JP2021161401A - Resin composition, light blocking film, method for producing light blocking film, and substrate with partition - Google Patents

Abstract

To provide a resin composition useful for forming a partition on a substrate of a display device, the resin composition capable of forming a thick partition having both of the tactlessness of the film after prebaking and heat resistance after curing.SOLUTION: A resin composition has a photoradical generator, a polysiloxane having specific two structures, and a (meth)acryl polymer having specific two structures, the weight ratio between the polysiloxane and the (meth)acryl polymer of 30/70-70/30.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin composition, a light-shielding film formed from the resin composition, a method for producing a light-shielding film, and a substrate with a partition wall having a patterned partition wall.

In recent years, as a color display device having high light utilization efficiency, a color display device including a light source, a wavelength conversion unit composed of a wavelength conversion phosphor, and a polarization separation means and a polarization conversion means has been proposed (for example, a patent). Reference 1). For example, a wavelength having a blue light source, a liquid crystal element, a phosphor excited by blue light to emit red fluorescence, a phosphor excited by blue light to emit green fluorescence, and a light scattering layer that scatters blue light. A color display device including a conversion unit has been proposed (see, for example, Patent Document 2).

However, a color filter containing a color conversion phosphor as described in Patent Documents 1 and 2 has low light extraction efficiency and insufficient brightness because fluorescence is generated in all directions. In particular, in high-definition display devices such as 4K and 8K, since the pixel size becomes small, the problem of luminance becomes remarkable, so that higher luminance is required.

In order to improve the brightness of the display device, it is effective to separate the color conversion phosphors with a highly reflective partition wall. Further, in order to prevent light color mixing between adjacent pixels, it is necessary to improve the light blocking effect of the partition wall. Therefore, there is a demand for a partition material that has both high reflectivity and high light-shielding property.

Japanese Unexamined Patent Publication No. 2000-131683 JP-A-2009-244383 Japanese Unexamined Patent Publication No. 2000-347394 Japanese Unexamined Patent Publication No. 2006-259421 WO2020 / 000869

In order to form a partition wall having both high reflectance and high light-shielding property, the inventors first used a material in which a black pigment was added to a white partition wall material using a titanium oxide white pigment exhibiting high reflectance. I examined how to do it. However, in this method, it has been clarified that the entire exposure light is absorbed by the white pigment and the black pigment, the light does not reach the bottom of the film at the time of exposure, and the pattern processability is poor.

Therefore, the inventors have devised a design that transmits exposure light during the process of pattern exposure after film formation, heats the exposed film at a temperature of 120 ° C. or higher and 250 ° C. or lower, and then increases the light-shielding property. Further, 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 is used. This was achieved (see Patent Document 5). In particular, it has been found that when polysiloxane is used as the resin, a partition wall having high heat resistance can be formed.

However, this technique has a problem that when polysiloxane is used as the resin, the film after prebaking has a tack property and it is difficult to handle the substrate during processing. On the other hand, when a (meth) acrylic polymer and / or a cardo-based polymer is used as the resin, the tackiness after prebaking is improved, but when forming a partition wall of a thick film having a height of 10 μm or more, the upper part and the bottom of the film are formed. It became clear that there was a difference in the degree of curing, and that wrinkles were generated due to the difference in stress after curing. Furthermore, it has become clear that the partition walls formed by using the (meth) acrylic polymer and / or the cardo-based polymer have lower heat resistance and weather resistance than those using the siloxane polymer.

Therefore, an object of the present invention is to provide a resin composition capable of forming a thick film partition wall having both tackless property of a film after prebaking and heat resistance after curing.

As a result of diligent research, the inventors of the present application include a photoradical generator, a polysiloxane containing a specific structure, a (meth) acrylic polymer containing a specific structure, and / or a cardo-based polymer containing a specific structure. By forming a partition wall of the display device with a resin composition in which the weight ratio of the polysiloxane to the (meth) acrylic polymer and / or the cardo-based polymer is 30/70 to 70/30. We have found that it is possible to form a thick-film partition wall that has both tacklessness of the film after prebaking and heat resistance after curing, and completed the present invention.

That is, the present invention provides the following.
(1)
(i) Photoradical generator and
(ii) A polysiloxane containing a structure having an aromatic ring represented by the following general formula (1) or (2) and a structure having a photoradical polymerizable group represented by the following general formula (3).
(iii) A (meth) acrylic polymer containing a structure having an aromatic ring represented by the following general formula (4) and a structure having a photoradical polymerizable group represented by the following general formula (5) and / or the following general. A cardo-based polymer having a structure represented by the formula (6) or the following general formula (7) and a photoradical polymerizable group, and
A resin composition containing the above, wherein the weight ratio of the polysiloxane to the (meth) acrylic polymer and / or the cardo-based polymer is 30/70 to 70/30.

(In the general formula (1) ~ (7), ^{R 1} and ^{R 2} each independently represents hydrogen, hydroxy group, a monovalent organic group group or 1 to 30 carbon atoms having a siloxane bond .R ³ and R ⁴ independently represents hydrogen, a hydroxy group, or a monovalent organic group having 1 to 30 carbon atoms. R ^{5 to} R ⁷ independently represent hydrogen, a monovalent organic group having 1 to 30 carbon atoms, and 6 carbon atoms, respectively. 20 aryl group or adjacent ^R 5 .R ⁸ that to R ⁷ ring formed by each other represents a group the aromatic ring is hydrogen, a monovalent organic group having 1 to 30 carbon atoms or 6 to 20 carbon atoms, X ₁ , X ₂ , X ₃ and X ₄ each independently represent an organic group having an aromatic ring. Y ₁ and Y ₂ each independently represent an organic group having a photoradical polymerizable group. .P, q, r are each independently an integer of 0 to 2, s represents an integer of 1 to 2. a, b, c, d, e, f and g are each independently an integer of 1 or more. 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, respectively.)
(2)
The weight average molecular weight of the polysiloxane is 5,000 to 300,000, and among all the repeating units of the polysiloxane, the repeating unit represented by the general formula (1) or (2) is 30 to 70 mol%. The resin composition according to claim 1, which contains 15 to 70 mol% of the repeating unit represented by the general formula (3).
(3) The resin composition according to (1) or (2), wherein the (meth) acrylic polymer and / or the cardo-based polymer has a glass transition temperature of 60 ° C. or higher.
(4) The resin composition according to any one of (1) to (3), which further contains a white pigment.
(5) In any one of (1) to (4), which further contains an organometallic compound containing a black pigment and / or at least one metal selected from the group consisting of silver, gold, platinum and palladium. The resin composition described.
(6) The resin composition according to any one of (1) to (5), which contains an oxime ester compound and a phosphine oxide compound as the photoradical generator.
(7) The resin composition according to any one of (1) to (6), which further contains a liquid-repellent compound having a photoradical polymerizable group.
(8) A light-shielding film obtained by curing the resin composition according to any one of (1) to (7).
(9) A substrate with a partition wall having a partition wall in which the pattern (A-1) is formed by the resin composition according to any one of (1) to (7) on the base substrate, and the thickness at a wavelength of 550 nm. A substrate with a partition wall having a reflectance of 10% to 60% per 10 μm and an OD value of 1.0 to 3.0 per 10 μm thickness.
(10) The partition wall formed with the pattern (A-1) contains a resin, a white pigment, a black pigment and / or a yellow pigment, and the black pigment is titanium nitride, zirconium nitride, carbon black, or red. A mixed pigment having a weight ratio of 20/80 to 80/20 of a pigment and a blue pigment, and at least one metal selected from the group consisting of palladium oxide, platinum oxide, gold oxide, silver oxide, palladium, platinum, gold, and silver. The substrate with partition according to (9), which is a pigment selected from particles composed of oxides or metals.
(11) The (A-1) patterned partition wall further contains a liquid-repellent compound, and the content of the liquid-repellent compound in the (A-1) patterned partition wall is 0.01% by weight to 10% by weight. The bulkhead substrate according to (9) or (10), which is% by weight.
(12) The partition wall according to any one of (9) to (11), wherein the partition wall formed with the pattern (A-1) has a surface contact angle of 10 ° to 70 ° with respect to propylene glycol monomethyl ether acetate. substrate.
(13) Patterned light-shielding between the base substrate and the (A-1) patterned partition wall, and (A-2) the OD value per 1.0 μm thickness is 0.5 or more. The substrate with a partition wall according to any one of (9) to (12), which has a partition wall.
(14) The item according to any one of (9) to (13), which has a pixel layer further containing (B) a color-converting light-emitting material arranged separated by a partition wall formed with the (A-1) pattern. Substrate with partition wall.
(15) The substrate with a partition wall according to (14), wherein the color conversion light emitting material contains a phosphor selected from quantum dots and a pyrromethene derivative.
(16) The substrate with a partition wall according to (14) or (15), further having a color filter having a thickness of 1 to 5 μm between the base substrate and the pixel layer containing the (B) color conversion light emitting material.
(17) A display device having the substrate with a partition wall according to any one of (9) to (16) and a light emitting light 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 partition pattern having excellent tackless properties after prebaking and heat resistance after curing.

It is sectional drawing which shows one aspect of the substrate with partition wall of this invention which has the partition wall which formed the pattern. It is sectional drawing which shows one aspect of the substrate with a partition wall of this invention which has the partition wall which formed the pattern and the pixel which contains the color conversion light emitting material. It is sectional drawing which shows one aspect of the substrate with a partition wall of this invention which has a partition wall which formed a pattern, a color conversion light emitting material, and a light-shielding partition wall. It is sectional drawing which shows one aspect of the substrate with a partition wall of this invention which has a partition wall formed with a pattern, a color conversion light emitting material, and a color filter. It is sectional drawing which shows one aspect of the substrate with a partition wall of this invention which has a partition wall which formed a pattern, a color conversion light emitting material, a light-shielding partition wall, and a color filter. It is sectional drawing which shows one aspect of the substrate with a partition wall of this invention which has a partition wall formed with a pattern, a color conversion light emitting material, and a low refractive index layer. It is sectional drawing which shows one aspect of the substrate with the partition wall of this invention which has the partition wall which formed the pattern, the color conversion light emitting material, the low refractive index layer and the inorganic protective layer I. It is sectional drawing which shows one aspect of the substrate with the partition wall of this invention which has the partition wall which formed the pattern, the color conversion light emitting material, the low refractive index layer and the inorganic protective layer I. It is sectional drawing which shows one aspect of the substrate with a partition wall of this invention which has a partition | partition which formed a pattern, a color conversion light emitting material, a light-shielding partition wall, a color filter, a low refractive index layer, and an inorganic protective layer I. It is sectional drawing which shows one aspect of the substrate with the partition wall of this invention which has the partition wall which formed the pattern, the color conversion light emitting material, the low refractive index layer and the inorganic protective layer II. FIG. 5 is a cross-sectional view showing an aspect of a substrate with a partition wall of the present invention having a patterned partition wall, a color conversion light emitting material, a color filter, and an inorganic protective layer III and / or a yellow organic protective layer. FIG. 5 is a cross-sectional view showing an aspect of a substrate with a partition wall of the present invention having a patterned partition wall, a color conversion light emitting material, an inorganic protective layer IV and / or a yellow organic protective layer. FIG. 5 is a cross-sectional view showing an aspect of a substrate with a partition wall of the present invention, which has pixels containing a pattern-formed partition wall and a light emitting light source selected from an organic EL cell, a mini LED cell, and a micro LED cell. FIG. 6 is a cross-sectional view showing an aspect of a substrate with a partition wall of the present invention having pixels containing a patterned partition wall, a color conversion light emitting material, and a light emitting light source selected from an organic EL cell, a mini LED cell, and a micro LED cell. be. It is sectional drawing which shows the structure of the display device used for the color mixing evaluation in an Example.

Hereinafter, a resin composition according to the present invention, a light-shielding film formed from the resin composition, a method for producing a light-shielding film, and a preferred embodiment of a substrate with a partition wall will be specifically described. It is not limited to the above-mentioned form, and can be variously modified and implemented according to the purpose and application.

The resin composition of the present invention can be suitably used as a material for forming a partition wall that separates a color conversion phosphor, a light emitting light source selected from an organic EL cell, a mini LED cell, a micro LED cell, and the like.

The resin composition of the present invention contains a photoradical generator, a polysiloxane containing a specific structure, a (meth) acrylic polymer containing a specific structure, and / or a cardo-based polymer containing a specific structure. The weight ratio of the polysiloxane to the (meth) acrylic polymer and / or the cardo-based polymer is preferably 30/70 to 70/30.

When the resin composition of the present invention is used for pattern formation of the partition wall (A-1) described later, it preferably has negative photosensitive property. In order to impart negative photosensitivity, the resin composition of the present invention preferably contains a photoradical generator. By containing the photoradical generator, a high-definition patterned partition wall can be formed.

The photoradical generator may be any one that decomposes and / or reacts with light (including ultraviolet rays and electron beams) to generate radicals.

For example, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl) Α-Aminoalkylphenone compounds such as −phenyl) -butane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; 2,4,6-trimethylbenzoylphenyl Phenyloxide compounds such as phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) -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-diphenylpropanthrion-2- (O-ethoxycarbonyl) oxime, Etanone-1- [9-ethyl-6- (2-methyl) Oxyme ester compounds such as benzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime); 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) ) -2-Hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone and other α-hydroxyketone compounds Benzophenone, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl- Benzophenone compounds such as 4'-methyl-diphenylsulfide, alkylated benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; 2,2-diethoxyacetophenone, 2,3-di Examples thereof include acetophenone compounds such as ethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone and 4-azidobenzalacetophenone. Two or more of these may be contained.

Among these, in order to form a thick film partition wall, an oxime ester compound that is resistant to oxygen damage and is effective for surface curability, and phosphine that is effective for bottom curability because it absorbs longer wavelength light and generates radicals. It preferably contains an oxide compound.

The content of the photoradical generator in the resin composition of the present invention is preferably 0.01% by weight or more, more preferably 1% by weight or more, based on the solid content, from the viewpoint of effectively advancing radical curing. On the other hand, from the viewpoint of suppressing elution of the residual photoradical generator, the content of the photoradical generator is preferably 20% by weight or less, more preferably 10% by weight or less in the solid content.

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

Polysiloxane is a hydrolyzed / dehydrated condensate of organosilane. The polysiloxane includes a structure having an aromatic ring represented by the following general formula (1) or (2) and a structure having a photoradical polymerizable group represented by the following general formula (3). Further, other repeating units may be included.

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

The ^{"group having a siloxane bond" represented by R 1} or R ² refers to a "-Si-O-Si-" bond formed by condensation of silanol groups. The functional group bonded to the Si atom of the bond destination 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 having 1 to 6 carbon atoms (including a linear and branched alkyl group) is preferable. .. Preferred specific examples thereof include a methyl group, an ethyl group, an n-propyl group and an 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 of these include a phenyl group, a benzyl group, a styryl group, a naphthyl group and a biphenyl group.

As "radical photopolymerizable group" represented by Y _1, preferably ethylenically unsaturated groups, more preferably a functional group containing a methacryl and / or acryl groups. Preferred specific examples thereof include 3-methacryloxypropyl group and 3-acryloxypropyl group.

The a, b, and c each independently represent an integer of 1 or more, where a is preferably 10 to 60, more preferably 20 to 55, b is preferably 10 to 60, and even 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 the general formula (1) or (2), the Tg of the polysiloxane can be improved, and the tackless property after prebaking can be improved. Can be improved.

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

Among the alkoxysilane compounds containing an organic group having an aromatic ring represented by the general formula (1) or (2), a bifunctional alkoxysilane containing two organic groups having an aromatic ring represented by the general formula (2). It preferably contains a compound-derived repeating unit. By containing the repeating unit derived from the bifunctional alkoxysilane compound represented by the general formula (2), excessive thermal polymerization (condensation) of the polysiloxane due to heating can be suppressed, and the crack resistance of the partition wall can be improved.

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

Further, the polysiloxane is a radical generated from a photoradical generator in the exposed portion by containing a repeating unit derived from an alkoxysilane compound containing an organic group having a photoradical polymerizable group represented by the general formula (3). The cross-linking reaction proceeds, and the degree of curing of the exposed portion can be increased.

It is preferable that 10 to 80 mol% of the repeating unit represented by the general formula (3) is contained in all the repeating units in the polysiloxane. By containing 10 mol% or more of the repeating unit represented by the general formula (3), radical cross-linking between polysiloxanes in the film can be efficiently promoted, and the degree of curing of the film can be improved. The content of the repeating unit represented by the general formula (3) is more preferably 12 mol% or more, further preferably 15 mol% or more. On the other hand, by containing 80 mol% or less of the repeating unit represented by the general formula (3), excessive radical cross-linking of polysiloxane can be suppressed and crack resistance of the partition wall can be improved. The content of the repeating unit represented by the general formula (3) is more preferably 75 mol% or less, further preferably 70 mol% or less.

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

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

In the general formulas (8), (9) and (10), R ¹ , R ² , X ₁ , X ₂ , X ₃ and Y ₁ are the general formulas (1), (2) and (3), respectively. Represents the same group as R ¹ , R ² , X ₁ , X ₂ , X ₃ , and Y _{1 in.} R ⁹ may be the same or different, and represents a monovalent organic group having 1 to 20 carbon atoms, and an alkyl group having 1 to 6 carbon atoms is preferable. In the general formulas (8), (9) and (10), the ^{notation "-(OR 9} ) ₂ " means that two "-(OR ⁹ )" are bonded to the Si atom. ..

Examples of the alkoxysilane compound represented by the general formula (8) include phenyltrimethoxysilane, phenyltriethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, and 2-. Naftyltrimethoxysilane, triltrimethoxysilane, triltriethoxysilane, biphenyltrimethoxysilane, biphenyltriethoxysilane, 1-phenylethyltrimethoxysilane, 1-phenylethyltriethoxysilane, 2-phenylethyltrimethoxysilane, 2 -Phenylethyltriethoxysilane, 3-trimethoxysilylpropylphthalic anhydride, 3-triethoxysilylpropylphthalic anhydride, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane , Arocyclic ring-containing alkoxysilane compounds such as phenylpropyldimethoxysilane, phenylpropyldiethoxysilane, styryltrimethoxysilane, and styryltriethoxysilane. Two or more of these may be used.

Examples of the alkoxysilane compound represented by the general formula (9) include diphenyldimethoxysilane, diphenyldiethoxysilane, 1-naphthylphenyldimethoxysilane, 1-naphthylphenyldiethoxysilane, tolylphenyldimethoxysilane, and tolylphenyldiethoxy. Silane, biphenylphenyldimethoxysilane, biphenylphenyldiethoxysilane, 1-naphthyllyldimethoxysilane, 1-naphthyllyldiethoxysilane, 1-naphthylbiphenyldimethoxysilane, 1-naphthylbiphenyldiethoxysilane, trirubiphenyldimethoxysilane, trilbiphenyl Examples thereof include alkoxysilane compounds containing two aromatic rings such as diethoxysilane. Two or more of these may be used.

Among these, diphenyldimethoxysilane, diphenyldiethoxysilane, styryltrimethoxysilane, and styryltriethoxysilane are preferable from the viewpoint of crack resistance and tacklessness.

