220NL, manufactured by Samco).

On these, in the same manner as in Example 36, a substrate with barrier ribs was formed in the same lattice pattern as the light-shielding barrier ribs with a pitch of 10 μm in height and 20 μm in width and a pitch of 40 μm on the short side and 280 μm on the long side. got it The color conversion light-emitting material composition (CL-2) obtained in Preparation Example 2 was applied to the area isolated by the barrier of the obtained barrier-equipped substrate using an inkjet method under a nitrogen atmosphere, dried at 100°C for 30 minutes, and the thickness was reduced. A 5.0 μm pixel was formed, and a substrate with a partition having the structure shown in FIG. 9 was obtained.

Example 75

A plasma CVD device (PD-220NL, (manufactured by Samco Corporation) was used to form a silicon nitride film with a thickness of 300 nm, corresponding to the inorganic protective layer III with a thickness of 50 to 1,000 nm. Additionally, the color conversion light-emitting material composition (CL-2) obtained in Preparation Example 2 was applied onto the inorganic protective layer III using an inkjet method under a nitrogen atmosphere, and dried at 100°C for 30 minutes to form a 5.0 μm thick layer. A pixel was formed, and a substrate with a partition having the structure shown in FIG. 11 was obtained.

Example 76

As a base substrate, a square alkali-free glass substrate (manufactured by AGC Techno Glass Co., Ltd., thickness 0.7 mm) with a side of 10 cm was used. On top of this, a plasma CVD device (PD-220NL, manufactured by Samco) was used to form a silicon nitride film with a thickness of 300 nm, corresponding to the inorganic protective layer IV with a thickness of 50 to 1,000 nm. A substrate with partitions having the configuration shown in FIG. 12 was obtained in the same manner as in Example 36, except that the substrate was used instead of a square alkali-free glass substrate with a side of 10 cm.

Example 77

The yellow organic material obtained in Preparation Example 7 was placed on a color filter of a substrate with partitions before forming pixels, on which a color filter layer with a thickness of 2.5 μm, a short side of 40 μm, and a long side of 280 μm was formed by the same method as in Example 71. A protective layer forming material (YL-1) was applied and dried in vacuum. A photomask designed to expose the opening area of the substrate with a partition was exposed at an exposure dose of 300 mJ/cm2 (g, h, i lines). After developing with a 0.3% by weight tetramethylammonium aqueous solution for 50 seconds, heat curing was performed at 230°C for 30 minutes to form a yellow organic protective layer with a thickness of 1.0 μm, a short side of 40 μm, and a long side of 280 μm. Additionally, the color conversion light-emitting material composition (CL-2) obtained in Preparation Example 2 was applied onto the yellow organic protective layer using an inkjet method under a nitrogen atmosphere, and dried at 100°C for 30 minutes to form a 5.0 μm thick layer. A pixel was formed, and a substrate with a partition having the structure shown in FIG. 11 was obtained.

Example 78

As a base substrate, a square alkali-free glass substrate (manufactured by AGC Techno Glass Co., Ltd., thickness 0.7 mm) with a side of 10 cm was used. The yellow organic protective layer forming material (YL-1) obtained in Preparation Example 7 was applied thereon and dried in vacuum. The dried film was exposed to light at an exposure dose of 300 mJ/cm2 (g, h, i lines) without a photomask, developed for 50 seconds with a 0.3 wt% tetramethylammonium aqueous solution, and heat cured at 230°C for 30 minutes. By doing this, a yellow organic protective layer with a thickness of 1.0 μm was formed. A substrate with a partition having the structure shown in FIG. 8 was obtained in the same manner as in Example 36, except that the substrate was used instead of a square alkali-free glass substrate with a side of 10 cm.

The composition of each example and comparative example is shown in Tables 4 and 5.

[Table 4]

[Table 5]

The evaluation method in each Example and Comparative Example is shown below.

