JP2023031448A - Substrate with partition wall, wavelength conversion substrate and method of manufacturing wavelength conversion substrate, and display device - Google Patents

Abstract

Kind Code: A1 A substrate with barrier ribs is provided, which has sufficient liquid repellency on the top surface of the barrier ribs, and which allows a wavelength conversion material to be applied with high accuracy when ink jet coating is performed.
SOLUTION: A substrate with barrier ribs characterized by having cells partitioned by a cured product for a display device, wherein XPS analysis of the upper surface of the barrier ribs is performed with a photoelectron detection angle of 45° and a C1s main peak of 284°. . eV, and when separated into four peaks of 284.6 eV, 286.0 eV, 288.6 eV, and 293.0 eV, the peak area C _CHx of 284.6 eV and the peak area C _COO of 288.6 eV are represented by the following relational expression: A substrate with partition walls, wherein (I) is satisfied, and the ratio F/C of fluorine atoms F to carbon atoms C in the XPS analysis satisfies the following relational expression (II).
0.1≦C _COO /C _CHx ≦0.4 (I)
0.1≦F/C≦0.4 (II)
[Selection drawing] Fig. 2

Description

The present invention relates to a substrate with partition walls, a wavelength conversion substrate, a method for manufacturing a wavelength conversion substrate, and a display device.

In recent years, with the development of information terminal devices such as smartphones and tablets, and the high definition of flat panel displays such as televisions, the demand for higher performance of displays is increasing. Among them, wavelength-converting OLED displays and LED displays are attracting attention as high-performance displays. These displays use OLEDs or LEDs driven by an active matrix method or the like as a light source, and display in full color by changing at least part of the light with a wavelength conversion material. Excellent for

As a method of using an OLED as a light source, a method of using an OLED that emits blue light is known (Patent Document 1). In this case, the blue sub-pixel transmits and scatters the light from the OLED without wavelength conversion, and the green and red sub-pixels change the blue light from the OLED to green and red by the wavelength conversion material, respectively.

As a method of using an LED as a light source, in addition to a method of using a blue-emitting LED similar to an OLED and using a wavelength-converting material to partially change the color of the light to red or green, an ultraviolet-emitting LED is used and a wavelength-converting material is used. A method of changing colors to blue, green, and red is known (Patent Document 2).

These wavelength-converted displays require a patterned arrangement of wavelength-converting materials with sizes corresponding to the sub-pixels of the OLED or LED light sources. A photolithography method and an inkjet method (Patent Document 3) are known as methods of patterning a wavelength conversion material.

Special Table No. 2006-501617 Special table 2016-523450 WO2018/123103

However, in the photolithography method, the wavelength conversion material, which will be described later, is applied to the entire surface, and after a predetermined position is exposed to light, most of the material is removed by development. There was a problem that it was necessary to repeat it several times and it was complicated. In addition, the inkjet method is excellent in material efficiency because the wavelength conversion layer, which will be described later, can be formed only at a desired position. There was a problem that the ink overflowed.

In order to solve the above-mentioned problems, the present inventors found that the liquid-repellent property of the upper surface of the partition walls can be solved by XPS analysis, by setting the composition of the elements on the upper surface of the partition walls to a range in which the following relational expression holds. I found That is, a substrate with partitions characterized by having cells partitioned by a cured product for a display device, and in XPS analysis of the upper surface of the partition, a photoelectron detection angle of 45 ° and a main peak of C1s of 284.6 eV When separated into four peaks of 284.6 eV, 286.0 eV, 288.6 eV, and 293.0 eV, the peak area C _CHx of 284.6 eV and the peak area C _COO of 288.6 eV are represented by the following relational expression ( I), and the ratio F/C of fluorine atoms F to carbon atoms C in the XPS analysis satisfies the following relational expression (II).
0.1≦C _COO /C _CHx ≦0.4 (I)
0.1≦F/C≦0.4 (II)

According to the partition wall of the present invention, since the upper surface of the partition wall has sufficient liquid repellency, the wavelength conversion material can be applied with high accuracy when ink jet coating is performed.

1 is a cross-sectional view showing one mode of a substrate with partitions having partitions of the present invention patterned on a base substrate; FIG. 1 is a cross-sectional view showing one embodiment of a substrate with partition walls having partition walls of the present invention patterned on a base substrate having a color filter. FIG. 1 is a cross-sectional view showing one embodiment of a substrate with partitions having partitions of the present invention patterned on a base substrate having an organic light-emitting element or a light-emitting diode; FIG. FIG. 2 is a cross-sectional view showing one embodiment of a wavelength conversion layer substrate in which a substrate with partitions having patterned partitions of the present invention comprises a wavelength conversion layer. FIG. 2 is a cross-sectional view showing one embodiment of a wavelength conversion layer substrate in which a substrate with partitions having partitions of the present invention patterned on a base substrate having a color filter is provided with a wavelength conversion layer. FIG. 2 is a cross-sectional view showing one embodiment of a wavelength conversion layer substrate in which a partition-attached substrate having partitions of the present invention patterned on a base substrate having an organic light-emitting element or a light-emitting diode is provided with a wavelength conversion layer. 1 is a cross-sectional view of a display device having a patterned barrier rib of the present invention; FIG.

The display device of the present invention is manufactured through a substrate with partition walls and a wavelength conversion substrate. Each substrate and partition are defined below.
<Partition wall>
The partition wall of the present invention refers to a wall that is formed by patterning in a cured product for a display device, which will be described later, and partitions a certain region.
<Partition wall top surface>
The upper surface of the partition wall of the present invention refers to the upper surface portion of the partition wall. That is, the surface does not include the side portions.
<Substrate with partition wall>
A substrate with partition walls of the present invention refers to a substrate having partitioned cells in which the partition walls are formed on a base substrate. The base substrate may be a glass substrate, a resin substrate, and a color filter, an organic light-emitting element or a light-emitting diode on these base substrates. More specifically, it refers to the structure shown in FIG. 1 (underlying a glass substrate or resin substrate), FIG. 2 (underlying a color filter), or FIG. 3 (underlying an organic light-emitting element or light-emitting diode).
<Wavelength conversion substrate>
The wavelength conversion substrate of the present invention refers to a substrate having a wavelength conversion layer, which will be described later, in partitioned cells in the substrate with partition walls. More specifically, it refers to the structures shown in FIGS.
<Display device>
The display device of the present invention has a structure in which a substrate having an organic light-emitting element or a light-emitting diode is attached to the wavelength conversion substrate shown in FIG. , and a structure (FIG. 7) in which a substrate having a color filter is attached to the wavelength conversion substrate shown in FIG.
<Cured products for display devices>
The cured product for a display device of the present invention is a cured product obtained by curing the composition. A cured product obtained by curing a negative photosensitive composition is preferable because the cured product for a display device is required to have fine workability. In the present invention, the cured product for a display device includes an alkali-soluble resin typified by a siloxane resin, an acrylic resin, or a phenol resin, (B) a photopolymerization initiator, (C) a photopolymerizable compound, (D) an intramolecular It is preferably a cured product obtained by processing a negative resin composition containing a compound having fluorine in it by the process described below. Next, a mode for carrying out the present invention will be described.

The substrate with partition walls of the present invention more preferably contains (A) a siloxane resin, (B) a photopolymerization initiator, (C) a photopolymerizable compound, (D) a compound having fluorine in the molecule, and (A) With partition walls obtained by curing a composition in which the siloxane resin contains 10 to 50 mol% of repeating units represented by the following general formula (1) and / or general formula (2) in all repeating units is the substrate.

(R ² represents a linear alkylene group having 1 to 6 carbon atoms, R ¹ represents a hydrogen atom or a methyl group, and R ³ represents an alkyl group having 1 to 20 carbon atoms. * represents a bonding site. )
(A) The siloxane resin has a specific structure, so that it has excellent heat resistance and light resistance. The polymerization of the photopolymerizable compound (C) proceeds by the radicals generated from the initiator, and the exposed portion of the negative photosensitive composition becomes insoluble in an alkaline aqueous solution, so that a negative pattern can be formed. .

In the XPS analysis of the upper surface of the barrier ribs of the substrate with barrier ribs of the present invention, the photoelectron detection angle is 45° and the main peak of C1s is 284.5°. eV, and when separated into four peaks of 284.6 eV, 286.0 eV, 288.6 eV, and 293.0 eV, the peak area C _CHx of 284.6 eV and the peak area C _COO of 288.6 eV are represented by the following relational expression: (I) is satisfied, and the ratio F/C of fluorine atoms F and carbon atoms C in the XPS analysis satisfies the following relational expression (II).
0.1≦C _COO /C _CHx ≦0.4 (I)
0.1≤F/C≤0.4 (II).