Examples of the alkoxysilane compound represented by the general formula (10) include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, γ-acryloylpropyltrimethoxysilane, and γ-acryloylpropyltri. Ethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, styrylmethyldimethoxysilane, styrylmethyldiethoxy Examples thereof include photoradical polymerizable group-containing alkoxysilane compounds such as silane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-acryloylpropylmethyldimethoxysilane, and γ-acryloylpropylmethyldiethoxysilane. Two or more of these may be used. Among these, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, and γ-methacryloylpropyltriethoxysilane are preferable from the viewpoint of photopolymerization reactivity.

Since the styryl group is a photoradical polymerizable group and also an aromatic group, the alkoxysilane compound represented by the general formula (10) contains a styryl group such as styryltrimethoxysilane or styryltriethoxysilane. When an alkoxysilane compound is used, the alkoxysilane compound represented by the general formula (8) or (9) may not be contained in addition to this. That is, when the polysiloxane contains a structure having a styryl group as the structure represented by the general formula (3), the structure represented by the general formula (1) or (2) may not be included.

Examples of other alkoxysilane compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, ethylmethyldimethoxysilane, ethylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. , 2- (3,4-epylcyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epylcyclohexyl) ethylethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, 3-dimethylmethoxysilylpropylsuccinic acid Bifunctional alkoxy compounds such as anhydride, 3-dimethylethoxysilylpropyl succinate anhydride, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane; Methyltrimethoxysilane, Methyltriethoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Propyltrimethoxysilane, Propyltriethoxysilane, Isobutyltrimethoxysilane, Isobutyltriethoxysilane, 3-Ixionpropyltrimethoxysilane, 3- Trifunctional alkoxysilane compounds such as isocyanatepropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-ethyl-3 -{[3- (Trimethoxysilyl) Propyl] Methyl} Oxetane, 3-Ethyl-3-{[3- (Triethoxysilyl) Propyl] Methyl} Oxetan and other epoxy or oxetane group-containing alkoxysilane compounds; 3- Trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 4-trimethoxysilylbutyric acid, 4-triethoxysilylbutyric acid, 5-trimethoxysilylvaleric acid, 5-triethoxysilylvaleric acid, 3-trimethoxysilylpropyl Succinic acid anhydride, 3-triethoxycysilylpropyl succinic acid anhydride, 3-trimethoxysilylp Carboxyl group-containing alkoxysilane compounds such as ropylcyclohexyldicarboxylic acid anhydride, 3-triethoxysilylpropylcyclohexyldicarboxylic acid anhydride, 3-trimethoxysilylpropylphthalic acid anhydride, and 3-triethoxysilylpropylphthalic acid anhydride; Fluorine group-containing alkoxysilane compounds such as trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, perfluoropentyltriethoxysilane; tetramethoxysilane, tetraethoxysilane, silicate 51 (tetraethoxysilane) Tetrafunctional alkoxysilane compounds such as oligomers); monofunctional alkoxysilane compounds such as trimethylmethoxysilane and triphenylmethoxysilane can be mentioned. Two or more of these may be used.

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

The weight average molecular weight (Mw) of the polysiloxane is preferably 1,000 or more, more preferably 2,000 or more, from the viewpoint of coatability. From the viewpoint of tacklessness, 5,000 or more is more preferable. On the other hand, from the viewpoint of developability, the Mw of the polysiloxane is preferably 500,000 or less, more preferably 300,000 or less. Here, the Mw of the polysiloxane in the present invention refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC). The measuring method is as described in Examples described later.

The polysiloxane can be obtained by hydrolyzing the above-mentioned organosilane compound and then dehydrating and condensing the hydrolyzate in the presence of a solvent or in the absence of a solvent.

Various conditions for hydrolysis can be set according to the physical characteristics suitable for the intended use in consideration of the reaction scale, the size and shape of the reaction vessel, and the like. Examples of various conditions include acid concentration, reaction temperature, reaction time, and the like.

For the hydrolysis reaction, acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitrate, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid and its anhydride, and 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 0.05% by weight with respect to 100 parts by weight of the total alkoxysilane compound used in the hydrolysis reaction from the viewpoint of allowing the hydrolysis to proceed more rapidly. More than parts are preferable, and 0.1 parts by weight or more is more preferable. On the other hand, from the viewpoint of appropriately adjusting the progress of the hydrolysis reaction, the amount of the acid catalyst added is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total alkoxysilane compound. Here, the total amount of the alkoxysilane compound means an amount including all of the alkoxysilane compound, its hydrolyzate and its condensate. The same shall apply hereinafter.

The hydrolysis reaction can be carried out in a solvent. The solvent can be appropriately selected in consideration of the stability, wettability, volatility and the like of the resin composition.

When a solvent is produced by the hydrolysis reaction, it is also possible to carry out the 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 the completion of the hydrolysis reaction. It is also possible to distill and remove all or part of the produced alcohol or the like by heating and / or under reduced pressure after hydrolysis, and then add a suitable solvent.

Examples of the method 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 lower than the boiling point of the solvent, and the heating time is preferably 1 to 100 hours. Further, in order to increase the degree of polymerization of the polysiloxane, reheating or addition of a base catalyst may be performed. Further, depending on the purpose, after the dehydration condensation reaction, an appropriate amount of the produced alcohol or the like may be distilled off and removed under heating and / or reduced pressure, and then a suitable solvent may be added.

The resin composition of the present invention further comprises a structure having an aromatic ring represented by the general formula (4) and a structure having a photoradical polymerizable group represented by (5) as a resin (meth) acrylic polymer. And / or contains a cardo-based polymer having a structure represented by the general formula (6) or the general formula (7) and a photoradical polymerizable group. (Meta) acrylic polymers and / or cardo-based polymers have a function of improving tacklessness after prebaking. The content of the (meth) acrylic polymer and / or the cardo-based polymer in the solid content of the resin composition is preferably 10% by weight or more, more preferably 15% by weight or more, from the viewpoint of improving the tacklessness after prebaking. .. On the other hand, from the viewpoint of improving the heat resistance of the partition wall, the content of the (meth) acrylic polymer and / or the cardo-based polymer in the solid content of the resin composition is preferably 55% by weight or less, more preferably 50% by weight or less. preferable.

As the (meth) acrylic polymer, a (meth) acrylic compound and / or a styrene compound radically polymerized is preferable. The catalyst for radical polymerization is not particularly limited, and azo compounds such as azobisisobutyronitrile and organic peroxides such as benzoyl peroxide are generally used.

The conditions of radical polymerization can be appropriately set. For example, a (meth) acrylic compound and / or a styrene compound and a radical polymerization catalyst are added in a solvent, and the inside of the reaction vessel is sufficiently degassed by bubbling or degassing under reduced pressure. After substitution with nitrogen, it is preferable to react at 60 to 110 ° C. for 30 to 300 minutes. Further, if necessary, a chain transfer agent such as a thiol compound may be used.

When the (meth) acrylic polymer has an ethylenically unsaturated bond, the (meth) acrylic polymer has, for example, a (meth) acrylic compound and / or a styrene compound radically polymerized and then has an ethylenically unsaturated double bond group. Those obtained by an addition reaction of a glycidyl compound are preferable. The catalyst used for the addition reaction of the glycidyl compound having an ethylenically unsaturated double-bonding group is not particularly limited, and known catalysts can be used. For example, dimethylaniline, 2,4,6-tris (dimethylaminomethyl) ) Amino catalysts such as phenol and dimethylbenzylamine, tin catalysts such as 2-ethylhexanoic acid tin (II) and dibutyltin laurate, titanium catalysts such as titanium 2-ethylhexanoate (IV), triphenylphosphine. Phosphorus-based catalysts such as, and chromium-based catalysts such as acetylacetonate chromium and chromium chloride are used. Among these, when used at the same time as 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 the general formulas (4) and (5), R ³ and R ⁴ 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. Represented. Y ₂ represents an organic group having a photoradical polymerizable group. D and e each independently represent an integer of 1 or more. When d and e are 2 or more, a plurality of R ³ , R ⁴ , X ₄ , And Y ₂ may be the same or different, respectively.)

As the ^{"monovalent organic group having 1 to 30 carbon atoms" represented by R 3} or R ⁴ , an alkyl group having 1 to 6 carbon atoms (including a linear and branched alkyl group) is preferable. Preferred specific examples thereof include a methyl group, an ethyl group, an n-propyl group and an isopropyl group.

X preferably aromatic hydrocarbon group having 6 to 15 carbon atoms as the "organic group having an aromatic ring" represented by _4. Preferred specific examples of these include a phenyl group, a benzyl group, a styryl group, a naphthyl group and a biphenyl group.

Preferably ethylenically unsaturated group as the "organic group having a radical photopolymerizable group" represented by Y _2, more preferably a functional group containing a methacryl and / or acryl groups. Preferred specific examples thereof include a functional group in which glycidyl methacrylate and / or glycidyl acrylate is added to a carboxylic acid group.

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

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

Among 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 the general formula (4), the tacklessness of the film after prebaking can be improved. The content of the repeating unit represented by the general formula (4) is more preferably 15 mol% or more, further preferably 20 mol% or more. On the other hand, the degree of hardening of the partition wall can be improved by containing 80 mol% or less of the repeating unit represented by the general formula (4). The content of the repeating unit represented by the general formula (4) is more preferably 75 mol% or less, further preferably 70 mol% or less.

Examples of the (meth) acrylic acid compound containing an organic group having an aromatic ring include phenyl (meth) acrylate, benzyl (meth) acrylate, trill (meth) acrylate, and naphthyl (meth) acrylate. Examples of the styrene compound include p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene and the like. Of these, styrene is preferable. By copolymerizing styrene, the heat resistance and moisture heat resistance of the obtained cured film are improved.

The repeating unit represented by the general formula (5) preferably has an ethylenically unsaturated group as a photoradical polymerizable group. By containing an ethylenically unsaturated group as the photoradical polymerizable group, the cross-linking reaction proceeds with the radicals generated from the photoradical generator in the exposed portion, and the degree of curing of the exposed portion can be enhanced.

Among 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 (5). By containing 10 mol% or more of the repeating unit represented by the general formula (5), radical cross-linking between the resins in the film can be efficiently promoted, and the degree of curing of the film can be improved. The content of the repeating unit represented by the general formula (5) is more preferably 15 mol% or more, further preferably 20 mol% or more. On the other hand, by containing 80 mol% or less of the repeating unit represented by the general formula (5), excessive radical cross-linking of the (meth) acrylic polymer can be suppressed and the crack resistance of the partition wall can be improved. The content of the repeating unit represented by the general formula (5) is more preferably 75 mol% or less, further preferably 70 mol% or less.

Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, a methacryl group and the like. As a method for adding such a side chain to the acrylic (co) polymer, an ethylenically unsaturated compound having a glycidyl group in the carboxylic acid group of the acrylic (co) polymer or (meth) as described above. A general method is to add an acrylic acid chloride reaction. In addition, a compound having an ethylenically unsaturated group can be added using isocyanate. Examples of the ethylenically unsaturated compound having a glycidyl group and acrylic acid or methacrylic acid chloride include glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, and α-n- (meth) acrylate. Propyl glycidyl, α-n-butyl glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxyheptyl (meth) acrylate, α-ethyl-6, (meth) acrylate 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-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6 -Diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-tri Examples thereof include glycidyloxymethylstyrene, 2,4,6-triglycidyloxymethylstyrene, acrylic acid chloride, and methacrylate chloride.

Other repeating units in the (meth) acrylic polymer preferably contain a carboxyl group and / or an acid anhydride group. By containing a carboxyl group and / or an acid anhydride group, the solubility contrast between the exposed portion and the unexposed portion is increased, and the resolution at which pattern processing is possible is improved. Examples of the (meth) acrylic compound containing a carboxyl group and / or an acid anhydride group include (meth) acrylic acid, (meth) acrylic acid anhydride, itaconic acid, itaconic acid anhydride, and mono (2-acryloyloxy) oxalate. Ethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-acryloyloxyethyl) tetrahydrophthalate and the like. Two or more of these may be used.

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

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 measured by gel permeation chromatography (GPC). By setting Mw in the above range, good coating characteristics can be obtained, and the solubility of the unexposed portion in the developing solution at the time of pattern formation is also good.

The (meth) acrylic polymer used in the resin composition of the present invention may be synthesized and used as described in the synthesis examples described later, or a commercially available product may be used. Examples of commercially available (meth) acrylic polymers include 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 (trade name, manufactured by Nippon Shokubai Co., Ltd.), SPCR-10X, SPCR-10P, SPCR-24XS PCR-18X, SPCR-215X (trade name, Showa Denko KK) (Company), X-4007 (trade name, manufactured by Nichiyu Co., Ltd.) and the like. Among these, SPCR-10X, SPCR-10P, SPCR-24XS PCR-18X, and SPCR-215X having an aromatic group and a photoradical polymerizable group are preferable. Two or more of these may be used.

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 photoradical polymerizable group. Other structures may be included.

(In the general formulas (6) and (7), R ^{5 to} R ⁷ are hydrogen, a monovalent organic group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, or adjacent R ^{5 to} R ^{7 to} each other. The formed ring represents a group that becomes an aromatic ring. R ⁸ represents hydrogen, a monovalent organic group having 1 to 30 carbon atoms, or an aryl group having 6 to 20 carbon atoms. P, q, r represent 0 to 2. S represents an integer of 1 to 2. f to g independently represent an integer of 1 or more. When f to g are 2 or more, a plurality of R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different.)

Here, as the "monovalent organic group having 1 to 30 carbon atoms", an alkyl group having 1 to 6 carbon atoms (including a linear and branched alkyl group) is preferable. Preferred specific examples thereof include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. Further, 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 of these include a phenyl group, a benzyl group, a styryl group, a naphthyl group and a biphenyl group. Further, 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.

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

As the "photoradical polymerizable group" contained in the cardo-based polymer, an ethylenically unsaturated group is preferable. By containing an ethylenically unsaturated group as the photoradical polymerizable group, the cross-linking reaction proceeds with the radicals generated from the photoradical generator in the exposed portion, and the degree of curing of the exposed portion can be enhanced.

Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a styryl group, an acrylic group, a methacryl group and the like. A functional group containing a styryl group, a methacrylic group and an acrylic group is preferable. As a preferable specific example, a functional group in which glycidyl methacrylate and / or glycidyl acrylate is added to a carboxylic acid group can be mentioned.

The cardo-based polymer used in the resin composition of the present invention preferably contains an alkali-soluble group as an "other structure". The alkali-soluble group preferably contains a carboxyl group and / or an acid anhydride group. By containing a carboxyl group and / or an acid anhydride group, the solubility contrast between the exposed portion and the unexposed portion is increased, and the resolution at which pattern processing is possible is improved.

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 measured by gel permeation chromatography (GPC) described later. By setting Mw in the above range, good coating characteristics can be obtained, and the solubility of the unexposed portion in the developing solution at the time of pattern formation is also 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. Examples of commercially available cardo-based polymers include "Oxol" (registered trademark) CR-TR, CR-TR2, CR-TR3, CR-TR4, CR-TR5, and CR-TR6 (above, trade name, Osaka Gas Chemicals). (Made by Co., Ltd.), INR-16 (Product name, manufactured by Nagase Chemtech Co., Ltd.), V-259ME (Product name, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), WR-301 (Product name, manufactured by ADEKA Corporation) And so on. Among these, V-259ME and WR-301 containing the structure represented by the general formula (6) or the general formula (7), a photoradical polymerizable group, and an alkali-soluble group are preferable. Two or more of these may be used.

The resin composition of the present invention preferably contains the above-mentioned polysiloxane and the above-mentioned (meth) acrylic polymer and / or cardo-based polymer as a resin in a weight ratio of 30/70 to 70/30. By containing this ratio, it is possible to achieve both high heat resistance derived from polysiloxane and tacklessness of the film after prebaking derived from (meth) acrylic polymer and / or cardo-based polymer. The weight ratio of the polysiloxane to the (meth) acrylic polymer and / or the cardo-based polymer is more preferably 35/65 to 65/35, and even 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. The high glass transition temperature can enhance the tacklessness of the film after prebaking. 65 ° C. or higher is more preferable. The glass transition temperature can be measured as described in Examples described later.

The resin composition of the present invention preferably further contains a white pigment. The white pigment has a function of further improving the reflectance of the partition wall.

Examples of the white pigment include titanium dioxide, zirconium oxide, zinc oxide, barium sulfate, and composite compounds thereof. Two or more of these may be contained. Among these, titanium dioxide having high reflectance and easy industrial use is preferable.

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 it has low photocatalytic activity.

The white pigment may be surface-treated. Surface treatment with a metal selected from Al, Si and Zr is preferable, and the light resistance and heat resistance of the formed partition wall can be improved.

The average primary particle size of the white pigment is preferably 100 to 500 nm, more preferably 150 nm to 350 nm, from the viewpoint of further improving the reflectance of the partition wall. Here, the average primary particle size of the white pigment can be measured by a laser diffraction method using a particle size distribution measuring device (N4-PLUS; manufactured by Beckman Coulter, Inc.) or the like.

The preferred titanium dioxide pigment for use as a white pigment, for example, R960; Dupont Co. (rutile _type, SiO 2 / _Al 2 _{O 3} process, the average primary particle size 210 nm), CR-97; manufactured by Ishihara Sangyo Kaisha, Ltd. Made by (rutile type, Al ₂ O ₃ / ZrO ₂ treatment, average primary particle diameter 250 nm), JR-301; manufactured by Teika Co., Ltd. (rutile type, Al ₂ O ₃ treatment, average primary particle diameter 300 nm), JR-405 Made by Teika Co., Ltd. (rutile type, Al ₂ O ₃ treatment, average primary particle diameter 210 nm), JR-600A; Teika Co., Ltd. (rutile type, Al ₂ O ₃ treatment, average primary particle diameter 250 nm), JR- 603; Takeka Co., Ltd. (rutile type, Al ₂ O ₃ / ZrO ₂ treatment, average primary particle size 280 nm) and the like can be mentioned. Two or more of these may be contained.

The content of the white pigment in the resin composition is preferably 10% by weight or more, more preferably 15% by weight or more in the solid content from the viewpoint of further improving the reflectance. On the other hand, from the viewpoint of improving the surface smoothness of the partition wall, the content of the white pigment is preferably 60% by weight or less, more preferably 55% by weight or less in the solid content.

The resin composition of the present invention further describes an organic metal compound containing a black pigment and / or at least one metal selected from the group consisting of silver, gold, platinum and palladium (hereinafter, referred to as "organic metal compound"). It is preferable to contain (may be). The black pigment and the organometallic compound have a function of further improving the light-shielding property of the partition wall.

Examples of the black pigment include black organic pigments, mixed color organic pigments, and black inorganic pigments.

Examples of the black organic pigment include carbon black, perylene black, aniline black, and benzofuranone pigments. These may be coated with a resin.