<Glass transition temperature of (meth)acrylic polymer and cardo-based polymer>

The (meth)acrylic polymer and/or cardo-based polymer in the resin composition of the present invention used in the examples and comparative examples was calculated from the thermogram obtained using a DSC device (“Thermo Plus DSC8230” manufactured by Rigaku). DSC measurement was performed under nitrogen at a temperature increase rate of 20°C/min. The glass transition temperature was calculated as the temperature corresponding to the intersection of the tangent line at the base line and the inflection point in the DSC temperature rise curve in the thermogram. The inflection point was set as the temperature corresponding to the peak in the DDSC (differential value of DSC) curve of the thermogram. In addition, to confirm the DSC baseline, the DDSC curve was referred to as appropriate. The glass transition temperature (Tg) was evaluated as “A” when it was 60°C or higher, and as “B” when it was less than 60°C.

<Refractive index of low refractive index layer>

The low refractive index layer forming material used in each example was applied on a silicon wafer with a spinner, and heated at 90°C for 2 minutes using a hot plate (product name: SCW-636, manufactured by Dainippon Screen Seizo Co., Ltd.). dried. After that, using an oven (IHPS-222; manufactured by Espec Co., Ltd.), it was heated in air at 90°C for 30 minutes to produce a cured film. Using a prism coupler (PC-2000 (manufactured by Metricon Co., Ltd.)), under atmospheric pressure and 20°C, light with a wavelength of 550 nm is irradiated in a direction perpendicular to the surface of the cured film, and the refractive index is measured. The third digit was rounded off.

<Non-adhesiveness of dried film>

Using a spin coater (brand name 1H-360S, manufactured by Mikasa Co., Ltd.), the resin composition for partitions used in each Example and Comparative Example was spread on a square alkali-free glass substrate with a side of 10 cm, and the film thickness after drying was It was spin-coated to a thickness of 10 μm and dried at a temperature of 100°C for 3 minutes using a hot plate (trade name: SCW-636, manufactured by Dainippon Screen Seizo Co., Ltd.) to produce a dried film with a film thickness of 10 μm. On the produced dried film, a square alkali-free glass substrate with a side of 10 cm, selected as a mask, was placed overlapping for 1 minute, and the non-adhesiveness of the dried film was evaluated according to the following criteria. The smaller the adhesion of the glass substrate, the higher the non-adhesiveness, indicating better handling.

A: Even if the dry film and the glass substrate overlap, there is no adhesion, and after separating the glass substrate, no contamination from the barrier material occurs on the glass substrate.

B: When the dry film and the glass substrate overlapped, they became sticky, but the glass substrate could be easily removed. There was some contamination on the glass substrate from the barrier material.

C: When the dry film and the glass substrate overlapped, they adhered and stuck together. The glass substrate could not be easily removed. After removing the glass substrate, contamination from the barrier material occurred on the glass substrate.

<Crack resistance>

The partition forming resin compositions used in each Example and Comparative Example were spin-coated so that the film thicknesses after heating were 10 μm, 15 μm, 20 μm, and 25 μm, respectively. Regarding the subsequent processes, except that the entire film was exposed without a photomask during exposure, the film was processed under the same conditions as each Example and Comparative Example to produce a solid film on a glass substrate. Using the obtained solid film as a partition model of the partition-equipped substrate obtained in each Example and Comparative Example, the glass substrate having the solid film was visually observed to evaluate the presence or absence of cracks in the solid film. When even one crack was confirmed, it was judged that there was no crack resistance at that film thickness. For example, when there were no cracks at a film thickness of 15 μm and cracks at a film thickness of 20 μm, the crack-resistant film thickness was determined to be “≥15 μm.” In addition, the crack-resistant film thickness when there were no cracks even at 25 ㎛ was determined as “≥25 ㎛”, and the crack-resistant film thickness when there were cracks at 10 ㎛ was determined as “<10 ㎛”, respectively, to determine crack resistance.