Relational expression (I)
The main peak of C1s in the present invention refers to the peak position where the height of the peak is maximum. Among the peaks separated by the peak separation method described above, the peak at 288.6 eV is derived from an ester bond. Examples of compounds having an ester bond include acrylic resins, acrylic monomers, methacrylic resins, methacrylic monomers, (A) side chains of siloxane resins, and (D) compounds having fluorine in the molecule. Only compounds present in are detected by XPS. Among the peaks separated in the same manner, the peak at 284.6 is a peak derived from CHx, and C _COO /C _CHx means the amount of ester bonds with respect to the amount of CHx. By designing the C _COO /C _CHx to be 0.1 or more, the partition wall can be processed by a photosensitizing method. In addition, by designing the C _COO /C _CHx to be 0.4 or less, highly hydrophilic ester bonds can be suppressed, and the liquid repellency of the top surface of the partition wall is not reduced.

Relational expression (II)
By setting F/C to 0.1 or more, the liquid-repellent property can be imparted to the upper surface of the partition wall, and by setting F/C to 0.4 or less, the cell part can apply the wavelength conversion material without repelling it. be able to.
When the upper surface of the partition wall satisfies the relational expression (I) and the relational expression (II) at the same time, it becomes possible to accurately separate the wavelength conversion material when ink jet coating is performed.

Furthermore, it is preferable that the board|substrate with a partition has an organic light emitting element or a light emitting diode as a light source. More preferably, a light source selected from blue OLEDs, blue LEDs, and ultraviolet light-emitting LEDs capable of active matrix driving is preferable.
Further, it is preferable that the barrier ribs reflect 20 to 85% of light having a wavelength of 550 nm per 10 μm thickness of the barrier ribs. By setting the reflectance to 20% or more, the luminance of the display can be improved by utilizing the reflection on the side surfaces of the partition walls. On the other hand, the reflectance is preferably 85% or less from the viewpoint of improving the partition pattern formation accuracy. Here, the thickness of the partition refers to the length of the partition in the vertical direction (height direction) with respect to the substrate.

Relational expression (III)
When XPS analysis was performed on the upper surface of the partition walls of the substrate with partition walls of the present invention, the ratio Si/C of silicon atoms Si and carbon atoms C was within the range of 0.02 ≤ Si/C ≤ 0.3 (relational expression (III)). preferably fulfilled. The Si/C ratio is 0.02 or more from the viewpoint of improving the reflectance of the partition wall for light at a wavelength of 550 nm, making it possible to reduce light leakage to adjacent cells, and improving the color gamut of the imaging device. is preferable. From the viewpoint of imparting flexibility to the partition walls, Si/C is preferably 0.3 or less.

The substrate with partition walls of the present invention preferably has an absorption peak at 1220 to 1290 cm ⁻¹ derived from Si—C in FT-IR analysis. Observation of a peak in this region improves the reflectance of the partition wall for light at a wavelength of 550 nm, making it possible to reduce light leakage to adjacent cells, leading to an improvement in the color gamut of the imaging device. As for the FT-IR analysis of the upper surface of the partition walls, known methods such as microscopic IR, ATR method, peeling off only the partition walls, grinding them with a mortar or the like and measuring them by the KBr method can be used.

<Wavelength conversion layer>
In the present invention, the wavelength conversion layer contains a wavelength conversion material. In the present invention, the wavelength conversion material refers to a material having wavelength conversion properties that absorbs electromagnetic waves and emits electromagnetic waves having a wavelength different from the wavelength of the absorbed electromagnetic waves. A solution containing a wavelength conversion material is formed into a pattern by inkjet coating or the like, applied to form a wavelength conversion substrate, and combined with an OLED light source or an LED light source to form a full-color display.

Inorganic phosphors and/or organic phosphors are preferably used as the wavelength conversion material. For example, in the case of a display in which an OLED that emits blue light and a wavelength conversion substrate are combined, a red phosphor that emits red fluorescence when excited by blue excitation light is used in a region corresponding to a red sub-pixel. It is preferable to use it as a wavelength conversion material, and it is preferable to use a green phosphor that emits green fluorescence when excited by blue excitation light as a wavelength conversion material in the region corresponding to the green subpixel. Preferably, no wavelength conversion material is used in the region corresponding to . Similarly, the wavelength conversion substrate of the present invention can also be used for a display that uses blue LEDs or ultraviolet light emitting LEDs corresponding to each sub-pixel as a backlight. Light emission of each sub-pixel can be turned on/off by, for example, active matrix driving of OLEDs or LEDs.

Inorganic phosphors emit light in colors such as green and red. Examples of inorganic phosphors include those that are excited by excitation light with a wavelength of 400 to 500 nm and have a peak emission spectrum in the region of 500 to 700 nm, inorganic semiconductor fine particles called quantum dots, and the like. Examples of the shape of the former inorganic phosphor include a spherical shape and a columnar shape. Examples of such inorganic phosphors include YAG-based phosphors, TAG-based phosphors, sialon-based phosphors, Mn ⁴⁺ -activated fluoride complex phosphors, and the like. You may use 2 or more types of these.

Among these, quantum dots are preferred. Quantum dots have sharp peaks in emission spectra compared to other phosphors, and thus can improve the color reproducibility of displays.

Quantum dot materials include, for example, II-IV group, III-V group, IV-VI group, and IV group semiconductors. 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, GeSe, GeTe, SnS, SnSe, SnTe, PbO, _PbS , PbSe, PbTe, CuF, CuCl, CuBr, CuI, _{Si3N4 , Ge3N4 , Al2O3} and the like. You may use 2 or more types of these.

Quantum dots may contain p-type dopants or n-type dopants. Quantum dots may also have a core-shell structure. In the core-shell structure, any appropriate functional layer (single layer or multiple layers) may be formed around the shell depending on the purpose, and the shell surface may be surface-treated and/or chemically modified. .

Examples of the shape of the quantum dots include spherical, columnar, scaly, plate-like, and irregular shapes. The average particle size of quantum dots can be selected according to the desired emission wavelength, and is preferably 1 to 30 nm. If the average particle size of the quantum dots is 1 to 10 nm, the peaks in the emission spectrum can be made sharper in each of blue, green and red. For example, when the average particle size of the quantum dots is about 2 nm, they emit blue light, when they are about 3 nm, they emit green light, and when they are about 6 nm, they emit red light. The average particle size of the quantum dots is preferably 2 nm or more, and preferably 8 nm or less. The average particle size of quantum dots can be measured by a dynamic light scattering method. A dynamic light scattering photometer DLS-8000 (manufactured by Otsuka Electronics Co., Ltd.) can be used as an apparatus for measuring the average particle size.

The substrate with partition walls of the present invention is a negative photosensitive material comprising (A) a siloxane resin, (B) a photopolymerization initiator, (C) a photopolymerizable compound, (D) a compound having fluorine in its molecule, and the like. It is preferably obtained by patterning and curing the composition. They will be explained in order below.

(A) siloxane resin (A) siloxane resin is a hydrolysis/dehydration condensate of organosilane, and in the present invention, at least the repeating unit represented by general formula (1) and / or general formula (2) contains the repeating unit represented.

(R ² represents a linear alkylene group having 1 to 6 carbon atoms, R ¹ represents a hydrogen atom or a methyl group, and R ³ represents an alkyl group having 1 to 20 carbon atoms. * represents a bonding site. ) By including these repeating units, the photopolymerization initiator (C) is cleaved upon exposure, and the generated radicals react with the side chains of the siloxane resin. As a result, the contrast between the degree of curing of the exposed portion and the unexposed portion is easily obtained, so that the resolution can be further improved and the development residue can be further suppressed.

(A) siloxane resin contains repeating units represented by general formula (1) and repeating units represented by general formula (2) in a total of 5 to 50 mol% of all repeating units of (A) siloxane resin. It is characterized by When the total content of the repeating unit represented by the general formula (1) and the general formula (2) is 5 mol% or more, the degree of curing contrast between the exposed area and the unexposed area is improved, and the resolution is improved. can be done. On the other hand, by containing 50 mol % or less of these repeating units, it is possible to suppress excessive curing of the exposed area and further improve the resolution.

The content ratio of the organosilane unit containing the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) was obtained by performing ²⁹ Si-NMR measurement, and integrating the total Si derived from the organosilane. It can be obtained by calculating the ratio of the integrated value of Si derived from the organosilane unit having the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) to the value.
Moreover, (A) the siloxane resin preferably contains a repeating unit represented by the general formula (3) and/or a repeating unit represented by the general formula (4).

In general formulas (3) and (4), R ⁴ represents a monovalent organic group having 1 to 20 carbon atoms and having a carboxyl group and/or a carboxylic acid anhydride group. R ⁵ represents an alkyl group having 1 to 20 carbon atoms. * represents a binding site. By containing the repeating unit represented by the general formula (3) and/or the repeating unit represented by the general formula (4), excellent solubility in development can be obtained and the resolution can be improved.

Further, the repeating unit represented by the general formula (3) and the repeating unit represented by the general formula (4) are preferably contained in an amount of 5 to 30 mol % in all the repeating units of the siloxane resin (A). By containing 5 mol % or more of these repeating units, development residue can be further suppressed. On the other hand, by containing 30 mol % or less of these repeating units, the resolution can be further improved. More preferably, it is 5 to 20 mol %.