Examples of the mixed color organic pigment include those obtained by mixing two or more kinds of pigments selected from red, blue, green, purple, yellow, magenta, cyan and the like to make a pseudo-black color. Among these, a mixed pigment of a red pigment and a blue pigment is preferable from the viewpoint of achieving both a moderately high OD value and pattern processability. The weight ratio of the red pigment to the blue pigment in the mixed pigment is preferably 20/80 to 80/20, more preferably 30/70 to 70/30. Specific examples of typical pigments by color index (CI) number include the following. Examples of the red pigment include Pigment Red (hereinafter abbreviated as PR) 9, PR177, PR179, PR180, PR192, PR209, PR215, PR216, PR217, PR220, PR223, PR224, PR226, PR227, PR228, PR240, PR254 and the like. Can be mentioned. Two or more of these may be contained. Examples of the blue pigment include Pigment Blue (hereinafter abbreviated as PB) 15, PB15: 3, PB15: 4, PB15: 6, and the like. Two or more of these may be contained.

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 oxides; metal composite oxides; Examples thereof include metal sulfides; metal nitrides; metal oxynitrides; and metal carbides. Two or more of these may be contained.

Among the above black pigments, since they have high light-shielding properties, pigments selected from titanium nitride, zirconium nitride, carbon black, and mixed pigments having a weight ratio of red pigment and blue pigment of 20/80 to 80/20 are selected. preferable. Further, from the viewpoint of easily adjusting the taper angle of the partition wall (A-1) to a preferable range described later, from titanium nitride, zirconium nitride, and a mixed pigment having a weight ratio of 20/80 to 80/20 of a red pigment and a blue pigment. The selected pigment is more preferred.

The content of the black pigment in the resin composition is preferably 0.01% by weight or more, more preferably 0.05% by weight or more in the solid content from the viewpoint of improving the light-shielding property. On the other hand, from the viewpoint of stably forming the fine thick film partition wall pattern, the content of the black pigment is preferably 5% by weight or less, and more preferably 3% by weight or less in the solid content. The average primary particle size of the black pigment is preferably 1 to 200 nm, more preferably 5 nm to 50 nm, from the viewpoint of achieving both light-shielding properties and pattern processability of the partition wall. Here, the average primary particle size of the black pigment can be measured by a laser diffraction method using a particle size distribution measuring device (N4-PLUS; manufactured by Beckman Coulter Co., Ltd.) or the like.

The organometallic compound becomes black particles or yellow particles by decomposing and agglutinating in the exposure step and / or the heating step in the pattern formation of the partition wall (A-1) described later, and the light shielding of the partition wall (A-1) described later. It has a function of improving the sex (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 step to be photocured or photodecomposed. If a pattern is formed in advance using a resin composition containing a large amount of black pigment in order to form a partition wall (A-1) having a high OD value, photocuring at the bottom tends to be insufficient. As a result, the shape of the obtained partition wall (A-1) tends to be a reverse taper type. When a pattern is formed using the resin composition of the present invention containing the above-mentioned organometallic compound, the taper angle can be easily set to a preferable range described later because the photocuring is sufficiently performed to the bottom.

Examples of the organic metal compound include silver-containing organic metal compounds such as silver neodecanoate, silver octylate, and silver salicylate; gold such as chloro (triphenylphosphine) gold and tetrachlorogold acid tetrahydrate. Organic metal compounds; Organic metal compounds containing platinum such as bis (acetylacetonato) platinum, dichlorobis (triphenylphosphine) platinum, dichlorobis (benzonitrile) platinum; bis (acetylacetonato) palladium, dichlorobis (triphenylphosphine) Examples thereof include organic metal compounds containing palladium such as palladium, dichlorobis (benzonitrile) palladium, tetrakis (triphenylphosphine) palladium, and dibenzylideneacetonepalladium. Two or more of these may be contained.

Among these, when an organic metal compound containing silver such as silver neodecanoate, silver octylate, and silver salicylate is contained, it decomposes and aggregates in the exposure process to cause blackening, and further decomposes and aggregates in the subsequent heating process. It turns yellow.

On the other hand, organometallic compounds containing platinum such as bis (acetylacetonato) platinum, dichlorobis (triphenylphosphine) platinum, and dichlorobis (benzonitrile) platinum; bis (acetylacetonato) palladium, dichlorobis (triphenylphosphine) palladium, When an organometallic compound selected from palladium such as dichlorobis (benzonitrile) palladium, tetrakis (triphenylphosphine) palladium, and dibenzylideneacetone palladium is contained, it becomes black due to decomposition and aggregation in the exposure step and / or the heating step. do.

Among these, organometallic compounds selected from bis (acetylacetonato) palladium, dichlorobis (triphenylphosphine) palladium, dichlorobis (benzonitrile) palladium and tetrakis (triphenylphosphine) palladium from the viewpoint of further improving the OD value. Is preferable.

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 wall 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 coordinating compound having a phosphorus atom (hereinafter, may be referred to as a “coordinating compound”). The coordinating compound coordinates with the organometallic compound in the resin composition, improves the solubility of the organometallic compound in the solvent, promotes the decomposition of the organometallic compound, and further improves the OD value of the obtained partition wall. Can be made to. Examples of coordinating compounds include triphenylphosphine, tri-t-butylphosphine, trimethylphosphine, tricyclohexylphosphine, tri-t-butylphosphine tetrafluoroborate, tri (2-furyl) phosphine, and tris (1-). Examples thereof include adamantyl) phosphine, tris (diethylamino) phosphine, tris (4-methoxyphenyl) phosphine, and tris (O-tolyl) phosphine. Two or more of these may be contained. The content of the coordinating compound in the resin composition of the present invention is preferably 0.5 to 3.0 molar equivalent with respect to the organometallic compound.

The resin composition of the present invention preferably 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 the photopolymerizable compound, it is possible to cause a radical cross-linking reaction with the (meth) acrylic group in the resin and improve the degree of curing of the film. Considering the ease of radical polymerization, the photopolymerizable compound preferably has a (meth) acrylic group.

Examples of the photopolymerizable compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, and trimethylolpropane. Triacrylate, Trimethylol Propane Dimethacrylate, Trimethylol Propane Trimethacrylate, 1,3-Butanediol Diacrylate, 1,3-Butanediol Dimethacrylate, Neopentyl glycol Diacrylate, 1,4-Butanediol Diacrylate, 1, 4-Butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecanediacrylate, pentaerythritol triacrylate, pentaerythritol tetra Acrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapenta Erislithol undecaacrylate, pentapentaerythritol decaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nona methacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate, pentapentaerythritol dodecamethacrylate, dimethyrole- Examples thereof include tricyclodecanediacrylate. Two or more of these may be contained.

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

The resin composition of the present invention preferably contains a liquid repellent compound having a photoradical polymerizable group.

The liquid-repellent compound is a compound that imparts the property of repelling water or an organic solvent (liquid-repellent performance) to the resin composition. The compound having such properties is not particularly limited, but specifically, a compound having a fluoroalkyl group is preferably used. By containing the liquid repellent compound, it is possible to impart liquid repellent performance to the top of the partition wall after forming the partition wall (A-1) described later. Thereby, for example, when forming pixels containing the color conversion light emitting material (B) described later, color conversion light emitting materials having different compositions can be easily applied to each pixel.

Examples of the liquid repellent compound include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, and octaethylene. Glycoldi (1,1,2,2-tetrafluorobutyl) ether, perfluoroalkylsulfonamide propyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bis phosphate (N-perfluorooctylsulfonyl-N) -Ethylaminoethyl), compounds having a fluoroalkyl or fluoroalkylene group at the terminal, main chain and / or side chain such as monoperfluoroalkyl ethyl phosphate. As commercially available liquid repellent compounds, "Megafuck" (registered trademark) F142D, F172, F173, F183, F444, F477 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.), Ftop EF301, 303, 352 (Manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC-430, FC-431 (manufactured by Sumitomo 3M Co., Ltd.), "Asahi Guard" (registered trademark) AG710, "Surflon" (registered trademark) S-382, SC -101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15, Examples include FTX-218 and DFX-18 (manufactured by Neos Co., Ltd.). Two or more of these may be contained. Among these, a liquid-repellent compound having a photoradical polymerizable group is more preferable because it has high reactivity and can form a strong bond with the resin. Examples of the liquid repellent compound having a photoradical polymerizable group include "Mega Fvck" (registered trademark) RS-72-A, RS-75-A, RS-76-E, RS-56, RS-72-K. , RS-75, RS-76-E, RS-76-NS, RS-76, RS-90 (above, trade name, manufactured by DIC Co., Ltd.) and the like. In this case, the photopolymerizable group may be photopolymerized in the partition wall (A-1) made of the photocured product of the negative photosensitive resin composition.

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

Further, the resin composition of the present invention may contain a polymerization inhibitor, a surfactant, an adhesion improver and the like, if necessary.

By containing a polymerization inhibitor in the resin composition of the present invention, the resolution can be further improved. Examples of the polymerization inhibitor include di-t-butylhydroxytoluene, butylhydroxyanisole, 4-methoxyphenol, 1,4-benzoquinone, and t-butylcatechol. In addition, as a commercially available polymerization inhibitor, "IRGANOX" (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, 295 (above, trade name, trade name, BASF Japan Co., Ltd.) and the like. Two or more of these may be contained. The content of the polymerization inhibitor in the resin composition of the present invention is not particularly limited and can be appropriately determined, but is usually preferably 10% by weight or less, more preferably 5% by weight or less in the solid content.

By containing a surfactant in the resin composition of the present invention, the flowability at the time of coating can be improved. Examples of the surfactant include "Megafuck" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, F477 (trade name, manufactured by Dainippon Ink and Chemicals Co., Ltd.), NBX-. 15, Fluorosurfactants such as FTX-218 (trade name, manufactured by Neos Co., Ltd.); "BYK" (registered trademark) -333, 301, 331, 345, 307 (above, trade name, Big Chemie) Silicone-based surfactants such as those manufactured by Japan Co., Ltd .; polyalkylene oxide-based surfactants; poly (meth) acrylate-based surfactants and the like can be mentioned. Two or more of these may be contained. The content of the surfactant in the resin composition of the present invention is not particularly limited and can be appropriately determined, but is usually preferably 10% by weight or less, more preferably 5% by weight or less in the solid content.

By containing the adhesion improver in the resin composition of the present invention, the adhesion with the underlying substrate is improved, and a highly reliable partition wall can be obtained. Examples of the adhesion improving agent include an alicyclic epoxy compound and a silane coupling agent. Among these, an alicyclic epoxy compound is preferable from the viewpoint of heat resistance.

Examples of the alicyclic epoxy compound include 3', 4'-epoxycycloheximethyl-3,4-epoxycyclohexanecarboxylate and 1,2-epoxy of 2,2-bis (hydroxymethyl) -1-butanol. 4- (2-oxylanyl) cyclohexane adduct, ε-caprolactone-modified 3', 4'-epoxycyclohexylmethyl 3', 4'-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, butanetetracarboxylic acid Tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone, 3,4-epoxycyclohexylmethylmethacrylate, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, water Examples thereof include supplemented bisphenol A bis (propylene glycol glycidyl ether) ether, hydrogenated bisphenol A bis (ethylene glycol glycidyl ether) ether, diglycidyl 1,4-cyclohexanedicarboxylate, and 1,4-cyclohexanedimethanol diglycidyl ether. Two or more of these may be contained.

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

The resin composition of the present invention preferably further contains a solvent. The solvent has a function of adjusting the viscosity of the resin composition within a range suitable for coating and improving the uniformity of the partition wall. As the solvent, it is preferable to combine a solvent having a boiling point of more than 150 ° C. and 250 ° C. or lower under atmospheric pressure and a solvent having a boiling point of 150 ° C. or lower.

Examples of the solvent include alcohols such as ethanol, propanol, isopropanol and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl. Ethers such as ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; ketones such as methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone; dimethylformamide, dimethylacetamide, etc. Amids; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate , Acetates such as butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, cyclohexane, γ-butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide and the like. Two or more of these may be contained. Among these, from the viewpoint of coatability, it is preferable to combine diacetone alcohol as a solvent having a boiling point of more than 150 ° C. and 250 ° C. or lower under atmospheric pressure, and propylene glycol monomethyl ether as a solvent having a boiling point of 150 ° C. or lower.

The content of the solvent can be arbitrarily set according to the coating method and the like. For example, when the film is formed by spin coating, the content of the solvent is generally 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-mentioned photoradical generator, polysiloxane, (meth) acrylic polymer and / or cardo-based polymer and, if necessary, other components.

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 above-mentioned resin composition of the present invention. 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 wall (A-1) described later. The film thickness of the light-shielding film is preferably 10 μm or more.

Next, the method for producing the light-shielding film of the present invention will be described with reference to an example. The method for producing a light-shielding film of the present invention includes a film-forming step of applying the resin composition of the present invention on a base substrate and drying to obtain a dry film, an exposure step of pattern-exposing the obtained dry film, and post-exposure. It is preferable to have a developing step of dissolving and removing a portion of the dry film that is soluble in the developing solution and a heating step of heating the developed dry film to cure it.

The heating temperature during the heating step is preferably 250 ° C. or lower, more preferably 240 ° C. or lower, from the viewpoint of suppressing the generation of cracks in the film to be heated. The heating time is preferably 15 minutes to 2 hours. When the resin composition of the present invention contains the above-mentioned organic metal compound, the film formed has a low OD value at the time of exposure and an OD value increases after pattern formation. It can be sufficiently photocured to obtain a partition wall having a preferable taper angle described later. In addition, a partition wall having a high light-shielding property can be obtained after pattern formation. The heating temperature is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, from the viewpoint of further improving the OD value.

Examples of the method for applying the resin composition in the film forming step include a slit coating method and a spin coating method. Examples of the drying device include a hot air oven and a hot plate. The drying time is preferably 80 to 120 ° C., and the drying time is preferably 1 to 15 minutes.

The exposure step is a step of photocuring a necessary part of the dry film by exposure or photodecomposing an unnecessary part of the dry film to make any part of the dry film soluble in a developing solution. .. In the exposure step, exposure may be performed through a photomask having a predetermined opening, or an arbitrary pattern may be directly drawn using laser light or the like without using a photomask.

Examples of the exposure apparatus include a proximity exposure machine. Examples of the active light beam to be irradiated in the exposure step include near infrared rays, visible rays, and ultraviolet rays, and ultraviolet rays are preferable. Examples of the light source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a halogen lamp, a germicidal lamp, and the like, and an ultra-high-pressure mercury lamp is preferable.

The exposure conditions can be appropriately selected depending on the thickness of the dry film to be exposed. Generally, using an ultra high pressure mercury lamp with an output of 1 to 100 mW / cm ^2, it is preferred to expose an exposure amount of 1~10,000mJ / cm ^2.

In the developing step, the part of the dry film after exposure that is soluble in the developing solution is dissolved and removed with the developing solution, and only the part that is insoluble in the developing solution remains. , Called a pre-heating pattern). Examples of the pattern shape include a grid shape, a stripe shape, a hole shape, and the like.

Examples of the developing method include a dipping method, a spraying method, and a brushing method.

As the developing solution, a solvent capable of dissolving unnecessary portions of 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 alkaline aqueous solution is preferable as the developing solution. Examples of the alkaline aqueous solution include inorganic alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate and calcium hydroxide; and organic alkaline aqueous solutions such as tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine and diethanolamine. Can be mentioned. Among these, an aqueous solution of potassium hydroxide or an aqueous solution of tetramethylammonium hydroxide is preferable from the viewpoint of improving the resolution. The concentration of the alkaline aqueous solution is preferably 0.05% by weight or more, more preferably 0.1% by weight or more, from the viewpoint of improving developability. On the other hand, the concentration of the alkaline aqueous solution is preferably 5% by weight or less, more preferably 1% by weight or less, from the viewpoint of suppressing peeling and corrosion of the pattern before heating. Further, from the viewpoint of improving the resolution, the developing solution may contain a surfactant. The development temperature is preferably 20 to 50 ° C. for facilitating process control.

The heating step is a step of heating and curing the preheating pattern formed in the developing step. Examples of the heating device include a hot plate, an oven, and the like. The preferred heating temperature and heating time are as described above.

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

In the substrate with a partition wall of the present invention, the partition wall (A-1) has a reflectance of 10% to 60% per 10 μm thickness and an OD value of 1.0 to 3.0 per 10 μm thickness at a wavelength of 550 nm. It is a feature. By setting the reflectance to 10% or more and the OD value to 3.0 or less, the brightness of the display device can be improved by utilizing the reflection on the side surface of the (A-1) partition wall. On the other hand, by setting the reflectance at a wavelength of 550 nm to 60% or less and the OD value to 1.0 or more, it is possible to suppress the transmitted light of the partition wall (A-1) and suppress the color mixing of light between adjacent pixels. ..

FIG. 1 shows a cross-sectional view of one aspect of the partition walled substrate of the present invention having a patterned partition wall. A patterned partition wall 2 is provided on the base substrate 1.

<Base substrate>
Examples of the base substrate include a glass plate, a resin plate, a resin film, and the like. As the material of the glass plate, non-alkali glass is preferable. As the material of the resin plate and the resin film, polyester, (meth) acrylic polymer, transparent polyimide, polyether sulfone and the like are preferable. The thickness of the glass plate and the resin plate is preferably 1 mm or less, preferably 0.8 mm or less. The thickness of the resin film is preferably 100 μm or less.

<Septum (A-1)>
The partition wall (A-1) is characterized in that the reflectance per 10 μm thickness at a wavelength of 550 nm is 10% to 60%, and the OD value per 10 μm thickness is 1.0 to 3.0. Here, the thickness of the partition wall (A-1) refers to the height of the partition wall (A-1) and / or the width of the partition wall (A-1). The height of the partition wall (A-1) refers to the length in the direction (height direction) perpendicular to the base substrate of the partition wall (A-1). In the case of the substrate with a partition wall shown in FIG. 1, the height of the partition wall 2 is represented by reference numeral H. The width of the partition wall (A-1) refers to the length in the horizontal direction with the base substrate of the partition wall (A-1). In the case of the substrate with a partition wall shown in FIG. 1, the width of the partition wall 2 is represented by reference numeral L. In this specification, "height" may be referred to as "thickness".

In the present invention, it is considered that the reflectance on the side surface of the partition wall contributes to the improvement of the brightness of the display device, and the light-shielding property contributes to the suppression of 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 and the width direction, the present invention focuses on the reflectance and OD value per thickness of the partition wall. As will be described later, the thickness (height) of the partition wall (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 the representative value of the thickness of the partition wall (A-1), and the reflectance and the OD value per 10 μm thickness were focused on.

If the reflectance of the partition wall (A-1) at a wavelength of 550 nm per 10 μm thickness is less than 20%, the visible light reflection on the side surface of the partition wall becomes small, and the brightness of the display device becomes insufficient. The reflectance per 10 μm thickness at a wavelength of 550 nm is preferably 20% or more, more preferably 30% or more, still more preferably 40% or more.

The reflectance of the partition wall (A-1) at a wavelength of 450 nm per 10 μm thickness is preferably 20% or more, more preferably 30% or more, still more preferably 40% or more. The higher the reflectance per 10 μm thickness at a wavelength of 450 nm, the greater the reflection of blue excitation light on the side surface of the partition wall. Therefore, when a pixel containing the color conversion light emitting material (B) described later is contained between the partition walls, the color conversion efficiency Can be improved and the brightness of the display device can be improved.