<Wrinkle resistance>

The partition forming resin compositions used in each Example and Comparative Example were spin-coated so that the film thicknesses after heating were 10 μm, 15 μm, 20 μm, and 25 μm, respectively. Regarding the subsequent processes, except that the entire film was exposed without a photomask during exposure, the film was processed under the same conditions as each Example and Comparative Example to produce a solid film on a glass substrate. Using the obtained solid film as a barrier model for the barrier rib-equipped substrates obtained in each Example and Comparative Example, the glass substrate with the solid film was visually observed to evaluate the presence or absence of wrinkles in the solid film. When wrinkles were confirmed, it was judged that there was no wrinkle resistance at that film thickness. For example, when there were no wrinkles at a film thickness of 15 μm, but there were wrinkles at a film thickness of 20 μm, the wrinkle resistance was determined to be “≥15 μm.” In addition, the wrinkle resistance when there were no wrinkles at 25 ㎛ was determined as “≥25 ㎛”, and the wrinkle resistance when there were wrinkles at 10 ㎛ was determined as “<10 ㎛”, respectively, and were determined as wrinkle resistance.

<1% weight loss temperature>

The partition forming resin composition used in each Example and Comparative Example was spin-coated on a Si wafer so that the film thickness after heating was 10 μm. Regarding the subsequent processes, except that the entire film was exposed without a photomask during exposure, the film was processed under the same conditions as each Example and Comparative Example to produce a solid film on a glass substrate. Next, a portion of the solid film produced on the Si wafer was carefully scraped off to avoid mixing impurities, and about 100 mg was placed in an aluminum cell. Using a thermogravimetric measuring device (TGA-50, manufactured by Shimadzu Seisakusho Co., Ltd.), the weight was measured by maintaining the temperature at 150°C for 30 minutes in a nitrogen atmosphere and then heating it to 400°C at a temperature increase rate of 10°C/min. . The temperature at which the weight decreased by 1% by weight from the start of temperature increase was designated as the 1% weight reduction temperature. The higher the 1% weight loss temperature, the higher the heat resistance.

<Resolution>

Using a spin coater (brand name 1H-360S, manufactured by Mikasa Co., Ltd.), the resin composition for partitions used in each Example and Comparative Example was spread on a square alkali-free glass substrate with a side of 10 cm, and the film thickness after heating was measured. It was spin-coated to a thickness of 10 μm and dried at a temperature of 100° C. for 3 minutes using a hot plate (trade name: SCW-636, manufactured by Dainippon Screen Seizo Co., Ltd.) to produce a dried film with a film thickness of 10 μm.

The produced dry film was aligned at 100㎛, 80㎛, 60㎛, 50㎛, 40㎛, 30㎛, 50㎛, 40㎛, 50㎛, 50㎛, 40㎛, 50㎛, 50㎛, 80㎛, 60㎛, 50㎛, 80㎛, 60㎛, 50㎛, 40㎛, 100㎛, 80㎛, 100㎛, 100㎛, 80㎛, 60㎛, 100㎛, 80㎛, 100㎛, 50㎛, 40㎛, 60㎛, 100㎛, 80㎛, 50㎛, 100㎛, 80㎛, 60㎛, 50㎛, 40㎛, etc. Exposure was performed at an exposure dose of 300 mJ/cm2 (i line) and a gap of 100 μm through a mask having a line and space pattern with a width of 20 μm. Afterwards, using an automatic developing device (“AD-2000 (brand name)” manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 100 seconds using a 0.045% by weight potassium hydroxide aqueous solution, followed by 30 seconds using water. rinsed.

Using a microscope adjusted to a magnification of 100x, the pattern after development was observed enlarged, and the narrowest line width among the patterns in which no residue was observed in the unexposed area was set as the resolution. However, if there was residue even in the unexposed area near the 100㎛ wide pattern, it was set as “>100㎛”.