The content ratio of the repeating unit represented by the general formula (3) and the organosilane unit containing the repeating unit represented by the general formula (4) was obtained by performing ²⁹ Si-NMR measurement, and integrating the total Si derived from the organosilane. It can be obtained by calculating the ratio of the integrated value of Si derived from the organosilane unit having the repeating unit represented by the general formula (3) and the repeating unit represented by the general formula (4) to the value.

In addition, (A) the siloxane resin may contain other repeating units. As another repeating unit, a repeating unit having a non-aromatic functional group is preferable, and having such a repeating unit makes it possible to improve the light resistance.

The repeating units represented by general formulas (1) to (4) are derived from organosilane compounds represented by general formulas (5) to (8), respectively.
That is, the repeating unit represented by the general formula (1) and / or the repeating unit represented by the general formula (2) is an organosilane compound represented by the general formula (5) and / or represented by (6) derived from the organosilane compounds used.
The repeating unit represented by the general formula (3) and/or the repeating unit represented by the general formula (4) is an organosilane compound represented by the general formula (7) and/or represented by (8). Derived from an organosilane compound.
The (A) polysiloxane resin having repeating units represented by general formulas (1) to (4) hydrolyzes and polycondenses the organosilane compounds represented by the corresponding general formulas (5) to (8). can be obtained by Still other organosilane compounds may be used.

In general formulas (5) and (6) above, R ¹ , R ² and R ³ represent the same groups as R ¹ , R ² and R ³ in general formulas (1) and (2) respectively. . Each R ^a may be the same or different and represents a monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms.

In general formulas (7) and (8) above, R ⁴ and R ⁵ represent the same groups as R ⁴ and R ⁵ in general formulas (3) and (4), respectively. R ^a represents the same group as R ^a in general formulas (5) and (6) above.

Examples of the organosilane compound represented by the general formula (5) include γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane, and the like. You may use 2 or more types of these mentioned.

Organosilane compounds represented by general formula (6) include, for example, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane. You may use 2 or more types of these.

Organosilane compounds having a structure represented by general formula (7) include, for example, 3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 4-trimethoxysilylbutyric acid, 4-triethoxysilylbutyric acid, 5-trimethoxysilylvaleric acid, 5-triethoxysilylvaleric acid, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride , 3-triethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride, 3-triethoxysilylpropylphthalic anhydride and the like. You may use 2 or more types of these.

Organosilane compounds having a structure represented by general formula (8) include, for example, 3-dimethylmethoxysilylpropionic acid, 3-dimethylethoxysilylpropionic acid, 4-dimethylmethoxysilylbutyric acid, 4-dimethylethoxysilylbutyric acid, 5-dimethylmethoxysilylvalerate, 5-dimethylethoxysilylvalerate, 3-dimethylmethoxysilylpropylsuccinic anhydride, 3-dimethylethoxysilylpropylsuccinic anhydride, 3-dimethylmethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-dimethylethoxysilylpropylcyclohexyldicarboxylic anhydride and the like. You may use 2 or more types of these.

Other organosilane compounds include, for example, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl). Examples include organosilane compounds such as propyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, silicate 51 (tetraethoxysilane oligomer), and the like. You may use 2 or more types of these.

(A) The weight average molecular weight (Mw) of the siloxane resin is preferably 1,000 or more, more preferably 2,000 or more, from the viewpoint of coating properties. On the other hand, from the viewpoint of developability, the Mw of (A) the siloxane resin is preferably 50,000 or less, more preferably 20,000 or less. Here, the Mw of the (A) siloxane resin in the present invention refers to a polystyrene conversion value measured by gel per emission chromatography (GPC).

In the negative photosensitive composition, the content of (A) the siloxane resin can be arbitrarily set depending on the desired film thickness and application, but the solid content of the negative photosensitive composition is 10 to 50% by weight. is common. The content of (A) the siloxane resin is preferably 10% by weight or more, more preferably 20% by weight or more, in the solid content of the negative photosensitive composition. On the other hand, the content of (A) the siloxane resin is preferably 50% by weight or less in the solid content of the negative photosensitive composition.

(A) The siloxane resin can be obtained by hydrolyzing the aforementioned organosilane compound and then subjecting the hydrolyzate to a dehydration condensation reaction in the presence or absence of a solvent.
Various conditions for hydrolysis can be set according to physical properties suitable for the intended use, taking into consideration the reaction scale, the size and shape of the reaction vessel, and the like. Various conditions include, for example, acid concentration, reaction temperature, and reaction time.

Acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acids and their anhydrides, and ion exchange resins can be used for the hydrolysis reaction. Among these, acidic aqueous solutions containing formic acid, acetic acid and/or phosphoric acid are preferred.

When an acid catalyst is used for the hydrolysis reaction, the amount of the acid catalyst to be added is 0.05 parts by weight with respect to 100 parts by weight of all the organosilane compounds used in the hydrolysis reaction, from the viewpoint of accelerating the hydrolysis. part or more is preferable, and 0.1 part 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, relative to 100 parts by weight of the total organosilane compound. Here, the term "total organosilane compound amount" refers to the amount including all of the organosilane compound, its hydrolyzate and its condensate, and the same shall apply hereinafter.

A hydrolysis reaction can be performed in an organic solvent. The organic solvent can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the negative photosensitive composition. Organic solvents include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3- Alcohols such as methoxy-1-butanol and diacetone alcohol; Glycols such as ethylene glycol and propylene glycol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl Ethers such as ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether; methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketones such as ketones, diisobutyl ketone, cyclopentanone, and 2-heptanone; amides such as dimethylformamide and dimethylacetamide; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether Acetates such as acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, cyclohexane; γ- butyrolactone, N-methyl-2-pyrrolidone, dimethylsulfoxide and the like. You may use 2 or more types of these.

Among these, diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono- t-Butyl ether, γ-butyrolactone and the like are preferably used.

If the hydrolysis reaction produces an organic solvent, the hydrolysis can be carried out without a solvent. After completion of the hydrolysis reaction, it is also preferable to add an organic solvent to adjust the concentration to be suitable as a negative photosensitive coloring composition. It is also possible to distill off and remove all or part of the alcohol produced by heating and/or under reduced pressure after hydrolysis, and then add a suitable organic solvent.

When an organic solvent is used for the hydrolysis reaction, the amount of the organic solvent added is preferably 50 parts by weight or more, and preferably 80 parts by weight or more, based on 100 parts by weight of the total organosilane compound, from the viewpoint of suppressing gel formation. more preferred. On the other hand, the amount of the organic solvent to be added is preferably 500 parts by weight or less, more preferably 200 parts by weight or less with respect to 100 parts by weight of all the organosilane compounds, from the viewpoint of accelerating the hydrolysis.

Moreover, ion-exchanged water is preferable as the water used for the hydrolysis reaction. Although the amount of water can be set arbitrarily, it is preferably 1.0 to 4.0 mol per 1 mol of all organosilane compounds.

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

From the viewpoint of storage stability of the negative photosensitive coloring composition, it is preferable that the siloxane resin solution after hydrolysis and dehydration condensation does not contain the catalyst, and the catalyst can be removed as necessary. As the method for removing the catalyst, washing with water, treatment with an ion-exchange resin, and the like are preferable from the viewpoint of ease of operation and removability. Washing with water is a method of diluting a siloxane resin solution with a suitable hydrophobic solvent, washing with water several times, and concentrating the obtained organic layer with an evaporator or the like. Ion exchange resin treatment is a method of contacting a siloxane resin solution with a suitable ion exchange resin.

(B) Photopolymerization initiator (B) The photopolymerization initiator may be any one that decomposes and/or reacts with light (including ultraviolet rays and electron beams) to generate radicals. 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl )-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and other α-aminoalkylphenone compounds; 2,4,6-trimethylbenzoylphenylphosphine 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-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl) )-9H-carbazol-3-yl]-,1-(O-acetyloxime) and other oxime ester compounds; benzyl ketal compounds such as benzyl dimethyl ketal; 2-hydroxy-2-methyl-1-phenylpropane-1- one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl- α-hydroxyketone compounds such as phenyl ketone; benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichloro 2,2- Diethoxyacetopheno acetophenone compounds such as amine, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, 4-azidobenzalacetophenone; aromatic ketoester compounds such as methyl 2-phenyl-2-oxyacetate; Benzoic acid ester compounds such as ethyl-dimethylaminobenzoate, (2-ethyl)hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, and methyl 2-benzoylbenzoate. You may contain 2 or more types of these.

The negative photosensitive composition contains (B) 2,4,6-trimethylbenzoylphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide to suppress coloring caused by a photopolymerization initiator. and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-phosphine oxide.