Further, the reflectance per 10 μm thickness of the partition wall (A-1) at a wavelength of 630 nm is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more. The higher the reflectance per 10 μm thickness at a wavelength of 630 nm, the greater the reflection of red light on the side surface of the partition wall. Therefore, when a pixel containing the color conversion light emitting material (B) described later is contained between the partition walls, light is emitted within the pixel. It is possible to efficiently reflect the red light and improve the brightness of the display device.

The OD value per 10 μm thickness of the partition wall (A-1) at a wavelength of 550 nm is preferably 1.0 or more, more preferably 1.5 or more, still more preferably 2.0 or more. The higher the OD value per 10 μm thickness at a wavelength of 550 nm, the greater the light-shielding property on the side surface of the partition wall, so that color mixing between adjacent pixels can be prevented and the contrast of the display device can be improved.

The OD value per 10 μm thickness of the partition wall (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. If the OD value per 10 μm thickness of the partition wall (A-1) at a wavelength of 450 nm is less than 1.0, blue excitation light leaks to adjacent pixels, and the color conversion light emitting material (B) described later is contained between the partition walls. When the pixels are included, light is emitted within the pixels, and color mixing occurs.

Further, the OD value per 10 μm thickness of the partition wall (A-1) at a wavelength of 630 nm is preferably 1.0 or more, more preferably 1.5 or more, still more preferably 2.0 or more. The higher the OD value per 10 μm thickness at a wavelength of 630 nm, the greater the light-shielding property of red light on the side surface of the partition wall. It is possible to efficiently block the emitted red light to prevent color mixing and improve the contrast of the display device.

The reflectance of the partition wall (A-1) at wavelengths of 450 nm, 550 nm, and 630 nm per 10 μm thickness is determined from the upper surface of the partition wall (A-1) having a thickness of 10 μm by a spectrocolorimeter (for example, CM manufactured by Konica Minolta Co., Ltd.). -2600d) can be used for measurement in SCI mode. However, if a sufficient area for measurement cannot be secured, or if a measurement sample having a thickness of 10 μm cannot be collected and the composition of the partition wall (A-1) is known, the composition is the same as that of the partition wall (A-1). A solid film having a thickness of 10 μm may be prepared, and the reflectance per 10 μm thickness may be obtained by measuring the reflectance of the solid film in the same manner instead of the partition wall (A-1). For example, using a material on which a partition wall (A-1) is formed, a solid film is produced under the same processing conditions as the partition wall (A-1) except that the thickness is 10 μm and no pattern is formed, and the solid film is obtained. The reflectance of the film may be measured from the upper surface in the same manner.

The OD value per 10 μm thickness of the partition wall (A-1) at wavelengths of 450 nm, 550 nm, and 630 nm is an optical densitometer (for example, U-4100 manufactured by Hitachi High-Tech Science) from the top surface of the partition wall (A-1) having a thickness of 10 μm. The intensity of the incident light and the transmitted light can be measured using the following equation (1). However, if a sufficient area for measurement cannot be secured, or if a measurement sample with a thickness of 10 μm cannot be collected and the composition of the partition wall (A-1) is known, the partition wall (similar to the measurement of reflectance) A solid film having the same composition as A-1) and having a thickness of 10 μm may be prepared, and the OD value per 10 μm thickness may be obtained by measuring the OD value of the solid film in the same manner instead of the partition wall (A-1). ..

OD value = log10 (I ₀ / I) ・ ・ ・ (1)
I ₀ : Incident light intensity I: Transmitted light intensity.

As a means for setting the reflectance and the OD value in the above range, for example, the partition wall (A-1) may have a preferable composition described later.

The taper angle of the partition wall (A-1) is preferably 45 ° to 110 °. The taper angle of the partition wall (A-1) refers to the angle formed by the side surface and the bottom surface of the partition wall cross section. In the case of the substrate with a partition wall shown in FIG. 1, the taper angle of the partition wall 2 is represented by the reference numeral θ. By setting the taper angle to 45 ° or more, the difference in width between the top and bottom of the partition wall (A-1) becomes small, and the width of the partition wall (A-1) can be easily formed in a preferable 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 the pixels containing the color conversion light emitting material (B) described later are formed by inkjet coating, the ink breakage is suppressed and the inkjet coating property is improved. Can be done. Here, the ink rupture refers to a phenomenon in which the ink gets over the partition wall and mixes with the adjacent pixel portion. The taper angle is more preferably 95 ° or less. The taper angle of the partition wall (A-1) is an acceleration voltage of 3 using an optical microscope (FE-SEM (for example, S-4800 manufactured by Hitachi, Ltd.)) for any cross section of the partition wall (A-1). It can be obtained by observing at a magnification of 2,500 kV and measuring the angle formed by the side and bottom of the cross section of the partition wall (A-1).

As a means for setting the taper angle of the partition wall (A-1) in the above range, for example, the partition wall (A-1) has a preferable composition described later, and the resin composition of the present invention described above is used. For example, forming.

When the partition wall (A-1) has pixels containing the color conversion light emitting material (B) described later, the thickness of the partition wall (A-1) is preferably larger than the thickness of the pixels. Specifically, the thickness of the partition wall (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 at the bottom of the pixel, the thickness of the partition wall (A-1) is preferably 100 μm or less, more preferably 50 μm or less. Further, the width of the partition wall (A-1) is preferably sufficient to further improve the brightness by utilizing the light reflection on the side surface of the partition wall and further suppress the color mixing of light in the adjacent pixels due to light leakage. Specifically, the width of the partition wall is preferably 1 μm or more, more preferably 5 μm or more. On the other hand, the width of the partition wall (A-1) is preferably 100 μm or less, more preferably 50 μm or less, from the viewpoint of securing a large amount of light emitting regions of the pixels and further improving the brightness.

The partition wall (A-1) has a repeating pattern for a predetermined number of pixels according to the screen size of the image display device. Examples of the number of pixels of the image display device include 4000 pixels in the horizontal direction and 2000 pixels in the vertical direction. The number of pixels affects the resolution (fineness) 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 preferable to determine the pattern formation dimension of the partition wall accordingly.

The partition wall (A-1) preferably contains a resin, a white pigment, a black pigment and / or a yellow pigment. The resin has a function of improving the crack resistance and light resistance of the partition wall. The white pigment has a function of further improving the reflectance of the partition wall. The black pigment and / or the yellow pigment has a function of adjusting the OD value and suppressing the color mixing of light in the adjacent pixels.

The resin and the white pigment are as described above as the materials constituting the resin composition. The content of the resin in the partition wall (A-1) is preferably 10% by weight or more, more preferably 20% by weight or more, from the viewpoint of improving the crack resistance of the partition wall in the heat treatment. On the other hand, from the viewpoint of improving the light resistance, the content of the resin in the partition wall (A-1) is preferably 60% by weight or less, more preferably 50% by weight or less.

The content of the white pigment in the partition wall (A-1) is preferably 10% by weight or more, more preferably 20% by weight or more, from the viewpoint of further improving the reflectance. On the other hand, from the viewpoint of improving the surface smoothness of the partition wall, the content of the white pigment in the partition wall (A-1) is preferably 60% by weight or less, more preferably 55% by weight or less.

The black pigment is as described above as a material constituting the resin composition. From titanium nitride, zirconium nitride, carbon black, mixed pigments with a weight ratio of 20/80 to 80/20 of red pigment and blue pigment, and palladium oxide, platinum oxide, gold oxide, silver oxide, palladium, platinum, gold, and silver. A pigment selected from at least one metal oxide selected from the group or particles made of metal is preferable.

The content of the black pigment in the partition wall (A-1) is preferably 0.05% by weight or more, more preferably 0.1% by weight or more in the solid content from the viewpoint of improving the light-shielding property. On the other hand, from the viewpoint of improving the reflectivity, the content of the black pigment is preferably 10% by weight or less, more preferably 6% by weight or less in the solid content.

The yellow pigment is, for example, a yellow organic pigment such as pigment yellow (hereinafter abbreviated as PY) PY137, PY138, PY139, PY147, PY148, PY150, PY153, PY154, PY166, PY168, PY185, and fine particles of metal such as silver and gold. Examples thereof include yellow inorganic pigments such as metal oxides; metal composite oxides; metal sulfides; metal nitrides; metal oxynitrides; and metal carbides. Among them, a yellow pigment selected from PY139, PY147, PY148 and PY150, silver particles, and gold particles is preferable from the viewpoint of selectively blocking blue light.

The content of the yellow pigment in the partition wall (A-1) is preferably 0.05% by weight or more, and more preferably 0.1% by weight or more in the solid content from the viewpoint of improving the light-shielding property of blue light. On the other hand, from the viewpoint of improving the reflectivity, the content of the yellow pigment is preferably 10% by weight or less, more preferably 6% by weight or less in the solid content.

The partition wall (A-1) preferably further contains a liquid repellent compound. By containing the liquid-repellent compound, the partition wall (A-1) can be imparted with liquid-repellent performance. For example, when forming pixels containing the color conversion light emitting material (B) described later, each pixel is formed. In addition, color-converting light-emitting materials having different compositions can be easily applied separately. The liquid-repellent compound is as described above as a material constituting the resin composition.

From the viewpoint of improving the liquid repellent performance of the partition wall and improving the inkjet coating property, the content of the liquid repellent compound in the partition wall (A-1) is preferably 0.01% by weight or more, preferably 0.1% by weight or more. More preferred. On the other hand, from the viewpoint of improving the compatibility with the resin and the white pigment, the content of the liquid repellent compound in the partition wall (A-1) is preferably 10% by weight or less, more preferably 5% by weight or less.

The surface contact angle of the partition wall (A-1) with respect to propylene glycol monomethyl ether acetate is preferably 10 ° or more, preferably 20 ° or more, from the viewpoint of improving inkjet coatability and facilitating the separation of color conversion luminescent materials. More preferably, 40 ° or more is further preferable. On the other hand, from the viewpoint of improving the adhesion between the partition wall and the base substrate, the surface contact angle of the partition wall (A-1) is preferably 70 ° or less, more preferably 60 ° or less. Here, the surface contact angle of the partition wall (A-1) conforms to the wettability test method of the substrate glass surface specified in JIS R3257 (establishment date = 1999/04/20) with respect to the upper part of the partition wall. Can be measured. Examples of the method for setting the surface contact angle of the partition wall (A-1) within the above range include a method using the above-mentioned liquid repellent compound.

As a method for forming a pattern of the partition wall (A-1) on the base substrate, the photosensitive paste method is preferable because the pattern shape can be easily adjusted. As a method of forming a pattern of the partition wall by the photosensitive paste method, for example, a coating step of applying the above-mentioned resin composition on a base substrate and drying to obtain a dry film, and a desired pattern of the obtained dry film. A method having an exposure step of pattern exposure according to the shape, a development step of dissolving and removing a portion of the dry film after exposure that is soluble in a developer, and a heating step of curing the partition wall after development is preferable. The resin composition preferably has a negative type photosensitive property. The pattern exposure may be performed through a photomask having a predetermined opening, or an arbitrary pattern may be directly drawn using a laser beam or the like without using a photomask. When the substrate with a partition wall has a color filter and / or a light-shielding partition wall (A-2) described later, the partition wall (A-1) is similarly placed on the color filter and / or the light-shielding partition wall (A-2). A pattern can be formed. Each step is as described above as a method for producing a light-shielding film.

The substrate with a partition wall of the present invention further includes pixels (hereinafter, may be referred to as “pixels (B)”) containing (B) color-converting light-emitting material arranged separated by the partition wall (A-1). It is preferable to have.

The pixel (B) has a function of converting at least a part of the wavelength region of the incident light and emitting the emitted light in the wavelength region different from the incident light to enable color display.

FIG. 2 shows a cross-sectional view of one aspect of the partition wall-equipped substrate of the present invention having a patterned partition wall (A-1) and pixels (B). A patterned partition wall 2 is provided on the base substrate 1, and pixels 3 are arranged in a region separated by the partition wall 2.

The color conversion material preferably contains a phosphor selected from an inorganic phosphor and an organic phosphor.

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

As the inorganic phosphor, one that emits each color such as green or red by blue excitation light, that is, one that is excited by excitation light having a wavelength of 400 to 500 nm and has a peak in the emission spectrum in the region of 500 to 700 nm is preferable. .. Examples of such inorganic phosphors include YAG-based phosphors, TAG-based phosphors, sialone-based phosphors, Mn ⁴⁺ activated fluoride complex phosphors, and inorganic semiconductors called quantum dots. Two or more of these may be used. Among these, quantum dots are preferable. Since the average particle size of quantum dots is smaller than that of other phosphors, the surface of the pixel (B) can be smoothed and light scattering on the surface can be suppressed, so that the light extraction efficiency can be further improved. The brightness can be further improved.

Examples of the quantum dot material include semiconductors of group II-IV, group III-V, group IV-VI, and group IV. Examples of these inorganic semiconductors include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, GeS, GeS Examples thereof include SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si ₃ N ₄ , Ge ₃ N ₄ , Al ₂ O ₃ . Two or more of these may be used.

As the organic phosphor, one that emits each color such as green or red by blue excitation light is preferable. As a phosphor that emits red fluorescence, a pyrromethene derivative having a basic skeleton represented by the following structural formula (11), and as a phosphor that emits green fluorescence, pyrromethene having a basic skeleton represented by the following structural formula (12). Examples include derivatives. Other examples include perylene-based derivatives, porphyrin-based derivatives, oxazine-based derivatives, and pyrazine-based derivatives that fluoresce red or green depending on the selection of the substituent. Two or more of these may be contained. Among these, a pyrromethene derivative is preferable because of its high quantum yield. The pyrromethene derivative can be obtained, for example, by the method described in JP-A-2011-241160.

Since the organic phosphor is soluble in a solvent, pixels (B) having a desired thickness can be easily formed.

The thickness of the pixel (B) is preferably 0.5 μm or more, more preferably 1 μm or more, from the viewpoint of improving the color characteristics. On the other hand, the thickness of the pixel (B) is preferably 30 μm or less, more preferably 20 μm or less, from the viewpoint of thinning the display device and processability of curved surfaces.

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

The pixels (B) are preferably arranged separated by a partition wall (A-1). By providing a partition wall between the pixels, it is possible to further suppress the diffusion and color mixing of the emitted light.

Examples of the method for forming the pixels (B) include a method of filling a space separated by a partition wall (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). Be done. The color conversion light emitting material coating liquid may further contain a resin or a solvent.

Examples of the method for filling the color-converting luminescent material coating liquid include a photolithography method and an inkjet method, but the inkjet coating method is preferable from the viewpoint of easily coating different types of color-converting luminescent materials on each pixel.

The obtained coating film may be dried under reduced pressure and / or dried by heating. In the case of vacuum drying, the vacuum drying temperature is preferably 80 ° C. or lower in order to prevent the drying solvent from recondensing on the inner wall of the vacuum chamber. The pressure for drying under reduced pressure is preferably equal to or lower than the vapor pressure of the solvent contained in the coating film, and is preferably 1 to 1000 Pa. The vacuum drying time is preferably 10 to 600 seconds. In the case of heat drying, examples of the heat drying device include an oven and a hot plate. The heating and drying temperature is preferably 60 to 200 ° C. The heating and drying time is preferably 1 to 60 minutes.

<Shading partition (A-2)>
The substrate with a partition wall of the present invention has an OD value of 0.5 or more per (A-2) thickness of 1.0 μm between the base substrate and the partition wall in which the pattern is formed (A-1). It is preferable to have a certain patterned partition wall (hereinafter, may be referred to as "light-shielding partition wall (A-2)"). By having the light-shielding partition wall (A-2), it is possible to improve the light-shielding property, suppress light leakage of the backlight in the display device, and obtain a high-contrast and clear image.

FIG. 3 shows a cross-sectional view showing an aspect of the substrate with a partition wall of the present invention having a light-shielding partition wall. A patterned partition wall 2 and a light-shielding partition wall 4 are provided on the base substrate 1, and pixels 3 are arranged in a region separated by the partition wall 2 and the light-shielding partition wall 4.

The light-shielding partition wall (A-2) has an OD value of 0.5 or more per 1.0 μm thickness. Here, the thickness of the light-shielding partition wall (A-2) is preferably 0.5 to 10 μm as described later. In the present invention, 1.0 μm was selected as the representative value of the thickness of the light-shielding partition wall (A-2), and attention was paid to the OD value per 1.0 μm thickness. By setting the OD value per 1.0 μm thickness to 0.5 or more, the light-shielding property can be further improved and a clear image with higher contrast can be obtained. The OD value per 1.0 μm thickness is more preferably 1.0 or more. On the other hand, the OD value per 1.0 μm thickness is preferably 4.0 or less, and the pattern processability can be improved. The OD value per 1.0 μm thickness is more preferably 3.0 or less. The OD value of the light-shielding partition wall (A-2) can be measured in the same manner as the OD value of the partition wall (A-1) described above. As a means for setting the OD value in the above range, for example, the light-shielding partition wall (A-2) may have a preferable composition described later.

The thickness of the light-shielding partition wall (A-2) is preferably 0.5 μm or more, more preferably 1.0 μm or more, from the viewpoint of improving the light-shielding property. On the other hand, from the viewpoint of improving flatness, the thickness of the light-shielding partition wall (A-2) is preferably 10 μm or less, more preferably 5 μm or less. Further, the width of the light-shielding partition wall (A-2) is preferably about the same as that of the above-mentioned partition wall (A-1).

The light-shielding partition wall (A-2) preferably contains a resin and a black pigment. The resin has a function of improving the crack resistance and light resistance of the partition wall. The black pigment has a function of absorbing incident light and reducing emitted light.

Examples of the resin include epoxy resins, (meth) acrylic polymers, polyurethanes, polyesters, polyimides, polyolefins, polysiloxanes, and the like. Two or more of these may be contained. Among these, polyimide is preferable because it has excellent heat resistance and solvent resistance.

Examples of the black pigment include those exemplified as the black pigment in the above-mentioned resin composition. A black pigment selected from titanium nitride, zirconium nitride, carbon black, palladium oxide, platinum oxide, gold oxide and silver oxide is preferable because of its high light-shielding property.

As a method of forming a pattern of the light-shielding partition wall (A-2) on the base substrate, for example, a photosensitive material described in JP-A-2015-1654 is used, and the light-shielding partition wall (A-1) is exposed to light in the same manner as the above-mentioned partition wall (A-1). A method of forming a pattern by the sex paste method is preferable.

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

FIG. 4 shows a cross-sectional view of one aspect of the substrate with a partition wall of the present invention having a color filter. It has a pattern-formed partition wall 2 and a color filter 5 on the base substrate 1, and has pixels 3 on the color filter 5.

Examples of the color filter include a color filter using a pigment-dispersed material in which a pigment is dispersed in a photoresist, which is used for a flat panel display such as a liquid crystal display. More specifically, a blue color filter that selectively transmits a wavelength of 400 nm to 550 nm, a green color filter that selectively transmits a wavelength of 500 nm to 600 nm, and a yellow color filter that selectively transmits a wavelength of 500 nm or more. Examples thereof include a red color filter that selectively transmits a wavelength of 600 nm or more.

Further, the color filter may be laminated at a distance from the pixel (B) containing the color conversion light emitting material, or may be integrally laminated.

The substrate with a partition wall of the present invention preferably has a color filter having a thickness of 1 to 5 μm, which is further separated by a light-shielding partition wall between the base substrate and the pixel (B).