<Reflectance>

The partition-forming resin composition used in each Example and Comparative Example was processed under the same conditions as each Example and Comparative Example, except that the entire resin composition was exposed without a photomask during exposure, and was placed on a glass substrate with a height of 10 μm. A solid film was produced. Using the obtained solid film as a barrier model for the barrier rib-equipped substrate obtained in each of the examples and comparative examples, a solid film was measured using a spectrophotometer (product name: CM-2600d, manufactured by Konica Minolta Co., Ltd.) on a glass substrate with a solid film. The reflectance at a wavelength of 350 to 750 nm was measured in SCI mode from the film side, and the value of 550 nm was compared as a representative value. However, when cracks or wrinkles occurred in the solid film, the reflectance was not measured because accurate values could not be obtained due to cracks, etc.

<OD value>

As a partition model of the partition-equipped substrate obtained in each Example and Comparative Example, a solid film with a height of 10 μm was produced on a glass substrate in the same manner as the evaluation of reflectance. For the obtained glass substrate with a solid film, the intensity of incident light and transmitted light was measured using an optical densitometer (U-4100 manufactured by Hitachi High-Tech Science), and the OD value at a wavelength of 300 to 800 nm was calculated using the above-mentioned equation (1). And the value of 450 nm was compared as a representative value.

Additionally, for Example 70, a solid film was similarly produced on a glass substrate as a model of the light-shielding partition A-2. For the obtained glass substrate with a solid film, the intensity of incident light and transmitted light was measured using an optical densitometer (U-4100 manufactured by Hitachi High-Tech Science) and calculated using the above-mentioned formula (1).

<Taper angle>

In each Example and Comparative Example, an arbitrary cross section of the substrate with a partition before pixel formation was examined using an optical microscope (FE-SEM (S-4800); manufactured by Hitachi Seisakusho Co., Ltd.) at an acceleration voltage of 3.0 kV. By observation, the taper angle was measured.

<Line width thickness>

As a base substrate, a square alkali-free glass substrate (manufactured by AGC Techno Glass Co., Ltd., thickness 0.7 mm) with a side of 10 cm was used, and the resin composition for partitions used in each Example and Comparative Example was spin-coated thereon, and then hot coated. A plate (trade name: SCW-636, manufactured by Dainippon Screen Seizo Co., Ltd.) was used and dried at a temperature of 100°C for 3 minutes to produce a dried film. The produced dry film was aligned with a photomask (design: partition width 20㎛, aperture short side 80㎛, aperture long) using a parallel light mask aligner (product name PLA-501F, manufactured by Canon Co., Ltd.) using an ultra-high pressure mercury lamp as a light source. Edges of 280 μm) were exposed at exposure doses of 100 mJ/cm 2 and 500 mJ/cm 2 (g, h, and i lines were irradiated. Exposure doses were converted to i line values). After that, using an automatic developing device (“AD-2000 (brand name)” manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 100 seconds using a 0.045% by weight potassium hydroxide aqueous solution, followed by 30 seconds using water. rinsed. Additionally, using an oven (trade name: IHPS-222, manufactured by Espec Co., Ltd.), it was heated in air at a temperature of 230°C for 30 minutes to form partition walls with a height of 10 μm formed in a lattice pattern on the glass substrate.

Using a microscope adjusted to a magnification of 100 times, the barrier pattern was observed enlarged, the barrier line width was measured, and the line widths at exposure doses of 100 mJ/cm 2 and 500 mJ/cm 2 were compared. The thickening of the line width was evaluated according to the following criteria. Additionally, evaluation was not conducted in cases where the pattern peeled off during development or when measurement was difficult because residues were generated.

A: The line width of the partition processed with an exposure dose of 500 mJ/cm2 is within +5.0㎛ compared to the line width of the partition processed with an exposure dose of 100 mJ/cm2.

B: The line width of the partition processed with an exposure dose of 500 mJ/cm2 is +5.0㎛ to +10㎛ compared to the line width of the partition processed with an exposure dose of 100 mJ/cm2.

C: The line width of the partition processed with an exposure dose of 500 mJ/cm2 is more than +10㎛ compared to the line width of the partition processed with an exposure dose of 100 mJ/cm2.