The content of the photopolymerization initiator (B) in the negative photosensitive coloring composition is preferably 0.01% by weight or more, more preferably 1% by weight or more, in the solid content from the viewpoint of effectively promoting radical curing. preferable. On the other hand, from the viewpoint of suppressing elution of the remaining photopolymerization initiator (B) and further suppressing coloration, the content of the photopolymerization initiator (B) is preferably 20% by weight or less in the solid content, and 10 Weight % or less is more preferred.

(C) Photopolymerizable compound (C) Photopolymerizable compound means a compound having two or more ethylenically unsaturated double bonds in the molecule. Considering the easiness of radical polymerizability, (C) the photopolymerizable compound preferably has a (meth)acrylic group. In addition, the double bond equivalent of (C) the photopolymerizable compound is preferably 400 g/mol or less from the viewpoint of further improving the sensitivity in pattern processing. On the other hand, the double bond equivalent of (C) the photopolymerizable compound is preferably 80 g/mol or more from the viewpoint of further improving the resolution in patterning.

Examples of the photopolymerizable compound (C) include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, Acrylates, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane 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-tricyclodecane diacrylate, pentaerythritol triacrylate Acrylates, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol Decaacrylate, pentapentaerythritol undecaacrylate, pentapentaerythritol dodecaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate, pentapentaerythritol Dodeca methacrylate, dimethylol-tricyclodecane diacrylate. You may contain 2 or more types of these.

Further, as other photopolymerizable compounds, it is possible to contain a photopolymerizable compound having a structure represented by general formula (9) and/or a photopolymerizable compound having a structure represented by general formula (10). preferable.

In general formula (9), each R ⁶ independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a phenyl group, and n represents an integer of 1-40.
In general formula (10), ^R7 represents a hydrogen atom or a methyl group, * represents a bonding site.
By having such a structure, even when processing a thick film of 10 μm or more, development is possible with an alkaline developer having a wide range of concentrations, and excellent crack resistance can be exhibited.

As a method for synthesizing the (C) photopolymerizable compound having a structure represented by the general formula (9), for example, a compound having a plurality of active hydrogens or a halide thereof is reacted with various alkylene oxides. A method of further reacting the polyol compound with (meth)acrylic acid is included. Further, as a method for synthesizing (C) the photopolymerizable compound having the structure represented by the general formula (10), for example, a compound having a plurality of glycidyl ether groups, or a compound having a glycidyl ether group and a radically polymerizable group and a method of reacting (meth)acrylic acid.

Examples of the photopolymerizable compound having the structure represented by the general formula (9) and the photopolymerizable compound having the structure represented by the general formula (10) include ethylene glycol diglycidyl ether (meth)acrylate and propylene glycol. diglycidyl ether (meth) acrylate, diethylene glycol diglycidyl ether (meth) acrylate, dipropylene glycol diglycidyl ether (meth) acrylate, triethylene glycol diglycidyl ether (meth) acrylate, tripropylene glycol diglycidyl ether (meth) acrylate, Tetraethylene glycol diglycidyl ether (meth) acrylate, tetrapropylene glycol diglycidyl ether (meth) acrylate, polyethylene glycol 200-diglycidyl ether (meth) acrylate, polyethylene glycol 300-diglycidyl ether (meth) acrylate, polyethylene glycol 400- diglycidyl ether (meth)acrylate, bisphenol A diglycidyl ether (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyethylene glycol 200-di(meth)acrylate, polyethylene glycol 300-di(meth)acrylate, polyethylene glycol 400-di(meth)acrylate, polyethylene glycol 500-di(meth)acrylate, polyethylene glycol 600-di(meth)acrylate, Polyethylene glycol 700-di(meth)acrylate, polyethylene glycol 800-di(meth)acrylate, polyethylene glycol 900-di(meth)acrylate, polyethylene glycol 1000-di(meth)acrylate, trimethylolpropane-EO modified tri(meth) Acrylate (average EO number = 3, EO = ethylene oxide), trimethylolpropane-EO-modified tri (meth) acrylate (average EO number = 6), trimethylolpropane-EO-modified tri (meth) acrylate (average EO number = 9 ), trimethylolpropane-PO-modified tri(meth)acrylate (average PO number = 3, PO = propylene oxide), trimethylolpropane-PO-modified tri(meth)acrylate (average PO number = 6), trimethylolpropane-PO-modified tri(meth)acrylate (average PO number = 9), glycerin-EO-modified tri(meth)acrylate (average EO number = 3), glycerin-EO-modified tri(meth)acrylate (average EO number = 6), glycerin-EO-modified tri (meth) acrylate (average EO number = 9), glycerin-PO-modified tri (meth) acrylate (average PO number = 3), glycerin-PO-modified tri (meth) acrylate ( Average PO number = 6), glycerin-PO-modified tri(meth)acrylate (average PO number = 9), bisphenol A-EO-modified tri(meth)acrylate (average EO number = 4), bisphenol A-EO-modified tri(meth) ) acrylate (average EO number = 10), bisphenol A-EO modified tri (meth) acrylate (average EO number = 30), bisphenol A-PO modified tri (meth) acrylate (average PO number = 4), bisphenol A-PO modified tri(meth)acrylate (average PO number = 10), bisphenol A-PO modified tri(meth)acrylate (average PO number = 30), isocyanuric acid-EO modified tri(meth)acrylate (average EO number = 3), Isocyanuric acid-EO-modified di (meth) acrylate (average EO number = 3), isocyanuric acid-PO-modified tri (meth) acrylate (average PO number = 3), isocyanuric acid-PO-modified di (meth) acrylate (average PO number = 3), 1,2-ethanedithiol-EO-modified di(meth)acrylate (average EO number = 4), 1,2 propanedithiol-EO-modified di(meth)acrylate (average EO number = 4), phthalic anhydride Propylene oxide (meth)acrylate or diethylene glycol (meth)trimellitate (meth)acrylate can be mentioned. You may contain 2 or more types of these.

The content of the (C) photopolymerizable compound in the negative photosensitive coloring composition is preferably 1% by weight or more based on the solid content of the negative photosensitive coloring composition, from the viewpoint of effectively promoting radical curing. On the other hand, the content of the photopolymerizable compound (C) is preferably 40% by weight or less in the solid content from the viewpoint of suppressing excessive reaction of radicals and further improving the resolution.

(D) compounds having fluorine in the molecule (D) compounds having fluorine in the molecule are, for example, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1 , 1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di(1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro pentyl) ether, octapropylene glycol di(1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, perfluorododecyl sulfone sodium acid, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N-[3-(per fluorooctanesulfonamido)propyl]-N,N'-dimethyl-N-carboxymethylene ammonium betaine, perfluoroalkylsulfonamidopropyl trimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bis(N-per fluorooctylsulfonyl-N-ethylaminoethyl), monoperfluoroalkylethyl phosphate, and other compounds having fluoroalkyl or fluoroalkylene groups at the terminal, main chain and/or side chain. In addition, commercially available compounds include "Megafac" (registered trademark) F142D, F172, F173, F183, F444, F477 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), Ftop EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), Florado FC-430, Florado 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 (Yutaka Sho Co., Ltd.), NBX-15, FTX-218, DFX-18 (manufactured by Neos Co., Ltd.). You may contain 2 or more types of these. Among these, those having a photopolymerizable group are more preferable because they are highly reactive and can form a strong bond with the resin. Liquid-repellent compounds having a fluorine atom and a photopolymerizable group include, for example, "Megafac" RS-76-E, RS-56, RS-72-K, RS-75, and RS-76-E. , RS-76-NS, and RS-90 (these are trade names, manufactured by DIC Corporation).

From the viewpoint of improving the liquid repellency of the cured film and improving the inkjet applicability, the content of (D) the compound having fluorine in the molecule is preferably 0.01% by weight or more, and 0.1% by weight or more. more preferred. On the other hand, from the viewpoint of improving compatibility with resins and white pigments, the content of the liquid-repellent compound is preferably 10% by weight or less, more preferably 5% by weight or less.

Moreover, the negative photosensitive composition of the present invention further contains (E) a silane coupling agent. (E) Examples of silane coupling agents include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, Diphenyldimethoxysilane, naphthyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane Silane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-ethyl-3-{[3-(trimethoxysilyl)propoxy]methyl}oxetane, 3-ethyl-3-{[3-(tri ethoxysilyl)propoxy]methyl}oxetane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, and the like. You may use 2 or more types of these.

In the negative photosensitive composition of the present invention, the content of (E) the silane coupling agent preferably satisfies the following relational expression.
E: Content of (E) silane coupling agent in the total solid content in the composition (wt%)
Mw: (A) polystyrene equivalent weight average molecular weight E ≤ 10 (wt%) of siloxane resin (IV)
E≧(−0.008×Mw+4.556) (wt %) (V)
According to the present invention, (E) the silane coupling agent promotes the cross-linking reaction of (A) the siloxane resin during prebaking during coating and film formation in the partition forming step, which will be described later on the negative photosensitive composition. Since it becomes possible to tie (D) the compound having fluorine in the molecule segregated to the , it can be retained on the upper surface of the partition wall without being washed away by the developer. As a result, liquid repellency can be exhibited on the top surface of the partition wall.