FIG. 5 shows a cross-sectional view of one aspect of the substrate with a partition wall of the present invention having a color filter separated by a light-shielding partition wall. A color filter 5 is provided on the base substrate 1 and separated by a light-shielding partition wall 4 in which a pattern is formed, and a partition wall 2 and pixels 3 are provided on the color filter 5.

The substrate with a partition wall of the present invention has a low refractive index layer (hereinafter, "low refractive index layer") having a refractive index of 1.20 to 1.35 at a wavelength of (C) 550 nm on the upper or lower portion of the pixel (B). (C) "may be described). By having the low refractive index layer (C), it is possible to further improve the light extraction efficiency and further improve the brightness of the display device.

FIG. 6 shows a cross-sectional view of one aspect of the substrate with a partition wall of the present invention having a low refractive index layer. A patterned partition wall 2 and pixels 3 are provided on the base substrate 1, and a low refractive index layer 6 is further provided on these partition walls 2.

In the display device, the refractive index of the low refractive index layer (C) is preferably 1.20 or more from the viewpoint of appropriately suppressing the reflection of the light of the backlight and efficiently incident the light on the pixel (B). 23 or more is more preferable. On the other hand, from the viewpoint of improving the brightness, the refractive index of the low refractive index layer (C) is preferably 1.35 or less, more preferably 1.30 or less. Here, the refractive index of the low refractive index layer (C) is measured by irradiating the cured film surface with light having a wavelength of 550 nm from the direction perpendicular to the cured film surface under the condition of 20 ° C. under atmospheric pressure using a prism coupler. Can be done.

The low refractive index layer (C) preferably contains polysiloxane and silica particles having no hollow structure. Polysiloxane has high compatibility with inorganic particles such as silica particles and functions as a binder capable of forming a transparent layer. Further, by containing silica particles, minute voids can be efficiently formed in the low refractive index layer (C) to reduce the refractive index, and the refractive index can be easily adjusted to the above-mentioned range. Can be done. Furthermore, by using silica particles that do not have a hollow structure, cracks can be suppressed because they do not have a hollow structure that easily causes cracks during curing shrinkage. In the low refractive index layer (C), the polysiloxane and the silica particles having no hollow structure may be contained independently of each other, or the polysiloxane and the silica particles having no hollow structure are bonded to each other. It may be contained in. From the viewpoint of the uniformity of the low refractive index layer (C), it is preferable that the polysiloxane and silica particles having no hollow structure are contained in a bonded state.

The polysiloxane contained in the low refractive index layer (C) preferably contains fluorine. By containing fluorine, the refractive index of the low refractive index layer (C) can be easily adjusted to 1.20 to 1.35. The fluorine-containing polysiloxane can be obtained by hydrolyzing and polycondensing a plurality of alkoxysilane compounds including at least a fluorine-containing alkoxysilane compound represented by the following general formula (13). Further other alkoxysilane compounds may be used.

In the above general formula (13), R ¹¹ represents a fluoroalkyl group having 3 to 17 fluorine numbers. R ¹⁰ represents the same group as ^{R 9} in the general formulas (8) to (10). m represents 1 or 2. 4-m-number of ^{R 10} and m pieces of ^{R 11} may be the same or different from each other. The number of carbon atoms of the fluoroalkyl group having 3 to 17 fluorines is preferably 1 to 30.

Examples of the fluorine-containing alkoxysilane compound represented by the general formula (13) include trifluoroethyltrimethoxysilane, trifluoroethyltriethoxysilane, trifluoropropyltrimethoxysilane, and trifluoropropyltriethoxysilane trifluoroethyl ethyl. Examples thereof include dimethoxysilane, trifluoroethyl ethyl diethoxysilane, and trifluoroethyl ethyl diisopropoxysilane. Two or more of these may be used.

The content of polysiloxane in the low refractive index layer (C) is preferably 4% by weight or more from the viewpoint of suppressing cracks. On the other hand, the content of polysiloxane is 32% by weight or less from the viewpoint of ensuring thixotropic property due to the network between silica particles, maintaining an appropriate air layer in the low refractive index layer (C), and further reducing the refractive index. Is preferable.

Examples of silica particles having no hollow structure in the low refractive index layer (C) include "Snowtex" (registered trademark) and "organosilica sol" (registered trademark) series (isopropyl alcohol dispersion) manufactured by Nissan Chemical Industries, Ltd. , Methyl ethyl ketone dispersion, Propylene glycol monomethyl ether dispersion, Methanol dispersion, etc. Part numbers PGM-ST, PMA-ST, IPA-ST, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, MEK- (ST-UP, etc.) can be mentioned. Two or more of these may be contained.

The content of the silica particles having no hollow structure in the low refractive index layer (C) ensures the thixo property due to the network between the silica particles, maintains an appropriate air layer in the low refractive index layer (C), and refracts. From the viewpoint of further reducing the rate, 68% by weight or more is preferable. On the other hand, the content of silica particles having no hollow structure is preferably 96% by weight or less from the viewpoint of suppressing cracks.

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 step 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, more preferably 10 μm or less, from the viewpoint of reducing stress that causes cracks in the low refractive index layer (C).

As a method for forming the low refractive index layer (C), a coating method is preferable because the forming method is easy. For example, the low refractive index layer (C) can be formed by applying a low refractive index resin composition containing polysiloxane and silica particles on the pixel (B), drying the mixture, and then heating the pixel (B).

Further, the substrate with a partition wall of the present invention preferably further has an inorganic protective layer I having a thickness of 50 to 1,000 nm on the low refractive index layer (C). Since the presence of the inorganic protective layer I makes it difficult for moisture in the atmosphere to reach the low refractive index layer (C), it is possible to suppress fluctuations in the refractive index of the low refractive index layer (C) and suppress brightness deterioration. can.

7 and 8 show a cross-sectional view of one aspect of the substrate with a partition wall of the present invention having the low refractive index layer and the inorganic protective layer (I). A patterned partition wall 2 and pixels 3 are provided on the base substrate 1, and a low refractive index layer 6 and an inorganic protective layer (I) 7 are further provided above or below these.

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

FIG. 9 shows a cross-sectional view of one aspect of the substrate with a partition wall of the present invention having the low refractive index layer and the inorganic protective layer (I) between the pixel (B) and the color filter. A color filter 5 separated by a light-shielding partition wall 4 was provided on the base substrate 1, a low refractive index layer 6 and an inorganic protective layer (I) 7 were provided on the color filters 5, and a pattern was further formed on them. It has a partition wall 2 and a pixel 3.

Further, the substrate with a partition wall of the present invention preferably further has an inorganic protective layer (II) having 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 material forming the pixel (B) to move from the pixel (B) to the low refractive index layer, so that the refractive index fluctuation of the low refractive index layer (C) is caused. It can be suppressed and the deterioration of brightness can be suppressed.

FIG. 10 shows a cross-sectional view of one aspect of the substrate with a partition wall of the present invention having the low refractive index layer and the inorganic protective layer (II). A patterned partition wall 2 and pixels 3 are provided on the base substrate 1, and an inorganic protective layer (II) 8 and a low refractive index layer 6 are further provided on the partition walls 2 and pixels 3.

Further, the substrate with a partition wall of the present invention preferably further has an inorganic protective layer (III) and / or a yellow organic protective layer having 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 material for forming the color filter to reach the pixel (B) containing the color conversion light emitting material from the color filter, so that the pixel (B) containing the color conversion light emitting material is difficult to reach. ) Brightness deterioration can be suppressed. Further, by having the yellow organic protective layer, it is possible to cut the blue leakage light that could not be completely converted by the pixel (B) containing the color conversion light emitting material, and to improve the color reproducibility.

FIG. 11 shows a cross-sectional view of one aspect of the partition-mounted substrate of the present invention having a color filter and an inorganic protective layer (III) and / or a yellow organic protective layer. A patterned partition wall 2 and a color filter 5 are provided on the base substrate 1, an inorganic protective layer (III) and / or a yellow organic protective layer 9 is provided on these, and a partition wall is further provided on these. It has pixels 3 arranged separated by two.

Further, the substrate with a partition wall of the present invention preferably further has an inorganic protective layer (IV) and / or a yellow organic protective layer having a thickness of 50 to 1,000 nm on the base substrate. The inorganic protective layer (IV) and / or the yellow organic protective layer can act as a refractive index adjusting layer to more efficiently extract the light emitted from the pixel (B) and further improve the brightness of the display device. Further, the yellow organic protective layer can cut the blue leaked light that could not be completely converted by the pixel (B) containing the color conversion light emitting material, and can improve the color reproducibility. It is more preferable that the inorganic protective layer (IV) and / or the yellow organic protective layer is provided between the base substrate and the partition wall (A) and the pixel (B).

FIG. 12 shows a cross-sectional view of one aspect of the partition-mounted substrate of the present invention having the inorganic protective layer (IV) and / or the yellow organic protective layer. An inorganic protective layer (IV) and / or a yellow organic protective layer 10 is provided on the base substrate 1, and a patterned partition wall 2 and pixels 3 are provided on the inorganic protective layer (IV) and / or a yellow organic protective layer 10.

Examples of the materials constituting the inorganic protective layers (I) to (IV) include metal oxides such as silicon oxide, indium tin oxide, and zinc oxide; metal nitrides such as silicon nitride; and fluorides such as magnesium fluoride. And so on. Two or more of these may be contained. 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, more preferably 100 nm or more, from the viewpoint of sufficiently suppressing the permeation of substances such as water vapor. On the other hand, from the viewpoint of suppressing the decrease in transmittance, the thickness of the inorganic protective layers (I) to (IV) is preferably 800 nm or less, more preferably 500 nm or less.

The thickness of the inorganic protective layers (I) to (IV) is determined by exposing a cross section perpendicular to the underlying substrate using a polishing device such as a cross section polisher and using a scanning electron microscope or a transmission electron microscope. Can be measured by magnifying and observing.

Examples of the method for forming the inorganic protective layers (I) to (IV) include a sputtering method. The inorganic protective layer is preferably colorless and transparent or yellow transparent.

The yellow organic protective layer is obtained, for example, by pattern-processing the resin composition of the present invention containing an organometallic compound containing silver as an organometallic compound. As described above, the silver-containing organometallic compound has a function of yellowing the protective layer by decomposing and agglutinating in the heating step during pattern formation to form yellow particles. Examples of the silver-containing organometallic compound include silver neodecanoate, silver octylate, and silver salicylate. Among these, silver neodecanoate is preferable from the viewpoint of yellowing. In the resin composition for the yellow organic protective layer, the content of the silver-containing organometallic compound is preferably 0.2 to 5% by weight in the solid content. By setting the content of the silver-containing organometallic compound to 0.2% by weight or more, more yellowing can be achieved. The content of the silver-containing organometallic compound is more preferably 1.5% by weight or more in the solid content. On the other hand, by setting the content of the silver-containing organometallic compound to 5% by weight or less in the solid content, the transmittance can be further improved.

The resin composition forming the yellow organic protective layer may contain a yellow pigment. Examples of the yellow pigment include pigment yellow (hereinafter abbreviated as PY) PY12, PY13, PY17, PY20, PY24, PY83, PY86, PY93, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY138, PY139, PY14. , PY148, PY150, PY153, PY154, PY166, PY168, PY185 and the like. Among them, a yellow pigment selected from PY139, PY147, PY148 and PY150 is preferable from the viewpoint of selectively blocking blue light.

As a method for forming a pattern of the yellow organic protective layer, a method of forming a pattern by a photosensitive paste method is preferable as in the case of the partition wall (A-1) described above.

When the yellow organic protective layer 8 is formed on the color filter 7 as shown in FIG. 7, the yellow organic protective layer 8 may serve as an overcoat layer for flattening each pixel of the color filter.

The thickness of the yellow organic protective layer is preferably 100 nm or more, more preferably 500 nm or more, from the viewpoint of sufficiently blocking blue leakage light. On the other hand, from the viewpoint of suppressing a decrease in light extraction efficiency, the thickness of the yellow organic protective layer is preferably 3000 nm or less, more preferably 2000 nm or less.

The substrate with a partition wall of the present invention can also be used in a display device using a mini or micro LED in which a large number of LEDs corresponding to each pixel separated by a partition wall formed on the substrate are arranged. Each pixel can be turned on / off by turning on / off the mini or micro LED, and no liquid crystal display is required. That is, the substrate with a partition wall of the present invention can be used not only as a partition wall for separating each pixel but also as a partition wall for separating a mini or micro LED in a backlight.

For example, the substrate with a partition wall of the present invention preferably further has a light emitting light source selected from an organic EL cell, a mini LED cell, and a micro LED cell on the base substrate. By separating the light emitting light sources selected from the organic EL cell, the mini LED cell, and the micro LED cell with a partition wall, it is possible to prevent color mixing between the pixels and improve the display color purity of the display.

FIG. 13 shows a cross-sectional view of one aspect of the substrate with a partition wall of the present invention having a light emitting light source selected from an organic EL cell, a mini LED cell, and a micro LED cell. A light emitting light source 11 selected from an organic EL cell, a mini LED cell, and a micro LED cell is provided between the partition walls 2 having a pattern formed on the base substrate 1.

Further, the substrate with a partition wall of the present invention preferably further has pixels (B) on a light emitting 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 partition-mounted substrate of the present invention having a light source and pixels selected from an organic EL cell, a mini LED cell, and a micro LED cell. A light emitting light source 11 selected from an organic EL cell, a mini LED cell, and a micro LED cell is provided between the partition walls 2 having a pattern formed on the base substrate 1, and a pixel 3 is further provided on the light emitting light source 11.

Next, the display device of the present invention will be described. The display device of the present invention includes the substrate with a partition wall and a light emitting light source. As the light emitting light source, a light emitting light source selected from a liquid crystal cell, an organic EL cell, a mini LED cell and a micro LED cell is preferable. An organic EL cell is more preferable as the light emitting light source because of its excellent light emitting characteristics. The mini LED cell refers to a cell in which a large number of LEDs having a vertical and horizontal length of about 100 μm to 10 mm are arranged. The micro LED cell refers to a cell in which a large number of LEDs having a length and width of less than 100 μm are arranged.

The method for manufacturing the display device of the present invention will be described with reference to an example of the display device having the substrate with a partition wall and the organic EL cell of the present invention. A photosensitive polyimide resin is applied onto a glass substrate, and an insulating film having an opening is formed by using a photolithography method. After sputtering aluminum on the aluminum, patterning of aluminum is performed by a photolithography method to form a back electrode layer made of aluminum in an opening without an insulating film. Subsequently, tris (8-quinolinolato) aluminum (hereinafter abbreviated as Alq3) was formed on it as an electron transport layer by a vacuum vapor deposition method, and then dicyanomethylenepyrine, quinacridone and 4,4'are formed on Alq3 as a light emitting layer. -A white light emitting layer doped with bis (2,2-diphenylvinyl) biphenyl is formed. Next, N, N'-diphenyl-N, N'-bis (α-naphthyl) -1,1'-biphenyl-4,4'-diamine is formed as a hole transport layer by a vacuum deposition method. Finally, ITO is formed as a transparent electrode by sputtering to produce an organic EL cell having a white light emitting layer. A display device can be manufactured by adhering the above-mentioned substrate with a partition wall and the organic EL cell thus obtained to face each other with a sealing agent.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these ranges. The names of the compounds used that use abbreviations are shown below.

PGMEA: Propylene glycol monomethyl ether acetate DAA: Diacetone alcohol EDM: Diethylene glycol ethyl methyl ether BHT: Dibutylhydroxytoluene.

The solid content concentration of the polysiloxane solution in Synthesis Examples 1 to 6 and the (meth) acrylic polymer solution in Synthesis Examples 7 to 9 was determined by the following method. 1.5 g of a polysiloxane solution or a (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 content. The weight of the solid content remaining in the aluminum cup after heating was weighed, and the solid content concentration was determined from the ratio to the weight before heating.

The weight average molecular weights 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 methods in terms of polystyrene.

Device: GPC measuring device with RI detector manufactured by Waters (2695)
Column: PLgel MIXED-C column (manufactured by Polymer Laboratories, 300 mm) x 2 (series connection)
Measurement temperature: 40 ° C
Flow rate: 1 mL / min
Solvent: Tetrahydrofuran (THF) 0.5% by mass Solution Standard substance: Polystyrene Detection mode: RI

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

Device: Nuclear magnetic resonance device (JNM-GX270; manufactured by JEOL Ltd.)
Measurement method: Gated decoupling method Measurement nuclear frequency: 53.6693 MHz ( ²⁹ Si nucleus)
Spectral width: 20000Hz
Pulse width: 12 μs (45 ° pulse)
Pulse repetition time: 30.0 seconds Solvent: Acetone-d6
Reference substance: Tetramethylsilane Measurement temperature: 23 ° C
Sample rotation speed: 0.0Hz

Synthesis Example 1 Polysiloxane (PSL-1) solution In a 1000 ml three-necked flask, 203.13 g (0.831 mol) of diphenyldimethoxysilane and 76.06 g (0.306 mol) of 3-methacryloxypropyltrimethoxysilane. 21.56 g (0.088 mol) of (3,4-epoxycyclohexyl) propyltrimethoxysilane, 42.08 g (0.350 mol) of dimethyldimethoxysilane, 45.91 g (3-trimethoxysilylpropylsuccinic anhydride). 0.175 mol), 1.475 g of BHT, and 308.45 g of PGMEA were charged, and 3.887 g of phosphoric acid (1.0% by weight based on the charged monomer) was dissolved in 76.39 g of water with stirring at 40 ° C. An aqueous solution of phosphoric acid was added over 30 minutes. Then, 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 rise, the solution temperature (internal temperature) reached 100 ° C., and the mixture was heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution. During the temperature rise and heating and stirring, a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liter / fraction. A total of 173.99 g of methanol and water, which are by-products, were distilled off during the reaction. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight to obtain a polysiloxane (PSL-1) solution. The weight average molecular weight of the obtained polysiloxane (PSL-1) was 6,000. Further, in polysiloxane (PSL-1), diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, dimethyldimethoxysilane, 3-trimethoxysilylpropyl succinate. The molar ratio of each repeating unit derived from acid anhydride was 47.5 mol%, 17.5 mol%, 5 mol%, 20 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 and 71.16 g (0.306 mol) of 3-methacryloxypropylmethyldimethoxysilane. 21.56 g (0.088 mol) of-(3,4-epoxycyclohexyl) propyltrimethoxysilane, 42.08 g (0.350 mol) of dimethyldimethoxysilane, 45.91 g of 3-trimethoxysilylpropylsuccinic anhydride (0.175 mol), 1.197 g of BHT, and 256.24 g of PGMEA were charged, and 3.455 g of phosphoric acid (1.0% by weight based on the charged monomer) was dissolved in 85.84 g of water with stirring at 40 ° C. An aqueous solution of phosphoric acid was added over 30 minutes. Then, 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 rise, the solution temperature (internal temperature) reached 100 ° C., and the mixture was heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution. During the temperature rise and heating and stirring, a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liter / fraction. A total of 195.52 g of methanol and water, which are by-products, were distilled off during the reaction. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight to obtain a polysiloxane (PSL-2) solution. The weight average molecular weight of the obtained polysiloxane (PSL-2) was 5,500. Further, in polysiloxane (PSL-2), phenyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, dimethyldimethoxysilane, 3-trimethoxysilylpropyl The molar ratio of each repeating unit derived from succinic anhydride was 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol% and 10 mol%, respectively.