<Surface contact angle>

As a model of the partition in the partition-equipped substrate obtained in each Example and Comparative Example, a solid film with a height of 10 μm was produced on a glass substrate in the same manner as the evaluation of the reflectance. For the surface of the obtained solid film, DM-700 manufactured by Kyowa Kaimen Chemical Co., Ltd., microsyringe: Teflon (registered trademark) coat needle for contact angle meter 22G manufactured by Kyowa Gaimen Chemical Co., Ltd., 25 The surface contact angle was measured in air at ℃ in accordance with the wettability test method for the substrate glass surface specified in JIS R3257 (date of establishment = 1999/04/20). However, propylene glycol monomethyl ether acetate was used instead of water, and the contact angle between the surface of the solid film and propylene glycol monomethyl ether acetate was measured.

<Inkjet applicability>

In the substrate with partitions before forming pixels obtained in each of the examples and comparative examples, an inkjet coating device (InkjetLabo, manufactured by Cluster Technology Co., Ltd.) was applied using PGMEA as ink for the pixel portion surrounded by the grid-like partitions. Inkjet coating was performed using . 160 pL of PGMEA was applied per grid pattern, the presence or absence of nodules (a phenomenon in which ink passes over the partition wall and mixes into adjacent pixel parts) was observed, and inkjet applicability was evaluated according to the following criteria. The smaller the nodules, the higher the liquid repellency, indicating excellent inkjet applicability.

A: The ink did not overflow within the pixel.

B: Ink begins to overflow from within the pixel onto the upper surface of the partition in some areas.

C: Ink begins to overflow from within the pixel to the upper surface of the partition on the entire surface.

<height>

For the substrates with partitions obtained in each of the examples and comparative examples, the height of the structure before and after forming the pixel B is measured using a Surfcom stylus film thickness measuring device, and the difference is calculated to determine the pixel B. The height was measured. For Examples 72 to 74, the film thickness of the low refractive index layer (C), for Examples 71, 74 to 75, and 77, the film thickness of the color filter, and for Examples 70 and 74, the thickness of the light-shielding partition. (height) and the thickness (height) of the yellow organic protective layer were measured similarly for Examples 77 and 78. Additionally, for Examples 73 to 76, a cross section perpendicular to the base substrate was exposed using a polishing device such as a cross section polisher, and the cross section was observed enlarged with a scanning electron microscope or transmission electron microscope, respectively. The height of the protective layer was measured.

<Luminance>

Using an area light emitting device equipped with a commercially available LED backlight (peak wavelength 465 nm) as a light source, the substrates with partitions obtained in each Example and Comparative Example were installed so that the pixel portion was on the light source side. A current of 30 mA is passed through this area light emitting device to light up the LED element, and the luminance (unit: cd/m2) based on the CIE1931 standard is measured using a spectroradiometer (CS-1000, manufactured by Konica Minolta). It was set as the initial luminance. However, the luminance was evaluated using relative values using the initial luminance of Example 67 as 100, which is the standard. Additionally, after the LED element was turned on for 48 hours at room temperature (23°C), the luminance was similarly measured to evaluate changes in luminance over time. However, the luminance was evaluated using relative values using the initial luminance of Example 67 as 100, which is the standard.

<Color characteristics>

On a commercially available white reflector, the substrates with partitions obtained in each Example and Comparative Example were installed so that the pixels were arranged on the white reflector side. Using a spectroscopic colorimeter (CM-2600d, manufactured by Konica Minolta, measurement diameter ϕ8 mm), light was irradiated from the base substrate side of the substrate with a partition, and the spectrum containing regular reflected light was measured.

The color gamut defined by BT.2020, a color standard that can almost reproduce the colors of the natural world, defines red, green, and blue as the three primary colors on the spectral locus shown in the chromaticity diagram, and the wavelengths of red, green, and blue are 630 nm and 532 nm, respectively. and 467 nm. From the reflectance (R) of the obtained reflection spectrum at three wavelengths of 470 nm, 530 nm, and 630 nm, the emission color of the pixel was evaluated according to the following criteria.