The relational expression (IV) represents the upper limit of the silane coupling agent (E), regardless of the molecular weight of (A) the siloxane resin. From the viewpoint of storage stability of the negative photosensitive composition, it is preferably 10 wt % or less.

The relational expression (V) means (A) the molecular weight of the siloxane resin and (E) the content of the silane coupling agent, and means the lower limit of each molecular weight. If the content is less than this relational expression, the aforementioned effect (D) of binding the compound having fluorine in the molecule cannot be exhibited, and the liquid repellency of the upper surface of the partition wall becomes insufficient. Furthermore, the range of Mw is preferably 2,000 or more, from which the effect of (D) binding fluorine-containing compounds in the molecule can be expected. From the viewpoint of developability, it is preferably 50,000 or less, more preferably 20,000 or less.

Moreover, the negative photosensitive composition of the present invention preferably contains (F) a white pigment. (F) White pigments include, for example, titanium dioxide, magnesium oxide, barium sulfate, zirconium oxide, zinc oxide, white lead, and the like. You may contain 2 or more types of these. Among these, it is preferable to contain at least one of titanium dioxide, zirconium oxide, zinc oxide, barium sulfate, and composite compounds thereof, and titanium dioxide is more preferable because it has a high reflectance and can be easily used industrially.

The crystal structure of titanium dioxide is classified into an anatase type, rutile type, and brookite type. Among these, rutile-type titanium oxide is preferable because of its low photocatalytic activity.

(F) The white pigment may be surface-treated. Surface treatment with Al, Si and/or Zr is preferable, and can improve the dispersibility of the (F) white pigment in the negative photosensitive composition and further improve the light resistance and heat resistance of the cured film.

(F) The average primary particle size of the white pigment is preferably 170 to 310 nm from the viewpoint of further improving the reflectance. Here, (F) the average primary particle size of the white pigment refers to the median size calculated from the particle size distribution measured by a laser diffraction method.

(F) Titanium dioxide pigments preferably used as white pigments include, for example, R960 manufactured by DuPont (rutile type, SiO ₂ /Al ₂ O ₃ treatment, average primary particle size 210 nm), CR-97; Ishihara Sangyo Co., Ltd. (rutile type, Al ₂ O ₃ /ZrO ₂ treatment, average primary particle size 250 nm), JR-301; Tayca Corporation (rutile type, Al ₂ O ₃ treatment, average primary particle size 300 nm), JR-405; Tayca Co., Ltd. (rutile type, Al ₂ O ₃ treatment, average primary particle size 210 nm), JR-600A; Tayca Co., Ltd. (rutile type, Al ₂ O ₃ treatment, average primary particle size 250 nm) , JR-603; Teika Co., Ltd. (rutile type, Al ₂ O ₃ /ZrO ₂ treatment, average primary particle size 280 nm), and the like. You may contain 2 or more types of these.

(F) The content of the white pigment is preferably 10% by weight or more, more preferably 20% by weight or more, based on the solid content of the negative photosensitive coloring composition, from the viewpoint of further improving the reflectance. On the other hand, the content of (F) white pigment is preferably 80% by weight or less, more preferably 60% by weight or less, based on the solid content, from the viewpoint of suppressing development residue and forming a higher-resolution pattern.

The negative photosensitive coloring composition may contain a pigment dispersant together with (F) the white pigment, and can improve the dispersibility of the (F) white pigment in the negative photosensitive composition. The pigment dispersant can be appropriately selected according to the type and surface condition of the white pigment used. The pigment dispersant preferably contains acidic groups and/or basic groups. Commercially available pigment dispersants include, for example, "Disperbyk" (registered trademark) 106", "Disperbyk" 108, "Disperbyk" 110, "Disperbyk" 180, "Disperbyk" 190, "Disperbyk" 2001, "Disperbyk" 2155, "Disperbyk" 140, "Disperbyk" 145 (the above are trade names, manufactured by BYK-Chemie Co., Ltd.), etc. Two or more of these may be contained.

(G) Organic Solvent The negative photosensitive composition of the present invention contains (G) an organic solvent.
As the organic solvent, it is preferable to combine an organic solvent having a boiling point of 150° C. or more and 250° C. or less and an organic solvent having a boiling point of less than 150° C. under atmospheric pressure. By containing an organic solvent having a boiling point of 150° C. or more and 250° C. or less, the organic solvent is volatilized appropriately during coating, and the coating film is dried, so that coating unevenness is suppressed and the film thickness uniformity is improved. can be done. Furthermore, by containing an organic solvent having a boiling point of less than 150° C. under atmospheric pressure, it is possible to suppress the organic solvent from remaining in the cured film of the present invention, which will be described later. From the viewpoint of suppressing the organic solvent remaining in the cured film and improving the chemical resistance and adhesion over a long period of time, an organic solvent having a boiling point of less than 150 ° C. under atmospheric pressure is added to 50% by weight or more of the total organic solvent. It is preferable to contain.

Organic solvents having a boiling point of less than 150° C. under atmospheric pressure include, for example, ethanol, isopropyl alcohol, 1-propyl alcohol, 1-butanol, 2-butanol, isopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol. monoethyl ether, methoxymethyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, 1-methoxypropyl-2-acetate, acetol, acetylacetone, Methyl isobutyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl lactate, toluene, cyclopentanone, cyclohexane, n-heptane, benzene, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-hydroxy -3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone. You may use 2 or more types of these.

Organic solvents having a boiling point of 150° C. or higher and 250° C. or lower under atmospheric pressure include, for example, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol mono-n-butyl ether, propylene glycol. mono t-butyl ether, 2-ethoxyethyl acetate, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate , propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, diisobutyl ketone, diacetone alcohol, ethyl lactate, butyl lactate, dimethylformamide, dimethylacetamide, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate , N-methylpyrrolidone, cyclohexanone, cycloheptanone, diethylene glycol monobutyl ether, ethylene glycol dibutyl ether. You may use 2 or more types of these.
The content of the organic solvent can be arbitrarily set according to the coating method and the like. For example, when forming a film by spin coating, it is generally 50% by weight or more and 95% by weight or less in the negative photosensitive composition.

Moreover, the negative photosensitive composition of the present invention may contain (H) a black pigment, if necessary. By containing (H) a black pigment, the light shielding property of the cured film can be improved. (H) Black pigments include, for example, black organic pigments, mixed color organic pigments, and black inorganic pigments. Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone pigments. These may be coated with a resin. Mixed organic pigments include, for example, pseudo-black pigments obtained by mixing two or more pigments such as red, blue, green, purple, yellow, magenta and/or cyan. 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 workability. The weight ratio of the red pigment and the blue pigment is preferably 20/80 to 80/20, more preferably 30/70 to 70/30. Specific examples of representative pigments are shown below by color index (CI) number. Examples of red pigments include Pigment Red (hereinafter abbreviated as PR) 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR192, PR209, PR215, PR216, PR217, and PR220. , PR223, PR224, PR226, PR227, PR228, PR240, PR254, and the like. You may contain 2 or more types of these. Examples of blue pigments include Pigment Blue (hereinafter abbreviated as PB) 15, PB15:3, PB15:4, PB15:6, PB22, PB60 and PB64. You may contain 2 or more types of these. Black inorganic pigments include, for example, 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; Metal sulfides; metal nitrides; metal oxynitrides; metal carbides and the like. You may contain 2 or more types of these.

Among the above black pigments, it is more preferable to include at least one of titanium nitride, zirconium nitride, carbon black, and a mixed pigment of red and blue pigments because of their high light-shielding properties. The content of the black pigment is preferably 0.2% by weight or more, more preferably 0.5% by weight or more, from the viewpoint of adjusting the reflectance and OD to suppress color mixture of light in adjacent pixels. On the other hand, from the viewpoint of adjusting the reflectance and OD, the content of the black pigment is preferably 5% by weight or less, more preferably 3% by weight or less.

Moreover, the negative photosensitive composition of the present invention can contain (I) an organometallic compound, if necessary. (I) The organometallic compound decomposes and agglomerates in the exposure step and/or the heating step during pattern formation of the cured film to become a black pigment, and has a function of improving light shielding properties.

(I) The organometallic compound more preferably contains at least one metal selected from the group consisting of silver, gold, platinum and palladium, since it has high light-shielding properties. Examples of metal compounds selected from the group consisting of silver, gold, platinum and palladium include organometallic compounds containing silver such as silver neodecanoate, silver octylate, silver salicylate; chloro(triphenylphosphine) gold, tetrachloro Organometallic compounds containing gold such as auric acid tetrahydrate; Organometallic compounds containing platinum such as bis(acetylacetonato)platinum, dichlorobis(triphenylphosphine)platinum, dichlorobis(benzonitrile)platinum; acetylacetonato)palladium, dichlorobis(triphenylphosphine)palladium, dichlorobis(benzonitrile)palladium, tetrakis(triphenylphosphine)palladium, dibenzylideneacetonepalladium, and other palladium-containing organometallic compounds; You may contain 2 or more types of these. Among these, bis(acetylacetonato)palladium, dichlorobis(triphenylphosphine)palladium, dichlorobis(benzonitrile)palladium, and tetrakis(triphenylphosphine)palladium are more preferable from the viewpoint of further improving light shielding properties.