Synthesis Example 3 Polysiloxane (PSL-3) solution 117.76 g (0.525 mol) of styryltrimethoxysilane and 71.16 g (0.306 mol) of 3-methacryloxypropylmethyldimethoxysilane in a 1000 ml three-mouth flask. -(3,4-epoxycyclohexyl) propyltrimethoxysilane 21.56 g (0.088 mol), dimethyldimethoxysilane 78.89 g (0.656 mol), 3-trimethoxysilylpropyl succinic anhydride 45.91 g (0.175 mol), 1.180 g of BHT, and 251.60 g of PGMEA were charged, and 3.353 g of phosphoric acid (1.0% by weight based on the charged monomer) was dissolved in 80.33 g of water while stirring at 40 ° C. An aqueous solution of phosphoric acid was added over 30 minutes. Then, 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 rise, the solution temperature (internal temperature) reached 100 ° C., and the mixture was heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution. During the temperature rise and heating and stirring, a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liter / fraction. A total of 182.96 g of methanol and water, which are by-products, were distilled off during the reaction. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight to obtain a polysiloxane (PSL-3) solution. The weight average molecular weight of the obtained polysiloxane (PSL-3) was 12,000. Further, in polysiloxane (PSL-3), styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, dimethyldimethoxysilane, 3-trimethoxysilylpropyl The molar ratio of each repeating unit derived from succinic anhydride was 30 mol%, 17.5 mol%, 5 mol%, 37.5 mol% and 10 mol%, respectively.

Synthesis Example 4 Polysiloxane (PSL-4) solution 186.45 g (0.831 mol) of styryltrimethoxysilane and 21.56 g of 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane in a 1000 ml three-necked flask. 0.088 mol), 78.89 g (0.656 mol) of dimethyldimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropyl succinic acid anhydride, 1.132 g of BHT, and 243.65 g of PGMEA. A phosphoric acid aqueous solution prepared by dissolving 3.328 g of phosphoric acid (1.0% by weight based on the charged monomer) in 85.84 g of water while stirring at 40 ° C. was added over 30 minutes. Then, 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 rise, the solution temperature (internal temperature) reached 100 ° C., and the mixture was heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution. During the temperature rise and heating and stirring, a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liter / fraction. A total of 195.52 g of methanol and water, which are by-products, were distilled off during the reaction. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight to obtain a polysiloxane (PSL-4) solution. The weight average molecular weight of the obtained polysiloxane (PSL-4) was 15,000. In addition, each repetition derived from styryltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-4). The molar ratio of units was 47.5 mol%, 5 mol%, 37.5 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 and 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane were added. 21.56 g (0.088 mol), 142.01 g (1.181 mol) of dimethyldimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropyl succinic anhydride, 0.954 g of BHT, and PGMEA. Was charged in 206.29 g, and an aqueous phosphoric acid solution prepared by dissolving 2.855 g of phosphoric acid (1.0% by weight based on the charged monomer) in 76.39 g of water was added over 30 minutes while stirring at 40 ° C. Then, 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 rise, the solution temperature (internal temperature) reached 100 ° C., and the mixture was heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution. During the temperature rise and heating and stirring, a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liter / fraction. A total of 173.99 g of methanol and water, which are by-products, were distilled off during the reaction. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight to obtain a polysiloxane (PSL-5) solution. The weight average molecular weight of the obtained polysiloxane (PSL-5) was 5,000. In addition, in polysiloxane (PSL-5), 3-methacryloxypropyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride The molar ratio of each derived repeating unit was 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 and 21.56 g (0) of 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane. .088 mol), 78.89 g (0.656 mol) of dimethyldimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropyl succinic acid anhydride, 1.312 g of BHT, and 275.12 g of PGMEA. , A phosphoric acid aqueous solution prepared by dissolving 3.495 g of phosphoric acid (1.0% by weight based on the charged monomer) in 70.88 g of water while stirring at 40 ° C. was added over 30 minutes. Then, 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 rise, the solution temperature (internal temperature) reached 100 ° C., and the mixture was heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution. During the temperature rise and heating and stirring, a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liter / fraction. A total of 161.44 g of methanol and water, which are by-products, were distilled off during the reaction. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight to obtain a polysiloxane (PSL-6) solution. The weight average molecular weight of the obtained polysiloxane (PSL-6) was 6,000. In addition, each repeating unit derived from diphenyldimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride in polysiloxane (PSL-6). The molar ratios were 47.5 mol%, 5 mol%, 37.5 mol% and 10 mol%, respectively.

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

Synthesis Example 7 Synthesis of (meth) acrylic polymer solution (PAL-1) After charging 3.00 g of 2,2'-azobis (isobutyronitrile) and 50.0 g of PGMEA in a 500 mL flask, 30 methacrylic acid was added. 2.0 g (0.349 mol), 22.48 g (0.216 mol) of styrene, and 35.0 g (0.149 mol) of tricyclo [5.2.1.02,6] decan-8-yl methacrylate were charged at room temperature. The mixture was stirred for a while, 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, and the mixture was heated at 90 ° C. for 4 hours. Stirring gave a (meth) acrylic polymer solution. PGMEA was added to the obtained (meth) acrylic polymer solution so that the solid content concentration became 40% by weight to obtain 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) After charging 3.00 g of 2,2'-azobis (isobutyronitrile) and 50.0 g of PGMEA in a 500 mL flask, 15 methacrylic acid was added. .0 g (0.174 mol), 38.06 g (0.216 mol) of benzyl methacrylate and 32.80 g (0.149 mol) of tricyclodecanyl methacrylate were charged, stirred at room temperature for a while, and the inside of the flask was replaced with nitrogen. The mixture was 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, and the mixture was 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 became 40% by weight to obtain a (meth) acrylic polymer solution (PAL-2). The weight average molecular weight of the (meth) acrylic polymer was 25,000.

Synthesis Example 9 Synthesis of (meth) acrylic polymer solution (PAL-3) After charging 3.00 g of 2,2'-azobis (isobutyronitrile) and 50.0 g of PGMEA in a 500 mL flask, 30 methacrylic acid was added. After charging 1.0 g (0.349 mol) and 116.98 g (0.498 mol) of tricyclo [5.2.1.02,6] decane-8-yl methacrylate, stirring at room temperature for a while, and replacing the inside of the flask with nitrogen. , 70 ° C. for 5 hours with stirring. 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, and the mixture was heated at 90 ° C. for 4 hours. Stirring gave a (meth) acrylic polymer solution. PGMEA was added to the obtained (meth) acrylic polymer solution so that the solid content concentration became 40% by weight to obtain 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 in Table 1.

Synthesis Example 10 Green organic phosphor 3,5-dibromobenzaldehyde (3.0 g), 4-t-butylphenylboronic acid (5.3 g), tetrakis (triphenylphosphine) palladium (0) (0.4 g), and Potassium carbonate (2.0 g) was placed in a flask and replaced 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, and then the organic layer was washed with saturated brine. The organic layer was dried over magnesium sulfate, filtered, and then the solvent was distilled off. The obtained reaction product was purified by silica gel column chromatography to obtain a white solid of 3,5-bis (4-t-butylphenyl) benzaldehyde (3.5 g). Next, 3,5-bis (4-t-butylphenyl) benzaldehyde (1.5 g) and 2,4-dimethylpyrrole (0.7 g) were placed in a flask, and dehydrated dichloromethane (200 mL) and trifluoroacetic acid (1) were placed. Droplets) were added, and the mixture was stirred for 4 hours under a nitrogen atmosphere. A dehydrated dichloromethane solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.85 g) was added to the reaction mixture, and the mixture was further stirred for 1 hour. After completion of the reaction, boron trifluorinated diethyl ether complex (7.0 mL) and diisopropylethylamine (7.0 mL) were added and stirred for 4 hours, then water (100 mL) was further added and stirred to separate the organic layer. bottom. The organic layer was dried over magnesium sulfate, filtered, and then 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 ¹ H-NMR analysis result of the obtained green powder is as follows, and it was confirmed that the green powder obtained above is [G-1] represented by the following structural formula.

^{1 1} H-NMR (CDCl ₃ (d = ppm)): 7.95 (s, 1H), 7.63-7.48 (m, 10H), 6.00 (s, 2H), 2.58 (s) , 6H), 1.50 (s, 6H), 1.37 (s, 18H).

Synthesis Example 11 A mixed solution of 300 mg of red organic phosphor 4- (4-t-butylphenyl) -2- (4-methoxyphenyl) pyrrole, 201 mg of 2-methoxybenzoyl chloride and 10 ml of toluene was prepared at 120 ° C. under a nitrogen stream. It was heated for 6 hours. After cooling to room temperature, the solvent was evaporated. The obtained residue was washed with 20 ml of ethanol and vacuum dried to obtain 260 mg of 2- (2-methoxybenzoyl) -3- (4-t-butylphenyl) -5- (4-methoxyphenyl) pyrrole. rice field. Next, 2- (2-methoxybenzoyl) -3- (4-t-butylphenyl) -5- (4-methoxyphenyl) pyrrole 260 mg, 4- (4-t-butylphenyl) -2- (4-) A mixed solution of 180 mg of methoxyphenyl) pyrrole, 206 mg of methanesulfonic acid anhydride and 10 ml of degassed toluene was heated at 125 ° C. for 7 hours under a nitrogen stream. The reaction mixture was cooled to room temperature, 20 ml of water was injected, and the mixture was extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, then evaporated and vacuum dried to obtain a pyrromethene 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 pyrromethene 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 poured into the reaction mixture and 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 reddish purple powder was obtained (yield 70%). The ¹ H-NMR analysis result of the obtained reddish purple powder is as follows, and it was confirmed that the reddish purple powder obtained above is [R-1] represented by the following structural formula.

^{1 1} H-NMR (CDCl ₃ (d = ppm)): 1.19 (s, 18H), 3.42 (s, 3H), 3.85 (s, 6H), 5.72 (d, 1H), 6.20 (t, 1H), 6.42-6.97 (m, 16H), 7.89 (d, 4H).

Synthesis Example 12 Silica particle-containing polysiloxane solution (LS-1)
In a 500 ml three-necked flask, 0.05 g (0.4 mmol) of methyltrimethoxysilane, 0.66 g (3.0 mmol) of trifluoropropyltrimethoxysilane, and 0.10 g (0) of trimethoxysilylpropylsuccinate anhydride. .4 mmol), 7.97 g (34 mmol) of γ-acryloxypropyltrimethoxysilane, and 15.6% by weight of silica particles in an isopropyl alcohol dispersion (IPA-ST-UP: manufactured by Nissan Chemical Industry Co., Ltd.). 224.37 g was added, and 163.93 g of ethylene glycol mono-t-butyl ether was added. While stirring at room temperature, an aqueous phosphoric acid solution prepared by dissolving 0.088 g of phosphoric acid in 4.09 g of water was added over 3 minutes. Then, 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. The internal temperature of the solution reaches 100 ° C. 1 hour after the start of temperature rise, and the solution is heated and stirred for another 2 hours (internal temperature is 100 to 110 ° C.) to obtain a silica particle-containing polysiloxane solution (LS-1). rice field. During the temperature rise and heating and stirring, 0.05 liter (liter) / fraction of nitrogen was flowed. A total of 194.01 g of methanol and water, which are by-products, were distilled off during the reaction. The solid content concentration of the obtained silica particle-containing polysiloxane solution (LS-1) was 24.3% by weight, and the contents of the polysiloxane and silica particles in the solid content were 15% by weight and 85% by weight, respectively. .. Methyltrimethoxysilane, trifluoropropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinate anhydride, and γ-acryloxypropyltrimethoxysilane of the polysiloxane in the obtained silica particle-containing polysiloxane (LS-1). The molar ratio of each repeating unit derived from was 1.0 mol%, 8.0 mol%, 1.0 mol% and 90.0 mol%, respectively.

Example 1 Resin composition for partition wall (P-1)
As a white pigment, 5.00 g of a titanium dioxide pigment (R-960; manufactured by BASF Japan Ltd. (hereinafter, “R-960”)) was used, and as a resin, a polysiloxane (PSL-1) solution obtained in Synthesis Example 1 was used. 5.00 g and 0.0188 g of titanium nitride as a black pigment were mixed and dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion liquid (MW-1).

Next, 8.27 g of the pigment dispersion (MW-1), 2.83 g of the polysiloxane (PSL-1) solution, and 4.48 g of the (meth) acrylic polymer (PAL-1) solution obtained in Synthesis Example 7. As a photopolymerization initiator, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (О-acetyloxime) ("Irgacure" (registered trademark) ) OXE-02, manufactured by BASF Japan Co., Ltd. (hereinafter "OXE-02")) 0.155 g, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ("Irgacure" 819, BASF Japan Co., Ltd.) ) (Hereinafter "IC-819")) 0.258 g, as a photopolymerizable compound, dipentaerythritol hexaacrylate ("KAYARAD" (registered trademark) DPHA, manufactured by Shin Nihon Yakuhin Co., Ltd. (hereinafter "DPHA")) ) 2.063 g, as a liquid repellent compound, a photopolymerizable fluorine-containing compound (“Megafuck” (registered trademark) RS-72A, 20 wt% PGMEA diluted solution product, manufactured by DIC Co., Ltd. (hereinafter “RS-72A”)) ) 0.258 g, 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("Celoxiside" (registered trademark) 2021P, manufactured by Daicel Co., Ltd. (hereinafter "Celoxiside (registered trademark) 2021P")) 0.021 g, ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] ("Irganox" (registered trademark) 1010, manufactured by BASF Japan Co., Ltd. (hereinafter 0.031 g of "IRGANOX (registered trademark) 1010"), and 10% by weight of PGMEA of acrylic solvent ("BYK" (registered trademark) 352, manufactured by Big Chemie Japan Co., Ltd. (hereinafter "BYK-352")) 0.103 g of the diluted solution (corresponding to a concentration of 500 ppm) was dissolved in 0.513 g of the solvent PGMEA and 1.653 g of DAA, and the mixture was 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 wall (P-2)
5.00 g of R-960 as a white pigment and 5.00 g of a 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 liquid (MW-2). .. Further, as an organometallic compound, 0.103 g of bis (acetylacetonato) palladium and 0.089 g of triphenylphosphine as a coordinating compound having a phosphorus atom (equal molar amount with respect to the organometallic compound) were DAA1. It was dissolved in .726 g to obtain an organometallic compound solution (OM-1).

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

Example 3 Resin composition for partition wall (P-3)
As the organometallic compound, 0.103 g of silver neodecanoate 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, and a (meth) acrylic polymer (PAL-1) solution were used. A resin composition for partition wall (P-3) was obtained in the same manner as in Example 2 except that 4.37 g and 1.366 g of PGMEA were added.

Examples 4 to 6 Resin compositions for partition walls (P-4) to (P-6)
Resin for partition wall in the same manner as in Example 2 except that the polysiloxane (PSL-2), (PSL-3), and (PSL-4) solutions were used instead of the polysiloxane (PSL-1) solution, respectively. Compositions (P-4) to (P-6) were obtained.

Example 7 Resin composition for partition wall (P-7)
Resin composition for partition wall (P-7) in the same manner as in Example 2 except that the (meth) acrylic polymer (PAL-2) solution was used instead of the (meth) acrylic polymer (PAL-1) solution. Got

Example 8 Resin composition for partition wall (P-8)
A resin composition for partition walls (P-8) was obtained in the same manner as in Example 2 except that a cardo-based polymer V-259ME was used instead of the (meth) acrylic polymer (PAL-1) solution.

Example 9 Resin composition for partition wall (P-9)
A resin composition for partition walls (P-9) was obtained in the same manner as in Example 2 except that the cardo-based polymer WR-301 was used instead of the (meth) acrylic polymer (PAL-1) solution.

Example 10 Resin composition for partition wall (P-10)
A resin composition for partition walls (P-10) was obtained in the same manner as in Example 2 except that the amount of IC-819 added was 0.413 g and OXE-02 was not added.

Example 11 Resin composition for partition wall (P-11)
A resin composition for partition walls (P-11) was obtained in the same manner as in Example 2 except that the amount of OXE-02 added was 0.413 g and IC-819 was not added.

Example 12 Resin composition for partition wall (P-12)
Resin composition for partition wall in the same manner as in Example 2 except that the amount of the polysiloxane (PSL-1) solution added was 0.905 g and the amount of the (meth) acrylic polymer (PAL-1) solution added was 5.96 g. A product (P-12) was obtained.

Example 13 Resin composition for partition wall (P-13)
Resin composition for partition wall in the same manner as in Example 2 except that the amount of the polysiloxane (PSL-1) solution added was 4.30 g and the amount of the (meth) acrylic polymer (PAL-1) solution added was 2.57 g. A thing (P-13) was obtained.

Example 14 Resin composition for partition wall (P-14)
The polysiloxane (PSL-1) solution was 7.68 g, the (meth) acrylic polyma (PAL-1) solution amount was 7.68 g, OXE-02 was 0.123 g, IC-819 was 0.205 g, and DPHA was 1. 64 g, 0.205 g of RS-72A, 0.016 g of celoxide 2021P, 0.025 g of IRGANOX1010, and 0.103 g of a 10 wt% diluted solution of BYK-352 PGMEA were dissolved in 0.619 g of solvent PGMEA and 2.214 g of DAA. Stirred. The obtained mixture was filtered through a 5.0 μm filter to obtain a resin composition for partition walls (P-14).

Example 15 Resin composition for partition wall (P-15)
Without adding the organic metal compound solution (OM-1), the amount of the polysiloxane (PSL-1) solution added was 2.85 g, and the amount of the (meth) acrylic polymer (PAL-1) solution added was 4.50 g. A resin composition for partition wall (P-15) was obtained in the same manner as in Example 2 except that the amount of PGMEA added was 0.284 g and the amount of DAA added was 1.86 g.

Example 16 Resin composition for partition wall (P-16)
0.20 g of titanium nitride as a black pigment and 7.00 g of a polysiloxane (PSL-1) solution as a resin were mixed and dispersed using a mill-type disperser filled with zirconia beads to prepare a pigment dispersion (MW-3). Obtained.

5.90 g of the pigment dispersion (MW-3), 0.79 g of the polysiloxane (PSL-1) solution, 6.54 g of the (meth) acrylic polyma (PAL-1) solution, and 0.108 g of OXE-02. , IC-819 0.180 g, DPHA 1.44 g, RS-72A 0.179 g, seroxide 2021P 0.014 g, IRGANOX 1010 0.022 g, and BYK-352 PGMEA 10 wt% diluted solution 0.103 g. , Dissolved in 1.804 g of solvent PGMEA and stirred. The obtained mixture was filtered through a 5.0 μm filter to obtain a resin composition for partition walls (P-16).