A: R ₅₃₀ /(R ₆₃₀ +R ₅₃₀ +R ₄₇₀ )≥0.55

B: R ₅₃₀ /(R ₆₃₀ +R ₅₃₀ +R ₄₇₀ )<0.55

<Display characteristics>

The display characteristics of the display device produced by combining the organic EL element and the barrier-walled substrate obtained in each Example and Comparative Example were evaluated based on the following criteria.

A: This is a display device with very rich rust marks and is clear and has excellent contrast.

B: Although the colors appear slightly unnatural, it is a display device with no problems.

<Color Mix>

In the barrier rib-equipped substrates obtained in each Example and Comparative Example before pixel formation, the color conversion light-emitting material composition (CL-2) is applied to a portion of the pixel portion surrounded by the grid-like barrier ribs using an inkjet method. and dried at 100°C for 30 minutes to form a pixel with a thickness of 5.0㎛. Thereafter, among the pixel portions surrounded by grid-like partitions, the color conversion light emitting material composition (CL-3) is applied to an area adjacent to the area where the color conversion light emitting material composition (CL-2) has been applied, using an inkjet method. , and dried at 100°C for 30 minutes to form a pixel with a thickness of 5.0 μm.

On the other hand, a blue organic EL cell having the same width as the pixel portion surrounded by the grid-like barrier ribs was fabricated, the barrier-equipped substrate described above and the blue organic EL cell were opposed to each other and bonded with a sealant to produce a display device with the configuration shown in Fig. 15. got it Among the blue organic EL cells 11 in FIG. 15, only the blue organic EL cell bonded immediately below the pixel 3 (CL-2) formed of the color conversion light-emitting material composition (CL-2) is turned on, For the pixel (3) (CL-3) portion formed of the color conversion light-emitting material composition (CL-3), the absorption intensity A at a wavelength of 630 nm was measured using a microspectrophotometer LVmicro-V (manufactured by Lambda Vision Co., Ltd.) (630 nm) was measured. The smaller the value of light absorption intensity A (630 nm), the more difficult it is to cause color mixing. Color mixing was determined based on the following criteria.

A: A(630nm)<0.01

B: 0.01≤A(630nm)≤0.5

C: 0.5<A (630nm)

The evaluation results of each Example and Comparative Example are shown in Tables 6 and 7.

[Table 6]

[Table 7]

1: not substrate
2: Bulkhead
3: Pixel
3 (CL-2): Pixel formed from color conversion light-emitting material composition (CL-2)
3 (CL-3): Pixel formed from color conversion light-emitting material composition (CL-3)
4: Light-shading bulkhead
5: Color filter
6: Low refractive index layer
7: Inorganic protective layer
8: Inorganic protection layer II
9: Inorganic protective layer III and/or yellow organic protective layer
10: Inorganic protective layer IV and/or yellow organic protective layer
11: Light emitting light source selected from organic EL cells, mini LED cells and micro LED cells
12: Blue organic EL cell
H: Thickness of bulkhead
L: Width of bulkhead
θ: Taper angle

Claims (16)

(i) a photo radical generator,
(ii) hindered phenol compounds and/or hindered amine compounds,
(iii) a polysiloxane containing a structure having an aromatic ring represented by the following general formula (1) or (2) and a structure having a radical photopolymerizable group represented by the following general formula (3),
(iv) a (meth)acrylic polymer comprising a structure having an aromatic ring represented by the following general formula (4) and a structure having a radical photopolymerizable group represented by the following general formula (5) and/or the following general formula ( 6) Alternatively, it is a resin composition containing a cardo-based polymer having a structure represented by the following general formula (7) and a radical photopolymerizable group, wherein the ratio of the weight of the polysiloxane to the total weight of the (meth)acrylic polymer and the cardo-based polymer is 30. /70 to 70/30, a resin composition.