The content of the organometallic compound (I) in the solid content of the negative photosensitive composition 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 can be further improved. The content of the organometallic compound is more preferably 1.5% by weight or more. On the other hand, by setting the content of the organometallic compound to 5% by weight or less, the reflectance can be further improved.

The negative photosensitive composition of the present invention can contain (J) a coordinating compound having a phosphorus atom (hereinafter sometimes referred to as "coordinating compound"), if necessary. The coordinating compound coordinates to the organometallic compound in the negative photosensitive coloring composition, improves the solubility of the organometallic compound in a solvent, promotes the decomposition of the organometallic compound, and further improves the light-shielding property. can be made

Coordinating compounds include, for example, triphenylphosphine, tri-t-butylphosphine, trimethylphosphine, tricyclohexylphosphine, tri-t-butylphosphine tetrafluoroborate, tri(2-furyl)phosphine, tris(1- adamantyl)phosphine, tris(diethylamino)phosphine, tris(4-methoxyphenyl)phosphine, tris(O-tolyl)phosphine and the like. You may contain 2 or more types of these. The content of the coordinating compound in the negative photosensitive coloring composition of the present invention is preferably 0.5 to 3.0 molar equivalents relative to the organometallic compound.

Moreover, the negative photosensitive composition of the present invention may further contain a cross-linking agent, an ultraviolet absorber, a polymerization inhibitor, a surfactant, and the like, if necessary.

When the negative photosensitive composition contains a cross-linking agent, cross-linking of the siloxane resin is promoted during heat curing, and the degree of cross-linking of the cured film is increased. Therefore, deterioration in pattern resolution due to melting of the fine pattern during heat curing is suppressed. Curing agents include, for example, nitrogen-containing organic substances, silicone resin curing agents, isocyanate compounds and their polymers, methylolated melamine derivatives, methylolated urea derivatives, various metal alcoholates, various metal chelate compounds, thermal acid generators, photoacid generation material, and the like. You may contain 2 or more types of these. Among these, methylolated melamine derivatives, methylolated urea derivatives, and photoacid generators are preferably used from the viewpoint of the stability of the curing agent, workability of the coating film, and the like.

When the negative photosensitive coloring composition contains an ultraviolet absorber, the light resistance of the cured film can be improved, and the resolution can be further improved. As the ultraviolet absorber, 2-(2H-benzotriazol-2-yl)phenol and 2-(2H-benzotriazol-2-yl)-4,6-tert-pentyl are used from the viewpoint of further suppressing color change due to heating. Phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2(2H-benzotriazol-2-yl)-6-dodecyl-4-methyl Benzotriazole compounds such as phenol, 2-(2′-hydroxy-5′-methacryloxyethylphenyl)-2H-benzotriazole; Benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone; 2-(4,6 -diphenyl-1,3,5triazin-2-yl)-5-[(hexyl)oxy]-phenol and other triazine compounds are preferably used. You may contain 2 or more types of these.

The resolution can be improved by including a polymerization inhibitor in the negative photosensitive composition. Examples of polymerization inhibitors include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone and t-butylcatechol. In addition, commercially available polymerization inhibitors include "IRGANOX" (registered trademark) 1010, "IRGANOX" 1035, "IRGANOX" 1076, "IRGANOX" 1098, "IRGANOX" 1135, "IRGANOX" 1330, "IRGANOX" 1726, " IRGANOX" 1425, "IRGANOX" 1520, "IRGANOX" 245, "IRGANOX" 259, "IRGANOX" 3114, "IRGANOX" 565, "IRGANOX" 295 (these are trade names, manufactured by BASF Japan Ltd.), and the like. . You may contain 2 or more types of these.

By including a surfactant in the negative photosensitive composition, it is possible to improve flowability during application. Examples of surfactants include "Megafac" (registered trademark) F142D, "Megafac" F172, "Megafac" F173, "Megafac" F183, "Megafac" F445, "Megafac" F470, "Megafac" F470, Fac "F475", "Megafac" F477 (these are trade names, manufactured by DIC Corporation) and other fluorine-based surfactants; "BYK" (registered trademark)-333, "BYK"-301, "BYK"-331 , "BYK"-345, "BYK"-307 (the above, trade names, manufactured by BYK-Chemie Japan Co., Ltd.) silicone-based surfactants; polyalkylene oxide-based surfactants; poly(meth)acrylate-based surfactants agents and the like. You may contain 2 or more types of these.

The solid content concentration of the negative photosensitive composition of the present invention can be arbitrarily set according to the coating method and the like. For example, when forming a film by spin coating as described later, it is common to set the solid content concentration to 5% by weight or more and 50% by weight or less. As used herein, the term "solid content" means all of the components contained in the negative photosensitive coloring composition, excluding volatile components such as solvents. The amount of solids can be determined by heating the negative photosensitive composition at 250° C. for 30 minutes to evaporate the volatile components and weighing the residue.

Next, the method for producing the negative photosensitive composition of the present invention will be described below. The negative photosensitive composition of the present invention can be obtained by mixing the aforementioned components (A) to (D) and, if necessary, other components. More specifically, for example, (A) a siloxane resin, (B) a photopolymerization initiator, (C) a photopolymerizable compound, (D) a compound having fluorine in the molecule and, if necessary, other components are stirred. It is preferable to dissolve it with water and filter it.

Next, the board|substrate with a partition of this invention is demonstrated. The substrate with partition walls of the present invention is preferably a cured film of the aforementioned negative photosensitive composition of the present invention. Moreover, the partition wall of the present invention preferably has a thickness of 5 μm or more in order to exhibit good reflectivity.

A method for manufacturing a substrate with partition walls of the present invention will be described. The partition of the present invention is the negative photosensitive composition of the present invention patterned on a base substrate, the base substrate has a function as a support in the substrate with the partition, and the partition will be described later. When pixels containing a wavelength conversion material are provided, it has a function of preventing color mixture of light between adjacent pixels.
The method for producing a substrate with partition walls of the present invention includes the steps of (i) applying the negative photosensitive composition of the present invention onto a base substrate to form a coating film, and (ii) exposing and developing the coating film. and (iii) heating the developed coating film. Each step will be described below.

(i) A step of applying the negative photosensitive composition of the present invention onto a base substrate to form a coating film. A plate, a resin film, etc. are mentioned. Polyester, (meth)acrylic polymer, transparent polyimide, polyethersulfone and the like are preferable as materials for the resin plate and the resin film. The thickness of the glass plate and the resin plate is preferably 1 mm or less, more preferably 0.8 mm or less. The thickness of the resin film is preferably 100 μm or less. Further, a substrate having a color filter layer preliminarily provided on these base substrates or a substrate preliminarily provided with light emitting diodes may be used.

Examples of coating methods include spin coating, slit coating, screen printing, inkjet coating, and bar coater coating.

It is preferable to dry (pre-bake) the substrate coated with the negative photosensitive composition. Examples of the drying method include drying under reduced pressure and drying by heating. Examples of heating devices include hot plates and ovens. The heating temperature is preferably 60 to 150° C., and the heating time is preferably 30 seconds to 3 minutes. The film thickness after prebaking is preferably 5 to 20 μm.

(ii) Step of exposing and developing the coating film Exposure may be performed through a desired mask, or may be performed without a mask. Exposing machines include, for example, a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner (hereinafter "PLA"), and the like. The exposure intensity is generally about 10 to 4000 J/m ² (converted to exposure amount at wavelength 365 nm). Examples of the exposure light source include ultraviolet rays such as i-line, g-line, and h-line, KrF (wavelength: 248 nm) laser, ArF (wavelength: 193 nm) laser, and the like.

Examples of developing methods include methods such as showering, dipping, and puddle. The immersion time in the developer is preferably 5 seconds to 10 minutes. Examples of the developer include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates; amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine; Aqueous solutions of quaternary ammonium salts such as ammonium hydroxide and choline are included. After development, rinsing with water is preferred, followed by dry baking at 50 to 140°C.

(iii) Step of heating the coating film after the development Examples of the heating device include a hot plate and an oven. The heating temperature is preferably 120 to 250° C., and the heating time is preferably 15 minutes to 2 hours.
Thus, the substrate with partition walls of the present invention can be obtained.

Next, the wavelength conversion substrate of the present invention will be explained.
It is preferable that the substrate with partitions of the present invention further includes pixels containing wavelength conversion materials arranged and separated by the partitions. A pixel has a function of performing color display by converting at least part of the wavelength region of incident light and emitting output light in a wavelength region different from that of the incident light. From the viewpoint of improving color characteristics, the thickness of the pixel is preferably 0.5 μm or more, more preferably 1 μm or more. On the other hand, the thickness of the pixel is preferably 30 μm or less, more preferably 20 μm or less, from the viewpoint of thinning the display device and curved surface processing. Also, the size of each pixel is generally about 20 to 200 μm. The pixels are preferably arranged separated by partition walls. By providing a partition between pixels, diffusion and color mixture of emitted light can be further suppressed.