Example 17 Resin composition for partition wall (P-17)
The organic metal compound solution (OM-1) is 4.00 g, the polysiloxane (PSL-1) solution is 6.21 g, the (meth) acrylic polyma (PAL-1) solution amount is 6.21 g, and OXE-02 is 0. .108 g, IC-819 0.180 g, DPHA 1.44 g, RS-72A 0.179 g, seroxide 2021P 0.014 g, IRGANOX 1010 0.022 g, and BYK-352 PGMEA 10 wt% diluted solution 0. 103 g was dissolved in 2.03 g of the solvent PGMEA and stirred. The obtained mixture was filtered through a 5.0 μm filter to obtain a resin composition for partition walls (P-17).

Example 18 Resin composition for partition wall (P-18)
Without adding the liquid repellent compound RS-72A, the amount of the polysiloxane (PSL-1) solution added was 2.67 g, the amount of the (meth) acrylic polymer (PAL-1) solution added was 4.32 g, and PGMEA was added. A resin composition for partition walls (P-18) was obtained in the same manner as in Example 2 except that the amount was 0.830 g.

Comparative Examples 1 and 2 Resin compositions for partition walls (P-19) to (P-20)
Resin composition for partition wall (P-19) in the same manner as in Example 2 except that the polysiloxane (PSL-5) and (PSL-6) solutions were used instead of the polysiloxane (PSL-1) solution, respectively. )-(P-20) were obtained.

Comparative Example 3 Resin composition for partition wall (P-21)
Resin composition for partition wall (P-21) in the same manner as in Example 2 except that the (meth) acrylic polymer (PAL-3) solution was used instead of the (meth) acrylic polymer (PAL-1) solution. Got

Comparative Example 4 Resin composition for partition wall (P-22)
Resin composition for partition wall in the same manner as in Example 2 except that the amount of the polysiloxane (PSL-1) solution added was 0.480 g and the amount of the (meth) acrylic polymer (PAL-1) solution added was 6.39 g. A thing (P-22) was obtained.

Comparative Example 5 Resin composition for partition wall (P-23)
Resin composition for partition wall in the same manner as in Example 2 except that the amount of the polysiloxane (PSL-1) solution added was 4.74 g and the amount of the (meth) acrylic polymer (PAL-1) solution added was 2.13 g. A thing (P-23) was obtained.

Comparative Example 6 Resin composition for partition wall (P-24)
A resin composition for a partition wall (meth) in the same manner as in Example 2 except that the amount of the polysiloxane (PSL-1) solution added was 6.87 g without adding the (meth) acrylic polymer (PAL-1) solution. P-24) was obtained.

Comparative Example 7 Resin composition for partition wall (P-25)
5.00 g of R-960 as a white pigment and 5.00 g of a (meth) acrylic polymer (PAL-1) solution as a resin were mixed and dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-4). Got

8.25 g of the pigment dispersion (MW-4) was added instead of the pigment dispersion (MW-2), and the (meth) acrylic polymer (PAL-1) was added without adding the polysiloxane (PSL-1) solution. A resin composition for partition walls (P-25) was obtained in the same manner as in Example 2 except that 6.87 g of the solution was added.

The compositions of Examples 1 to 18 and Comparative Examples 1 to 7 are summarized in Table 3.

Preparation Example 1 Color conversion luminescent material composition (CL-1)
20 parts by weight of 0.5 wt% toluene solution of green quantum dot material (Lumidot 640 CdSe / ZnS, average particle size 6.3 nm: manufactured by Aldrich), 45 parts by weight of DPHA, "Irgacure" (registered trademark) 907 (registered trademark) Mix 5 parts by weight of BASF Japan Ltd., 166 parts by weight of 30% by weight PGMEA solution of acrylic resin (SPCR-18 (trade name), Showa Denko Corporation) and 97 parts by weight of toluene and stir. And dissolved uniformly. The obtained mixture was filtered through a 0.45 μm syringe filter to prepare a color conversion luminescent material composition (CL-1).

Preparation Example 2 Color conversion luminescent material composition (CL-2)
The color was the same as in Preparation Example 1 except that 0.4 parts by weight of the green phosphor G-1 obtained in Synthesis Example 10 was used instead of the green quantum dot material and the amount of toluene added was changed to 117 parts by weight. A conversion light emitting material composition (CL-2) was prepared.

Preparation Example 3 Color conversion luminescent material composition (CL-3)
The color was the same as in Preparation Example 1 except that 0.4 parts by weight of the red phosphor R-1 obtained in Synthesis Example 11 was used instead of the green quantum dot material and the amount of toluene added was changed to 117 parts by weight. A conversion light emitting material composition (CL-3) was prepared.

Preparation Example 4 Color filter forming material (CF-1)
C. I. Pigment Green 59 90g, C.I. I. Pigment Yellow 150 60 g, polymer dispersant (“BYK” (registered trademark) -6919 (trade name) manufactured by Big Chemie (hereinafter “BYK-6919”)) 75 g, binder resin (“ADEKA ARCLUS” (registered trademark)” ) 100 g of WR301 (trade name) manufactured by ADEKA Corporation) and 675 g of PGMEA were mixed to prepare a slurry. A beaker containing the slurry was connected to a dyno mill with a tube, and zirconia beads having a diameter of 0.5 mm were used as a medium for dispersion treatment at a peripheral speed of 14 m / s for 8 hours. Pigment Green 59 dispersion (GD-1) Was produced.

Pigment Green 59 Dispersion (GD-1) 56.54g, Acrylic Resin (“Cyclomer” (Registered Trademark) P (ACA) Z250 (Product Name) Made by Daicel Ornex Co., Ltd. (hereinafter “P (ACA) Z250”” )) 3.14 g, DPHA 2.64 g, photopolymerization initiator (“Optomer” (registered trademark) NCI-831 (trade name) manufactured by ADEKA Co., Ltd. (hereinafter “NCI-831”)) 0.330 g, 0.04 g of surfactant (BYK (registered trademark) -333 (trade name) manufactured by Big Chemie (hereinafter “BYK-333”)), 0.01 g of BHT as a polymerization inhibitor, and 37. PGMEA as a solvent. 30 g was mixed to prepare a color filter forming material (CF-1).

Preparation Example 5 Resin composition for light-shielding partition carbon black (MA100 (trade name) manufactured by Mitsubishi Chemical Corporation) 150 g, polymer dispersant BYK-6919 (75 g), P (ACA) Z250 (100 g), and PGMEA (675 g) are mixed. To prepare a slurry. A beaker containing the slurry is connected to a dyno mill with a tube, and zirconia beads having a diameter of 0.5 mm are used as a medium for dispersion treatment at a peripheral speed of 14 m / s for 8 hours to prepare a pigment dispersion liquid (MB-1). bottom.

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

Preparation Example 6 Low Refractive Index Layer Forming Material 5.350 g of 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. After mixing, it was filtered through a 0.45 μm syringe filter to prepare a low refractive index layer forming material.

Preparation Example 7 Yellow Organic Protective Layer Forming Material (YL-1)
C. I. Pigment Yellow 150 (150 g), polymer dispersant ("BYK" (registered trademark) -6919 (trade name) manufactured by Big Chemie (hereinafter "BYK-6919")) (75 g), binder resin ("ADEKA ARCLUDS" (registered trademark)) ) 100 g of WR301 (trade name) manufactured by ADEKA Corporation) and 675 g of PGMEA were mixed to prepare a slurry. A beaker containing the slurry was connected to a dyno mill with a tube, and zirconia beads having a diameter of 0.5 mm were used as a medium for dispersion treatment at a peripheral speed of 14 m / s for 8 hours. Pigment Yellow 150 dispersion (YD-1) Was produced.

Pigment Yellow 150 dispersion (YD-1) 3.09 g, polysiloxane (PSL-1) solution 23.54 g as resin, DPHA 6.02 g as photopolymerizable compound, and silver neodecanoate as organic metal compound. 6.02 g of the prepared organic metal compound solution (OM-2), 0.20 g of OXE-02 as a photopolymerization initiator, 0.40 g of IC-819, 0.060 g of IRGANOX® 1010, and BYK. 0.050 g (corresponding to a concentration of 500 ppm) of a 10 wt% diluted solution of PGMEA of -352 was dissolved in 61.15 g of the 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 19 to 37, Comparative Examples 8 to 14)
A 10 cm square non-alkali glass substrate (manufactured by AGC Technoglass Co., Ltd., thickness 0.7 mm) was used as the base substrate. The resin composition for partition walls shown in Tables 4 to 5 is spin-coated on the resin composition, and dried at a temperature of 100 ° C. for 3 minutes using a hot plate (trade name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.). , A dry film was prepared. The prepared dry film was subjected to a parallel light mask aligner (trade name PLA-501F, manufactured by Canon Inc.) using an ultrahigh pressure mercury lamp as a light source, and an exposure amount of 300 mJ / cm ² (g, h) via a photomask. , I line). Then, using an automatic developing device (“AD-2000 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 100 seconds using a 0.045 wt% potassium hydroxide aqueous solution, and then 30 using water. Rinse for seconds. Further, using an oven (trade name IHPS-222, manufactured by ESPEC CORPORATION), the partition is heated in air at a temperature of 230 ° C. for 30 minutes, and a partition wall having a height of 10 μm and a width of 20 μm is formed on a glass substrate with a short side of 80 μm. , A partition wall formed in a grid pattern with a pitch interval of 280 μm on the long side was formed.

The color conversion luminescent material composition shown in Tables 4 to 5 was applied to the region of the obtained substrate with a partition wall separated by the partition wall in a nitrogen atmosphere by an inkjet method, dried at 100 ° C. for 30 minutes, and thickened. A 5.0 μm pixel was formed, and a substrate with a partition wall having the configuration shown in FIG. 2 was obtained.

(Example 38)
A 10 cm square non-alkali glass substrate (manufactured by AGC Technoglass Co., Ltd., thickness 0.7 mm) was used as the base substrate. On it, the light-shielding partition wall forming material obtained in Preparation Example 5 was spin-coated and dried at a temperature of 100 ° C. for 3 minutes using a hot plate (trade name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.). , A dry film was prepared. The prepared dry film was subjected to a parallel light mask aligner (trade name PLA-501F, manufactured by Canon Inc.) using an ultrahigh pressure mercury lamp as a light source, and an exposure amount of 40 mJ / cm ² (g, h) via a photomask. , I line). Then, using an automatic developing device (“AD-2000 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), it was developed with a 0.3 wt% tetramethylammonium aqueous solution for 50 seconds, and then rinsed with water for 30 seconds. bottom. Further, using an oven (trade name IHPS-222, manufactured by ESPEC CORPORATION), the mixture is heated in air at a temperature of 230 ° C. for 30 minutes, and is placed on a glass substrate with a height of 2.0 μm, a width of 20 μm, and a thickness of 1. A substrate with a light-shielding partition wall was obtained in which a partition wall having an OD value of 2.0 per 0 μm was formed in a grid pattern with a short side of 40 μm and a long side of 280 μm at pitch intervals.

Then, by the same method as in Example 20, a partition wall having a height of 10 μm and a width of 20 μm is formed on the light-shielding partition wall in a grid pattern similar to that of the light-shielding partition wall having a pitch interval of 40 μm on the short side and 280 μm on the long side. Obtained a substrate with. The color conversion luminescent material composition (CL-2) obtained in Preparation Example 2 was applied to the region of the obtained substrate with a partition wall separated by the partition wall in a nitrogen atmosphere by an inkjet method, and at 100 ° C. It was dried for 30 minutes to form pixels having a thickness of 5.0 μm, and a substrate with a partition wall having the configuration shown in FIG. 3 was obtained.

(Example 39)
The color obtained in Preparation Example 4 so that the film thickness after curing is 2.5 μm in the region separated by the partition wall of the substrate with the partition wall before pixel formation, which was obtained by the same method as in Example 18. A filter forming material (CF-1) was applied and vacuum dried. ^{Exposure was performed at an exposure amount of 40 mJ / cm 2} (g, h, i-line) through a photomask designed to expose the area of the opening of the substrate with a partition wall. After developing for 50 seconds with a 0.3 wt% tetramethylammonium aqueous solution, heat curing was performed at 230 ° C. for 30 minutes, and the height was 2.5 μm, the short side was 40 μm, and the long side was 280 μm in the region separated by the partition wall. A color filter layer was formed. Then, the color conversion luminescent material composition (CL-2) obtained in Preparation Example 2 was applied onto the color filter under a nitrogen atmosphere using an inkjet method, dried at 100 ° C. for 30 minutes, and the thickness was 5. A pixel of 0 μm was formed, and a substrate with a partition wall having the configuration shown in FIG. 4 was obtained.

(Example 40)
The low refractive index layer forming material obtained in Preparation Example 6 was spin-coated on a substrate with a partition wall after pixels were formed by the same method as in Example 20, and a hot plate (trade name SCW-636, Dainippon Screen Mfg. Co., Ltd.) was manufactured. A dry film was prepared by drying at a temperature of 100 ° C. for 3 minutes using a product manufactured by Co., Ltd. Further, using an oven (trade name IHPS-222, manufactured by ESPEC CORPORATION), the mixture is heated in air at a temperature of 90 ° C. for 30 minutes to form a low refractive index layer having a height of 1.0 μm and a refractive index of 1.25. Then, a substrate with a partition wall having the configuration shown in FIG. 6 was obtained.

(Example 41)
Inorganic protection with a height of 50 to 1,000 nm using a plasma CVD device (PD-220NL, manufactured by SAMCO Corporation) on the low refractive index layer of the substrate with a partition wall having the low refractive index layer obtained in Example 40. A silicon nitride film having a thickness of 300 nm corresponding to layer I was formed, and a substrate with a partition wall having the configuration shown in FIG. 7 was obtained.

(Example 42)
A 10 cm square non-alkali glass substrate (manufactured by AGC Technoglass Co., Ltd., thickness 0.7 mm) was used as the base substrate. On it, the light-shielding partition wall forming material obtained in Preparation Example 5 was spin-coated and dried at a temperature of 100 ° C. for 3 minutes using a hot plate (trade name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.). , A dry film was prepared. The prepared dry film was subjected to a parallel light mask aligner (trade name PLA-501F, manufactured by Canon Inc.) using an ultrahigh pressure mercury lamp as a light source, and an exposure amount of 40 mJ / cm ² (g, h) via a photomask. , I line). Then, using an automatic developing device (“AD-2000 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), it was developed with a 0.3 wt% tetramethylammonium aqueous solution for 50 seconds, and then rinsed with water for 30 seconds. bottom. Further, using an oven (trade name IHPS-222, manufactured by ESPEC CORPORATION), the mixture is heated in air at a temperature of 230 ° C. for 30 minutes, and is placed on a glass substrate with a height of 2.0 μm, a width of 20 μm, and a thickness of 1. A substrate with a light-shielding partition wall was obtained in which a partition wall having an OD value of 2.0 per 0 μm was formed in a grid pattern with a short side of 40 μm and a long side of 280 μm at pitch intervals.

Then, the color filter forming material (CF-1) obtained in Preparation Example 4 was applied to the region separated by the light-shielding partition wall so that the film thickness after curing was 2.5 μm, and vacuum-dried. ^{Exposure was performed at an exposure amount of 40 mJ / cm 2} (g, h, i-line) through a photomask designed to expose the area of the opening of the substrate with a partition wall. After developing for 50 seconds with a 0.3 wt% tetramethylammonium aqueous solution, heat curing was performed at 230 ° C. for 30 minutes, and the height was 2.5 μm, the short side was 40 μm, and the long side was 280 μm in the region separated by the partition wall. A color filter layer was formed.

Then, 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 (trade name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.). , A dry film was prepared. Further, using an oven (trade name IHPS-222, manufactured by ESPEC CORPORATION), the mixture is heated in air at a temperature of 90 ° C. for 30 minutes to form a low refractive index layer having a height of 1.0 μm and a refractive index of 1.25. bottom.

After that, a silicon nitride film having a film thickness of 300 nm, which corresponds to an inorganic protective layer I having a height of 50 to 1,000 nm, was formed on the low refractive index layer using a plasma CVD apparatus (PD-220NL, manufactured by SAMCO Corporation). Formed.

On top of these, a partition wall having a height of 10 μm and a width of 20 μm is formed in a grid pattern similar to a light-shielding partition wall having a short side of 40 μm and a long side of 280 μm in the same manner as in Example 20. Got The color conversion luminescent material composition (CL-2) obtained in Preparation Example 2 was applied to the region of the obtained substrate with a partition wall separated by the partition wall in a nitrogen atmosphere by an inkjet method, and at 100 ° C. It was dried for 30 minutes to form pixels having a thickness of 5.0 μm, and a substrate with a partition wall having the configuration shown in FIG. 9 was obtained.

(Example 43)
The plasma CVD apparatus ( PD-220NL (manufactured by SAMCO) was used to form a silicon nitride film having a film thickness of 300 nm, which corresponds to an inorganic protective layer III having a thickness of 50 to 1,000 nm. Further, the color conversion luminescent material composition (CL-2) obtained in Preparation Example 2 was applied onto the inorganic protective layer III under a nitrogen atmosphere using an inkjet method, dried at 100 ° C. for 30 minutes, and thickened. A 5.0 μm pixel was formed, and a substrate with a partition wall having the configuration shown in FIG. 11 was obtained.

(Example 44)
A 10 cm square non-alkali glass substrate (manufactured by AGC Technoglass Co., Ltd., thickness 0.7 mm) was used as the base substrate. On it, a plasma CVD apparatus (PD-220NL, manufactured by SAMCO Corporation) was used to form a silicon nitride film having a film thickness of 300 nm, which corresponds to an inorganic protective layer IV having a thickness of 50 to 1,000 nm. A substrate with a partition wall having the configuration shown in FIG. 12 was obtained by the same method as in Example 20 except that the substrate was used instead of a 10 cm square non-alkali glass substrate.

(Example 45)
According to Preparation Example 7, a color filter layer having a thickness of 2.5 μm, a short side of 40 μm, and a long side of 280 μm, which was obtained by the same method as in Example 35, was formed on a color filter of a substrate with a partition wall before pixel formation. The obtained yellow organic protective layer forming material (YL-1) was applied and vacuum dried. ^{Exposure was performed at an exposure amount of 300 mJ / cm 2} (g, h, i-line) through a photomask designed to expose the area of the opening of the substrate with a partition wall. After developing with a 0.3 wt% tetramethylammonium aqueous solution for 50 seconds, it was heat-cured at 230 ° C. for 30 minutes to form a yellow organic protective layer having a thickness of 1.0 μm, a short side of 40 μm, and a long side of 280 μm. Further, the color conversion luminescent material composition (CL-2) obtained in Preparation Example 2 was applied onto the yellow organic protective layer under a nitrogen atmosphere using an inkjet method, dried at 100 ° C. for 30 minutes, and thickened. A 5.0 μm pixel was formed, and a substrate with a partition wall having the configuration shown in FIG. 11 was obtained.

(Example 46)
A 10 cm square non-alkali glass substrate (manufactured by AGC Technoglass Co., Ltd., thickness 0.7 mm) was used as the base substrate. The yellow organic protective layer forming material (YL-1) obtained in Preparation Example 7 was applied thereto, and the mixture was vacuum dried. The dried film was exposed to an exposure amount of 300 mJ / cm ² (g, h, i-line) without using a photomask, then developed with a 0.3 wt% tetramethylammonium aqueous solution for 50 seconds, and then developed at 230 ° C. for 30. By heat-curing for 1 minute, a yellow organic protective layer having a thickness of 1.0 μm was formed. A substrate with a partition wall having the configuration shown in FIG. 8 was obtained by the same method as in Example 20 except that the substrate was used instead of a 10 cm square non-alkali glass substrate.