(In General Formulas (1) to (7), R ¹ and R ² each independently represent hydrogen, a hydroxy group, a group having a siloxane bond, or a monovalent organic group having 1 to 30 carbon atoms. R ³ and R ⁴ are each independently R ⁵ to R ⁷ each independently represent hydrogen, a hydroxy group, or a monovalent organic group having 1 to 30 carbon atoms, a monovalent organic group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an adjacent R ⁵ to 30. R ⁸ represents hydrogen, a monovalent organic group having ₁ to ₃₀ carbon atoms _, or ^an aryl group having 6 to 20 carbon atoms _. Y ₁ and Y ₂ each independently represent an organic group having a radical photopolymerizable group, and p, q, and r are each independently an integer of 0 to 2. a, b, c, d, e, f and g each independently represent an integer of 1 or more, and when a to e are 2 or more, a plurality of R ¹ , R ² , R ³ , R ⁴ . R ⁵ , R ⁶ , R ⁷ , R ⁸ , X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ and Y ₂ may be the same or different.) The resin composition according to claim 1, wherein the hindered phenol compound is a hindered phenol compound having two or more hindered phenol groups in one molecule. The resin composition according to claim 1 or 2, wherein the hindered amine compound is a piperidine compound. The resin composition according to claim 1 or 2, wherein the hindered amine compound is a piperidine compound having a photopolymerizable group. The method according to claim 1 or 2, wherein the weight average molecular weight of the polysiloxane is 5,000 to 300,000, and the repeating unit represented by the general formula (1) or (2) is 30 to 70 moles among all repeating units of the polysiloxane. A resin composition containing 15 to 70 mol% of a repeating unit represented by the general formula (3). The resin composition according to claim 1 or 2, wherein the (meth)acrylic polymer and/or cardo-based polymer has a glass transition temperature of 60°C or higher. The method according to claim 1 or 2, further comprising at least one of a white pigment, a light-shielding pigment, and an organometallic compound containing at least one metal selected from the group consisting of silver, gold, platinum, and palladium. Resin composition. The resin composition according to claim 1 or 2, which contains an oxime ester compound and a phosphine oxide compound as the photo radical generator. The resin composition according to claim 1 or 2, further comprising a liquid-repellent compound having a photopolymerizable group. A light-shielding film formed by curing the resin composition according to claim 1 or 2. A substrate with barrier ribs having barrier ribs patterned (A-1) with the resin composition according to claim 1 or 2 on a base substrate, wherein the barrier ribs have a reflectance of 10% to 60% per 10 μm of thickness at a wavelength of 550 nm. , a substrate with a partition having an OD value of 1.0 to 3.0 per 10 μm of thickness at a wavelength of 450 nm. The method according to claim 11, wherein the (A-1) patterned partition contains a resin, a white pigment, and a light-shielding pigment, and the light-shielding pigment is one of titanium nitride, zirconium nitride, carbon black, a red pigment, and a blue pigment. A mixed pigment with a weight ratio of 20/80 to 80/20 and at least one metal oxide selected from the group consisting of palladium oxide, platinum oxide, gold oxide, silver oxide, palladium, platinum, gold, and silver, or particles containing a metal. Pigment, substrate with partition walls. The substrate with a barrier rib according to claim 11, wherein the (A-1) patterned barrier rib further contains a hindered amine compound. The substrate with a partition according to claim 11, further comprising a patterned light-shielding partition between the base substrate and the patterned partition (A-1) and (A-2) having an OD value of 0.5 or more per 1.0 μm of thickness. 12. The substrate with a barrier rib according to claim 11, which has a pixel layer further containing (B) color conversion light emitting material arranged and separated by the (A-1) patterned barrier rib. A display device comprising the barrier rib-equipped substrate according to claim 11 and a light emission source selected from a liquid crystal cell, an organic EL cell, a mini LED cell, and a micro LED cell.