As a method of forming pixels, for example, a method of filling a space separated by a partition wall with a wavelength conversion material coating liquid containing a wavelength conversion material can be used. The wavelength conversion material coating liquid may further contain a resin and a solvent.

As a method for filling the wavelength conversion material coating liquid, an ink jet coating method or the like is preferable from the viewpoint of easily separately coating different types of color conversion luminescent materials on each pixel.

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

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Among the compounds used in Synthesis Examples, Preparation Examples and Examples, those using abbreviations are shown below.
PGMEA: propylene glycol monomethyl ether acetate DAA: diacetone alcohol BHT: dibutylhydroxytoluene.

The solid content concentrations of the siloxane resin solutions in Synthesis Examples 1 to 5 were determined by the following method. 1.5 g of siloxane resin solution or acrylic resin solution was put into an aluminum cup and heated at 250° C. for 30 minutes using a hot plate to evaporate the liquid component. The weight of the solid content remaining in the aluminum cup after heating was weighed, and the solid content concentration of the siloxane resin solution or acrylic resin solution was obtained from the ratio to the weight before heating.

The weight average molecular weight of the acrylic resin in the siloxane resins in Synthesis Examples 1 to 5 was obtained by the following method. Using a GPC analyzer (HLC-8220; manufactured by Tosoh Corporation) and using tetrahydrofuran as a fluidized bed, GPC analysis was performed based on "JIS K7252-3 (enacted date = 2008/03/20)", A polystyrene equivalent weight average molecular weight was measured.

The content ratio of each repeating unit in the siloxane resin in Synthesis Examples 1 to 5 was obtained by the following method. The siloxane resin solution is injected into a “Teflon” (registered trademark) NMR sample tube with a diameter of 10 mm and ²⁹ Si-NMR measurement is performed, and the Si derived from a specific organosilane is compared with the integrated value of the entire Si derived from the organosilane. The content ratio of each repeating unit was calculated from the ratio of the integrated value of. ²⁹ Si-NMR measurement conditions are shown below.

Apparatus: Nuclear magnetic resonance apparatus (JNM-GX270; manufactured by JEOL Ltd.)
Measurement method: Gated decoupling method Measurement nucleus frequency: 53.6693 MHz ( ²⁹ Si nuclei)
Spectrum 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: 0.0 Hz.

Synthesis Example 1 Siloxane resin (A-1) solution In a 500 ml three-necked flask, 59.15 g (0.400 mol) of propyltrimethoxysilane and 41.32 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride were added. , 36.60 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, 11.09 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 24 g (0.05 mol) of methyltrimethoxysilane. 52 g (0.200 mol), 0.561 g of BHT, and 122.34 g of PGMEA were charged, and 1.727 g of phosphoric acid (1.0% by weight based on the charged monomers) was dissolved in 48.60 g of water while stirring at room temperature. Aqueous phosphoric acid was added over 30 minutes.

After that, the flask was immersed in an oil bath at 70° C. and stirred for 90 minutes, and then the oil bath was heated to 115° C. over 30 minutes. One hour after the start of heating, the temperature of the solution (internal temperature) reached 100° C., and the solution was heated and stirred for 1 hour and 30 minutes (internal temperature: 100 to 110° C.) to obtain a siloxane resin solution. A mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liter/min during the temperature rise and heating and stirring. A total of 110.70 g of methanol and water, which are by-products, were distilled during the reaction. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration was 40% by weight to obtain a siloxane resin (A-1) solution. The weight average molecular weight of the obtained siloxane resin (A-1) was 3,700 (converted to polystyrene).

Further, from the measurement results of ²⁹ Si-NMR, propyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-methacryloxypropylmethyldimethoxysilane, 2-(3, The molar ratios of repeating units derived from 4-epoxycyclohexyl)ethyltrimethoxysilane and methyltrimethoxysilane were 40 mol %, 17.5 mol %, 17.5 mol %, 5 mol % and 20 mol %, respectively.

Synthesis Example 2 Siloxane Resin (A-2) Solution The procedure was carried out in the same manner as in Synthesis Example 1 except that the phosphoric acid in Synthesis Example 1 was changed from 1.727 g to 2.590 g to obtain a siloxane resin (A-2) solution. rice field. The weight average molecular weight of the obtained siloxane resin (A-2) was 6,500 (converted to polystyrene).
Further, from the measurement results of ²⁹ Si-NMR, propyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-methacryloxypropylmethyldimethoxysilane, 2-(3, The molar ratios of repeating units derived from 4-epoxycyclohexyl)ethyltrimethoxysilane and methyltrimethoxysilane were 40 mol %, 17.5 mol %, 17.5 mol %, 5 mol % and 20 mol %, respectively.

Synthesis Example 3 Siloxane Resin (A-3) Solution The procedure was carried out in the same manner as in Synthesis Example 1 except that the phosphoric acid in Synthesis Example 1 was changed from 1.727 g to 0.863 g to obtain a siloxane resin (A-3) solution. rice field. The weight average molecular weight of the obtained siloxane resin (A-3) was 2,800 (converted to polystyrene).
Further, from the measurement results of ²⁹ Si-NMR, propyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-methacryloxypropylmethyldimethoxysilane, 2-(3, The molar ratios of repeating units derived from 4-epoxycyclohexyl)ethyltrimethoxysilane and methyltrimethoxysilane were 40 mol %, 17.5 mol %, 17.5 mol %, 5 mol % and 20 mol %, respectively.

Synthesis Example 4 Siloxane resin (A-4) solution In a 500 ml three-necked flask, 87.97 g (0.400 mol) of diphenyldimethoxysilane, 41.32 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 36.60 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, 11.09 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 24.52 g of methyltrimethoxysilane (0.200 mol), 0.743 g of BHT, and 158.37 g of PGMEA were charged and stirred at room temperature. The aqueous acid solution was added over 30 minutes.

After that, the flask was immersed in an oil bath at 70° C. and stirred for 90 minutes, and then the oil bath was heated to 115° C. over 30 minutes. One hour after the start of heating, the temperature of the solution (internal temperature) reached 100° C., and the solution was heated and stirred for 1 hour and 30 minutes (internal temperature: 100 to 110° C.) to obtain a siloxane resin solution. A mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liter/min during the temperature rise and heating and stirring. A total of 95.94 g of methanol and water, which are by-products, were distilled during the reaction. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration was 40% by weight to obtain a siloxane resin (A-4) solution. The weight average molecular weight of the obtained siloxane resin (A-4) was 1,800 (converted to polystyrene).

Further, from the measurement results of ²⁹ Si-NMR, diphenyldimethoxy, 3-trimethoxysilylpropylsuccinic anhydride, 3-methacryloxypropylmethyldimethoxysilane, 2-(3,4- The molar ratios of repeating units derived from epoxycyclohexyl)ethyltrimethoxysilane and methyltrimethoxysilane were 40 mol %, 17.5 mol %, 17.5 mol %, 5 mol % and 20 mol %, respectively.

Synthesis Example 5 Acrylic resin (A-5) solution After charging 3.00 g of 2,2′-azobis(isobutyronitrile) and 50.0 g of PGMEA into a 500 mL flask, 30.0 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, stirred at room temperature for a while, and the flask was After purging the inside with nitrogen, the mixture was 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 resulting solution and heated at 90° C. for 4 hours. The mixture was stirred to obtain a (meth)acrylic polymer solution. PGMEA was added to the obtained (meth)acrylic polymer solution so that the solid content concentration was 40% by weight to obtain a (meth)acrylic polymer solution (A-5). The (meth)acrylic polymer had a weight average molecular weight of 16,000.

Tables 1 and 2 show raw material compositions of the siloxane resins of Synthesis Examples 1 to 4 and the acrylic resin of A-5.

Evaluation in each example and comparative example was performed by the following methods.

<Preparation of cured film>
Using a spin coater (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), the negative photosensitive compositions obtained in each example and comparative example were coated on a 10 cm square alkali-free glass substrate after curing. It was spin-coated to a film thickness of 10 μm and dried at 25° C. and 100 Pa for 1 minute using a vacuum hot plate (manufactured by Toray Industries, Inc.). The dried film was further prebaked at 100° C. for 3 minutes using a hot plate (trade name: SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) to prepare a prebaked film having a thickness of 10 μm.

Using a parallel light mask aligner (trade name: PLA-501F, manufactured by Canon Inc.), the prepared pre-baked film is exposed with an exposure amount of 400 mJ/cm ² (i-line) without a mask, using an ultra-high pressure mercury lamp as a light source. bottom. Then, using an automatic developing device ("AD-1200 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.), shower development is performed using a 0.045% by weight potassium hydroxide aqueous solution for 80 seconds, and then water is used for 30 seconds. Rinse for seconds. The obtained film after development was cured in air at a temperature of 230° C. for 30 minutes using an oven (trade name: IHPS-222, manufactured by ESPEC Co., Ltd.) to prepare a cured film.