The configurations of each Example and Comparative Example are shown in Tables 4 to 5.

The evaluation methods in each Example and Comparative Example are shown below.

<Glass transition temperature of (meth) acrylic polymer / cardo polymer>
The (meth) acrylic polymer and / or cardo-based polymer in the resin composition of the present invention used in Examples and Comparative Examples was obtained from a thermogram obtained using a DSC apparatus (Rigaku's "Thermo Plus DSC8230"). Calculated. The DSC measurement was carried out under nitrogen at a heating rate of 20 ° C./min. The glass transition temperature was calculated as the temperature corresponding to the intersection of the baseline and the tangent at the inflection point in the DSC temperature rise curve on the thermogram. The inflection point was the temperature corresponding to the peak in the DDSC (differential value of DSC) curve of the thermogram. Further, in order to confirm the baseline of DSC, 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 lower than 60 ° C.

<Refractive index of low refractive index layer>
The low refractive index layer forming material used in each example was applied onto a silicon wafer with a spinner, and a hot plate (trade name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) was used at a temperature of 90 ° C. It was dried for 2 minutes. Then, using an oven (IHPS-222; manufactured by ESPEC CORPORATION), it was heated in air at 90 ° C. for 30 minutes to prepare a cured film. Using a prism coupler (PC-2000 (manufactured by Metrocon Co., Ltd.)), the cured film surface is irradiated with light having a wavelength of 550 nm from the vertical direction under atmospheric pressure and at 20 ° C., and the refractive index is measured. , Rounded to the third decimal place.

<Tackless property of dry film>
Using a spin coater (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), the resin composition for partition walls used in each Example and Comparative Example was placed on a 10 cm square non-alkali glass substrate, and the film thickness after drying. Was spin-coated to a thickness of 10 μm and dried using a hot plate (trade name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) at a temperature of 100 ° C. for 3 minutes to prepare a dry film having a film thickness of 10 μm. .. A 10 cm square non-alkali glass substrate, which was likened to a mask, was placed on the prepared dry film for 1 minute so as to overlap with each other, and the tackless property of the dry film was evaluated according to the following criteria. The less adhesive the glass substrate is, the higher the tacklessness is and the better the handleability is.

A: Even if the dry film and the glass substrate were overlapped, they did not adhere to each other, and after the glass substrate was separated, the glass substrate was not contaminated with the partition material.
B: When the dry film and the glass substrate were overlapped, they adhered to each other, but the glass substrate could be easily separated. The glass substrate was slightly contaminated with the bulkhead material.
C: When the dry film and the glass substrate were overlapped, they adhered and stuck together. The glass substrate could not be easily pulled apart. After pulling the glass substrate apart, the glass substrate was contaminated with the bulkhead material.

<Crack resistance>
The partition wall-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. The subsequent steps were processed under the same conditions as in each Example and Comparative Example except that the entire surface was exposed without using a photomask at the time of exposure to prepare a solid film on a glass substrate. The obtained solid film was used as a model of the partition wall of the substrate with a partition wall obtained in each Example and Comparative Example, and the glass substrate having the solid film was visually observed to evaluate the presence or absence of cracks in the solid film. If 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 when the film thickness was 15 μm and there were cracks when the film thickness was 20 μm, the crack resistance film thickness was determined to be “≧ 15 μm”. Further, the crack resistance film thickness when there was no crack even at 25 μm was determined as “≧ 25 μm”, and the crack resistance film thickness when there was a crack even at 10 μm was determined as “<10 μm”, respectively, and the crack resistance was determined.

<Wrinkle resistance>
The partition wall-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. The subsequent steps were processed under the same conditions as in each Example and Comparative Example except that the entire surface was exposed without using a photomask at the time of exposure to prepare a solid film on a glass substrate. The obtained solid film was used as a model of the partition wall of the substrate with a partition wall obtained in each Example and Comparative Example, and the glass substrate having 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 when the film thickness was 15 μm and there were wrinkles when the film thickness was 20 μm, the wrinkle resistance was determined to be “≧ 15 μm”. Further, the wrinkle resistance when there was no wrinkle even at 25 μm was determined as “≧ 25 μm”, and the wrinkle resistance when there was wrinkle even at 10 μm was determined as “<10 μm”, respectively, and the wrinkle resistance was determined.

<1% weight loss temperature>
The partition wall-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. The subsequent steps were processed under the same conditions as in each Example and Comparative Example except that the entire surface was exposed without using a photomask at the time of exposure to prepare a solid film on a glass substrate. Next, a part of the solid film formed on the Si wafer was scraped off carefully so as not to mix impurities, and about 100 mg was put into an aluminum cell. Using a thermogravimetric analyzer (TGA-50, manufactured by Shimadzu Corporation), hold at 150 ° C for 30 minutes in a nitrogen atmosphere, and then heat to 400 ° C at a heating rate of 10 ° C / min to measure the weight. bottom. The temperature reduced by 1% by weight from the weight at the start of temperature rise was defined as the 1% weight loss temperature. The higher the 1% weight loss temperature, the higher the heat resistance.

<Resolution>
Using a spin coater (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), the resin composition for partition walls used in each Example and Comparative Example was placed on a 10 cm square non-alkali glass substrate, and the film thickness after heating. Was spin-coated to a thickness of 10 μm and dried using a hot plate (trade name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) at a temperature of 100 ° C. for 3 minutes to prepare a dried film having a film thickness of 10 μm. ..

The prepared dry film is used as a parallel light mask aligner (trade name: PLA-501F, manufactured by Canon Inc.) with an ultra-high pressure mercury lamp as a light source, and has widths of 100 μm, 80 μm, 60 μm, 50 μm, 40 μm, 30 μm, and 20 μm. Through a mask having the line & space pattern of, the exposure was performed with an exposure amount of 300 mJ / cm ² (i-line) and a gap of 100 μm. Then, using an automatic developing device (“AD-2000 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 100 seconds using a 0.045 wt% potassium hydroxide aqueous solution, and then 30 using water. Rinse for seconds.

The developed pattern was magnified and observed using a microscope adjusted to a magnification of 100 times, and the narrowest line width was defined as the resolution among the patterns in which no residue was observed in the unexposed portion. However, when there was a residue in the unexposed portion near the pattern having a width of 100 μm, it was set to “> 100 μm”.

<Reflectance>
The partition wall-forming resin composition used in each Example and Comparative Example was processed under the same conditions as in each Example and Comparative Example except that the entire partition-forming resin composition was exposed without using a photomask at the time of exposure, and was processed on a glass substrate. A solid film having a size of 10 μm was prepared. Using the obtained solid film as a model of the partition wall of the substrate with a partition wall obtained in each Example and Comparative Example, a spectrocolorimeter (trade name CM-2600d, manufactured by Konica Minolta Co., Ltd.) was used for a glass substrate having a solid film. ) Was used to measure the reflectance at wavelengths of 450 nm, 550 nm and 630 nm in the SCI mode from the solid film side. However, when cracks or wrinkles were generated in the solid film, the reflectance was not measured because an accurate value could not be obtained due to the cracks or the like.

<OD value>
As a model of the partition wall of the substrate with a partition wall obtained in each Example and Comparative Example, a solid film having a height of 10 μm was prepared on the glass substrate in the same manner as in the evaluation of the reflectance. With respect to the obtained glass substrate having a solid film, the intensities of incident light and transmitted light were measured using an optical densitometer (U-4100 manufactured by Hitachi High-Tech Science), and wavelengths of 450 nm, 550 nm and 630 nm were measured by the above formula (1). The OD value in was calculated. Regarding the OD value, the solid film before the heating step and the OD value after the heating step were measured, and the differences are shown in Tables 6 to 7.

Further, in Example 34, a solid film was similarly produced on a glass substrate as a model of the light-shielding partition wall (A-2). With respect to the obtained glass substrate having a solid film, the intensities of incident light and transmitted light were measured using an optical densitometer (U-4100 manufactured by Hitachi High-Tech Science), and calculated by the above formula (1).

<Taper angle>
In each Example and Comparative Example, an arbitrary cross section of the substrate with a partition wall before pixel formation was subjected to an acceleration voltage of 3.0 kV using an optical microscope (FE-SEM (S-4800); manufactured by Hitachi, Ltd.). It was observed and the taper angle was measured.

<Surface contact angle>
As a model of the partition wall in the partition wall-equipped substrate obtained in each Example and Comparative Example, a solid film having a height of 10 μm was prepared on the glass substrate in the same manner as in the evaluation of the reflectance. Regarding the surface of the obtained solid film, DM-700 manufactured by Kyowa Interface Science Co., Ltd., microsyringe: Teflon (registered trademark) coated needle 22G for contact angle meter manufactured by Kyowa Interface Science Co., Ltd. was used at 25 ° C. for the atmosphere. Among them, the surface contact angle was measured in accordance with the wettability test method for the surface of the substrate glass specified in JIS R3257 (establishment date = 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 coatability>
In the substrate with a partition wall before forming the pixels obtained in each Example and Comparative Example, an inkjet coating device (InkjetLabo, Cluster Technology) (InkjetLabo, Cluster Technology) using PGMEA as an ink for the pixel portion surrounded by the grid-like partition walls. Inkjet coating was performed using (manufactured by Co., Ltd.). 160 pL of PGMEA was applied to one grid pattern, and the presence or absence of breakage (a phenomenon in which the ink got over the partition wall and mixed into the adjacent pixel portion) was observed, and the inkjet coatability was evaluated according to the following criteria. The smaller the number of breaks, the higher the liquid repellency and the better the inkjet coating property.

A: The ink did not overflow from the inside of the pixel.
B: Ink overflowed from the inside of the pixel to the upper surface of the partition wall in a part.
C: Ink overflowed from the inside of the pixel to the upper surface of the partition wall on the entire surface.

<Height>
For the substrates with partition walls obtained in each Example and Comparative Example, the height of the structure before and after the formation of the pixel (B) was measured using a surfcom stylus type film thickness measuring device, and the difference was calculated. , The height of the pixel (B) was measured. For Examples 36 to 38, the film thickness of the low refractive index layer (C) is further increased, for Examples 35, 38 to 39, 41, the film thickness of the color filter is further increased, and for Examples 34, 38, the film thickness of the light-shielding partition wall is further increased. The thickness (height) of Examples 41 and 42 was further measured, and the thickness (height) of the yellow organic protective layer was measured in the same manner.

Further, in Examples 37 to 404, a cross section perpendicular to the base substrate is exposed using a polishing device such as a cross section polisher, and the cross section is magnified and observed with a scanning electron microscope or a transmission electron microscope. , The heights of the inorganic protective layers I to IV were measured, respectively.

<Brightness>
Using a planar light emitting device equipped with a commercially available LED backlight (peak wavelength 465 nm) as a light source, the substrates with partition walls 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 planar light emitting device to light the LED element, and a spectral radiance meter (CS-1000, manufactured by Konica Minolta) is used to measure the brightness (unit: cd / m ² ) based on the CIE 1931 standard. It was measured and used as the initial brightness. However, the evaluation of the brightness was performed by a relative value with the initial brightness of Example 31 as the standard 100.

Further, after the LED element was lit for 48 hours at room temperature (23 ° C.), the brightness was measured in the same manner to evaluate the change in brightness with time. However, the evaluation of the brightness was performed by a relative value with the initial brightness of Example 31 as the standard 100.

<Color characteristics>
On a commercially available white reflector, the substrates with partition walls obtained in each Example and Comparative Example were installed so that the pixels were arranged on the white reflector side. Using a spectrophotometer (CM-2600d, manufactured by Konica Minolta, measurement diameter φ8 mm), light was irradiated from the base substrate side of the substrate with a partition wall, and the spectrum including specular reflected light was measured.

A color standard BT that can almost reproduce the colors of the natural world. The color gamut defined by 2020 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 correspond to 630 nm, 532 nm, and 467 nm, respectively. From the reflectance (R) of three wavelengths of 470 nm, 530 nm and 630 nm of the obtained reflection spectrum, 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 manufactured by combining the substrate with a partition wall and the organic EL element obtained in each Example and Comparative Example were evaluated based on the following criteria.

A: The green display is very colorful, and it is a clear and high-contrast display device.
B: This is a display device that has no problem, although the colors are slightly unnatural.

<Mixed color>
In the substrate with a partition wall before forming the pixels, which was obtained in each Example and Comparative Example, a color-converted light-emitting material composition (a color-converted light-emitting material composition) was used on a part of the pixel portion surrounded by the lattice-shaped partition walls by using an inkjet method. CL-2) was applied and dried at 100 ° C. for 30 minutes to form pixels having a thickness of 5.0 μm. Then, in the pixel portion surrounded by the lattice-shaped partition wall, the area adjacent to the area to which the color conversion light emitting material composition (CL-2) is applied is subjected to the color conversion light emitting material composition (CL) by using the inkjet method. -3) was applied and dried at 100 ° C. for 30 minutes to form pixels having 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 lattice-shaped partition wall is produced, the above-mentioned substrate with partition wall and the blue organic EL cell are opposed to each other and bonded with a sealing agent, and is shown in FIG. Obtained a configuration display.

Of the blue organic EL cells 11 in FIG. 15, only the blue organic EL cells bonded directly under the pixel 3 (CL-2) formed of the color conversion light emitting material composition (CL-2) are lit. , Absorption intensity at a wavelength of 630 nm for the pixel 3 (CL-3) portion formed of the color conversion light emitting material composition (CL-3) using a microspectrophotometer LVmicro-V (manufactured by Lambda Vision Co., Ltd.). A (630 nm) was measured. The smaller the value of the absorption intensity A (630 nm), the less likely it is that color mixing will occur. Color mixing was determined according to the following criteria.

A: A (630 nm) <0.01
B: 0.01 ≤ A (630 nm) ≤ 0.5
C: 0.5 <A (630 nm).

The evaluation results of each example and comparative example are shown in Tables 6 to 7.

1 Base substrate 2 Partition 3 Pixels 3 (CL-2) Pixels formed of color conversion luminescent material composition (CL-2) 3 (CL-3) Pixels formed of color conversion luminescent material composition (CL-3) Pixel 4 Light-shielding partition 5 Color filter 6 Low refractive index layer 7 Inorganic protective layer I
8 Inorganic protective 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 source selected from organic EL cell, mini LED cell and micro LED cell 12 Blue organic EL cell H partition Thickness L Partition width θ Taper angle

Claims (17)

(i) Photoradical generator and
(ii) A polysiloxane containing a structure having an aromatic ring represented by the following general formula (1) or (2) and a structure having a photoradical polymerizable group represented by the following general formula (3).
(iii) A (meth) acrylic polymer containing a structure having an aromatic ring represented by the following general formula (4) and a structure having a photoradical polymerizable group represented by the following general formula (5) and / or the following general. A cardo-based polymer having a structure represented by the formula (6) or the following general formula (7) and a photoradical polymerizable group, and
A resin composition containing the above, wherein the weight ratio of the polysiloxane to the (meth) acrylic polymer and / or the cardo-based polymer is 30/70 to 70/30.

(In the general formula (1) ~ (7), ^{R 1} and ^{R 2} each independently represents hydrogen, hydroxy group, a monovalent organic group group or 1 to 30 carbon atoms having a siloxane bond .R ³ and R ⁴ independently represents hydrogen, a hydroxy group, or a monovalent organic group having 1 to 30 carbon atoms. R ^{5 to} R ⁷ independently represent hydrogen, a monovalent organic group having 1 to 30 carbon atoms, and 6 carbon atoms, respectively. 20 aryl group or adjacent ^R 5 .R ⁸ that to R ⁷ ring formed by each other represents a group the aromatic ring is hydrogen, a monovalent organic group having 1 to 30 carbon atoms or 6 to 20 carbon atoms, X ₁ , X ₂ , X ₃ and X ₄ each independently represent an organic group having an aromatic ring. Y ₁ and Y ₂ each independently represent an organic group having a photoradical polymerizable group. .P, q, r are each independently an integer of 0 to 2, s represents an integer of 1 to 2. a, b, c, d, e, f and g are each independently an integer of 1 or more. 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, respectively). The weight average molecular weight of the polysiloxane is 5,000 to 300,000, and among all the repeating units of the polysiloxane, the repeating unit represented by the general formula (1) or (2) is 30 to 70 mol%. The resin composition according to claim 1, which contains 15 to 70 mol% of the repeating unit represented by the general formula (3). The resin composition according to claim 1 or 2, wherein the (meth) acrylic polymer and / or the cardo-based polymer has a glass transition temperature of 60 ° C. or higher. The resin composition according to any one of claims 1 to 3, further containing a white pigment. The resin composition according to any one of claims 1 to 4, further containing an organometallic compound containing a black pigment and / or at least one metal selected from the group consisting of silver, gold, platinum and palladium. .. The resin composition according to any one of claims 1 to 5, which contains an oxime ester compound and a phosphine oxide compound as the photoradical generator. The resin composition according to any one of claims 1 to 6, further containing a liquid repellent compound having a photoradical polymerizable group. A light-shielding film obtained by curing the resin composition according to any one of claims 1 to 7. A substrate with a partition wall having a partition wall in which the pattern (A-1) is formed by the resin composition according to any one of claims 1 to 7 on the base substrate, and the reflectance per 10 μm thickness at a wavelength of 550 nm is high. A substrate with a partition wall having an OD value of 10% to 60% and an OD value of 1.0 to 3.0 per 10 μm thickness. The partition wall formed with the pattern (A-1) contains a resin, a white pigment, a black pigment and / or a yellow pigment, and the black pigment is titanium nitride, zirconium nitride, carbon black, red pigment and blue. A mixed pigment having a weight ratio of 20/80 to 80/20 with the pigment, 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. The substrate with a partition wall according to claim 9, which is a pigment selected from particles made of metal. The (A-1) pattern-formed partition wall further contains a liquid-repellent compound, and the content of the liquid-repellent compound in the (A-1) pattern-formed partition wall is 0.01% by weight to 10% by weight. A substrate with a partition wall according to claim 9 or 10. The substrate with a partition wall according to any one of claims 9 to 11, wherein the surface contact angle of the partition wall formed with the pattern (A-1) with respect to propylene glycol monomethyl ether acetate is 10 ° to 70 °. Between the base substrate and the (A-1) patterned partition wall, there is further a (A-2) patterned light-shielding partition wall having an OD value of 0.5 or more per 1.0 μm thickness. , The substrate with a partition wall according to any one of claims 9 to 12. The substrate with a partition wall according to any one of claims 9 to 13, further comprising a pixel layer further containing (B) a color conversion light emitting material arranged separated by a partition wall formed with the (A-1) pattern. The substrate with a partition wall according to claim 14, wherein the color conversion light emitting material contains a phosphor selected from quantum dots and a pyrromethene derivative. The substrate with a partition wall according to claim 14 or 15, further comprising a color filter having a thickness of 1 to 5 μm between the base substrate and the pixel layer containing the (B) color conversion light emitting material. A display device having the substrate with a partition wall according to any one of claims 9 to 16 and a light emitting light source selected from a liquid crystal cell, an organic EL cell, a mini LED cell, and a micro LED cell.

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