<Surface free energy>
For the obtained cured film, using a contact angle meter DropMaster DM501 (manufactured by Kyowa Interface Science Co., Ltd.), the values of surface free energy, dispersion force, polar force, and hydrogen bonding force were measured at 25 ° C. and 65% RH. The contact angles of water, diiodomethane, and 1-bromonaphthalene were measured as known measurement liquids. The measurement was performed 5 times for one measurement surface, and the average value was defined as the contact angle (θ). From the obtained contact angle (θ) value and the known value of each liquid to be measured (Method IV by Panzer (described in the Journal of the Adhesion Association of Japan, Vol. 15, No. 3, p. 96), the formula of Kitazaki and Hata Values of dispersion force, polar force, and hydrogen bonding force of the cured film were calculated using the following equations to be introduced.

Here, γLd, γLp, and γLh represent the dispersion force, polar force, and hydrogen bonding force of the measured liquid, respectively, and θ represents the contact angle of each measured liquid on the cured film. γSd, γSp, and γSh represent the dispersion force, polar force, and hydrogen bonding force of the surface of the cured film, respectively, and γL represents the surface energy of each liquid to be measured. γSd, γSp, and γSh on the surface of the cured film were obtained by solving simultaneous equations obtained by substituting known values and θ into the above equations. From these values, the surface free energy was calculated by the following formula.
Surface free energy = γSd + γSp + γSh.

<XPS>
The cured film obtained by the method described above was analyzed using an XPS analyzer (Quantera SXM (manufactured by PHI) under the following conditions.
Excitation X-ray: monochromatic AlKα _1,2 ray (1,486.6 eV)
X-ray diameter: 200 μm
Photoelectron detection angle: 45° (tilt of detector with respect to sample surface Detection elements: fluorine, oxygen, carbon, silicon, nitrogen, titanium and wide scan data processing: C1s main peak is set to 284.6 eV, and the peak attributed to C1s is Separated into four peaks of 284.6 eV, 286.0 eV, 288.6 eV, and 293 eV Analysis items: C _{CHx for the area of 284.6 eV, and} C _{COO for the area of 288.6 eV.}

<Reflectance>
For the cured film obtained by the method described above, a spectrophotometer (trade name: CM-2600d, manufactured by Konica Minolta, Inc.) was used to measure the reflectance at a wavelength of 550 nm in SCI mode from the film side. .

<FT-IR>
The cured film obtained by the method described above was measured by total reflection infrared spectroscopy (ATR). Avatar 360FT-IR measuring instrument manufactured by Nicolet Co., Ltd. is used as the measuring instrument, and a single reflection horizontal ATR measuring instrument (OMNI-Sampler) manufactured by Nicolet Co., Ltd. and a diamond ATR crystal are used as accessories for total reflection measurement. to measure the sample surface. As measurement conditions, the resolution was set to 4 cm −1 and the number of scans was set to 32 times. The obtained spectrum was expressed in terms of absorbance, and after performing auto-baseline correction, analysis was carried out for the presence of an absorption peak derived from Si—C bonds at 1220 to 1290 cm ⁻¹ .

Example 1
(F) As a white pigment, 5.00 g of titanium dioxide pigment (R-960; manufactured by BASF Japan Co., Ltd.) is mixed with 5.00 g of siloxane resin (A-1) solution as (A) siloxane resin, and zirconia Dispersed using a mill-type disperser filled with beads to obtain a pigment dispersion (MW-1). Furthermore, as a black pigment, titanium nitride (manufactured by Wako Pure Chemical Industries, Ltd.; particle size: 50 nm, titanium content: 74.3% by weight, nitrogen content: 20.3% by weight, oxygen content: 2.94% by weight %) and 5.00 g of siloxane resin (A-1) solution as (A) siloxane resin, and dispersed using a mill-type dispersing machine filled with zirconia beads to obtain a pigment dispersion (MW -2) was obtained.

Next, 4.800 g of pigment dispersion (MW-1), 0.08 g of pigment dispersion (MW-2), 11.21 g of siloxane resin (A-1) solution, (B) ethanone as a photopolymerization initiator, 1 -[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (“Irgacure” (registered trademark) OXE-02 (trade name) BASF Japan Co., Ltd. (hereinafter “OXE-02”)) 0.180 g, bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide (“Irgacure”-819 (trade name), manufactured by BASF Japan Ltd.) ) 0.36 g, (C) as a photopolymerizable compound, pentaerythritol acrylate (“Light Acrylate” (registered trademark) PE-4A (trade name), manufactured by Kyoeisha Chemical Co., Ltd.) 3.00 g, 3′, 4′ -epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (“Celoxide” (registered trademark)-2021P (trade name), manufactured by Daicel Corporation) 0.24 g, ethylenebis(oxyethylene)bis[3-(5 -tert-butyl-4-hydroxy-m-tolyl)propionate] (“Irganox” (registered trademark)-1010 (trade name), manufactured by BASF Japan Co., Ltd.) 0.04 g, KBM-303 (Shin-Etsu Chemical Co., Ltd. Ltd.) 0.24 g, (D) as a compound having fluorine in the molecule (“Megafac” (registered trademark) RS-72-A (trade name) manufactured by DIC Corporation (hereinafter “RS-75-A” ))) 0.20 g of a 30% by weight PGMEA diluted solution, 0.15 g of a 10% by weight diluted solution of PGMEA (concentration equivalent to 500 ppm) was dissolved in a mixed solvent of 0.90 g of DAA and 8.60 g of PGMEA and stirred. Then, filtration was performed with a 5.0 μm filter to obtain a negative photosensitive composition (P-1). The resulting negative photosensitive composition (P-1) was evaluated for surface free energy, XPS analysis, and reflectance.

Examples 2-9, Comparative Examples 1-3
As shown in Table 3, negative photosensitive compositions (P-2) to (P-12) were obtained in the same manner as in Example 1. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive compositions (P-2) to (P-12).
Table 3 shows the compositions of Examples 1 to 9 and Comparative Examples 1 to 3, and Table 4 shows the evaluation results.

a: Underlying substrate b1: Partition b2: Upper surface of partition c: Black matrix (BM)
d: color filter e: overcoat (OC)
f: organic light-emitting element or light-emitting diode g: wavelength conversion layer

Claims (9)

A substrate with barrier ribs, characterized by having cells partitioned by a cured product for a display device, wherein XPS analysis of the top surface of the barrier ribs has a photoelectron detection angle of 5°, a main peak of C1s of 284.6 eV, and 284 When separated into four peaks of .6 eV, 286.0 eV, 288.6 eV, and 293.0 eV, the peak area C _CHx of 284.6 eV and the peak area C _COO of 288.6 eV satisfy the following relational expression (I): and a ratio F/C of fluorine atoms F to carbon atoms C in the XPS analysis satisfies the following relational expression (II).
0.1≦C _COO /C _CHx ≦0.4 (I)
0.1≦F/C≦0.4 (II) 2. The substrate with partition walls according to claim 1, wherein the ratio Si/C of silicon atoms Si and carbon atoms C in the XPS analysis of the upper surfaces of the partition walls satisfies relational expression (III).
0.02≦Si/C≦0.3 (III) 3. The substrate with partition walls according to claim 1, wherein the partition walls have an absorption peak at 1220 to 1290 cm ⁻¹ derived from Si—C bonds in FT-IR analysis. 4. The substrate with partition walls according to claim 1, wherein the partition walls reflect 20 to 85% of light with a wavelength of 550 nm. The wavelength conversion substrate according to any one of claims 1 to 4, wherein the substrate with partition walls has a wavelength conversion layer in cells partitioned by the partition walls. 6. The method of manufacturing a wavelength conversion substrate according to claim 5, wherein the wavelength conversion layer is applied by an inkjet method or a nozzle coating method. The partition contains (A) a siloxane resin, (B) a photopolymerization initiator, (C) a photopolymerizable compound, and (D) a compound having fluorine in the molecule, and (A) the siloxane resin has the following general formula ( 1) and/or a cured composition containing 10 to 50 mol % of repeating units represented by general formula (2) in all repeating units. A substrate with partitions as described.

(R ² represents a linear alkylene group having 1 to 6 carbon atoms, R ¹ represents a hydrogen atom or a methyl group, and R ³ represents an alkyl group having 1 to 20 carbon atoms. * represents a bonding site. ) 8. The substrate with partition walls according to claim 7, wherein the composition further contains (E) a silane coupling agent. 9. The substrate with partition walls according to claim 8, wherein the composition satisfies the following relational expression.
E: (E) Content of silane coupling agent in total solid content in composition (wt%)
Mw: (A) polystyrene equivalent weight average molecular weight E ≤ 10 (wt%) of siloxane resin (IV)
E≧(-0.008Mw+4,566) (wt%) (V)

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